Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts
The selective production of hydrocarbons for the chemical industry from biogenic feedstock is a significant challenge when ensuring hydrocarbon and fuel supply, despite the heterogeneity of this feed. In this study, guaiacol, as a surrogate for complex lignin-based biomass resources, is converted by...
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| Format: | Article |
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MDPI AG
2023-02-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/13/2/425 |
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| author | Nils Kretzschmar Oliver Busse Markus Seifert |
| author_facet | Nils Kretzschmar Oliver Busse Markus Seifert |
| author_sort | Nils Kretzschmar |
| collection | DOAJ |
| description | The selective production of hydrocarbons for the chemical industry from biogenic feedstock is a significant challenge when ensuring hydrocarbon and fuel supply, despite the heterogeneity of this feed. In this study, guaiacol, as a surrogate for complex lignin-based biomass resources, is converted by an inert silica carrier material with different d-metal impregnation (Mo, W, Re, Fe, Co, Ni, Cu, Pd, Ag) to reveal the reasons for different product selectivity to hydrogenated and deoxygenated hydrocarbon products. Hydrogen at 15 bar (gauge) and guaiacol are converted on metal/silica catalysts between 250 °C and 400 °C, while the physicochemical catalyst properties are characterized before and after catalytic tests. Volcano plots for the conversion, hydrogenation and deoxygenation products versus the d-band energy, surface atom distance and fouling properties reveal three groups of metals: (i) those that are less active and show high coking (Ag, α-Fe); (ii) those that show high activity for hydrogenation (β-Co, Ni, Pd) and, therefore, preferably yielded cyclohexane, cyclohexanol and 2-methoxycyclohexanol; (iii) those that preferably promote deoxygenation (Mo, W, Re, Cu) and, therefore, promoted the formation of phenol, benzene, anisole and catechol. The results are summarized in a pseudo van Krevelen diagram and interpreted as a complex interdependency from Sabatier’s principle of geometric correspondence of hexagonal metal surface for hydrogenation, electronic correspondence for the activation of hydrogen and electronic correspondence by oxophilicity for deoxygenation from the d-band center model. |
| first_indexed | 2024-03-11T09:00:38Z |
| format | Article |
| id | doaj.art-2282bd9ac8184bb1ac510c17c137b130 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-11T09:00:38Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-2282bd9ac8184bb1ac510c17c137b1302023-11-16T19:42:58ZengMDPI AGCatalysts2073-43442023-02-0113242510.3390/catal13020425Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica CatalystsNils Kretzschmar0Oliver Busse1Markus Seifert2Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, GermanyFaculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, GermanyFaculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, GermanyThe selective production of hydrocarbons for the chemical industry from biogenic feedstock is a significant challenge when ensuring hydrocarbon and fuel supply, despite the heterogeneity of this feed. In this study, guaiacol, as a surrogate for complex lignin-based biomass resources, is converted by an inert silica carrier material with different d-metal impregnation (Mo, W, Re, Fe, Co, Ni, Cu, Pd, Ag) to reveal the reasons for different product selectivity to hydrogenated and deoxygenated hydrocarbon products. Hydrogen at 15 bar (gauge) and guaiacol are converted on metal/silica catalysts between 250 °C and 400 °C, while the physicochemical catalyst properties are characterized before and after catalytic tests. Volcano plots for the conversion, hydrogenation and deoxygenation products versus the d-band energy, surface atom distance and fouling properties reveal three groups of metals: (i) those that are less active and show high coking (Ag, α-Fe); (ii) those that show high activity for hydrogenation (β-Co, Ni, Pd) and, therefore, preferably yielded cyclohexane, cyclohexanol and 2-methoxycyclohexanol; (iii) those that preferably promote deoxygenation (Mo, W, Re, Cu) and, therefore, promoted the formation of phenol, benzene, anisole and catechol. The results are summarized in a pseudo van Krevelen diagram and interpreted as a complex interdependency from Sabatier’s principle of geometric correspondence of hexagonal metal surface for hydrogenation, electronic correspondence for the activation of hydrogen and electronic correspondence by oxophilicity for deoxygenation from the d-band center model.https://www.mdpi.com/2073-4344/13/2/425hydrodeoxygenationguaiacolsabatier’s principleelectronic correspondencegeometric correspondenceoxophilicity |
| spellingShingle | Nils Kretzschmar Oliver Busse Markus Seifert Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts Catalysts hydrodeoxygenation guaiacol sabatier’s principle electronic correspondence geometric correspondence oxophilicity |
| title | Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts |
| title_full | Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts |
| title_fullStr | Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts |
| title_full_unstemmed | Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts |
| title_short | Impact of Geometric and Electronic Factors on Selective Hydro-Deoxygenation of Guaiacol by Surface-Rich Metal/Silica Catalysts |
| title_sort | impact of geometric and electronic factors on selective hydro deoxygenation of guaiacol by surface rich metal silica catalysts |
| topic | hydrodeoxygenation guaiacol sabatier’s principle electronic correspondence geometric correspondence oxophilicity |
| url | https://www.mdpi.com/2073-4344/13/2/425 |
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