MOF‐derived 1D/3D N‐doped porous carbon for spatially confined electrochemical CO_(2) reduction to adjustable syngas  

作　　者：Wei Zhang Hui Li Daming Feng Chenglin Wu Chenghua Sun Baohua Jia Xue Liu Tianyi Ma 

机构地区：[1]Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials,Institute of Clean Energy Chemistry,College of Chemistry,Liaoning University,Shenyang,Liaoning,China [2]School of Science,RMIT University,Melbourne,Victoria,Australia [3]School of Pharmaceutical and Chemical Engineering,Taizhou University,Taizhou,Zhejiang,China [4]Department of Chemistry and Biotechnology,Swinburne University of Technology,Hawthorn,Victoria,Australia

出　　处：《Carbon Energy》2024年第8期1-13,共13页碳能源（英文）

基　　金：National Natural Science Foundation of China,Grant/Award Numbers:51873085,52071171,52202248;The Australian Government through the Cooperative Research Centres Projects,Grant/Award Number:CRCPⅩⅢ000077;Linkage Project,Grant/Award Numbers:LP210100467,LP210200345,LP210200504,LP220100088;Natural Science Foundation of Liaoning Province‐Outstanding Youth Foundation,Grant/Award Number:2022‐YQ‐14;Discovery Project,Grant/Award Number:DP220100603;China Scholarship Council(CSC Scholarship),Grant/Award Number:202006800009;Liaoning Revitalization Talents Program,Grant/Award Number:XLYC2007056;Australian Research Council(ARC)through Future Fellowship,Grant/Award Numbers:FT210100298,FT210100806;Shenyang Science and Technology Project,Grant/Award Number:21‐108‐9‐04;Industrial Transformation Training Centre schemes,Grant/Award Number:IC180100005;Natural Science Foundation of Liaoning Province,Grant/Award Number:2020‐MS‐137;Key Research Project of Department of Education of Liaoning Province,Grant/Award Number:LJKZZ20220015;Liaoning BaiQianWan Talents Program,Grant/Award Number:LNBQW2018B0048。

摘　　要：Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.

关 键 词：electrochemical CO_(2)reduction reaction melamine sponge metal‐organic frameworks porous carbon SYNGAS 

分 类 号：O646[理学—物理化学]