Duan Delong, Wu Di, Shou Hongwei, Hu Chuansheng, Hu Canyu, Zhou Min, Long Ran, Bi Yingpu, Xiong Yujie
Hefei National Research Center for Physical Sciences at the Microscale, Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, National Synchrotron Radiation Laboratory, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, Anhui, 230026, China.
Suzhou Institute for Advanced Research, University of Science and Technology of China, Suzhou, Jiangsu, 215123, China.
Adv Sci (Weinh). 2024 Dec 4;12(4):e2409048. doi: 10.1002/advs.202409048.
The transition metal nanocatalysts containing disordered active sites can potentially achieve efficient Sabatier reactions with high selectivity. However, it remains a challenge to maintain the stability of these active sites in such an exothermic reaction. Here, a thermal management approach is reported to address this challenge. Specifically, an efficient and stable catalytic system is developed by integrating urchin-like Ru nanoparticles with disordered active sites (d-RuNUs) and multi-walled carbon nanotubes (MWCNTs) as heat transfer framework, which achieves a CH yield of 3.3 mol g h with nearly 100% selectivity in 12 h. The characterizations reveal that the thermal-induced crystallization seriously weakens the adsorption of CO, leading to significant degradation of catalytic performance. The heat transfer simulation confirms that the MWCNTs with high thermal conductivity play a key role in rapidly redistributing the reaction heat, thereby preventing the crystallization of disordered structures. This work elucidates the deactivation mechanism of disordered active sites in exothermic reactions and opens the avenue for local thermal management of non-thermal equilibrium reactions.
含有无序活性位点的过渡金属纳米催化剂有可能实现具有高选择性的高效萨巴蒂尔反应。然而，在这种放热反应中维持这些活性位点的稳定性仍然是一个挑战。在此，报道了一种热管理方法来应对这一挑战。具体而言，通过将具有无序活性位点的海胆状钌纳米颗粒（d-RuNUs）与作为传热框架的多壁碳纳米管（MWCNTs）相结合，开发了一种高效且稳定的催化体系，该体系在12小时内实现了3.3 mol g h的CH产率，选择性接近100%。表征结果表明，热诱导结晶严重削弱了CO的吸附，导致催化性能显著下降。传热模拟证实，具有高导热性的MWCNTs在快速重新分配反应热方面起着关键作用，从而防止无序结构的结晶。这项工作阐明了放热反应中无序活性位点的失活机制，并为非热平衡反应的局部热管理开辟了道路。
