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Synopsis of thesis entitled “Electrochemical and Photoelectrochemical Investigations of Co, Mn and Ir-based Catalysts for Water Splitting” by Ahamed Irshad M (SR No: 02-01-02-10-11-11-1-08823) under the supervision of Prof. N. Munichandraiah, Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India), for the Ph.D. degree of the Institute under the Faculty of Science. Hydrogen is considered as the fuel for future owing to its high gravimetric energy density and eco-friendly use. In addition, H2 is an important feedstock in Haber process for ammonia synthesis and petroleum refining. Although, it is the most abundant element in the universe, elemental hydrogen is not available in large quantities on the planet. Consequently, H2 must be produced from its various chemical compounds available on earth. Currently, H2 is produced in large scale from methane by a process called steam-methane reforming (SMR). This process releases huge amount of CO2 into atmosphere as the by-product causing serious environmental issues. The development of alternate clean methods to generate H2 is a key challenge for the realization of hydrogen economy. Production of H2 gas by water splitting using electricity or sunlight is known. Low cost, high natural abundance and carbon neutrality make water as the best source of hydrogen. Thermodynamically, splitting of H2O needs 237 kJ mol-1 of energy, which corresponds to 1.23 V according to the equation, ΔG = -nFE. However, commercial electrolyzers usually operate between 1.8 to 2.1 V, due to the need of large overvoltage. The high overvoltage and subsequent energy losses are mainly associated with the sluggish kinetics of oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode. The overvoltage can be considerably reduced using suitable catalysts. Hence, the design and development of stable, robust and highly active catalysts for OER and HER are essential to make water splitting efficient and economical. Attempts in the direction of preparing several novel OER and HER catalysts, physicochemical characterizations and their electrochemical or photoelectrochemical activity are described in the thesis. A comprehensive review of the literature on various types of catalysts, thermodynamics, kinetics and mechanisms of catalysis are provided in the Chapter 1 of the thesis. Chapter 2 furnishes a brief description on various experimental techniques and procedures adopted at different stages of the present studies. Chapter 3 explains the results of the studies on kinetics of deposition and stability of Nocera’s Co-phosphate (Co-Pi) catalyst using electrochemical quartz crystal microbalance (EQCM). The in-situ mass measurements during CV experiments on Au electrode confirm the deposition of Co-Pi at potential above 0.87 V vs. Ag/AgCl, 3 M KCl (Fig.1a and b). The catalyst is found to deposit via a nucleus mediated process at a rate of 1.8 ng s-1 from 0.5 mM Co2+ in 0.1 M neural phosphate solution at 1.0 V. Further studies on the potential and electrolyte dependent stability of the Co-Pi suggest that the catalyst undergoes severe corrosion at high overpotential and in non-buffer electrolytes. Current/ Fig.1 (a) Cyclic voltammograms and (b) mass variations vs. potential of Au-coated quartz crystal in 0.1 M potassium phosphate buffer solution (pH 7.0) containing 0.5 mM Co(NO3)2 Chapter 4 deals with the electrochemical deposition of a novel OER catalyst, namely, Co-acetate (Co-Ac) from a neutral acetate electrolyte containing Co2+ ions. Use of acetate solution instead of phosphate avoids the solubility limitations and helps to get thick layer of the catalyst in a short time from concentrated Co2+ solutions. In addition, the Co-Ac is found to be catalytically superior to Co-Pi (Fig. 2a). It is also observed that the Co-Ac catalyst undergoes ion exchange with electrolyte species during electrolysis in phosphate buffer solution, which results in the formation of a hybrid Co-Ac-Pi catalyst (Fig. 2b). The presence of both acetate and phosphate ions in the catalyst and their synergistic catalytic effect enhance the OER activity. Fig.2. (a) Linear sweep voltammograms of Co-Ac in (i) phosphate and (ii) acetate electrolytes, and that of Co-Pi in (iii) acetate and (iv) phosphate electrolytes. (b) SEM image showing the formation of two layers of the catalysts after electrolysis in phosphate solution. In Chapter 5, high OER activity of an electrodeposited amorphous Ir-phosphate (Ir-Pi) is investigated. The catalyst is prepared by the anodic polarization of a carbon paper electrode in neutral phosphate solution containing Ir3+ ions (Fig. 3). The Ir-Pi film deposited on the electrode has Ir and P in an approximate ratio of 1:2 with Ir in an oxidation state higher than +4. Phosphate ions play a major role for both the electrochemical deposition process and its catalytic activity towards OER. The Ir-Pi catalyst is superior to similarly deposited IrO2 and Co-Pi catalysts both in terms of onset potential and current density at any potential in the OER region. Tafel measurements and pH dependence studies identify the formation of a high energy intermediate during oxygen evolution. Fig.3. (a) Cyclic voltammograms during the Ir-Pi deposition and (b) SEM image of Ir-Pi on C. Chapter 6 is on the preparation of a composite of Mn-phosphate (MnOx-Pi) and reduced graphene oxide (rGO) and its utilization as an OER catalyst. The composite is prepared by the simultaneous electrochemical reduction of KMnO4 and graphene oxide (GO) in a phosphate solution (pH 7.0). Various analytical techniques such as TEM, XPS, Raman spectroscopy, etc. confirm the formation of a composite (Fig. 4) and electrochemical studies indicate the favourable role of rGO towards OER. Under identical conditions, MnOx-Pi-rGO gives 6.2 mA cm-2 at 2.05 V vs. RHE whereas it is only 2.9 mA cm-2 for MnOx-Pi alone. However, the catalyst is not very stable during OER which is ascribed to slow oxidation of Mn3+ in the catalyst. Fig.4. (a) Raman spectrum and (b) TEM image of MnOx-Pi-rGO. In Chapter 7, an amorphous Ni-Co-S film is prepared by a potentiodynamic deposition method using thiourea as the sulphur source. The electrodeposit is used as a catalyst for the HER in neutral phosphate solution. The composition of the catalyst and the HER activity are tuned by varying the ratio of concentrations of Ni2+ and Co2+. The bimetallic Ni-Co-S catalyst exhibits better HER activity than both Ni-S and Co-S (Fig. 5a). Under optimized deposition conditions, Ni-Co-S requires just 150 mV for the onset of HER and 10 mA cm-2 is obtained for 280 mV overpotential. The Ni-Co-S shows two different Tafel slopes, indicating two different potential dependent HER mechanisms (Fig. 5b). Presence of two different catalytic sites which contribute selectively in different potential regions is proposed. Fig.5. (a) Linear sweep voltammograms of HER at 1 mV s-1 in 1 M phosphate solutions (pH 7.4) using (i) Ni-S, (ii) Co-S and (c) Ni-Co-S. (b) Tafel plot of Ni-Co-S showing two Tafel slopes. Photoelectrochemical OER using ZnO photoanode and Co-acetate (Co-Ac) cocatalyst is studied in Chapter 8 of the thesis. Randomly oriented crystalline ZnO nanorods are prepared by the electrochemical deposition of Zn(OH)2 followed by heat treatment at 350 ºC in air. Co-Ac is then photochemically deposited onto ZnO nanorods by UV illumination in the presence of neutral acetate buffer solution containing Co2+ ions. The hybrid Co-Ac-ZnO shows higher photoactivity in comparison with bare ZnO towards PEC water oxidation (Fig. 6). Co-Ac acts as a cocatalyst and reduces the charge carrier recombination at the electrode/electrolyte interface. Fig.6. (a) Linear sweep voltammograms of ZnO under (i) dark and (ii) light conditions, and that of Co-Ac-ZnO in (iii) dark and (iv) light in 0.1 M phosphate (pH 7.0) electrolyte. Chapter 9 deals with PEC water oxidation using α-Fe2O3 photoanode and Ir-phosphate (Ir-Pi) cocatalyst. α-Fe2O3 is prepared by direct heating of Fe film in air which in turn is deposited by the electrochemical reduction of Fe2+. Thickness of the film as well as calcination temperature is carefully optimized. In order to further enhance the OER kinetics, Ir-Pi is electrochemically deposited onto α-Fe2O3. Under optimized conditions, Ir-Pi deposited α-Fe2O3 shows around 3 times higher photocurrent than that of bare α-Fe2O3 at 1.23 V vs. RHE (Fig. 7). Ir-Pi acts as a cocatalyst for OER and reduces the photogenerated charge carrier recombination. Fig.7. Photocurrent variation of α-Fe2O3 electrode at 1.23 V vs. RHE for (i) front and (ii) back side illuminations, against Ir-Pi deposition time. The thesis ends with a short summary and future prospectus of studies described in the thesis. The research work presented in the thesis is carried out by the candidate as the part of Ph.D. program. Some of the results have already been published in the literature and some manuscripts are under preparation. A list of publications is included at the end of the thesis. It is anticipated that the studies reported in the thesis will constitute a worthwhile contribution.