Pd/FeOx催化剂动态生成Pd^δ+⁃Fe^2+界面高效催化逆水煤气变换反应  

Dynamic Formation of Pd^δ+⁃Fe^2+Interface Promoting Reverse Water Gas Shift Reaction over Pd/FeOx Catalyst

作　　者：张殿宇 刘放 杜鹏飞 李梦维 吴兆萱 丰义兵 赵阳 徐晓燕 张新星 路军岭 杨冰 ZHANG Dian-Yu;LIU Fang;DU Peng-Fei;LI Meng-Wei;WU Zhao-Xuan;FENG Yi-Bing;ZHAO Yang;XU Xiao-Yan;ZHANG Xin-Xing;LU Jun-Ling;YANG Bing(Dalian National Laboratory for Clean Energy(DNL),Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,Liaoning 116023,China;University of Chinese Academy of Sciences,Beijing 100049,China;Department of Chemical Physics,University of Science and Technology of China,Hefei 230026,China;Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201210,China;Department of Chemistry,the University of Chicago,Chicago,IL 60637,United States)

机构地区：[1]洁净能源国家实验室,大连化学物理研究所,大连116023 [2]中国科学院大学,北京100049 [3]中国科学技术大学化学物理系,合肥230026 [4]中国科学院,上海高等研究院,上海201210 [5]芝加哥大学化学系,美国芝加哥IL 60637

出　　处：《无机化学学报》2021年第1期140-150,共11页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21673215,21872145);中国科学院洁净能源创新研究院合作基金(No.DNL201907);大连化物所创新研究基金(No.DICP I201943)资助。

摘　　要：通过一系列原位、非原位表征,包括透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)、程序升温解吸/还原/氧化(TPD/TPR/TPO)、X射线光电子能谱(XPS)等,系统地研究了Pd/FeOx催化剂的逆水煤气变换反应(RWGS)。以Pd(acac)2为前驱体合成了高度分散的Pd/FeOx催化剂,在400℃下,RWGS的CO2转化率高达29%,CO选择性超过98%,在目前文献中报道的催化剂中处于领先水平。通过原位表征方法,我们进一步研究了Pd/SiO2和Pd-Fe/SiO2,并明确指出了Pd-FeOx界面对促进RWGS反应的重要作用。准原位XPS实验进一步揭示了Pd/FeOx界面上动态形成的Pd^δ+-Fe^2+物种是高效催化C=O离解的活性位点。因此,实验结果证明,反应过程中动态形成的Pd^δ+-Fe^2+界面可以显著提高RWGS的活性和选择性,对CO2吸附、C=O解离和CO脱附都起到的促进作用。We systematically investigated Pd/FeOx for the reverse water gas shift(RWGS)reaction using a combination of ex situ and in situ characterizations,including transmission electron microscopy(TEM),Fourier-transform infrared(FTIR)spectroscopy,temperature-programmed desorption/reduction/oxidation(TPD/TPR/TPO),and X-ray photoelectron spectroscopy(XPS).A highly dispersed Pd/FeOx catalyst was synthesized using Pd(acac)2 as the precursor.The catalyst exhibited high activity,with CO2 conversion of~29%and CO selectivity ogreater than 98%at 400℃,which are among the highest values in the literature.Moreover,Pd/SiO2 and Pd-Fe/SiO2 were further studied to determine the significant role of the Pd-FeOx interface in promoting the RWGS reaction.Semi-in situ XPS revealed the dynamic formation of Pd^δ+-Fe^2+species at the Pd-FeOx interface;the species acted as highly active sites for CO2 dissociation.Our results also showed the formation of the Pd^δ+-Fe^2+interface during the RWGS reaction remarkably enhanced the activity and selectivity of the Pd-FeOx catalyst for the reaction,benefiting CO2 adsorption,C=O dissociation,and CO desorption.

关 键 词：钯 二氧化碳 界面 反应机理 多相催化 

分 类 号：O643.31[理学—物理化学]