Ti_(3)C_(2) MXene负载Cu基催化剂的草酸酯加氢制乙醇酸甲酯催化性能  

Catalytic performance of Cu-based catalyst supported on Ti_(3)C_(2) MXene for hydrogenation of dimethyl oxalate to methyl glycolate

作　　者：石晓丹 赵江涛 张雨[1] 艾培培 黄伟[1] SHI Xiaodan;ZHAO Jiangtao;ZHANG Yu;AI Peipei;HUANG Wei(State Key Laboratory of Clean and Efficient Coal Utilization,College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China)

机构地区：[1]太原理工大学化学与化工学院省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024

出　　处：《低碳化学与化工》2025年第3期47-57,共11页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金青年科学基金(22008166);山西省自然科学研究面上项目(202403021211029);山西省面上青年基金(201901D211047);山西省高等学校科技创新项目(2019L0185)。

摘　　要：乙醇酸甲酯(MG)作为生产可降解塑料聚乙醇酸的关键原料,具有广阔的市场空间和较高的经济价值。草酸二甲酯(DMO)加氢制MG是实现煤炭和天然气资源转化与增值利用的途径之一。但MG是DMO不饱和加氢的产物,现有催化剂难以实现其高效制备。Cu基催化剂虽在DMO加氢反应中应用广泛,但其更倾向于催化DMO深度加氢。选用二维层状Ti_(3)C_(2) MXene为载体,对其进行碱处理制备了alk-Ti_(3)C_(2) MXene,进而通过超声浸渍法制备了alk-Ti_(3)C_(2) MXene负载Cu基催化剂。结果表明,碱处理不仅可以增大载体的层间距(由1.02 nm增大至1.25 nm左右)和比表面积(由3.61 m^(2)/g增大至7.10 m^(2)/g以上),同时也能增加载体表面—OH数量,进而调控载体表面—OH和Cu物种之间的相互作用,最终影响Cu物种的粒径以及价态组成。NaOH处理后的Na-Ti_(3)C_(2) MXene载体负载Cu催化剂(Cu/Na-Ti_(3)C_(2) MXene)表现出良好的催化性能和稳定性,其MG收率高达60.63%(反应26 h),且230 h内未出现失活现象。相对适宜的Cu粒径(43.4 nm)、较高的n(Cu^(0))/n(Cu^(0)+Cu^(+))(71.17%)以及Cu物种与载体表面—OH间的强相互作用,使Cu/Na-Ti_(3)C_(2) MXene具有良好的催化性能和稳定性。Methyl glycolate(MG),as a key raw material for the production of degradable plastic polyethylene glycol acid,has broad market space and high economic value.Hydrogenation of dimethyl oxalate(DMO)to MG is one of the ways to realize the conversion and value-added utilization of coal and natural gas resources.However,MG is the product of unsaturated hydrogenation of DMO,and the existing catalysts are difficult to achieve its efficient preparation.Although Cu-based catalysts are widely used in DMO hydrogenation,they are more inclined to catalyze deep hydrogenation of DMO.Alk-Ti_(3)C_(2) MXene supports were prepared through alkali treatment using two-dimensional layered Ti_(3)C_(2) MXene as the support,and alk-Ti_(3)C_(2) MXene supported Cu-based catalyst was prepared by ultrasonic impregnation method.The results show that the alkali treatment can not only increase the interlayer spacing(from 1.02 nm to about 1.25 nm)and surface area of the supports(from 3.61 m^(2)/g to more than 7.10 m^(2)/g),but also increase the number of—OH on the support surface,thereby regulating the interaction between—OH on the support surface and Cu species,ultimately affecting the particle size and valence state composition of Cu species.It is worth mentioning that the Cu/Na-Ti_(3)C_(2) MXene catalyst supported on Na-Ti_(3)C_(2) MXene after NaOH treatment shows good catalytic performance and stability.The MG yield is up to 60.63%(reaction time of 26 h)and no deactivation occurs within 230 h.The relatively suitable Cu particle size(43.4 nm),high n(Cu^(0))/n(Cu^(0)+Cu^(+))(71.17%)and the strong interaction between Cu species and the surface—OH on the support together endow the Cu/Na-Ti_(3)C_(2) MXene catalyst with good catalytic performance and stability.

关 键 词：Ti_(3)C_(2)MXene 草酸二甲酯加氢 Cu基催化剂 乙醇酸甲酯 金属-载体相互作用 

分 类 号：TQ530.2[化学工程—煤化学工程]