北京交通大学王熙团队报道了丙烷脱氢过程中，通过静态双掺杂和动态微量CO₂共进料提高负载型钴催化剂的选择性和稳定性。相关研究成果发表在2024年9月9日出版的《德国应用化学》。

同时提高负载型丙烷脱氢（PDH）催化剂的选择性和稳定性仍然是一个艰巨的挑战。

该文中，研究人员报告了一种静态和动态相结合的策略，以协同解决这些问题。首先，研究人员展示了一种可行的溶胶-凝胶方法，用于制备原子分散的铋修饰金属纳米粒子催化剂（MBi/Al₂O₃，M=Fe、Co、Ni和Zn）。在PDH测试中，由于静态Bi掺杂，CoBi催化剂的副产物（CH₄和C₂H₆）的总选择性显著降低至4%，而Co负载催化剂的总选择性为16%。

其次，为了提高催化稳定性，研究人员引入了一种动态痕量CO₂共进料路线。10CoBi/Al₂O₃催化剂在40%C₃H₈气氛下在PDH中对焦炭形成具有330小时的优异耐久性，然后在600°C下在纯C₃H₈条件下保持96%的丙烯选择性。值得注意的是，引入微量二氧化碳会导致失活速率常数（kd）显著降低6倍。

多重表征和密度泛函理论计算表明，从原子分布的铋到钴纳米粒子的电荷转移有利于降低C₃H₆吸附的能量，从而抑制副产物。此外，微量二氧化碳的动态共进料有助于去除焦炭，抑制催化剂失活。静态铋掺杂和动态痕量二氧化碳共进料策略，同时有助于提高负载型PDH催化剂的选择性和稳定性。

附：英文原文

Title: Improving the Selectivity and Stability of Supported Cobalt Catalysts via Static Bi-Doping and Dynamic Trace CO2 Co-feeding during Propane Dehydrogenation

Author: Yongbin Yao, Jingnan Wang, Qiang Liu, Can Yu, Zhan Gao, Fangli Yuan, Xi Wang

Issue&Volume: 2024-09-09

Abstract: Simultaneously enhancing selectivity and stability on supported propane dehydrogenation (PDH) catalysts remains a formidable challenge. Here, we report a combined static and dynamic strategy to address these issues synergistically. Firstly, we demonstrate a feasible sol-gel method for preparing atomically-dispersed Bi-decorated metal nanoparticle catalysts (MBi/Al2O3, M= Fe, Co, Ni, and Zn). In PDH testing, the total selectivity of by-products (CH4 and C2H6) significantly decreases to 4% for CoBi catalysts due to the static Bi-doping, compared with 16% for Co-supported catalysts. Secondly, to enhance catalytic stability, we introduce a dynamic trace CO2 co-feeding route. 10CoBi/Al2O3 catalysts exhibit superior durability against coke formation for 330 hours in PDH under a 40% C3H8 atmosphere followed by pure C3H8 conditions at 600 °C while maintaining propylene selectivity at 96%. Notably, introducing trace CO2 leads to a remarkable 6-fold decrease in the deactivation rate constant (kd). Multiple characterizations and density functional theory calculations reveal that charge transfer from atomically-distributed Bi to Co nanoparticles benefits lowering the energy of C3H6 adsorption thereby suppressing by-products. Furthermore, the dynamic co-feeding of trace CO2 facilitates coke removal, suppressing catalyst deactivation. The static Bi-doping and dynamic trace CO2 co-feeding strategy contributes simultaneously to increased selectivity and stability on supported PDH catalysts.

DOI: 10.1002/anie.202415295

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202415295