Liu Xiaolin, Liu Chenxi, Song Xiaojuan, Ding Xu, Wang Hailong, Yu Baoqiu, Liu Heyuan, Han Bin, Li Xiyou, Jiang Jianzhuang
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering University of Science and Technology Beijing Beijing 100083 China
School of Materials Science and Engineering China University of Petroleum (East China) Qingdao 266580 China
Chem Sci. 2023 Aug 10;14(34):9086-9094. doi: 10.1039/d3sc01816d. eCollection 2023 Aug 30.
Herein, we introduce a comprehensive study of the photophysical behaviors and CO reduction electrocatalytic properties of a series of cofacial porphyrin organic cages (CPOC-M, M = H, Co(ii), Ni(ii), Cu(ii), Zn(ii)), which are constructed by the covalent-bonded self-assembly of 5,10,15,20-tetrakis(4-formylphenyl)porphyrin (TFPP) and chiral (2-aminocyclohexyl)-1,4,5,8-naphthalenetetraformyl diimide (ANDI), followed by post-synthetic metalation. Electronic coupling between the TFPP donor and naphthalene-1,4 : 5,8-bis(dicarboximide) (NDI) acceptor in the metal-free cage is revealed to be very weak by UV-vis spectroscopic, electrochemical, and theoretical investigations. Photoexcitation of CPOC-H, as well as its post-synthetic Zn and Co counterparts, leads to fast energy transfer from the triplet state porphyrin to the NDI unit according to the femtosecond transient absorption spectroscopic results. In addition, CPOC-Co enables much better electrocatalytic activity for CO reduction reaction than the other metallic CPOC-M (M = Ni(ii), Cu(ii), Zn(ii)) and monomeric porphyrin cobalt compartment, supplying a partial current density of 18.0 mA cm at -0.90 V with 90% faradaic efficiency of CO.
在此，我们介绍了一系列共面卟啉有机笼（CPOC-M，M = H、Co(ii)、Ni(ii)、Cu(ii)、Zn(ii)）的光物理行为和CO还原电催化性能的综合研究。这些有机笼是通过5,10,15,20-四(4-甲酰基苯基)卟啉（TFPP）和手性(2-氨基环己基)-1,4,5,8-萘四甲酰二亚胺（ANDI）的共价键自组装构建而成，随后进行后合成金属化。通过紫外-可见光谱、电化学和理论研究表明，无金属笼中TFPP供体和萘-1,4 : 5,8-双(二甲酰亚胺)（NDI）受体之间的电子耦合非常弱。飞秒瞬态吸收光谱结果表明，CPOC-H及其后合成的Zn和Co对应物的光激发导致三重态卟啉向NDI单元的快速能量转移。此外，与其他金属CPOC-M（M = Ni(ii)、Cu(ii)、Zn(ii)）和单体卟啉钴隔室相比，CPOC-Co对CO还原反应具有更好的电催化活性，在-0.90 V时提供18.0 mA cm的分电流密度，CO的法拉第效率为90%。
