Zhang Mengrui, Zhang Dan, Jing Xu, Xu Baijie, Duan Chunying
School of Chemistry, Dalian University of Technology, Dalian, 116024, China.
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, China.
Angew Chem Int Ed Engl. 2024 Apr 24;63(18):e202402755. doi: 10.1002/anie.202402755. Epub 2024 Mar 27.
Selective photoreduction of CO to multicarbon products, is an important but challenging task, due to high CO activation barriers and insufficient catalytic sites for C-C coupling. Herein, a defect engineering strategy for incorporating copper sites into the connected nodes of defective metal-organic framework UiO-66-NH for selective overall photo-reduction of CO into acetone. The Cu site in well-modified CuNO units served as a trapping site to capture electrons via efficient electron-hole separation, forming the active Cu site for CO reduction. Two NH groups in CuNO unit adsorb CO and cooperated with copper ion to functionalize as a triple atom catalytic site, each interacting with one CO molecule to strengthen the binding of *CO intermediate to the catalytic site. The deoxygenated *CO attached to the Cu site interacted with CH fixed at one amino group to form the key intermediate CO-CH, which interacted with the third reduction intermediate on another amino group to produce acetone. Our photocatalyst realizes efficient overall CO reduction to C product acetone CHCOCH with an evolution rate of 70.9 μmol g h and a selectivity up to 97 % without any adducts, offering a promising avenue for designing triple-atomic sites to producing C product from photosynthesis with water.
将CO选择性光还原为多碳产物是一项重要但具有挑战性的任务，这是由于CO的高活化能垒以及用于C-C偶联的催化位点不足。在此，我们提出了一种缺陷工程策略，即将铜位点引入缺陷金属有机框架UiO-66-NH的连接节点中，以实现将CO选择性地整体光还原为丙酮。经过良好修饰的CuNO单元中的Cu位点作为捕获位点，通过有效的电子-空穴分离来捕获电子，形成用于CO还原的活性Cu位点。CuNO单元中的两个NH基团吸附CO，并与铜离子协同作用，作为三原子催化位点发挥功能，每个NH基团与一个CO分子相互作用，以增强CO中间体与催化位点的结合。附着在Cu位点上的脱氧CO与固定在一个氨基上的CH相互作用，形成关键中间体CO-CH，该中间体与另一个氨基上的第三个还原中间体相互作用，从而生成丙酮。我们的光催化剂实现了将CO高效整体还原为C产物丙酮CH₃COCH₃，产率为70.9 μmol g⁻¹ h⁻¹，选择性高达97%，且无需任何添加剂，为设计三原子位点以利用水通过光合作用生产C产物提供了一条有前景的途径。
