Synergistic Bifunctional Covalent Organic Framework for Efficient Photocatalytic CO2 Reduction and Water Oxidation

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Qiang Xu, Jingwei Han, Fengkun Tian, Xue Zhao, Jiaxin Rong, Jing Zhang, Ping She, Jun-Sheng Qin and Heng Rao*, 
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Abstract

The scientific community has been actively researching artificial photosynthesis to promote ecologically sustainable living and address environmental issues. However, designing photocatalysts with active sites that are effective for both CO2 reduction and water oxidation remains a significant challenge. Thus, we present the development of a donor–acceptor covalent organic framework (D–A COF), that integrates two distinct metal coordination environments through structure–activity relationships. Either cobalt or nickel ion is anchored on the D–A COF backbone to create N-metal–nitrogen and N-metal–sulfur coordination configurations, serving as bifunctional reduction and oxidation active sites, respectively. Remarkably, the as-synthesized Co-Btt-Bpy COF generated CO at a rate of 9,800 μmol g–1 h–1 and O2 at 242 μmol g–1 h–1 under visible light irradiation. The CO generation rate was 127 times higher than that of pristine D–A COF. More importantly, Co-Btt-Bpy COF facilitates artificial photosynthesis with a CO release rate of 7.4 μmol g–1 h–1. The outstanding photocatalytic performance can be attributed to the synergistic interaction between the dispersed single-atom sites and Btt-Bpy COF, as well as the rapid migration of photogenerated electrons. In situ attenuated total reflection Fourier transform infrared (ATR FT-IR) spectra and theoretical calculations indicated that introducing Co sites effectively lowered the reaction energy barriers for the crucial intermediates *COOH and *OH. This work provides state-of-the-art designs of photocatalysts at the molecular level and in-depth insights for efficient artificial photosynthesis.

Abstract Image

高效光催化CO2还原和水氧化的协同双功能共价有机框架
科学界一直在积极研究人工光合作用,以促进生态可持续生活和解决环境问题。然而,设计具有有效的二氧化碳还原和水氧化活性位点的光催化剂仍然是一个重大挑战。因此,我们提出了一种供体-受体共价有机框架(D-A - COF)的发展,它通过结构-活性关系集成了两种不同的金属配位环境。钴离子或镍离子被锚定在D-A - COF主链上,形成n -金属-氮和n -金属-硫配位构型,分别作为双功能还原和氧化活性位点。在可见光照射下,CO - btt - bpy COF的CO生成速率为9800 μmol g-1 h-1, O2生成速率为242 μmol g-1 h-1。CO生成速率是原始D-A COF的127倍。更重要的是,CO - btt - bpy COF有利于人工光合作用,CO释放速率为7.4 μmol g-1 h-1。优异的光催化性能可归因于分散的单原子位与Btt-Bpy COF之间的协同相互作用,以及光电子的快速迁移。原位衰减全反射傅里叶变换红外(ATR FT-IR)光谱和理论计算表明,引入Co位有效降低了关键中间体*COOH和*OH的反应能垒。这项工作在分子水平上提供了最先进的光催化剂设计,并深入了解了有效的人工光合作用。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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