Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/165542
Title: Porphyrin-based covalent organic frameworks anchoring Au single atoms for photocatalytic nitrogen fixation
Authors: He, Ting
Zhao, Zhanfeng
Liu, Ruoyang
Liu, Xinyan
Ni, Bing
Wei, Yanping
Wu, Yinglong
Yuan, Wei
Peng, Hongjie
Jiang, Zhongyi
Zhao, Yanli
Keywords: Science::Chemistry
Issue Date: 2023
Source: He, T., Zhao, Z., Liu, R., Liu, X., Ni, B., Wei, Y., Wu, Y., Yuan, W., Peng, H., Jiang, Z. & Zhao, Y. (2023). Porphyrin-based covalent organic frameworks anchoring Au single atoms for photocatalytic nitrogen fixation. Journal of the American Chemical Society, 145(11), 6057-6066. https://dx.doi.org/10.1021/jacs.2c10233
Project: RG3/21 
MOE2019-T2-2-049 
MOET2EP10120-0003 
M21K2c0105 
Journal: Journal of the American Chemical Society 
Abstract: The development of efficient photocatalysts for N2 fixation to produce NH3 under ambient conditions remains a great challenge. Since covalent organic frameworks (COFs) possess predesignable chemical structures, good crystallinity, and high porosity, it is highly significant to explore their potential for photocatalytic nitrogen conversion. Herein, we report a series of isostructural porphyrin-based COFs loaded with Au single atoms (COFX–Au, X = 1–5) for photocatalytic N2 fixation. The porphyrin building blocks act as the docking sites to immobilize Au single atoms as well as light-harvesting antennae. The microenvironment of the Au catalytic center is precisely tuned by controlling the functional groups at the proximal and distal positions of porphyrin units. As a result, COF1–Au decorated with strong electron-withdrawing groups exhibits a high activity toward NH3 production with rates of 333.0 ± 22.4 μmol g–1 h–1 and 37.0 ± 2.5 mmol gAu–1 h–1, which are 2.8- and 171-fold higher than that of COF4–Au decorated with electron-donating functional groups and a porphyrin–Au molecular catalyst, respectively. The NH3 production rates could be further increased to 427.9 ± 18.7 μmol g–1 h–1 and 61.1 ± 2.7 mmol gAu–1 h–1 under the catalysis of COF5–Au featuring two different kinds of strong electron-withdrawing groups. The structure–activity relationship analysis reveals that the introduction of electron-withdrawing groups facilitates the separation and transportation of photogenerated electrons within the entire framework. This work manifests that the structures and optoelectronic properties of COF-based photocatalysts can be finely tuned through a rational predesign at the molecular level, thus leading to superior NH3 evolution.
URI: https://hdl.handle.net/10356/165542
ISSN: 0002-7863
DOI: 10.1021/jacs.2c10233
Schools: School of Chemistry, Chemical Engineering and Biotechnology 
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © 2023 American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.2c10233.
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:CCEB Journal Articles

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