Wang Jie, Cai Jinmeng, Ren Kai-Xin, Liu Lin, Zheng Su-Jun, Wang Zhao-Yang, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Sci Adv. 2024 May 3;10(18):eadn7556. doi: 10.1126/sciadv.adn7556. Epub 2024 May 1.
Atomically precise metal nanoclusters (NCs) are emerging as idealized model catalysts for imprecise metal nanoparticles to unveil their structure-activity relationship. However, the directional synthesis of robust metal NCs with accessible catalytic active sites remains a great challenge. In this work, we achieved bulky carboranealkynyl-protected copper NCs, the monomer ·3PF and -carboranealkynyl bridged dimer ·4PF, with fair stability as well as accessible open metal sites step by step through external ligand shell modification and metal-core evolution. Both ·3PF and ·4PF demonstrate remarkable catalytic activity and selectivity in electrocatalytic nitrate (NO-) reduction to NH reaction, with the dimer ·4PF displaying superior performance. The mechanism of this catalytic reaction was elucidated through theoretical computations in conjunction with in situ FTIR spectra. This study not only provides strategies for accessing desired copper NC catalysts but also establishes a platform to uncover the structure-activity relationship of copper NCs.
原子精确的金属纳米团簇（NCs）正成为揭示非精确金属纳米颗粒结构-活性关系的理想模型催化剂。然而，定向合成具有可及催化活性位点的稳健金属纳米团簇仍然是一个巨大的挑战。在这项工作中，我们通过外部配体壳修饰和金属核演化逐步实现了具有适度稳定性以及可及开放金属位点的大体积碳硼烷炔基保护的铜纳米团簇，即单体·3PF和碳硼烷炔基桥联二聚体·4PF。·3PF和·4PF在电催化硝酸盐（NO₃⁻）还原为NH₃反应中均表现出显著的催化活性和选择性，二聚体·4PF展现出更优异的性能。通过理论计算结合原位傅里叶变换红外光谱阐明了该催化反应的机理。这项研究不仅提供了获得所需铜纳米团簇催化剂的策略，还建立了一个揭示铜纳米团簇结构-活性关系的平台。
