在氟苯连接的苝二酰亚胺光催化下，纯水中CO选择性转化为CH 。

Selective conversion of CO to CH in pure water photocatalyzed by fluorobenzene-linked perylene diimide.

作者信息

Xiao Yin, Ding Guixiang, Tao Jiayu, Wang Zhaoqiang, Chen Zihe, Chen Lihui, Shuai Li, Liao Guangfu

机构信息

National Forestry and Grassland Administration Key Laboratory of Plant Fiber Functional Materials, College of Materials Engineering, Fujian Agriculture and Forestry University, Fuzhou, China.

出版信息

Nat Commun. 2025 Aug 12;16(1):7476. doi: 10.1038/s41467-025-62369-7.

DOI:10.1038/s41467-025-62369-7

PMID:40796900

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12343815/

Abstract

Photochemical CO conversion to valuable C products is desirable but challenging due to high C-C coupling barriers. This study constructs an acceptor-donor-acceptor type N, N'-bis(4-fluorophenyl) perylene-3,4,9,10-bis(dicarboximide)-supramolecular photocatalyst for efficiently and selectively photo-converting CO and water vapor into CH, achieving a high production rate of 124.84 μmol g h with 85% selectivity under continuous 50-hour illumination. The performance is mainly attributed to giant internal electric field induced by the incorporation of fluorobenzene into the perylene diimide framework, greatly enhancing the separation and transfer of photogenerated charges. Theoretical calculations further elucidate the critical role of fluorobenzene in lowering the activation energy of the reaction and promoting the formation of the key C-C coupling intermediate (*COCO). This work provides insight for the design of high-performance catalysts for CO photoreduction.

摘要

将光化学一氧化碳转化为有价值的碳产物是很有必要的，但由于碳-碳偶联障碍较高，这一过程具有挑战性。本研究构建了一种受体-供体-受体型N，N'-双（4-氟苯基）苝-3,4,9,10-双（二甲酰亚胺）超分子光催化剂，用于将一氧化碳和水蒸气高效且选择性地光转化为甲烷，在连续50小时光照下实现了124.84 μmol g⁻¹ h⁻¹的高产率以及85%的选择性。该性能主要归因于将氟苯引入苝二酰亚胺骨架所诱导的巨大内电场，极大地增强了光生电荷的分离和转移。理论计算进一步阐明了氟苯在降低反应活化能和促进关键碳-碳偶联中间体（*COCO）形成中的关键作用。这项工作为设计用于一氧化碳光还原的高性能催化剂提供了思路。