Yan Fang-Qin, Dong Xiao-Yu, Wang Yi-Man, Wang Qian-You, Wang Shan, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Adv Sci (Weinh). 2024 Jun;11(23):e2401508. doi: 10.1002/advs.202401508. Epub 2024 Mar 15.
3D porous organic frameworks, which possess the advantages of high surface area and abundant exposed active sites, are considered ideal platforms to accommodate single atoms (SAs) and metal nanoclusters (NCs) in high-performance catalysts; however, very little research has been conducted in this field. In the present work, a 3D porous organic framework containing Ni SAs and Ni NCs is prepared through the metal-assisted one-pot polycondensation of tetraaldehyde and hexaaminotriptycene. The single metal sites and metal clusters confined in the 3D space created a favorable micro-environment that facilitated the activation of chemically inert CO molecules, thus promoting the overall photoconversion efficiency and selectivity of CO reduction. The 3D-NiSAs/NiNCs-POPs, as a CO photoreduction catalyst, demonstrated an exceptional CO production rate of 6.24 mmol g h, high selectivity of 98%, and excellent stability. The theoretical calculations uncovered that asymmetrical interaction between Ni SAs and Ni NCs not only favored the bending of CO molecules and reducing the CO reduction energy, but also regulated the electronic structure of the catalyst leading to the optimal binding strength of intermediates.
三维多孔有机框架具有高比表面积和丰富暴露活性位点的优势，被认为是在高性能催化剂中容纳单原子（SAs）和金属纳米团簇（NCs）的理想平台；然而，该领域的研究非常少。在本工作中，通过四醛和六氨基三蝶烯的金属辅助一锅法缩聚制备了一种包含镍单原子和镍纳米团簇的三维多孔有机框架。限制在三维空间中的单金属位点和金属簇创造了一个有利的微环境，促进了化学惰性的一氧化碳分子的活化，从而提高了一氧化碳还原的整体光转换效率和选择性。作为一氧化碳光还原催化剂的三维镍单原子/镍纳米团簇-多孔有机聚合物表现出6.24 mmol g h的优异一氧化碳产率、98%的高选择性和出色的稳定性。理论计算表明，镍单原子和镍纳米团簇之间的不对称相互作用不仅有利于一氧化碳分子的弯曲并降低一氧化碳还原能，还调节了催化剂的电子结构，导致中间体具有最佳的结合强度。
