The dynamic catalysis of Ga/ZSM-5 catalysts for propane-CO_(2) coupling conversion to aromatics and syngas  

作　　者：Yonggui Song Zhong-Pan Hu Haohao Feng Enze Chen Le Lv Yimo Wu Zhen Liu Yong Jiang Xiaozhi Su Feifei Xu Mingchang Zhu Jingfeng Han Yingxu Wei Svetlana Mintova Zhongmin Liu 

机构地区：[1]The Key Laboratory of the Inorganic Molecule-Based Chemistry of Liaoning Province and Laboratory of Coordination Chemistry,Shenyang University of Chemical Technology,Shenyang110142,Liaoning,China [2]National Engineering Research Center of Lower-Carbon Catalysis Technology,Dalian National Laboratory for Clean Energy,iChEM(Collaborative Innovation Center of Chemistry for Energy Materials),Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China [3]Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201203,China [4]Normandie University,Laboratory of Catalysis and Spectrochemistry(LCS),NSICAEN,UNICAEN,CNRS,Caen 1450,France

出　　处：《Journal of Energy Chemistry》2024年第10期513-519,I0011,共8页能源化学（英文版）

基　　金：supported by the National Key Research and Development Program of China (No.2022YFE0116000);the National Natural Science Foundation of China (No.22288101,21991092,21991090,22202193,and 22172166);the Youth Innovation Promotion Association CAS (2021182);the Innovation Research Foundation of Dalian Institute of Chemical Physics,Chinese Academy of Sciences (DICP I202429 and I202217)。

摘　　要：Alkane coupling with CO_(2) by metal-containing zeolites catalysis is found to be a promising way to produce aromatics and syngas in recent years,but the real active sites and the role of CO_(2) are still unclear owing to the quick evolution of the metallic active sites and the complex reaction processes including direct propane aromatization,CO_(2) hydrogenation,reverse water-gas shift reaction,and propane-CO_(2) coupling aromatization.Herein,Ga/ZSM-5 catalysts were constructed to study the dynamic evolution of the metallic active sites and the role of CO_(2) during the propane and CO_(2) coupling reaction.After optimizing the reaction conditions,a notable propane conversion rate of 97.9%and an impressive aromatics selectivity of 80.6%in hydrocarbons can be achieved at the conditions of 550℃and CO_(2)/C_(3)H_(8) of 4.^(13)CO_(2)isotope experiments illustrate that C-atoms of CO_(2) can enter into CO(86.5%)and aromatics(10.8%)during the propane-CO_(2) coupling reaction process.In situ XANES and FTIR spectroscopies at 550℃and H_(2)/C_(3)H_(8) atmosphere reveal that GaO_(x) species can be gradually dispersed into[GaH_(2)]^(+)/[GaH]^(2+)on the Bronsted acid sites of ZSM-5 zeolite during H_(2) and/or C_(3)H_(8) treatment,which are the real active sites for propane-CO_(2) coupling conversion.In situ CO_(2)-FTIR experiments demonstrate that the[GaH_(2)]^(+)/[GaH]^(2+)species can react with CO_(2) and accelerate the propane and CO_(2) coupling process.This work not only presents a cost-effective avenue for CO_(2) utilization,but also contributes to the active site design for improved alkane and CO_(2) activation in coupling reaction system.

关 键 词：Carbon dioxide Propane aromatization Ga/ZSM-5 Gallium hydride Spectroscopy 

分 类 号：TQ426[化学工程] O621.251[理学—有机化学]