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.

H2 -Free Re-Based Catalytic Dehydroxylation of Aldaric Acid to Muconic and Adipic Acid Esters.

As one of the most demanded dicarboxylic acids, adipic acid can be directly produced from renewable sources. Hexoses from (hemi)cellulose are oxidized to aldaric acids and subsequently catalytically dehydroxylated. Hitherto performed homogeneously, we present the first heterogeneous catalytic process for converting an aldaric acid into muconic and adipic acid. The contribution of leached Re from the solid pre-reduced catalyst was also investigated with hot-filtration test and found to be inactive for dehydroxylation. Corrosive or hazardous (HBr/H2 ) reagents are avoided and simple alcohols and solid Re/C catalysts in an inert atmosphere are used. At 120 °C, the carboxylic groups are protected by esterification, which prevents lactonization in the absence of water or acidic sites. Dehydroxylation and partial hydrogenation yield monohexenoates (93 %). For complete hydrogenation to adipate, a 16 % higher activation barrier necessitates higher temperatures.

Controlling the radical-induced redox chemistry inside a liquid-cell TEM.

With Liquid-Cell Transmission Electron Microscopy (LCTEM) we can observe the kinetic processes taking place in nanoscale materials that are in a solvated environment. However, the beam-driven solvent radiolysis, which results from the microscope's high-energy electron beam, can dramatically influence the dynamics of the system. Recent research suggests that radical-induced redox chemistry can be used to investigate the various redox-driven dynamics for a wide range of functional nanomaterials. In view of this, the interplay between the formation of various highly reactive radiolysis species and the nanomaterials under investigation needs to be quantified in order to formulate new strategies for nanomaterials research. We have developed a comprehensive radiolysis model by using the electron-dose rate, the temperature of the solvent, the H2 and O2 gas saturation concentrations and the pH values as the key variables. These improved kinetic models make it possible to simulate the material's specific radical-induced redox reactions. As in the case of the Au model system, the kinetic models are presented using Temperature/Dose-rate Redox potential (TDR) diagrams, which indicate the equilibrium [Au0]/[Au+] concentration ratios that are directly related to the temperature-/dose-rate-dependent precipitation or dissolution regions of the Au nanoparticles. Our radiolysis and radical-induced redox models were successfully verified using previously reported data from low-dose experiments with γ radiation and experimentally via TDR-dependent LCTEM. The presented study represents a holistic approach to the radical-induced redox chemistry in LCTEM, including the complex kinetics of the radiolysis species and their influence on the redox chemistry of the materials under investigation, which are represented here by Au nanoparticles.