Qiu Xuan, Chen Jianmin, Zou Xinwei, Fang Ruiqi, Chen Liyu, Chen Zhijie, Shen Kui, Li Yingwei
State Key Laboratory of Pulp and Paper Engineering , School of Chemistry and Chemical Engineering , South China University of Technology , Guangzhou 510640 , China . Email:
Chem Sci. 2018 Sep 26;9(48):8962-8968. doi: 10.1039/c8sc03549k. eCollection 2018 Dec 28.
Fabrication and modification of few-atom metal clusters and even single atoms in the pores of porous materials for catalysis are highly desired from an atom-efficiency aspect but remain a great challenge. Herein, we propose a facile and efficient strategy for the encapsulation of C-N-decorated Pd sub-nanoclusters (MSNCs)/single atoms (SAs) into MOFs by the confined thermolysis of Pd-based metal-organic polyhedra (MOPs) in MOF pores. The obtained hybrids contained both Pd MSNCs (∼0.8 nm) and Pd SAs, which were stabilized by the formed C-N fragments and the confinement effect of MOF pores. Benefiting from the highly exposed Pd atoms and synergistic effect between Pd and C-N fragments, these catalysts exhibited extremely high catalytic activity and stability in various important chemical processes, making them comparable to the most active Pd-based catalysts reported in the literature even under milder reaction conditions. Considering the high tunability of MOPs, this proposed strategy might provide a new toolbox for enriching the family of decorated MSNC/SA catalysts.
从原子效率的角度来看，在多孔材料的孔中制备和修饰用于催化的少原子金属簇甚至单原子是非常有必要的，但这仍然是一个巨大的挑战。在此，我们提出了一种简便高效的策略，通过在MOF孔中对基于钯的金属有机多面体（MOP）进行受限热解，将C-N修饰的钯亚纳米簇（MSNCs）/单原子（SAs）封装到MOF中。所得到的杂化物同时包含钯MSNCs（约0.8纳米）和钯SAs，它们通过形成的C-N片段和MOF孔的限域效应得以稳定。受益于高度暴露的钯原子以及钯与C-N片段之间的协同效应，这些催化剂在各种重要的化学过程中表现出极高的催化活性和稳定性，甚至在更温和的反应条件下，其性能也可与文献中报道的最具活性的钯基催化剂相媲美。考虑到MOP的高度可调控性，这种提出的策略可能为丰富修饰的MSNC/SA催化剂家族提供一个新的工具箱。
