Accepted Manuscript

Recent developments and advances in boron-doped diamond electrodes for

electrochemical oxidation of organic pollutants

Yapeng He, Haibo Lin, Zhongcheng Guo, Wenli Zhang, Hongdong Li, Weimin
Huang

PII: S1383-5866(17)34257-0
DOI: https://doi.org/10.1016/j.seppur.2018.11.056
Reference: SEPPUR 15106

To appear in: Separation and Purification Technology

Received Date: 27 December 2017

Revised Date: 16 November 2018
Accepted Date: 16 November 2018

Please cite this article as: Y. He, H. Lin, Z. Guo, W. Zhang, H. Li, W. Huang, Recent developments and advances
in boron-doped diamond electrodes for electrochemical oxidation of organic pollutants, Separation and Purification
Technology (2018), doi: https://doi.org/10.1016/j.seppur.2018.11.056

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 Recent developments and advances in boron-doped diamond

electrodes for electrochemical oxidation of organic pollutants

Yapeng He a, b, Haibo Lin *a, c, Zhongcheng Guo b, Wenli Zhang a, Hongdong Li d,
Weimin Huang *a, c
a
College of Chemistry, Jilin University, Changchun 130012, China
b
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology,
Kunming 650093, China
c
Key Laboratory of Physics and Technology for Advanced Batteries of Ministry of Education, Jilin
University, Changchun 130012, China
d
State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012, China
* Corresponding author. Tel.: +86 431 85155189;
E-mail address: lhb910@jlu.edu.cn (H. Lin), huangwm@jlu.edu.cn (W. Huang)

Abstract

Boron-doped diamond (BDD) electrode has been considered as an optimal

electrode material for electrochemical oxidation of organic contaminants in the

aquatic environment due to its good physical and chemical properties. The

fundamental research and practical application of BDD electrode in the mineralization

of organic pollutants have been well developed up to now. In this review, the

preparation and electrochemical properties of BDD film electrode are focused first.

Then, we investigate the electrocatalytic process and degradation mechanisms on

BDD electrodes based on the electrochemical oxidation of refractory pollutants in

recent years. The enhancement approaches towards electrochemical oxidation kinetics

are further highlighted, which include the establishment of high activity BDD

electrodes and enhancement of mass transfer process during the electrochemical

oxidation. Other combination technologies based on electrochemical oxidation with

BDD electrode are also described to expand the application of BDD electrode in

wastewater treatment. Further, the opportunity and prospective of BDD electrode are

1
forecasted according to the existing problems in wastewater treatment.

Keywords

Boron-doped diamond electrode; Electrochemical oxidation; Wastewater treatment;

Organic contaminants; Degradation kinetics

Contents

1. Introduction

2. Electrochemical oxidation mechanisms and electrode materials

2.1 Direct and indirect oxidation

2.2 Electrode materials

3. Preparation and properties of BDD

3.1 BDD electrode and its preparation

3.2 Research on the properties of BDD

3.3 Construction of porous BDD

4. Application of BDD to electrochemical oxidation

4.1 Electrochemical mineralization on BDD electrode

4.2 Electrochemical degradation kinetic

4.3 Enhancement approaches for electrochemical mineralization

5. Combination of other processes for elimination

5.1 Composite electrodes

5.2 Energy-assisted

5.3 Photo-assisted

5.4 Electro-Fenton

5.5 Other combination technologies

6. Perspectives and outlook

7. Summary and conclusions

2
1. Introduction

With the rapid development of modern economy and society, thousands of tons

of complex anthropogenic chemicals are consumed and discharged into the water

environment worldwide each year. As a consequence, numbers of contaminants have

been detected at the surface, ground or even in drinking water, and they would present

a potential hazard to human health even at trace level as the contaminants are highly

toxic and difficult to degrade. The existence of toxic and refractory organic pollutants

further increases the complexity of the wastewater treatment in the following stage,

which will potentially generate severe risks to both human body [1] and ecosystem

especially when no appropriate wastewater treatments are adopted before reaching the

aquatic system. Besides, the presence of these contaminants has caused a rising public

concern and affects the sustainable development of the whole earth. Particularly, the

removal of environmental pollutants becomes a major issue and crucial factor for the

sustainable development of modern industrial processes.

Until now, various treatment methods, such as biological, physical and chemical

remediation technology have been extensively investigated to eliminate organic

pollutants in the aquatic environment [2, 3]. Unfortunately, above methods usually

meet diverse problems when taking into account the efficiency, feasibility and cost,

etc. On the other hand, electrochemical advanced oxidation processes (EAOPs) [4-6],

which involve in situ generation of strong oxidants, have been considered as a

powerful technology in degradation of a wide variety of organic pollutants over the

past years [7-9]. The green technology has exhibited great potential and promising

3
prospect in the removal of contaminants, due to the merits of versatility,

environmental compatibility and potential cost effectiveness. Up to now, many

researchers have provided a deep overview on the fundamental aspects of

electrochemical oxidation and give updated information on the application of the

technology in wastewater treatment [10-14].

During electrochemical oxidation, it is necessary to establish certain indexes

including current efficiency and energy consumption for project evaluation and

efficiency assessment towards the electrochemical treatment first. Current efficiency

(Φ) is generally defined as the percentage of the experimental charge for the oxidation

of organic compound to the total charge passed during electrolysis. Despite the fact

that different expressions of current efficiency are proposed, the equations most

commonly adopted in the literature are determined by Chemical Oxygen Demand

(COD) and Total Organic Carbon (TOC) using the following relationships [15, 16]:

QExp COD0 - CODt

  FV
QTotal 8I t (1)

TOCexp

TOCtheor (2)
Itnc M
TOCtheor  103
Vne F (3)

where COD0 and COD∆t are the COD values at times 0 and ∆t (in g O2 L−1),

respectively, I is the current (A), F is Faraday’s constant (96485 C mol−1), V is the

electrolyte volume (L), and 8 is the oxygen equivalent mass (g eq −1). ∆TOCexp and

∆TOCtheor are the experimental and theoretical TOC change values during treatment

time (mg L−1), respectively, ne is the number of electrons consumed in the

4
mineralization of organic pollutant molecule, nc is the number of carbon atoms in

organic pollutant molecule, M is the molar mass of carbon (12 g mol−1). The specific

energy consumption (Esp), expressed in Wh L−1 (or Wh kg COD−1, Wh kg TOC−1,), is

the energy consumed to remove a unit volume (or mass COD, TOC) wastewater and

can be calculated using the following relationships [14, 15]:

U c It
Esp 
V (4)

U c It
Esp 
V CODexp (5)

U c It
Esp 
V TOCexp (6)

where Uc is the voltage (V), I is the applied current (A), t is the electrolysis time (h),

and V is the solution volume (L); ∆CODexp and ∆TOCexp are the concentrations of the

removed COD and TOC (mg L−1).

Generally speaking, electrochemical oxidation essentially proceeds on the

electrode/solution interface. Electrode materials, as a key part in the electrolysis

process, play a crucial role in the electrochemical oxidation process, which directly

concerns the efficiency, selectivity and energy of the process. Among the electrode

materials for electrochemical oxidation, BDD electrode has been considered as an

optimal electrode material to mineralize organic contaminants in the aquatic

environment due to its good physical and chemical properties [17]. The general study

on electrochemical oxidation with BDD electrodes has been well developed, and this

review presents an in-depth overview on the approaches and application for removal

of pollutants in wastewaters on BDD electrodes based on recent literature. First, we

5
briefly summarize the electrochemical oxidation approaches towards organic

pollutants and corresponding electrode materials for wastewater treatment. Then, the

preparation courses and specific features of BDD electrodes are discussed in more

details. Moreover, we investigate the enhancement approaches towards

electrochemical oxidation kinetics from the available references. Finally, the

combination of other technologies with electrochemical oxidation technique is

analyzed in terms of enhancing the removal efficiency and expanding the application

of the BDD electrode in wastewater treatment.

2. Electrochemical oxidation mechanisms and electrode materials

2.1 Direct and indirect oxidation

Based on degradation mechanisms during electrochemical oxidation, anodic

oxidation of organic contaminants could be primarily performed in two patterns,

direct and indirect oxidation [15]. During direct anodic oxidation, there is usually only

involvement of electron transfer without any other substances, where the pollutants

are directly destroyed by electron after the adsorption on anode surface. Hence, the

process is mainly controlled by the compound transport and electron transfer rate at

electrode/solution interface. In general, oxidation of pollutant is theoretically possible

at less positive potentials than those required for oxygen evolution reaction. However,

this process commonly results in electrode fouling due to the formation of polymer

layers on the electrode surface, which consequently yields very poor chemical

decontamination capacity and shortens the service life of anode materials [18]. For

example, Comninellis and co-workers [19] observed the electro-oxidation behavior of

6
phenol involving direct electron transfer reactions in the potential region of water

stability (E<2.3 V vs SHE) on BDD surface via cyclic voltammetry and

chronoamperometry. They concluded that an anodic current peak corresponding to the

oxidation of phenol at about 1.67 V results in electrode fouling due to the formation

of polymeric adhesive film on the electrode surface.

Indirect oxidation involves in-situ electrogeneration of chemical oxidant species

with high oxidizing power, such as H2O2, O3, persulfate and active chlorine, which are

able to facilitate the contaminant mineralization and have shown to be more efficient

for the oxidation of various organic compounds [20, 21]. At the present stage, indirect

oxidation based on oxygen evolution reaction is mostly employed in electrochemical

oxidation process, which could avoid some drawbacks of direct oxidation for organic

pollutants. The procedure allows partial or total decontamination of organic pollutants

at the anodes due to the participation of the electrogenerated intermediates, called

physically adsorbed ‘‘active oxygen’’ (adsorbed hydroxyl radicals •OH) or

chemisorbed “active oxygen” (oxygen in the lattice of metal oxide (MO) anode). Here,

what needs to be emphasized is that the formation of oxide depends heavily on the

nature of anode materials, which could be distinguished as active and non-active

electrodes. Higher oxidation states are available on active electrode surface and

adsorbed •OH radicals interact with the anode, forming the so-called higher oxide. In

other words, MO/M redox couples, called chemisorbed “active oxygen”, act as a

mediator in the conversion and selective oxidation of organics on “active” electrodes

sometimes. For the non-active anodes, the formation of •OH radicals, called

7
physisorbed “active oxygen”, could assist the non-selective oxidation of organics,

which ensures the complete combustion of organic compounds to CO2. According to

above oxidation mechanisms, oxygen evolution overpotential (OEP) is commonly

served as an evaluation criteria to distinguish the anode materials, where anodes with

low OEP have an active anode behavior, and anodes with high OEP possess a

non-active anode behavior. The detailed mechanisms of electrochemical degradation

of organic pollutants are displayed in Fig. 1. In fact, both direct and indirect oxidation

behavior usually exist in the practical electrochemical oxidation system. Rocha and

co-workers [22] discussed the electrochemical oxidation of Novacron Yellow C-RG

on Pt and BDD anodes, concluding that the direct/indirect electrochemical processes

favor specific oxidation pathways depending on electrocatalytic material due to the

strong oxidants electrogenerated on the electrode surface in the presence of halogen

salt. Finally, Pt anode favors preferentially color removal by direct and indirect

oxidation with 100% color removal due to the cleavage of the azo dye bonds.

Meanwhile, BDD electrode favors color and organic load removals in both processes

(95% and up to 87%, respectively) due to its chemical structure rupture in different

parts of dye.

8
Figure 1 Mechanism diagram of electrochemical degradation organic pollutants on non-active

(reactions a, b and e) and active anodes (reactions a, c, d and f); black line indicates the direct

oxidation; (a) generation of hydroxyl radicals, •OH, (b) oxygen evolution based on •OH, (c)

formation of the higher metal oxide, MO, (d) oxygen evolution base on chemical decomposition

of MO, (e) electrochemical combustion of the organic compound via •OH, (f) electrochemical

conversion of the organic compound, R, via MO. Reprinted with permission from Ref. [15]

2.2 Electrode materials

As described above, electrode materials play a crucial role in the electrochemical

oxidation [23-25], which straightway determines the Φ, selectivity and Esp for the

organic pollutants. Table 1 list the anode materials adopted in wastewater treatment

according to their types and oxidation power. Active anodes such as IrO2, RuO2 or Pt

favor the partial and selective oxidation of pollutants, while non-active anodes such as

SnO2, PbO2 or BDD can give the complete combustion. Thus, non-active anodes are

regarded as desirable electrodes for the complete oxidation of organics to CO 2 during

wastewater treatment. Simultaneously, the degradation of various pollutants has been

9
conducted on different electrode materials, and the merits/demerits have been also

well investigated [26] according to actual experimental results.

Table 1 Classification of anode materials based on oxidation power and potential for OER in

acidic media. Reprinted with permission from Ref. [27]

Anode Compostion Electrocata Oxidation Over- Adsorption Oxidat

type lytic ability Potential potential enthalpy of ion
for OER (V) (V) M-•OH power
RuO2-TiO2 Good 1.4-1.7 0.18 Chemisorption Lower
(DSA® -Cl2)
IrO2-Ta2O5 Good 1.5-1.8 0.25
Active (DSA®-O2)
(Ti/Pt) Good 1.7-1.9 0.30
Carbon and Good 1.7
Graphite
Non- Ti/PbO2 Poor 1.8-2.0 0.50
active Ti/SnO2-Sb2O5 Poor 1.9-2.2 0.70
BDD Poor 2.2-2.6 1.3 Phyisorption Higher

Platinum (Pt) electrodes with relatively low OEP (i.e., 1.6 V vs SHE in 0.5 M

H2SO4) have been reported in the oxidation of a wide range of bio-refractory organic

compounds in many studies. During degradation of aromatic compounds on Pt,

aromatic intermediates were initially formed during the electrolysis process, and the

aromatic ring opened subsequently with the formation of aliphatic acids. However,

complete TOC removal could not be achieved, and the characters of high price and

fouling of Pt electrode further restrict the practical application in the real system.

Dimensionally stable anodes (DSA) [28] coated with metal oxides layers have

been extensively employed in many electrochemical industries, such as the chlorine

alkali industry, water electrolysis, and metal electrowinning due to their mechanical

resistance as well as relatively inexpensive. Meanwhile, successful scale-up has

10
demonstrated the practicability of DSA electrodes in the field of wastewater treatment.

However, because they favor the secondary oxygen evolution reaction, DSA-type

anodes usually encounter low current efficiency for complete combustion of organic

pollutants. The development of PbO2 anodes for the oxidation of organics has gained

great interest in environmental applications because of their good conductivity and

relative large overpotential for oxygen evolution reaction in acidic media, which

enables the production of hydroxyl radicals during water discharge. However,

practical applications in the oxidation of organics with PbO2 electrode have been

limited due to its relatively shorter service life as well as concerns from the possible

release of Pb(IV) ions into the water. The detailed reason could be related to the

occurrence of cracks from the increasing internal stress in PbO2 coating. In order to

improve the stability and electrocatalytic activity of PbO2 electrodes, one common

approach being widely investigated is the incorporation of foreign species into the

PbO2 layer [29, 30].

Meanwhile, the usage of BDD electrodes in chemical destruction of pollutants

has received great attention in recent years. High oxygen evolution potential with 2.4

V vs SHE distinguishes BDD electrode from conventional anodes. BDD electrode has

been considered as an optimal electrode material for electrochemical oxidation of

organic contaminants in aquatic environment [31-34] and received great attention in

the last decades as a new electrode material. In the following, we will discuss the

relevant information and application of BDD electrode in wastewater treatment

in-depth.

11
3. Preparation and properties of BDD

3.1 BDD electrode and its preparation

As we know, face-centered-cubic crystallite structure consisting of

sp3-hybridised orbital endows diamond film excellent properties in many fields, for

instance, mechanical, electronical, thermology and chemical. However, intrinsic

diamond film with a wide band gap of 5.47 eV is one typical insulation material and

the resistivity reaches as high as 1012 Ω cm−1, which could not be applied in the field

of electrochemistry unless the successful transformation to semiconductor or

conductor. Then, the introduction of impurity atoms into the carbon lattice becomes

the common approach to accomplish the transformation [35]. Based on the impurity

atoms and corresponding doping functionality, there are two types of diamond doping,

including p-type and n-type doping, and schematic illustrations for doping at the

atomic level are graphically depicted in Fig. 2a. In the diamond lattice structure, each

C atom is shared with four other C atoms and possesses four electrons in its outer

shell. Here, the valence band is completely filled with eight electrons per C atom,

forming an extremely stable crystal structure. Introduction into diamond of group IV

impurity atoms with five electrons in valence shell, such as N, P atom, results in

n-type doping, where additional free electrons are supplied to the diamond lattice

when N, P (donor atom) is incorporated into the diamond lattice [36, 37]. On the

contrary, introduction into diamond of group III impurity atoms with three electrons

in valence shell, for instance B atoms, leads to p-type doping in turn. When B (here

called acceptor atom) is incorporated into the diamond lattice, an electron deficiency

12
or a positively charged hole is directly created in the energy level above the valence

band of diamond. The hole can be filled by the electron movement from the valence

shell of a neighbouring C atom to the hole of B atom. Simultaneously, BDD is one

widely researched electrode material among doped diamonds due to its easily

available doping way. At the same time, the conductivity of BDD film increases with

the dopant level of B atom [38], exhibited in Fig. 2b, and the electrode presents a

metal-like conductivity when containing enough boron. Moreover, electrical

measurements demonstrate that average [B]~3× 1020 atoms cm–3 is found to be

optimal. Then, BDD electrode could be further adopted as an optional electrode in

electrochemistry research, such as electrochemical oxidation, electroanalysis,

electrosynthesis and energy conversion.

Due to the rare reserve of natural diamond on the earth, numerous artificial

attempts were made to synthesize diamond. High Pressure High Temperature (HPHT)

was firstly adopted to produce diamond from graphite via imitating the natural

process. Whereas, the procedure usually requires metal solvent, and the quality or size

of end diamond products are not satisfactory with many impurities (graphite, alloy,

etc.), leading to application-limiting defects during the diamonds production. One

more friendly and flexible method was obtained with the development of Chemical

Vapor Deposition (CVD) technique, allowing the operation under lower pressure and

temperature regimes [39]. The procedure enables the activation of carbon-containing

gas precursor consisting of methane (CH4 ) and hydrogen gas (H2) by

energy/heat-assisted way (hot wire, microwave or plasma etc.), resulting in the

13
deposition of diamond grains on certain substrates. With this technique, it became

possible to deposit thin diamond film on a variety of substrates within reasonable time

scale and controllable dopant level, which is regarded as the most adopted deposition

method for high quality diamond film [40].

On the other hand, the successful deposition of high quality diamond usually

requires strict and proper reaction conditions [41-43], which could include carbon

source concentration, temperature, pressure and bias voltage etc. These parameters

affect the nucleation rate of diamond grain, then the growth rate and quality during

the deposition. Depending on the size of the diamond crystals, diamond is composed

of microcrystalline diamond (MCD), nanocrystalline diamond (NCD) and

ultrananocrystalline diamond (UNCD) [44], as presented in Fig. 2c. Commonly, MCD

diamond exhibits grain size larger than 1 µm with large roughness, and some special

applications usually require grain size reduced to the nanometer level. NCD coatings

exhibit grain sizes between 10 nm and 1 µm with moderate amount sp 2-bonded carbon

trapped at defects or grain boundaries. UNCD possesses extremely low grain size

(<10 nm) and roughness (<100 nm), where the small grain size and high grain

boundary density could facilitate the incorporation of graphitic carbon [44-46]. The

deposition of NCD films was investigated employing 1% CH4 in H2 gas mixture to

explore the effect of pressure [47]. It was found that a gradual reduction of diamond

grain sizes from sub-micrometer to tens of nanometers was achieved and the surface

roughness of diamond films also decreased with the reduction of deposition pressure

from 5.0 kPa to 0.125 kPa. Besides, diamond films grown in hydrogen plasma were

14
predominantly MCD. Different techniques for growing NCD have been reported in

the literature, where the nucleation density can be further increased if the growth of

diamond occurs on an MCD film using CH4 concentration above 1.6%, leading to the

formation of NCD. However, the film still consists of graphite particles as well as

amorphous carbon, and the following hydrogen plasma treatment is an effective way

to remove such non-diamond and amorphous carbon phases. Beyond that, it could

also be found that UNCD with fine grain size can be prepared from a hydrogen-poor

deposition situation. As for the performance, there is an intimate connection between

the electron transfer/mineralization ability and the grain size of diamond film [45],

which would be discussed in the next part.

Figure 2 (a) Schematic diagram of n-type and p-type semiconductor material at the atomic level;

(b) The resistivity as a function of boron doping concentration; (c) SEM images of micro-, nano-

and ultranano-diamond film. Reprinted with permission from Ref. [35] and [38]

Commonly, researchers obtain BDD electrodes from three different approaches:

their own home-built systems, commercial growth systems and purchasing from

commercial companies, as listed in Table 2. The size, stability and construction cost of

the electrodes are the main considerations in the commercial application. One

important challenge to make BDD large-scale commercial reality is its high

15
 manufacturing cost and lack of ideal substrate material. However, the deposition

equipment and practical production cost for BDD anodes are not optimistic at the

current period though single piece BDD anode with magnitude of square meters have

been produced from the industry.

Table 2 Lists of commercial companies selling BDD electrodes.

Diamond Supplier Country Website Material properties

Condias Germany http://condias.de/en/ Microcrystalline BDD films
(Diachem®) coated on Ti, W, Nb, Si
CSEM Switzerland http://www.csem.ch/home Microcrystalline BDD electrodes
coated on Ti, W, Nb, Si
Advanced Diamond USA http://www.thindiamond.c UNCN BDD film electrodes on
Technology (UNCD®) om/ Si, Mo, SiC, W, TiAl4V6, SiO2
METAKEM Germany http://www.metakem.de/ Polycrystalline diamond on Nb
W, Ta, graphite, Si, SiC
Element Six Luxembourg http://www.e6.com/ DIAFILM EA and EP grades
NeoCoat Switzerland http://www.neocoat.ch/en Microcrystalline BDD film
electrodes coated on Nb, Ta or Si

For the deposition process, BDD film must be deposited on a substrate material,

such as Si, Ti, Nb, Mo and carbon material. Among them, Titanium (Ti) substrate [48]

turns out to be a desirable material as a result of its high conductivity, corrosion

resistance, and other excellent physical and mechanical properties. Ti has been studied

as an attractive material over the past six decades for industry and biomedical

application. Especially, its low density and high strength will obviously improve the

industrial feasibility of Ti/BDD. Correspondingly, Ti/BDD electrode will exhibit

excellent application in the future as a promising electrode material. According to the

reports and experience in real experiment, the service life is the main problem for

Ti/BDD electrode as the presence of TiC intermediate layer, which was formed due to

the diffusion of carbon species into titanium phase prior to the diamond formation.
16
The TiC layer could improve the conductivity of the electrode first, on the other hand,

the rough and porous structure would result in deterioration of the film adhesion and

stability of the electrode [49]. Thus, many efforts have been made to improve the

stability or lifetime of BDD based on Ti substrate. Chen and co-workers [50]

fabricated stable Ti/BDD electrode using two-stage substrate temperature by

developing a Ti/TiC/(diamond+amorphous carbon)/diamond multilayer structure to

increase the film adhesion, thus significantly increase accelerated lifetime tests to 804

h. Moreover, for the Ti/BDD film electrode, high boron concentration in the reactor

could ensure the conductivity of BDD electrode and inhibit the formation of TiC

phase as reported by Gerger and co-workers [51], which had a favorable effect on the

stability of Ti/BDD electrode. As boron element influences the interlayer formation,

the high concentration of doped boron can inhibit the formation of TiC, and addition

of boron is favored for adhesion enhancement. Sun and co-workers [52] proposed a

two-stage boron approach to inhibit the formation of TiC layer and further improved

the stability of the BDD electrode. Although many efforts have been made for the

practical application of Ti/BDD electrode in real system, further improvement of the

stability is still required to be developed in the future.

3.2 Research on the properties of BDD

High quality BDD film electrodes exhibit several important technological

properties including excellent physical and chemical properties that distinguish them

from conventional electrode materials, as shown in the following [17].

(1) Wide potential window in aqueous and non-aqueous solution

17
 The H2 evolution commences at ~−1.2 V vs SHE and O2 evolution begins at

~+2.4 V vs SHE, which endow BDD electrode wide potential window. Generally,

H2/O2 evolution reaction is a multi-step electron transfer reaction and conducted

based on adsorption of reaction intermediates. There is a closed relationship between

potential window and sp3-hybridised orbital structure of diamond, where sp3 orbital

carbon shows weak adsorption ability towards intermediates. Moreover, the width of

the window decreases with the film quality and incorporation of non-diamond sp2

carbon impurities.

(2) Good stability and corrosion resistivity

Just as described above, the strongest atomic connection could be realized on

each carbon atom of diamond, which leads to the good stability of diamond electrodes.

Besides, sp3-hybridised orbital structure guarantees the corrosion resistivity of

diamond electrode during long-term cycling from hydrogen to oxygen evolution even

in strong acidic media.

(3) Inert surface and low adsorption

The fouling phenomenon always happened on conventional glass carbon

electrode due to the adsorption function or polymer film formation on electrode

surface. Yet, diamond electrodes show weak adsorption property for many species and

polarization of polymer film could be performed to realize self-cleaning of BDD.

(4) Low background current

The feature of low background current is connected with double-layer

capacitance of BDD electrode [53], where the double-layer capacitance is up to one

18
order of magnitude lower than that of glassy carbon. Furthermore, the feature could

be utilized to detect the redox reactions [54] in solution and obtain lower detection

limits for trace analysis compared with other electrode materials.

Moreover, the surface termination, graphite ratio, surface defects, B content,

crystal size and morphology roughness of diamonds also possess evident impact on

their electrochemical properties. For example, the researchers found that the potential

window of BDD with hydrogen-terminated is narrower than that of

oxygen-terminated BDD, while significantly varying the diamond film resistances and

capacitances. These differences could be not only attributed to the own electronic

structures, but also reflected by the surface band gap [55]. For example, sp3/sp2 ratio

could clearly modify the adsorption characteristic due to the relaxation of the grains

on diamond surface. In addition, due to the influence of doping level on the sp2

distribution at grain boundaries and detailed defect level in diamond lattice, the

potential window tends to decrease with the increase of the boron doping level and

sp2-carbon impurities in BDD [56], achieving similar voltammetric features of glassy

carbon (GC) electrode, as indicated in Fig. 3. According to the strong correlation

between electrocatalytic properties (voltammetric background current, potential

window, molecular adsorption, electron-transfer kinetics) and sp3/sp2 ratio reported in

the references, high sp3/sp2 ratio is regarded suitable in disinfection water as avoiding

the generation of hazardous species. Moreover, it could be noted that mineralization

capacity for organics increases with increasing of sp3/sp2 proportion in BDD. The

grain size and surface morphology of BDD electrode, depending basically on the

19
operating conditions of the CVD process, could also greatly decide their

electrochemical performances. Gomez-Ruiz and co-workers [57] elucidated the

electrochemical function related to crystal and chemical properties of diamond films.

The results revealed that higher sp3 carbon content, lower boron and H-terminated

carbon content of the MCD favor faster and more efficient PFOA degradation than

UNCD. On the contrary, surface features and higher conductivity of UNCD anode

limited the electrochemical activity for PFOA electrolysis, which strongly impacts the

process energy consumption in the following.

Figure 3 Background cyclic voltammetry curves in 0.5 M H2SO4 for BDD electrodes with (1)

low sp2 content, (2) high sp2 content and (3) GC. Reprinted with permission from Ref. [56]

3.3 Construction of porous BDD electrode

Generally, the efficiency of the electrochemical process is vital related to the

nature and structure of electrode materials [58]. BDD deposited on flat substrate

material renders a substantial obstacle on electro-catalysis capacity and poor

utilization rate of surface space. To further improve the electrochemical activity,

constructing porous electrode [59, 60] with large surface area becomes a feasible

condition, which would provide more active sites and contract region for
20
electrochemical reaction compared with the conventional two-dimensional electrode.

Then, porous electrode has been an attractive research topic in the development of

electrode materials, and the application of porous electrodes in the fields of energy

storage, sensors and water treatment has been widely studied in recent years [61-63].

Up to now, many researchers have investigated the construction of porous BDD

film, and two main approaches including top-down [64] and down-top could be

summarized according to the deposition ways of diamond films, as displayed in Fig. 4

and Fig. 5. First, one approach, which could be called top-down method, to produce

porous electrode is to etch diamond film via energy-assisted way [65, 66], such as

plasma, stream activation or thermal treatment. Highly order honeycomb diamond

structures were obtained after oxygen plasma treatment through a porous alumina

membrane by Honda and co-workers [67], which presented a capacitance values 1.97

mF cm−2 and surface area 10.5 times larger compared to the flat surface. Ohashi and

co-workers [68] adopted a stream activation process to prepare BDD electrode with

porous microstructure, where the electrochemical active surface area is up to 20 times

Figure 4 Representative preparation mechanisms for porous BDD electrode with top-down [64]

21
approach and SEM images of porous BDD electrodes based on the approach

than pristine BDD electrode. However, complex or multistep treatments are usually

required for above methods along with poor feasibility in economy and industry

application, which could be a disadvantage for the energy-assisted approach.

Normally, BDD films are deposited on a certain substrate, and the porous

substrate becomes another approach to deposit CVD diamond films, such as porous

silicon, silicon nanowires, carbon fiber and nanotubes. The top-down method

becomes one solution to achieve porous film electrodes, and the key issue is the

choice of appropriate porous substrate materials [69-71]. After the deposition, the

ideal situation is that the diamond film adheres and conformably covers the substrate

surface without pinholes while maintaining large-area porous structure. For example,

Luo and co-workers [72] prepared BDD nanorod forest electrode on Si NWs,

exhibiting improved sensitivity and selectivity for biomolecule detection, which

makes the electrode material an exceptional choice for a wide range of

bio-functionalization schemes and biomarker detection. In addition, nanostructured

porous electrodes by depositing BDD thin film onto a densely packed “forest” of

vertically aligned multi-walled carbon nanotube substrates have been produced by

Zanin and co-workers [73] with the double-layer capacitance values ~450 times

greater than those for flat BDD electrode. Finally, BDD or diamond-like carbon with

teepee and honeycomb nanostructure surface makes them ideal candidates for

electrochemical electrodes.

However, due to the poor conductivity, low mechanical stability or not suitable

22
for large scale, substrates above usually restrict the practical application of BDD

electrodes. In general, the ideal substrate material should withstand the harsh CVD

growth conditions and possess the features of high porosity, mechanical stability and

Figure 5 Representative preparation mechanism of porous BDD electrode with bottom-up

approach and SEM images of porous BDD electrodes based on the approach [70-73]

electrical conductivity. At this point, porous titanium obtained by power metallurgy

technique (P/M) with diverse porosity and interconnected structure could be a novel

substrate material for diamond growth, which would be beneficial to improve the

catalytic activity of Ti/BDD electrode, owing to its high surface area and rough factor.

Especially, its low density and high strength would obviously improve the industrial

feasibility of Ti/BDD. In other words, porous Ti/BDD film electrode would exhibit

excellent application as a promising electrode material in the future. The influence of

parameters (pressure, methane concentration, temperature) on the diamond quality on

porous Ti substrate has been investigated by Braga and co-workers [74], and the

relationship between the porous Ti structure and electrochemical performances of

BDD film is systematically studied by Lin and co-workers [52, 75]. In addition,
23
though above two approaches are mainly collected for porous BDD electrodes, other

preparation methods and innovative porous diamond films will gradually emerge into

the public with the advances of preparation technology.

4. Application of BDD to electrochemical oxidation

4.1 Electrochemical mineralization on BDD electrode

The first BDD patent by Carey and co-workers [76] in 1995 claimed that BDD

could be employed as anode material for the oxidation of organics in wastewater. The

outstanding properties of BDD as an electrode confer its superiority in the

electrochemical oxidation process and provide a new research direction for the

electrochemical treatment of organic wastewater. Since then, numerous of papers and

patents have demonstrated that BDD can be effective in the destruction of organic

pollutants. Table 3 presents the current application of commercial BDD films to

degrade varieties of organic pollutants. The results indicate the superiority of BDD

electrodes; many commercialization companies have noticed the importance and

prospects of BDD anodes.

Table 3 Performance comparison of commercial BDD film electrodes for various wastewater

treatments with electrochemical oxidation in recent application

24
Commercial BDD Pollutants Degradation conditions Performances Ref
BDD from Reactive Undivided filter flow 80% color removal and 70% [77]
Metakem yellow HF press reactor; 64 cm2; 100-300 degradation efficiency under
mg L−1; pH=3 30-50 mA cm−2 with 120 min
BDD on Nb Hexachloro Undivided and cylindrical mineralization degree of 90% [78]
substrate from cyclohexane electrolytic cell; 24 cm2; under current of 400 mA at 4 h
CONDIAS TOC0 = 9 mg L−1; pH=7.0
BDD film from Procion Red Single compartment flow cell; Achieve full dye and COD [79]
2 −1
NeoCoat 50 cm ; 100 mg L with removal under current density
−2
volume 0.4 L; pH=6 10-60 mA cm with 240 min
DiaCell electrode Reverse Electrolytic cell with batch Total micro-pollutant from 149 [80]
from Adamant osmosis mode; 70 cm2; flow-rate of 10 μg L−1 to 10 μg L−1 under 100
−1 −2
Technologies concentrate L min with volume 2 L mA cm with 60 min
−1
BDD film by Paper Undivided electrolytic flow 16.2 kW m−3 with 2 g L of [81]
2 −1
CSEM mill wastew cell; 50 cm ; 100 mg L with NaCl under applied current of
ater volume 0.3 L; pH=6.8 0.25-1.5 A
BDD thin film Pharmaceuti One-compartment flow 100% removal with current [82]
from Adamant cals filter press reactor; 69 cm2; density 0.72-2.72 mA cm−2 in
Technologies flow rate=360 L h−1; pH=4 300 min
DiaCell system Reverse Batch mode; 70 cm2; flow-rate 92% removal with current [83]
−1
from Adamant osmosis 3
of 0.01 m min with work density 20-200 mA cm−2 in 2 h
Technologies concentrate volume 2 L

Generally, the electrochemical incineration mechanism of organic pollutants in

aqueous solution is proposed below [17, 18, 84].

BDD  H 2O  BDD(OH )  H   e (7)

BDD(OH )  R  BDD  Mineralization products  H   e

(8)

BDD(OH )  BDD  O2  H   e
(9)

The initial step involves the formation of •OH radical from the discharge of water

molecule. Then, organic oxidation is indirectly mediated by the •OH radical, which is

weakly adsorbed onto the BDD electrode surface and causes the following oxidative

degradation due to its extremely high reactivity. The reaction is in competition with

the oxygen evolution side reaction generated from the adsorbed •OH. Hence, the

25
amount of electrogeneration oxidation radicals, in principle the reactive BDD(•OH),

could reflect the indirect electrochemical oxidation capacity of the electrode materials.

The electrochemical generation and detection of •OH has been confirmed by many

researchers [84]. For example, due to the instability of •OH radical, an indirect

approach involving a “spin trap”, where the compound reacted with a radical to form

a relatively stable species, was considered as a common approach.

N,N-dimethyl-p-nitrosoaniline (RNO) and salicylic acid are primarily adopted as the

spin traps to confirm the formation of •OH radicals at diamond anodes. Based on the

analysis above, quantitative analysis was performed to characterize the efficiency of

BDD anodes during electro-oxidation.

BDD electrodes have been widely applied in the electrochemical oxidation of a

diversity of organic contaminants and real wastewater systems. Table 4 displays a

summary of the literature on the electrochemical oxidation of different organic

contaminants on BDD anodes. As displayed in Table 4, complete mineralization of

contaminants could be conducted on BDD electrodes by the reaction with

electrogeneration •OH radicals while maintaining higher current efficiency versus

other anode materials, such as SnO2, PbO2, and IrO2 [85, 86]. The researchers

speculated that the enhanced oxidation ability of BDD electrodes could be related to

the high electrogeneration ability and weak adsorption towards •OH, where more •OH

could divorce from the anode surface and goes into the bulk solution to react with

contaminants.

Phenolic compounds and carboxylic acids were the earliest contaminants

26
adopted to evaluate the performance of BDD electrodes due to their widespread

distribution and simple chemical composition, for example, phenol, chlorophenols,

nitrophenols and oxalic acid [87-89]. It was concluded that phenolic compounds could

be oxidized by •OH radicals on the electrode surface and inorganic oxidants

(primarily active chlorine, ozone and peroxydisulfate) electrogenerated in the bulk

solution depending on the electrolyte composition. Polcaro and co-workers [90]

investigated the performance of BDD electrodes during oxidation of phenolic aqueous

solution compared to Ti/RuO2 anodes, and the main reaction intermediates were

identified as benzoquinone, maleic acid and hydroquinone. Based on the discussion,

some configurations could be adopted to evaluate the performance of the

electrochemical treatment; high current density and mass transfer coefficient must be

adopted in order to accelerate the process with high space-time yield.

Among the contaminants in aquatic environment, medical intermediates have

emerged as a novel class of water contaminants [91-93] detected at the surface,

underground and even in drinking water. The presence of these contaminants

including herbicides and pesticides, has caused an increasing public concern, but their

consumption is unlikely to be restricted since they are beneficial to humankind.

Therefore, BDD electrodes, as typical efficient electrode materials, are exploited to

eliminate the contaminants above and copious research has been conducted regarding

the removal of these emerging contaminants [94-97] from wastewater system. For

instance, total mineralization of the sulfonylurea herbicide chlorsulfuron was attained

regardless of the supporting electrolyte medium by Souza and co-workers [98].

27
Meanwhile, they found that electrolyte choice clearly influenced the efficiency and

degradation rate of the oxidation process and that the process tended to be more

efficient at low current densities. Moreover, the mediated electrochemical process of

ultrasound irradiation could lead to the mineralization rate enhancement as compared

to the single electrolytic process, most importantly in the removal of chlorsulfuron,

while UV irradiation results in decreased efficiency.

BDD anodes have also been extensively employed for the removal of surfactants

in the wastewater system; the previous report mostly emphasized the anionic or

cationic surfactants, such as SDBS and CTAC. However, perfluorinated compounds

(PFCs) received little attention as micropollutants in organisms despite the fact that

they were commercialized over fifty years ago. PFCs have become persistent

refractory environmental pollutants due to the high energy of the C-F bond among

surfactants [99, 100]. The electrochemical degradation of environmentally persistent

long-chain perfluorinated carboxylic acids, i.e., perfluorononanoic acid (PFNA) and

perfluorodecanoic acid (PFDA) was investigated over Ti/SnO2-Sb-Ce,

Ti/SnO2-Sb/Ce-PbO2, and Ti/BDD anodes under galvanostatic control at room

temperature by Lin and co-workers using BDD electrodes [101]. After 180 min

electrolysis of 100 mL 0.25 mmol L−1 long-chain PFNA under current density 10 mA

cm−2 with 10 mmol L−1 NaClO4 as the supporting electrolyte, the PFNA removals on

BDD electrode were 98.7±0.4%, respectively, while the corresponding PFDA

removals were 96.0±1.4%. The degradation rates showed pseudo-first order kinetics

and intermediates of PFCAs were detected including short-chain PFCAs and F−. On

28
the basis of these results, three potential degradation routes of PFCAs were also

proposed: the formation of short-chain PFCAs by stepwise removal of CF2, direct

mineralization to CO2 and HF, and conversion to volatile fluorinated organic

compounds. A. Urtiaga and co-workers also investigated the electrochemical

degradation of perfluoroalkyl substances (PFASs), including perfluorooctanoic acid

(PFOA) and perfluorooctane sulfonate (PFOS) on BDD anode [102, 103] in

consideration of toxicity and recalcitrance to many natural degradation mechanisms.

Finally, PFOA removal was faster than PFOS, and shorter chain perfluorinated

compounds were also amenable to treatment using BDD anodes. Moreover, the

presence of chloride and the subsequent generation of oxidized chlorine species had

only a slight (within 20%) impact on the defluorination rate of PFOA or PFOS.

According to the literature, approximately 280,000 tons of textile dyes [104] are

currently discharged into effluents annually as large volumes of wastewaters are

generated in various industrial processes such as sizing, scouring, bleaching,

mercerizing, dyeing, printing and finishing. Brillas and Martínez-Huitle [105] have

reviewed the knowledge on the electrochemical methods utilized at laboratory and

pilot plant scale to decontaminate synthetic and real effluents containing dyes. The

advantages of electrocatalysis with metal oxide anodes and the great ability of BDD

electrodes to generate heterogeneous •OH radicals as mediated oxidants in

electrochemical oxidation are extensively discussed. In addition, effective

mineralization of dyes on Ti/BDD anodes has been demonstrated by Chen and

co-workers [106-108], where Orange and Reactive Red HE-3B in solution were

29
considered as the model pollutants and the study was conducted in the stirred

undivided single cell. The results showed that COD of a 750 mg dm−3 Orange II

solution containing 2 g dm−3 Na2SO4 under pH 1.15 was reduced by 92% under

current density 20 mA cm−2 after energy consumption of 6.25 Ah dm−3 on BDD anode

(12.7 mm in diameter). Finally, the process was much more efficient than that of the

Ti/Sb2O5-SnO2 anode because of the much higher oxidation ability of BDD(•OH).

In consideration of practical employment within the actual systems, BDD

electrodes are also applied in real wastewater [32, 109-112]. In the system,

wastewater treatment is intricate owing to complex compositions of various organic

pollutants and inorganic salts. The electrochemical oxidation of landfill leachate from

an old municipal solid waste landfill with average COD values of 780 mg dm−3 has

been conducted and compared on Ti-Ru-Sn ternary oxide (TiRuSnO2), PbO2 and

BDD anodes by Panizza and co-workers [113], where the major indicators involved

measuring the evolution time of aromatic compounds, COD, ammonium, color

removal, current efficiency and energy consumption. The results revealed that BDD

enables complete COD, color and ammonium removal due to the electrogeneration of

both •OH radicals from water discharge and active chlorine from chloride ion

oxidation. The BDD anode also exhibited greater current efficiency, along with a

significantly lower energy cost, while the TiRuSnO2 anode yielded only 35% COD,

52% color and 65% ammonium removal. The specific Esp on the BDD anode was 82

kWh m−3 for 95% COD removal while direct cost could be estimated as 10 € m−3. In

contrast, the treatment cost for TiRuSnO2 and PbO2 anodes was more than 30 € m−3

30
with 36% and 80% COD removal, respectively. The obtained results indicated that the

electrochemical oxidation with BDD anode is an effective and feasible process for the

treatment of landfill leachate. Electrochemical oxidation of biologically pretreated dye

wastewater was carried out in a BDD anode system by Zhu and co-workers [114]. The

results showed that COD was decreased to 99 from an initial 532 mg L−1 after 12 h

electrolysis, accompanied by simpler compounds and less toxicity using a reactor

equipped with BDD anode (2904 cm2) under pH 7.76. Meanwhile, the corresponding

Esp was 199 kWh m−3 with an average current efficiency of 6.17%. This study

demonstrated that electrochemical oxidation of biologically pretreated dye wastewater

with BDD anode was very effective and safe [115]. Especially, the performance of

BDD anode system in the degradation of large molecular organics such as humic

substances makes it very promising as an advanced treatment of biologically

pretreated wastewaters in practical applications. Zou and co-workers [116]

investigated the electrochemical oxidation of real wastewaters discharged by the

textile industry using a Diacell®201 commercial electrolytic cell with working surface

of 70 cm2. Under the optimum operational conditions (60 mA cm−2, 3.0 g L−1 NaCl,

pH 2.0), the cell required just 3 h to completely remove COD from the genuine textile

wastewaters and the specific energy consumption could be as low as 11.12 kWh kg −1

COD. In conclusion, the related research demonstrated that the electrochemical

oxidation based on BDD anodes would have practical industrial application for the

treatment of real wastewater.

[120]

[121]

[122]

[123]

[124]

[125]

[126]

[127]
[117]

[118]

[119]
[18]
Ref

31
 Type Pollutants Degradation conditions Removal rate and
Ref consumption energy

Phenol Single compartment electrolytic cell; 1.5 cm2 BDD; current density=12 mA cm−2; 95% COD removal with 8.15
[128] concentration 0.1-1 mM with volume 100 mL under pH 2.0 kWh m−3
Phenol and O-nitrophenol One-compartment thermostated cylindrical cell; 42 cm2 BDD; current density=60 92% COD removal in 8 h
derivatives mA cm−2; concentration 2 mM with volume 150 mL under pH 3.0
[129]
4-chlorophenol One-compartment electrolytic flow cell; 50 cm2 BDD; current density=15-60 mA 100% COD removal in 25 Ah
[98] cm−2; concentration 7.8 mM in 1M H2SO4 solution L−1
Oxalic acid Batch pilot reactor; 9.14 cm2 BDD; current density= 17-56 mA cm−2; 77-99% conversion ratio in
[130] concentration 100 mM with volume 250 mL under pH 2.0 8000 C
Carboxylic Salicylic acid Single compartment electrolytic cell; 3.0 cm2 BDD; current density=33 mA cm−2; Nearly 100% TOC removal in 4
acids concentration 100 mg L−1 with volume 100 mL under pH 3.0 Ah L−1

32
[131]
Gallic acid One-compartment electrolytic flow cell; 50 cm2 BDD; current density=40 mA 100% removal in 2.5 h with 66
cm−2; concentration 1 g L−1 in 0.1M HClO4 kWh m−3
[132]
SCP Open, cylindrical, undivided glass cell; 25 cm2 BDD; current density=12mA 100% TOC removal in 600 min
cm−2; concentration 0.21 mM with 250mL under pH 3.0
[133]
Medical 17β-estradiol Conventional single compartment cell;4.0 cm2 BDD; current density=50 mA 94% TOC removal with 7.37
intermediate cm−2; concentration 500 μg L−1 under pH 6.0 Wh L−1
[134] s
Aspirin Single compartment cell; current density=30 mA cm−2; concentration of 100 mg 100% COD removal in 2.7 Ah
L−1 with volume 100 mL under pH 2 L−1
[135]
Methyl orange Undivided electrochemical cell; 3.0 cm2 BDD; current density 50 mA cm−2; 82.3% COD removal with 2-3
concentration 50 mg L−1 with 0.05M NaCl kWh m−3
[136]
Pigment and Acid yellow Single cell; 2.0 cm2 BD-NCD; current density 10 mA cm−2, concentration 20 mg 100% color and COD removal
dyes L−1 with volume 150mL under pH 3.0
[137]
Xylenol orange Single compartment cell; current density 30 mA cm−2; concentration 100 mg L−1 100% COD removal in 3.6 Ah
with volume 100 mL L−1
 Type Pollutants Degradation conditions Removal rate and
consumption energy

Glyphosate Single compartment e flow cell; 78 cm2 BDD; current density 10 mA cm−2; 79% TOC removal in 6.0 Ah
Herbicides concentration 100 mg L−1 with volume 0.6 L under pH 2.0 L−1
and pesticides
Chlorpyrifos Two-compartment thermostatted cell; 6.0 cm2 BDD; current density 20 mA 100% COD removal in 6 h
cm−2; concentration 456 mg L−1 under pH 2.0
Sulfonylurea Single compartment electrochemical flow cell; 78 cm2 BDD; current density 90% TOC removal in 5.5 Ah
30 mA cm−2 concentration 50m g L−1 with volume 1 L L−1
SDBS Undivided electrolytic flow cell; 25 cm2 BDD; current density 25-75 mA 100% COD removal in 25 Ah
Surfactants cm−2; concentration 0.75 g L−1 under pH 7.8 L−1

33
CTAC Undivided electrolytic cell; 70 cm2 BDD; current density 4 mA cm−2; 70-80% TOC removal with
concentration 20 mg L−1 under pH 10 10-20 kWh m−3
Textile effluent One-compartment filter-press reactor; 32.76 cm2 BDD; current density 5-20 100% COD removal with 30
mA cm−2; effluent volume 0.40 L with flow rate 360 L h−1 kWh m−3
Tertiary Single-compartment cell; 19 cm2 BDD; current density 2.1 mA cm−2 85% COD removal with 0.2
wastewater kWh m−3
Carwash Undivided electrolytic flow cell; 50 cm2 BDD; current density 20-60 mA 85-100% in 5h with 375 kWh
Real
wastewater cm−2 flow rate 100 L h−1 m−3
wastewater
Landfill leachate Single compartment electrolytic flow-cell; 70 cm2 BDD; current density 120 30% COD removal after 3 h
mA cm−2; flow rate 60 L h−1 with 98 kWh m−3
Saline industrial Single compartment electrolytic flow-cell; 1.05 m2 BDD; current density 300 58% TOC removal with 389

Table 4 Summary of different organic contaminants electrochemical oxidation on BDD anodes

wastewater A m−2 kWh kg−1 TOC
Tetrahydrofuran Single compartment electrolytic flow-cell; 140 cm2 BDD; current density COD < 200 mg L−1 with 105.9
wastewater 1200 A m−2; flow rate 600 L h−1 kW h kg−1 COD
4.2 Electrochemical degradation kinetic

There exists a crucial relationship between the process efficiency or kinetic and

degradation parameters. To improve the treatment efficiency and decrease the Esp

during electrochemical oxidation, many researchers have paid more attention to

optimization of the experimental conditions (such as current density, nature and

concentration of the target pollutant, pH of the electrolyte, etc.) on electrochemical

decomposition. Overall, these factors affect the generation concentrations of •OH,

active sites and mass transfer rate of pollutants, which subsequently influence the

electrochemical oxidation efficiency in wastewater.

Among the variables usually altered in electrochemical oxidation processes,

current density, which corresponds to the ratio between the applied current and the

working electrode surface, may be the most frequently modified as it directly

determines the reaction rate. Previous works [87, 138] have demonstrated that higher

current density led to the generation of larger amounts of •OH, which resulted in

higher degradation efficiency for the target pollutant. It should be highlighted that an

increase in current density does not necessarily lead to an increase in the oxidation

efficiency or oxidation rate for a given anode material: the effect of current density on

the treatment efficiency also depends on the characteristics of the effluent to be

treated. However, the employment of higher current densities commonly results in

higher operating costs due to the increase in energy consumption and opportunity for

oxygen evolution side reaction. The influence of current density on the removal

efficiency for ethidium bromide (EtBr) was investigated by Zhang and co-workers

34
[139]. The result indicated that current and removal efficiencies strongly depend on

current densities. As expected, the apparent rate constant (kappl) values for the

degradation of EtBr increase with rising currents; their values are 0.0209, 0.0370,

0.0847 and 0.1221 min−1 for applied current densities (jappl) of 2.10, 6.30, 18.90 and

37.80 mA cm−2, respectively. However, the current efficiency of the process decreases

progressively with rising currents. Finally, increasing the jappl from 2.1 to 37.8 mA

cm−2 does not proportionally enhance EtBr oxidation, which may be explained by

promotion of parasitic reactions such as oxygen evolution. Thus, it can be concluded

that a compromise must be made to balance energy consumption with treatment time

to achieve the desired removal efficiency.

The physicochemical characteristics of the wastewater (nature and concentration

of electrolyte, pH value and concentration of targets) also connect with the

electrochemical oxidation process [140, 141]. In this case, the electrolytes play an

important role in the process because of the possible formation of side products,

which could increase or diminish the efficiency decided for the actual system.

Canizares and co-workers [142] observed that the electrochemical treatment of

ethylene glycol in a Na2SO4 or Na3PO4 medium was more effective than in NaCl.

Meanwhile, some researchers discovered that chloride could also be oxidized to form

active chlorine (Cl2, HClO and ClO), which could further promote the degradation of

target pollutants. Although no agreement has been reached on the variation

mechanisms of the nature of electrolyte on the overall oxidation efficiency, it must be

kept in mind that high conductivity of the electrolyte leads to faster electron transport

35
and better degradation rate for organic pollutants, consequently lowering the cell

voltage for a given current density and leading to reduced energy consumption.

The natural structure of organic compounds is also in relation to their

electrochemical activity [143]. Electrochemical oxidation of some p-substituted

phenols (-nitrophenol, -hydroxybenzaldehyde, phenol, p-cresol and -methoxyphenol)

with electron-donating and -withdrawing substituents was studied to reveal the

relationship between the structure and electrochemical reactivity of p-substituted

phenols using BDD electrode by Zhu and co-workers [144]. It was concluded that the

release of p-substituted groups from the aromatic ring became the rate-limiting step

under the attack of •OH radicals. Since electron-withdrawing groups are readily

released from the substrate, the p-substituted phenols with these groups are degraded

faster than those with electron-donating groups. Therefore, the degradation rates of

the p-substituted phenols rise with an increase of Hammett’s constants, which is

opposite to the result obtained on Pt electrode.

The influent pH has been established to be a significant operating factor

influencing the performance of electrochemical processes. It is generally

acknowledged that the pH value affects the •OH generation concentrations and

oxygen overpotential, which subsequently concerns the electrochemical oxidation

efficiency. Due to the differences in organic structures and electrode materials, the

results regarding the influence of solution pH are also diverse and even contradictory.

Hence, a review of previous publications does not allow us to reach a conclusion on

whether increasing or decreasing pH favors pollutant removal in electrochemical

36
oxidation of wastewaters. Some authors reported that the oxidation process is more

favorable in acidic media [120]. In contrast, others indicated that the efficiency of the

process was increased in alkaline media [145]. For example, previous studies have

found that the electrochemical oxidation was more favorable in the acidic condition

because the low pH inhibits the oxygen evolution reaction, leading to the

improvement of degradation efficiency. According to the above literature, it can be

concluded that the effect of pH strongly depends on the nature of the inspected

organics and supporting electrolyte. Rabaaoui [117] investigated the effect of pH on

the degradation rate of ortho-nitrophenol (ONP) over a large pH range from acidic to

basic, concluding that the degradation of ONP in the acidic medium was more

efficient than in alkaline and neutral media. COD reduction of >96% was attained at

pH 3.0, with a total disappearance of the color, while it did not exceed 50% at pH 10.0.

The researchers summarized that the formation of polymeric intermediate products by

the hydroxyl group of ONP makes the degradation much more difficult at pH 10.0.

Hence, maximum pollutant removal efficiency by the electrochemical oxidation

process could be obtained at an optimum solution pH when taking into account the

practical chemical situation of the pollutants.

In addition, some kinetic models describing the oxidation of organic substrates at

BDD anodes have also been developed for the evaluation of the degradation process,

where the experimental data obtained at laboratory scale were well fitted to the kinetic

models under various conditions [27, 146, 147]. Comninellis and co-workers [27, 148]

investigated the oxidation behavior for a wide range of pollutants on Si/BDD anodes

37
using an undivided electrolytic flow cell. It was found that current efficiency and

intermediates were affected by the relative proportion of local concentrations of •OH

to concentration of organics on the anode surface, which were independent of organic

pollutant nature. Based on this observation, the group proposed a comprehensive

kinetic model to associate COD concentrations and current efficiencies for the

electrochemical oxidation of a wide range of pollutants with BDD electrodes. The

energy consumption during the process could also be predicted based on the

experimental conditions of applied current intensity, organic concentration, and

mass-transfer coefficient.

Depending on applied current density (jappl) with respect to limiting current

density (jlim), which decreased during treatment, two distinct operating regimes were

identified:

• jappl < jlim: The reaction kinetics was controlled by the current when the applied

current was low or the concentration of the organics was sufficiently high, current

efficiency was 100% and COD decreased linearly over time.

• jappl > jlim: The reaction kinetics was under mass-transport control when the

applied current was high or the concentration of the organics was low, and secondary

reactions (such as oxygen evolution) commenced, resulting in current efficiency

decrease (<100%). In this regime, COD removal, due to mass-transport limitation,

followed an exponential trend.

A graphical representation of the proposed kinetic model and the equations that

describe the trends of COD and ICE over time in both regimes are displayed in Fig. 6.

38
Based on the kinetic model, system behavior can be predicted if the experimental

conditions (applied current intensity, organic concentration, and mass-transfer

coefficient) are provided. Agreement between the experimental data and modeling

results obtained in all cases validated the assumptions for electrochemical treatment

of solutions containing acetic acid, isopropanol, naphthol, phenol, chlorophenols,

polyacrylates, benzoic acid, and chloromethylphenoxy herbicides [149-151]. In

practice, the occurrence of side reactions or the accumulation of intermediate

compounds during the combustion process is usually approximated from the models,

which are not entirely satisfactory for theory and practice. Previous studies had

already demonstrated that the kinetics for the loss of a single substrate and

mineralization may be different for complex substrates.

Figure 6 Kinetics models for evolution of (a) COD and (b) ICE as a function of time or specific

charge under different situations during electrochemical oxidation. (A) represents the charge

transport control, (B) the mass transport control. Reprinted with permission from Ref. [27]

The researcher also developed a generalized mathematical model for the

description of the electro-oxidation kinetics of COD and NH4+ contained in landfill

39
leachates at BDD anodes, considering both the contribution of direct and indirect

mechanisms [152]. For jlim, COD < jappl ≤ jlim, COD+jlim, NH4+, only direct and •OH

mediated oxidation reactions close to the anode surface occurred, and the process was

mass transfer controlled. For jappl >jlim, COD+jlim, NH4+, indirect oxidation in the bulk

took place, the process could be quantified by an adjustable parameter, defined as a

function of jappl/(jlim,COD+ jlim, Cl).

4.3 Enhancement approaches for electrochemical mineralization

Though satisfactory removal efficiency could be realized on BDD electrode,

higher kinetic rates and faster removal rates are still expected to be realized for

organic contaminants during the electrochemical oxidation process. First, the

electrode material, as a key part of the electrolysis process, plays an important role in

the electrochemical oxidation of pollutants. Higher efficiency could be obtained on

BDD electrode with respect to traditional anodes, and researchers continue to strive to

develop higher performance BDD electrodes. For example, BDD electrodes with

different boron doping levels were employed for pollutant removal to assess the

optimal boron level and electrochemical performance of BDD electrodes.

Bogdanowicz and co-workers [153] investigated the influence of boron doping level

of diamond electrodes on the number of crystallites with small diameter, the density

of active sites on the surface, and oxidation rate for reactive dye. The results

suggested a close dependence between oxidant generation efficiency and doping level

of diamond electrode, which was that high B-doped BDD film is more efficient for

dye removal. The influence of sp3/sp2 ratio [154] of diamond electrode on

40
electrochemical oxidation performance was analyzed to evaluate the effect of graphite

content on the direct electrochemical activity and electro-oxidation pathway of

Rhodamine B on BDD electrode [155]. The results indicated that the higher the

diamond-carbon content, the greater are the TOC and COD decay rates and hence the

oxidation of organic to CO2, where high graphite content promotes direct

electrochemical conversion of pollutants. The research was of paramount significance

for the choice of electrodes that could guarantee high efficiencies in the wastewater

remediation process. Furthermore, the role of surface termination in the oxidation of

dopamine and ascorbic acid was examined by Tryk and co-workers [156],

representing a preliminary step in attempting to understand the local interactions of

solution-phase reactants with hydrogen- and oxygen-terminated BDD surfaces.

Most of the studies above are focused on the chemical or surface composition of

BDD electrode. Generally, BDD electrodes are deposited on a flat substrate, resulting

in a smaller specific surface area and space utilization. It is believed that the

electrochemical performance would be improved by adopting a porous electrode as

material due to increasing specific surface area and the presence of many additional

active sites for electrochemical reaction. Therefore, porous electrode has become a

feasible condition and an attractive research topic in the development of electrode

materials. Section 3.3 mentions the construction of porous BDD electrode with high

surface area, and the effort is focused on the development of porous BDD electrode or

the enhancement of capacitance, little work is devoted to the applications in

wastewater treatment. Lee and co-workers [157] fabricated boron-doped diamond

41
nanowire (BDDNW) electrodes via metal-assisted chemical etching (MACE) to

provide a large surface area during the electrochemical oxidation process, as in Fig. 7.

The uniformly covered BDD on nanotextured Si substantially enhanced the

electrochemical activity of the electrode substantially, and nanostructuring reduced

specific energy consumption by a factor of more than 2 for 80% mineralization of

phenol as compared to the conventional planar BDD electrode. In addition, BDD film

was deposited on porous Ti substrate via HFCVD method by He and co-workers [124,

127, 158]. The porous Ti substrate endowed the Ti/BDD film with a

three-dimensional porous structure and BDD electrode deposited on porous Ti

substrate exhibited the potential to raise the electrochemical oxidation capacity for

organic pollutants as the surface area expanded. Higher •OH radical generation ability

and rate of could be obtained on 3D-Ti/BDD, leading to 30% higher current efficiency

compared with flat BDD electrode. Though higher •OH radical could be obtained on

porous Ti/BDD electrode, the discrepancy between the COD removal and •OH radical

amount also existed in the system, which is that the degradation of aspirin does not

proceed as expected. The possible mechanisms could be speculated as the •OH

radicals utilization rate on the surface and mass transfer limitation in the inner pores.

During the electrochemical oxidation process, the contaminants should be transported

to the electrode surface first, and then reacted with active •OH formed on the anode

surface. Here, the mass transfer process, involving the transport of contaminants from

the bulk solution to the electrode surface, usually comes to be a limiting step toward

the electrochemical oxidation of contaminants. The increase of mass transfer

42
resistance generated from irregular structure [71] additional reduces the advantages of

porous electrodes. Correspondingly, the research on the enhancement of

electrochemical ability accompanied by mass transfer in electrochemical oxidation is

becoming a hot area and challenge.

Figure 7 Schematic of the fabrication process for a BDDNW electrode. Reprinted with permission

from Ref. [157]

At high current density or low concentration of contaminants, the

electrochemical oxidation process is controlled by the mass transfer step [159, 160].

Though the mass transfer of contaminants is important for anode materials for the

electrochemical oxidation, the mass transfer process receives little attention from

researchers. A three-dimensionally networked BDD (3DN-BDD) electrode with a

microstructure is fabricated on a mesh titanium substrate to improve the kinetic rate

towards the electrochemical oxidation [161, 162]. The probably mechanisms for

enhancement of electrochemical oxidation of contaminants on 3DN-BDD electrode

are speculated as the following: (i) the microstructure providing higher surface area

and active sites for electrochemical reaction; (ii) high utilization of •OH due to the

hydrophobic surface; (iii) the enhancement of mass transfer of the solution originated

from the network structure, as displayed in Fig. 8.

43
Figure 8 (a) Schematic diagram of the fabrication process for 3DN-BDD film electrode and

corresponding SEM images; (b) Enhancement mechanisms of 3DN-BDD electrode towards

electrochemical oxidation. Reprinted with permission from Ref. [161]

The cell configuration is also a significant factor for the electrochemical

degradation [5, 163, 164]. Due to the limitation of electrode materials or cell design,

the electrochemical oxidation is commonly conducted in flow-by model or

single-compartment electrolytic cell [165]. Unfortunately, though relatively high

removal rate could be realized on different material anodes, the pollutant removal

efficiency is still unsatisfactory due to the low space-time treatment efficiency, high

operational cost and mass transfer limitation during the electrochemical degradation

process. To the best of our knowledge, several trials for the scale-up of BDD

electro-oxidation generated laboratory data that could be potentially useful for the

scale-up of the system [166, 167]. However, the laboratory scale of electrochemical

44
oxidation could still not satisfy the current requirements for industrialization at the

current stage, and usefulness or practicality for large-scale applications should be

seriously taken into account. In comparison, there are not many reports on

electrochemical reactor design, which is also essential to increase the degradation

efficiency and reduce the treatment cost. For example, previous reports have indicated

that tubular porous electrode reactor [159, 168] could improve the degradation rate

and efficiency because porous structure endows the electrode with a large

electrochemical active area and mass transfer efficiency 6.7 times that of batch mode.

As far as we known, some novel flow-through reactors have been applied to

wastewater treatment technologies, including adsorption and electro-Fenton, [169]

and the reaction rate acceleration and treatment efficiency improvement could be

related to the facts that the mass transfer rate of the target pollutant molecules are

accelerated and contaminants can be effectively enriched on the surface. Therefore,

flow-through reactors and corresponding electrode materials represent an imperative

future research direction in cell configuration.

5. Combination of other processes for elimination

Although the EO technique could degrade contaminants efficiently, there are

many additional technologies available for elimination of contaminants, and

integration with other techniques/materials has also been investigated for

improvement of current efficiency and reduction of energy consumption. The

combinations lead to a new and interesting possibility for treatment of pollutants from

wastewater, and the corresponding information is illustrated in Table 5.

45
 Assisted Pollutant Degradation conditions Removal rate Ref
Technology
Adsorption Phenol Batch reactor; 7 cm2 BDD; 215 mA cm−2; 29 mg L−1 with 1 g Sawdust adsorbent 99.99% in 90 min [170]

Biological Naphthalenesulfon Biofilm airlift suspension reactor; 25 cm2 BDD; 40 mA cm−2 under pH 7 100% [171]
ates
Microwave 2,4-dichloropheno Cylindrical singlecompartment cell; 5.5 cm2 Si/BDD; 10mA cm−2; 100 mg L−1 with 88.46% COD in 3 h [172]
xyacetic acid volume 90 mL under 2450 kHz

Hydrothermal Perfluorooctanoic Teflon-lined stainless steel autoclave cell; 5.5 cm2 BDD; 20 mA cm−2 ; 200 mg L−1 89.2% TOC in 6 h [173]
Acid under heating (0.30 MPa)
Progesterone Single compartment electrochemical flow cell; 78 cm2 Si/BDD; 30 mA cm−2 with More than 90% [174]
Ultraviolet light wavelength of 254 nm under pH 4 TOC in 800 min
RO concentrate Flow-through, undivided, spacer-filled cell; 10 cm2 DiaChem®; 20 mA cm−2 under 80% in 5 h [175]
254 nm under pH 8.8

46
O3 Industrial Batch cylindrical electrochemical reactor; 50 cm2 Nb/BDD; 30 mA cm−2 with O3 5 ± 99.9% in 60 min [176]
wastewater 0.5 mg L−1 with volume 0.70 L
Ultrasound Phthalic acid Cylindrical single-compartment cell; 24 cm2 BDD; 20 mA cm−2; COD 531 mg L−1 100% in 3.4 h [177]
with volume 60 mL, frequency of 33 kHz, power of 50 W
Photoelectrode Ibuprofen Cylindrical quartz reactor; 10 cm2 BDD/Bi2MoO6; 10 mg L−1; bias potential 2.0 V About 85% in 2 h [178]

Sulfamethazine Open electrolytic cell; 24 cm2 BDD; 4.81-41.66 mA cm−2; 28.8 mg L−1 with 0.2 mM 100% in 6 h [179]
EF Fe2+
Black TRS Undivided filter flow press reactor; 64 cm2 Nb/BDD; 31 mA cm−2; 100 mg L−1 with 90% color removal [180]
0.5 mM Fe2+ in 180 min
Photo-EF Congo Red Open and undivided cell; 3 cm2 BDD; 100 mA cm−2; 0.260 mM with 0.50 mM Fe2+ 99% DOC in 6 h [181]

Solar-photo-EF real wastewater Flow plant in batch mode; 20 cm2 BDD; 10 mA cm−2 with 0.20 mM Fe2+ 66% TOC in 240 [182]
matrix min
Table 5 Combination with other processes for elimination of organic contaminants with BDD

anodes

5.1 Composite electrodes

As mentioned above, despite BDD electrode being considered as an excellent

electrode material towards electrochemical oxidation of pollutants, the material

presents problems of conductivity and electrocatalytic activity, many efforts have

been made to modify the BDD surface to further improve the electrocatalytic

performance. For example, Sb-doped SnO2 nanoparticles were assembled onto the

BDD surface using micelles of the block copolymer surfactant and homogeneous

precipitation approaches by Zhao and co-workers [183]. The conductivity was greatly

improved, where the resistance decreased to 1.2 from 60.8 kΩ and the reaction

activation energy was also reduced from 8.02 to 4.93 kJ mol−1. Moreover, Sb-doped

SnO2-NPs/BDD showed higher oxidation ability for 2, 4-dichlorophenol owing to the

excellent electrocatalytic performance. The research provided a new idea for

exploration of the electrode materials with high electrochemical degradation ability.

Based on the recent literature, some other metal or metal oxides nanoparticle could be

also decorated on diamond electrode while BDD electrodes have appeared to be

excellent substrate materials for various chemical modifications [184]. The

subsequent application to electroanalysis and energy conversion field has been also

well developed. However, due to the superior properties of the BDD electrode in

wastewater, such kind of efficient electrodes into electrochemical oxidation for

pollutants is rarely reported and awaits further development in the following.

47
5.2 Energy-assisted

Some energy assisted methods have also been utilized to improve the

degradation efficiency, including O3, UV light and ultrasound irradiation. [176,

185-187] Generally, the degradation of pollutants proceeds on the electrode/solution

surface, and the mass transport of pollutant components becomes an important role

during the oxidation process. It is noted that one of the most important issues attached

to cell design is maintaining high mass transfer rates, since the electrochemical

oxidation processes primarily occur on electrode surfaces. To improve mass transfer

to the electrode surface, common methods such as gas sparging, high fluid velocity,

baffles and incorporation of various types of turbulence promoters are employed

[159]. Synergistic combination effects of irradiation and the electrochemical process

were observed in recent studies with greater removal efficiency over the expected

separate contributions. To the best of our knowledge, sono-electrochemical processes

have been most explored to examine the effect of ultrasound on the electrochemical

combustion of organics on BDD anode in order to activate the electrode surface and

enhance mass transfer efficiency.

It is widely accepted that the degradation of pollutants or the enhancement of

oxidation processes by ultrasound is due to cavitation [188]. Under ultrasound, the

mass transfer is promoted so that the pollutants and oxidant or catalytic reaction

surface are brought into intimate contact. At the same time, some active substances

such as hydroxyl radicals are produced in bulk under the high temperature and

pressure resulting from the cavitation by ultrasound, which may degrade the pollutant

48
to some degree, as presented in Fig. 9a. The depletion of the herbicide 2,

4-dichlorophenol on diamond electrodes using electrolysis and sono-electrolysis was

studied by Souza and co-workers [189] to investigate the influence of ultrasound

irradiation on the formation of oxidants in the reaction media. Electrolysis combined

with US irradiation leads to a very efficient process due to the production of extra

oxidants (chlorine/hypochlorite) in the reaction media under ultrasound irradiation,

which can be explained by the promotion of mass transport processes by enhanced

oxidant transport to the bulk solution. The efficiency of conductive diamond

electrochemical oxidation (CDEO) coupled to UV light or ultrasound was recently

reported for the degradation of progesterone, and synergistic effects of irradiating UV

light and US are clearly observed in the degradation rate. The higher removal

achieved in the system was explained with the increase in mass transport,

minimization of the electrode fouling, and the combined generation of •OH by both

US and polarized BDD surface in Fig. 9b. Similar trends for these processes have

been described for the mineralization of herbicide [174], diuron [190], antibiotic

triclosan [191], etc. [192, 193]

49
Figure 9 (a) Schematic mechanism for efficient decomposing PFOA by ultrasonic electrochemical

oxidation; (b) Comparison of US, EO and US-EO processes for diuron. Reprinted with permission

from Ref. [190]

5.3 Photo-assisted

Making use of semiconducting materials to generate holes and free radicals,

semiconductor photocatalysis has been extensively investigated in environmental

pollutants degradation by applying a biased voltage across a photo-electrode.

Electro-oxidation combined with photocatalysis with a semiconductor film electrode

has demonstrated promising results for the destruction of organic contaminants

compared with individual electro-oxidation and photocatalysis in recent years. In

previous work, the semiconductor ZnO, TiO2, ZnWO4, γ-Bi2MoO6 and Bi2WO6 were

deposited onto the semiconductor substrate, and the obtained film electrodes

efficiently degraded organic contaminants via combined photocatalysis and

electro-oxidation processes [194-197]. Commonly, BDD electrodes exhibit p-type

50
semiconductor properties, and most photocatalysts such as TiO2, ZnWO4, γ-Bi2MoO6

and Bi2 WO6 exhibit n-type semiconductor properties, causing the formation of p-n

junctions, where electrons are depleted and the depletion region is known as the space

charge region, as displayed in Fig. 10a. The space charges establish an electrostatic

field inside the semiconductor that facilitates the transport of electrons from n-type

semiconductor to p-type semiconductor. In a conventional photocatalytic system, the

excited electrons and holes may migrate to the photocatalyst surface or otherwise

recombine. If the conduction band electrons survive further recombination at the

catalyst surface, the electrons and holes may undergo redox reactions with adsorbed

species such as water, hydroxide ions, oxygen, and air pollutants. In the

photoelectrocatalytic process, photo-induced electrons and holes can be well

separated under the application of an applied electric field.

Consequently, a number of studies have shown that metal oxide electrodes can

be utilized in photo-assisted electrochemical degradation processes, in which the

limitation of generation of highly reactive oxidants can be overcome through UV light

irradiation, as detailed in Fig. 10b and c. Among all, TiO2 has been employed

frequently for observing reductive as well as oxidative reactions on its surface. P-N

hybrid electrodes of BDD and TiO2 were designed and fabricated via selective

deposition of TiO2 onto BDD electrode via a sol-gel dip-coating method by Qu and

co-workers [196]. The removal rate of Acid Orange II (AOII) in the PEC process was

three times that of the electrochemical oxidation process at the bias potential of 2.5 V

for 4 h, while the removal rate of 2,4-dichlorophenol (2, 4-DCP) was enhanced five

51
times at the bias potential of 1.0 V for 3 h. The hybrid electrode exhibited high

photoelectrocatalytic activities towards degradation of AOII and 2, 4-DCP due to the

P-N effect and high electrocatalytic and photocatalytic activities of BDD electrode

and TiO2 particles. Furthermore, different degradation mechanisms of AOII and 2,

4-DCP in the electro-oxidation, photocatalysis, and photoelectrocatalysis are

proposed.

Figure 10 (a) Schematic band diagram of ZnO NRs/p-diamond heterojunction and the transfer

processes of photogenerated carriers; (b) Degradation of 2,4-DCP under various conditions; (c)

DMPO spin-trapping ESR spectra under photocatalysis, electro-oxidation, and PEC process

5.4 Electro-Fenton

Electro-Fenton (EF) [198], as one of the typical EAOPs, could also enable

efficient degradation of persistent organic pollutants in aqueous medium via in situ

generation of highly reactive oxidizing agents such as •OH radicals, which are able to

oxidize almost all organic contaminants efficiently. One of the most popular

approaches is electrogeneration of H2O2 based on the continuous supply of O2 to an

acidic contaminated solution from the two-electron reduction of O2, as exhibited in

52
reaction (10). A wide variety of carbonaceous electrodes with high surface area, such

as activated carbon fiber, reticulated vitreous carbon, graphite, carbon-felt,

carbon-PTFE and gas diffusion electrodes, have been tested as reaction cathodes in

search of enhanced efficiency. Cruz-González and co-workers [199] also reported that

the EF process was able to decolorize and degrade the azo dye Acid Yellow 36 using a

carbon felt as cathode to produce H2O2 by oxygen reduction reaction (10). Formation

of homogeneous •OH then starts via Fenton reaction once a catalytic amount of Fe2+

is added to the media via reaction (11). The process is electrocatalytic since Fe2+ ions

are electroregenerated from the reduction of Fe3+ produced above via reaction (12).

During the EF process, organics are simultaneously degraded during electrolysis by: (i)

•OH radicals formed in bulk medium and (ii) adsorbed •OH radicals generated at the

anode surface.

O2  2H   e  H 2O2
(10)

Fe2  H 2O2  Fe3  OH  OH 

(11)

Fe3  e  Fe2 (12)

BDD thin film electrodes are the most potent anodes known as described above.

The weak BDD-•OH interaction results in a higher OEP than in case of other anodes,

such as Pt and PbO2, as well as formation of higher amounts of heterogeneous

hydroxyl radicals. When an undivided cell with a BDD anode is used in EF, organics

can be not only attacked by •OH produced in the bulk from Fenton’s reaction, but also

by heterogeneous •OH formed from water oxidation at the anode surface. In addition,

combining EO treatment with other electrochemical technologies has also proven to

53
be a cost-efficient treatment of wastewaters. For example, the mineralization of

sulfachloropyridazine (SCP) has been studied by EF reaction using an undivided

electrochemical cell with a BDD anode and carbon-felt cathode to generate H2O2

[122]. Finally, electrogeneration H2O2 in the presence of Fe2+ yielded •OH in the

solution bulk, which acted concomitantly with •OH adsorbed at the anode

(BDD(•OH)) to promote the oxidative degradation of SCP and its byproducts. The

detailed processes are exhibited in Fig. 11. The open, cylindrical, undivided glass cell

with BDD (5 cm2) allowed >95% mineralization of 0.21 mM SCP at pH 3.0 under

current density of 12 mA cm−2 after only 480 min instead of 600 min required for Pt,

where BDD anode contributes to the degradation of even the most refractory

byproducts byproducts. It could be concluded that the electro-Fenton technology with

electrochemical oxidation on BDD anode is a very effective technology for the

treatment of aqueous SCP solutions.

Figure 11 Mechanism illustration of electro-Fenton based on Pt or BDD anode and carbon-felt

carbon cathode, and the corresponding degradation pathway of SCP. Reprinted with permission

from Ref. [122]

5.5 Other combination technologies

54
 Additional, other combination technologies could also be integrated on the basis

of increasing capability of removal and reducing energy consumption for wastewaters

in practical situations, such as electrocoagulation (EC), bio-adsorption, microwave

and hydrothermal. [170-172, 200] For instance, Bouaziz and co-workers [170]

investigated a new hybrid process combining adsorption on sawdust and

electroxidation using a BDD anode for the treatment of dilute wastewater containing

phenol. High porosity of sawdust leads to its high adsorption capacity for phenol

while more than 100% of sawdust regeneration was reached even after four cycles.

This study demonstrated that coupling adsorption with electrochemical degradation

on BDD anode could provide a promising approach for the efficient elimination of

persistent organic pollutants from dilute wastewater and for the reuse of the

adsorbent.

6. Perspectives and outlook

Although conducting diamonds seem to be an extremely promising electrode

material for the treatment of recalcitrant pollutants in wastewater systems, some

crucial aspects still require further investigation for the full development of the

electrochemical oxidation process.

(1) First, the deposition mechanisms and processes of diamond films on various

deposition substrates or systems have mature developed from the recent reports.

Whereas, the detailed deposition parameters in all literature are decoupled from each

other as a results of the discrepancy between operation conditions and experimental

facilities. Despite the presence of various differences in energy supply, temperature,

55
pressure and gas chemical composition among the deposition techniques and devices,

the desired diamond quality, deposition rate and layer size could be achieved

according to the requirements. However, the size and service lifetime of diamond film

still present severe challenges for industrial scale applications due to the limitations of

the deposition equipment and proper substrates. Presently, several companies are

producing large area diamond films on a commercial basis, and the broad introduction

of industrial diamond anodes for practical application would be expected in the future.

(2) Unique properties and the recent advances of diamond electrodes from

numerous references increasingly enable electrochemical oxidation processes and

confer significant advantages, which distinguish them with respect to conventional

DSA anodes in term of CE, energy consumption and stability. The application of

diamond electrodes also opens new perspectives for wastewater treatment via

electrochemical technology. As displayed in Section 4, electrode materials and other

experimental parameters, including the electrolyte composition, pollutant

concentration and current density largely decide the efficiency of the EO process. The

design and construction of highly active diamond materials has become a research

hotspot and will ascend a long time to enhance degradation kinetics towards

pollutants. On the other hand, the current research emphasis of diamond anode on

wastewater treatment is focused on the degradation kinetics and application to various

pollutants. Further emphasis should weigh on the theoretical explanation (e.g.,

simulation modeling, density functional theory) and the experimental results, which

would be more meaningful for practical application when considering the complexity

56
of the wastewater system.

(3) Possible problems involving the formation of undesired secondary products,

toxic byproducts and high costs of electrochemical oxidation processes should also be

assessed in the future. During the degradation process, the possible formation of

undesired secondary products (e.g., chlorates, perchlorates and organichlorinated

compounds) represents a serious problem in some cases before industrial scale

installations, as they are usually toxic or involve refractory by-products, greatly

increasing the difficulty to treatment. Hence, related generation mechanisms should

be studied and avoidance measures must be proposed. Furthermore, it is known that

single electrochemical oxidation technology, leading to the high costs of EO

processing, is in fact not economically suitable for treating most wastewater. In the

following study, the combination of additional eliminating technologies would be an

inevitable trend to enhance both the removal efficiency along with the economic

evaluation of the entire process.

(4) In recent years, specific cell configurations have been developed to reduce

the energy consumption and achieve high space-time yield [163, 201], but the

emergence or development of novel efficient electrocatalytic reactor remains a slow

process after all. The development of the electrochemical reactors and the

optimization of cell configuration represent important aspects of the application of

electrochemical oxidation towards wastewater treatment. Meanwhile, the insight into

the theoretical aspects of the electrocatalytic reactor (e.g., mechanism, current density

distribution, thermodynamics and hydromechanics model) may not be sufficiently

57
mature, and the thermodynamic model for the analysis of complex electrochemical

reactions should be further appreciated and discussed. Moving onward from

fundamental mechanisms, effectively applying electrochemical reactions on the

reactor scale also needs further studies from the reactor perspective.

7. Summary and conclusions

Electrochemical oxidation is an effective method for treating different

wastewater containing various organic pollutants. As presented in this review, the

features of high oxygen evolution potential, weak adsorption, etc., endow BDD

electrodes significant advantages during electrochemical oxidation in wastewater

treatment, and numerous papers have been published on utilizing BDD electrodes for

electrochemical degradation of organic pollutants. Results available in the recent

literature demonstrated the high current or mineralization efficiency and widely

exploitation of BDD electrode over other electrode materials. On the other hand, the

reaction during electrochemical oxidation is a complex process involving electrode

material, electrode/solution interface and bulk solution, which correspond with many

basic complicated research areas. The detailed research emphasis mainly consists of

the exact relationship/regulation between electrode material and oxidation activity,

reaction mechanism on electrode/solution interface, mass transfer scheme of

contaminant from bulk solution to electrode surface. Moreover, some combination

technologies based on electrochemical oxidation on BDD electrode are also employed

to greatly enrich the application in wastewater treatment, and other combination

technologies/materials could also be developed in the future to further improve the

58
removal efficiency and reduce total energy consumption on BDD electrode. Although

laboratory and pilot tests of BDD electrode have been successful, the practical

industrial application of diamond electrode is still largely limited mainly due to

relatively high cost, limited size, complex equipment and appropriate substrate.

However, thanks to the development of understanding for excellent proprieties of

BDD electrode and preparation method, industrialization of BDD electrode could be

realized in a certain period of time and adopted in practical industrial application in

the future.

Acknowledgments

The financial support from the National Key Research and Development Program
(No.2016YFC1102802), National Natural Science Foundation of China
(No.21273097, 21573093), China Postdoctoral Science Foundation (2018M623418),
and the Innovative R&D Team Introduction Program of Guangdong (No. 2013C092)
are gratefully acknowledged.

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Highlights

Focus on the preparation and electrochemical property of BDD film electrode

Insight into the electrocatalytic process and mechanism on BDD electrodes towards

pollutants

The enhancement approaches towards electrochemical oxidation kinetics are included

Other combination technologies based on electrochemical oxidation on BDD

electrode are also described

Perspectives and outlooks for BDD electrodes in electrochemical oxidation

73