Scalable Mechanochemical Amorphization of Bimetallic Cu-Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol

Selective catalytic reduction of CO₂ to methanol has tremendous importance in the chemical industry. It mitigates two critical issues in the modern society, the overwhelming climate change and the dependence on fossil fuels. The most used catalysts are currently based on mixed copper and zinc phases, where the high surface of active copper species is a critical factor for the catalyst performance. Motivated by the recent breakthrough in the controllable synthesis of bimetallic MOF-74 materials by ball milling, we targeted to study the potential of ZnCu-MOF-74 for catalytic CO₂ reduction. Here, we tested whether the nanosized channels decorated with readily accessible and homogeneously distributed Zn and Cu metal sites would be advantageous for the catalytic CO₂ reduction. Unlike the inactive monometallic Cu-MOF-74, ZnCu-MOF-74 shows moderate catalytic activity and selectivity for the methanol synthesis. Interestingly, the postsynthetic mechanochemical treatment of desolvated ZnCu-MOF-74 resulted in amorphization and a significant increase in both the activity and selectivity of the catalyst despite the destruction of the well-ordered and porous MOF-74 architecture. The results emphasize the importance of defects for the MOF catalytic activity and the potential of amorphous MOFs to be considered as heterogeneous catalysts. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and ¹³C magic angle-spinning nuclear magnetic resonance (MAS NMR) were applied to establish quantitative structure-reactivity relationships. The apparent activation energy of rate reaction kinetics has indicated different pathway mechanisms, primarily through reverse water-gas shift (RWGS). Prolonged time on stream productivity, stability and deactivation were assessed, analysing the robustness or degradation of metal-organic framework nanomaterials. Scalable MOF production processes are making the latter more appealing within emerging industrial decarbonisation, in particular for carbon capture and utilisation (CCU) or hydrogen carrier storage. Acknowledging scale, the costs of fabrication are paramount.