Co3O4 Thin Films: Sol-Gel Synthesis, Electrocatalytic Properties & Photoelectrochemistry THESIS Presented in Partial Fulfillment of the Requirements

for the Degree Master of Science in the Graduate School of The Ohio State University By Tushar S Kabre Graduate Program in Chemistry The Ohio State University 2011 Master's Examination Committee: Associate Professor Yiying Wu, Adviser Assistant Professor Joshua Goldberger Copyright by Tushar S Kabre 2011 ii Abstract World energy consumption is bound to increase with the increasing population. Fossil fuels widely used today, are limited in their supply. Moreover, high CO2 emission from their widespread usage is believed to have caused the global warming. Clearly, in the long run an economy based entirely on the fossil fuels is not a sustainable economy. It is therefore very important than ever before, to innovate new and sustainable ways to harvest the solar energy. With this view, work presented here investigates the electrocatalytic and photo-electrochemical properties of Co3O4 thin films prepared by the sol-gel method, for the purpose of water splitting and solar cells. The thin films synthesized were characterized by using x-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS). The electrocatalysis studies were done for the oxygen evolution reaction (OER). OER reaction is the half reaction occurring at anode in water splitting cell. It has large overpotential, which brings the overall efficiency of the electrochemical water splitting down. Therefore, better OER electrocatalysts are required. In the OER experiments, we used the electrochemical milling (ECM) on Co 3O4 thin films, to generate the nanoporous Co3O4. Electrochemical measurements were done in iii 1M NaOH solution with the thin films as working electrode in a typical three-electrode assembly. OER performance for these ECM treated sample increased compared to samples without ECM treatment. Scanning electron microscopy (SEM) images of samples were taken at different stages of experiments to detect any change in surface morphology. The planar surface of the thin films was found to have changed to hexagonal plates after ECM treatment, and they were only formed after exposing ECM treated samples to 1M NaOH. XPS investigation revealed the formation of CoO from Co3O4 because of ECM. These hexagonal plates were identified to be cobalt oxyhydroxide, using Raman

spectroscopy and X-ray diffraction (XRD). CoO(OH) is known to have higher conductivity. Hence increased OER performance of CoO(OH) thin films is maybe due to the overall increase in effective active sites. Wide band gap semiconductors such as TiO2 or ZnO are limited to UV region of solar spectrum. Therefore, small band gap semiconductors such as Co3O4 with absorption in visible solar spectrum can potentially harvest higher amount of the solar energy. Reported studies of photo-electrochemical (PEC) properties of Co3O4 are very scarce. Hence, this work is partly focused on developing working procedure of stable iv photocurrent measurement for Co3O4 thin films. High absorption in the visible region of the solar spectrum was the initial motivating factor for pursuing the PEC study of Co 3O4. Photocurrent measurements were done using a Xe lamp as the light source. In all electrochemical measurements, a typical three-electrode assembly was used with Co3O4 used as working electrode. Many different electrolytes - aqueous as well as nonaqueous were used. The photocurrent obtained was found to be very low, ~ 10-20 A at the maximum. Transient photocurrent was observed, maybe due to the surface trapped minority carriers. Large background dark current was present in almost all systems. It could be due to porous nature of the thin films, exposing FTO to the electrolyte. v Dedication This thesis is dedicated to all my teachers. vi Acknowledgments I would like to thank my advisor, Dr. Yiying Wu for giving me all essential guidance through different stages of this work. I am also thankful to Dr. Yanguang Li for the thorough discussions and practical help in getting the initial set up going for electrochemistry experiments. I would like to specially mention Ms. Gayatri Natu, Dr. Zhiqiang Ji and Mr. Panitat Hasin for all their help, encouragement and support. Moreover, thanks are due to all the new graduate and undergraduate students of our group, for keeping a sincere and friendly working atmosphere. Sincerely, Tk Tushar S Kabre vii Vita 2005................................................................B.S. Chemistry, University of Mumbai 2007................................................................M.S. Chemistry, University of Mumbai 2008 to present ..............................................Graduate Teaching Associate, Department of Chemistry, The Ohio State University Field of Study Major Field: Chemistry viii

Table of Contents Abstract ............................................................................................................................... ii Dedication ........................................................................................................................... v Acknowledgments.............................................................................................................. vi Vita ................................................................................................................................... vii List of Tables ...................................................................................................................... x List of Figures ................................................................................................................... xii List of Abbreviations ........................................................................................................ xv Chapter 1: Introduction ...................................................................................................... 1 Chapter 2: Co3O4 thin films synthesis and characterization ........................................... 5 2.1 Introduction ........................................................................................................... 5 2.2 Sol-gel synthesis .................................................................................................... 5 2.3 Co3O4 thin film synthesis by sol-gel method......................................................... 8 2.4 Characterization of the Co3O4 thin films ............................................................. 10 Chapter 3: Electro-catalytic study of Co3O4 .................................................................... 18 3.1 Introduction ......................................................................................................... 18 ix 3.2 Introduction to electrochemical milling .............................................................. 24 3.3 Experiments ......................................................................................................... 26 3.4 Results ................................................................................................................. 28 3.4 Discussion ............................................................................................................ 47 Chapter 4: Photoelectrochemical study of Co3O4 ............................................................ 54 4.1 Introduction ......................................................................................................... 54 4.2.1 Fundamentals of Photoelectrochemistry .......................................................... 55 4.2.2 Introduction to Photoelectrochemistry of Co3O4 .............................................. 58 4.3 Experiments ......................................................................................................... 60 4.4 Results ................................................................................................................. 67 Chapter 5: Conclusions and future work .......................................................................... 81 5.1 Electrocatalysis .................................................................................................... 81 References ......................................................................................................................... 84 x List of Tables

Table 1: Assignment of Co3O4 optical absorption peaks13 ............................................... 16 Table 2: Literature survey of Co3O4 OER experiments .................................................... 23 Table 3: Electrochemical charge and discharge time for Co3O4 thin film samples. Refer to Figure 9 ............................................................................................................................. 28 Table 4: Tafel slope and Exchange current density for Co3O4 thin film samples before and after ECM as calculated from Tafel plot in Fig. 10. (Sample 2 plot is not shown in Fig. 10) .............................................................................................................................. 32 Table 5: Summary of Co2p and O1s peak positions for different samples of Co 3O4 thin films from experiments and literature ............................................................................ 42 Table 6: Literature survey of different methods for synthesis of CoO(OH) ..................... 49 Table 7: Comparison of Co3O4 with CoO(OH) ................................................................ 50 Table 8: Different band gap transitions in Co3O4, ............................................................ 59 Table 9: Different reference electrode used ...................................................................... 62 Table 10:Preparation of different electrolytes used in the PEC experiments ................... 65 Table 11: Summary of the PEC data obtained under different experimental conditions. Working electrode is thin film of Co3O4 on FTO, unless specifically mentioned. ........... 72 xi Table 12: Summary of the PEC data obtained under different experimental conditions. Working electrode is thin film of Co3O4 on FTO, unless specifically mentioned. ........... 73 xii List of Figures Figure 1: World marketed energy consumption from year 1990 to 2035 ........................... 2 Figure 2: Image (a) blank FTO slide (b) Co3O4 thin film on FTO substrate .................... 10 Figure 3: XRD spectrum of Co3O4 thin films on FTO substrate ..................................... 11 Figure 4: SEM micrograph of Co3O4 thin films on FTO substrate .................................. 13 Figure 5: UV-Vis spectrum (K-M transformed DRS spectrum) of Co3O4 thin film on glass substrate. .................................................................................................................. 15 Figure 6: The overpotential for oxygen evolution as a function of the enthalpy change

from the lower to higher oxide transition in acidic and basic medium for different metal oxides ............................................................................................................................... 20 Figure 7: Schematic illustration of structural Changes occurring in electrode during discharging and charging process by conversion mechanism .......................................... 24 Figure 8: SEM micrographs of starting CuO (a) and discharged product (metallic Cu) obtained at the current density of 0.32mA/cm2 (b), 0.065mA/cm2 (c) and 0.032mA/cm2 (d). .................................................................................................................................... 25 Figure 9: Electrochemical charge-discharge curves for Co3O4 thin film samples cycled between 0-3V at constant current of 30 A. ..................................................................... 29 xiii Figure 10: (a) Cyclic voltammograms of sample before and after ECM in 1M NaOH at 5mV/s scan rate. (b) Tafel plots of sample before and after ECM. .................................. 31 Figure 11: SEM micrographs of Co3O4 thin film samples after various treatments ......... 33 Figure 12: SEM micrograph of exposed (to NaOH) and unexposed (outside of circle) area of the sample. .................................................................................................................... 36 Figure 13: SEM micorgraphs of ECM trated samples after NaOH exposure for different amount of time. a) 15 min b) 30 min c) after CV d) after OER measurements ................ 37 Figure 14: Co2p region of XPS spectrum of Co3O4 thin film samples without ECM and with ECM ......................................................................................................................... 39 Figure 15: O1s region of XPS spectrum of Co3O4 thin films without ECM .................... 40 Figure 16: O1s region of XPS spectrum of Co3O4 thin film samples after ECM (CoO) . 41 Figure 17: XRD spectrum of ECM treated sample after OER. ........................................ 45 Figure 18: Raman spectrum of ECM treated samples after OER measurements ............. 46 Figure 19: Crystal structure of CoO(OH) ......................................................................... 53 Figure 20: Energetic position of fermi level under different conditions .......................... 57 Figure 21: Schematic diagram and photograph of PEC cell, front and lateral view ........ 64 Figure 22: LSV curve for TiO2 sample under chopped light at pH of 6.884 ................... 68 Figure 23: Photocurrent square against potential vs N.H.E For TiO2 PEC experiment in acetate buffer ..................................................................................................................... 69

xiv Figure 24: Change in flat band potential with pH of the acetate buffer used in TiO 2 aqueous PEC experiment .................................................................................................. 70 Figure 25: Chopped light LSV curve for Co3O4 thin films in ferrocene based nonaqueous electrolyte............................................................................................................ 71 xv List of Abbreviations
BTU British Thermal Unit (1BTU = 1055 joules) CV Cyclic voltammetry CVD Chemical vapor deposition ECM Electrochemical milling FTO Fluorine doped Tin oxide GAA Glacial acetic acid IPCE Incident photon to electron conversion efficiency K-M Kubelka-Munk Laser Light amplification by stimulated emission of radiation LSV Linear sweep voltammetry OER Oxygen evolution reaction PDF Powder diffraction file PEC Photoelectrochemistry PLD Pulse Laser Deposition SEI Solid electrolyte interface SEM Scanning electron microscopy TCO Transparent conducting oxide TEM Transmission electron microscopy TEOS Tetraethyl orthosillicate TGA Thermo-gravimetric analysis UV-Vis Ultra violet and visible XPS X-ray photoelectron spectroscopy XRD X-ray diffraction

1 Chapter 1: Introduction The demand for the energy supply required to maintain the steady growth in economy increases with the increasing population. Todays industrial economy is based on the rapid consumption of fossil fuels, which are non-renewable and finite in their amount. Hence, there is an urgent need to find new renewable and cheap sources of energy. Year wise energy demand of the world, starting from the year 1990 and projected into year 2035 is shown in Figure 1. The projection in future is based on the current data of the total marketed energy consumption of the world and the percentage GDP growth. It will hold true, only if the current trend continues in a business as usual fashion. The current research on the alternative energy focuses on different areas including various types of solar cells for capturing the solar energy, fuel cells for cleaner and efficient consumption of existing fuels, hydrogen generation and so on. 1 Invariably, almost all these technologies involve the use of semiconductors as the energy transducer. Current grid infrastructure may or may not be usable with these renewable energy

sources, depending on the amount and rate of energy generation. However, the current scenario clearly indicates that there will be a huge volume of off grid usage of electrical energy in the form of batteries, supercapcitors or fuel cells. 2 Most of these forms of electrochemical storage or generation involve the use of semiconductor in one way or the other. This underlines the importance of the study of the semiconductor electrochemistry, especially metal oxide semiconductors, as they have shown potential for application in almost all the research directions mentioned above. Co3O4 has been extensively studied for various applications such as electro-catalyst for the oxygen evolution reaction (OER), as a surface coating of solar selective absorber, as a photo-electrode in photo electrochemical (PEC) studies, as a catalyst for hydrocracking of crude oil and as an anode in a lithium ion battery. A brief survey of literature published on the application of Co3O4 as the OER catalyst and for the PEC will be covered in the respective introductions of the following chapters.
0 200 400 600 800 1990 1995 2000 2007 2015 2020 2025 2030 2035 Quadrillion BTU History Projections Figure 1: World marketed energy consumption from year 1990 to 2035, history and projections based on current data 2

3 Physical and chemical properties of bulk Co3O4 have been extensively investigated. It is known to have a spinel type crystal structure. It can be described as a regular cubic closed packed oxygen framework with Co3+ filling half of the octahedral interstices and Co2+ occupying one eighth of tetrahedral interstices. Such site occupancy has been widely studied using magnetic susceptibility and Mssbauer spectroscopy. An antiferromagnetic transition observed in Co3O4 at around 40K has been explained based on the site occupancy of Co2+ and Co3+ metal ions oxygen framework of Co3O4.3 For both PEC and OER experiments, mechanically and chemically stable Co 3O4 films were required. Sol-gel type of method was used to prepare thin films on different substrates. Experimental details and characterization of these films are covered in chapter 2. Co3O4 is also known to be a good electro-catalyst for variety of reactions. Reaction studied in this work is oxygen evolution reaction (OER). Co3O4 is one of the good candidates as an anode for this reaction. Work reported here shows a simple and effective method of synthesizing nanoporous Co3O4 with higher surface area. Nanoporous Co3O4

was then used as electro-catalyst for the OER reaction. An increase in the OER activity was observed along with a change in chemical composition. In fact Co 3O4 was found to have changed into CoO(OH), and it was responsible for the increased the OER activity. It will be described in chapter 3. 4 Co3O4 is a p-type semiconductor. Various studies involving Mott-Schottky4 measurement and Seebeck coefficient5 measurement have been done to confirm that. This current work uses the photo-electrochemical approach to investigate Co3O4 semiconductor nature, in order to explore its use in liquid junction solar cells and water splitting. The work on PEC of Co3O4 is discussed in detail in chapter 4. Moreover, all the work is summarized in chapter 5 along with the future work plans. 5 Chapter 2: Co3O4 thin films synthesis and characterization 2.1 Introduction In the current work, thin films of Co3O4 were chosen as the form of the samples to be synthesized because it serves as a good starting point for basic experiments. Thin films can be synthesized by various methods such as spray pyrolysis, chemical vapor deposition (CVD), chemical vapor transport reactions, pulse laser deposition (PLD), sputtering, electrophoresis, and electrochemical deposition. 6-9 For the purpose of our OER and PEC experiments, we synthesized the thin films using sol-gel synthesis. General introduction to sol-gel synthesis, experimental details of the sol-gel synthesis method used, and characterization results of the thin film sample will be covered in the following sections of this chapter. 2.2 Sol-gel synthesis Sol-gel synthesis has a long history. Early work in this field was focused on the synthesis of ceramic materials. Basic principle of the sol-gel synthesis involves formation of colloidal sol, which disperses the precursors of the final intended product in uniform manner. Then this sol was coated in layer-by-layer fashion on a suitable substrate. 6 Choice of the substrate depends on the requirement constraint set by the experiment. Each layer is air dried to form a gel. Hence, the name is sol-gel. The gel holds residual amount of solvents used as trapped droplets. However, the overall volume of the layers is reduced; such reductions in volume can potentially build up stress. It may result in a granular, brittle structure. Hence, a drastic change in volume is not desired. The gel formed can be annealed at required temperature to get desired product. Most of the initial studies were focused on silica based sols such as tetraethylorthosilicate (TEOS), Si(OC2H5)4. Various other systems are possible as long as some precursor is available. The stability of aqueous precursor is greatly affected by the pH. In case of non-aqueous sols, various ligands can be used to increase the stability of the metal-based system. As evident from its basic principles, the sol-gel method gained wide popularity because

of its robustness, procedural control over composition of precursor and thus the stoichiometry of the final product. Ease of doping at various concentrations is an additional advantage in some cases. Most of the sols are based on organic solvents, which reduce the time required for gel formation. 7 Following is the summary of basic processes involved in sol-gel synthesis. 1. Formation of sol: This involves the mixing of precursor solutions to form suspension of colloidal particles in the solvent of choice. As mentioned earlier, water based systems are affected by the choice of the pH. Colloid can be stabilized through charge stabilization. Hence, pH can be chosen to have some residual amount of charge on colloidal particles. Thorough mixing improves the homogeneity and phase pureness of the final product. 2. Casting: This is a step to mold the sol in particular shape, this can be replaced by dip coating or spin coating procedures. For the dip coating and the spin coating, higher viscosity sols with small amount solvents are required. 3. Gelation: In this step, colloidal particles slowly form 3-D network and trap small droplets of solvent remaining in those networks. Time required for the gelation depends on the viscosity of the sol. In case of polymer-based sols, fibers can be spun from such sols. 4. Aging: This is a process of syneresis of colloids. During aging, condensation continues along with localized solution and reformation of the gel network, which increases the thickness of the inter particle necks, decreases the porosity. Hence, with aging gel becomes strengthened. There should be a resistance to the stress developed in gel after aging to avoid cracking later in the drying process. 5. Drying: During drying, the liquid is removed from the interconnected pore network. Large capillary stresses can develop during drying when the pores are small (< 20 nm). These stresses will cause the gels to crack catastrophically, if the 8 drying process is not controlled by decreasing the liquid surface tension. The liquid surface tension can be lowered by addition of surfactants or elimination of very small pores, by hypercritical evaporation - which avoids the solid-liquid interface, or by obtaining monodisperse pore sizes by controlling the rates of hydrolysis and condensation. 6. Dehydration: Dehydration removes any residual hydrated material remaining at the surface of the sample. 7. Densification and annealing: This is the final step of heating to make the material compact, remove any residual organic groups remaining. High temperatures are preferred for this step. Thermo gravimetric (TGA) curve data for the final intended product can be used to choose appropriate range of temperature for annealing. Atmosphere of heating can be changed from neutral air to reducing or to oxidizing based on the specific requirement. 2.3 Co3O4 thin film synthesis by sol-gel method Cobalt oxide thin films were prepared using a previously described method 10 with some modifications. Co3O4 thin films were dip coated on pre-cleaned Ti foils using cobalt oxide precursor sol. The sol preparation was started with a 12.5mmol Co(II) nitrate

precursor (Co(NO3)2.6H2O, Sigma Aldrich). Cobalt was precipitated as Co(OH)2 using equivalent amount of NaOH. Precipitate was washed three times with deionized water, and was re-dispersed using 25mL of glacial acetic acid (GAA). Sol thus obtained was 9 heated at 140 C to remove excess water and was replenished again with glacial acetic acid to 25 mL. Sol stored in closed container was observed to be stable for a day. For the oxygen evolution reaction (OER) experiments thin films were coated on one side of Ti foil cut into appropriate dimensions, whereas for photoelectrochemical measurements thin films were coated on Fluorine doped Tin oxide (FTO) coated glass slides. FTO is a transparent conducting oxide (TCO) which provides good electrical contact to the cobalt oxide thin film and acts as transparent window, for back illumination on the sample in PEC cell. Sol was then dip coated at a withdrawal speed of 90 mm/min on pre-cleaned Ti foils. The withdrawal speed was optimized to get thick and uniformly coated thin films. The thickness of the gel is related to the withdrawal rate. Cleaning of the substrate is important for sol-gel film to adhere firmly. Ti foils were cleaned with alcoholic KOH and rinsed first with water and then with acetone, and dried in oven for 15 min at 60 C. Titanium does not react with alcoholic KOH at temperatures below 80 C. After each dipping, samples were annealed at 350 C for 5 min and then left to cool in air. After four such dip-anneal cycles, samples were heated at 400 C for 1 hr for final annealing treatment. Number of dip-anneal cycles can be changed to change the thickness of the thin film. Four cycles were used in our experiment. A similar procedure was used to coat Co3O4 thin films on FTO for PEC experiments. Washing procedure used was same as in case of Ti foils. After 3 dip-anneal cycles samples were heated to 500 C for 4 hours. The higher temperature and longer heating 10 time leads to better crystallinity11, 12. It is a favorable condition for higher photocurrents. This will be explained in details in discussion section of PEC experiments in chapter 4. 2.4 Characterization of the Co3O4 thin films Co3O4 is known for the non-stoichiometry in its composition. It is a stable oxide of cobalt in the temperature range of 350 C to 750 C. Beyond 850 C, Co 3O4 is decomposed into cobalt monoxide. Characterization was done using x-ray diffraction (XRD), Scanning electron microscopy (SEM) and UV-Visible spectroscopy.
Figure 2: Image (a) blank FTO slide (b) Co3O4 thin film on FTO substrate after 3 dip-annealing cycles

(a) (b) 11 2.4.1 X-ray diffraction Thin films prepared on FTO substrate were characterized using XRD. (XRD, Cu K_, Geirgerflex, Rigaku Co, Japan). Scanning angle range was limited to 30 to 60 degrees as major peaks for Co3O4 occur in that region. Small peaks for Co3O4 were observed with relatively intense peaks of Tin oxide (SnO2). Peaks for Co3O4were indexed according to

the JADE database. (PDF # 71-0816). From previous SEM experiments on crosssection of the Co3O4 coated FTO, thickness of the thin films is known to be of the order of 50100 nm. Because of such a low thickness very small amount of sample is interacting with the x-rays, hence the diffracted peaks are low in intensity.
Figure 3: XRD spectrum of Co3O4 thin films on FTO substrate
Co3O4 PDF# 71-0816

12 2.4.2 Scanning electron microscopy SEM measurements were done using Sirion (SEM, Sirion, FEI Co., Hillsboro, OR). Sample showed uniformly thick porous surface. The porous nature is maybe due to the gel 3D network formed during the Sol-gel process, which is annealed afterwards. Porous films with grains attached to each other may help for better contact with electrolyte. Films were firmly attached to the substrate, good mechanical stability is important for robustness of the experiments. SEM images at two different magnifications are shown in Figure 4 from various regions of the sample to show the film quality in different regions. Some of the SEM images show cracks on the surface of about 20 nm width. Such cracks may have been developed during dip annealing part of the procedure. Films were cooled to room temperature during each dip-annealing cycle to avoid building up of stress in the films. 13 2.4.3 UV-Vis Spectroscopy UV-Vis spectrum was obtained with a Lambda 950 spectrophotometer using the diffuse reflectance spectroscopy mode (DRS). (Perkin Elmer, Waltham, MA, USA). Films deposited on the glass substrate were used for the measurement. A blank glass slide was
Figure 4: SEM micrograph of Co3O4 thin films on FTO substrate (a) showing uniform coating of thin film and (b) its porous nature.

(a) (b) 14 used as a reference. Kubelka-Munk transformation was done on the DRS data to get UVVisible spectrum of the Co3O4 thin films. Kubelka-Munk (K-M) is a widely used theoretical model of reflectance. It assumes a homogeneous and continuous sample, and that the angular distribution of intensities is equal. The K-M equation used for the conversion can be written as follows. ____ _ __ _ ___ _ _ _ _ Where, k = molar absorption coefficient

R = Absolute reflectance s = scattering coefficient Figure 5 shows the UV-Vis spectra obtained after the K-M conversion of the DRS spectra for dip-annealed sample. Co3O4 has been reported to show all the four types of transitions. 15 Co3O4 is known to show strong optical absorption in visible and infrared region, it is easily evident from its dark black color. Absorption bands are assigned to the transition in 3d level electrons from Co2+ and Co3+ ions.13 The optical absorption for semiconductors is generally further analyzed using the classical relation, __ _ ___ _ ____ Where _ = absorption coefficient h = Plancks constant v = frequency of light in m Eg = optical band gap energy in eV n = 1,2,3 or depending on the types of transition
Figure 5: UV-Vis spectrum (K-M transformed DRS spectrum) of Co3O4 thin film on glass substrate.

16 Such an analysis of the absorption spectrum has been reported in the earlier works 9. It will be discussed in chapter 4.
Observed Energy (eV) Assigned transition 0.8 Co2+ (_*e) _ Co2+ (_*t2) 1.0 Co2+ (_2t2) _ Co3+(_*e) 1.3 Co3+ (_2t2) _ Co2+(_*t2) 2.1 O2- (_*T) _ Co2+(_*t2)

In the Table 1 above, Co2+ and Co3+ along with their oxygen ligands were considered together rather than non-interacting individual sites. Valence orbitals for oxygen are the three 2p orbitals and for Co2+ and Co3+ 3d, 4s and 4p. Initial valence state ionization energies for Co3+, Co2+ and O2- ions were calculated using Paulings electro-neutrality principle. According to Paulings electro-neutrality principle, stable ionic structure preserves local electronic neutrality. Moreover, orbital energies of isolated gas phase ions are obtained from empirical ionization potentials. The final assignment of the transitions is understandably approximate as no orbital can be described as a pure metal or a pure oxygen orbital. Table 1 summarizes the different charge transfer transitions allowed in unit cell of Co3O4. The first transition shown in Table 1 is the most localized transition having ligand field character of Co2+ ion. However, oxygen ligands participation as ligands for both Co2+ and Co3+ results in broader band with higher intensity. The second transition shows internal oxidation-reduction process within lattice
Table 1: Assignment of Co3O4 optical absorption peaks13

17 for Co2+ - Co3+ charge transfer process. This is peculiar to most the mixed valence states oxides. The third transition is exactly opposite of second one and occurs at higher energy.

The fourth transition is ligand to metal charge transfer transition. In simple binary oxides, such transitions are simple in nature. However, in mixed valence oxides they are more complicated. Unequal inter-electrons repulsion splits the ligand orbitals, which results in many more such transitions with broader bands. O2- to Co3+ ligand to metal charge transfer transition occurs at even more higher energy however, it is not resolvable from the broad bands of O2- - Co2+ ligand to metal charge transfer transitions. Any irregularities in the symmetric environment of the Co3O4 lattice, such as defects or lattice distortions brought by doping will destroy the local symmetries and hence reduce the degeneracy of orbitals. This may introduce new transitions in case of doping with different intensities and bandwidth. 18 Chapter 3: Electro-catalytic study of Co3O4 3.1 Introduction Overpotential is an inherent problem with any electrode reaction. It is a kinetic constraint, which results in the need of application of higher magnitude bias than what is expected based on thermodynamic standard reduction potentials. Since voltage is just the amount of energy needed to pass a unit charge across the circuit, this results in low efficiency output of the system. An electro-catalyst effectively brings down this overpotential activation barrier. The oxygen evolution reaction, which is oxidation of water, is one of the important reactions that occur at the anode. Since it is coupled with other important reactions such as hydrogen evolution in water splitting, it is important to investigate and develop new strategies to get better electro-catalysts. Many factors such as mechanism of electrode reaction, kinetics, thermodynamics, effective surface area, conductivity and chemical and mechanical stability decide the overall performance of an electro-catalyst. 19 Metal oxides have proven to be good electro-catalysts. Early work in this field includes research efforts of S Trassiti and Rasiyah14, 15. Efforts were made to correlate metaloxygen bond strength with the enthalpy change associated with increasing the oxidation state of metal ion with overpotential. Such correlation mostly show a volcano shaped curve, which suggest that lowest overpotential is observed at an optimum value of metaloxygen bond strength. Any deviation from this optimum value results in a higher overpotential. This is illustrated in Figure 6. Data is presented for both acidic and basic medium. Metal oxides at the top of this volcano curve, such as RuO2, have really low overpotential and have proven to be really good electro-catalysts. Unfortunately, they are economically not feasible for wide scale application. Hence, the main thrust in this field has been to improve the efficiency of metal oxides like MnO2, Co3O4. A good review of the history of the research in this area can be found here16. The most commonly proposed mechanism in literature for oxygen evolution on Co 3O4

can be written as follows17 ________ _ _______ ______ _______ ____ _ ____________ _______ ____________ ____ _ _______ _ _ __ ____ ______ _ !_ ______ 20 Considering the low current densities obtained in practical water splitting cell, increasing the surface area will increase the exchange current density. Therefore, we have attempted to increase the surface area of the thin film Co3O4 electrode, and the results are reported here. In contrast to the solution-based synthesis of Co3O4 nanostructures, a top down approach was used in this study with thin films as the starting point.
Figure 6: The overpotential for oxygen evolution as a function of the enthalpy change from the lower to higher oxide transition in acidic and basic medium for different metal oxides 18

21 In the previous work reported in literature, various approaches have been taken to correlate different properties of metal oxide surfaces to the electrochemical overpotential observed. The step of desorption rather that adsorption was found to be the rate determining step in the OER. Many studies involving homo nuclear isotopic exchange on oxide catalyst has been reported, which in a way measure looseness of the surface oxygen bonds. Work done in this direction is reported by Boreskov et al19 and Winter et al20-22. The volcano curve in Figure 6 is based on data obtained from these references. Tseng and Jasem23 found that during the different intermediate reaction steps, the metal oxide surface changes from lower oxidation state to higher oxidation state. For example, cobalt oxide changes from Co3O4 to Co2O3, which is today understood as an oxidation of Co(II) to Co(III). The enthalpy change associated with such a transition was found to be correlated with the free energy change in adsorption. Hence, the plot of free energy changes during adsorption/desorption against overpotential of different metal oxides shows volcano behavior. Their work led to the prediction that RuO2 and the spinel NiCo2O4 are two of the best available electro catalysts. Since then many studies have been done on RuO2 and NiCo2O4. In general, doping cobalt oxides with Li, Ni or Cu have been shown to enhance their electro-catalytic property. Nikolov et al in their work have showed that different extent of

doping affects the geometric and electronic factors which change the electro-catalytic behavior.24 A decrease in the Tafel slope with increase in the dopant content was observed, which was thought to be due to the increase in the number of active sites. This 22 results in larger charge transfer coefficients. Mechanistic studies on NiCo 2O4 in KOH using various electro-analytical methods show formation of higher valence oxides of Ni and Co on NiCo2O4 surface before the oxygen evolution maxima 25-28. Since such formation of higher-valence-oxide was found to be limited to the surface, higher surface area of electrode facilitates the formation of more active centers. It has been shown that Co3O4 nanowires (NW) doped with Ni gives higher performance over pure cobalt oxide NW 29. The increased performance can be understood based on the higher effective surface area. Ni doping also increases conductivity of the NWs and makes more active sites accessible to electrons. This demonstrates that increasing the surface area and changing the electronic factors by doping are two viable research approaches to get better performing electro-catalysts. S. Trassiti et. al have shown that OER performance of Co3O4 is affected by pH, presence of support layer and calcination temperatures. Support layer reduces the current drop at the electrode-substrate interface. 30 Recently it has also been shown by Frei H. et al that a mesoporous silica as support layer works well for Co3O4 and MnO2 31-33. Nano-rod bundled structures in these mesoporous catalyst were reported to be the main factor increasing the surface area and turnover frequency. The turnover frequency is the number of oxygen molecules evolved per second per active site. Table 2 summarizes up to date information on the different literature published on Co3O4 OER experiments. It has partly been adopted from supporting information of reference 29. 23
Reference Number Preparation Method Experimental Conditions Tafel plot (mV/dec) Exchange Current Density (A/cm2) 29 Chemical Growth 1M NaOH @ RT 60 6.6 x 10-12

34 Electrodeposition 1M NaOH @ 25 C 40 NR 24 Teflon bonded film from thermal decomposition @ 350 C @400 C 3.5 KOH 50 42 NR 35 Electrodeposition 1M NaOH 43 3.2 x 10-6 36 Spray Pyrolysis @ 400 C 1M KOH, 25 C 60 NR 10 Dip coated solgel fim annealed @300 C @500 C 1M KOH 53-55 57-59 NR 37 Spray Pyrolysis @ 500C 1M KOH 50-68 NR
Table 2: Literature survey of Co3O4 OER experiments

24 3.2 Introduction to electrochemical milling The method used to increase the surface area is called electrochemical milling (ECM). In this process, the sample is used as a cathode, and electrode is repeatedly lithiated and delithiated in a Li ion battery. Because of structural changes occurring during the discharge and charging processes, electrode materials tend to form smaller grains of 30-50 size. Figure 7 illustrates such changes in a typical metal oxide electrode38. Metal oxide on discharging forms metal domains of various sizes in the matrix of Li2O, depending on the discharge current density. During the charging, the reaction reverses and these metal domains react with Li2O to form nano-sized metal oxide. This is also known as the process of pulverization.
Figure 7: Schematic illustration of structural Changes occurring in electrode during discharging and charging process by conversion mechanism 25

25 The first work published on this topic 39 includes the use of a CuO cathode, which turned into nanostructures of Cu after discharging. Depending on the discharging current, morphology of the electrode material was changed. In a way it gives better control over the size of grains as we change discharging/charging currents.
Figure 8: SEM micrographs of starting CuO (a) and discharged product (metallic Cu) obtained at the

current density of 0.32mA/cm 2 (b), 0.065mA/cm2 (c) and 0.032mA/cm2 (d). 26

26 Similar work on Pt and RuO2 has shown the applicability of such a phenomenon in applications such as super capacitors and catalysis. 40 Another similar attempt on Si, ZnO, and Ag NWs was done to show that with different current densities applied for ECM, nanopores of 1-10 nm size could be developed in 1D nanostructure. Improved super capacitor performance of such porous Si NW was then demonstrated. 41 3.3 Experiments Preparation of the Co3O4: Thin films of the Co3O4 were prepared on Ti foil substrate as described in section 2.3. Electrochemical Milling: Battery cycling was done in Swagelok cells using Maccor battery testing unit. (Model 4300, 4-channel unit) Samples of cobalt oxide dip coated on one side of Ti foil were cut to the size of ~1cm x 1 cm. Swagelok assembly was used in which cobalt oxide samples were placed as cathode against Li metal anode. Samples were cycled for one discharge-charge cycle at a constant current of 30A. Entire procedure was carried out inside a glove box under argon atmosphere. OER activity measurement: OER activity was measured for the same sample, both before and after the electrochemical lithiation, to avoid any apparent change in the current due to the variation in the mass of Co3O4 per unit area of the Ti foil. 27 Samples obtained after battery cycling were washed three times with Isopropyl alcohol (IPA), and were transferred to the indigenously made OER cell. The electrochemical experiments were performed with a Gamry Reference 600 model of computer-controlled potentiostat-galvanostat. A typical three-electrode system was used, in which Co3O4 coated on Ti foil acted as the working electrode. Hg | HgO (1M NaOH) electrode was used as a reference (Eref= 0.135V vs. NHE) and Graphite as the counter electrode. Only an area of 0.246 cm2 of the working electrode was exposed to the electrolyte through a circular window at the base of the cell. Approximately 10ml of 1M NaOH was used as the electrolyte. Scanning electron microscopy: Samples at various stages of experiment were examined under SEM microscope (Sirion FEG SEM) to record the changes in surface morphology. X-ray photoelectron spectroscopy (XPS): XPS was performed with a Kratos axis instrument for examining the surface composition of the samples. Monochromatic Al source was used with charge compensation module to neutralize the residual charge building up on surface of poorly conducting samples. For quantitative comparison, the non-linear curve fitting was done using CasaXPS package.

28 3.4 Results Lithiation cycling: A typical battery-cycling curve is reported in Figure 9. Charge-discharge behavior is quite similar to what was previously reported for Co3O4. Reaction taking place in discharge step is38, 42 Co3O4 + 8Li _ 4Li2O + 3 Co This reaction is not surprising given that the Li is a strong reducing agent. The reaction forms small domains of about 3nm diameter of Co metal embedded in Li2O. There are numerous literature reports providing same observation. 42, 43 Since the current used for the battery-cycling is same in both the samples, the variation in the time to complete the cycle can only be due to the variation in the amount of Co3O4 per unit area of the Ti foil. Sample Discharge Time (hour) Charge Time (hour) Sample 1 5.4975 3.4855 Sample 2 7.0961 4.6427
Table 3: Electrochemical charge and discharge time for Co3O4 thin film samples. Refer to Figure 9

29 During the charging step, delithiation of this matrix occurs in which Li2O reacts backwards to Co metal under the applied potential to give CoO. 43-45 The charging reaction is therefore can be written as follows. Co + Li2O _ CoO + 2Li Such formation of CoO on charging can be explained based on similarity in crystal structure of CoO and Li2O. Li2O has antifluorite crystal structure and CoO has rock salt structure, hence both Li2O and CoO have same Oxygen lattice of cubic close packing, therefore the conversion is inherently more favored. 43
Figure 9: Electrochemical charge-discharge curves for Co3O4 thin film samples cycled between 0-3V at constant current of 30 A. Time taken for discharging and charging is shown in Table 1.

Charge Discharge 1 12 2 30 It should be noted that all the experiments in reports mentioned above were either mesoporous or thin films or nano size structures. Other reports involving bulk Co 3O4 as electrode show formation of Co3O4 after charging step. 42, 46 Our Co3O4 samples were found to be converted into CoO after ECM of Co3O4 thin films which was confirmed with XPS analysis of those samples. Results pertaining that is discussed in corresponding section. OER measurement (before and after Lithiation cycling): Cyclic voltammetry scans were done in the potential range of 0.0-0.85 V (Vs. Hg | HgO

reference). Four fold increases in the current at 0.8V (vs. ref. electrode) was observed for the same geometrical area exposed to the electrolyte. Multiple samples were used to check the reproducibility of this observation. The increase in magnitude of the current was found to be reproducible in all the samples with the same ~4 fold increase. A representative comparison of the current before and after the lithiation of the same sample is shown in Figure 10 a. This increase in current was initially thought to be only due to increase in the surface area because of the nanopores evolution as reported previously for ZnO41. 31
Figure 10: (a) Cyclic voltammograms of sample before (black) and after (red) ECM in 1M NaOH at 5mV/s scan rate. (b) Tafel plots of sample before (black) and after (red) ECM. Only sample 1 data is shown here.

(a) (b) Before ECM After ECM After ECM Before ECM 32 This increase in the current at the same potential is reflected on the Tafel plots as decrease in the slope. If the surface area is increasing, then it can be expected that the exchange current density would also increase. Instead, an anomalous decrease in the exchange current density was observed. This is explained in the discussion in section 3.4. SEM analysis: Surfaces of the samples were observed under SEM to notice the change in the surface texture with lithiation and OER processing. Figure 11shows all the SEMs obtained for the thin film samples after various treatments. Figure 11 a, b and c are samples without ECM and Figure 11 d and e are samples after ECM. Samples without lithiation showed no formation of nanoplates on the surface after exposure to NaOH or after OER Sample Tafel Slope j0 in mAcm-2 R2 Sample 1 101 1.8E-05 0.995 Sample 1 after ECM 80 4.4E-06 0.999 Sample 2 91 1.5E-05 0.990 Sample 2 after ECM 77 6.3E-06 0.986
Table 4: Tafel slope and Exchange current density for Co3O4 thin film samples before and after ECM as

calculated from Tafel plot in Fig. 10. (Sample 2 plot is not shown in Fig. 10)

33 measurements. On the other hand, sample after ECM clearly shows nanoplates growth on the surface after OER measurement in Figure 11(e). continued
Figure 11: SEM micrographs of Co3O4 thin film samples after various treatments

(a)
(a) Pristine Co3O4 thin film on Ti foil (b) dipped in NaOH for 1day (c) after OER measurement (d) after ECM (e) OER measurement after ECM

34 Figure 11 continued (c) (b) 35 Figure 11 continued (d) (e) 36 Further investigation showed (Figure 12) that only the region exposed to the sodium hydroxide during the OER measurements is converted to nanoplates. To check whether nanoplates are formed during, the initial exposure to 1M NaOH of ECM treated Co3O4 or at some later stage, the ECM treated samples were exposed to the 1 M NaOH for different amount of time and at different stages of the OER experiment. The following list shows the different time intervals used. 1. 15 min exposure without any CV. 2. 30 min exposure without any CV 3. After CV measurements
Figure 12: SEM micrograph of exposed (to NaOH) and unexposed (outside of circle) area of the sample.

37 4. After OER measurements Images obtained are presented below. It clearly indicates that nanoplates were formed during the first 15 minutes of exposure to the NaOH solution. continued
Figure 13: SEM micorgraphs of ECM trated samples after NaOH exposure for different amount of time. a) 15 min b) 30 min c) after CV d) after OER measurements

(a) (b) 38 Figure 13 continued (c) (d) 39 XPS analysis: XPS spectrums were collected for Co3O4 thin film samples before and after ECM to study the possible change in chemical composition of Co3O4 because of ECM.
810 800 790 780 770

5000 10000 15000 20000 25000 Co 2p3/2 Co

2p1/2

CPS Binding Energy (eV)

ss Co
2p1/2

ss Co
2p3/2

with ECM without ECM

Figure 14: Co2p region of XPS spectrum of Co3O4 thin film samples without ECM (bottom) and with ECM (top)

40
536 534 532 530 528 526 0 2000 4000 6000 8000 10000 12000

CPS Binding Energy (eV)

Without ECM 530.9 529.3

Figure 15: O1s region of XPS spectrum of Co3O4 thin films without ECM

41
536 534 532 530 528 526 0 2000 4000 6000 8000 10000 12000

CPS Binding Energy (eV)

with ECM 531 529.3

Figure 16: O1s region of XPS spectrum of Co3O4 thin film samples after ECM (CoO)

42
Sample Co2p3/2 (eV) Satellite (eV) Co2p1/2 (eV) Satellite (eV) O1s (eV)

Intensity Ratio Co2p1/2 Sat./Main. Co3O4 solgel thin film 779.0 780.0 789.6 794.1 795.5 803.7 529.3 531.0 0.20 Co3O4 thin film after ECM treatment 780.5 785.3 796.3 802.3 529.3 531.0 0.46 Co3O4
47

779.6 780.7 789.5 794.5 796.0 804.5 529.5 530.8 0.32 CoO 48 780.5 786.4 796.3 803.0 529.6 531.2 0.90

Figure 14 shows the Co2p region of thin film samples Co3O4 both with and without ECM treatment. It clearly shows that satellite peaks for the Co3O4 sample without the ECM treatment are smaller that the peaks for Co3O4 samples with ECM treatment. In addition, the binding energy difference in main peak and satellite peak is higher in sample without the ECM treatment. Based on literature values of binding energies and height of satellite peaks, the Co3O4 sample with ECM treatment was found to be matching with Co2p region of CoO. 48
Table 5: Summary of Co2p and O1s peak positions for different samples of Co3O4 thin films from experiments and literature

43

Moreover, for Co3O4 sample without ECM the peak fitting of the Co2p region, main peaks were de-convoluted in two constituent peaks due to Co3+ and Co2+ in which Co3+ peaks appear at lower binding energy that that of Co2+. This can be explained based on final state relaxation effects in addition to Koopmans theorem. 49 Koopmans theorem calculates the binding energy of the electron assuming that all the other electrons are frozen in their respective energy levels and dont have any effect on the binding energy of the electron knocked out by X-Ray photon. However, in real samples there are atomic as well as extra-atomic factors which cause the binding energy of the electron to be less than the one expected based on Koopmans theorem. 49 For CoO (Co3O4 with ECM treatment) Co2p region is very different with only one peak each at 2p 1/2 and 2p3/2 positions with binding energies matching to Co2+ in CoO. 48 In theory, O1s region of Cobalt Oxides should have only peak corresponding to the lattice oxygen appearing at 529.3 eV. However, in reality surface of these oxide sample is covered with OH- and other common Oxygen containing species, hence additionally one small peak is present in the O1s region of the Co3O4 sample in Fig 15. Similarly, Figure 16 shows the O1s region for CoO thin film sample, main peak around 529.3 eV is due to lattice Oxygen. Other peak around 531 eV is due to chemi-adsorbed OH- species. 48 44 Table 5 summarizes all the binding energy values form all the samples. Ratio of heights of Co2p1/2 satellite peak to that of the corresponding main peak was used to compare with literature results mentioned in bottom two rows. From the absence of overlapping peaks and increased height of the satellite peaks, it is confirmed that thin films of Co3O4 are converted in to CoO after ECM treatment. This agrees with the literature reports mentioned in section 3.1 about the lithiation cycling of Co3O4. In addition to the XPS experiments, XRD and GAXRD measurements were done on ECM treated Co3O4 thin film sample. However no peaks from the sample were observed even in the GAXRD experiments. This could likely be due to the sample being amorphous in nature. XRD analysis: XRD spectrum of the samples was taken after ECM treatment and OER measurement to identify the product formed. XRD of thin films on the Ti foil was taken. It is shown below in Figure 17. Peaks obtained for the sample were very small compared to the peaks obtained for Ti foil substrate. Peaks for the sample were identified to be due to CoO(OH) phase and none of the peaks of Ti interfered with peak positions of CoO(OH). 45 Peak matching was done according to PDF card # 73-1213 for CoO(OH) and card # 441294 for Ti. CoO(OH) crystal structure is brucite type layered structure. Crystal structure and related aspects are treated in the discussion section.
Figure 17: XRD spectrum of ECM treated sample after OER.

46

Raman analysis: Raman spectrum was obtained for these samples with a He-Ne laser (633 nm edge). Spectrum obtained was compared with the reference spectrum of CoO(OH). Main characteristic peak was observed at 503 cm-1. This peak is unique to CoO(OH). Other possible products with Co and O are Co3O4 and Co(OH)2 have characteristic peaks at 481cm-1 and 523 cm-1 respectively which were not observed in the spectrum.
Figure 18: Raman spectrum of ECM treated samples after OER measurements

47 3.4 Discussion The complete conversion of Co3O4 thin films to CoO(OH) can be schematically written as follows. Co3O4 thin films form CoO after ECM treatment. This ECM treated solid layer was most likely amorphous hence it was not observed in GAXRD spectra. This CoO layer reacts with NaOH to form CoO(OH). Each aspect of this multistep process is discussed below. 3.4.1 Formation of CoO(OH) from CoO. As evident from the XRD spectrum in Figure 17 and Raman spectrum in Figure 18, it is clear that the hexagonal shaped nanoplates are CoO(OH) (heterogenite) phase and not oxides of Cobalt. To understand the formation of CoO(OH) it was important to identify the phase formed after ECM treatment of Co3O4 thin films. The XPS studies on after ECM Co3O4 thin film samples clearly suggest formation of CoO from Co3O4 thin films after ECM treatment. And CoO must be reacting with NaOH to form CoO(OH). Co3O4 has two different oxidation states of Cobalt namely 3+ and 2+ in Co
3

O
4

ECM CoO NaOH CoO_OH_ 48 2:1 ratio. Moreover, it is known that the Co2+ is more stable in water compared to Co3+.50 CoO on the other hand is composed entirely of Co2+ which is more easy to react with OHto form CoO(OH). A plausible mechanism for such formation of CoO(OH) from CoO can be written as follows, a) Dissolution of solid CoO in basic medium to form Co_OH_,
_ _-._

In very basic solution such as 1M NaOH used in our experiment, Co(II) forms charged species such as Co_OH_, __ CoO_/_ _ OH_ _-._ _ H_O_0_ 1Co_OH_,
_ _-._

b) Oxidation of Co(II) to Co(III) with dissolved oxygen 4Co_OH_,

_ _-._ _O__-._ 1

4CoO_OH__-._ _

H_O_-._ _ 4OH_

_-._

c) Precipitation of CoO(OH) to form hexagonal shaped crystals And this formed CoO(OH) then precipitates back as hexagonal platelets. CoO_OH__-._ 1 CoO_OH__/_ Net reaction is therefore, 4CoO_/_ _O__-._ _H_O_0_ 1 4CoO_OH__/_ This conclusion also agrees with the Pourbaix diagrams for Cobalt which predicts Cobaltic acid HCoO_ _as the stable phase at the pH =14 and E=0. 51 49 The following table summarizes the different methods of synthesizing CoO(OH) under different conditions.
Reference Method Description Product morphology Application tested for and other comments 52 Co-electro-deposition from Co containing Ni(NO3)2 solution Grainy in appearance OER, high current due to synergistic effect of Co and Ni hydroxides 53 Conversion of Co to Co(OH)2 and then to CoOOH under applied bias NR NiMH battery electrode 54 Chemical precipitation: _-CoOOH formation from CoSO4 precursor mixed with H2O2 _-CoOOH formation from Co(OH)2 and KOH NR(NO SEM done) Positive electrode for Ni batteries 55 Air oxidation of commercial and lab made sample of Co(OH)2 at 100C Broken hexagonal shaped plates Characterization using TEM was done. SAED patterns

obtained to identify 56 Potentiostatic electrolysis of Co containing nitrate solution at pH = 7.4 Gathered crystallite well adhered to the substrate 57 Synthesis of CoO(OH) from Co(OH)2 precursor by ozonation Rough surface platelets of varying size Chemical stability under various electrochemical conditions was studied

Most methods reported above have used electrochemical method or chemical method to convert Co precursor into CoO(OH). Co(OH)2 is the most commonly used precursor, and
Table 6: Literature survey of different methods for synthesis of CoO(OH)

50 mostly alkaline solutions are used to convert the precursor to the final desired product under ambient conditions. In the current work reported here, formation of CoO(OH) takes place spontaneously without any assistance of heat, oxidizing agents or electric potential. Moreover, CoO(OH) formed is growing on the substrate itself which is therefore likely to have better contact with substrate and hence smaller current drop across the active material substrate interface. 3.4.2 Higher OER performance of CoO(OH) The following table summarizes the difference in conductivity and Co 3+ content percentage of Co3O4 and CoO(OH). Most of the values are obtained from one or more literature reports.
Physical or Chemical Property /nature Co3O4 CoO(OH) References Molecular weight 240.797 g/mol 91.940 g/mol Calculated Crystal Type Spinel Brucite [58, 59, 60 ] Electrical resistivity 14.2 Ohm.cm 0.2 Ohm.cm [9]

Co3+ % of total cobalt content by stoichiometry 66% 100% Calculated

Table 7: Comparison of Co3O4 with CoO(OH)

51 Co3O4 has spinel structure, which can be described as corner sharing octahedra and tetrahedra of oxide ions with Co3+ in the center of the octahedra and Co2+ in the center of the tetrahedra. It is known that normal spinels have hopping kind of mechanism for carrier conductivity, which tends to put spinel structured metal oxide in less conducting category. 61 On the other hand CoO(OH) structure can be described as edge sharing Co(III) oxohydroxo octahedra. Conductivity of as high as 5 Scm -1 has been reported in the literature.62 This higher conductivity has already been utilized in the Ni-MH type of batteries, in which use of CoO(OH) coating on NiO(OH) electrode has shown to increase the electrode performance. 63 Co4+ sites formed through oxidation of Co3+ on surface are known to act as the active sites. 17 The reaction of desorption of adsorbed OH- species is known to be the rate determining step in most cases. Higher conductivity might be reducing the Ohmic overpotential due to current transport in the electrode. Most of the Co3+ sites for CoO(OH) are exposed through edge planes and not through basal planes. (See Figure 19) Hydrogen atoms occupy the planes in between two layers, they have not been show in Figure 19 for more clarity. There is an interesting study on dissolution of CoO(OH). It shows that dissolution only occurs through the edge sites. 64 In their experiment, they dissolved CoO(OH) with chelating ligand. If dissolution occurred 52 through basal planes, then the height of the plates is expected to decrease. However, no such decrease in height was observed. From the SEM images, it can be seen that most of the surface is made up of basal planes and not edge type surface. It suggests a decrease in OER activity rather than increase. However, a four times increase in OER activity was observed, which is currently thought to be due to the improved kinetics of the OER reaction because of the increased conductivity of CoO(OH). Surface area argument is yet to be proven decisively. BET surface area measurement was not allowed because of the microscopic quantities of sample produced. Electrochemical methods were proved to be unsuccessful because of very low current in potentials regions away from the redox peaks. It is difficult to correlate the Tafel plot data of two chemically different electro-catalysts. Generally, less overpotential at the same current density or high current density at the

same overpotential is needed to prove any improvement. Increase in the current density at same overpotential can be seen in Figure 10 b. However, at the same time, there is substantial decrease in exchange current density. More investigation is needed to understand the causes of decrease in the exchange current density. 53
Figure 19: Crystal structure of CoO(OH)

54 Chapter 4: Photoelectrochemical study of Co3O4 4.1 Introduction In the photoelectrochemistry (PEC) of semiconductors, the electrochemical response of the system is studied under the illumination of light. A typical PEC device is a threeelectrode system with either p or n type semiconductor as the working electrode, a counter electrode typically platinum, a suitable reference electrode in an electrolyte. Incident photons generate electron-hole pairs in the semiconductor. Energized electrons get excited to the conduction band and corresponding holes are created in the valence band. Further movement and recombination lifetime of the minority and the majority carriers depend on the type of semiconductor and its physical properties. Many factors affect the overall performance of the PEC cell. They are discussed at length in section 4.5. The first reported experiment in PEC was carried out in the year 1839. In that experiment photocurrent was obtained after the light illumination of the two platinum electrodes immersed in the electrolyte of metal halide salts65. Later, after the oil embargo of 1970s, research on liquid junction solar cells again picked up. 55 An important paper in this direction was published by Fujishima and Honda in Nature in 1972.66 It involved the use of TiO2 as the semiconductor electrode for water photolysis. Later in 1991 M. Grtzel and co-workers demonstrated the possibility of using the TiO2 nano particles along with the dye for efficient solar energy harvesting.67 TiO2 soon became the material vastly studied for its properties and used as the photo-anode in different electrochemical systems. TiO2 has a wide band gap of about 3.1 eV, which restricts its use to the UV region of the sunlight. Visible radiations lack the energy to get the necessary excitation required. Hence, it is important to investigate other semiconductors with optical absorption in the visible solar spectrum. 4.2.1 Fundamentals of Photoelectrochemistry In principle, PEC is the electrochemistry of a semiconductor electrode surface in a suitable electrolyte, under light illumination. Semiconductors can be considered as a giant connected molecule, which forms broad bands of electronic energy levels. The valence band is analogous to the highest occupied molecular orbital (HOMO) and conduction band is analogous to the lowest unoccupied molecular orbital (LUMO). The energy separation between the valence and conduction band in such a picture is called the band gap. The band gap of a semiconductor governs the optical properties of it.

56 The Fermi level of a semiconductor specifies the electrochemical potential of an e - in the semiconductor. The probability of the Fermi level being occupied with the electron is exactly . In the case of the p-type semiconductors, it is closer to the valence band and in the case of the n-type semiconductor; it is closer to conduction band. Doping the semiconductor changes the carrier concentrations and correspondingly changes Fermi level. At a fixed doping level, the Fermi energy level can be manipulated using applied bias across the semiconductor. Generally, the Fermi level of the semiconductor and the Fermi level of electrolyte (the standard reduction potential for the electrode reaction of the electrolyte can be considered as its Fermi level) are different from each other. Thus, when a semiconductor electrode is kept in contact with an electrolyte, charge transfer happens in order to equilibrate the Fermi level, which forms a depletion region inside the semiconductor and a Helmholtz layer at the interface of semiconductor and electrolyte. The thickness of the depletion region depends on various factors such as doping level, carrier conductivity of the semiconductor and surface trap states. This process is similar in its effect as a p-n junction. Charge balancing builds up a potential difference called as the space-charge layer, and it helps in the separation of the electron-hole pair generated with the incident light. Figure 20 schematically shows the band levels from bulk to surface both n and p type semiconductor at accumulation, depletion, and inversion. 57 Effectively, all the radiation of required wavelength absorbed in this region contributes towards the overall photocurrent registered in the PEC cell. The minimum energy required for the electron hole pair generation depends on the band gap of the semiconductor material.
Figure 20: Energetic position of fermi level under different conditions68

58 In the PEC method, the flat band potential of the semiconductor can be measured from the onset of the photocurrent. Photocurrent is the difference in the current magnitude at the same potential under dark and under light conditions. In practice, dark and light I-V curve are measured together as a chopped light I-V curve, where the working electrode is scanned across the voltage range at a constant sweep rate and the current is measured. The light falling on the working electrode is chopped at a constant periodic rate. Chopping of the light is done in part to minimize the effect of the temperature increase caused by the local heating of the sample surface because of the light exposure. The effect of local heating causing the temperature variation and the other environmental factors are difficult to reproduce or eliminate by blank correction method. Hence chopping serves as an effective practical approach to avoid such experimental variations altogether. 4.2.2 Introduction to Photoelectrochemistry of Co3O4 Co3O4 is a p-type semiconductor. It is black in color and has a high absorption in the

visible region of the solar spectrum. K-M transformed diffuse reflectance spectrum of Co3O4 is presented in Figure 5 of section 2.4.3. It demonstrates the ability of Co3O4 to absorb a high percentage of the incident solar radiation. However, this high optical absorption efficiency has not been observed to translate into high photocurrent. Previous PEC experiments done with Co3O4 thin films in 1M NaOH as electrolyte have shown really small photocurrents of the order of 10 A.69 Clearly, more investigation is required on the PEC of Co3O4.The band gap values of Co3O4 reported in the literature vary from 59 1.50 to 2.07eV.69, 70 In reality, Co3O4 shows the different types of the band gaps as mentioned in Table 8. Assignment of the different transitions based on theoretical studies has been discussed in section 2.4.3. Further discussion in terms of direct/indirect allowed and forbidden band gap transitions has been done extensively in literature. 9, 71 P.S. Lokhande et. al have discussed different types of transitions in Co3O4 thin films prepared by spray pyrolysis. They recorded optical density (_t) in the wavelength range of 350-550 nm at 300 K, and used classical relation 2_ _ _2_ _ ____ to analyze the data. They found the presence of all the four types of the transitions. The following table summarizes the data presented in their work. 9
Type of band gap Band Gap in eV Direct Allowed 2.06 and 1.44 Direct Forbidden 1.38 and 1.26 Indirect Allowed 1.10 (Ep = 0.02) Indirect Forbidden 0.75 (Ep = 0.27)

In the PEC work presented here for Co3O4, thin films were investigated for their magnitude of photocurrent response. Pilot experiments were done on TiO2 as a reference system to test the accurate reproduction of experiments from literature. Because of the robust nature of the TiO2 - PEC experiment, it is a good method to check the correctness of the working protocol.
Table 8: Different band gap transitions in Co3O4, Ep = Energy of phonon assisting indirect transition

60 Initial experiments with Co3O4 thin films showed small photocurrents of the order of 1020 A. Higher photocurrent of the order of 100A was required to further the investigation of variation of photocurrent with intensity and wavelength of the incident light. Results of these experiments have been discussed in the next few sections and future studies will be proposed in chapter 5. 4.3 Experiments Preparation of Co3O4 thin films: Thin films of Co3O4 were prepared on FTO-coated glass substrate as described in section 2.3. The transparent conductive oxide (TCO) is required in this case to allow back illumination of the PEC cell set up. Preparation of TiO2 thin films on FTO: Thin films of TiO2 were obtained by making P-25 TiO2 slurry in ethylene glycol and

acetic acid 1:1 mixture, and applying it by doctor blade method on the conductive side of the pre cleaned FTO slides, of 2.5cm * 2.5 cm dimension by doctor blade method. Typically, thin films were only deposited on 1 cm2 area at the center of the FTO, this area is enough to cover the circular window of PEC cell. Excess TiO2 is wiped off gently and the film is air dried and then annealed at 550 C for 1.5 hours. Before using for the PEC experiment, the mechanical strength of the film was checked by gently tapping the FTO edges. This is important in order to avoid dissolution or falling off the particles during the experimental workflow. 61 PEC cell set up: A typical PEC cell set up is shown in the Figure 21 below. A Co3O4 thin film on the FTO substrate is used as the working electrode. A limited area of the working electrode is exposed to the electrolyte, through a hole in the wall of the teflon cell, with an O-ring in between to ensure a good seal that would prevent the leakage. The counter electrode is a graphite rod in the case of aqueous electrolytes and a platinum wire in the case of nonaqueous electrolytes. A stable reference electrode can be chosen depending on the electrolyte. Details of the different reference electrodes used are summarized in Table 9. Figure 21 shows the photograph of a working PEC cell used for non-aqueous PEC experiments. One edge of the conductive side of the working electrode is taped with double-sided Cu tape to provide a convenient connection to the electrode. The conductive side of the working electrode is then pressed against the circular window of the PEC cell, through which it is exposed to electrolyte. The O-ring seals the edges of the window and prevents the leakage of the electrolyte. A metal support tightened with screws is then placed to secure the working electrode in place. The opposite window holds only clear quartz glass secured in similar fashion. In case of PEC cell used for non-aqueous electrolytes, reference, and counter electrode are connected to the top, which is threaded to fit into the main body of PEC cell and seal the cell completely. In case of the PEC cell 62 for an aqueous electrolyte, no such sealing is required; the reference and counter electrodes are dipped in the cell directly
Reference Electrode Used for electrolytes (Error! Reference source not found. for more details) Method of preparation Comments

R1 Non aqueous Reference electrode S6, S7 and S8 Pt wire dipped in 0.5 M TBP New reference electrode is prepared every time in a small capillary with porous glass bottom R2 Aqueous Reference electrode S1-S5 Ag wire dipped in saturated KCl solution, This is standard reference electrode from Accumet for 1M KCl, 1M KCl was changed to sat. KCl Reference electrode was standardized against commercially obtained Ag | AgCl | KCl (1M) from Accumet R3 Non aqueous reference electrode S9, S10 Pt wire dipped in Triiodide solution with 0.04LiI + 0.02M I2 New reference electrode is prepared every time in a small capillary with porous glass bottom

The non-aqueous cell setup was assembled in a glove box maintained at low humidity under argon atmosphere. It is important to avoid traces of water in the electrolyte,
Table 9: Different reference electrode used

63 because even a small amount of water quenches the overall photocurrent observed, because of strong adsorption at photoelectrode and affects the reproducibility of photocurrent magnitude. In case of an aqueous PEC, cell was set up under ambient conditions, and argon gas was flowed at a moderate rate for 10-15 minutes before the actual PEC experiment in order to flush out dissolved oxygen, otherwise oxygen redox chemistry might affect the I-V curves recorded. 64

Other experimental details for various experiments carried out are mentioned as required in the following sections. Preparation of different electrolytes is summarized as in Error! Reference source not found..
Figure 21: Schematic diagram (Top) and photograph of PEC cell, front (bottom left) and lateral (bottom right) view

65
Electrolyte Preparation Comments S1 acetate Buffer 0.1 M Acetic acid + 0.1 M Dipotassium phosphoric acid + 1M KCl pH = 7 maintained with acetate buffer and measured with calibrated pH meter. pH was then be adjusted in the same way within pH range of 4-10 S2 sodium hydroxide 0.1M NaOH -S3 FeCl3 1M KCl + 0.01 M FeCl3 + 0.1M Disodium phosphoric acid pH = 7 maintained with Phosphoric acid and NaOH, Small amount of Fe precipitates as Fe(OH)3 so remaining solution was used as electrolyte after filtration S4 Aqueous triiodide system 1M KCl + 0.01 M I2 + 0.02 M LiI + 0.1 M Disodium phosphoric acid pH was maintained at 7 with Phosphoric acid and NaOH S5 K3Fe(CN)6 1M KCl + 0.01M K3Fe(CN)6 + 0.1 M Disodium phosphoric acid pH was maintained at 7 with Phosphoric acid and NaOH S6 Triiodide 0.7M LiI + 0.05 M I2 in pure ACN in side glove box Precaution must be taken to avoid any introduction of moisture

continued

Table 10:Preparation of different electrolytes used in the PEC experiments

66 Table 10:Preparation of different electrolytes used in the PEC experiments continued

S7 DSSC electrolyte 0.02 M I2 + 0.04 M LiI + 0.5 M 1,2-DMPII (1,2Dimethyl-3propylimidazolium iodide) in pure ACN in side glove box -S8 DSSC + 0.5 TBP S7 electrolyte + 0.5 TBP (4-t-butylpyridine) in pure ACN in side glove box -S9 Triiodide 0.2 M LiI + 0.1M I2 in pure ACN in glove box Different composition otherwise same as S6 S10 Ferrocene 0.05M Ferrocene + 0.1M LiClO2 in pure ACN in glove box --

PEC measurement with Gamry: Gamry reference 600 was used for electrochemical measurements with the PEC cell in the standard three-electrode configuration as described above. CV was measured initially for each set of experiment to get the understanding of the general behavior of the system and to determine the range of voltage, over which photocurrent measurement can be done. The first CV is not stable because the surface of working electrode is not equilibrated with the electrolyte. After 5-10 cycles of scanning the selected voltage range, CV stabilizes. Then the linear sweep voltammograms (LSV) were recorded in dark as 67 well as light condition, at a rate of 100 mV/s. This helps to identify dark and light parts of the chopped light I-V curve. In case of n-type semiconductor, photocurrent is anodic in nature and in case of p-type semiconductor, it is cathodic in nature. 100W Xe arc lamp (Oriel Apex) was used as the light source. 4.4 Results Pilot experiment with TiO2 TiO2 photo anode was used in PEC cell with electrolyte S1 acetate buffer, see Table 9 for detailed composition. A Ag | AgCl | Sat KCl (R2) electrode was used as the reference electrode. pH of the acetate buffer electrolyte was changed by varying the ratio of acid and salt. pH values were measured before the PEC measurement using a pH meter. A three-point

calibration of the pH meter was done on each day of the pH measurement, using standard buffers of 4.0, 7.0 and 10.0 pH. Figure 22 shows a typical LSV curve obtained under the chopped light source. Onset of photocurrent in this graph indicates the flat band potential. Photocurrent gradually increases and reaches a stable saturated value and forms the plateau on the right side of the graph. Photocurrent is anodic in nature, which is consistent with the fact that TiO2 is n-type. Photocurrent is the difference in the light and dark current in the chopped LSV curve. Maximum Photocurrent obtained is about 175 A. Figure 23 shows the plot of 68 square of the photocurrent vs. voltage. From the extrapolation of the straight line as shown in figure 23, one can obtained the flat band potential.
Figure 22: LSV curve for TiO2 sample under chopped light at pH of 6.884

69 In aqueous electrolyte such as the acetate buffer, Helmholtz layer on the surface of the working electrode is made up of OH- ions hence it is affected by the pH. Effect of pH on flat band potential of working electrode can be studied by repeating same procedure as mentioned above at different pH of the electrolyte. Figure 24 shows plot of flat band potential of TiO2 from graphs similar to Figure 23, at different pH of the acetate buffer.
Figure 23: Photocurrent square against potential vs N.H.E For TiO 2 PEC experiment in acetate buffer pH = 6.884

70 Typically it shows slope of 59mV/ pH. Value of 54.6mV/pH was obtained in case of this pilot experimental. It proves the correctness of the working protocol. PEC results for Co3O4 thin films The procedure of the PEC experiments for Co3O4 was same as TiO2. The thickness of the films was typically ~ 70 nm -100 nm as roughly estimated from SEM measurements. Photocurrent obtained with different electrolytes is summarized in Table 12.
Figure 24: Change in flat band potential with pH of the acetate buffer used in TiO 2 aqueous PEC experiment

71 Figure 25 shows a typical chopped light LSV curve obtained for the Co3O4 thin films. Photocurrent is cathodic in nature because Co3O4 being p-type semiconductor. Dark current is non-zero and increasing in magnitude as scanned from 0.4V to -1.0V. In addition, the maximum photocurrent obtained is ~3A, in contrast to ~200A photocurrent in TiO2 in an acetate buffer solution and near zero dark current. Table 12 summarizes the data obtained for different PEC experiments with the set of conditions used. Since this initial part of the work is focused on optimizing the
Figure 25: Chopped light LSV curve for Co3O4 thin films in ferrocene based non-aqueous electrolyte, electrolyte S10 in table 7.

72 experimental conditions to achieve higher photocurrent, only the maximum photocurrents for those graphs are reported here.
PEC cell configuration

Max. Photocurrent A Other comments on the observations Aqueous: Counter electrode is graphite. R.E. = R2 Electrolyte = S1 0 A No chopping in current-voltage curve except small continuous changes which could be due to local temperature variation R.E. = R2 Electrolyte = S2 ~ 1.5A Noisy Ohmic behavior in overall IV curve R.E. = R2 Electrolyte = S3 0 A Near zero dark in -0.25V to 0.5 V region. R.E. = R2 Electrolyte = S5 0 A Well defined peaks around 0.2234 V (vs R2) in CV R.E. = R2 Electrolyte = S4 3 A Very small photocurrent Non-aqueous: Counter electrode is Pt wire R.E. = R1 Electrolyte = S6 6 A Scanned only in -0.3 to 0.0V region

continued
Table 11: Summary of the PEC data obtained under different experimental conditions. Working electrode is thin film of Co3O4 on FTO, unless specifically mentioned.

73 Error! Reference source not found. continued

R.E. = R1 Electrolyte = S7 ~ 0.5 A Noisy data with transient spikes at the point where light is chopped R.E. = R1 Electrolyte = S8 4A Almost flat dark current from -0.4 to 0 V R.E. = R3 Electrolyte = S9 3A Stable photocurrent with ohmic behavior of IV curve R.E. = R3 Electrolyte = S10 15 A Quite stable photocurrent with high background dark current , it shows ohmic behavior in ve region from 0.5 onwards R.E = R3

Electrolyte = S9 W.E. = Co3O4 NW 0A Completely ohmic nature in IV curve no photocurrent except small current, possibly due to local temperature variation

4.5 Discussion: As summarized above, IV curves obtained for Co3O4 thin films in different electrolyte medium have three main issues to be addressed to get higher photocurrent. A. Small photocurrent B. Ohmic Behavior of the dark current C. Transient current
Table 12: Summary of the PEC data obtained under different experimental conditions. Working electrode is thin film of Co3O4 on FTO, unless specifically mentioned.

74 4.5.1 Small photocurrent There are several ways in which small photocurrent for Co3O4 thin films can be explained. Photocurrent generation broadly involves three parts, light absorption, charge carrier separation, and charge carrier collection. Light absorption depends on the band gap and extinction coefficient of the semiconductor and also the thickness of the film. Wide band gap semiconductors absorb in UV region. Most of the solar energy reaching the earth is in the form of visible and NIR radiations; therefore, semiconductor with absorption in this region of solar spectrum is desired for a practical device. Light penetration depth is decided by absorption coefficient (_) of the semiconductor material. Higher thickness beyond this light penetration depth does not absorb light and hence will not contribute to the photocurrent. In fact for the charge separation to occur, local electric field of depletion region is necessary. Hence, most of the electron hole pair generated outside the depletion region, beyond minority diffusion length will most likely recombine to give away heat. Therefore, optimization of the thickness of the films is necessary. 75 Photocurrent generated by a semiconductor is modeled by Gartner model. Following is a typical equation: _34__ _ 5_ _ 6 7 _ 34___689:__ 5_qua4tumYie3d_Jphoto/Io 6_absorptio4coefficie4t w_spacechargeregio4width Lmi4_diffusio43e4gth Gartner model is a theoretical model to find theoretical quantum yield of the semiconductor photo-electrode, using space charge region width, diffusion length, and extinction coefficient. However, this model does not take into account the effects such as multi-electron processes causing photocurrent doubling, effect of surface states, and

recombination effects. Hence, effectively Gartner equation predicts the upper limit for the photocurrent, except in case of multi-electron processes, where photocurrent obtained ends up being higher than the upper limit set by Gartner equation. In the actual PEC experiments, the photocurrent density ends up being lower due recombination effects. Thickness of the depletion region depends on doping density and crystal purity. In case of Co3O4, it is known to have varying stoichiometry depending on the method of preparation. P-type nature of the Co3O4 is due to O2- deficiency in Co3O4 lattice. In a sol76 gel method, extent of deficiency depends on variety of conditions such as, pH of the sol, temperature of annealing, atmosphere of annealing and precursor used. It is difficult to control it very precisely. As evident from its UV-Vis absorption spectrum, Co3O4 absorbs very strongly in the visible region. However, it does not translate into high photocurrent. This could be due to fast recombination of the electron and hole generated after the light absorption. Recombination of a minority carrier and a majority carrier can be seen as a pseudo first order reaction.72 Because majority carrier is present in excess compared to minority carrier, majority carrier concentration practically stays constant during recombination process. Lifetime of the minority carrier can be used to characterize the extent of recombination. This lifetime of minority carrier is a measure of time for which it exists before recombining. Following expression relates minority carrier lifetime to minoritycarrier diffusion coefficient. It is another way of comparing the different materials; judged for potential application in PEC cell as photo-electrode. Minority-carrier diffusion length is a measure of distance, that minority carrier travels before recombining with majority carrier. With diffusion length, it is convenient to compare that to thickness of the depletion region and overall thickness of the film. 77 Following equation underlines the relation of minority-carrier diffusion length to minority carrier lifetime. 89:_ _ _ P9:__
Q _

Lmin = Minority Diffusion length D = Diffusion coefficient _min = Minority Carrier lifetime In a strict sense, this equation is only applied in a field free diffusion of minority carriers. However, the general relation of lifetime to diffusion length even holds true in the depletion region. It shows that short-lived minority carrier diffuses smaller distance and makes it more likely to recombine. In fact, most spinel structured metal oxides have hopping mechanism for carrier mobility. In case of cobalt oxide valence and conduction band is made up of weak overlap of d-orbitals of cobalt ions. 70 Hence, it puts an intrinsic limit on minority-carrier diffusion length. This may explain low photocurrent observed in the PEC experiments for Co3O4 thin films.

Higher doping in a semiconductor facilitates recombination. In the case of p-type Co3O4, higher doping means more O2- deficiency or lower O/Co ratio. Theoretically, in absence of O2- deficiency, O/Co ratio of 1.33 is expected. However in practice O/Co ratio of as 78 low as 1.15 has been reported in literature.70 This could be one possible cause of high recombination. 4.5.2 Ohmic behavior of dark current Dark current occurs due to reactions occurring at working electrode in absence of light. Ideally very low or no current is observed under dark, within a certain potential bias range. This is known as the diode behavior of the semiconductor. Figure 22 shows chopped photocurrent spectrum for the TiO2 thin films. TiO2 is n-type semiconductor, hence it acts as photo-anode, and anodic photocurrent is observed under illumination of light. Moreover, a nearly zero dark current observed suggests that TiO 2 shows diode behavior. In this flat region, no faradic current is observed. If applied bias is too positive or negative, it results in breakdown of diode behavior. This limit is called Zener limit. Outside of this potential window, semiconductor electrode effectively acts as metal electrode. Zener limit is dependent on surface state concentration and electric field applied. This may explain the large increase in the dark current at 1.0V. In case of Co3O4, all the IV curves obtained under chopped illumination had non zero dark current, which went on increasing as scanned beyond -0.5 V. Figure 25 shows one such curve as a representative example. Curve in Figure 25 shows almost ohmic behavior. This is maybe due to the tunneling of electrons across the barrier region, which 79 is likely to be thin if doping or O2- is high. Such tunneling would increase as scan into more negative region. Moreover, such dark current depends on the types of reactions that are possible for a given electrolyte at the semiconductor surface. Co3O4 surface has many Co3+ sites, which can act as catalytic sites. In case of aqueous PEC experiments, partial dissolution was observed on prolonged illumination. This indicates that Co3O4 surface reacts with electrolyte. The non-zero dark current could also be due to the exposure of FTO to the electrolyte. In case of K3Fe(CN)6 as electrolyte, well formed redox peaks of Fe(CN)6 3+ were obtained in cyclic voltammetry. Such peaks are likely to appear on metal like electrode. It suggests that either Co3O4 is behaving like metal at too negative bias, or electrolyte is in direct contact with FTO. 4.5.3 Photocurrent Transient Photocurrent transient response is the sudden spikes observed in current density, as the light is chopped in the PEC experiment. The transient overshoot is dependent on the

capacitance of the space charge layer, and concentration of surface states. When light is switched on, photocurrent shoots to give a high transient value, which subsequently decays to a stable steady-state photocurrent value. Magnitude of this stable photocurrent depends on magnitude of rate of recombination and rate of charge transfer. 72 When 80 going from light to dark in chopped light experiment, electrons on surface continue to recombine with the holes, in case of p-type semiconductor. Since holes are effectively moving in opposite direction, current has negative sign. This recombination continues to decay and shows gradual decrease to steady state photocurrent. To check whether this is because of surface recombination, surface passivation studies can be carried out. 81 Chapter 5: Conclusions and future work Clearly more work is required to get the complete understanding of the photoelectrochemistry and the OER electrocatalysis on Co3O4. All the work presented in chapters 2, 3 and 4 is summarized here, and future work is outlined. 5.1 Electrocatalysis Conclusion ECM treatment was used to generate nanopores in thin films of Co3O4. Such an ECM treatment showed a significant increase in the OER activity of the thin film sample compared to the samples without the ECM treatment. The SEM images of the thin films after the OER measurement showed different surface morphology for samples with ECM and without ECM treatment. Hexagonal plates observed after OER measurement on the surface of ECM treated thin film samples, were identified as CoO(OH) using XRD. On further characterization done using Raman spectroscopy, it was confirmed to be CoO(OH) with possible minute contamination of Co3O4 and Co(OH)2. 82 CoO(OH) is known to have higher conductivity compared to Co3O4. Hence, it may be decreasing overall Ohmic overpotential in electrode, and increasing the OER activity. In subsequent experiments it was confirmed that CoO(OH) plates are formed as they are exposed to 1M NaOH. Formation of CoO(OH) from Co3O4 happened only in case of ECM treated sample, and not in case of untreated samples. This method of synthesis of CoO(OH) is unique compared to the solution-based synthesis methods, and produces well formed hexagonal plates. XPS analysis Co3O4 of thin film samples after ECM treatment showed formation of CoO. Future work The reasons for the increase in OER performance of CoO(OH) electro-catalyst are still not completely clear. Many aspects of the experiment such as variation of pH, change in product morphology with thickness of original thin film, are yet to be investigated. For example, TEM diffraction patterns could be obtained to check for disorder in crystal lattice.73 5.2 Photoelectrochemistry

Conclusion In PEC studies, we first studied TiO2 as a model system in acetate buffer solution as electrolyte. The chopped I-V curve showed photocurrent of the order of ~150 A. The flat band potential was calculated from the plot of square of photocurrent vs. potential. The variation in flat band potential with pH was Nearnstian in behavior. 83 In case of the Co3O4 PEC, we used different aqueous as well as non-aqueous electrolytes with Co3O4 as photocathode in a three-electrode type cell assembly. However, a small photocurrent of the order of ~3-5 A was obtained in almost all experiments. Most of the chopped I-V curves showed a high dark current value with no diode behavior. It was difficult to find the flat band potential because of such a small photocurrent. The small photocurrent obtained is thought to be due to the small diffusion length of the carriers in Co3O4. Future work In the PEC studies of Co3O4, a higher photocurrent is required, to further the investigation of the band positions and the diffusion length measurement. The flat band position can be obtained using the Butler-Volmer method. Also the IPCE measurement can be done to demonstrate the wavelength dependence of the photocurrent. Better practical methods are needed to control the recombination of photo-generated carriers and to get the higher and reproducible photocurrent of at least ~50-70 A. The surface of the semiconductor plays an important role in change collection. Interfacial kinetics of different possible reactions also needs to be considered while using different electrolytes. Annealing at temperatures higher than 550 C may improve crystallinity in the Co 3O4 thin films, which may improve the carrier diffusion length. However, glass supported FTO substrate used for these thin films, tends to deform at temperatures higher than 600 C. This puts inherent upper limit for annealing temperature. 84 References 1. Baxter, J.; Bian, Z. X.; Chen, G.; Danielson, D.; Dresselhaus, M. S.; Fedorov, A. G.; Fisher, T. S.; Jones, C. W.; Maginn, E.; Kortshagen, U.; Manthiram, A.; Nozik, A.; Rolison, D. R.; Sands, T.; Shi, L.; Sholl, D.; Wu, Y. Y., Nanoscale design to enable the revolution in renewable energy. Energy & Environmental Science 2009, 2, (6), 559-588. 2. http://www.eia.doe.gov/oiaf/ieo/world.html. 3. Roth, W. L., The magnetic structure of Co3O4. Journal of Physics and Chemistry of Solids 1964, 25, (1), 1-10 4. Pontinha, M.; Faty, S.; Walls, M. G.; Ferreira, M. G. S.; Belo, M. D. C., Electronic structure of anodic oxide films formed on cobalt by cyclic voltammetry. Corrosion Science 2006, 48, (10), 2971-2986. 5. Cheng, C. S.; Serizawa, M.; Sakata, H.; Hirayama, T., Electrical conductivity of Co3O4 films prepared by chemical vapour deposition. Materials Chemistry and Physics 1998, 53, (3), 225-230. 6. Pasko, S.; Abrutis, A.; Hubert-Pfalzgraf, L. G.; Kubilius, V., Cobalt (II) [beta]-

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