Zhang Yu-Xiao, Zhang Shengbo, Huang Helai, Liu Xiaolong, Li Beibei, Lee Yiyang, Wang Xingdong, Bai Yun, Sun Mingze, Wu Yanfen, Gong Shuyan, Liu Xiangwen, Zhuang Zhongbin, Tan Ting, Niu Zhiqiang
State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
Laboratory of Theoretical and Computational Nanoscience, CAS Key Laboratory of Nanophotonic Materials and Devices, National Center for Nanoscience and Technology, Chinese Academy of Sciences, Beijing 100190, China.
J Am Chem Soc. 2023 Mar 1;145(8):4819-4827. doi: 10.1021/jacs.2c13886. Epub 2023 Feb 15.
Heterogeneous catalysts containing diatomic sites are often hypothesized to have distinctive reactivity due to synergistic effects, but there are limited approaches that enable the convenient production of diatomic catalysts (DACs) with diverse metal combinations. Here, we present a general synthetic strategy for constructing a DAC library across a wide spectrum of homonuclear (Fe, Co, Ni, Cu, Mn, and Pd) and heteronuclear (Fe-Cu, Fe-Ni, Cu-Mn, and Cu-Co) bimetal centers. This strategy is based on an encapsulation-pyrolysis approach, wherein a porous material-encapsulated macrocyclic complex mediates the structure of DACs by preserving the main body of the molecular framework during pyrolysis. We take the oxygen reduction reaction (ORR) as an example to show that this DAC library can provide great opportunities for electrocatalyst development by unlocking an unconventional reaction pathway. Among all investigated sites, Fe-Cu diatomic sites possess exceptional high durability for ORR because the Fe-Cu pairs can steer elementary steps in the catalytic cycle and suppress the troublesome Fenton-like reactions.
含有双原子位点的多相催化剂通常被认为由于协同效应而具有独特的反应活性，但能够方便地制备具有多种金属组合的双原子催化剂（DACs）的方法有限。在此，我们提出了一种通用的合成策略，用于构建一个跨越广泛的同核（铁、钴、镍、铜、锰和钯）和异核（铁 - 铜、铁 - 镍、铜 - 锰和铜 - 钴）双金属中心的DAC库。该策略基于一种封装 - 热解方法，其中一种多孔材料封装的大环配合物通过在热解过程中保留分子框架的主体来介导DACs的结构。我们以氧还原反应（ORR）为例，表明这个DAC库可以通过开启一条非常规的反应途径为电催化剂的开发提供巨大机遇。在所有研究的位点中，铁 - 铜双原子位点对ORR具有极高的耐久性，因为铁 - 铜对可以引导催化循环中的基元步骤并抑制麻烦的类芬顿反应。
