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Last Decade of Research on Activated Carbons as Catalytic Support in


Chemical Processes
V. Calvino-Casildaa; A. J. López-Peinadob; C. J. Durán-Vallec; R. M. Martín-Arandab
a
Catalytic Spectroscopy Laboratory, Instituto de Catálisis y Petroleoquímica (CSIC), Madrid, Spain b
Dpto. de Química Inorgánica y Química Técnica, Facultad de Ciencias, Universidad Nacional de
Educación a Distancia (UNED), Madrid, Spain c Dpto. de Química Orgánica e Inorgánica, Facultad de
Ciencias, Universidad de Extremadura, Badajoz, Spain

Online publication date: 11 August 2010

To cite this Article Calvino-Casilda, V. , López-Peinado, A. J. , Durán-Valle, C. J. and Martín-Aranda, R. M.(2010) 'Last
Decade of Research on Activated Carbons as Catalytic Support in Chemical Processes', Catalysis Reviews, 52: 3, 325 —
380
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Catalysis Reviews: Science and Engineering, 52:325–380, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 0161-4940 print / 1520-5703 online
DOI: 10.1080/01614940.2010.498748

Last Decade of Research on


Activated Carbons as
Catalytic Support in Chemical
Processes
V. Calvino-Casilda1, A.J. López-Peinado2, C.J. Durán-Valle3,
and R.M. Martín-Aranda2
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1
Catalytic Spectroscopy Laboratory, Instituto de Catálisis y Petroleoquímica (CSIC),
Madrid, Spain
2
Dpto. de Química Inorgánica y Química Técnica, Facultad de Ciencias, Universidad
Nacional de Educación a Distancia (UNED), Madrid, Spain
3
Dpto. de Química Orgánica e Inorgánica, Facultad de Ciencias, Universidad de
Extremadura, Badajoz, Spain
This review is devoted to the application and knowledge developed in the past 10 years in
the area of chemical processes catalyzed by activated carbon supported catalysts.
Activated carbons are well known for their catalytic properties and for being used as
support in heterogeneous catalysis. The supported catalysts have been successfully used
in the chemical industries for long time. In the last decade, carbon supported catalysts
have opened the door for new chemical catalytic processes based on their intrinsic
features. However, fundamental understanding of molecular structure-reactivity
relationship of these carbon materials remains unexplored. Futures advances in all
areas may be possible through combined experimental and theoretical approaches.

Keywords Activated carbons, Heterogeneous catalysis, Supported catalysis, Acid


reactions, Basic reactions, C-C bond formation, Oxidation reactions, Reduction reactions.

INTRODUCTION
Only a small number of chemical processes are still conducted without the
addition of a catalyst (1). Catalysis is of crucial importance for today’s chemical
industry and particularly nowadays in the field of fine chemicals.

Received November 20, 2009; accepted May 24, 2010


Address correspondence to V. Calvino-Casilda, Catalytic Spectroscopy Laboratory,
Instituto de Catálisis y Petroleoquímica (CSIC), Marie Curie, 2. E-28049-Madrid,
Spain. E-mail: vcalvino@icp.csic.es

325
326 V. Calvino-Casilda et al.

Supported catalysts are of special interest. They allow the fine dispersion
and stabilisation of small metallic particles providing access to a much larger
number of catalytically active atoms. In particular, it has been observed that
activated carbon exhibit optimum properties and performance, stability in both
acidic and basic media that let them to be used as catalyst support in multitude
of different applications in the chemical industry.
At the beginning of last decade, Rodríguez-Reinoso remarked the use of
carbon as catalyst support for different industrial processes (2). In the past,
the lack of fundamental understanding of many aspects of the use of carbon in
catalysis caused a limited employ of carbon as catalyst and still more as catalysts
support. But the continuous studies on understanding of all aspects of the
physical and chemical characteristics of carbon material, especially activated
carbon, AC (surface area and porosity) and even more, the possibility of control-
ling the surface chemistry of such materials is the origin of important researches
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carried out in industrial chemistry during the last decade. As a result, this paper
reports the evolution in the last decade of the use of activated carbon as catalyst
support employed in a variety of current industrial processes.
In heterogeneous catalysis, carbon materials have been used for long time
because they can be used directly as catalysts, and moreover, they can satisfy
most of the properties desired for a suitable support. It has been shown that
although the surface area and the shape of carbon porosity may be very impor-
tant in the preparation and properties of the corresponding catalysts, the role of
carbon surface chemistry is also extremely important. The most common het-
eroatoms present on carbon surface are hydrogen, oxygen, nitrogen, sulphur and
phosphorus. These atoms are arranged in the forms of functional groups, such
acidic ones as carboxylic, lactonic, phenoclic, or basic groups, such as pyranes
and chromene. The number and strenght of these groups influence the apparent
acidity or basicity of the carbon surface. Moreover, a few percent of inorganic
matter from the organic precursor (e.g. coal or wood) could be present on carbons
and this fact is considered important for their perfomance, especially when they
are used as catalyst supports. However, although the catalytic effect is mainly
headed by the chemical properties of the active phase, the dispersion and the
local distribution of the active phase across the activated carbon support as well
as the interaction active phase-support are significantly important. These are
just the aspects of carbon supports that make them so attractive for heteroge-
neous catalysis. These parameters can be modified to satisfy any specific
requirement during catalyst preparation making the surface not only physically
but also chemically accessible to the precursor and diminishing the deactivation
by sinterization. It seems obviously that the future is promising once it is under-
stood that not only the surface area and porosity of carbon materials are the key
for their uses, and that both physical and chemical surface properties of carbon
support have to be taken into account when designing a solid catalyst. Due to the
constant interest in heterogeneous catalysis of using activated carbon as
Last Decade of Research on Activated Carbons 327

catalyst support in search of suitable catalysts for certain chemical processes,


this review will be mainly concerned with the use of carbon as catalyst support to
highlight the great contribution of this material during the last decade.

CATALYTIC OXIDATIONS (TABLE 1)


The identification of new catalyzed reactions is of key importance to the chemical
industry and, in particular in the production of fine chemicals. Selective hetero-
geneous oxidation catalysis is crucial to the well being of society, since it pro-
duces about 25% of the most important industrial organic chemicals and
intermediates used in the manufacture of industrial products and consumer
goods. Most of the reactions for the synthesis of fine chemicals and pharmaceu-
ticals involve one or more steps of oxidation of organic functional groups. In the
last decade, industrial researchers have expended great efforts to make selective
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oxidation processes and their catalysts even more efficient and environmentally
friendlier. Among these catalysts activated carbon supported materials have
been briefly employed in different oxidation reactions.
Volatile organic compounds (VOCs) and chlorinated volatile organic com-
pounds are environmental pollutants and are the subject of stringent regula-
tions. Different methodologies have been considered to diminish the emissions.
Activated carbons are finding increasing applications as catalyst supports in the
treatment of gaseous effluents to destroy the VOCs emissions, where advantage
is taken of the enhanced retention of organic pollutants in the pore system of the
carbon. Platinum supported on activated carbon has been used as catalyst and
other less expensive alternatives have been also considered; an increasing inter-
est is associated with activated carbons impregnated with transition metal
oxides (3–5). Recently Lu et al. have tested transition metals (Cu, Co, Fe and
Ni) supported on activated carbon in the simultaneous removal of VOC and NO
in combustion flue gas (6) and Wu et al. have prepared Pt/AC catalysts for
benzene, toluene and xylene (BTX) deep oxidation at low-temperature on the
catalytic destruction of VOC (7). Suh et al. have investigated a Co/AC catalyst
activated with ozone for removing chemically offensive odors such as benzene,
toluene, mercaptans, and sulfides (8). Cherkezova-Zheleva et al. have also
investigated the total oxidation of benzene over Fe-Pd/AC and Fe-Pt/AC cata-
lysts (9). Since basicity is an important factor for efficient removal of methyl
mercaptan on activated carbons, the performance of materials can be enhanced
by impregnation of activated carbon with basic compounds such as NaOH,
Na2CO3, KOH and K2CO3 (10,11). They are able to improve the capacity of
carbons for methyl mercaptan removal by a factor of two (10). Other possibility
to improve this capacity is to promote redox surface reaction by surface impreg-
nation with other compounds such as Fe2O3, KI and KIO3 increasing the capa-
city by a factor 3–5 (10,12 ).
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Table 1: Main oxidation reactions catalysed by activated carbon supported metal, non-metal and their compound catalysts in
the last decade.

Alkali
Precious Alkali earths Transition
metals metals metals metals Others
Catalytic
oxidations Pd Pt Ru Rh Ag Au Na K Ca V Cr Mn Fe Co Ni Mo W Re Sn Bi Cu Zn P Ce

-Oxidation of hydrocarbons
- Alkanes/ cycloalkanes ! ! ! ! ! !
- Methane reformation ! ! !
- Alkenes/ cycloalkenes ! ! ! !
- Aromatics ! ! ! ! ! ! !
- Oxidation of halocarbons ! ! ! ! ! !
- Oxidation of aldehydes ! ! ! ! !

328
- Oxidation of carboxylic acids !
- Oxidation of alcohols
- Aliphatics ! ! ! ! ! ! ! ! ! ! ! ! !
- Phenols ! ! ! ! ! ! ! ! !
- Carbohydrates ! ! ! ! !
- Oxidation of cyclic ketones !
- Oxidation of dye wastewater ! ! !
- Ethers and esthers !
- CO oxidation ! ! ! ! ! ! ! ! ! ! !
- NO oxidation ! ! ! !
- SO2 oxidation ! ! ! ! !
- H2S and sulphides oxidation ! ! ! ! ! ! ! ! !
- H2oxidation ! !
- Desulphurisation reaction ! ! !
- Ammonia ! ! ! ! ! ! ! !
Last Decade of Research on Activated Carbons 329

Some authors have carried out low temperature hydroxylation of aromatic


compounds by hydrogen peroxide over Fe/AC and Pd/AC catalysts (13).
Alkylated benzenes are an important class of hydrocarbons because they com-
prise a significant portion of gasoline and diesel fuels. Alvarez-Merino et al. have
reported the catalytic combustion of toluene over tungsten oxide supported on
activated carbon catalysts for removing toluene from dilute streams (14).
Halocarbons represent the most abundant family of industrial toxic compounds
as it has been recently recognized from different polluting sources like herbi-
cides, pesticides, chemical and solvent manufacturing, the paint industry, and
the dechlorination of drinking water. The application of innovative advanced
oxidation technologies (AOTs) like the oxidation of 4-chlorophenol (an important
toxic pollutant) with hydrogen peroxide in aqueous solution using Fe/AC cata-
lysts is of interest to abate efficiently and also reduce the treatment cost through
destructive techniques mineralizing the halocarbon (15). Wang et al. have also
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carried out the oxidation of 4-chlorophenol over Pd/AC catalysts used for gas-
diffusion electrode (16). Qin et al. have carried out the catalytic wet oxidation of
aqueous p-chlorophenol over supported noble metal activated carbon catalysts
and Sun et al. have examined the chemical reactivity of AC-supported iron as a
catalyst to decompose polychlorinated biphenyls (PCBs) under air or N2 atmo-
sphere (17,18). Several activated carbon-supported chromium oxide catalysts
were effective for complete chlorinated volatile organic compounds (CVOCs)
oxidation such as methylene chloride and perchloroethylene (19,20).
The catalytic wet-air oxidation (CWAO) process is effective in converting
organic pollutants such as phenolic pollutants to innocuous carbon dioxide
currently found in industrial wastewaters. Pt on TiO2-grafted activated carbon,
CuO/AC and Fe/AC are some of the catalysts employed for the wet air oxidation
(21–23). Noble metal catalysts on activated carbon (Pt/AC and Ru/AC) and base-
metal catalysts (Cu/AC, CoMo/AC, Mo/AC and Mn/AC) were developed and
examined for the simultaneous removal of organic pollutants and ammonia
from wastewater using the wet air oxidation (WAO) process in the liquid phase
(24,25). Bandosz et al. also reported the removal of ammonia from air on acti-
vated carbons modified with aluminium-zirconium polycations and micro/meso-
porous activated carbons modified with molybdenum and tungsten oxides by
providing new Brönsted acidic centers that form strong interactions with the
adsorbed gas in its protonated form (26,27). Zazo et al. and Quintanilla et al.
have studied the catalytic wet peroxide oxidation of phenol with a Fe/AC catalyst
in aqueous solution (28,29). Lei et al. have reported the behaviour of Cu-Ce/AC
catalyst-sorbent in the dry oxidation of phenol showing high phenol adsorption
capacities and high phenol oxidation activities (30). Wen et al. have prepared Co-
Ce/AC as a new catalyst for catalytic wet air oxidation of phenol (31) and Kim
et al. have studied the effects of inorganic cocatalysts (Ce, Co, Mn and Cu) and
initial states of Pd on the oxidative carbonylation of phenols over heterogeneous
Pd/AC catalysts following the well-known “redox” or “multi-step electron
330 V. Calvino-Casilda et al.

transfer mechanism” between a Pd complex and organic/inorganic cocatalysts


(32). Due to their observation in previous works that the metallic character of
palladium was significantly enhanced after the reaction, they investigated the
effects of the initial state of Pd on the catalyst activity and product selectivities
for a fixed amount of Pd added with a fixed amount of cocatalys concluding that
the catalytic performance was independent of the different initial states of Pd in
Pd/AC catalysts. Recently Bo et al. have carried out the removal of phenolic
pollutant in aqueous solution by microwave-assisted catalytic oxidation using
Pt/AC catalysts showing better results than in the catalytic wet air oxidation
previously reported (33).
Nowadays gold supported on activated carbon is the preferred catalyst for
the oxidation of the alcoholic and the aldehydic groups and one of the best
preparation methods of those catalysts is the immobilisation of colloidal
particles.
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A large number of products can be formed from glycerol oxidation being one of
the key problems the selectivity by which the individual products can be formed
(Fig. 1). Nevertheless, if the products could be formed in high selectivity, they are
potentially valuable as chemical intermediates in the fine chemicals industry.
Prati et al. have presented Au/AC and Au-Pd/AC as selective catalysts for the
oxidation of alcohols such as glycerol, including diols, under relatively mild condi-
tions (34–37). More recently, they have established that by using bimetallic cata-
lysts (Au-Pd/AC and Au-Pt/AC) a strong synergistic effect was shown and high
activity and a prolonged catalyst life were also found (38,39). Demirel-Gulen et al.

Glycolic acid

Glyceraldehyde Glyceric acid Tartronic acid

Glyoxilic acid

Glycerol

Dihydroxyacetone Hydroxypyruvic acid Mesoxalic acid

Figure 1: General reaction pathways for glycerol oxidation.


Last Decade of Research on Activated Carbons 331

and Carrettin et al. have also investigated the glycerol oxidation reaction (40).
Glycerol can be oxidised to glyceric acid with 100% selectivity at high conversion
using Au/AC as catalyst (41). Porta et al. have used Au/AC catalysts for the
selective liquid phase oxidation of ethylene glycol to glycolate (42).
Pratti et al. have oxidized in liquid-phase carbohydrates and aldehydes to
the corresponding carboxylic acids with O2 under mild conditions using Au/AC
catalysts without loss of activity on recycling (43). Deffernez et al., have studied
the oxidation of glyoxal into glyoxalic acid over Pd/C catalysts (44). Comotti et al.
have also oxidized in liquid-phase carbohydrates and alcohols using gold acti-
vated carbon catalysts (45). Bian et al. have reported the oxidation of glucose to
obtain sodium gluconate by Bi promoted Pd/AC catalysts (46).
Hayashi et al. and Korovchenko et al. have investigated the oxidation of
alcohols to the corresponding aldehydes and carboxylic acids with air in the
presence of catalytic amount of transition metals such as copper, ruthenium,
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palladium, and platinum compounds on activated carbon (47,48). Paneva et al.


have studied the catalytic behavior of Fe and/or Ru supported on activated
carbon in methanol decomposition to CO and methane (49). This group have
also studied the catalytic behaviour of nanosized iron and mixed iron-cobalt
oxides supported on activated carbon materials in methanol decomposition to
H2, CO, and CH4 (50). CuO/MnO/AC, Re-Cu/AC and Re-Mn/AC have been
studied in the reaction of methanol decomposition to H2 and CO by Tsoncheva´
s group (51–53) and Pt/AC and Pd/AC catalysts by Ubago-Pérez et al. (54).
Diethyl carbonate (DEC) is a promising oxygenated organic additive for
gasoline and diesel fuel to reduce pollutant emissions. Many research groups
have readily prepared diethyl carbonate from the oxidative carbonylation of
ethanol in gas phase with high selectivity using Wacker-type catalysts, CuCl2/
PdCl2 and CuCl2/PdCl2/KOH supported on activated carbon (55–58). Ma et al.
have studied the catalytic vapor phase synthesis of diethyl carbonate from CO
and ethyl nitrite over catalysts prepared from PdCl2-CuCl2 and PdCl2-CuCl2-
CeCl3 supported on activated carbon (59).
Dimethyl carbonate (DMC) is a unique molecule having a versatile reactivity
being very useful for environmentally benign reactions. Some research groups
have prepared supported Wacker-type catalysts by impregnation of the acti-
vated carbon support with KOAc promoter and CuCl2 or PdCl2/CuCl2 showing
a higher performance in the gas-phase oxidative carbonylation of methanol for
the dimethyl carbonate synthesis (DMC) (Fig. 2) (60–62). Some authors have
studied the role of copper chloride (63,64) and copper chloride hydroxides

2CH3OH + CO + 1/2 O2 (CH3O)2 CO + H2O

Figure 2: Oxidative carbonylation of methanol process for the dimethyl carbonate synthesis
(DMC).
332 V. Calvino-Casilda et al.

deposited on the activated carbon in the oxidative carbonylation of methanol for


dimethyl carbonate (DMC) synthesis using vapour phase flow reactor system
(65–67). More recently, Cui et al. have reported the dimethyl carbonate synth-
esis over catalysts prepared loading KI and K2CO3 on activated carbon (68).
Zoeller et al., have used gold activated carbon catalysts in the vapor phase
carbonylation of lower aliphatic alcohols, ethers, esters, and ester-alcohols mix-
tures, and desirably, methanol, to produce carboxylic acid, esters and mixtures
thereof. The solid supported catalyst includes an effective amount of gold asso-
ciated with activated carbon in the presence of a halide promoter (69).
Pt-SnOx/AC and Pt-CeOx catalysts supported on un-oxidized and oxidized
activated carbon (AC) have been employed in the selective CO oxidation in H2-rich
gas streams containing CO2 and H2O simulating the reformate coming from fuel
processors (70). Non-noble metal catalysts have also been employed in this reac-
tion such as Ni, Co and Co-Ni/AC (71). Polymetals (Cu, Cr and Ag) supported on
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activated carbon were used in the catalytic oxidation of carbon monoxide in a fixed
bed reactor (72). Wacker-type catalysts as for example Pd-Cu/AC catalysts were
tested in the catalytic oxidation and chemisorption of CO for smoke applications
(73). Pt/AC and Pt-Sn/AC catalysts have also been employed in CO oxidation (74).
Presently, most of the industrial hydrogen production is based on steam
methane reforming (SMR) process, which is a source of significant CO2 emis-
sions into the atmosphere. New routes to hydrogen production from natural gas
(or methane) with drastically reduced CO2 emissions have been investigated.
The direct decomposition of methane shows a promising alternative to the
traditional hydrogen production methods such as steam methane reforming
(SMR) and partial oxidation of methane (POM) because there is no further
byproduct except carbon. Activated carbon has been suggested as a good support
for metal catalyst for COx-free hydrogen production by methane decomposition
because AC is relatively stable, non-toxic as itself, easily obtained from various
raw materials and the textural properties and surface structure can be easily
controlled in the manufacture process, which makes it more favourable to be a
catalyst support. Muradov et al. have reported the oxygen-assisted decomposi-
tion of methane over AC-supported iron catalysts experimenting over wide
range of temperatures and O2/CH4 ratios (75). An advantage of producing syngas
by this route instead of processes like steam reforming or partial oxidation is the
low H2/CO ratio obtained, which is of particular interest for the synthesis of
valuable oxygenated chemicals, such as alcohols or aldehydes. Okumura et al.
have prepared supported gold catalysts on activated carbon for low-temperature
oxidation of CO and H2 (76) and some other authors have investigated the CO
selective oxidation on Au/AC and Ag/AC catalysts in hydrogen-rich gas to elim-
inate CO impurities when hydrogen is produced via the reforming reaction to be
used as a source of energy for stationary power plants, moving vehicles and fuel
cell applications (77,78).
Last Decade of Research on Activated Carbons 333

The preparation of metal supported activated carbon with Ni can catalyze


the decomposition of methane and ethylene forming carbon nanofibers (CNFs)
under relatively mild conditions (79,80).
But the reforming of methane with carbon dioxide to synthesis gas has recently
attracted renewed interest. Numerous supported catalysts have been proposed for
methane reforming. In 1998 Wang et al. proposed Ni/AC catalyst to develop this
reaction and now Diaz et al. have reached representative methane conversions at
mild experimental conditions using Ni-Ca/AC catalysts where Ca plays a cosupport
role inhibiting the deactivation of catalyst during long periods of reaction (81,82).
Valente et al. have reported the oxidation of cycloalkanes such as pinane using
transition metal, cupper and cobalt acetylacetonate complexes inmobilized on
activated carbon at room temperature and atmospheric pressure. This group and
also Langhendries et al. have reported the selective oxidation of cycloalkanes using
activated carbon supported iron-phtalocyanine catalysts (83–85).
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Kishi et al. have carried out the oxidation of cycloalkenes such as cyclopentene
under oxygen atmosphere using a Wacker type catalysts, Pd(OAc)2 supported on
activated carbon combined with molybdovanadophosphate (NPMoV) (86). The
oxidation of terpenes such as limonene over activated carbon anchored transition
metal Schiff base complexes catalysts is reported by Oliveira et al. (87).
Some other authors have studied the catalytic oxidation of sulphur contain-
ing compounds; Hui-Hsin Tseng et al. have investigated the catalytic oxidation
of SO2 from incineration flue gas over Cu/AC and bimetallic Cu-Ce/AC catalysts
and they have also carried out the simultaneous catalytic oxidation of sulfur
dioxide/hydrogen chloride from incineration flue gas over activated carbon-
supported copper, iron or vanadium oxide catalysts and this group have also
carried out (88,89).
The Pd/AC and Pt/AC catalysts were found to be oxidation catalysts at high
temperature for hydrogen sulphide oxidation and methane oxidation (90). Dalai
et al. have also reported activated carbon supported catalysts impregnated with
ammonium iodide, potassium iodide and potassium carbonate for hydrogen
sulphide oxidation (91). Radkevich et al. have studied the influence of surface
functionalization of activated carbon on palladium dispersion in the preparation
of Pd/AC catalyst and the catalytic activity in hydrogen oxidation (92).
The Zn/AC and CuO/AC catalysts were tested in desulphurisation reaction
(DeSO2) (93). Wang et al. have carried out the electrochemical desulphurisation
reaction over CeO2/AC catalysts (94). Xiao et al. have reported the catalytic
oxidation of hydrogen sulphide over activated carbon impregnated with Na2CO3
(95) and Ma et al. the catalytic oxidation reaction for purifying H2S and PH3
contained in tail gas over activated carbon impregnated with Na2CO3 and also
with HCl (96). Activated carbons impregnated with caustic materials (NaOH or
KOH) have been used for removal H2S in sewage treatment plants. The residual
H2S quickly reacts with the strong base and is immobilized (97–99). However the
shortcoming in the applications of caustic impregnated carbon is the fact that
334 V. Calvino-Casilda et al.

impregnation decreases the ignition temperature of the carbon and poses a risk of
self-ignition. In addition, the activity of caustic carbons in H2S oxidation is worn
out when caustic is consumed and the carbon pores are blocked by sulfur and
sodium or potassium salts.
Ramirez et al. have reported the degradation and mineralization of the non-
biodegradable azo dye Orange II making use of a Fenton-like oxidation process
over a Fe/AC catalyst (100). Zhang et al. have prepared CuFe2O4/AC catalysts for
the removal of acid Orange II which combined the magnetic and the excellent
catalytic properties of powdered CuFe2O4 (101). Sun et al. have studied the
catalytic performance of activated carbon supported tungsten carbide for hydra-
zine decomposition (102).

CATALYTIC REDUCTIONS (TABLE 2)


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Hydroprocessing is a group of technologies where catalytic reactions take place


in presence of hydrogen at elevated pressure to fulfil some or all of the following
major objectives:

1. Hydrogenation. Increase H/C, saturation of unsaturated hydrocarbon com-


pounds (e.g. olefins and aromatics).

(a) Stabilizing distillate fuels like gasoline, jet fuel by preventing sediment
formation.

(b) Upgrading (decreasing boiling point range) of residue.


2. Hydrocracking. Cracking of heavier hydrocarbon molecules to lighter ones
for production of desired fuels and lubes.
3. Hydrotreating. Removal of hetero-atoms and impurities from hydrocarbon
streams. (e.g. sulfur, hydrodesulphurization (HDS); nitrogen, hydrodenitro-
genation (HDN); metals such as chlrorine (hydrodechlorination, HDC); con-
densed ring aromatics etc.).

Catalysts are commonly used for the hydrogenation of alkenes, alkynes,


aromatics, aldehydes, esters, carboxylic acids, nitro groups, nitriles, and imines.
The selective hydrogenation of carbon-carbon double and triple bonds is one of
the fundamental reactions for the synthesis and manufacture of fine and indus-
trial chemicals. A wealth of processes and applications in the pharmaceutical,
agrochemical and petrochemical industries is based on catalytic hydrogenation
of unsaturated hydrocarbons by heterogeneous catalysts. The classical hetero-
geneous catalysts for carbon-carbon multiple bond hydrogenation involves sup-
ported precious metals, activated base metal catalysts and Ni supported on
oxides all being able to activate hydrogen under mild reaction conditions.
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Table 2: Main reduction reactions catalysed by activated carbon supported metal, non-metal and their compound catalysts in the last
decade.

Alkali
Precious Alkali earths Transition
metals metals metals metals Others
Catalytic
reductions Pd Pt Ir Ru Rh Ag Au Li Na K Rb Cs Mg Ba V Cr Mn Fe Co Ni Cu Zn Mo W Re Al Sn Pb P Ce Ge

- Hydrogenation ! ! ! ! ! !
of alkenes/
cycloalkenes
- Hydrogenation !
of alkynes
- Hydrogenation ! ! ! !
of aromatic rings
- Hydrogenation of nitro ! ! !
compounds
- Hydrogenation ! ! ! ! ! ! ! ! ! ! !
of aldehydes
- Hydrogenation ! ! ! !
of ketones

335
- Hydrogenation ! ! ! !
of carboxylic
acid derivatives
- Hydrogenation ! ! ! ! !
of esters
- Hydrogenation !
of azides
- Hydrogenation ! !
of terpenes
- Hydrogenation of !
carbohydrates
- Hydrodesulphurisation ! ! ! ! ! ! ! ! !
- Hydrodenitrogenation ! ! ! ! ! ! !
- Hydrodehalogenation ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
- Hydrogenolysis ! ! ! ! ! ! !
- CO2 hydrogenation ! !
- CO2 reduction ! !
- CO hydrogenation ! ! !
- Reductive amination !
- NOx reduction ! ! ! ! ! ! ! ! ! ! ! ! !
- Methanol ! ! ! ! ! ! ! !
decomposition
336 V. Calvino-Casilda et al.

However, these materials have commenced to be repleaced by activated carbons


during the last decades.
Matos et al., have reported Ni/AC and Ni-Mo/AC catalysts for the hydro-
genation of simple insaturated hydrocarbons such as ethylene (103–105).
Precious metals supported-activated carbon catalysts such as Pd, Pt, Rh and
Ir, have been tested on hydrogenation of alkenes and cycloalkenes (106–112).
Kirm et al. have prepared Pd and Pt/AC catalysts for gas-phase hydrogenation of
styrene oxide to produce 2-phenylethanol, a compound with bacteriostatic and
antifungic properties, used in formulation of cosmetics and with important
applications in the manufacture of chemical compounds (113,114). Domínguez-
Domínguez et al. have carried out a reaction of great industrial interest such as
the semihydrogenation of phenylacetylene in liquid phase over Pd/AC catalysts
(115). Recently Mori et al. have developed a diphenyl sulphide inmobilized on
Pd/AC system for chemoselective hydrogenation of alkenes, acetylenes, azides,
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and nitro groups in presence of aromatic ketones, halides, benzyl esters, and N-
benzyloxycarbonyl groups (116).
In general, the aromatic ring hydrogenation requires more severe conditions
than the hydrogenation of other functional groups and highly homogeneous
catalytic systems have disadvantages concerning stability, productivity, and
manufacture. Pt-Sn and Pt/AC catalysts have been tested on benzene hydroge-
nation to cyclohexane (117,118), Ru/Ac catalysts have been tested on benzene
and toluene hydrogenation (119) and Pd/AC catalysts have been developed for
the hydrogenation of phenol to cyclohexanols or cyclohexanone, in aqueous
phase and in vapour phase to explore a possible way for the treatment of phenolic
wastewaters and to obtain intermediates for the fragance and pharmaceutical
industry (Fig. 3) (120–123). Hiyoshi et al. have reported the hydrogenation of
naphthalene in supercritical carbon dioxide solvent over Rh/AC catalysts (124).
Esters, carboxylic acids, and ketones can be reduced to their respective alco-
hols using precious metals (Pt, Pd, Ru, and Rh) and nickel supported-activated
carbon catalysts (125–130). Wolfson et al. have reported the enantioselective
hydrogenation of a β-ketoesters such as methyl acetoacetate to β-hydroxyesters
over Ni/AC catalysts (131). These compounds are useful building blocks for the
synthesis of biologically active compounds and natural products. Perez-Cadenas

OH O OH

H2 H2

H2

Figure 3: Reaction paths in phenol hydrogenation over activated carbon supported catalysts.
Last Decade of Research on Activated Carbons 337

et al. have reported the hydrogenation of fatty acid methyl esters (vegetable oils)
on palladium catalysts supported on carbon-coated monoliths (132). Gulyukina
et al., have carried out the hydrogenation of α-oxophosphonates with molecular
hydrogen over Pd/AC catalysts for the synthesis of α-hydroxyphosphonates (133).
The hydrogenation of α,β-unsaturated aromatic aldehydes is accompanied
by the formation of several by-products. The hydrogenation of cinnamaldehyde
has been attracting increasing interest due to the importance of the derivatives
in the fine chemicals industry. The selectivity to the desired products is still an
important issue in the case of the industrial hydrogenation of cinnamaldehyde
towards the clean production of the desired intermediates. Some authors have
investigated the reaction using precious metals supported-activated carbon
catalysts such as Pd, Pt, and Ru (134–136). Others authors have studied the
hydrogenation of α,β-unsaturated aldehydes such as crotonaldehyde and citral
over activated carbon-supported metal catalysts (Pt-Zn/AC Coloma et al. (137);
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MoC/AC, Guerrero et al. (138); Cu/AC, Dandekar et al. (139); Ru and Ru-Fe/AC,
Bachiller-Baeza et al. (140); Pt/AC, Thomson et al. and Silvestre et al. (141,142);
PtSn/AC and PtGe/AC, Vilella et al. (143,144), J.C. Serrano-Ruiz et al. (145), and
molybdophosphoric acid-V2O5/AC) (146).
The hydrogenation of nitro compounds to the corresponding amines is a very
important reaction, as these chemicals are used as basic raw materials for
urethanes, rubber chemicals, dyes, and pharmaceuticals. Jaganathan et al.
have reported Pd/AC catalysts for the catalytic hydrogenation of p-nitrocumene
to p-cumidine in a slurry reactor (147). Activated carbon supported platinum
catalysts have been employed in the hidrogenation of ortho-nitrochlorobenzene
to 2,20 -Dichloro-hydrazobenzene and in the hydrogenation of nitrobenzene
(148,149). On the other hand, activated carbon supported nickel catalyst have
been used in the hydrogenation of p-chloronitrobenzene to p-chloroaniline (150).
It has also reported that Pt/AC catalysts can convert primary amines into
secondary amines in good yield, via retro-reductive and reductive amination
upon microwave irradiation in water (151).
Mahmudov et al. have reported the hydrogenation of perchlorate over Co-Pt/
AC, Ni-Pt/AC, W-Pt/AC and Pt/AC catalysts (152).
Heinen et al. have reported the hydrogenation of sugars such as fructose on
Ru/AC catalysts and De Miguel et al. have studied the effect of the activated
carbon support in Pt and PtSn catalysts used for selective hydrogenation of
terpenes such as carvone (Fig. 4) (153–156).
Sakata et al. have studied the catalytic activity in CO2 hydrogenation to
methanol of activated carbon-supported Cu-ZnO catalysts (157) and Zhongrui Li
et al. have reported the mixed alcohol synthesis over Mo-K- and Co-Mo-K/AC
catalysts via CO hydrogenation (158,159). The reduction of carbon dioxide with
water has been investigated for the direct synthesis of methane over Raney Fe-
Ru/AC catalysts by Kudo et al. (160).
338 V. Calvino-Casilda et al.

CHO O
O

Figure 4: Reaction scheme of the catalyzed carvone hydrogenation.

A closely related reaction to hydrogenation is hydrogenolysis where a molecule


of hydrogen is added over a carbon-carbon single bond, effectively causing a “lysis”
of the bond. Ru/AC catalysts were tested on the hydrogenolysis of n-hexane and Pt-,
Pd- and Ru/AC catalysts in the catalytic transfer hydrogenolysis of 2-phenyl-2-
propanol over Pd/AC catalysts. Markus et al. have carried out the hydrogenolysis of
a wood extractive, the natural ocurring lignan hydroxymatairesinol, to an antic-
arcinogenic and antioxidative compound using Pd/AC catalysts (161–163).
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Chlorofluorocarbons (CFCs) have had a lasting effect on the environment.


They are a major source of stratospheric chlorine, which is responsible for the
depletion of the ozone layer. Catalytic hydrodechlorination (HDC) has emerged
as a promising non-destructive technology not only for the safe conversion of
chlorinated waste, but also producing value-added products. Noble metals have
mainly been used as catalysts in the hydrodechlorination reaction of CFCs. In
particular, supported palladium is the most widely used catalyst for this reac-
tion. Catalysts employed for HDC reaction are often susceptible for deactivation,
due to strong adsorption of HCl produced as a by-product. In this context, the
development of a poison-resistant catalyst has gained significant importance in
recent years. The hydrodechlorination activity depends on the nature of active
sites, which are influenced by several factors such as the method of preparation,
the mean particle size, and the nature of precursor salt used in the preparation of
catalysts. The selective hydrogenolysis of CFCs such as CCl2F2 (CFC-12) into
CH2F2 (HFC-32) and CFC-115 into HFC-15 over Pd/AC catalysts have been
studied by many authors (108,164–173). There are also many studies using
other noble metal supported-activated carbon catalysts. Pt, Pd, Rh, Ru, Ir, and
Re/AC catalysts, and bynary metal mixtures (Pt-Cu, Pt-Ag, Pt-Fe, and Pt-Co)
supported-activated carbon catalysts have been used in the hydrodechlorination
of CFC-12 and CFC-13 (175–179).
There are also authors who have investigated non-noble metals supported-
activated carbon catalysts such as Ni/AC. These catalysts have shown similar
catalytic behaviour to the noble catalysts, but only a few studies in the last
decade have dealt with the hydrogenolysis reaction of chlorofluorocarbons.
Morato et al. have prepared activated-carbon-supported nickel (Ni/AC), nickel-
potassium oxide (NiK/AC), nickel-copper (NiCu/AC) and nickel-aluminium oxide
(NiAl/AC) catalysts for the hydrogenolysis of halogenated chlorofluorocarbons
(CFC-12) (180). Calvo et al. have carried out the hydrodechlorination of Alachlor
Last Decade of Research on Activated Carbons 339

in water using Pd, Ni and Cu/AC catalysts (181) and Keane et al. have studied
the hydrodechlorination of chlorobenzene over Ni/AC catalysts (182).
Water pollution is a major concern for the pulp and paper industry due to the
large quantities of effluents generated. The effluents from pulp bleaching are
responsible for most of the colour, organic matter and toxicity of the water dis-
charges of this industry. Catalytic hydrodechlorination is proposed as an interesting
alternative/complement for the elimination of chlorinated organics from bleaching
effluents. Calvo et al. have employed Pd/AC catalysts for the hydrodechlorination of
chlorophenols with the aim of reducing the toxicity of a type of wastewaters
(183–185). Santoro et al. (186) and Keane et al. (187), have carried out the hydro-
dechlorination (HDC) of chlorobenzene over Ni and Fe/AC catalysts and other
authors over Ni, Fe, W, Ni-Mo, Pt and Pd supported-activated carbon catalysts
(187–191). In the study of catalytic reduction of contaminated waters, containing
nitrates Barrabes et al. have employed Pt-Cu/AC and Pd-Cu/AC catalysts (192).
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The Pt/AC catalysts have been prepared for the hydrodechlorination of


aliphatic organochlorinated compounds that are released into the environment
in the greatest amounts (dichloromethane, chloroform, carbon tetrachloride,
1,1,1-trichlorethane, trichloroethylene and tetrachloroethylene) (193,194).
Early et al. have carried out the hydrogen-assisted 1,2,3-trichloropropane
dechlorination on Pt-Sn/AC catalysts (195).
Dhandapani et al. have used the reactivity of molybdenum carbide sup-
ported on activated carbon with phosphorous additive as catalysts for hydro-
processing reactions such as hydrogenation, hydrodesulfurization (HDS) and
hydrodenitrogenation (HDN) using model liquid compounds (196). Other
supported-activated carbon containing metal, binary metal mixtures such as
CoMo/AC, NiMo(W) and PNiMo(W)/AC, Fe-Mo/AC, Re/AC, Ni-Re/AC, Ni-Mo/AC
and sulfided metals such as Ni-Mo/AC have been employed as catalysts in
hydrotreatment processes by other authors (197–204). More recently, Pinto
et al. have prepared vanadium nanoparticles supported on activated carbon
catalysts for tiophene hydrodesulphurization (206) and Park et al. the synthesis
of ZnO/AC catalyst for the effective removal of a very low concentration of sulfur
compounds contained in a gasified fuel gas (207).
Xing et al. have employed V2O5-CoO/AC catalysts for flue gas SO2 removal and
elemental sulfur production (208) and Guo et al. have reported V2O5/AC catalysts
in simultaneous sulfur dioxide and nitric oxide removal from flue gas (209).
Selective catalytic reduction (SCR) of NOx is a tecnhology to remove nitrogen
oxides, the most abundant and polluting component in exhaust gases, through a
chemical reaction between the exhaust gases, a reductant additive, and a catalyst. A
gaseous or liquid reductant (most commonly ammonia or urea) is added to a stream
of flue or exhaust gas and is absorbed onto a catalyst. The reductant reacts with NOx
in the exhaust gas to form harmless H2O and N2. Special catalytic converters are
required to make an SCR system work, the current options being a vanadium-based
catalyst, or a catalyst with zeolites in the washcoat.
340 V. Calvino-Casilda et al.

Previous studies on supported-activated carbon catalysts exhibit low catalytic


activity for NOx reduction. Hence, an enhancement of the activity for NOx reduc-
tion was required through a proper modification of the carbon characteristics and
the use of active phase. For that reason in the last decade many authors have
worked on improving their catalytic activity by optimisation of char preparation;
increasing surface area and porosity, loading of some metals and its oxides, such
as Na, K (210–212) ; Pt (213–216); Fe, Co, Ce, Cu, La (217–222); Ni (223–226); V
(227–231) and binary mixtures, such as K, Ba, Co, Cu, Fe, Mg, Mn, Ni, Pb and V
(232–236) and improving the active phase distribution.

BASIC-CATALYZED REACTIONS (TABLE 3)


Although catalysis by solid acids had always received much attention due to its
importance in petroleum refining and petrochemical processes, relatively few
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studies had been focused on catalysis by bases until last decade. However,
during this period, base catalysts have played a decisive role in a number of
reactions mainly for fine-chemical synthesis. Easier separation and recovery of
the products, catalysts, and solvents are some of the many advantages presented
by solid-base catalysts. From the point of view of fine chemicals synthesis,
environmentally benign and more economical pathways are advantages that
have caused a remarkably increase in this research field (237). In this respect,
heterogeneous catalysts are considered as an eco-friendly alternative. Martín-
Aranda and coworkers have reported the use of basic solids such as alkali-doped
activated carbons to catalyze selectively several reactions (238–245).
Recent years have seen the development of a number of new technologies,
which offer the hope of providing the chemist with innovative synthetic routes as
sonochemical and microwave activated reactions. In general, the sonication
presents beneficial effects on the chemical reactivity, such as reaction accelera-
tion, to reduce the induction period, and to enhance the catalyst efficiency.
Martín-Aranda et al. have synthesized α,β-unsaturated nitriles by sonochemical
activated reactions of carbonylic compounds with malononitrile using two basic
carbons (Naþ– and Csþ–Norit) as catalysts. A substantial enhancing effect in
yields and selectivities was observed by this group when the carbon catalyst was
activated under ultrasonic waves.There is not before any report for the use of
activated carbons as catalysts in combination with ultrasounds. The sonochem-
ical phenomena originate from the interaction between a suitable field of acous-
tic waves and a potentially reacting chemical system; the interaction takes place
through the intermediate phenomenon of the acoustic cavitation. When one of
the phases is a solid, the ultrasonic irradiation has several additional enhance-
ment effects especially when the solid acts as catalyst. The cavitation effects
form microjects of solvent, which bombard the solid surface. This fact causes the
exposition of unreacted surfaces of solid, increasing the interphase surface able
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Table 3: Main acid- and base-catalysed reactions using activated carbon supported metal, non-metal or their compound as
catalysts in the last decade.

Precious
metals Alkali metals Transition metals Others

Ru Li Na K Cs Mn Fe Cu W P Si N

Acid-catalyzed reactions
- Aziridination of olefins !
- Acylation of alcohols and amines ! ! !

341
- Acetals and ketals synthesis ! !
- Ethers synthesis ! !
- Esters synthesis ! !
- Enaminones synthesis ! !
- Darkin-West reaction ! !
Basic-catalyzed reactions
- N- and C-Alkylations ! ! ! ! !
- Synthesis of α,β-Unsaturated nitriles ! !
- Claisen–Schmidt condensation ! !
- Alkene epoxidation !
342 V. Calvino-Casilda et al.

to react. (238). Enhancement effect on the reaction rate by combining the basicity
of the carbon with ultrasounds is also presented as an alternative method for the
production of differently substituted chalcones and, in general, for the produc-
tion of other fine chemicals due to the mild conditions that this method offers.
Chalcones are important intermediates in the synthesis of many pharmaceuti-
cals and they are commonly synthesized via the Claisen–Schmidt condensation
between acetophenone and benzaldehyde (Fig. 5) (239).
They have also reported the catalytic selective synthesis of N-alkylated imi-
dazoles, which are key intermediates in the synthesis of pharmaceutically impor-
tant anticonvulsants and bactericidal products. Basic carbons such as Na-, K- and
Cs-Norit or their binary combinations have been tested in the N-alkylation of
imidazolic rings with medium-chain and long-chain alkyl halides activated by
ultrasounds or under conventional thermal activation (Fig. 6) and in the N-
propargylation of imidazole activated by microwaves and conventional thermal
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activation. Carbon is known in microwave terminology as a very “lossy” material,


which means that it is a very efficient absorber of microwave energy and converts
that energy to heat. In their studies, they demonstrate how this fact can be used to
reduce the reaction temperature and how the selectivity is modified (240–245).

O O O O

Carvone Carvomenthone
Carvotanacetone Dihydrocarvone

OH OH OH
OH

Carveol Carvotanalcohol Dihydrocarveol Carvomenthol

Figure 5: Preparation of chalcones by Claisen-Schmidt condensation.

N N
basic carbon
+ Br
N
N
H

Figure 6: N-alkylation of imidazole with 1-bromobutane.


Last Decade of Research on Activated Carbons 343

Wang et al. have reported the catalytic synthesis of propionitrile from alkyla-
tion of acetonitrile by addition of methanol as a carbon source over activated carbon-
supported alkali catalysts (LiNO3/AC, NaNO3/AC, KNO3/AC, CsNO3/AC and
Ch3COONa/AC, NaHCO3/AC) (246).
The chiral manganese (III) Schiff base complexes with a N2O2 coordination
sphere, generally known in the literature as manganese(III) salen complexes, have
been reported by Silva et al. as very efficient catalysts in the asymmetric epoxida-
tion of unfunctionalised alkenes (247). The importance of this system is due to its
practical use in laboratory and industry scale and to the broad use of epoxides as
intermediates in organic synthesis; they can be easily transformed into a large
variety of compounds by means of regioselective ring opening reactions (248).
Fan et al. have reported the catalytic synthesis of dipropyl carbonate from
the transesterification of dimethyl carbonate and propyl alcohol over K2CO3/AC
catalysts that show better catalytic activity than other base catalysts used in
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this type of reaction (249).

ACID-CATALYZED REACTIONS (TABLE 3)


Though last decade is the decade for base catalysis, acid catalysis is continuously
in expansion and trying to improve the reaction conditions according to the
increasing interest of getting environmentally friendly processes. So for example
the need to develop a reusable and economic solid acid catalyst for the selective
acylation of alcohols and amines employing carboxylic acids as acylating agents
to achieve high atom economy, have driven to Sreedhar et al. to prepare iron (III)
oxide-containing activated carbon catalyst (250).
The aziridination of alkenes is a reaction of great importance since aziridines
are used as intermediates in organic synthesis for pharmaceuticals and agrochem-
icals. Silva et al. have reported the catalytic activity of copper (II) acetylacetonate
complexes anchored onto an activated carbon in the aziridination of styrene using
nitrene reagents (PhI ¼ NTs) as nitrogen source at room temperature (251).
Ketones and aldehydes can react with excess alcohol in acid medium to give
ketals and acetals, respectively. Acetals and ketals are among the most important
perfume materials and industrial materials of organic synthesis. Yang et al. have
reported the synthesis of acetals and ketals catalyzed by tungstosilicic acid supported
on activated carbon. Heteropoliacids and their salts have interesting catalytic prop-
erties for fine chemicals industries, and pharmaceutical and food and flavors indus-
tries, etc. Activated carbon has been found to be able to entrap a certain amount of
heteropoly acids by equilibrium impregnation with water solvent (252).
Vegetable oils and animal fats can be transesterified to biodiesel for use as an
alternative diesel fuel. Conversion of low cost feedstocks such as used frying oils is
complicated if the oils contain large amounts of free fatty acids that will form
soaps with alkaline catalysts. The soaps can prevent separation of the biodiesel
344 V. Calvino-Casilda et al.

from the glycerin fraction. Kulkami et al. have prepared 12-tungstophosphoric


acid (TPA) impregnated on activated carbon for the biodiesel production from low
quality canola oil containing up to 20 wt% free fatty acids (253). Mohammadpoor-
Baltork et al. have also prepared 12-Tungstophosphoric acid (TPA)/AC catalysts
for the synthesis of oxazolines, imidazolines, and thiazolines in dry media (254).
Rafiee et al. have studied the catalytic activity of tungstophosphoric acid
supported on activated carbon in the synthesis of enaminones and in Dakin-
West reaction for the production of β-acetamido ketones (255,256) and Obali
et al. in the synthesis of tert-amyl ethyl ether (257).
Shi et al. have reported the catalytic synthesis of n-dibutyl adipate by
activated carbon supported tungstophosphoric acid (258) and Liu et al., have
supported phosphotungstic acid on activated carbon to prepare catalysts for the
synthesis of dibutyl sebacate (259).
Lin et al. have investigated SiW12/AC catalysts prepared loading silico-
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tungstic acid on activated carbon for the synthesis of trioxane (260).


Zhou et al. have reported heteropolyacid supported on activated carbon by
vaporization for the catalytic synthesis of aliphatic acetate by esterification of
acetic acid with various alcohols obtaining high yields (261). Juan et al. have
investigated the esterification of oleic acid by n-butanol over zirconium sulfate
suported on activated carbon catalysts (262).
Epoxide ring-opening reactions are useful tools in organic chemistry. Reactions
of epoxides are key processes for the transformation of aliphatic and aromatic
compounds. Durán-Valle et al. have investigated the epoxides (1,2-epoxyhexane
and styrene oxide) ring-opening reaction with 1-butanol (Fig. 7) and more recently
with ethanol under microwave irradiation using activated carbons treated with
mineral acids (HNO3 and sulfonitric mixture) as acid catalysts (263,264).
Sulfonated activated carbon catalysts have been employed in different organic
reactions such as the selective hydrolysis of cellulose into glucose (265), the alcohol
acylation (etherification) and the epoxide-opening (266).

CATALYTIC C—C BOND FORMATION (TABLES 4A AND 4B)


There are several practical reactions to be applied to cost-effective large-scale
production of multifunctional intermediates for drug-synthesis such as Suzuki,
Heck, Sonogashira, and Ullmann reaction.

O O
OH + R OH
R
R = –Ph, –CH2CH2CH2CH3

Figure 7: Epoxides ring opening reaction with 1-butanol.


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Table 4: Main catalytic reactions of C—C bond formation and other applications using activated carbon supported metal, non
metal and their compound catalysts in the last decade (Table 4A and Table 4B).

Precious metals Alkali/ Alkali earths metals


Table 4A Pd Pt Ir Ru Rh Au Ag Na K Rb Cs Ba Mg Ca

Catalytic C–C bond formation


Carbonylation of methanol/aliphatic alcohols/ethers/esters/ R-X ! ! !
Hydroformylation !
Heck reaction !
Suzuki and Miyaura reaction !
Ullmann reaction !
Fukuyama reaction !
Sonogashira reaction !
Knoevenagel condensation ! !
Reductive coupling of haloaryls ! !
Markovnikov addition !
Other applications

345
Dehydrohalogenation (β-Elimination reaction) !
Dehydrogenation of alkanes/cycloalkanes (production of H2) ! ! !
Dehydrogenation of alcohols !
Cyanosylilation of aldehydes
Isomerization of polyunsaturated fatty acids ! ! ! ! !
1-butene isomerization
Catalyst-anode for fuel cell ! ! !
Ozonation
Polymerization of cycloalkenes
Oligomerization of hydrocarbons !
Denitrification of water (DeNOx) ! !
Photocatalyst
Hydrosilylation of alkenes !
Fischer-Tropsch synthesis !
Ammonia synthesis ! ! !
Ammonia decomposition !
CF3I synthesis ! ! ! !
Oil yield (coal extraction)
Antibacterial activity ! ! !
Glycerol dehydration
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Table 5:

Transition metals Others


Table 4B Ti V Mn Fe Co Ni Mo W Re Os Bi Cu Zn Sn Ce Zr La Cr Si

Catalytic C–C bond formation


- Carbonylation of methanol/aliphatic alcohols/ethers/ ! !
esters/ R-X
- Hydroformylation
- Heck reaction
- Suzuki and Miyaura reaction !
- Ullmann reaction
- Fukuyama reaction
- Sonogashira reaction
- Knoevenagel condensation
- Reductive coupling of haloaryls
- Markovnikov addition
Other applications
Dehydrohalogenation (β-Elimination reaction) !
Dehydrogenation of alkanes/cycloalkanes (production ! ! ! ! !

346
of H2)
Dehydrogenation of alcohols ! ! !
Cyanosylilation of aldehydes !
Isomerization of polyunsaturated fatty acids ! !
1-butene isomerization !
Catalyst-anode for fuel cell ! ! !
Ozonation ! ! ! ! ! !
Polymerization of cycloalkenes ! ! !
Oligomerization of hydrocarbons !
Denitrification of water (DeNOx) ! !
Photocatalyst ! ! !
Hydrosilylation of alkenes !
Fischer-Tropsch synthesis ! ! ! ! ! !
Ammonia synthesis ! !
Ammonia decomposition
CF3I synthesis
Oil yield (coal extraction) ! ! !
Antibacterial activity ! ! ! !
Glycerol dehydration ! !
Last Decade of Research on Activated Carbons 347

The Suzuki reaction (or Suzuki-Miyaura reaction) is the organic reaction of


an aryl- or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palla-
dium catalyst. It is widely used to synthesize poly-olefins, styrenes, and sub-
stituted biphenyls. Several reviews have been published using different
palladium supported catalysts such as palladium nanoparticles supported on
activated carbon (267–269).
The Heck reaction is the chemical reaction of an unsaturated halide with an
alkene and a strong base and palladium catalyst to form a substituted alkene.
The halide or triflate is an aryl, benzyl, or vinyl compound and the alkene
contains at least one proton and is often electron-deficient such as acrylate
ester or an acrylonitrile.The catalysts employed have been tetrakis(triphenyl-
phosphine)palladium, palladium chloride or palladium acetate. The ligand is
triphenylphosphine or BINAP (2,2’-bis(diphenylphosphino)-1,1’-binaphthyl).
The base is triethylamine, potassium carbonate, or sodium acetate. Several
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investigations are reported in literature about the Heck reaction catalyzed by


palladium-supported activated carbon catalysts (Fig. 8) (270–275).
Other catalysed C–C coupling organic reactions besides Heck reaction, have
been carried out over palladium complexes and palladium on activated carbon
catalysts. For example, Sonogashira reaction, a coupling reaction of terminal
alkynes with aryl or vinyl halides, Ullmann reaction is a coupling reaction
between aryl halides and Fukuyama reaction is a palladium catalysed coupling
of organozinc compounds with thioesters to form ketones. In organic synthesis,
Ullmann reaction is less typical, and it is often replaced by Heck reaction and
Sonogashira coupling (276,277).
Mukhopadhyay et al. have reported the coupling of substituted haloben-
zenes to the respective biphenyls using a combination of a reducing agent and
a weak base (Na2CO3) in the presence of catalytic tetrabutylammonium bromide
(TBAB) and palladium that are both supported on activated carbon. The results
are explained with postulation of a physical micro-membrane formed in situ by
the phase-transfer catalyst (278).
Carbonylation reactions are of major importance in both organic and indus-
trial chemistry. Due to the availability, price, and reactivity pattern, carbon

Br
Pd/C, base
+ +
solvent, 140 ºC
R -HBr R
E- and Z-isomers R
R = H, OCH3, COCH3

Figure 8: Heck coupling of bromoarenes with styrene catalyzed by Pd supported activated


carbon catalysts.
348 V. Calvino-Casilda et al.

monoxide is becoming a more and more important building block for fine and
bulk chemicals. Carbonylation reactions involve the insertion of 4C¼O moiety
with or without other groups (if any, as -OMe, -OEt, etc.) into a substrate which
may be of varied types such as alkenes, alcohols, alkynes, alkyl halides, amines,
nitro compounds or substituted aromatic analogs of these. Protzmann et al. have
improved the selectivity in the catalytic carbonylation of 1,3-butadiene to 3-
pentenoic acid immobilizing rhodium on activated carbon (279). Some authors
have studied the stability of Rh/AC and Ni/AC catalysts in the liquid-phase and
vapour-phase carbonylation of methanol (280–282). Merenov et al. and Peng
et al. have reported the direct vapor-phase carbonylation of methanol on Ni/AC
and NiCl2-CuCl2/AC catalysts obtaining a high selectivity to methyl acetate
(283,284). More recently, Kosmambetova et al. have carried out the methane
oxidative carbonylation catalyzed by rhodium chalcogen halides over activated
carbon support (285).
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Some authors have reported a variety of carbonylation reactions, the hydro-


formylation (oxo synthesis) of long-chain alkenes over rhodium complex inmobi-
lized on activated carbon. This reaction is an important industrial process for the
production of aldehydes from alkenes. It is important because the resulting
aldehydes are easily converted into many secondary products (286–291).
There is another type of reaction catalysed by alkali solid catalysts and
reported by Calvino-Casilda et al., the Knoevenagel condensation, which has
been used to measure the strength of the basis sites and can be used to form C–C
bonds through the reaction of a carbonyl with an activated methylenic group.
They have reported the condensation of benzaldehyde and different substituted
benzaldehydes with ethyl cyanoacetate using Na-Norit and Cs-Norit as catalysts
in dry media. The reaction products are precursors in the production of 1,4-
dihydropyridine derivatives, which have expanding practical applications as
pharmaceuticals in the line of calcium channel blockers (Fig. 9) (292).

OTHER REACTIONS (TABLES 4A AND 4B)


During the 20th century, the catalytic ammonia synthesis has grown to be among
the most important industrial processes. Ru-based materials are the second-
generation catalysts for ammonia synthesis. Ruthenium is less inhibited by

CHO
R1 O COCH3
COOEt catalyst
+ COOEt
R2 R1
R2

Figure 9: Knoevenagel condensation between substituted benzaldehydes and ethyl acetoacetate


for the synthesis of benciliden derivatives in the production of 1,4-dihydropyridines (R1¼NO2, H, R2¼H,
NO2).
Last Decade of Research on Activated Carbons 349

ammonia, less sensitive to poisons, and more active than the traditional iron-based
catalyst. Ru-based activated carbon supported catalysts with promoters as barium
and potassium have been reported by many authors to be active for ammonia
synthesis (293–300). Fe, Co and Fe-Co/AC catalysts were proposed by Rarog-
Pilecka et al. as catalysts for ammonia synthesis using barium and potassium
promoters (301).
Catalytic ammonia decomposition has attracted significant and increasing
attention as a means of supplying pure hydrogen for fuel cells. Rarog-Pilecka
et al. have reported Ru/AC catalysts for ammonia decomposition (302). Pd/AC
and Pt/AC catalysts have been employed on cyclohexane dehydrogenation and
Pt/AC and Pt-Re/AC catalysts have been employed in the dehydrogenation of
decalin in the hydrogen supply to fuel cells (108,303–306). Shimada et al. have
carried out the dehydrogenation of iso-butane over Fe/AC catalysts and Silvestre
et al. over Pt-Zn/AC catalysts obtaining high selectivity to isobutene (143,307).
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Vanadium and iron oxides, vanadium and magnesium and copper supported on
activated carbon have been proposed as catalysts for ethylbenzene dehydrogena-
tion to styrene a high value chemical (Fig. 10) (308–312). Pt, Cu-Pt, Cu, CoO,
Co3O4, Cu2O, and NiO supported on activated carbon catalysts were employed
on dehydrogenation of alcohols such as cyclohexanol and isopropanol (313–315).
The catalytic decomposition of ozone is an important area of research from
environmental and health point of view. Ozone decomposition has been reported
over metal oxide supported on activated carbon catalysts, MnO2, Co3O4, Fe2O3,
and NiO/AC by Heisig et al. (316).
Nitrogen occurs in raw surface water in the form of organic nitrogen, ammonia,
nitrate and nitrite, all of which are undesirable in drinking water. The biological
denitrification of water is a convenient and cost-effective alternative method for the
removal of nitrate and nitrite ions from waters. Most studies on denitrification by
heterotrophic denitrifying bacteria have shown that the cultures require a carbon as
an electron donor for the reduction of nitrate and nitrite, which must be added to the
water being treated. Lemaignen et al. have reported the catalytic denitrification of
water using metal-activated carbon supported catalysts, Pd- and PdSn/AC catalysts
for nitrate reduction (317) and Soares et al. have recently reported the nitrate and

CH3
H2C
CH2 CH

+ H2

Ethylbenzene Styrene

Figure 10: Ethylbenzene dehydrogenation to styrene.


350 V. Calvino-Casilda et al.

nitrite reduction in water over bimetallic catalysts Rh-Cu/AC and Pd-Cu/AC (318).
Under anaerobic conditions, many bacteria use nitrate and nitrite ions contained in
contaminated waters for respiration. Moreno-Castilla et al. have studied the deni-
trification of water under anaerobic conditions by using Escherichia coli supported
or immobilised on different activated carbons. Activated carbons offer the advan-
tages of a large adsorptive capacity and an irregular shape, which acts as a shelter
for bacteria from high fluid shear forces (319).
Environmental photochemistry using semiconductors is the part of a general
group of chemical remediation methods known as Advanced Oxidation Processes
(AOPs). These methods are based on one distinguishing feature—the generation
and use of hydroxyl radicals as the primary oxidant for the degradation of organic
pollutants. Among the several semiconductors, TiO2 is reported to be a Benchmark
photocatalyst. TiO2 is anchored or embedded onto support materials such as silica,
alumina, zeolites, clay and activated carbon being this last the most commonly
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used adsorbent for water treatment. Activated carbon has a large specific surface
area and a well-developed porous structure, resulting in an attractive force toward
organic molecules (320–328). Many authors have based their investigations on
using TiO2/AC as catalyst; Arana et al., the gas-phase alcohols photocatalytic
degradation (329); Parra et al. the photocatalytic degradation of atrazine (330);
Zou et al. the photocatalytic degradation of toluene (331); Subramani et al. the
photocatalytic degradation of indigo carmine dye (332); Chen et al. the photocata-
lytic degradation of methylene blue (333); Li et al. the photocatalytic degradation
of Rhodamine B (334); Gauthier et al. the photocatalytic degradation of esters as
ethyl hexanoate (335); some other authors the removal of phenol and phenol
derivatives from water (336–338); Geng et al. the decomposition of aqueous hydro-
quinone (339); Sleiman et al. the photocatalytic removal of pesticide dichlorvos
from indoor air (340) and Nada et al. have studied the photocatalytic hydrogen
production (341). Wang et al. have reported the photodegradation of L-acids under
visible light over Mo-TiO2/AC catalysts and Follansbee et al. the photodegradation
of reactive red dye (342,343). Hilal et al. supported TiO2/TPPHS (2,4,6-triphenyl
hydrogen sulphate) onto activated carbon (AC) to yield a new class of catalytic
system AC/TiO2/TPPHS for the photo-degradation of phenol and benzoic acid in
water (344). More recently, Puma et al. have reviewed the preparation of titanium
dioxide loaded onto activated carbon support and its photocatalytic activity in a
variety of investigations as i.e. from water decontamination to direct pollutant
degradation in aqueous and gas phase systems using UV irradiation and lately
with the assistance of ultrasonic sound waves (345).
However, ZnO is found to be a suitable alternative to TiO2. For practical applica-
tions there are some difficulties such as either filtration of fine TiO2 or fixation of
catalyst particles and efficient utilization of UV/Solar light. For these reasons many
researchers have been working to increase the efficiencies of this process by mod-
ification of its surface. Sobana et al. have evaluated the degradation efficiency of ZnO
loaded activated carbon catalysts (AC–ZnO composite photocatalyst) with solar light
Last Decade of Research on Activated Carbons 351

at room temperature using an azo dye Direct blue 53 (DB53) and have also studied its
photocatalytic activity on 4-acetylphenol degradation (346,347). Lee et al. have
studied the photochemical activity of Zn/AC catalysts by measuring the humic acid
(HA) removal efficiency using UV/photocatalyst system (348). Xu et al. have synthe-
sized fluorine-doped titania-coated activated carbon catalysts with photocatalytic
activity in the degradation of phenol under visible light (349).
The Fischer-Tropsch process is a catalyzed chemical reaction in which carbon
monoxide and hydrogen are converted into liquid hydrocarbons of various forms.
Typical catalysts used are based on iron and cobalt. The principal purpose of this
process is to produce a synthetic petroleum substitute, typically from coal or
natural gas, for use as synthetic lubrication oil or as synthetic fuel. Some authors
have proposed Fe-Co/AC, Fe-Cu-K/AC and Fe-Mo-Cu-K/AC catalysts for Fischer-
Tropsch synthesis (350) and more recently Wang et al. have reported the influence
of lanthanum on the performance of Zr-Co/AC catalyst in this reaction (351).
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Electrochemical fuel cells convert the chemical energy of a fuel directly into
electric power employing a catalytic process. Fuels for this kind of power gen-
eration, such as hydrogen or methane, are oxidised at the anode of the fuel cell,
while oxygen is simultaneously reduced at the cathode. The only off-gas product
of hydrogen fed fuel cell is water vapour. Maruyama et al. have found that
platinum supported on activated carbon is an effective electrocatalyst for poly-
mer electrolyte fuel cells improving the activity for oxygen reduction (352–354)
and Guha et al. have employed Pt/AC catalysts in fuel cell electrodes (355).
Ominde et al. have studied the effect of oxygen reduction on activated carbon
electrodes loaded with manganese dioxide catalyst (356). Zhou et al. have
reported Pt-based anode catalyst supported on activated carbon for direct etha-
nol fuel cells (357) and more recently, Tapan et al. have tested activated carbon-
based Ag-Cu electro-catalyst for anode electrode in direct ethanol fuel cells (358).
PtRu/AC catalysts have been tested in the methanol electro-oxidation and as
anode catalyst of the direct methanol fuel cell (DMFC) by some authors
(359,360). More recently, Kerzenmacher et al. have reported Pt-Bi based anode
catalyst supported on activated carbon for glucose oxidation (361).
Organosilicon compounds have attracted much interest from viewpoints of
organic synthesis as well as new functional materials. This trend of organome-
tallic chemistry has prompted us to develop new methodologies for stereoselec-
tive formation of silicon-carbon bonds. The utility of hydrosilylation as a
synthetic tool has even been extended into the area of enantioselective reactions.
Maciejewski et al. have presented Pt-Cu/AC catalysts for the hydrosilylation of
alkenes with poly(hydro,methyl)siloxanes in the synthesis of silicone waxes
(362).Baleizao et al. have reported that aldehydes can react with trimethylsilyl
cyanide under both thermal and catalytic conditions to give α-silyloxy nitriles
which may be useful intermediates and protective groups in organic synthesis.
They tested chiral vanadyl salen complex anchored on activated carbon catalysts
in the studied reaction (363).
352 V. Calvino-Casilda et al.

Nagasaki et al. have reported a novel catalytic reaction and its mechanism
for CF3I synthesis using alkali metal salts supported on activated carbon. There
is incentive to synthesize this molecule in a low-cost route for using it as a
refrigerant and also because it useful a foam blowing agent and can be used to
replace more environmentally damaging foam blowing agent previously
employed in the production of polymeric foams (364).
Polymerization of α-pinene using cooper, nickel, and vanadium oxides sup-
ported on activated carbon was carried out by Encarnação et al. to obtain poly-
mers of low molecular weigh. Pinene homopolymers belong to the family of
terpenic resins that are low molecular weight valuable commercial products
used by the adhesive, sealant, wax coating, and casting industries. They are
bicyclic isomers that undergo cationic polymerization by ring opening of their
cyclobutane ring (Fig. 11) (365). Later Milewska et al. carried out the hydro-
genation of α-pinene in high-pressure carbon dioxide using Pt/C catalysts (366).
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Experiments were performed at different carbon dioxide pressures, so that the


reaction mixture in contact with the solid catalyst would either be biphasic
(liquid þ gas) or a single supercritical phase. The hydrogenations in biphasic
conditions, at lower carbon dioxide pressures, are completed faster than in
supercritical conditions.

HC3

HC3
CH3
HC
3

+ Limonene
CH3 CH3 Tricyclene
CH3 γ -Terpinene
+
H3C CH3

CH3 H3C
H2C
Camphene
α -Pinene

CH3 CH3
H2C CH3
H3C CH3
+
H3C CH3

H3C CH3 H3C CH3

Terpinolene α -Terpinene

Figure 11: Polymerization of α-pinene.


Last Decade of Research on Activated Carbons 353

Chakraborty et al. have reported the formation of oligomerization hydro-


carbon products from an equimolar mixture of CF2Cl2 and H2 catalyzed by
activated carbon-supported Pt-Cu catalysts (367).
Moreno-Castilla group has prepared tungsten oxide catalysts supported on
activated carbons for the isomerization of 1-butene (368,369). Bernas et al. have
reported the isomerization of polyunsaturated fatty acids such as linoleic acid to
conjugated linoleic acid (CLA) over the following catalysts; Ru, Ni, Pd, Pt, Rh, Ir,
Os and bimetallic Pt-Rh supported by activated carbon. Conjugated linoleic acid
(CLA), is being sold as a panacea that has the capability of reduce or even
eliminate cancer, preventing heart disease, improve immune function, and altere
the body composition in order to treat obesity or build lean body mass (370).
Ucar et al., have reported the upgrading scrap tire derived oils using Co-Ni/
AC, Co-Mo/AC and Ni-Mo/AC catalysts (371).
Methakhup et al. have improved oil yield from coal extraction using Fe-Ni/
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AC, Ni-Mo/AC and sulphide catalysts Fe2S3/AC (372).


Nosheen et al. have investigated the microwave assisted cracking of n-
hexane over Pt/AC catalysts to produce lower hydrocarbons (C2 and C3) to
efficiently activate automobile catalysts (373).
Faria et al. have reported cerium, manganese and cobalt oxides as catalyst for
the ozonation of selected organic compounds (aniline and sulfanilic acid) and azo
dyes (374) and Li et al. have reported the catalytic ozonation of p-chlorobenzoic over
Ni/AC catalysts (375). Hammad et al. have prepared catalysts doping activated
carbon with chromia gel for ozone decomposition and DEHP degradation (376).
Xu et al. have generated hydrogen from alkaline NaBH4 solution via hydro-
genolysis using Co/AC catalysts (377).
Shargi et al. have prepared cobalt(III)-salen complex supported on activated
carbon as an efficient heterogeneous catalyst for synthesis of 2-arylbenzimidazole
derivatives from phenylenediamines and aromatic aldehydes (378).
Hisashi et al. have reported the antibacterial activity of Co, Zn, Ni, Mg and Ca/
AC catalysts against bacteria’s such as S. aureus and B.subtilis (379) and later
Kennedy et al. reported the use of Cu/AC catalysts for the destruction of these
pathogens in water (380). More recently, Liu et al. have reported the antibacterial
activity of Ag/AC catalysts against S. Aureus and for bacteria’s E. coli (381).
Hutchings have carried out the ethyne hydrochlorination over Au/AC cata-
lyst with the formation Markovnikov addition products (382). Ning et al. have
reported the glycerol dehydration to acrolein over activated carbon-supported
silicotungstic acids (383).

CONCLUSIONS AND FUTURE TRENDS


Catalytic processes report more than 90% of the chemical manufacturing pro-
cesses in use all over the world. The catalyst increases the rate of a reaction and
controls its selectivity. Catalyst development is a complex process, requiring
354 V. Calvino-Casilda et al.

extensive research to produce the high performance catalysts used today.


Activated carbons have been used for some time in heterogeneous catalysis, acting
as direct catalysts and not long as catalyst support. It is now recognized that
activated carbon as a catalyst support offers unparallel flexibility in tailoring their
physical (surface area and porosity) and chemical (surface functional groups)
properties to specific needs, thus showing the remarkably wide range of potential
applications. However, the future growth of the use of the activated carbon in
catalysis depends on the better understanding and subsequent control of the
chemistry of activated carbon surface. Specifically the role of the chemical nature
of the activated carbon surface has become widely recognized during the last few
years. In this way, physical and chemical surface properties of activated carbon
have to be taken into account when designing a catalyst. Since in 1998 Rodríguez-
Reinoso reviewed the properties of activated carbon as catalyst and catalyst
support, many advances has been got in this field especially on activated carbon
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supported catalytsts. Therefore, this review gives an overview of current chemical


processes catalyzed by activated carbon supported catalysts in the last decade.
The properties and requeriments of activated carbon supports are closely
related to the requirements of the catalyst. The important parameters for activity
and selectivity of a catalyst are not only surface area, porosity, inertness, purity,
surface functional groups (catalyst manufacturing), cost efectiveness but also
mechanical stability needs to be considered for the recyclability of the catalyst
(green chemistry).

ACKNOWLEDGMENTS
V.C.C. acknowledges CSIC for the award of a JAE-Doctor contract. The work has
been supported by Spanish Ministry of Education and Science (project:
CTM2007-60577/TECNO). This review is dedicated to Prof. J. de Dios López-
González, who showed us how attractive, is catalysis on activated carbons.

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