Reaction-Induced Metal-Metal Oxide Interactions in Pd In2O3/ZrO2 Catalysts Drive Selective and Stable CO2 Hydrogenation to Methanol

Ternary Pd-In2O3/ZrO2 systems hold promise as industrial catalysts for CO2-based methanol synthesis, but maximization of their productivity requires appropriate structuring of the active phase, promoter, and carrier. Here, we report that Pd-In2O3/ZrO2 systems prepared by impregnation evolve into a unique catalyst architecture under CO2 hydrogenation conditions, leading to selective and stable behavior. Detailed space and time-resolved operando characterization and simulations reveal that the restructuring process, completed within the first 30 min under reaction conditions, is governed by the energetics of metal-metal oxide interactions. The resulting architecture comprises InPdx alloy particles decorated by InOx layers, whose proximity is crucial to avoiding performance losses typically observed when palladium agglomerates. The findings highlight the potential beneficial role of reaction-induced restructuring in advancing catalyst design.三元钯-氧化铟/二氧化锆（Pd-In₂O₃/ZrO₂）催化体系作为二氧化碳基甲醇合成的工业催化剂极具应用潜力，但要最大化其催化产率，需对活性相（active phase）、助催化剂（promoter）与载体（carrier）进行合理的结构设计。本研究表明，浸渍法（impregnation）制备的Pd-In₂O₃/ZrO₂体系在二氧化碳加氢反应条件下会演变为一种独特的催化剂结构，展现出优异的催化选择性与稳定性。详细的时空分辨原位（operando）表征与模拟结果显示，该重构过程在反应条件下于初始30分钟内完成，其进程受金属-金属氧化物相互作用（metal-metal oxide interactions）的能量学特性支配。最终形成的催化剂结构由被氧化铟（InOₓ）层修饰的铟钯合金（InPdₓ）颗粒组成，二者的紧密邻近对于规避钯团聚（palladium agglomerates）时通常出现的催化性能损失至关重要。本研究结果凸显了反应诱导重构在推动催化剂设计优化领域的潜在积极作用。