High performance non precious lithiated cobalt oxide spinel electro-catalyst for oxygen evolution reaction Thandavarayan Maiyalagan

and Arumugam Manthiram* Abstract Development of efficient electrocatalysts for the oxygen evolution reaction (OER) is critical for rechargeable metal-air batteries and water electrolysis. IrO2 is known to be the best OER electrocatalyst, but the high cost and low abundance of iridium hamper its practical utility. We present here the inexpensive, earth-abundant low-temperature (LT) lithium cobalt oxide (designated as LT-LiCoO2) having a lithiated spinel structure {Li2}16c[Co2]16dO4 in which the Li+ ions occupy the empty 16c octahedral sites of the [Co2]16dO4 spinel framework as a replacement for the expensive IrO2 electrocatalyst. The LT-LiCoO2 shows OER catalytic activity comparable to that of IrO2 in alkaline medium. A comparison of the catalytic activities of LT-LiCoO2 prepared by different methods reveals that LT-LiCoO2 nanorods obtained by a co-precipitation method followed by firing at 400 oC shows much enhanced electrochemical performance compared to the conventional LT-LiCoO2 nanoparticles prepared by a solid state method at 400
o

C. Furthermore, the LT-LiCoO2 synthesized at 400 oC shows much higher catalytic activity than

the high-temperature LiCoO2 (HT-LiCoO2) synthesized at 800 oC, which has a layered structure and is used as a cathode in lithium-ion batteries. The cubical metal-oxo (M4O4) subunits present in LT-LiCoO2 plays a key role in imparting high OER activity. ___________________________ Electrochemical Energy Laboratory, Materials Science and Engineering Program The University of Texas at Austin, Austin, TX 78712, USA * Correspondence should be addressed to A.M. (email: rmanth@mail.utexas.edu).

Introduction
The oxygen electrochemistry plays a major role in energy conversion and storage devices, particularly in the field of fuel cells, metal-air batteries, and water electrolysers1-3. The major challenge in metal-air batteries and water electrolysis is to design and develop economically feasible, earth-abundant, inexpensive efficient catalysts for oxygen evolution reaction (OER)4. Nature does water electrolysis using photosystem II water-oxidizing complex containing CaMn4Ox clusters that are capable of promoting water oxidation with significant turnover frequencies at low overpotentials4-8. However, it is difficult to use these naturally occurring enzymes in commercial devices due to the instability under operating conditions.9 Precious metal catalysts such as Pt, IrO2, and RuO2 are normally employed, but their low abundance and high cost prohibit their practical use.10 Pt exhibits inadequate OER activity due to the formation of the insulating platinum oxides. RuO2 becomes unstable at high potentials due to the formation of higher-valent oxides. IrO2 is the best catalyst so far for OER. A burgeoning effort by chemists is to create earth-abundant materials as catalysts with high activity and stability for OER, but it remains a significant scientific challenge. Also, electrolysis in alkaline medium is generally preferred over acidic medium because of less expensive materials for construction and less susceptibility to corrosion.11,12 Transition metal oxides containing highly oxidized redox couples such as Ir4+/6+, Ru4+/8+, Co3+/4+, Ni3+/4+, Mn3+/4+, and Fe3+/4+ are known as active centres for OER. The electrochemical performances of oxides for OER follows the order, IrO2 > RuO2 > Co3O4 and Ni containing cobalt oxides > Fe, Pb, Mn containing oxides. The remarkable chemistry of cobalt has inspired chemists

to develop earth-abundant low-cost electro-catalysts for both OER and oxygen reduction reaction (ORR) 14-18. Among the numerous materials investigated, cobalt oxides are promising and have been largely studied as stable electrocatalysts for OER in highly alkaline solutions.19 The low-cost spinel NiCo2O4 and Co3O4 have been found by several groups to show good efficiency and long term performance, but they underperform relative to IrO220. Co3O4 nanoparticles have also been anchored on suitable supports in order to increase the active sites without agglomeration and thereby increase the catalytic activity. Recently, Liang et al21 have used Co3O4 nanocrystals anchored on graphene, while Frei and co-workers22 have developed efficient water oxidation catalysts by supporting MnOx and Co3O4 clusters on mesoporous silica scaffolds. Also, kannan et al23 have used cobalt phosphate catalyst for water oxidation. With an aim to develop highly active, earth-abundant catalysts as a replacement for IrO2, we focus here on LiCoO2 as an elecrocatalyst for OER. LiCoO2 has been intensively studied as a cathode material for lithium-ion batteries.24 LiCoO2 is known to exist in two forms: the LiCoO2 sample synthesized at high temperatures (~ 800 oC) has the -NaFeO2 structure (R3m) in which the Li+ and Co3+ ions order on the alternate {111} planes of the rock salt structure due to the large size and charge differences between Li+ and Co3+ ions 25. We designate this high-temperature form here as HT-LiCoO2. In contrast, the LiCoO2 sample synthesized at a lower temperatures (~ 400 oC) adopts a lithiated spinel structure {Li2}16c[Co2]16dO4 in which the Co3+ ions occupy all the 16d octahedral sites while the Li+ ions occupy all the 16c octahedral sites of the spinel framework (space group Fd3m) 26. We designate this low-temperature form as LT-LiCoO2. We compare here the activities of LT-LiCoO2 and HT-LiCoO2 having different structures for OER in alkaline medium. The

LT-LiCoO2 and HT-LiCoO2, both consisting of Co3+ ions, oer a unique platform to explore the structure-activity relationships for OER. While the LT-LiCoO2 consists of the cubic Co4O4 units, the HT-LiCoO2 consists of LiCo3O4 units. Results Crystal and electronic structure of the catalyst Both the crystal and electronic structures along with the surface structures under the electrochemical operating conditions play a critical role in imparting OER activity. Fig 1 shows the XRD patterns of LT-LiCoO2, HT-LiCoO2, and Co3O4. While the LT-LiCoO2 synthesized at 400 oC shows a single peak around 2 63o corresponding to the {440} reflection of the cubic lithiated spinel (Fd3m), the peak splits into the (108) and (110) reflections of the layered HT-LiCoO2 structure (R-3m) on heating to 800 oC.27-30 Also, the (220) peak present Co3O4 is absent in LT-LiCoO2 due to the absence of ions with high scattering power in the tetrahedral sites of LT-LiCoO2. Moreover, the distribution of Li+ ions in the spinel lattice is reflected in the changes of relative intensities of (222), (400) and (440) peaks indicates Co3O4 are significantly transformed towards a rock salt distribution when compared to 100 % (311) peak, suggesting the overlap of spinel Co3O4 peaks with the rock salt LiCo2O4.31 Co3O4 has a cubic spinel structure with a cation distribution of (Co2+)8a[Co23+]16dO4 in which all the Co3+ ions occupy the 16d octahedral sites while and all Co2+ ions occupy the 8a tetrahedral sites. In contrast, while all the Co3+ ions in LT-LiCoO2 also occupy the 16d octahedral sites of the spinel lattice, the Li+ ions occupy all the 16c octahedral sites to give a cation distribution of {Li2}16c[Co2]16dO4. Figure S1 in the supplementary information shows the Rietveld renement of the XRD prole of

LT-LiCoO2 and HT-LiCoO2 along with Co3O4. The observed and calculated patterns match well with each other, validating the lithiated spinel structure of LT-LiCoO2. The structural parameters obtained from the Rietveld renement are given in Table S1 in the supplementary information. I have edited up to this, but it may need reorganization. Electrochemical behavior of the catalyst Cyclic voltammograms recorded for all the electrocatalysts with same experimental conditions are presented in Fig. 2. The electro-catalytic behavior of LT-LiCoO2 catalyst for oxygen evolution reaction, depend upon the surface redox properties of the catalyst and the ability of the catalyst to shuttle oxygen in a controlled manner. The real oxidation state of metal ions in the catalyst determines the charge transfer process. The close thermodynamic stability of the Co3+ oxidation states and the formation of Co4+ is a key feature in these mechanisms. The finger print of Co3O4 is characterized by a pair of redox peaks at 1.5 V prior to oxygen evolution reaction at a scan rate of 20 mV/sec. These peaks were attributed to the confined quasireversible redox couple, CoO2/CoOOH limited by diffusion controlled process occur at the Co3O4 surface. Similar well defined electrochemical behavior of Co3O4 has been reported by others and assigned to the formation of a redox couple, CoO2/CoOOH.32,33 LT-LiCoO2 is highly active with KOH electrolyte and electrochemical properties of LT-LiCoO2 differ considerably from HT-LiCoO2. We find interesting electrochemical feature of the LT-LiCoO2 material, i.e., its lower potential for quasi reversible peak for the redox couple Co3+ / Co4+ at 1.43 V against 1.51 V(vs. RHE) for HT-LiCoO2. A redox couple for LT-LiCoO2 occurs at lower potential whereas both Co3O4 and HT-LiCoO2 occurs nearly at same higher potential.

The electrochemical behavior of LT-LiCoO2 differs greatly from HT-LiCoO2 is strongly due to LT-LiCoO2 has taken spinel structure and HT-LiCoO2 has taken layered structure. A well-defined extra peak observed in HT-LiCoO2 at 1.53 V is related to order/disorder phase transitions suggesting that LT-LiCoO2 has slower Li transport than HT-LiCoO2.The following reaction is possible in LT-LiCoO2 involves the redox species Co3+ and Co4+. Co2O3 + 2OH2CoO2 + H2O + 2e-

Cyclic voltammetric studies in Fig 2 has been proven instrumental in establishing that the observed catalysis originates from Co3+/Co4+ oxide couple to furnish the active O2 evolving site. Several studies in the literature have proved that the involvement of structurally strained unstable Co4+ species on the surface acts as intermediate species for oxygen evolution reaction. Further Nocera et al has demonstrated Co4+ active site formation by EPR during oxygen evolution reaction conditions.34 Tseung et al correlates the relationship of minimum onset potential for OER with potential of lower oxide/higher oxide couple. The redox couple of IrO2 and RuO2 occurs at lower potential resulted in better OER onset potential.35 However, it is important to note that though this lower oxide/higher oxide redox couple hypothesis can be used to predict the minimum voltage at which oxygen evolution takes place.35 However the hypothesis has been extended to LT-LiCoO2 catalyst in which lower/higher metal oxide couple occurs at lower potential favor lower OER onset potential. LT-LiCoO2 has lower OER onset potential compared to HT-LiCoO2 and Co3O4 (Supplementary Table. S2).35 Oxygen evolution reaction involving LT-LiCoO2 is typically considered as surface phenomena rather than resulting from the complete dissolution and

reformation of the catalyst. The electro-catalytic performance strongly depends on the population of active stable redox species on the catalyst surface.6 Electrochemical performance of the catalyst. The electrochemical performance of the catalysts for oxygen evolution reaction was studied by linear sweep voltammetry in oxygen saturated 0.1 M KOH solution at a scan rate of 20 mV s-1. Electro-catalytic activities for all the catalyst samples during OER reaction were expressed in terms of mass activity. The mass normalized OER activities (Fig. 3) of the catalysts increased in the order; HT-LiCoO2 bulk < Co3O4 nanorods < IrO2 nanoparticles < LT-LiCoO2 bulk < LT-LiCoO2 nanorods. Among the catalyst studied layered bulk HT-LiCoO2 shows the least performance. The Co3O4 nanorods obtained by co-precipitation method with a rod length of 50-100 nm and diameter of 20-30 nm shows better electrochemical performances than HT-LiCoO2 catalyst (Fig 4c). It is a reasonable hypothesis that a porous catalyst with higher surface area will have a mass activity higher that of the bulk electrode. Furthermore enhancement in catalytic activity of LT-LiCoO2 catalyst was achieved by high surface area through small particle size. The LT-LiCoO2 catalyst prepared by co-precipitation method yields mass activity nearly an order of magnitude higher than the conventional solid state method. High performance of the co-precipitated LT-LiCoO2 spinels catalysts can be attributed to higher surface area of 24 m2/g than the LT-LiCoO2 solid state method (9 m2/g). From present studies, it is well known that there are substantial differences in catalytic activity between nanoscale LT-LiCoO2 and bulk LT-LiCoO2 catalyst. The benefits of targeting nanoscale LT-LiCoO2 architectures have scarcely

been explored. Further SEM micrograph confirms co-precipitated LT-LiCoO2 spinels yields nanorod morphology with a rod length of 50-100 nm and diameter of 20-30 nm than the conventional solid state method (Fig 4b). The LT-LiCoO2 catalyst synthesized by solid state method is aggregated with particle size around 50-100 nm. HT-LiCoO2 catalysts have very lower surface area of 1.7 m2/g (Supplementary Fig. S2d) due to non-uniform submicron-sized particles. These large particles may either be a result of locally enhanced sintering or Li2CO3 filled aggregates of small LiCoO2 particles (Fig 4d). Typical literature mass activities for IrO2 and Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF) catalysts are shown for reference and are exceeded by the activities of both IrO2 and BSCF (Supplementary Table S3). The electro-catalytic performance of LT-LiCoO2 is exciting, particularly because of high mass activity than that of expensive IrO2. As can be seen from (Supplementary Table S3), the LT-LiCoO2 catalyst showed the highest mass activity. Both bulk LT-LiCoO2 and LT-LiCoO2 nanorods shows better performance than IrO2. In order for a material to have good OER activity, it should have high electronic conductivity and great affinity for adsorbed OH- intermediates. For example, IrO2 is the most active and stable catalyst for OER in acid and alkaline media due to its interesting electronic structure and metallic conductivity. The OER reaction with IrO2 involves an oxidation of low-spin Ir4+:3d5 (t2g5eg0) ions to Ir6+:3d5 (t2g3eg0) on the surface. The loss of crystal field stabilization energy (CFSE) during this process makes Ir6+ unstable, favouring a facile OER reaction.The loss of CFSE during the oxidation of low-spin Co3+:3d6 (t2g6eg0) ions to Co4+:3d5 (t2g5eg0) on the surface along with the high (possibly metallic) conductivity arising from the

partially filled t2g orbitals of Co4+ across the shared octahedral edges could favour high catalytic activity for OER. In addition, the overlap of the Co3+/4+:3d energy with the top of the O2-:2p band and the resulting pinning of the metal: 3d orbitals with the oxygen 2p orbitals may play a role in imparting high catalytic activity (Supplementary Fig. S3). The performance of bulk LT-LiCoO2 is higher compared to Co3O4 nanorods despite the lower surface area (9 m2/g). The reason for higher electrochemical performance of low temperature lithiated cobalt oxide compared to Co3O4 nanorods was all the Co3+ active sites is in octahedral position, whereas in the case of Co3O4, oxidation state transition occurred as follows Co2+ (t) Co3+ (t) Co4+ (t). The Co3+ in octahedral coordination is more stable and active for oxygen evolution than Co3+ in tetrahedral coordination. Co3+ in an octahedral coordination is regarded as active site for oxygen evolution reaction, whereas the Co2+, Co3+ in tetrahedral coordination is inactive. Thus in LT-LiCoO2 all Co3+ ions exist in octahedral sites, provides extra stability to the material and energetically feasible Co3+ (o) Co4+ (o) transition for oxygen evolution reaction. The lower electrochemical performance of layered HT-LiCoO2 compared to cubic LT-LiCoO2 is establishes the crystal structure difference of the two materials and the major advantage is the presence of well-known cubic M4O4 cubane in LT-LiCoO2 is a general feature for efficient catalysis for water oxidation.

Mechanism of the oxygen evolution reaction and structural correlation of LT-LiCoO2 catalyst at molecular level The cubane-like M4O4 units in LT-LiCoO2 spinel and other spinels (Co3O4, Mn3O4, and -MnO2), resembles the catalytic core found in Natures water-oxidation catalyst CaMn4O5, may play a critical role in OER. On the basis of above experimental results of high performance of LT-LiCoO2 (Fig. 3), we tentatively propose the mechanism of oxygen evolution reaction on LT-LiCoO2 catalysts in neutral medium mediated by Co4+ ions depicted in Fig. 5. The proposed mechanism is based on adjacent Co4+ ions in cubane units assist in forming the OO bond ; 36 In general, high catalytic activity were observed for LT-LiCoO2 catalyst that contains substantial amounts of Co3+, consistent with this species being the catalyst resting state. Two adjacent Co3+(OH) moieties in cubane are oxidized to Co4+ (O) through deprotonation. However it is postulated that Co3+/4+ redox transformations in the LT-LiCoO2 catalysts during OER are coupled to proton loss from surface bound OH ligands. The proton loss from OH ligands results unpaired spin density is consistent with subsequent reactivity of the Co4+ moieties. In the LT-LiCoO2 catalyst, it is believed that terminal and bridging Co4+ -oxos couple to form the O-O bond and release molecular oxygen.34 Also So far, cyclic voltammetric studies (Fig. 2) have shown that LT-LiCoO2 is capable of generating Co4+ on the surfaces is catalyzing water oxidation. Direct coupling occurs on adjacent CoIV(O) oxo groups across a cube face has as a facile possible mechanism for OO bond formation. Computational studies confirms the proposed mechanism occurs to form OO bond with a a low kinetic barrier and a strong thermodynamic driving force.37

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Electrochemical stability of the catalyst The long-term stability of the catalyst was still a substantial challenge, and major efforts are directed to address these problems. The electro-catalyst stability is seriously influenced by selection of electrolytes. Since Co3O4 dissolves in acid medium, the stability is done in neutral (pH-7) and alkaline medium (pH-14). The electro-catalyst stability for OER at an applied potential of 1.7 V for pH 7 and 14 was evaluated by chronoamperometry (Fig 6). The Co3O4 prepared by co-precipitation is stable both in alkaline medium (pH=14) and neutral medium (pH=7). The exceptional performance of LT-LiCoO2 catalysts was further confirmed by long term stability measurements, which manifested no degradation in the OER activity (fig. 6). HT-LiCoO2 layered spinels were less stable than Co3O4 prepared by co-precipitation method in both alkaline and neutral medium. The OER activity of LT-LiCoO2 catalysts was found to be stable for 4 hrs confirming the extraordinary stability of the species in highly alkaline solution. Long term stability of LT-LiCoO2 catalysts for OER conrm that the spinel-type structure shows high activity and excellent stability stable than the HT-LiCoO2 layered structure. They also indicate that structural stability of LT-LiCoO2 has a determinative effect on the electrochemical performance. It is noteworthy to mention that HT-LiCoO2 is even unstable in neutral pH. This low stability of layered HT-LiCoO2 structures has to do with the overall differences in the structural stability of such phases. The electrochemical stability of the layered HT-LiCoO2 structure can be discussed in terms of its lower crystallinity (or higher disorder), due mainly to a greater density of structural defects. LT- LiCoO2 catalysts synthesized by co-precipitation shows

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increased stability and performance than the LT-LiCoO2 prepared by solid state method in alkaline and neutral medium. The increase of OER current during chronoamperometry may be attributed to smaller diameter of LT- LiCoO2 nanorods resulted in larger specific surface area. Notably, the electrochemical performance of our LT-LiCoO2 nanorods was higher to some of the best reported catalyst materials (including IrO2 and BSCF) with high stability (Supplementary Table S3). The nanorod morphology provides increased oxygen pathway and is beneficial for electronic conduction. Also higher stability (performance) related to the better phase crystallization provided by the co-precipitation method. Discussion In summary, we have successfully demonstrated the non-noble metal LT-LiCoO2 catalysts perform better than the noble metal IrO2 catalysts. This is the highest mass activity reported to date for a non-noble metal catalyst and noble metal catalysts. Higher catalytic activity and stability of LT-LiCoO2 structure catalysts was attributed to the higher Co3+ content and cubane structure. Enhancement in catalytic activity of LT-LiCoO2 catalysts is due to the formation of Co (IV) species during the water oxidation, by stabilizing the Co (III) state. The co-precipitation synthesis of LT-LiCoO2 catalysts was superior to conventional synthesis for the formation of high surface area small sized particles and, hence, for improved electrochemical performance. Better electrochemical performance of LT-LiCoO2 catalyst would be highly beneficial to water electrolysis technology. We anticipate that the successful design of LT-LiCoO2 structure catalysts with nitrogen doped graphene would lead to improved

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performance. We are continuing to probe the mechanism and to improve the catalysis, in particular doping the Ni and Cu ions in the low temperature lithiated spinel.

Methods Synthesis and characterization. Iridium oxide samples were purchased from Alfa Aesar was used as the same. LT-LiCoO2 samples were synthesized by solid state reaction from stoichiometric amount of mixed Li2CO3 and Co3O4 powders heated at 400 0C for 7 days. HT-LiCoO2 samples were synthesized by solid state reaction from stoichiometric amount of mixed Li2CO3 and Co3O4 powders heated at 800 0C for 24 hrs. The dry samples of LT-LiCoO2 and HT-LiCoO2 were obtained by slow furnace cooling to room temperature. Nanosized low temperature Lithium cobalt oxide was synthesized using the co-precipitation method, by drop wise addition of required amounts of cobalt acetates to a 150 ml, 3 M KOH solution. The resulting Co(OH)2 suspension was aged overnight under continuous stirring. The co-precipitated cobalt hydroxides powders were then washed with distilled water and dried in an air oven at 100 0C.The Co(OH)2 samples were mixed with a stoichiometric amount of lithium hydroxide This mixture was ground for 30 minutes to ensure adequate mixing and then placed in a furnace at 400 oC for 24 hour with a cooling rate of 1 oC/min cooling rate. Nanorod shaped Co3O4 reference sample was synthesized by heating the Co(OH)2 powders in the absence of Lithium hydroxide at 400 oC for 24hrs. The phase purity of the compounds was conrmed by powder X-ray diffraction (PXRD) with a Philips Xpert diffractometer (Cu K radiation, =1.5418 Ao) in BraggBrentano reection geometry. A Rietveld structure renement was carried out with the Full prof program. The scanning electron microscopy (SEM) Images were taken by Hitachi S5500, 30 kV. Multi-point BrunauerEmmettTeller (BET) surface area data of the samples collected with an automatic nitrogen gas sorption analyzer (NOVA 2000, Quantachrome) using physical adsorption at 77 K Electrochemical Methods. Sixteen milligrams of catalysts and 3.2 mg carbon black were dispersed in 8 ml ethanol/H2O (1:1) ratio, 73.2 l of 5 % nafion solution assisted by ultrasonication for 30 mins to form a homogeneous

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catalyst ink. The catalyst ink was coated on the RDE (0.196 cm2) at a loading of 0.25 mgoxide cm-2disk and dried at room temperature. Prior to the coating of the catalyst onto the glassy carbon (GC) electrode (5 mm diameter) was polished with Al2O3 paste (0.05 m) and washed ultrasonically in double-distilled water. All the electrochemical measurements were performed by using an SCE reference electrode for 0.1 M KOH and a platinum foil counter electrode at a scan rate of 20 mV/s. The rotation speed of RDE is at 1600 rpm for all measurements.0.1 M KOH was used throughout the experiment. iR (current times internal resistance) compensation was applied linear sweep voltammetry experiments using Nova software supplied with the Autolab cyclic voltammetry instrument. All potentials are reported in this paper are relative to the reversible hydrogen electrode (RHE). The mass activity was normalized to the loading of the oxide catalyst. A slow stream of purified oxygen gas was purged towards the working electrode throughout the measurements. References 1. Mallouk,T.E, Water electrolysis: Divide and conquer, Nature Chem. 5,362363 (2013) 2. Suntivich J, May K. J, Gasteiger H.A, Goodenough J.B& Shao-Horn Y, A Perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles Science 334, 1383-1385 (2011). 3. Turner, J. A. Sustainable hydrogen production. Science, 305, 972974 (2004). 4. Kanan, M. W. & Nocera, D. G. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science, 321, 1072-1075 (2008). 5. Ferreira, K. N.; Iverson, T. M.; Maghlaoui, K.; Barber, J. & Iwata, S. Architecture of the photosynthetic oxygen-evolving center. Science, 303, 1831-1838 (2004). 6. Dismukes, G. C. et al. Development of bioinspired Mn4O4-cubane water oxidation catalysts: lessons from photosynthesis. Acc. Chem. Res. 42, 19351943 (2009). 7. Manchanda, R.; Brudvig, G. W. &Crabtree, R. H. High-valent oxomanganese clusters Structural and mechanistic work relevant to the oxygen-evolving center in photosystem-II. Coord. Chem. Rev. 144, 138 (1995). 8. Brimblecombe, R.; Bond, A. M.; Dismukes, G. C.; Swiegers, G. F. & Spiccia, L. Electrochemical investigation of Mn4O4-cubane water-oxidizing clusters. Phys.Chem. Chem. Phys. 11, 6441644 (2009).

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9. Trasatti, S. Electrocatalysis by oxides e attempt at a unifying approach, J. Electroanal. Chem. 111,125-131(1980). 10. Gordon, R. B., Bertram, M. & Graedel, T. E. Metal stocks and sustainability. Proc. Natl Acad. Sci. 103, 1209-1214 (2006). 11. Divisek, J. Malinowski,P. J. Mergel & H. Schmitz, Improved components for advanced alkaline water electrolysis Int.J. Hydrogen Energy, 13, 141150 (1988). 12. Yin, Q. S. et al. A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals. Science, 328, 342-345 (2010). 13. Risch, M. et al. Cobalt-oxo core of a water-oxidizing catalyst film. J. Am.Chem. Soc. 131, 6936-6937 (2009). 14. Jiao, F. & Frei, H. Nanostructured cobalt and manganese oxide clusters as efficient water oxidation catalysts. Energy Environ. Sci. 3, 1018-1027 (2010). 15. Chou, N. H., Ross, P. N., Bell, A. T. & Don Tilley, T. Comparison of cobalt-based nanoparticles as electrocatalysts for water oxidation. Chem.Sus.Chem. 11, 1566-1569 (2011). 16. McAlpin, J.G., Stich, T.A., Casey, W.H., & Britt, R.D Comparison of cobalt and manganese in the chemistry of water oxidation Coord. Chem. Rev., 256, 2445-2452 (2012). 17. Bashyam, R. & Zelenay, P., A class of non-precious metal composite catalysts for fuel cells, Nature, 443, 63-66 (2006). 18. Petitto, S. C., Marsh, E. M., Carson, G. A. & Langell, M. A. Cobalt oxide surface chemistry: the interaction of CoO (100), Co3O4 (110) and Co3O4 (111) with oxygen and water. J. Mol. Catal. A 281, 49-58 (2008). 19. Miles, M. H. Evaluation of electrocatalysts for water electrolysis in alkaline-solutions. J. Electroanal. Chem. 60, 89-96 (1975). 20. Singh, R. N., Koenig, J.-F., Poillerat & G., Chartier, P. Electrochemical studies on oxygen evolution. J. Electrochem. Soc., 137, 1408, (1990). 21. Liang, Y., Li, H. Wang, J. Zhou, J. Wang, T. Regier, et al., Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction, Nat. Mater.10, 780-786(2011). 22. Jiao, F. & Frei, H. Nanostructure manganese oxide clusters supported on mesoporous silica as efcient oxygen-evolving catalysts. Chem. Commun. 46, 29202922 (2010).

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23. Kanan, M.W., Surendranath, Y. & Nocera, D.G. Cobalt-phosphate oxygen evolving compound, Chem. Soc. Rev. 38, 109-114(2009). 24. Goodenough J.B., Challenges for rechargeable Li-ion batteries, Chem. Mater, 22, 587-603, (2010). 25. Gummow, R.J., Liles, D.C., Thackeray, M.M. Spinel versus layered structures for lithium cobalt oxide synthesised at 400C, Mat. Res. Bull, 3, 235-246 (1993). 26. Gummow, R.J., Thackeray, M.M., David, W. I. F & Hull, S. Structure and Electrochemistry of Lithium Cobalt Oxide Synthesised at 400C, Mat. Res. Bull., 27, 327-337 (1992). 27. Gummov, R. J. & Thackeray, M.M. Lithium-cobalt-nickel-oxide Cathode Materials Prepared at 400 Degrees C for Rechargeable Lithium Batteries, Solid State Ionics, 681, 53-56, (1992). 28. Rossen, E., Reimers, J. N., Dahn, J. R., Synthesis and electrochemistry of spinel LT-LiCoO2, Solid State Ionics 62,53-60 (1993). 29. Garcia, B., Barboux, P., Ribot, F., Kahn-Harari, A., Mazerolles, L., Baffier, N. The structure of low temperature crystallized LiCoO2 Solid State Ionics 86,111-118 (1995). 30. Garcia, B., Farcy, J., Pereira-Ramos, J.P., Baffier, N. Electrochemical properties of low temperature crystallized LiCoO2 J. Electrochem. Soc. 62, 1179-1184 (1997). 31. Thackeray, M., Baker, S., Adendorff, K., Goodenough, J. Lithium Insertion into Co3O4 : a Preliminary Investigation. Solid State Ionics 17, 175-181(1985). 32. Liang, Y., Li, H. Wang, J. Zhou, J. Wang, T. Regier, Dai, H., Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction, Nat. Mater. 10,780-786 (2011). 33. Chou, N.H.; Ross, P.N, Bell A.T.; Don Tilley, T. Comparison of cobalt-based nanoparticles as electrocatalysts for water oxidation. ChemSusChem, 11, 1566-1569 (2011). 34. McAlpin, J.G., Surendranath, Y., Dinc, M., Stich, T.A., Stoian, S.A., Casey, W.H., Nocera, D.G., Britt, R.D. EPR Evidence for Co (IV) Species Produced During Water Oxidation at Neutral pH. J. Am. Chem. Soc. 132, 6882-6883, (2010). 35. Rasiyah, P., & Tseung, A. C. C. The Role of the lower metal oxide/higher metal oxide couple in oxygen evolution reactions, J. Electrochem. Soc. 131, 803-808 (1984).

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36. Surendranath, Y., Kanan, M. W. & Nocera, D. G. Studies of the oxygen evolution reaction by a cobalt phosphate catalyst at neutral pH. J. Am. Chem. Soc. 132, 1650116509 (2010). 37. Wang, L.-P.; Van Voorhis, T. Direct-coupling O2 bond forming a pathway in cobalt oxide water oxidation, catalysts. J. Phys. Chem. Lett. 2, 22002204 (2011).

Acknowledgements Financial support by Author Contributions T.M. carried out the experimental work. A. M. supervised the research work and involved in the scientific discussions. Both participated in the preparation of the manuscript. Additional Information Competing financial interests: The authors declare no competing financial interests.

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Figure 1 XRD patterns of Co3O4, LT-LiCoO2 and HT-LiCoO2 catalysts. (a) The (222) reections in LT-LiCoO2 spinel splits into the hexagonal (0 0 6) and (0 1 2) reflections of the samples HT-LiCoO2, respectively and (b) an enlarged view of the (440) reections in LT-LiCoO2 splits in to hexagonal (1 0 8) and (1 1 0) reflections.

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Figure 2 | Electrochemical behaviour of catalyst. (a) Cyclic Voltammograms of Co3O4 (b) LT-LiCoO2 and (c) HT-LiCoO2 in 0.1M KOH at scan rate 20 mV/Sec.

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Figure 3 | Electrochemical Performance of catalysts. Linear sweep voltammograms of (a) LT-LiCoO2 nanorods (black line), (b) LT-LiCoO2 bulk (green line), (c) IrO2 nanoparticles (Red line), (d) Co3O4 nanorods and (e) HT-LiCoO2 bulk catalysts at a scan rate of 20 mV/s at 1600 rpm in 0.1M KOH at pH 13.The GC RDE electrodes were held under rotation at 1600 rpm during the course
of the experiment in order to effectively remove the bubbles formed during the OER. All activities are iRcorrected and normalized to the mass activity.

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Figure 4|SEM images of catalysts (a) LT-LiCoO2 prepared by solid state method and (b) LT-LiCoO2 nanorods by coprecipitation method (c) Co3O4 nanorods by co-precipitation method and (d) HT-LiCoO2 prepared by solid state method (Insets in are the enlarged pictures)

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Figure 5 | Mechanism of Water oxidation on Co4O4 cubane in LT-LiCoO2. Co3+/Co4+ redox couple is used as a hydrogen sink. The formation of O-O bond is assumed to occur between two Co=O moeities

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Figure 6 | Electrochemical stability of catalysts. (a) Chronoamperometry of the catalysts recorded at 1.7 V rotated at 1600 rpm in 0.1M KOH (pH 13) and (b) 0.1 M Phosphate buffer solution at (pH=7). More fluctuations observed at high pH than neutral pH in the current vs time profile arise from the formation of bubbles on the surface of the catalyst electrode.

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