Engineering Single Ni Sites on 3D Cage-like Cucurbit[n]uril Ligands for Efficient and Selective CO2 Photocatalytic Reduction

Jingyi Wang, Xiyi Li*, Chia Hao Chang, Tianyu Zhang, Xuze Guan, Qiong Liu, Liquan Zhang, Ping Wen, Ivan Tang, Yuewen Zhang, Xiaofeng Yang, Junwang Tang*, Yang Lan*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Solar-driven CO2 selective reduction with high conversion is a challenging task yet holds immense promise for both CO2 neutralization and green fuel production. Enhancing CO2 adsorption at the catalytic centre can trigger a highly efficient CO2 capture-to-conversion process. Herein, we introduce cucurbit[n]urils (CB[n]), a new family of molecular ligands, as a key component in the creation of a 3D cage-like metal (nickel, Ni)-complex molecular co-catalyst (CB[7]-Ni) for photocatalysis. It exhibits an unprecedented CO yield rate of 72.1 μmol ⋅ h−1 with a high selectivity of 97.9 % under visible light irradiation. To verify the origin of the carbon source in the products, a straightforward isotopic tracing method is designed based on tandem reactions. The catalytic process commences with photoelectron transfer from Ru(bpy)32+ to the Ni2+ site, resulting in the reduction of Ni2+ to Ni+. The locally enriched CO2 molecules in the cage ligand CB[7] undergo selective reduction by the Ni+ nearby to form CO product. This work exemplifies the inspiring potential of ligand structure engineering in advancing the development of efficient unanchored molecular co-catalysts.

Original languageEnglish
Article numbere202417384
JournalAngewandte Chemie - International Edition
DOIs
Publication statusE-pub ahead of print - 28 Oct 2024

Bibliographical note

Publisher Copyright:
© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Funding

We are thankful for the experimental platform provided by UCL Centre for Nature-Inspired Engineering. Y.L. and X.L. acknowledge the financial support of the CNIE Inspiration Grants. J.W. acknowledges financial support from H. Walter Stern studentship. Y.L. acknowledges the financial support from the Royal Society (RGS\R2\202203). P.W. and Y. Z. thank the Natural Science Foundation of Gansu Province, China (21JR7RA462) and the National Natural Science Foundation of China (No. 22204065). Q.L. acknowledge the financial support of the National Natural Science Foundation of China (22309032) and the Guangdong Basic and Applied Basic Research Foundation (2022A1515011737). The authors appreciate the great help from Dr Han Wu and Dr Barry Reid in CNIE research group in the Department of Chemical Engineering at UCL for instrument (FTIR) operations, Prof McArthur at UCL Earth Sciences for the assistance of ICP test, Dr Kersti Karu in the Department of Chemistry at UCL for the assistance of mass spectroscopy and Mr Bryan White for the advice on gas chromatography.

FundersFunder number
CNIE Inspiration Grant
H. Walter Stern studentshipRGS\R2\202203
Royal Society21JR7RA462
Natural Science Foundation of Gansu Province, China22309032
National Natural Science Foundation of China2022A1515011737
Guangdong Basic and Applied Basic Research Foundation

    Keywords

    • 3D ligand
    • CO reduction
    • Cucurbit[n]uril
    • molecular co-catalyst
    • photocatalysis

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