TY - JOUR
T1 - Transition metal oxide manipulating ZrO2-based non-precious metal catalysts for enhanced CO2-mediated oxidative dehydrogenation of propane
AU - Ma, Zelin
AU - Wang, Fang
AU - Zhao, Luomeng
AU - Ma, Zhuangzhuang
AU - Zhao, Weihao
AU - Wang, Shiyuan
AU - Yazhou, Shuang
AU - Wang, Jiulong
AU - Jian, Jie
AU - Guo, Pengfei
AU - Wang, Hongqiang
N1 - Publisher Copyright:
© 2025 Society of Chemical Industry (SCI).
PY - 2025
Y1 - 2025
N2 - BACKGROUND: Developing highly stable and cost-effective catalysts for CO2-mediated oxidative dehydrogenation of propane (CO2-ODP) is critical to advancing sustainable propylene production. While ZrO2-based supports offer promising thermal stability and tunable acid–base properties, integrating transition metal oxides (TMOx) as active sites to optimize CO2 activation and propane conversion remains underexplored. RESULTS: Here, we systematically design a series of non-precious metal TMOx/ZrO2 catalysts (TM = Cr, Fe, Co, Ni, Cu, Zn) via a coprecipitation–gel method to uncover structure–activity relationships. Among them, CrOx/ZrO2 emerges as the optimal candidate, achieving notable C3H8/CO2 conversions of 46.24%/38.27% and 86.49%/27.03% C3H6 selectivity/yield at 600 °C. Characterization reveals that the coexistence of Cr3+/Cr4+ species (XPS) and mixed-phase Cr2O3/CrO2 (XRD/Raman) creates abundant oxygen vacancies and enhances CO2 adsorption (TPD), while HRTEM/EDX confirms uniform CrOx dispersion on ZrO2. Further optimizing the Cr/Zr ratio to 1:1 maximizes active site exposure while preventing excessive aggregation, thereby balancing redox activity and structural stability. CONCLUSIONS: This work elucidates how tailored TMOx/ZrO2 interfaces leverage synergistic electronic and geometric effects to drive CO2-ODP efficiency, offering a blueprint for designing high-performance non-precious metal catalysts for alkane valorization.
AB - BACKGROUND: Developing highly stable and cost-effective catalysts for CO2-mediated oxidative dehydrogenation of propane (CO2-ODP) is critical to advancing sustainable propylene production. While ZrO2-based supports offer promising thermal stability and tunable acid–base properties, integrating transition metal oxides (TMOx) as active sites to optimize CO2 activation and propane conversion remains underexplored. RESULTS: Here, we systematically design a series of non-precious metal TMOx/ZrO2 catalysts (TM = Cr, Fe, Co, Ni, Cu, Zn) via a coprecipitation–gel method to uncover structure–activity relationships. Among them, CrOx/ZrO2 emerges as the optimal candidate, achieving notable C3H8/CO2 conversions of 46.24%/38.27% and 86.49%/27.03% C3H6 selectivity/yield at 600 °C. Characterization reveals that the coexistence of Cr3+/Cr4+ species (XPS) and mixed-phase Cr2O3/CrO2 (XRD/Raman) creates abundant oxygen vacancies and enhances CO2 adsorption (TPD), while HRTEM/EDX confirms uniform CrOx dispersion on ZrO2. Further optimizing the Cr/Zr ratio to 1:1 maximizes active site exposure while preventing excessive aggregation, thereby balancing redox activity and structural stability. CONCLUSIONS: This work elucidates how tailored TMOx/ZrO2 interfaces leverage synergistic electronic and geometric effects to drive CO2-ODP efficiency, offering a blueprint for designing high-performance non-precious metal catalysts for alkane valorization.
KW - CO-ODP
KW - precious metal-free catalysts
KW - transition metal oxides
KW - ZrO support
UR - http://www.scopus.com/inward/record.url?scp=105005192163&partnerID=8YFLogxK
U2 - 10.1002/jctb.7873
DO - 10.1002/jctb.7873
M3 - 文章
AN - SCOPUS:105005192163
SN - 0268-2575
JO - Journal of Chemical Technology and Biotechnology
JF - Journal of Chemical Technology and Biotechnology
ER -