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

ABSTRACT CO ₂ 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 ZrO ₂ /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 ZrO ₂ /Cu catalyst through physical mixing with polydivinylbenzene (PDVB). The optimized ZrO ₂ /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.