物理化学学报2024，Vol.40Issue(4)：26-51,26.DOI:10.3866/PKU.WHXB202304003
基于碳化钼材料CO2加氢制备高附加值化学品的热催化研究进展
Review on Using Molybdenum Carbides for the Thermal Catalysis of CO2 Hydrogenation to Produce High-Value-Added Chemicals and Fuels
摘要
Abstract
CO2 hydrogenation is critical to producing high-value-added carbon-based chemicals and fuels to achieving both hydrogen energy storage and CO2 utilization.Examples of CO2 hydrogenation include methanation(Sabatier process)to produce methane,reverse water-gas shift reaction(RWGS)to generate CO,methanol synthesis for the methanol economy,and CO2 direct Fischer-Tropsch(CO2-FT)reaction to produce olefins.The precious metal catalysts used in these reactions are efficient but too expensive to be used on a large scale.Further,although some non-precious metal catalysts can be used for these hydrogenation reactions,they suffer from deactivation during long-term processes.Over the past few decades,molybdenum carbides,which are transition metal carbides(TMCs),have attracted significant attention owing to their low cost and similar catalytic performance to precious metal catalysts in CO2 hydrogenation reactions.Recently,two-dimensional molybdenum carbide MXenes have shown impressive activity in CO2 hydrogenation reactions.Owing to the presence of carbon,the MXene lattice is expanded;this leads to an increase in valence electrons and endows the two-dimensional molybdenum carbide-based catalyst with different properties than metallic Mo.The two-dimensional molybdenum carbide-based materials can be prepared by temperature-programmed carburization,selective etching,mechanical alloying synthesis,chemical vapor deposition,in situ thermal carburization,and solution-phase synthesis methods.Thus far,a host of studies have been performed on CO2 conversion with molybdenum carbide-based materials,which show promising activity during CO2 conversion and selectivity towards target products.Both α-MoC1-x and β-MoCy have shown outstanding thermocatalytic activity,product selectivity,and reaction stability during CO2 hydrogenation to CO at 300-600 ℃.In addition,molybdenum carbide-based materials were also found to be an interesting catalyst for direct CO2 Fischer-Tropsch synthesis.The application potential of the molybdenum carbide-based materials could be further tuned by changing the C/Mo ratio in the bulk molybdenum carbide,strengthening the interactions between molybdenum carbide and the supported metal,and tailoring the interface structure of the materials.However,the thermal catalytic CO2 conversion based on molybdenum carbide-based materials is still in its infancy.This paper summarizes the progress toward molybdenum carbide catalysis of CO2 hydrogenation process for producing high-value-added chemicals and fuels.Furthermore,the challenges and opportunities for molybdenum carbide materials as catalysts for CO2 hydrogenation are discussed to provide insights for future development in this emerging field.关键词
CO2加氢/碳化钼/热催化/异相催化/MXenesKey words
CO2 hydrogenation/Molybdenum carbide/Thermal catalysis/Heterogeneous catalysis/MXenes分类
化学引用本文复制引用
徐勇庆,Robert E. Przekop,Bogna Sztorch,Dariusz Brzakalski,周会,杨玉瑶,武孟娜,杨潇潇,别璇,张时语,李清海,张衍国,张宸伟..基于碳化钼材料CO2加氢制备高附加值化学品的热催化研究进展[J].物理化学学报,2024,40(4):26-51,26.基金项目
The project was supported by the National Natural Science Foundation of China(52276202,52206147),International Joint Mission On Climate Change and Carbon Neutrality,Tsinghua-Toyota Joint Research Fund,State Key Laboratory of Chemical Engineering,China(SKL-ChE-22A03),Huaneng Group Science and Technology Research Project,China(KTHT-U22YYJC12),and Tsinghua University-Shanxi Clean Energy Research Institute Innovation Project Seed Fund,China.国家自然科学基金(52276202,52206147),国际气候变化与碳中和联合基金,清华-丰田联合研究基金,化学工程国家重点实验室(SKL-ChE-22A03),华能集团科学技术研究项目(KTHT-U22YYJC12),清华大学山西省清洁能源研究院创新项目种子基金 （52276202,52206147）
