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.

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. We studied the effect of the HPW loading on TiO2 (from 1.4 to 2.7 monolayers) on the dispersion and acid characteristics of the HPW clusters. When the concentration of the heteropoliacid is slightly higher than the monolayer (1.4 monolayers) the acidity of the clusters is perturbed by the surface of titania, while for concentration higher than 1.7 monolayers results in the formation of three-dimensional HPW nanocrystals with acidity similar to the bulk heteropolyacid. Physical hybridization of supported heteropolyacids with the Cu-ZnO(Al) catalyst modifies both the acid characteristics of the supported heteropolyacids and the copper surface area of the Cu-ZnO(Al) catalyst. Hybridization gives rise to a decrease in the copper surface area and the disappearance of the strong acidic sites typical of HPW nanocrystals, showing all hybrids similar acid sites of weak or medium strength. The activity of the hybrids was tested for direct DME synthesis from syngas at 30 bar and 250 °C; only the hybrids with HPW loading higher than 1.4 monolayers showed activity for the direct synthesis of DME, showing that the sample loaded with 2.7 monolayers of heteropolyacid had higher activity than the reference hybrid representative of the most widely applied catalysts based on the combination of Cu-ZnO(Al) with HZSM-5. In spite of the high activity of the hybrids, they show a moderate loss in the DME production with TOS that denotes some kind of deactivation of the acidity function under reaction conditions.

This contribution describes the modification in the structure and activity of Cu/ZnO catalyst in the methanol synthesis reaction induced by the co-modification with a low amount of Al and Ga (Al + Ga = 3% atom). To elucidate the effect of the co-modification, the catalysts were characterized by means of variety of techniques (XRD, N2 physisorption, FTIR, TGA, TEM, TPR and N2O chemisorption) and tested in the methanol synthesis reaction carried out in a flow reactor at 250 °C and total pressure of 3 MPa using syngas. The combined characterization and activity tests demonstrated that the co-doping with Al and Ga affects the structure and activity of Cu/ZnO catalysts in a different manner depending on the Al/Ga ratio used. The best catalyst co-loaded with Ga and Al in equal amount shows an improvement in the activity for methanol synthesis respect to the activity obtained on catalysts individually loaded with Al and Ga. The difference in the activity of the samples co-loaded with Al and Ga normalized by N2O chemisorption point to a different participation of the copper surfaces in combination with the defect sites of ZnO depending on the Al and Ga loading.

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