Electro-oxidation of 5-hydroxymethylfurfural (HMFOR) is a promising green approach to realize the conversion of biomass into value-added chemicals. However, considering the complexity of the molecular structure of HMF, an in-depth understanding of the electrocatalytic behavior of HMFOR has rarely been investigated. Herein, the electrocatalytic mechanism of HMFOR on nickel nitride (Ni₃N) is elucidated by operando X-ray absorption spectroscopy (XAS), in situ Raman, quasi in situ X-ray photoelectron spectroscopy (XPS), and operando electrochemical impedance spectroscopy (EIS), respectively. The activity origin is proved to be Ni^2+δN(OH)_ads generated by the adsorbed hydroxyl group. Moreover, HMFOR on Ni₃N relates to a two-step reaction: Initially, the applied potential drives Ni atoms to lose electrons and adsorb OH⁻ after 1.35 V_RHE, giving rise to Ni^2+δN(OH)_ads with the electrophilic oxygen; then Ni^2+δN(OH)_ads seizes protons and electrons from HMF and leaves as H₂O spontaneously. Furthermore, the high electrolyte alkalinity favors the HMFOR process due to the increased active species (Ni^2+δN(OH)_ads) and the enhanced adsorption of HMF on the Ni₃N surface. This work could provide an in-depth understanding of the electrocatalytic mechanism of HMFOR on Ni₃N and demonstrate the alkalinity effect of the electrolyte on the electrocatalytic performance of HMFOR.

5-羟甲基糠醛（HMFOR）的电氧化是一种有前途的绿色方法，可实现将生物质转化为增值化学品。但是，考虑到HMF分子结构的复杂性，很少研究对HMFOR的电催化行为的深入了解。这里，HMFOR对氮化镍的电机构（倪₃ N）是由operando X射线吸收光谱（XAS）阐明，原位拉曼，准原位X射线光电子能谱（XPS），以及operando电化学阻抗谱（ EIS）。活性来源被证明是Ni 2 ^{+ δN}（OH）_ad由吸附的羟基产生。此外，在Ni HMFOR ₃ Ñ涉及一种两步反应：首先，施加的电势驱动Ni原子失去电子并吸附OH ^-后1.35V，_RHE，产生的Ni ^{2+ δ} N（OH）_广告与亲电氧; 然后镍^{2+ δ} N（OH）_广告从HMF掌握到质子和电子和叶以H ₂ ö自发。此外，高电解质碱度有利于HMFOR过程由于增加的活性种（镍^{2+ δ} N（OH）_广告）和HMF的对Ni增强吸附₃N面。这项工作可以提供对HMFOR对Ni ₃ N的电催化机理的深入了解，并证明电解质的碱度效应对HMFOR的电催化性能。