Single Zn Atoms with Acetate-Anion-Enabled Asymmetric Coordination for Efficient H2O2 Photosynthesis

Yunxiang Li, Yan Guo, Guilan Fan, Deyan Luan, Xiaojun Gu*, Xiong Wen (David) Lou*

*Corresponding author for this work

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

27 Citations (Scopus)
14 Downloads (CityUHK Scholars)

Abstract

Exploring unique single-atom sites capable of efficiently reducing O2 to H2O2 while being inert to H2O2 decomposition under light conditions is significant for H2O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single-Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single-Zn sites on CN, forming asymmetric Zn−N3O moiety on CN (denoted as CN/Zn−OAc), in contrast to the obtained Zn−N4 sites when sulfate (SO4) is adopted (CN/Zn−SO4). Both experimental and theoretical investigations demonstrate that the Zn−N3O moiety exhibits higher intrinsic activity for O2 reduction to H2O2 than the Zn−N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn−OAc catalyst exhibits significantly improved photocatalytic H2O2 production activity under visible light irradiation. © 2023 Wiley-VCH GmbH.
Original languageEnglish
Article numbere202317572
JournalAngewandte Chemie - International Edition
Volume63
Issue number8
Online published20 Dec 2023
DOIs
Publication statusPublished - 19 Feb 2024

Research Keywords

  • Asymmetric Coordination
  • H2O2 Photosynthesis
  • O2 Reduction
  • Photocatalysis
  • Single-Atom Catalysis

Publisher's Copyright Statement

  • COPYRIGHT TERMS OF DEPOSITED POSTPRINT FILE: This is the accepted version of the following article: Li, Y., Guo, Y., Fan, G., Luan, D., Gu, X., & Lou, X. W., (2024). Single Zn Atoms with Acetate-Anion-Enabled Asymmetric Coordination for Efficient H2O2 Photosynthesis. Angewandte Chemie - International Edition, 63(8), Article e202317572
  • which has been published in final form at https://doi.org/10.1002/anie.202317572. 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.

Fingerprint

Dive into the research topics of 'Single Zn Atoms with Acetate-Anion-Enabled Asymmetric Coordination for Efficient H2O2 Photosynthesis'. Together they form a unique fingerprint.

Cite this