文献类型：期刊文献

英文题名：Engineering the Mo site in Ce-doped MoO3-ZrO2 for enhanced CO2-assisted propane dehydrogenation

作者：Kuang, Weiwei Zhang, Xinxin Qin, Qianqiu Zou, Yu Wang, Keliang Li, Ziwei Liu, Fei Li, Min

第一作者：Kuang, Weiwei

通信作者：Li, ZW[1];Liu, F[1];Li, M[1]

机构：[1]Guizhou Univ, Sch Chem & Chem Engn, Guizhou Prov Key Lab Green Chem & Clean Energy Tec, Guiyang 550025, Peoples R China;[2]Guizhou Inst Technol, Sch Civil Engn, Guiyang 550003, Peoples R China;[3]Moutai Inst, Sch Brewing Engn, Renhuai 564507, Peoples R China

第一机构：Guizhou Univ, Sch Chem & Chem Engn, Guizhou Prov Key Lab Green Chem & Clean Energy Tec, Guiyang 550025, Peoples R China

通信机构：corresponding author), Guizhou Univ, Sch Chem & Chem Engn, Guizhou Prov Key Lab Green Chem & Clean Energy Tec, Guiyang 550025, Peoples R China.

年份：2026

卷号：462

外文期刊名：JOURNAL OF CATALYSIS

收录：;EI(收录号：20263121237724);Scopus(收录号：2-s2.0-105046331325);WOS:【SCI-EXPANDED(收录号:WOS:001843779900001)】；

基金：This work was supported by National Natural Science Foundation of China (22279024, 22168013) , China; Natural Science Foundation of Guizhou (QiankehejichuMS [2025] 185) , China; Young Top Talents Program of Science and Technology of Guizhou Province (Qianjiaoji [2024] 315) , China; SRT project of Guizhou University (2023SRT197) , China;.

语种：英文

外文关键词：Coordination environment; Configuration and electron state of Mo; MvK mechanism coupled with PDH-RWGS; mechanism; CO(2)oxidative C3H8 dehydrogenation; CO2 activation

摘要：CO2 oxidative dehydrogenation of propane (CO2-ODHP) is a promising technology for propylene production and CO2 utilization, yet it demands efficient catalysts for CO2 activation. Herein, MoCeZrOx catalysts with tunable Mo coordination were designed by varying the Ce/Zr ratio. With increasing Ce/Zr ratio, the Mo site evolves from electron-rich tetrahedral-pyramidal (tp-Mo) to electron-deficient octahedral coordination (oh-Mo), as confirmed from Raman and X-ray absorption spectroscopy (XAS). The optimized 1M3C6Z catalyst features moderate electron density on tp-Mo, which creates suitable acidity and enhances CO2 activation and C-H bond cleavage. It achieves stable performance over 4 cycles, maintaining 25% C3H8 conversion and 89% C3H6 selectivity after regeneration. Both the Mars-van-Krevelen (MvK) and the coupled propane dehydrogenation-reverse water-gas shift (PDH-RWGS) mechanisms occurred over the 1M3C6Z catalyst, evidenced by 18O-isotopic TPSR-QMS, in situ DRIFTS measurements, and DFT calculations. Interestingly, 1M3C6Z catalyst greatly promoted PDH-RWGS mechanism compared with MvK mechanism evidenced by the significantly lower Gibbs free energy. This study provides new insights into the coupling of structural and electronic effects in the modification of oxide catalysts by tailoring the coordination environment of Mo for the rational design of high-efficiency CO2ODHP catalysts.