New Strategy for Cluster-Based Covalent Organic Framework: Thermally Induced Covalent Crosslinking of Highly Stable Copper Clusters.

IF 14.1 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Jian-Peng Dong, Yue Xu, Ling Yao, Le Wang, Gang Li, Rui Wang, Shuang-Quan Zang
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Abstract

Copper nanoclusters (Cu NCs) have emerged as a remarkable class of CO2 reduction reaction catalysts that are distinguished by their unparalleled reactivity, but effectively modulating the transport pathway of charge carriers between Cu NCs by feasible chemical means is still challenging. Herein, a thermally induced covalent crosslinking strategy is proposed to modulate the fast electron transport pathway formed between clusters. A copper-sulfur-nitrogen cluster [Cu4(SN)4] (denoted Cu4SN) is first synthesized; subsequently, the SN ligands in Cu4SN are coupled covalently via a thermally induced covalent crosslinking strategy to yield CC-Cu4SN, which exhibits enhanced conductivity and photocarrier transport. As expected, CC-Cu4SN shows a high photocatalytic CO production rate of 29.98 µmol g-1 h-1 with ≈99.5% selectivity in CO2 reduction with H2O as sacrificial agents, which is more than 10 times superior to that observed with Cu4SN. Systematic experiments and density functional theory calculations reveal that the covalent crosslinks between clusters accelerate the dynamic transfer of photoexcited charge carriers, increase the light utilization ability, favor CO2 adsorption and *COOH generation, thereby accounting for the increased CO2 photoreduction activity. This work presents a novel thermally induced internal covalent crosslinking strategy for synthesizing novel cluster-based covalent polymers with enhanced stability and catalytic activity.

基于团簇的共价有机骨架的新策略:高稳定铜团簇的热诱导共价交联。
铜纳米簇(Cu NCs)以其无与伦比的反应活性而成为一类引人注目的CO2还原反应催化剂,但通过可行的化学手段有效调节Cu纳米簇之间载流子的运输途径仍然是一个挑战。本文提出了一种热诱导共价交联策略来调节团簇之间形成的快速电子传递途径。首次合成了铜-硫-氮团簇[Cu4(SN)4](记为Cu4SN);随后,通过热诱导的共价交联策略,将Cu4SN中的SN配体共价偶联得到CC-Cu4SN,其电导率和光载流子输运能力增强。结果表明,CC-Cu4SN光催化CO产率为29.98µmol g-1 h-1,以H2O为牺牲剂还原CO2的选择性为99.5%,比Cu4SN高10倍以上。系统实验和密度泛函理论计算表明,团簇间的共价交联加速了光激发载流子的动态转移,提高了光利用能力,有利于CO2的吸附和*COOH的生成,从而解释了CO2光还原活性的增加。本工作提出了一种新的热诱导内共价交联策略,用于合成具有增强稳定性和催化活性的新型簇基共价聚合物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Advanced Science
Advanced Science CHEMISTRY, MULTIDISCIPLINARYNANOSCIENCE &-NANOSCIENCE & NANOTECHNOLOGY
CiteScore
18.90
自引率
2.60%
发文量
1602
审稿时长
1.9 months
期刊介绍: Advanced Science is a prestigious open access journal that focuses on interdisciplinary research in materials science, physics, chemistry, medical and life sciences, and engineering. The journal aims to promote cutting-edge research by employing a rigorous and impartial review process. It is committed to presenting research articles with the highest quality production standards, ensuring maximum accessibility of top scientific findings. With its vibrant and innovative publication platform, Advanced Science seeks to revolutionize the dissemination and organization of scientific knowledge.
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