Regulating the Electronic Configuration of Ni Sites by Breaking Symmetry of Ni-Porphyrin to Facilitate CO2 Photocatalytic Reduction

Yuan Hui Zhong, Yang Wang, Sheng Yi Zhao, Ze Xiang Xie, Lai Hon Chung, Wei Ming Liao, Lin Yu, Wai Yeung Wong (Corresponding Author), Jun He (Corresponding Author)

Research output: Journal article publicationJournal articleAcademic researchpeer-review

11 Citations (Scopus)

Abstract

Adapting the coordination environment to influence the electronic configuration of active sites represents an efficient approach for improving the photocatalytic performance of the CO2 reduction reaction (CO2RR) but how to execute it precisely remains challenging. Herein, heteroatom-substitution in Ni-porphyrin to break the coordination symmetry of Ni center is proposed to be an effective solution. Based on this, two symmetry-breaking Ni-porphyrins, namely Ni(Cl)ON3Por and Ni(Cl)SN3Por, are designed and successfully prepared. By theoretical calculation, it is found that symmetry-breaking efficiently regulates the 3d orbital energy levels of Ni center. Furthermore, experimental and theoretical findings jointly revealed that coordination symmetry-breaking of Ni-porphyrins facilitates the generation of highly reactive NiI species during the catalytic process, effectively stabilizing and reducing the energy barrier of formation of the key *COOH intermediate. As a result, Ni(Cl)ON3Por and Ni(Cl)SN3Por gave CO production rates of 24.7 and 38.8 mmol g−1 h−1 as well as selectivity toward CO of 94.0% and 96.4%, respectively, outperforming that of symmetric NiN4Por (CO production rate of 6.6 mmol g−1 h−1 and selectivity of 82.8%). These findings offer microscopic insights into how to modulate the catalytic activity by precisely tuning the coordination environment of active sites and rational design of competent catalyst for CO2RR photocatalysis.

Original languageEnglish
Article number2316199
JournalAdvanced Functional Materials
Volume34
Issue number25
Early online date10 Feb 2024
DOIs
Publication statusPublished - 19 Jun 2024

Keywords

  • carbon dioxide reduction
  • electronic configuration regulation
  • heteroatom substituted porphyrin
  • photocatalysis
  • symmetry-breaking

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • General Chemistry
  • Biomaterials
  • General Materials Science
  • Condensed Matter Physics
  • Electrochemistry

Fingerprint

Dive into the research topics of 'Regulating the Electronic Configuration of Ni Sites by Breaking Symmetry of Ni-Porphyrin to Facilitate CO2 Photocatalytic Reduction'. Together they form a unique fingerprint.

Cite this