| Summary: | The quest for efficient catalysts based on abundant elements that can promote the selective CO<sub>2</sub> hydrogenation to green methanol still continues. Most of the reported catalysts are based on Cu/ZnO supported in inorganic oxides, with not much progress with respect to the benchmark Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> catalyst. The use of carbon supports for Cu/ZnO particles is much less explored in spite of the favorable strong metal support interaction that these doped carbons can establish. This manuscript reports the preparation of a series of Cu-ZnO@(N)C samples consisting of Cu/ZnO particles embedded within a N-doped graphitic carbon with a wide range of Cu/Zn atomic ratio. The preparation procedure relies on the transformation of chitosan, a biomass waste, into N-doped graphitic carbon by pyrolysis, which establishes a strong interaction with Cu nanoparticles (NPs) formed simultaneously by Cu<sup>2+</sup> salt reduction during the graphitization. Zn<sup>2+</sup> ions are subsequently added to the Cu–graphene material by impregnation. All the Cu/ZnO@(N)C samples promote methanol formation in the CO<sub>2</sub> hydrogenation at temperatures from 200 to 300 °C, with the temperature increasing CO<sub>2</sub> conversion and decreasing methanol selectivity. The best performing Cu-ZnO@(N)C sample achieves at 300 °C a CO<sub>2</sub> conversion of 23% and a methanol selectivity of 21% that is among the highest reported, particularly for a carbon-based support. DFT calculations indicate the role of pyridinic N doping atoms stabilizing the Cu/ZnO NPs and supporting the formate pathway as the most likely reaction mechanism.
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