Water oxidation catalysis

X-ray Crystal structure of the Mn4O5Ca core of the oxygen evolving complex of Photosystem II at a resolution of 1.9 Å.[1]

Water oxidation catalysis (WOC) is the acceleration (catalysis) of the conversion of water into oxygen and protons:

2 H2O → 4 H+ \+ 4 e− \+ O2

Many catalysts are effective, both homogeneous catalysts and heterogeneous catalysts. The oxygen evolving complex in photosynthesis is the premier example. There is no interest in generating oxygen by water oxidation since oxygen is readily obtained from air. Instead, interest in water oxidation is motivated by its relevance to water splitting, which would provide "solar hydrogen," i.e. water oxidation would generate the electrons and protons for the production of hydrogen.[2] An ideal WOC would operate rapidly at low overpotential, exhibit high stability and be of low cost, derived from nontoxic components.

## Contents

* 1 Mechanistic and energetic principles
* 2 Homogeneous catalysis
* 2.1 Ruthenium complexes
* 2.2 Cobalt and iron complexes
* 2.3 Iridium complexes
* 3 Heterogeneous catalysis
* 4 Additional reviews
* 5 References

## Mechanistic and energetic principles

Water is more difficult to oxidize than its conjugate base hydroxide. Hydroxide is stabilized by coordination to metal cations. Some metal hydroxides, those featuring redox-active metal centers, can be oxidized to give metal oxo complexes.[2][3] Attack of water on metal oxo centers represents one pathway for the formation of the O-O bond, leading to dioxygen. Alternatively, the crucial O-O bond forming step can arise by coupling suitably positioned pairs of metal hydroxo centers. The molecular mechanism of the OEC has not been elucidated.

The conversion of even metal hydroxo complexes to O2 requires very strong oxidants. In photosynthesis, such oxidants are provided by electron holes on porphyrin radical cations. For device applications, the aspirational oxidant is a photovoltaic material. For screening WOCs, ceric ammonium nitrate is a typical electron acceptor.

Solar panels are the aspirational power sources for driving water splitting, including water oxidation catalysis.

## Homogeneous catalysis

### Ruthenium complexes

A number of ruthenium-aqua complexes catalyze the oxidation of water. Most catalysts feature bipyridine and terpyridine ligands.[4][5][2] Catalysts containing pyridine-2-carboxylate exhibit rates (300 s−1) comparable to that of photosystem II.[6][7] Work in this area has ushered in many new polypyridyl ligands.[8][9]

The "blue dimer" {[Ru(bipyridine)2(OH2)]2O}4+ and two derivatives are catalysts (and intermediates) in water oxidation.[2]

### Cobalt and iron complexes

Early examples of cobalt-based WOCs suffered from instability.[10] A homogeneous WOC [Co(py)5(H2O)](ClO4)2[11] operates by a proton-coupled electron transfer to form a [CoIII\--OH]2+ species, which on further oxidation forms a CoIV intermediate. The intermediate formed reacts with water to liberate O2. The cobalt-polyoxometalate complex [Co4(H2O)2(α-PW9O34)2]10− is highly efficient WOC.[12]

Some iron complexes catalyze water oxidation. A water-soluble complex [Fe(OTf)2(Me2Pytacn)] (Pytacn=pyridine-substituted trimethyltriazacyclononane; OTf= triflate) is an efficient WOC. The concentration of the catalyst and the oxidant were found to be strongly affecting the oxidation process. Many related complexes with cis labile sites are active catalysts. Most complexes were found to undergo degradation in a few hours. Higher stability of the molecular catalyst may be achieved using robust clathrochelate ligands that stabilize high oxidation states of iron and prevent rapid degradation of the catalyst.[13] The number and stereochemistry of reactive coordination sites on Fe have been evaluated but few guidelines have emerged.[14]

### Iridium complexes

The complexes [Ir(ppy)2(OH2)2]+ (ppy = 2-phenylpyridine) exhibit high turnover numbers, but low catalytic rates. Replacing ppy with Cp* (C5Me5) results in increased catalytic activity but decreased the turnover number.[15] Water nucleophilic attack on Ir=O species was found to be responsible for the O2 formation.[16]

## Heterogeneous catalysis

Iridium oxide is a stable bulk WOC catalyst with low overpotential.[17]

Ni-based oxide film liberates oxygen in quasi-neutral conditions at an overpotential of ~425 mV and shows long lasting stability.[18] X-ray spectroscopy revealed the presence of di-μ-oxide bridging between NiIII/NiIV ions but no evidence of mono-μ-oxide bridging was found between the ions.[19] Similar structures can be found in Co-WOC films and Mn-WOC catalysts.[20][21]

Cobalt oxides (Co3O4) have been investigated to work on the same pattern as other cobalt salts.[22] Cobalt phosphates are also active WOCs at neutral pH.[23] Stable and highly active WOCs can be prepared by adsorbing CoII on silica nanoparticles.[24]

The spinel compounds are also very efficient in oxidizing water. When nanodimensional spinels are coated over the carbon materials hydrothermally, followed by a further reduction, can exhibit high efficiency in splitting the water electrochemically.[25][26]

## Additional reviews

* Balzani, V.; Credi, A.; Venturi, M., Photochemical Conversion of Solar Energy. ChemSusChem 2008, 1, 26–58.
* Sala, X.; Romero, I.; Rodríguez, M.; Escriche, L.; Llobet, A., Molecular Catalysts that Oxidize Water to Dioxygen. Angewandte Chemie International Edition 2009, 48, 2842–2852.
* Gratzel, M., Photoelectrochemical cells. Nature 2001, 414, 338–344.
* Eisenberg, R.; Gray, H. B., Preface on Making Oxygen. Inorganic Chemistry 2008, 47, 1697–1699.
* Sun, L.; Hammarstrom, L.; Akermark, B.; Styring, S., Towards artificial photosynthesis: ruthenium-manganese chemistry for energy production. Chemical Society Reviews 2001, 30, 36–49.
* Gust, D.; Moore, T. A.; Moore, A. L., Solar Fuels via Artificial Photosynthesis. Accounts of Chemical Research 2009, 42, 1890–1898.

## References

1. ↑ Umena, Yasufumi; Kawakami, Keisuke; Shen, Jian-Ren; Kamiya, Nobuo (May 2011). "Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å". Nature 473 (7345): 55–60. doi:10.1038/nature09913. PMID 21499260. Bibcode: 2011Natur.473...55U. http://ousar.lib.okayama-u.ac.jp/files/public/4/47455/20160528084139320094/Nature_473_55–60.pdf.
2. ↑ 2.0 2.1 2.2 2.3 Liu, F.; Concepcion, J. J.; Jurss, J. W.; Cardolaccia, T.; Templeton, J. L.; Meyer, T. J. (2008). "Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II.". Inorganic Chemistry 47 (6): 1727–1752. doi:10.1021/ic701249s. PMID 18330966.
3. ↑ Meyer, Thomas J. (1989). "Chemical Approaches to Artificial Potosynthesis". Accounts of Chemical Research 22 (5): 163–170. doi:10.1021/ar00161a001.
4. ↑ Wada, T.; Tsuge, K.; Tanaka, K. (2000). "Electrochemical Oxidation of Water to Dioxygen Catalyzed by the Oxidized Form of the Bis(ruthenium – hydroxo) Complex in H2O". Angewandte Chemie International Edition 39 (8): 1479–1482. doi:10.1002/(SICI)1521-3773(20000417)39:8<1479::AID-ANIE1479>3.0.CO;2-4. PMID 10777648.
5. ↑ Sens, C.; Romero, I.; Rodríguez, M.; Llobet, A.; Parella, T.; Benet-Buchholz, J. (2004). "A New Ru Complex Capable of Catalytically Oxidizing Water to Molecular Dioxygen". Journal of the American Chemical Society 126 (25): 7798–7799. doi:10.1021/ja0486824. PMID 15212526.
6. ↑ Duan, L.; Fischer, A.; Xu, Y.; Sun, L. (2009). "Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH]− Bridging Ligand as an Intermediate for Catalytic Water Oxidation". Journal of the American Chemical Society 131 (30): 10397–10399. doi:10.1021/ja9034686. PMID 19601625.
7. ↑ Duan, L.; Bozoglian, F.; Mandal, S.; Stewart, B.; Privalov, T.; Llobet, A.; Sun, L. (2012). "A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II". Nat. Chem. 4 (5): 418–423. doi:10.1038/nchem.1301. PMID 22522263. Bibcode: 2012NatCh...4..418D.
8. ↑ Zong, R.; Thummel, R. P. (2005). "A New Family of Ru Complexes for Water Oxidation". Journal of the American Chemical Society 127 (37): 12802–12803. doi:10.1021/ja054791m. PMID 16159265.
9. ↑ Zhang, G.; Zong, R.; Tseng, H.-W.; Thummel, R. P. (2008). "Ru(II) Complexes of Tetradentate Ligands Related to 2,9-Di(pyrid-2'-yl)-1,10-phenanthroline". Inorganic Chemistry 47 (3): 990–998. doi:10.1021/ic701798v. PMID 18183971. .
10. ↑ Brunschwig, B. S.; Chou, M. H.; Creutz, C.; Ghosh, P.; Sutin, N., Mechanisms of water oxidation to oxygen: cobalt(IV) as an intermediate in the aquocobalt(II)-catalyzed reaction. Journal of the American Chemical Society 1983, 105, 4832-4833.
11. ↑ Wasylenko, D. J.; Ganesamoorthy, C.; Borau-Garcia, J.; Berlinguette, C. P., Electrochemical evidence for catalytic water oxidation mediated by a high-valent cobalt complex. Chemical communications 2011, 47, 4249-4251.
12. ↑ Yin, Q.; Tan, J. M.; Besson, C.; Geletii, Y. V.; Musaev, D. G.; Kuznetsov, A. E.; Luo, Z.; Hardcastle, K. I.; Hill, C. L., A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals. Science 2010, 328, 342-345.
13. ↑ Fritsky, Igor O.; Berggren, Gustav; Sá, Jacinto; Mamedov, Fikret; D'Amario, Luca; Pavliuk, Mariia V.; Shylin, Sergii I. (2019-02-18). "Efficient visible light-driven water oxidation catalysed by an iron(IV) clathrochelate complex" (in en). Chemical Communications 55 (23): 3335–3338. doi:10.1039/C9CC00229D. ISSN 1364-548X. PMID 30801592.
14. ↑ Fillol, J. L.; Codolà, Z.; Garcia-Bosch, I.; Gómez, L.; Pla, J. J.; Costas, M., Efficient water oxidation catalysts based on readily available iron coordination complexes. Nat Chem 2011, 3, 807-813.
15. ↑ Hull, J. F.; Balcells, D.; Blakemore, J. D.; Incarvito, C. D.; Eisenstein, O.; Brudvig, G. W.; Crabtree, R. H. (2009). "Highly Active and Robust Cp* Iridium Complexes for Catalytic Water Oxidation". Journal of the American Chemical Society 131 (25): 8730–8731. doi:10.1021/ja901270f. PMID 19496565.
16. ↑ Blakemore, J. D.; Schley, N. D.; Balcells, D.; Hull, J. F.; Olack, G. W.; Incarvito, C. D.; Eisenstein, O.; Brudvig, G. W. et al. (2010). "Half-Sandwich Iridium Complexes for Homogeneous Water-Oxidation Catalysis". Journal of the American Chemical Society 132 (45): 16017–16029. doi:10.1021/ja104775j. PMID 20964386.
17. ↑ Youngblood, W. J.; Lee, S.-H. A.; Maeda, K.; Mallouk, T. E. (2009). "Visible Light Water Splitting Using Dye-Sensitized Oxide Semiconductors". Accounts of Chemical Research 42 (12): 1966–1973. doi:10.1021/ar9002398. PMID 19905000.
18. ↑ Dincă, M.; Surendranath, Y.; Nocera, D. G., Nickel-borate oxygen-evolving catalyst that functions under benign conditions. Proceedings of the National Academy of Sciences 2010, 107, 10337-10341.
19. ↑ Risch, M.; Klingan, K.; Heidkamp, J.; Ehrenberg, D.; Chernev, P.; Zaharieva, I.; Dau, H., Nickel-oxido structure of a water-oxidizing catalyst film. Chemical communications 2011, 47, 11912-11914.
20. ↑ Zaharieva, I.; Najafpour, M. M.; Wiechen, M.; Haumann, M.; Kurz, P.; Dau, H., Synthetic manganese–calcium oxides mimic the water-oxidizing complex of photosynthesis functionally and structurally. Energy & Environmental Science 2011, 4, 2400-2408.
21. ↑ Kanan, M. W.; Yano, J.; Surendranath, Y.; Dincă, M.; Yachandra, V. K.; Nocera, D. G., Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst Determined by in Situ X-ray Spectroscopy. Journal of the American Chemical Society 2010, 132, 13692-13701.
22. ↑ Harriman, A.; Pickering, I. J.; Thomas, J. M.; Christensen, P. A., Metal oxides as heterogeneous catalysts for oxygen evolution under photochemical conditions. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1988, 84, 2795-2806.
23. ↑ Matthew W. Kanan; Yogesh Surendranatha; Daniel G. Nocera (2009). "Cobalt–phosphate oxygen-evolving Compound". Chem. Soc. Rev. 38 (1): 109–114. doi:10.1039/B802885K. PMID 19088970.
24. ↑ Zidki, T.; Zhang, L.; Shafirovich, V.; Lymar, S. V. (2012). "Water Oxidation Catalyzed by Cobalt(II) Adsorbed on Silica Nanoparticles". Journal of the American Chemical Society 134 (35): 14275–14278. doi:10.1021/ja304030y. PMID 22913479.
25. ↑ P. Sahoo, J. Tan, Z.-M. Zhang, S. K. Singh, T.-B. Lu. Engineering Surface Structure of Binary/Ternary Ferrite nanoparticles as High Performance Electrocatalysts for Oxygen Evolution Reaction. ChemCatChem, 2018, 10, 1075. doi: 10.1002/cctc.201701790
26. ↑ J. Tan, P. Sahoo, J.-W. Wang, Y.-W. Hu, Z. Zhang, Z.-M. Zhang, T.-B. Lu, Highly efficient oxygen evolution electrocatalysts prepared by reduction-engraved ferrites on graphene oxide. Inorganic Chemistry Frontiers, 2018, 5, 310. doi: 10.1039/C7QI00681K

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