Dong Jian-Peng, Xu Yue, Yao Ling, Wang Le, Li Gang, Wang Rui, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, P. R. China.
College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang, 473061, P. R. China.
Adv Sci (Weinh). 2025 Sep;12(35):e07510. doi: 10.1002/advs.202507510. Epub 2025 Jul 30.
Copper nanoclusters (Cu NCs) have emerged as a remarkable class of CO 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 [Cu(SN)] (denoted CuSN) is first synthesized; subsequently, the SN ligands in CuSN are coupled covalently via a thermally induced covalent crosslinking strategy to yield CC-CuSN, which exhibits enhanced conductivity and photocarrier transport. As expected, CC-CuSN shows a high photocatalytic CO production rate of 29.98 µmol g h with ≈99.5% selectivity in CO reduction with HO as sacrificial agents, which is more than 10 times superior to that observed with CuSN. 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 CO adsorption and COOH generation, thereby accounting for the increased CO 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.
铜纳米团簇（Cu NCs）已成为一类卓越的一氧化碳还原反应催化剂，其以无与伦比的反应活性著称，但通过可行的化学方法有效调控电荷载流子在Cu NCs之间的传输途径仍然具有挑战性。在此，提出了一种热诱导共价交联策略来调控团簇之间形成的快速电子传输途径。首先合成了一种铜 - 硫 - 氮团簇[Cu(SN)]（记为CuSN）；随后，通过热诱导共价交联策略使CuSN中的SN配体共价偶联，得到CC - CuSN，其表现出增强的导电性和光载流子传输能力。正如预期的那样，以HO作为牺牲剂进行一氧化碳还原时，CC - CuSN显示出29.98 µmol g h的高光催化一氧化碳产率，对一氧化碳的选择性约为99.5%，这比CuSN的产率高出10倍以上。系统实验和密度泛函理论计算表明，团簇之间的共价交联加速了光激发电荷载流子的动态转移，提高了光利用能力，有利于一氧化碳吸附和羧基生成，从而解释了一氧化碳光还原活性的提高。这项工作提出了一种新颖的热诱导内部共价交联策略，用于合成具有增强稳定性和催化活性的新型基于团簇的共价聚合物。
