Highly Efficient Electro‐reforming of 5‐Hydroxymethylfurfural on Vertically Oriented Nickel Nanosheet/Carbon Hybrid Catalysts: Structure–Function Relationships

Abstract

Ni‐promoted electrocatalytic biomass reforming has shown promising prospect in enabling high value‐added product synthesis. Here, we developed a novel hybrid catalyst with Ni nanosheet forests anchored on carbon paper. The hybrid catalyst exhibits high efficiency in electrooxidation of HMF to FDCA coupling with H2 production in high purity. The Ni nanosheets have small crystal grain sizes with abundant edges, which is able to deliver an efficient HMF oxidation to FDCA (selectivity >99 %) at low potential of 1.36 VRHE with high stability. The post‐reaction structure analysis reveals the Ni nanosheets would transfer electrons to carbon and readily turn into NiOx and Ni(OH)x during the reaction. DFT results suggest high valence Ni species would facilitate the chemical adsorption (activation) of HMF revealing the reaction pathway. This work emphasizes the importance of the precise control of Ni activity via atomic structure engineering.

Selective Electrooxidation of Biomass‐Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel‐Oxide‐Supported Ruthenium Single‐Atom Catalyst

“…Further oxidation leads to a high FFCA yield of 75.8 %, which is another aldehyde product of HMFOR and exhibits great potential as an intermediate [32] . It is noted that the formation of FDCA is largely inhibited in 1.0 M PBS, distinct form the previously reported HMFOR in alkaline medium [15, 16] . Accordingly, a possible HMFOR pathway in 1.0 M PBS over the Ru 1 ‐NiO catalyst is proposed in Figure 3e.…”

“…[32] It is noted that the formation of FDCA is largely inhibited in 1.0 M PBS, distinct form the previously reported HMFOR in alkaline medium. [15,16] Accordingly, a possible HMFOR pathway in 1.0 M PBS over the Ru 1 -NiO catalyst is proposed in Figure 3e.…”

“…The past years have witnessed a great progress in the development of the BDAOR, with efficient carboxylic acid production being extensively reported [13, 14] . Successful cases include 5‐hydroxymethylfurfural (HMF) oxidation to 2,5‐furandicarboxylic acid (FDCA), [15 16] and glycerol oxidation to formic acid [4, 11] . Currently, alkaline electrolyte is the most used medium for the BDAORs, as non‐noble metal‐based catalysts are generally active and durable in such electrolyte.…”

Unraveling the mechanism for paired electrocatalysis of organics with water as a feedstock

“…Additionally, the energy barrier of the whole reaction for 5-HMF EOR (0.66 eV) is far lower than that of OER (1.70 eV). The aforementioned results illustrate that 5-HMF oxidation is more competitive than OER 60 . Based on the above analysis, the integration of 4-NBA ERR with 5-HMF EOR substantially decreases energy consumption in comparison with water splitting.…”

Intrinsic Carbon Defects Induced Reversible Antimony Chemistry for High‐Energy Aqueous Alkaline Batteries

“…[24] Moreover, the full with at half maximum (FWHM) values of Sb on D-CS (Sb/D-CS) are higher than that of Sb on the CS electrode (Sb/CS) (Figure S11 and Table S1, Supporting Information), indicating the smaller crystal grain size of Sb based on the Scherrer equation. [25] The electron probe microanalyzer (EPMA) quantitatively analyzed Sb and C signals in a broader range scanning. For the Sb on D-CS (Sb/D-CS) sample, the wavelength-dispersive spectroscopy (WDS) mapping shows a uniform distribution and higher concentration of the Sb element across the whole sample region (Figure 2c).…”