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  • Title: Toward Methanol Production by CO2 Hydrogenation beyond Formic Acid Formation.
    Author: Onishi N, Himeda Y.
    Journal: Acc Chem Res; 2024 Oct 01; 57(19):2816-2825. PubMed ID: 39284577.
    Abstract:
    ConspectusThe Paradigm shift in considering CO2 as an alternative carbon feedstock as opposed to a waste product has recently prompted intense research activities. The implementation of CO2 utilization may be achieved by designing highly efficient catalysts, exploring processes that minimize energy consumption and simplifying product purification and separation. Among possible target products derived from CO2, methanol is highly valuable because it can be used in various chemical feedstocks and as a fuel. Although it is currently produced on a plant scale by heterogeneous catalysis using a Cu/ZnO-based catalyst, a limited theoretical conversion ratio at high reaction temperatures remains an issue. In addition, a catalytic system that can be adjusted to accommodate a variable renewable energy source for the synthesis of methanol is more desirable than current continuous-operation systems, which require a reliable energy supply. Recently, significant progress has been made in the field of homogeneous catalysis, which primarily relies on an indirect route to synthesize methanol via the hydrogenation of carbonate or formate derivatives in the presence of additives and solvents. However, homogeneous catalysis is inappropriate for industrial-scale methanol production because of the inefficient separation and purification processes involved.In this Account, we demonstrate a novel approach for methanol production under mild reaction conditions by CO2 hydrogenation catalyzed by multinuclear iridium complexes under heterogeneous gas-solid phase conditions without any additives and solvents. One of the aims of this Account provides insights for overcoming the barriers for efficient CO2 hydrogenation by focusing on catalyst design, specifically by incorporating varying functionalities into the ligand. The fundamental strategy entails activating hydrogen molecule and enhancing the hydricity of the resulting metal-hydride species, which is based on the following two concepts of catalyst design: (i) Activating a metal-hydride by electronic effects; and (ii) accelerating H2 heterolysis. We have elucidated the mechanism for accelerating H2 heterolysis using a state-of-the-art catalyst that contains an actor-ligand that responds to or participates in catalysis as opposed to a classical spectator-ligand.We have also demonstrated a novel heterogeneous catalysis using a molecular catalyst as a key step for the hydrogenation of CO2 to methanol beyond formic acid formation. The dehydrogenation of formic acid as a reverse reaction of formic acid hydrogenation is strongly favored in acidic aqueous solution. To circumvent the equilibrium limitation, we have envisioned an alternative route that both prevents the liberation of formic acid into the reaction medium, and develops a multinuclear complex to facilitate the transfer of multiple reactive hydrides. The unconventional gas-solid phase catalysis is capable of preventing the liberation of formate species and promoting further hydrogenation of formic acid through multihydride transfer.This novel catalytic system, which is the fusion of a molecular catalyst in heterogeneous catalysis, provides high performance for methanol synthesis through a sophisticated catalyst design and straightforward separation processes. A detailed mechanistic analysis of molecular catalysts in the gas phase would lead to significant progress in the field of Surface Organometallic Chemistry (SOMC).
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