Electronic Modulation Induced by Ni‐VN Heterojunction Reinforces Electrolytic Hydrogen Evolution Coupled with Biomass Upgrade

Abstract

The renewable electricity‐driven hydrogen evolution reaction (HER) coupled with biomass oxidation is a powerful avenue to maximize the energy efficiency and economic feedback, but challenging. Herein, porous Ni‐VN heterojunction nanosheets on nickel foam (Ni‐VN/NF) are constructed as a robust electrocatalyst to simultaneously catalyze HER and 5‐hydroxymethylfurfural electrooxidation reaction (HMF EOR). Benefiting from the surface reconstruction of Ni‐VN heterojunction during the oxidation process, the derived NiOOH‐VN/NF energetically catalyzes HMF into 2,5‐furandicarboxylic acid (FDCA), yielding the high HMF conversion (>99%), FDCA yield (99%), and Faradaic efficiency (>98%) at the lower oxidation potential along with the superior cycling stability. Ni‐VN/NF is also surperactive for HER, exhibiting an onset potential of ≈0 mV and Tafel slope of 45 mV dec−1. The integrated Ni‐VN/NF||Ni‐VN/NF configuration delivers a compelling cell voltage of 1.426 V at 10 mA cm−2 for the H2O‐HMF paired electrolysis, about 100 mV lower than that for water splitting. Theoretically, for Ni‐VN/NF, the superiority in HMF EOR and HER is mainly dominated by the local electronic distribution at the heterogenous interface, which accelerates the charge transfer and optimize the adsorption of reactants/intermediates by modulating the d‐band center, therefore being an advisable thermodynamic and kinetic process.

Co- and V2O3-Modified Ni-Based Nanocatalyst for 5-Hydroxymethylfurfural Electrooxidation

“…However, during 10 consecutive electrolysis cycles, the leaching content of V gradually decreases, which could be the fact that the in situ formed NiOOH prevents the leaching of V (Table S3). Overall, Co–Ni/V 2 O 3 /NF possesses a good HMFOR stability.…”

“…7 Jia et al revealed that 1.352 V RHE is required to reach 10 mA cm −2 on Ni-VN/NF and the derived NiOOH reacts with the HMF molecule during HMFOR. 13 Additionally, Luo et al proposed that the in situ generated NiOOH during the electrocatalysis process could chemically oxidize HMF and be reduced to low-valent species. 14 In this case, the reaction process follows an indirect oxidation mechanism, and NiOOH is reduced to Ni(OH) 2 by oxidizing aldehyde and hydroxyl groups of HMF (eqs 1−4).…”

“…For example, Zhou et al discovered that the formation of NiOOH on NiCo 2 O 4 electrode is beneficial to the electrochemical oxidation of HMF to FDCA (>99% selectivity and Faradaic efficiency at 1.45 V RHE ) . Jia et al revealed that 1.352 V RHE is required to reach 10 mA cm –2 on Ni-VN/NF and the derived NiOOH reacts with the HMF molecule during HMFOR . Additionally, Luo et al proposed that the in situ generated NiOOH during the electrocatalysis process could chemically oxidize HMF and be reduced to low-valent species .…”

Metal–Organic Framework-Derived Cu2O–Cu2S Heterojunction Nanostructures on Copper Foams for Furfural Electrohydrogenation

“…28 For example, proficient biomass upgrading was accomplished through the construction of Ni−vanadium nitride (Ni−VN) heterojunctions as well as the modulation of electronic dynamics. 29 Inspired by the results presented above, we successfully synthesized MOF-derived Cu 2 O−Cu 2 S heterojunction nanostructures on copper foams (Cu 2 O−Cu 2 S@CF) via a meticulously designed two-step methodology. The resulting Cu 2 O−Cu 2 S@CF electrocatalyst was subsequently deployed to investigate the electrohydrogenation performance of FF in a KOH aqueous solution under ambient conditions.…”

CuO–Ni(OH)2 heterostructure nanosheets: a high-performance electrocatalyst for 5-hydroxymethylfurfural oxidation

“…19 The interaction between the catalyst and reactants is a key factor in determining catalytic effectiveness, which is heavily influenced by the electronic arrangement at the surface/interface. 20 One effective strategy for modifying the electronic distribution and enhancing electrocatalytic performance is the construction of heterogeneous interfaces by combining different components. 21 These interfaces leverage the strengths of each component, leading to improved overall performance.…”