Haoyu Zhan , Baixue Cheng , Yankun Lu , Danning Xing , Xingshuai Lv , Huining Huang , Thomas Frauenheim , Tao Wang , Peng Zhou
{"title":"铂修饰金属钴缺陷位点以实现 5-羟甲基糠醛的高效电催化氧化","authors":"Haoyu Zhan , Baixue Cheng , Yankun Lu , Danning Xing , Xingshuai Lv , Huining Huang , Thomas Frauenheim , Tao Wang , Peng Zhou","doi":"10.1016/j.jechem.2024.09.054","DOIUrl":null,"url":null,"abstract":"<div><div>Co<sub>3</sub>O<sub>4</sub> possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural (HMF). However, the enrichment and activation effects of Co<sub>3</sub>O<sub>4</sub> on OH<sup>−</sup> and HMF are weak, which limits its further application. Metal defect engineering can regulate the electronic structure, optimize the adsorption of intermediates, and improve the catalytic activity by breaking the symmetry of the material, which is rarely involved in the upgrading of biomass. In this work, we prepare Co<sub>3</sub>O<sub>4</sub> with metal defects and load the precious metal platinum at the defect sites (Pt-Vco). The results of in-situ characterizations, electrochemical measurements, and theoretical calculations indicate that the reduction of Co–Co coordination number and the formation of Pt–Co bond induce the decrease of electron filling in the antibonding orbitals of Co element. The resulting upward shift of the <em>d</em>-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH<sup>−</sup> species, thus exhibiting excellent HMF oxidation activity (including a lower onset potential (1.14 V) and 19 times higher current density than pure Co<sub>3</sub>O<sub>4</sub> at 1.35 V). In summary, this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail, provides a new option for improving the HMF oxidation activity of cobalt-based materials, broadens the application field of metal defect based materials, and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1000,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural\",\"authors\":\"Haoyu Zhan , Baixue Cheng , Yankun Lu , Danning Xing , Xingshuai Lv , Huining Huang , Thomas Frauenheim , Tao Wang , Peng Zhou\",\"doi\":\"10.1016/j.jechem.2024.09.054\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Co<sub>3</sub>O<sub>4</sub> possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural (HMF). However, the enrichment and activation effects of Co<sub>3</sub>O<sub>4</sub> on OH<sup>−</sup> and HMF are weak, which limits its further application. Metal defect engineering can regulate the electronic structure, optimize the adsorption of intermediates, and improve the catalytic activity by breaking the symmetry of the material, which is rarely involved in the upgrading of biomass. In this work, we prepare Co<sub>3</sub>O<sub>4</sub> with metal defects and load the precious metal platinum at the defect sites (Pt-Vco). The results of in-situ characterizations, electrochemical measurements, and theoretical calculations indicate that the reduction of Co–Co coordination number and the formation of Pt–Co bond induce the decrease of electron filling in the antibonding orbitals of Co element. The resulting upward shift of the <em>d</em>-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH<sup>−</sup> species, thus exhibiting excellent HMF oxidation activity (including a lower onset potential (1.14 V) and 19 times higher current density than pure Co<sub>3</sub>O<sub>4</sub> at 1.35 V). In summary, this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail, provides a new option for improving the HMF oxidation activity of cobalt-based materials, broadens the application field of metal defect based materials, and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.</div></div>\",\"PeriodicalId\":15728,\"journal\":{\"name\":\"Journal of Energy Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2024-10-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Energy Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S209549562400679X\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"Energy\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Energy Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S209549562400679X","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Energy","Score":null,"Total":0}
Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural
Co3O4 possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural (HMF). However, the enrichment and activation effects of Co3O4 on OH− and HMF are weak, which limits its further application. Metal defect engineering can regulate the electronic structure, optimize the adsorption of intermediates, and improve the catalytic activity by breaking the symmetry of the material, which is rarely involved in the upgrading of biomass. In this work, we prepare Co3O4 with metal defects and load the precious metal platinum at the defect sites (Pt-Vco). The results of in-situ characterizations, electrochemical measurements, and theoretical calculations indicate that the reduction of Co–Co coordination number and the formation of Pt–Co bond induce the decrease of electron filling in the antibonding orbitals of Co element. The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH− species, thus exhibiting excellent HMF oxidation activity (including a lower onset potential (1.14 V) and 19 times higher current density than pure Co3O4 at 1.35 V). In summary, this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail, provides a new option for improving the HMF oxidation activity of cobalt-based materials, broadens the application field of metal defect based materials, and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.
期刊介绍:
The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies.
This journal focuses on original research papers covering various topics within energy chemistry worldwide, including:
Optimized utilization of fossil energy
Hydrogen energy
Conversion and storage of electrochemical energy
Capture, storage, and chemical conversion of carbon dioxide
Materials and nanotechnologies for energy conversion and storage
Chemistry in biomass conversion
Chemistry in the utilization of solar energy