A way to address the challenge of carbon dioxide emissions causing global warming and climate change is the heterogeneous catalytic hydrogenation of CO₂. When surplus electrical energy is available, hydrogen may be produced and used for conversion of CO₂ into fuels and chemicals. Industrially, a multifunctional metallic copper and zinc oxide catalyst on alumina (CZA) is commonly used. Presently, first-principles multiscale modelling was accomplished for a commercial-like catalyst (Zn₃O₃/Cu) and three other Cu/metal oxide combinations (Cr₃O₃/Cu, Fe₃O₃/Cu, and Mg₃O₃/Cu), synthesised via co-precipitation, characterised and experimentally tested. Ab initio plane wave density functional theory calculations were performed using different structural models to elucidate the adsorption of intermediates and elementary reaction steps, considering thermodynamics and kinetics. The results were fed into mean-field micro-kinetic expressions to calculate the conversion and selectivity in a continuous flow stirred-tank reactor vessel for various temperatures and pressures. Kinetic Monte Carlo simulations were used to obtain the detailed surface coverage, turnover frequency and catalytic performance. Although no experimental input besides the structure was applied for physico-chemical mechanism description, measurements were in agreement with theoretical predictions. It was shown that the formate species pathway (HCOO → H₂COO → H₂COOH → H₂CO → H₃CO) predominates on the examined Cu-based catalysts, although there are variations in the rate determining steps and the most abundant surface intermediate fractions. Whereas Zn₃O₃/Cu exhibited the highest conversion and a moderate CH₃OH product selectivity, the former was lower for Mg₃O₃/Cu. Interestingly, Cr₃O₃/Cu was optimal in terms of yield, but with extremely low CH₃OH productivity, while Fe₃O₃/Cu performed poorly overall. Our results highlight the superiority of Zn₃O₃/Cu, combining the estimations on micro-, meso- and reactor operation scales. Insights beyond traditional activity experiments may be attained and employed in full-scale reactor engineering and optimisation.

Chitin is the most abundant marine biopolymer, being recovered during the shell biorefining of crustacean shell waste. In its native form, chitin displays a poor reactivity and solubility in most solvents due to its extensive hydrogen bonding. This can be overcome by deacetylation. However, this process requires a high concentration of acids or bases at high temperatures, forming large amounts of toxic waste. Herein, we report on the first deacetylation with deep eutectic solvents (DESs) as an environmentally friendly alternative, requiring only mild reaction conditions. Biocompatible DESs are efficient in disturbing the native hydrogen-bonding network of chitin, readily dissolving it. First, quantum chemical calculations have been performed to evaluate the feasibility of different DESs to perform chitin deacetylation by studying their mechanism. Comparing these with the calculated barriers for garden-variety alkaline/acidic hydrolysis, which are known to proceed, prospective DESs were identified with barriers around 25 kcal·mol^–1 or lower. Based on density functional theory results, an experimental screening of 10 distinct DESs for chitin deacetylation followed. The most promising DESs were identified as K₂CO₃:glycerol (K₂CO₃:G), choline chloride:acetic acid ([Ch]Cl:AA), and choline chloride:malic acid ([Ch]Cl:MA) and were subjected to further optimization with respect to the water content, process duration, and temperature. Ultimately, [Ch]Cl:MA showed the best results, yielding a degree of deacetylation (DDA) of 40% after 24 h of reaction at 120 °C, which falls slightly behind the threshold value (50%) for chitin to be considered chitosan. Further quantum chemical calculations were performed to elucidate the mechanism. Upon the removal of 40% N-acetyl groups from the chitin structure, its reactivity was considerably improved.

Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H₂ and CO (syngas). CeO₂ nanorods, nanocubes, and nanospheres were decorated with 1-4 wt % Ni. The materials were structurally characterized using TEM and in situ XANES/EXAFS. The CO₂ activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO₂ morphologies expose {111} and {100} terminating facets, varying the strength of the CO₂ interaction and redox properties, which influence the CO₂ activation. Temperature-programmed CO₂ DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to H₂O and CO. In excess hydrogen, methane is the preferred reaction product. The CeO₂ cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria's surface, resulting in less-abundant surface sites for CO₂ dissociation.