Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation

Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation

Advanced Materials

10.1002/adma.202207041

https://doi.org/10.1002/adma.202207041

Tianze Wu, Yuanmiao Sun, Xiao Ren, Jiarui Wang, Jiajia Song, Yangdan Pan, Yongbiao Mu, Jianshuo Zhang, Qiuzhen Cheng, Guoyu Xian, Shibo Xi, Chengmin Shen, Hong‐Jun Gao, Adrian C. Fisher, Matthew P. Sherburne, Yonghua Du, Joel W. Ager, Jose Gracia, Haitao Yang, Lin Zeng, Zhichuan J. Xu

25 October 2022

Wu, T., Sun, Y., Ren, X., Wang, J., Song, J., Pan, Y., Mu, Y., Zhang, J., Cheng, Q., Xian, G., Xi, S., Shen, C., Gao, H., Fisher, A. C., Sherburne, M. P., Du, Y., Ager, J. W., Gracia, J., Yang, H., … Xu, Z. J. (2022). Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation. Advanced Materials, 35(2). Portico. https://doi.org/10.1002/adma.202207041

Water electrolysis is a promising technique for carbon neutral hydrogen production. A great challenge remains at developing robust and low‐cost anode catalysts. Many pre‐catalysts are found to undergo surface reconstruction to give high intrinsic activity in the oxygen evolution reaction (OER). The reconstructed oxyhydroxides on the surface are active species and most of them outperform directly synthesized oxyhydroxides. The reason for the high intrinsic activity remains to be explored. Here, a study is reported to showcase the unique reconstruction behaviors of a pre‐catalyst, thiospinel CoFe2S4, and its reconstruction chemistry for a high OER activity. The reconstruction of CoFe2S4 gives a mixture with both Fe–S component and active oxyhydroxide (Co(Fe)OxHy) because Co is more inclined to reconstruct as oxyhydroxide, while the Fe is more stable in Fe–S component in a major form of Fe3S4. The interface spin channel is demonstrated in the reconstructed CoFe2S4, which optimizes the energetics of OER steps on Co(Fe)OxHy species and facilitates the spin sensitive electron transfer to reduce the kinetic barrier of O–O coupling. The advantage is also demonstrated in a membrane electrode assembly (MEA) electrolyzer. This work introduces the feasibility of engineering the reconstruction chemistry of the precatalyst for high performance and durable MEA electrolyzers.

Publisher Copyright

This research / project is supported by the Agency for Science, Technology and Research (A*STAR) - Low Carbon Energy Research Finding Initiative (LCERFI01-0033 | U2102d2006).
Grant Reference no. : U2102d2006

This research / project is supported by the Singapore Ministry of Education - Academic Research Fund Tier 2
Grant Reference no. : MOE-T2EP10220-0001

This research / project is supported by the Singapore National Research Foundation - Campus for Research Excellence and Technological Enterprise (CREATE) programme
Grant Reference no. :

This is the peer reviewed version of the following article: Wu, T., Sun, Y., Ren, X., Wang, J., Song, J., Pan, Y., Mu, Y., Zhang, J., Cheng, Q., Xian, G., Xi, S., Shen, C., Gao, H., Fisher, A. C., Sherburne, M. P., Du, Y., Ager, J. W., Gracia, J., Yang, H., … Xu, Z. J. (2022). Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation. Advanced Materials, 35(2). Portico. , which has been published in final form at https://doi.org/10.1002/adma.202207041. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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