Technological approaches which enable the effective utilization of CO2 for manufacturing value-added chemicals and fuels can help to solve environmental problems derived from large CO2 emissions associated with the use of fossil fuels. One of the most interesting products that can be synthesized from CO2 is methanol, since it is an industrial commodity used in several chemical products and also an efficient transportation fuel. In this review, we highlight the recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to methanol. The main efforts focused on the improvement of conventional Cu/ZnO based catalysts and the development of new catalytic systems targeting the specific needs for CO2 to methanol reactions (unfavourable thermodynamics, production of high amount of water and high methanol selectivity under high or full CO2 conversion). Major studies on the development of active and selective catalysts based on thermodynamics, mechanisms, nano-synthesis and catalyst design (active phase, promoters, supports, etc.) are highlighted in this review. Finally, a summary concerning future perspectives on the research and development of efficient heterogeneous catalysts for methanol synthesis from CO2 will be presented.

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An amorphous aluminophosphate (ALPO) catalyst containing weak acid and base centers can carry out the aldol condensation of heptanal with benzaldehyde at much higher rates and selectivities than conventional solid acid (amorphous or crystalline aluminosilicates) or base catalysts (MgO, hydrotalcites, KF/Al2O3, nitrurated ALPO). With the weak acid‐base catalyst, the reaction occurs through a bifunctional acid‐base mechanism that involves the activation of benzaldehyde, by protonation‐polarization of the carbonyl group on the acid sites, and the attack of the enolate heptanal intermediate generated on the basic sites. With this type of bifunctional acid‐base catalyst, compounds with weak basicities are already able to undergo the reaction with a much higher selectivity than those obtained on stronger acid or base catalysts.

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