Leveraging Metal Organic Framework Derived Indium/Zirconium Oxide for Unprecedented Catalytic Performance in CO₂ Hydrogenation to Methanol

The hydrogenation of CO₂ to methanol is a promising route for carbon capture and utilization, but achieving high selectivity and productivity remains a challenge. This study presents a novel catalyst synthesized by pyrolyzing a zirconium-based metal-organic framework (Zr-BDC) impregnated with indium, yielding ultrafine In₂O₃ nanoparticles uniformly embedded within a ZrO₂ and carbon matrix. The resulting In₂O₃/ZrO₂ heterojunction exhibits abundant oxygen vacancies at the interface, which is crucial in enhancing catalytic performance. Under gas-phase conditions, the catalyst achieves an exceptional methanol selectivity of 81% with a record-high productivity of 2.64 gMeOH·gcat⁻¹·h⁻¹, while in liquid-phase hydrogenation, methanol selectivity reaches 96%. Comprehensive structural characterizations confirm that oxygen vacancies and the heterointerface serve as active sites, facilitating CO₂ activation and methanol stabilization. Mechanistic insights from in situ DRIFTS and ATR-IR spectroscopy reveal that methanol formation proceeds via the formate pathway, further supported by in situ ambient-pressure X-ray photoelectron spectroscopy, demonstrating electronic structural modulation and an increased concentration of oxygen vacancies. These findings underscore the critical role of defect engineering in optimizing CO₂ hydrogenation catalysts and provide a pathway for designing highly efficient systems for sustainable methanol production.