The pivot to achieve high current density for biomass electrooxidation: Accelerating the reduction of Ni3+ to Ni2+

被引：70

作者：

Yang, Zhaohui ^{[1
]}

Zhang, Baolong ^{[1
]}

Yan, Chuanyu ^{[2
]}

Xue, Zhimin ^{[3
]}

Mu, Tiancheng ^{[1
]}

机构：

[1] Renmin Univ China, Dept Chem, Key Lab Adv Light Convers Mat & Biophoton, Beijing 100872, Peoples R China

[2] Natl Univ Singapore, Dept Chem Engn & Biomol Engn, 4 Engn Dr 4, Singapore 117585, Singapore

[3] Beijing Forestry Univ, Coll Mat Sci & Technol, Beijing Key Lab Lignocellulos Chem, Beijing 100083, Peoples R China

来源：

APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2023年 / 330卷

基金：

中国国家自然科学基金;

关键词：

5-hydroxymethylfurfural electrooxidation; Actual current density; Reduction of Ni 3+to Ni 2+; Rate-determining step; ELECTROCHEMICAL OXIDATION; WATER; EVOLUTION;

D O I：

10.1016/j.apcatb.2023.122590

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Electrochemical oxidation is a promising method to convert 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with high selectivity at room temperature. Developing catalysts with high current densities is crucial for the industrial application of HMF electrooxidation reaction (HMFOR). Herein, we demonstrate that the current densities exhibited by the LSV curves are falsely high and propose to evaluate catalyst activity using anodic peak current density rather than overpotential for the comparison of actual efficiency. Besides, the reduction of Ni3+ to Ni2+ accompanied by proton coupled electron transfer (PCET) process of HMF dehydrogenation is confirmed as the rate-determining step affecting the conversion efficiency of HMF rather than Ni2+ electrooxidated to Ni3+. Theoretical calculations reveal differences in the hydrogen transfer energy barriers of PCET process. Furthermore, Ni(OH)2/NF with appropriate Cr doping shows superb activity with actual current densities of over 230 mA cm-2 at HMF concentrations of 10 mM and over 360 mA cm-2 at 20 mM (the ever highest current densities for HMFOR), and obtain a yield of more than 98% of FDCA.

引用

页数：9