Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural

IF 13.1 1区 化学 Q1 Energy Journal of Energy Chemistry Pub Date : 2024-10-17 DOI:10.1016/j.jechem.2024.09.054
Haoyu Zhan , Baixue Cheng , Yankun Lu , Danning Xing , Xingshuai Lv , Huining Huang , Thomas Frauenheim , Tao Wang , Peng Zhou
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Abstract

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.

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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
Co3O4 具有直接和间接氧化作用,被认为是一种很有前景的 5-hydroxymethylfurfural (HMF) 氧化催化剂。然而,Co3O4 对 OH- 和 HMF 的富集和活化效应较弱,限制了其进一步应用。金属缺陷工程可以调节电子结构,优化中间产物的吸附,并通过打破材料的对称性来提高催化活性,而这在生物质升级中很少涉及。在这项工作中,我们制备了具有金属缺陷的 Co3O4,并在缺陷位点上负载贵金属铂(Pt-Vco)。原位表征、电化学测量和理论计算的结果表明,Co-Co 配位数的减少和 Pt-Co 键的形成导致 Co 元素反键轨道中电子填充的减少。由此产生的 Co 的 d 带中心上移与 Pt 物种的吸附特性协同增强了有机分子和 OH- 物种的富集和活化,从而表现出优异的 HMF 氧化活性(包括较低的起始电位(1.14 V)和比纯 Co3O4 高 19 倍的电流密度(1.35 V))。综上所述,该研究详细探讨了贵金属修饰金属缺陷位点的吸附增强机理,为提高钴基材料的 HMF 氧化活性提供了新的选择,拓宽了金属缺陷基材料的应用领域,为金属缺陷位点在生物质转化中的功能化利用提供了创新性指导。
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来源期刊
Journal of Energy Chemistry
Journal of Energy Chemistry CHEMISTRY, APPLIED-CHEMISTRY, PHYSICAL
CiteScore
19.10
自引率
8.40%
发文量
3631
审稿时长
15 days
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
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