Hydrogen Spillover-Mediated Spatial Decoupling Process Boosts Syngas Conversion to Higher Oxygenates

作者：Li Su, Zili Ma, Xinyu Zhong, Bo Wu, Jingxuan Guo, Bin Chai, Jianfei Ji, Chengyuan Liu, Jungang Wang, Qiang Wang, Jun Bao, Kegong Fang, Yuhan Sun · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c14341 · 被引用次数：10 · 研究领域：Catalysts for Methane Reforming、CO2 Reduction Techniques and Catalysts、Catalytic Processes in Materials Science

The direct conversion of syngas to higher oxygenates presents a fundamental challenge in simultaneously achieving high CO conversion, superior oxygenate selectivity, and minimal undesired C 1 byproducts. Here, we develop a series of multifunctional Cu x Pd 1 /SiO 2 |CoMn catalysts with granule stacking architecture, which overcome the challenge by precisely controlling the spatial arrangement of active sites and the intermediate transport pathway. Systematic optimization reveals a distinct volcano-shaped relationship on Pd loadings, with the Cu 28 Pd 1 /SiO 2 |CoMn composite emerging as the optimal candidate. Such a catalyst achieves an exceptional oxygenates molar selectivity of 44.4% (C 2+ OH/ROH = 95.4%) while maintaining low C 1 products (6.4% CO 2 and 5.7% CH 4 ) at considerable 27.3% CO conversion. Mechanistic studies reveal that the breakthrough stems from precise control of spatial intimacy of functional components, optimized mass balance between CH x O* and CH x *, and isolated Pd atom-mediated hydrogen spillover effects. Based on spectroscopic evidence with theoretical calculations, we propose a synergistic catalytic system wherein PdCu single-atom alloys facilitate H 2 activation and CH x O* formation through hydrogen spillover, while Co 0 -Co 2 C interfaces produce abundant CH x * species. The synergistic interaction enables the migration of CH x O* intermediates from single-atom alloy sites to Co 0 -Co 2 C interfaces, where they undergo further insertion into CH ...