Li Panjie, Chen Weibin, Yang Yong, Shen Jinyou
School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China.
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China.
ACS Appl Mater Interfaces. 2023 Aug 30;15(34):40519-40528. doi: 10.1021/acsami.3c07609. Epub 2023 Aug 21.
CO photoconversion to syngas with superb selectivity is a splendid and bright option to achieve environmental improvement, energy substitution, and industrial needs. Herein, a series of Ni-porphyrin covalent organic polymers (COPs) interspersed with furan and thiophene using a mixed-blocks-engineering strategy, named as OS-Ni COPs ( and refer to the relative amounts of furan and thiophene blocks, respectively), are synthesized for photocatalytic CO-to-syngas. Ni-coordinated porphyrin cores prefer to act as mediators of CO-to-CO photoconversion because of the higher adsorption capacity of CO. Ni-free porphyrins work mainly as active sites of H photoevolution. Furthermore, introducing different amounts of furan and thiophene modulates jointly the electronic structure of Ni-porphyrin COPs and optimizes the conduction band alignment. The above controllable variables achieve a wonderful syngas (CO/H) ratio range from 2:1.06 to 1:1.04 for the Fischer-Tropsch process within common industrial reactions. Notably, the COP of the OS-Ni COPs exhibits excellent photocatalytic CO-to-syngas activity under visible light, with a syngas yield of 8442.5 μmol g h (CO/H = 1:1.02) and an apparent quantum efficiency (AQE) of 1.92% at 450 nm. This strategy would provide a significance path to design functional and efficient organic semiconductors.
将一氧化碳光催化转化为合成气并具有超高选择性，是实现环境改善、能源替代和工业需求的一个出色且光明的选择。在此，采用混合嵌段工程策略合成了一系列穿插有呋喃和噻吩的镍卟啉共价有机聚合物（COPs），命名为OS-Ni COPs（ 和 分别指呋喃和噻吩嵌段的相对含量），用于光催化一氧化碳转化为合成气。由于一氧化碳具有较高的吸附能力，镍配位的卟啉核更倾向于作为一氧化碳到一氧化碳光催化转化的媒介。无镍卟啉主要作为析氢的活性位点。此外，引入不同量的呋喃和噻吩共同调节了镍卟啉COPs的电子结构，并优化了导带排列。上述可控变量在常见工业反应中实现了费托合成过程中合成气（CO/H）的比例范围为2:1.06至1:1.04。值得注意的是，OS-Ni COPs中的COP在可见光下表现出优异的光催化一氧化碳转化为合成气的活性，合成气产率为8442.5 μmol g h（CO/H = 1:1.02），在450 nm处的表观量子效率（AQE）为1.92%。该策略将为设计功能高效的有机半导体提供一条重要途径。
