石油与天然气化工2026，Vol.55Issue(3)：37-51,15.DOI:10.3969/j.issn.1007-3426.2026.03.005
CuNP-TiO2-(OH)CNTs催化CO2电合成碳酸二甲酯
CuNP-TiO2-(OH)CNTs-catalyzed CO2 electrosynthesis of dimethyl carbonate
摘要
Abstract
Objective Although anatase TiO2 is known for its abundance and tunable defect structure,it is widely believed that its poor electrical conductivity and low selectivity for multi-carbon products limit its application in the electrocatalytic synthesis of multi-carbon products from CO2.To overcome this perceived limitation,this study successfully reconstructed TiO2 into an efficient composite system for the electrocatalytic synthesis of dimethyl carbonate(DMC)from CO2 through a strategy combining lattice regulation,interfacial electronic coupling,and carbon nanotube synergy.Method The lattice structure and oxygen vacancy concentration TiO2 were precisely controlled via heat treatment at 500℃,providing anchoring sites for small-sized copper clusters.Hydroxylated carbon nanotubes((OH)CNTS)were introduced to construct a three-dimensional conductive and mass transport network,synergistically optimizing electron transport and mass diffusion.Furthermore,the electronic metal-support interaction(EMSI)was induced via Cu-O-Ti interfacial coordination,forming Cu5+-OV-Ti3+electronic synergistic sites.Result Comprehensive characterizations including aberration-corrected electron microscopy,synchrotron-based XANES/EXAFS,and DFT calculations confirm that the EMSI effect not only reduces the formation energy barrier of the key CO2 reduction intermediate *COOH(from 2.36 eV to 2.05 eV)but also moderately weakens the adsorption strength of the methanol activation intermediate *OCH3(from 0.71 eV to 0.52 eV),achieving precise temporal matching of the multi-step reaction.Electrochemical tests demonstrate that under optimal conditions at-2.4 V(vs.Ag/AgCl),the Faradaic efficiency(FE)for DMC reaches 44.68％.After a 10-hour long-term cycling test,the performance retention exceeds 95％,with only 1.30％(by mass)copper leaching.Conclusion This work breaks the conventional perception regarding the application of TiO2-based catalysts in multi-carbon product synthesis and provides new insights for designing cost-effective copper-based catalysts and the valorization of CO2.关键词
CO2电还原/碳酸二甲酯/TiO2晶格调控/铜团簇/电子金属-载体相互作用/羟基化碳纳米管Key words
CO2 electroreduction/dimethyl carbonate/TiO2 lattice regulation/copper clusters/electronic metal-support interaction/hydroxylated carbon nanotubes引用本文复制引用
王有佳,王文超,安星宇,马欣,田博琛,田玉心,刘艳升,侯军伟..CuNP-TiO2-(OH)CNTs催化CO2电合成碳酸二甲酯[J].石油与天然气化工,2026,55(3):37-51,15.基金项目
国家自然科学基金"量子点修饰TiO2电极合成及催化处理新疆高砷地下水研究"(52360003),新疆维吾尔自治区天山英才基金"流动电极电容去离子技术耦合光电联合催化处理新疆化工废水技术研究"(2023TSYCJC0065) （52360003）
