Efficient Electrooxidation of 5‐Hydroxymethylfurfural Using Co‐Doped Ni₃S₂ Catalyst: Promising for H₂ Production under Industrial‐Level Current Density

Abstract

Replacing oxygen evolution reaction (OER) by electrooxidations of organic compounds has been considered as a promising approach to enhance the energy conversion efficiency of the electrolytic water splitting proces. Developing efficient electrocatalysts with low potentials and high current densities is crucial for the large‐scale productions of H2 and other value‐added chemicals. Herein, non‐noble metal electrocatalysts Co‐doped Ni3S2 self‐supported on a Ni foam (NF) substrate are prepared and used as catalysts for 5‐hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) under alkaline aqueous conditions. For HMFOR, the Co0.4NiS@NF electode achieves an extremely low onset potential of 0.9 V versus reversible hydrogen electrode (RHE) and records a large current density of 497 mA cm–2 at 1.45 V versus RHE for HMFOR. During the HMFOR‐assisted H2 production, the yield rates of 2,5‐furandicarboxylic acid (FDCA) and H2 in a 10 mL electrolyte containing 10 × 10−3 M HMF are 330.4 µmol cm–2 h–1 and 1000 µmol cm–2 h–1, respectively. The Co0.4NiS@NF electrocatalyst displays a good cycling durability toward HMFOR and can be used for the electrooxidation of other biomass‐derived chemicals. The findings present a facile route based on heteroatom doping to fabricate high‐performance catalyses that can facilitate the industrial‐level H2 production by coupling the conventional HER cathodic processes with HMFOR.

Electrocatalytic oxidation of 5‐hydroxymethylfurfural for sustainable 2,5‐furandicarboxylic acid production—From mechanism to catalysts design

“…synthesized an efficient and low‐cost Co‐doped Ni 3 S 2 @NF electrocatalyst for HMF oxidation via a simple hydrothermal method. The results supported that the successful introduction of Co resulted in the lattice distortion and crystallinity reduction of Ni 3 S 2 , tuning the local environment of electrons 84 . Moreover, the microstructure of the sample was well regulated, which significantly increased the ECSA (Figure 6E), endowing the catalyst with an ultralow onset potential (0.9 V vs. RHE) and excellent cycling durability in a 10 ml electrolyte containing 1.0 M KOH and 10 × 10 −3 M HMF at a constant potential of 1.45 V (Figure 6F).…”

“…(A) Polarization curves of V o ‐NiO, NiO, and Ni plate; (B) 5‐hydroxymethylfurfural (HMF) adsorption energy of V o ‐NiO, and NiO 78 ; (C) volcanic plot of HMF electrooxidation on TMOs 79 ; (D) schematic illustration and linear voltammetry scanning (LSV) curves of HMF oxidation over catalysts 83 ; (E) the capacitive current densities for HMF oxidation reaction (HMFOR) of Co 0.4 NiS@NF and Ni 3 S 2 @NF; (F) the FE and selectivity of 2,5‐furandicarboxylic acid (FDCA), and the conversion of HMF obtained by the Co 0.4 NiS@NF for 11 consecutive cycles of HMFOR; (G) oxygen evolution reaction (OER) (1.0 M KOH) and half‐way injected HMF (10 × 10 −3 M HMF) under 1.45 V 84 ; (H) TEM images of the 5.2%Ce–CoP nanosheets; (I) HRTEM image of the 5.2%Ce–CoP nanosheets (the yellow circles indicate lattice defects and deformations); (J) the two‐dimensional charge difference isosurface of 5.2%Ce–CoP (red: electron‐rich area, blue: deficient area) 85 ; source : (A and B) Copyright 2022, Elsevier; (C) Copyright 2022, Elsevier; (D) Copyright 2022, American Chemical Society; (E–G) Copyright 2022, Wiley; (H–J) Copyright 2022, the Royal Society of Chemistry…”

“…87 For example, Wang et al successfully prepared carbon paper-supported NiFelayered double hydroxide (LDH) rich in cation defects (d-NiFe LDH/CP) for catalytic HMF oxidation to FDCA via hydrothermal and alkaline etching methods. 83 Characterization results showed that the electron density of d-NiFe LDH could be effectively increased by the implantation 84 Moreover, the microstructure of the sample was well regulated, which significantly increased the ECSA (Figure 6E), endowing the catalyst with an ultralow onset potential (0.9 V vs. RHE) and excellent cycling durability in a 10 ml electrolyte containing 1.0 M KOH and 10 × 10 −3 M HMF at a constant potential of 1.45 V (Figure 6F). In situ Raman spectroscopy studies showed that the surface of Co 0.4 NiS@NF is quickly reconstructed into nickel (oxy) hydroxide, which was the actual active site of HMFOR.…”

Fe-Doped Ni3S2 Nanosheets on Ni Foam for Alkaline Seawater Oxidation

“…The Ni 2p peaks are slightly shifted by 0.2 eV to higher binding energies compared with those of Ni 3 S 2 /NF, which indicates that the electronic structure of the Ni center could be changed significantly via doping the Fe element. Meanwhile, a new peak appears at 851.8 eV in the Ni 2p spectra of Ni 3 S 2 /NF, belonging to Ni 0 , while a peak of Ni 0 could not be found in Fe 1 -Ni 3 S 2 /NF, highlighting the above-mentioned results that the electronic structure of the Ni center could be modulated after Fe incorporation (Figure b). , The Fe 2p spectra contain a couple of peaks at 711.4 and 725.1 eV, which are assigned to Fe 2p 3/2 and Fe 2p 1/2 , respectively, implying successful introduction of the Fe atoms and the presence of the Fe ion in Ni 3 S 2 /NF (Figure c). , As for the S 2p spectrum, the peaks at 161.8 and 163.1 eV confirm the presence of the metal–S bonds in Fe 1 -Ni 3 S 2 /NF (Figure d) . The XRD and XPS results show that Fe 2+ is successfully doped into the lattice of Ni 3 S 2 in Fe 1 -Ni 3 S 2 /NF.…”

Growing Co–Ni–Se nanosheets on 3D carbon frameworks as advanced dual functional electrodes for supercapacitors and sodium ion batteries

“…The two peaks at 873.0 and 855.5 eV are assigned to the Ni 2p 1/2 and Ni 2p 3/2 orbitals of Ni 2+ , and the two peaks at 874.2 and 857.6 eV correspond to the Ni 2p 1/2 and Ni 2p 3/2 signals of Ni 3+ . 31 Fig. 5c shows the high-resolution Co 2p spectrum, in which the deconvoluted peaks at 797 and 782.2 eV correspond to the Co 2p 1/2 and Co 2p 3/2 orbitals of Co 2+ .…”