Ye Wenqiang, Wang Yuepeng, Ji Guipeng, Zhang Fengtao, Zhao Yanfei, Liu Zhimin
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Zhongguancun North First Street 2, 100190, Beijing, P. R. China.
School of Science, China University of Geosciences, 100083, Beijing, P. R. China.
ChemSusChem. 2022 Aug 19;15(16):e202200759. doi: 10.1002/cssc.202200759. Epub 2022 Jun 24.
Visible-light-driven CO photoreduction with H O to value-added chemicals in high efficiency and selectivity is significant but challenging. Herein, a series of carbazolic conjugated organic polymers (CB-COPs) with electron donor-acceptor (D-A) structures were prepared, which showed high efficiency for visible-light-driven photocatalytic reduction of CO with H O in a solid-gas mode, affording CO as the exclusive carbonaceous product. Especially, CB-COP-mpd derived from 3,5-di(9H-carbazol-9-yl)pyridine exhibited the highest CO evolution rate up to 191.46 μmol g h with a selectivity of 100 %. Mechanism studies showed that carbazolyl is a promising electron donor candidate for constructing CB-COPs with D-A structures, capable of improving the catalytic efficiency and suppressing H generation. The acceptor building block with excessive electron withdrawing capability was favorable to H O adsorption, thus resulting in the generation of H . This work provides new insights for designing COPs photocatalysts for CO photocatalytic reduction.
利用水将可见光驱动的一氧化碳光催化还原为高附加值化学品具有重要意义，但也具有挑战性。在此，制备了一系列具有电子供体-受体（D-A）结构的咔唑共轭有机聚合物（CB-COPs），它们在固-气模式下对可见光驱动的一氧化碳与水的光催化还原表现出高效率，以一氧化碳作为唯一的含碳产物。特别是，由3,5-二（9H-咔唑-9-基）吡啶衍生的CB-COP-mpd表现出高达191.46 μmol g⁻¹ h⁻¹的最高一氧化碳析出速率，选择性为100%。机理研究表明，咔唑基是构建具有D-A结构的CB-COPs的有前景的电子供体候选物，能够提高催化效率并抑制氢气生成。具有过度吸电子能力的受体结构单元有利于水的吸附，从而导致氢气的生成。这项工作为设计用于一氧化碳光催化还原的COPs光催化剂提供了新的见解。
