Engineering the Electronic Structure of NiFe Layered Double Hydroxide Nanosheet Array by Implanting Cationic Vacancies for Efficient Electrochemical Conversion of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

Abstract

The utilization of biomass resources is essential for constructing a carbon neutral society. Electrochemical conversion of biomass-derived platform molecule 5-hydroxymethylfurfural (HMF) to 5-furandicarboxylic acid (FDCA) is a highly promising alternative pathway for the production of valuable biobased oxygenated chemicals, which primarily takes advantage of the ongoing development of efficient, robust, and inexpensive catalysts. In the present work, a carbon paper-supported nickel-iron layered double hydroxide (LDH) nanosheet array implanted with abundant cationic vacancies (d-NiFe LDH/CP) is employed as a self-standing electrode for oxidation of HMF to FDCA. A 97.35% conversion of HMF and a 96.8% yield of FDCA could be achieved at 1.48 V, with a faradaic efficiency as high as 84.47% in 1 M KOH electrolyte. More importantly, it also exhibits excellent stability for 10 cycles. The successful introduction of M 2+ vacancies was proved by electron paramagnetic resonance spectroscopy. X-ray photoelectron spectroscopy results confirmed that the implanted cationic vacancies would effectively raise the electron density of d-NiFe LDH and tailor the electronic structures of metal sites. This results in a significantly increased active site number and lowered charge transfer resistance that facilitate the electrocatalytic performance improvement. Postreaction characterization indicates that the in situ generated metal (oxy)hydroxides are the active species, and the HMF would be oxidized through both chemical and electrochemical pathways. These interesting findings shed light on the innovation of defect-rich catalysts and their promising application in electrochemical biomass derivative upgrading.

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

“…(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…”

“…For example, Wang et al. successfully prepared carbon paper–supported NiFe‐layered 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 of cationic vacancies, which was beneficial to improve the electrocatalytic performance (Figure 6D).…”

“…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.…”

Interfacial Engineering of Ni/Ni0.2Mo0.8N Heterostructured Nanorods Realizes Efficient 5-Hydroxymethylfurfural Electrooxidation and Hydrogen Evolution

“…22−24 The pioneering work of Grabowski and his colleagues in 1991 demonstrated the selective HMF oxidation electrocatalyzed by nickel oxide/hydroxide, leading to the production of FDCA with 71% yield. 25 Over the past decades, various transitionmetal-based electrocatalysts have been developed as efficient alternatives to selectively produce FDCA, owing to their prominent catalytic performance, stability, low cost, as well as environmental friendship. 26−29 However, most of the developed electrocatalysts have been exclusively dedicated to accelerate anodic oxidation of HMF, and the use of distinct catalysts is highly required to pair the hydrogen evolution reaction (HER) on the cathode with the HMF electrooxidation reaction (HMFOR) on the anode, which would bring about manipulative complexity and cost issues.…”

Paired Electrolysis of Acrylonitrile and 5-Hydroxymethylfurfural for Simultaneous Generation of Adiponitrile and 2,5-Furandicarboxylic Acid

“…In the search for a suitable anode reaction, we noticed that water-soluble 5-hydroxymet hylfurfural (HMF) produced by glucose (a downstream product of lignin biomass [3]) dehydration [4] could be selectively oxidized to 2,5-furandicarboxylic acid (FDCA). As a crucial renewable polymer monomer to replace petroleum-based terephthalic acid, FDCA might polymerize into poly(ethylene 2,5-furandicarboxylate) (PEF), which is regarded as a substitute for petroleum-based polyethylene terephthalate (PET) [5].…”