Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame
The growing demand for new energy sources governs the intensive research into CO<sub>2</sub> hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during...
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MDPI AG
2023-11-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/13/23/2996 |
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| author | Svetlana A. Sorokina Nina V. Kuchkina Stepan P. Mikhailov Alexander V. Mikhalchenko Alexey V. Bykov Valentin Yu. Doluda Lyudmila M. Bronstein Zinaida B. Shifrina |
| author_facet | Svetlana A. Sorokina Nina V. Kuchkina Stepan P. Mikhailov Alexander V. Mikhalchenko Alexey V. Bykov Valentin Yu. Doluda Lyudmila M. Bronstein Zinaida B. Shifrina |
| author_sort | Svetlana A. Sorokina |
| collection | DOAJ |
| description | The growing demand for new energy sources governs the intensive research into CO<sub>2</sub> hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during the reaction and low selectivity. Here, we report a new strategy of controlling the selectivity and stability of bimetallic magnetically recoverable indium-based catalysts deposited onto a solid support. This was accomplished by the introduction of a structural promoter: a branched pyridylphenylene polymer (PPP). The selectivity of methanol formation for this catalyst reached 98.5%, while in the absence of PPP, the catalysts produced a large amount of methane, and the selectivity was about 70.2%. The methanol production rate was higher by a factor of twelve compared to that of a commercial Cu-based catalyst. Along with tuning selectivity, PPP allowed the catalyst to maintain a high stability, enhancing the CO<sub>2</sub> sorption capacity and the protection of In against sintering and over-reduction. A careful evaluation of the structure–activity relationships allowed us to balance the catalyst composition with a high level of structural control, providing synergy between the support, magnetic constituent, catalytic species, and the stabilizing polymer layer. We also uncovered the role of each component in the ultimate methanol activity and selectivity. |
| first_indexed | 2024-03-09T01:45:48Z |
| format | Article |
| id | doaj.art-4296ccf2778c416ea417b29fc2302f82 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T01:45:48Z |
| publishDate | 2023-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-4296ccf2778c416ea417b29fc2302f822023-12-08T15:22:51ZengMDPI AGNanomaterials2079-49912023-11-011323299610.3390/nano13232996Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer FrameSvetlana A. Sorokina0Nina V. Kuchkina1Stepan P. Mikhailov2Alexander V. Mikhalchenko3Alexey V. Bykov4Valentin Yu. Doluda5Lyudmila M. Bronstein6Zinaida B. Shifrina7A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaDepartment of Biotechnology and Chemistry, Tver State Technical University, 22 A. Nikitina St., 170026 Tver, RussiaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaDepartment of Biotechnology and Chemistry, Tver State Technical University, 22 A. Nikitina St., 170026 Tver, RussiaDepartment of Biotechnology and Chemistry, Tver State Technical University, 22 A. Nikitina St., 170026 Tver, RussiaDepartment of Chemistry, Indiana University, 800 E. Kirkwood Av., Bloomington, IN 47405, USAA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St., 119991 Moscow, RussiaThe growing demand for new energy sources governs the intensive research into CO<sub>2</sub> hydrogenation to methanol, a valuable liquid fuel. Recently, indium-based catalysts have shown promise in this reaction, but they are plagued by shortcomings such as structural instability during the reaction and low selectivity. Here, we report a new strategy of controlling the selectivity and stability of bimetallic magnetically recoverable indium-based catalysts deposited onto a solid support. This was accomplished by the introduction of a structural promoter: a branched pyridylphenylene polymer (PPP). The selectivity of methanol formation for this catalyst reached 98.5%, while in the absence of PPP, the catalysts produced a large amount of methane, and the selectivity was about 70.2%. The methanol production rate was higher by a factor of twelve compared to that of a commercial Cu-based catalyst. Along with tuning selectivity, PPP allowed the catalyst to maintain a high stability, enhancing the CO<sub>2</sub> sorption capacity and the protection of In against sintering and over-reduction. A careful evaluation of the structure–activity relationships allowed us to balance the catalyst composition with a high level of structural control, providing synergy between the support, magnetic constituent, catalytic species, and the stabilizing polymer layer. We also uncovered the role of each component in the ultimate methanol activity and selectivity.https://www.mdpi.com/2079-4991/13/23/2996CO<sub>2</sub> hydrogenationsupported catalystsmethanolindium oxidepolymercobalt |
| spellingShingle | Svetlana A. Sorokina Nina V. Kuchkina Stepan P. Mikhailov Alexander V. Mikhalchenko Alexey V. Bykov Valentin Yu. Doluda Lyudmila M. Bronstein Zinaida B. Shifrina Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame Nanomaterials CO<sub>2</sub> hydrogenation supported catalysts methanol indium oxide polymer cobalt |
| title | Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame |
| title_full | Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame |
| title_fullStr | Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame |
| title_full_unstemmed | Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame |
| title_short | Highly Selective CO<sub>2</sub> Hydrogenation to Methanol over Complex In/Co Catalysts: Effect of Polymer Frame |
| title_sort | highly selective co sub 2 sub hydrogenation to methanol over complex in co catalysts effect of polymer frame |
| topic | CO<sub>2</sub> hydrogenation supported catalysts methanol indium oxide polymer cobalt |
| url | https://www.mdpi.com/2079-4991/13/23/2996 |
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