Structure–Performance Relationships in Metal–Organic Framework Mg ₂ (olz) Catalysts for CO ₂ Adsorption and Hydrogenation to Methanol

We investigated a Cu–Zn‐modified Mg ₂ (olz) catalyst for carbon dioxide (CO ₂ ) hydrogenation to methanol under low CO ₂ partial pressures, relevant to dilute CO ₂ streams in industrial gas treatment and carbon capture. The catalyst was prepared via wet impregnation of presynthesized Cu–Zn species into the metal‐organic framework (MOF). Batch tests under mild temperatures and low CO ₂ concentration showed that the MOF‐based system achieved higher methanol yields than a commercial catalyst at 150 °C. Step‐response experiments in a plug‐flow reactor revealed that the MOF retained a significant amount of CO ₂ under high‐pressure and dynamic conditions. In situ diffuse reflectance infrared Fourier transform spectroscopy identified methanol‐related surface intermediates, while ex situ postreaction ¹ H nuclear magnetic resonance spectroscopy supported the formation and retention of methanol and oxygenated species in the MOF‐based catalyst. X‐ray absorption spectroscopy showed partial reduction of oxygenated Cu species during reaction, while in situ X‐ray diffraction demonstrated structural stability of the Mg ₂ (olz) MOF framework. These results indicate that Mg ₂ (olz)‐based materials combine CO ₂ adsorption capacity with catalytic functionality. Adsorption and catalytic functions coexist rather than being directly coupled. The material exhibits methanol productivity at low temperature in the presence of a solvent phase and remains structurally stable under the investigated catalytic conditions.