Non‐Destructive Hydrophobic Engineering of Inverse Catalysts for Methanol Synthesis from CO ₂

CO₂ hydrogenation to green methanol using renewable hydrogen offers a promising approach for achieving a sustainable carbon cycle. Among various catalyst designs, inverse catalysts have attracted growing interest due to their unique structural advantages. However, the performance of inverse catalysts, such as ZrO₂/Cu, is hindered by their hydrophilic nature, while the systematic investigations into their surface wettability remain rare. In this study, we report a non-destructive hydrophobic modification strategy for ZrO₂/Cu catalyst through physical mixing with polydivinylbenzene (PDVB). The optimized ZrO₂/Cu-PDVB (1:1 mass ratio) catalyst achieves a methanol space-time yield of 920.10 mg_CH3OH g_cat ^- ¹ h^- ¹ under mild conditions, outperforming the unmodified catalyst by 30%. Additionally, the optimized catalyst also demonstrates outstanding 200 h thermal stability. In situ DRIFTS and related analyses reveal that the PDVB effectively promotes water desorption and diffusion, alleviating its negative impact on the rate-determining step of formate hydrogenation. This also preserves the size, metallic state of Cu particles, and the abundance of oxygen vacancies, crucial for maintaining the active ZrO_x-Cu interface. This work presents a simple, scalable method for adjusting the local microenvironment of inverse catalysts, highlighting the critical yet underexplored role of hydrophobic surface engineering in optimizing water-sensitive catalytic systems.