Thermodynamically stable synthesis of high entropy alloys and efficiently catalyzed oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under base-free conditions
The high activity and high selectivity in the catalytic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) under non-alkaline conditions has always been a significant challenge in the field of biomass utilization. In this work, a thermodynamically stabilized high-entro...
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Veröffentlicht in: | Green chemistry : an international journal and green chemistry resource : GC 2024-11, Vol.26 (22), p.11316-11327 |
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creator | Lv, Guangqiang Liu, Shan Chen, Xiaoyan Chen, Mengxin Wu, Yanjuan Gao, Yuji Wang, Shuai Tao, Furong Wang, Jingui Niu, Liwei |
description | The high activity and high selectivity in the catalytic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) under non-alkaline conditions has always been a significant challenge in the field of biomass utilization. In this work, a thermodynamically stabilized high-entropy alloy (HEA) structure with relatively low Pt content was synthesized via a simple impregnation–calcination procedure by tuning the mixing enthalpy and the Gibbs free energy of the metal-mixing system. The prepared HEA shows excellent catalytic performance in the aerobic oxidation of HMF into FDCA under base-free conditions. Experiments and DFT calculations revealed that molecular O 2 can be easily activated into highly oxidative hydroxyl radicals (˙OH) in the presence of water over the HEA surface, and facilitates the oxidation of HMF to FDCA under base-free conditions. This work provides a valuable reference for similar aerobic oxidation processes in which alkaline promoters and noble metal catalysts are needed. |
doi_str_mv | 10.1039/D4GC04186K |
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In this work, a thermodynamically stabilized high-entropy alloy (HEA) structure with relatively low Pt content was synthesized via a simple impregnation–calcination procedure by tuning the mixing enthalpy and the Gibbs free energy of the metal-mixing system. The prepared HEA shows excellent catalytic performance in the aerobic oxidation of HMF into FDCA under base-free conditions. Experiments and DFT calculations revealed that molecular O 2 can be easily activated into highly oxidative hydroxyl radicals (˙OH) in the presence of water over the HEA surface, and facilitates the oxidation of HMF to FDCA under base-free conditions. 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In this work, a thermodynamically stabilized high-entropy alloy (HEA) structure with relatively low Pt content was synthesized via a simple impregnation–calcination procedure by tuning the mixing enthalpy and the Gibbs free energy of the metal-mixing system. The prepared HEA shows excellent catalytic performance in the aerobic oxidation of HMF into FDCA under base-free conditions. Experiments and DFT calculations revealed that molecular O 2 can be easily activated into highly oxidative hydroxyl radicals (˙OH) in the presence of water over the HEA surface, and facilitates the oxidation of HMF to FDCA under base-free conditions. This work provides a valuable reference for similar aerobic oxidation processes in which alkaline promoters and noble metal catalysts are needed.</description><subject>Chemical synthesis</subject><subject>Enthalpy</subject><subject>Free energy</subject><subject>Free radicals</subject><subject>Gibbs free energy</subject><subject>High entropy alloys</subject><subject>Hydroxyl radicals</subject><subject>Hydroxymethylfurfural</subject><subject>Molecular structure</subject><subject>Noble metals</subject><subject>Oxidation</subject><issn>1463-9262</issn><issn>1463-9270</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpFkctKBDEQRRtR8LnxCwLuxNY8u3uWMj5RcDOum3RSsTP0JGOSAeNv-YNmUBQKqoo6995FVdUpwZcEs9nVDb-fY0665mmnOiC8YfWMtnj3b27ofnUY4xJjQtqGH1RfixHCyuvs5MoqOU0ZxSSHCVDMLo0QbUTeoNG-jQhcCn6dUaF8jkg6jcAYq2w5FJ2SSU75EzTyH1bLZL3bSkU9Zh38R15BGvNkNqGUnJB1ySN6Iert6nQJD0OhJquQVFajjdMQ0CAj1CYAIOULtDWNx9WekVOEk99-VL3e3S7mD_Xzy_3j_Pq5VoR3qdZMCaqxEVxwzvjAhDZGi1YyPeuo4BQM4AED4y1gyjtjKB-6wXRYtLOhw-yoOvvxXQf_voGY-qXfBFcie0Zo07Ssa2ihzn8oFXyMAUy_DnYlQ-4J7rdP6f-fwr4B7w6ECA</recordid><startdate>20241111</startdate><enddate>20241111</enddate><creator>Lv, Guangqiang</creator><creator>Liu, Shan</creator><creator>Chen, Xiaoyan</creator><creator>Chen, Mengxin</creator><creator>Wu, Yanjuan</creator><creator>Gao, Yuji</creator><creator>Wang, Shuai</creator><creator>Tao, Furong</creator><creator>Wang, Jingui</creator><creator>Niu, Liwei</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7ST</scope><scope>7U6</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0003-3531-0415</orcidid><orcidid>https://orcid.org/0000-0002-1288-3408</orcidid><orcidid>https://orcid.org/0000-0001-9947-9821</orcidid><orcidid>https://orcid.org/0000-0003-1610-4966</orcidid></search><sort><creationdate>20241111</creationdate><title>Thermodynamically stable synthesis of high entropy alloys and efficiently catalyzed oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under base-free conditions</title><author>Lv, Guangqiang ; 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In this work, a thermodynamically stabilized high-entropy alloy (HEA) structure with relatively low Pt content was synthesized via a simple impregnation–calcination procedure by tuning the mixing enthalpy and the Gibbs free energy of the metal-mixing system. The prepared HEA shows excellent catalytic performance in the aerobic oxidation of HMF into FDCA under base-free conditions. Experiments and DFT calculations revealed that molecular O 2 can be easily activated into highly oxidative hydroxyl radicals (˙OH) in the presence of water over the HEA surface, and facilitates the oxidation of HMF to FDCA under base-free conditions. 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source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
subjects | Chemical synthesis Enthalpy Free energy Free radicals Gibbs free energy High entropy alloys Hydroxyl radicals Hydroxymethylfurfural Molecular structure Noble metals Oxidation |
title | Thermodynamically stable synthesis of high entropy alloys and efficiently catalyzed oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under base-free conditions |
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