Multimetal oxyhydroxides have recently been reported that outperform noble metal catalysts for oxygen evolution reaction (OER). In such 3d-metal-based catalysts, the oxidation cycle of 3d metals has been posited to act as the OER thermodynamic-limiting process; however, further tuning of its energetics is challenging due to similarities among the electronic structures of neighbouring 3d metal modulators. Here we report a strategy to reprogram the Fe, Co and Ni oxidation cycles by incorporating high-valence transition-metal modulators X (X = W, Mo, Nb, Ta, Re and MoW). We use in situ and ex situ soft and hard X-ray absorption spectroscopies to characterize the oxidation transition in modulated NiFeX and FeCoX oxyhydroxide catalysts, and conclude that the lower OER overpotential is facilitated by the readier oxidation transition of 3d metals enabled by high-valence modulators. We report an ~17-fold mass activity enhancement compared with that for the OER catalysts widely employed in industrial water-splitting electrolysers.
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Zhang, J., Zhao, Z., Xia, Z. & Dai, L. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat. Nano. 10, 444–452 (2015).
Ng, J. W. D. et al. Gold-supported cerium-doped NiOx catalysts for water oxidation. Nat. Energy 1, 16053 (2016).
Liang, Y. et al. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 10, 780–786 (2011).
Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355, eaad4998 (2017).
Seitz, L. C. et al. A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science 353, 1011–1014 (2016).
Bergmann, A. et al. Unified structural motifs of the catalytically active state of Co(oxyhydr)oxides during the electrochemical oxygen evolution reaction. Nat. Catal. 1, 711–719 (2018).
Guan, J. et al. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nat. Catal. 1, 870–877 (2018).
Martin-Sabi, M. et al. Redox tuning the Weakley-type polyoxometalate archetype for the oxygen evolution reaction. Nat. Catal. 1, 208–213 (2018).
Roy, C. et al. Impact of nanoparticle size and lattice oxygen on water oxidation on NiFeOxHy. Nat. Catal. 1, 820–829 (2018).
Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).
Jouny, M., Luc, W. & Jiao, F. General Techno-Economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).
Galán-Mascarós, J. R. Water oxidation at electrodes modified with earth-abundant transition-metal catalysts. ChemElectroChem 2, 37–50 (2015).
Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012).
Roger, I., Shipman, M. A. & Symes, M. D. Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting. Nat. Rev. Chem. 1, 0003 (2017).
Fabbri, E. et al. Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting. Nat. Mater. 16, 925–931 (2017).
Zhang, B. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 352, 333–337 (2016).
Rosalbino, F., Delsante, S., Borzone, G. & Scavino, G. Electrocatalytic activity of crystalline Ni–Co–M (M = Cr, Mn, Cu) alloys on the oxygen evolution reaction in an alkaline environment. Int. J. Hydrog. Energy 38, 10170–10177 (2013).
Chen, J. Y. C., Miller, J. T., Gerken, J. B. & Stahl, S. S. Inverse spinel NiFeAlO4 as a highly active oxygen evolution electrocatalyst: promotion of activity by a redox-inert metal ion. Energy Environ. Sci. 7, 1382–1386 (2014).
Gerken, J. B., Shaner, S. E., Masse, R. C., Porubsky, N. J. & Stahl, S. S. A survey of diverse earth abundant oxygen evolution electrocatalysts showing enhanced activity from Ni-Fe oxides containing a third metal. Energy Environ. Sci. 7, 2376–2382 (2014).
Friebel, D. et al. Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. J. Am. Chem. Soc. 137, 1305–1313 (2015).
Bajdich, M., García-Mota, M., Vojvodic, A., Nørskov, J. K. & Bell, A. T. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water. J. Am. Chem. Soc. 135, 13521–13530 (2013).
Novák, M. et al. Primary oxide minerals in the system WO3–Nb2O5–TiO2–Fe2O3–FeO and their breakdown products from the pegmatite No. 3 at Dolní Bory-Hatě, Czech Republic. Eur. J. Mineral. 20, 487–499 (2008).
Kuepper, K. et al. Electronic and magnetic properties of highly ordered Sr2FeMoO6. Phys. Stat. Sol. (a) 201, 3252–3256 (2004).
Liu, X., Yang, W. & Liu, Z. Recent progress on synchrotron-based in-situ soft X-ray spectroscopy for energy materials. Adv. Mater. 26, 7710–7729 (2014).
de Groot, F. M. F. et al. 1s2p resonant inelastic X-ray scattering of iron oxides. J. Phys. Chem. B 109, 20751–20762 (2005).
Mitsui, T. in Magmas Under Pressure (eds Kono, Y. & Sanloup, C.) 179–210 (Elsevier, 2018).
Zheng, X. et al. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption. Nat. Chem. 10, 149–154 (2018).
Liu, P. F., Yang, S., Zheng, L. R., Zhang, B. & Yang, H. G. Mo6+ activated multimetal oxygen-evolving catalysts. Chem. Sci. 8, 3484–3488 (2017).
Liu, P. F., Yang, S., Zheng, L. R., Zhang, B. & Yang, H. G. Electrochemical etching of α-cobalt hydroxide for improvement of oxygen evolution reaction. J. Mater. Chem. A 4, 9578–9584 (2016).
Qiu, Z., Tai, C.-W., Niklasson, G. A. & Edvinsson, T. Direct observation of active catalyst surface phases and the effect of dynamic self-optimization in NiFe-layered double hydroxides for alkaline water splitting. Energy Environ. Sci. 12, 572–581 (2019).
Zhang, B. et al. High-valence metals improve OER performance by modulating 3d metal oxidation cycle energetics. Zenodo Digital Repository https://doi.org/10.5281/zenodo.4008830 (2020).
This work was supported by MOST (grant no. 2016YFA0203302), NSFC (grant nos. 21875042, 21634003 and 51573027), STCSM (grant nos. 16JC1400702 and 18QA1400800), SHMEC (grant no. 2017-01-07-00-07-E00062) and Yanchang Petroleum Group. This work was also supported by The Programme for Professor of Eastern Scholar at Shanghai Institutions of Higher Learning. This work was supported by the Ontario Research Fund—Research Excellence Program, NSERC and the CIFAR Bio-Inspired Solar Energy program. This work has also benefited from the use of the SGM beamlines at Canadian Light Source; the 1W1B and 4B9B beamlines at the Beijing Synchrotron Radiation Facility; the BL14W1, BL08U1-A beamline at Shanghai Synchrotron Radiation Facility; and the 44A beamline at Taiwan Photon Source (TPS). Mössbauer spectroscopy measurements were conducted at the Advanced Photon Source, a Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. We acknowledge the Paul Scherrer Institut, Villigen, Switzerland, for provision of synchrotron radiation beamtime at the beamline SuperXAS of the SLS and would like to thank M. Nachtegaal for assistance. We thank M. García-Melchor and Y. Zhang for discussions on DFT calculations. We thank J. Wu for the assistance with the TEM measurements. We thank R. Wolowiec and D. Kopilovic for their assistance. For computer time, this research used the resources of the Supercomputing Laboratory at KAUST.
The authors declare no competing interests.
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Zhang, B., Wang, L., Cao, Z. et al. High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics. Nat Catal (2020). https://doi.org/10.1038/s41929-020-00525-6