safym

• Safy, Mohamed E. A.; Rama, Raquel J.; Both, Niklas F.; Badia, David Balcells; Junge, Kathrin & Beller, Matthias [Show all 7 contributors for this article] (2026). Leveraging Diamines to Unlock the Mn‐MACHO Catalyst in the Reduction of CO2 to Methanol. Angewandte Chemie International Edition. ISSN 1433-7851. 65(10). doi: 10.1002/anie.202524012. Full text in Research Archive Show summary

  The conversion of CO 2 into energy‐dense liquid fuels, such as methanol, represents a cornerstone of sustainable chemistry; however, most homogeneous catalytic systems still rely on noble metals or Lewis acid additives. Here, we report the first protocol for amine‐assisted CO 2 hydrogenation to methanol using a Mn–MACHO catalyst without any Lewis acid co‐catalyst, achieving turnover numbers up to 45.2, the highest reported for Mn systems. A combined computational, microkinetic, and experimental study reveals that diamines dramatically enhance activity compared to monoamines by promoting a highly exergonic double amidation step. This thermodynamic driving force shifts the equilibrium away from formate resting states toward the active catalyst, thereby accelerating methanol formation. The correlation established between amidation free energies (Δ G amidation ) and methanol productivity provides a rational design principle for tailoring amine promoters across Ru‐ and Mn‐based MACHO catalysts. These insights advance the development of sustainable, base‐metal‐catalyzed CO 2 conversion strategies and open opportunities for integrated carbon capture and utilization.

• Safy, Mohamed E. A.; Rama, Raquel J.; Both, Niklas F.; Junge, Kathrin; Beller, Matthias & Nova, Ainara (2025). Kinetic Modeling of the Ru‐MACHO‐Catalyzed CO2 Hydrogenation to Methanol. ChemCatChem. ISSN 1867-3880. 17(19). doi: 10.1002/cctc.202500883. Full text in Research Archive Show summary

  One of the most efficient and extensively studied homogeneous catalysts for CO 2 hydrogenation to methanol is the Ru‐MACHO‐Ph complex. However, the exact nature of the resting states of the catalyst, which could be Ru‐formate, Ru‐carbamate, and [Ru‐CO]⁺, as well as the contribution of various pathways for amide hydrogenation, remain unresolved questions. In this study, we employed a computational protocol including conformational search with a semiempirical method (GFN2‐xTB), followed by geometry optimization and energy calculations using density functional theory (M06/M06L) and coupled‐cluster (DLPNO‐CCSD(T)) methods to investigate the most plausible pathways for the CO 2 hydrogenation reaction assisted by dimethylamine (DMA). Microkinetic modeling was used to predict the methanol turnover number (TON), which aligns well with experimental data, and to analyze the proposed mechanisms and resting states of the catalyst. Our model indicates that dimethylformamide (DMF) is initially hydrogenated to hemiaminal through a metal‐ligand cooperative mechanism. The resulting hemiaminal is then decomposed via a methanol‐assisted organic reaction in a catalyst‐independent process. Additionally, Ru‐formate ( 3 ) was identified as the primary resting state, along with Ru‐carbamate ( 8 ). Furthermore, we found that increasing the DMA concentration enhances the methanol TON, in agreement with previous experimental results.

• Liu, Jiali; Rama, Raquel J.; Cordero-Lanzac, Tomás; Safy, Mohamed E. A.; Franke, Robert & Flores, Ainara Nova (2025). Outer-Sphere CO Release Mechanism in the Methanol-to-Syngas Reaction Catalyzed by a Ru-PNP Pincer Complex. ACS Catalysis. 15(6), p. 5113–5122. doi: 10.1021/acscatal.4c06818. Full text in Research Archive Show summary

  Methanol can be used as a surrogate molecule for CO and H2 in the synthesis of a large variety of chemicals. In this work, the mechanism for the methanol-to-syngas reaction catalyzed by a Ru-PNP complex was studied using density functional theory. In the proposed mechanism, the CO is directly released from the methyl formate intermediate, forming a Ru-OCH3 species. The preference for this pathway compared to others proposed in literature was supported by a microkinetic model constructed from the computed Gibbs free energies and coupled to a liquid–vapor batch reactor describing the gas phase composition. After including energy corrections of ≤6 kcal mol–1 to three organic intermediates and CO, our model could reproduce the experimental CO and H2 turnover numbers over the time previously reported. Further, this model was used to evaluate the influence of solvent polarity and methanol concentration on the formation of products and catalyst resting states. These results suggest that in methanol, CO formation is limited by the organic reaction thermodynamics, whereas in toluene, it is limited by Ru–CO formation. Overall, this work shows the potential of microkinetic models to benchmark reaction mechanisms and computational methods and provide the relevant information required for catalyst design.

• Franke, Robert; Liu, Jiali; Neumann, Helfried; Sang, Rui; Safy, Mohamed E. A. & Rama, Raquel J. [Show all 9 contributors for this article] (2025). Palladium-catalyzed ethylene methoxycarbonylation using bidentate phosphines: How the stereochemistry of the ligand affects the catalyst's activity. Chemistry - A European Journal. ISSN 0947-6539. 31(35). doi: 10.1002/chem.202500476. Full text in Research Archive Show summary

  To elucidate the diastereomeric control of bidentate P-ligands in the ethylene methoxycarbonylation, a comparative and systematic experimental and computational investigation was conducted on the catalytic activity of the Pd-complexes of the racemic, meso, and epimerized LIKATphos ligands (pytbpx, B) as well as the Lucite ligand (dtbpx, A). The experimental study revealed that the racemic ligand (pytbpx, B) exhibited the highest catalytic activity, while the Lucite ligand (dtbpx, A) exhibited the lowest activity, and the meso ligand (pytbpx, B) exhibited moderate activity. This activity order follows the same trend as the CO coordination energy to the palladium hydride complex for B, while the methanolysis is the rate-limiting step with A. The enhanced catalytic activity exhibited by the chiral pytbpx (B) is attributed to the higher stability of the hydride complex and lower stability of the CO complex compared to the meso pytbpx (B). The higher activity of the Pd-complexes of pytbpx (B) over the Pd-complexes of dtbpx (A) is attributed to the built-in base effect.

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• Safy, Mohamed E. A.; Flores, Ainara Nova & Badia, David Balcells (2026). How Mechanistic Understanding Guides the Design of New CO2-to-Methanol Catalysts. Full text in Research Archive
• Safy, Mohamed E. A. (2025). Computational Design Rules for Amine-Assisted CO2 Hydrogenation to Methanol: Mechanistic Investigation and Microkinetic Modeling. Full text in Research Archive
• Safy, Mohamed E. A. (2025). From CO₂ to Methanol: How Amines Switch Catalysts On. Full text in Research Archive
• Safy, Mohamed Eid Ahmed; Rama, Raquel Jimenez; Badia, David Balcells & Flores, Ainara Nova (2024). CO2 hydrogenation to methanol beyond Ru-MACHO: A DFT and microkinetic modeling study. Full text in Research Archive
• Safy, Mohamed Eid Ahmed; Nova, Ainara & Balcells, David (2022). COMBINING DFT AND MACHINE LEARNING TOWARDS DISCOVERING OF SUPERIOR CATALYSTS FOR CO2 REDUCTION TO METHANOL. Full text in Research Archive
• Safy, Mohamed E. A.; Balcells, David & Nova, Ainara (2022). COMBINING DFT AND MACHINE LEARNING TOWARDS DISCOVERING OF NEW CATALYSTS FOR CO2 REDUCTION TO METHANOL. Full text in Research Archive
• Safy, Mohamed E. A.; Balcells, David & Nova, Ainara (2022). Hydrogenation of CO2 to methanol: What is beyond Ru-MACHO? Full text in Research Archive
• Safy, Mohamed E. A.; Flores, Ainara Nova; Olsbye, Unni & Badia, David Balcells (2026). Computationally guided CO2 to methanol catalysis: From a mechanistic investigation to a descriptor-based screening. Universitetet i Oslo. Full text in Research Archive Show summary

  CO2 hydrogenation to liquid fuels, especially methanol, is among the most attractive carbon capture and utilization techniques. This conversion can reduce CO2 emissions and produce green liquid fuels. Methanol is considered an attractive liquid organic hydrogen carrier and a valuable feedstock for important chemical industries. In basic media, Ru-MACHO-Ph combined with an amine co-catalyst is among the most active homogeneous systems reported for CO2 hydrogenation to methanol. However, the mechanistic origin of this high activity remains unclear, hindering the development of earth-abundant metal catalysts for direct CO2 hydrogenation to methanol. In this thesis, the first publication combined computational mechanistic investigations with microkinetic modeling to elucidate the mechanisms of amine-assisted CO2 hydrogenation to methanol. The theoretically obtained methanol turnover number from the microkinetic model was validated against experimental results. The model was used to analyze and compare competing mechanisms, thereby proposing the most consistent pathway and investigating the effect of the reactants’ initial concentrations on methanol production. The second publication explored why diamines exhibit enhanced activity relative to monoamines as co-catalysts and showed that a simple thermodynamic calculation can serve as a rational design principle for selecting effective amines. This work also shows that methanol can be produced in basic media using an earth-abundant metal catalyst (Mn-MACHO-Ph). The third paper integrated linear free energy scaling relationships with the energy span model to construct a molecular volcano plot, providing a predictive screening framework for bifunctional pincer complexes in CO2 hydrogenation to methanol. The resulting volcano plot correctly ranks the experimentally reported active catalyst among the most active candidates for amine-assisted CO2 hydrogenation to methanol. The model was also used to screen a newly designed Fe- and Mn-based chemical space, identifying promising systems for further computational and experimental evaluation. Overall, the thesis established a detailed mechanistic understanding and a computational model that links free energy calculations to catalytic performance, enabling the rational design of base-metal catalysts for amine-assisted CO2 hydrogenation to methanol.

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