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Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4
Nature Catalysis ( IF 37.8 ) Pub Date : 2021-08-19 , DOI: 10.1038/s41929-021-00665-3
Jian Li 1 , Hongliang Huang 1 , Wenjuan Xue 1 , Xiaohui Song 1 , Chunrui Wu 1 , Lei Nie 1 , Yang Li 1 , Donghai Mei 1 , Chongli Zhong 1 , Kang Sun 2 , Chengyuan Liu 2 , Yang Pan 2 , Hai-Long Jiang 2
Affiliation  

Solar-light-driven reduction of CO2-to-CH4 is a complex process involving multiple elementary reactions and various by-products. Achieving high CH4 activity and selectivity therefore remain a significant challenge. Here we show a bioinspired photocatalyst with flexible dual-metal-site pairs (DMSPs), which exhibit dynamic self-adaptive behaviour to fit mutative C1 intermediates, achieving CO2-to-CH4 photoreduction. The Cu and Ni DMSPs in their respective single-site forms under flexible microenvironment are incorporated into a metal-organic framework (MOF) to afford MOF-808-CuNi. This dramatically boosts CH4 selectivity up to 99.4% (electron basis) and 97.5% (product basis), and results in a high production rate of 158.7 μmol g−1 h−1 with a sacrificial reagent. Density functional theory calculations reveal that the flexible self-adaptive DMSPs can stabilize various C1 intermediates in multistep elementary reactions, leading to highly selective CO2-to-CH4 process. This work demonstrates that efficient and selective heterogeneous catalytic processes can be achieved by stabilizing reaction intermediates via the self-adaptive DMSP mechanism.



中文翻译:

金属有机框架中的自适应双金属位点对用于选择性 CO2 光还原为 CH4

太阳光驱动的 CO 2还原为CH 4是一个复杂的过程,涉及多个基本反应和各种副产物。因此,实现高 CH 4活性和选择性仍然是一项重大挑战。在这里,我们展示了一种具有柔性双金属位点对 (DMSP) 的仿生光催化剂,它表现出动态自适应行为以适应突变的 C1 中间体,实现 CO 2到 CH 4的光还原。将柔性微环境下各自单点形式的 Cu 和 Ni DMSP 结合到金属有机框架 (MOF) 中,得到 MOF-808-CuNi。这极大地提高了 CH 4选择性高达 99.4%(基于电子)和 97.5%(基于产品),使用牺牲试剂产生 158.7 μmol g -1  h -1的高产率。密度泛函理论计算表明,柔性自适应DMSPs可以稳定多步基本反应中的各种C1中间体,从而实现高选择性的CO 2制CH 4过程。这项工作表明,通过自适应 DMSP 机制稳定反应中间体,可以实现高效和选择性的多相催化过程。

更新日期:2021-08-19
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