Liu Xupo, Wang Xihui, Mao Chenxing, Qiu Jiayao, Wang Ran, Liu Yi, Chen Ye, Wang Deli
Henan Engineering Research Center of Design and Recycle for Advanced Electrochemical Energy Storage Materials, School of Materials Science and Engineering, Henan Normal University, Xinxiang, 453007, P. R. China.
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China.
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202408109. doi: 10.1002/anie.202408109. Epub 2024 Sep 3.
Electrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high-valence metal active sites toward 5-hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value-added chemical of 2,5-furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand-hybridized NiCo(OH) nanowires (BZ-NiCo(OH)) with ample electron-deficient Ni/Co sites for HMFOR. The robust electron-withdrawing capability of benzoic acid ligands in BZ-NiCo(OH) speeds up the electrochemical activation and dehydrogenation of lattice-hydroxyl-groups (M-O-H⇌M-O), boosting the formation of abundant electron-deficient and high-valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ-NiCo(OH) delivers a remarkable current density of 111.20 mA cm at 1.4 V for HMFOR, exceeding that of NiCo(OH) by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand-hybridized strategy in this work introduces a novel perspective for designing high-performance transition metal-based electrocatalysts for biomass conversion.
氢氧化物的电化学脱氢在形成用于5-羟甲基糠醛氧化反应（HMFOR）的高价金属活性位点以生产增值化学品2,5-呋喃二甲酸（FDCA）中起着至关重要的作用。在此，我们构建了具有大量缺电子Ni/Co位点的苯甲酸配体杂化的NiCo(OH)纳米线（BZ-NiCo(OH)）用于HMFOR。BZ-NiCo(OH)中苯甲酸配体强大的吸电子能力加速了晶格羟基（M-O-H⇌M-O）的电化学活化和脱氢，促进了大量缺电子和高价Ni/Co位点的形成。密度泛函理论计算表明，脱嵌质子易于与苯甲酸中的羰基形成氢键，促进质子转移。再加上Ni/Co位点对羟基和醛基的协同氧化作用，BZ-NiCo(OH)在1.4 V下对HMFOR的电流密度高达111.20 mA cm，比NiCo(OH)高出约四倍。并且FDCA产率和法拉第效率分别高达95.24 %和95.39 %。这项工作中的配体杂化策略为设计用于生物质转化的高性能过渡金属基电催化剂引入了新的视角。
