Embedded‐Type Cu Nanoparticle with Largely Enhanced Catalytic Activity and Stability Toward Methanol Steam Reforming

作者：Hao Meng, Tianyao Shen, Zhiming Yin, Yusen Yang, Jian Zhang, Kai Feng, Shaoteng Yuan, Lei Wang, Enze Xu, Lirong Zheng, Song Hong, Feng‐Shou Xiao, Min Wei · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202506458 · 被引用次数：38 · 研究领域：Catalytic Processes in Materials Science、Catalysts for Methane Reforming、Catalysis and Oxidation Reactions

Abstract Hydrogen production through low‐temperature methanol steam reforming (MSR) reaction plays a critical role in the development of new energy but remains a great challenge. Herein, we report a Cu/Zn(Ga)O x catalyst, which is prepared via an interface reconstruction strategy. Interestingly, this catalyst is featured with a unique mortise‐and‐tenon structure: Cu nanoparticles are embedded into the Zn(Ga)O x substrate, which ensures a stable Zn–O–Cu + –O v –Ga δ + interface structure. The resulting Cu/Zn(Ga)O x catalyst exhibits 99.3% CH 3 OH conversion with an H 2 production rate of 124.6 µmol g cat −1 s −1 at 225 °C, which is preponderant to the state‐of‐the‐art catalysts. Furthermore, an ultra‐high catalytic stability was demonstrated through a 400 h stream‐on‐line test without obvious decline. Kinetic isotope analysis, in situ spectroscopy characterizations, and theoretical calculations reveal that the MSR reaction over Cu/Zn(Ga)O x catalyst follows the formaldehyde oxidation route. The CH 3 O* and H 2 O molecule adsorb at the adjacent Cu + −O v interface (intrinsic active site) with an oxygen‐terminal adsorption configuration, which promotes electron transfer from the d ‐band center of Cu to the O ( s , p )‐band of the substrate molecule. This significantly reduces the energy barrier of C─H bond cleavage in CH 3 O* dehydrogenation (the rate‐determining step) and H 2 O dissociation, accounting for the extraordinarily enhanced H 2 production.