Replacing the anodic oxygen evolution reaction (OER) in water splitting with 5-hydroxymethylfurfural oxidation reaction (HMFOR) can not only reduce the energy required for hydrogen production but also yield the valuable chemical 2,5-furandicarboxylic acid (FDCA). Co-based catalysts are known to be efficient for HMFOR, with high-valent Co being recognized as the main active component. However, efficiently promoting the oxidation of Co 2+ to produce high-valent reactive species remains a challenge. In this study, Ni-doped CoTe (CoNiTe) nanorods were prepared as efficient catalysts for HMFOR, achieving a high HMFOR current density of 65.3 mA cm −2 at 1.50 V. Even after undergoing five successive electrolysis processes, the Faradaic efficiency (FE) remained at approximately 90.7 %, showing robust electrochemical durability. Mechanistic studies indicated that Ni doping changes the electronic configuration of Co, enhancing its charge transfer rate and facilitating the oxidation of Co 2+ to high-valent CoO 2 species. This work reveals the effect of Ni doping on the reconfiguration of the active phase during HMFOR.
R. Zhang,F. Gao,C. Yang,Y. Bian,G. Wang,K. Xue,J. Zhang,C. Wang,X. Gao
Coupling electrocatalytic 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) with hydrogen evolution reaction (HER) is capable of potentially enhancing energy efficiency for hydrogen production and converting biomass into high-valued products. Herein, a novel metallic heterostructure based on Ni 3 S 2 and Co 9 S 8 (Co 9 S 8 @Ni 3 S 2 /NF) was designed for H 2 production and selective oxidation of HMF into 2, 5-furandicarboxylic acid (FDCA). Benefiting from the merit of metal heterojunction, Co 9 S 8 @Ni 3 S 2 /NF not only possesses appropriate H∗ adsorption energy , but also promotes the adsorption and desorption process of organic, thus making reaction dynamics for both HER and HMFOR more exceptional. Furthermore, the anion exchange membrane (AEM) electrolyzer with Co 9 S 8 @Ni 3 S 2 /NF as anode and cathode electrodes toward HMFOR and HER only required a low potential of 1.61 V for continuous hydrogen and FDCA production at the initial current density of 50 mA/cm 2 . The generation rate of H 2 and FDCA are as high as 45.6 L/h/m 2 and 7.25 mg/h/cm 2 , corresponding to the Faraday efficiency of ∼100% and 93.0%, respectively. The in-situ Raman and theoretical calculations demonstrated that the electron transfer from Ni 3 S 2 to Co 9 S 8 at heterogeneous interface contributes to the formation of Ni/Co–OOH, which is the active species of HMFOR.
Construction of highly active and stable bifunctional catalysts for 5-hydroxymethylfurfural oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is meaningful but remains a challenge. Herein, the NiCo–Mo 2 N heterostructure nanosheets catalyst with excellent HMFOR/HER performance is obtained by a simple hydrothermal and calcination method. The heterogeneous interface between NiCo and Mo 2 N induces electron redistribution, regulating the electronic structure of the catalyst and thus optimizing the adsorption/desorption behavior of HMFOR/HER intermediates. Consequently, NiCo–Mo 2 N/NF exhibits superior catalytic activity with a potential of 1.14 V RHE /−17 mV RHE (HMFOR/HER) at ±10 mA cm −2 , and the HMF conversion rate, FDCA yield, and Faradaic efficiency (FE) are ∼100%, 99.98%, and 98.65%, respectively. Besides, it only requires a low voltage of 1.36 V to achieve 100 mA cm −2 for HMFOR-assisted H 2 production. This study provides a strategy for the development of efficient bifunctional catalysts for sustainable production of high value-added products and hydrogen.
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