Porous poly(triazine-heptazine)s:low-temperature solvothermal synthesis,^(*)HCO intermediate activation and photocatalytic CO_(2)reduction to CH_(4)  

作　　者：Zhu Gao Zhiwei Jiang Min Liu Yumin Yang Shahzad Ali Qiujian Xie Yuqiang Li Shuai Gu Younian Liu Juntao Tang Chunyue Pan Jiayin Yuan Guipeng Yu 

机构地区：[1]Department of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China [2]Hunan Joint International Research Center for Carbon Dioxide Resource Utilization,School of Physics and Electronics,Central South University,Changsha 410083,China [3]State Key Laboratory of Superlattices and Microstructures,Institute of Semiconductors,Chinese Academy of Sciences,Beijing 100083,China [4]Department of Materials and Environmental Chemistry,Stockholm University,Stockholm SE-10691,Sweden

出　　处：《Science China Chemistry》2025年第3期1099-1106,共8页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China (52173212 and 52103275);Hunan Province Funds for Distinguished Young Scientists (2022JJ10080);financial support from the European Research Council (ERC)Consolidator (PARIS-101043485);the Swedish Research Council (2022-04533);the Wallenberg Academy Fellow Program (KAW 2017.0166)from the Knut&Alice Wallenberg Foundation in Sweden;the Olle Engkvists Foundation (213-0206)in Sweden。

摘　　要：High-temperature ionothermal synthesis has been proven effective in preparing environment-friendly carbon nitride(CN)-based photocatalysts in either triazine or heptazine form for CO_(2)reduction reaction(CO_(2)RR).However,such a process is usually energy-intensive and suffers from partial carbonization that results in non-porous catalysts and degenerating their activities.Herein,we report the preparation of highly porous CN polymers(porous C_(6)N_(7),C_3N_3,C_(4.5)N_5)through a low-temperature solvothermal polymerization of cyameluric chloride itself or cyanuric chloride itself,or both,respectively.As such,it avoids unfavorable carbonization and allows for fine control of its chemical structure and significantly enlarged surface area(up to 669 m^(2)g^(-1)).The pincer-like 2,2′-bipyridine sites of porous C_(6)N_(7)alter the photocatalytic CO_(2)reduction pathways via stabilizing the^(*)HCO intermediates,which promotes further hydrogenation to produce CH_(4)in a high selectivity.Benefiting from the carbonization-free polymerization,high porosity,and^(*)HCO intermediate activation,porous C_(6)N_(7)gave a superior CO_(2)RR to CH_(4)performance(17.18μmol g^(-1)h^(-1))as well as high stability(5 successive cycles),outperforming the bulk and state-of-the-art counterparts of CN.This opens an avenue for the rational construction of efficient porous CN-based photocatalytic systems,demonstrating their great potential in energy conversion reactions.

关 键 词：porous organic polymer HEPTAZINE photocatalysis CO_(2)reduction methane 

分 类 号：TQ221.11[化学工程—有机化工] O643.36[理学—物理化学] O644.1[理学—化学]