Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol
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 benchma...
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MDPI AG
2024-03-01
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| Online Access: | https://www.mdpi.com/2079-4991/14/5/476 |
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| author | Lu Peng Bogdan Jurca Alberto Garcia-Baldovi Liang Tian German Sastre Ana Primo Vasile Parvulescu Amarajothi Dhakshinamoorthy Hermenegildo Garcia |
| author_facet | Lu Peng Bogdan Jurca Alberto Garcia-Baldovi Liang Tian German Sastre Ana Primo Vasile Parvulescu Amarajothi Dhakshinamoorthy Hermenegildo Garcia |
| author_sort | Lu Peng |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-25T00:23:14Z |
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| language | English |
| last_indexed | 2024-04-25T00:23:14Z |
| publishDate | 2024-03-01 |
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| series | Nanomaterials |
| spelling | doaj.art-569182cca1234f798b28129228c5cdb62024-03-12T16:51:43ZengMDPI AGNanomaterials2079-49912024-03-0114547610.3390/nano14050476Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to MethanolLu Peng0Bogdan Jurca1Alberto Garcia-Baldovi2Liang Tian3German Sastre4Ana Primo5Vasile Parvulescu6Amarajothi Dhakshinamoorthy7Hermenegildo Garcia8Instituto de Tecnología Química, Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, SpainDepartment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, 030016 Bucharest, RomaniaInstituto de Tecnología Química, Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, SpainInstituto de Tecnología Química, Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, SpainInstituto de Tecnología Química, Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, SpainInstituto de Tecnología Química, Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, SpainDepartment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, B-dul Regina Elisabeta 4-12, 030016 Bucharest, RomaniaDepartamento de Química, Universitat Politècnica de València, C/Camino de Vera, s/n, 46022 Valencia, SpainInstituto de Tecnología Química, Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022 Valencia, SpainThe 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.https://www.mdpi.com/2079-4991/14/5/476heterogeneous catalysisCO<sub>2</sub> hydrogenationN-doped graphenemethanol synthesis |
| spellingShingle | Lu Peng Bogdan Jurca Alberto Garcia-Baldovi Liang Tian German Sastre Ana Primo Vasile Parvulescu Amarajothi Dhakshinamoorthy Hermenegildo Garcia Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol Nanomaterials heterogeneous catalysis CO<sub>2</sub> hydrogenation N-doped graphene methanol synthesis |
| title | Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol |
| title_full | Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol |
| title_fullStr | Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol |
| title_full_unstemmed | Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol |
| title_short | Nanometric Cu-ZnO Particles Supported on N-Doped Graphitic Carbon as Catalysts for the Selective CO<sub>2</sub> Hydrogenation to Methanol |
| title_sort | nanometric cu zno particles supported on n doped graphitic carbon as catalysts for the selective co sub 2 sub hydrogenation to methanol |
| topic | heterogeneous catalysis CO<sub>2</sub> hydrogenation N-doped graphene methanol synthesis |
| url | https://www.mdpi.com/2079-4991/14/5/476 |
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