The electrocatalytic oxidation of
5-hydroxymethylfurfural (HMF),
one of biomass-derived platform compounds, is an attractive route
to produce 2,5-furandicarboxylic acid (FDCA), an important monomer
of bio-based polyesters. Here, we successfully synthesized a highly
efficient and stable nickel phosphate (Ni3 (PO4)2) electrocatalyst by a simple hydrothermal method for
the electrocatalytic oxidation of HMF to FDCA, in which the yield
of FDCA reached 94.2% and the Faraday efficiency was 93.5% in 0.1
M KOH. Compared with nickel hydroxide (Ni (OH)2), the introduction
of phosphorus enhanced the charge transfer ability of Ni-based catalysts
by EIS and Tafel slope analysis. At the same time, the Ni2+ species in Ni3(PO4)2 was more likely
to be oxidized to active nickel species than that in Ni (OH)2 from XPS and in situ Raman results. Moreover, in situ attenuated
total reflection-surface enhanced infrared absorption spectroscopy
(ATR-SEIRAS) over Ni3(PO4)2 were
carried out to study the changes of nickel phosphate during the electrocatalytic
oxidation of HMF. According to ATR-SEIRAS, XPS, and Raman results,
it can be concluded that Ni2+ species under applied potential
in KOH solution was transformed to the high-valence nickel species/Ni3+ species with P–OH and the ring-shaped P–O
group. In addition, the phosphorus group was also involved in the
electrocatalytic oxidation of HMF. Based on these evidences, a complete
electrocatalytic oxidation process of HMF to FDCA on Ni3(PO4)2 was proposed.