NiCrO x @silicalite-1 with Advanced CO 2 Utilization in Oxidative Dehydrogenation of Propane: Insights into Bifunctional Catalysis and Reaction Efficiency

作者：Ruiqi Wu, Biaohua Chen, Ning Liu, Chengna Dai, Ruinian Xu, Gangqiang Yu, Ning Wang, Yubing Xu, Hongxia Han · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2025 · DOI：10.1021/acssuschemeng.5c02033 · 被引用次数：8 · 研究领域：Catalysis and Oxidation Reactions、Catalytic Processes in Materials Science、Mesoporous Materials and Catalysis

CO 2 -mediated oxidative dehydrogenation of propane (CO 2 -ODHP) has attracted great attention, as it not only efficiently favors propylene production but also provides a promising route for carbon neutralization. The present work has developed a highly efficient CO 2 -ODHP catalyst Ni 2.1% Cr 3.6% O x @S1-1.0 with exceptional C 3 H 8 conversion (51.7%), C 3 H 6 selectivity (91.4%), long-term stability (passing through a 36 h test), and significantly enhanced CO 2 conversion (21.9% → 52.7%). This can be closely related to the incorporation of Ni into the lattice of CrO x, forming NiCrO x, which facilitates the adsorption and activation of CO 2, thereby promoting the timely removal of subtracted H from C 3 H 8 . Additionally, the evenly dispersed NiCrO x species encapsulated by silicalite-1 (S1) also play crucial roles in the remarkable reaction efficiency and stability of Ni 2.1% Cr 3.6% O x @S1–1.0. The specific CO 2 -ODHP mechanism was systematically investigated based on the combined experimental ( in situ FTIR and in situ UV–vis) and theoretical (Density Functional Theory) simulations, which illustrates a bifunctional catalysis process that the dehydrogenation of C 3 H 8 to C 3 H 6 predominantly occurs over the Cr site, while CO 2 adsorption, activation, and subsequent reaction with dissociated H mainly occurs over the Ni site. The DFT-based microkinetic modeling quantitatively validates the significantly higher reaction efficiency following Ni incorporation (7.42 × 10 –7...