Surface-confined self-reconstruction to sulfate-terminated ultrathin layers on NiMo3S4 toward biomass molecule electro-oxidation

Wu, Tong; Xu, Zhongyi; Wang, Xunlu; Luo, Min; Xia, Yu; Li, Jiantao; Liu, Jie; Wang, Jiacheng; Wang, Hsing‐Lin; Huang, Fuqiang

doi:10.1016/j.apcatb.2022.122126

Cited by 39 publications

(10 citation statements)

References 55 publications

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“…[7] A recent study reported that the S evolution to SO 4 2− in the NiMo 3 S 4 structure during the electrochemical process can effectively prevent the deep oxidation of the surface and thus increase the reaction kinetics of HMFOR. [8] Nevertheless, the influence of different S doping on the behavior of surface reconstruction, HMF adsorption, and oxidation mechanism of these Ni-based catalysts is still rarely reported and lacks deep and systematic study.…”

mentioning

confidence: 99%

S‐Species‐Evoked High‐Valence Ni²⁺^δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

et al. 2023

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An efficient NiSx‐modified β‐Ni(OH)2 electrode is reported for the selective oxidation reaction of 5‐hydroxymethylfurfural (HMFOR) with excellent electrocatalytic 5‐hydroxymethylfurfural (HMF) selectivity (99.4%), conversion (97.7%), and Faradaic efficiency (98.3%). The decoration of NiSx will evoke high‐valence Ni2+δ species in the reconstructed β‐Ni(OH)2 electrode, which are the real active species for HMFOR. The generated NiSx/Ni(OH)O modulates the proton‐coupled electron‐transfer (PCET) process of HMFOR, where the electrocatalytically generated Ni(OH)O can effectively trap the protons from the CHO end in HMF to realize electron transfer. The oxygen evolution reaction (OER) competes with the HMFOR when NiSx/Ni(OH)O continues to accumulate, to generate the NiSx/NiOx(OH)y intermediate. Density functional theory (DFT) calculations and experimental results verify that the adsorption energy of HMF can be optimized through the increased NiSx composition for more efficient capture of protons and electrons in the HMFOR.

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mentioning

confidence: 99%

S‐Species‐Evoked High‐Valence Ni²⁺^δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

et al. 2023

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“…And two peaks located at around 510 and 1060 cm −1 belong to the first-order longitudinal optical (LO) and the frequency doubled mode (2LO) of NiO, respectively 45,46 . From the above analysis, it can be inferred that hydroxyl hydroxide is formed on the surface of Co-NiMoO/NF nanorods after HMFOR stability test, which serves as active species for HMFOR, and covers the MoOx 39,40,47 .…”

Section: Hmfor Performancementioning

confidence: 97%

Electronic Modulation of Ni-Mo-O Porous Nanorods by Co Doping for Selective Oxidation of 5-Hydroxymethylfurfural Coupled with Hydrogen Evolution

Zheng¹,

Jia²,

Wang³

et al. 2023

Acta Physico Chimica Sinica

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Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy. Biomass, a sustainable organic carbon source, can meet the huge demand for energy and chemicals. Among them, 5hydroxymethylfurfural (HMF) is an important biomass-derived platform molecule, which can be converted into various high-value chemicals. One of its oxidation products, 2,5-furandicarboxylic acid (FDCA), is expected to replace terephthalic acid as a raw material for the synthesis of bio-based degradable plastics. The electrooxidation of HMF emerges as a promising green route for preparing FDCA due to its advantages of mild conditions, fast reaction rate, and high selectivity. The theoretical potential of the HMF electrooxidation reaction (HMFOR, 0.3 V vs. reversible hydrogen electrode, RHE) is also lower than that of the oxygen evolution reaction (OER, 1.23 V vs. RHE). Coupling anodic HMFOR with cathodic hydrogen evolution reaction (HER) is expected to simultaneously produce valuable FDCA and reduce the cell voltage of hydrogen (H2) evolution. However, the construction of efficient and stable bifunctional catalysts for HMFOR-assisted H2 production is still challenging. In this study, Co-doped Ni-Mo-O porous nanorods grown on a nickel foam (Co-NiMoO/NF) is prepared by simple hydrothermal and calcination methods for both HMFOR and HER. Results of electrocatalytic studies indicate that Co-NiMoO/NF exhibits enhanced performance for HMFOR (E10/100 = 1.31/1.37 V vs. RHE) and HER (E−10/−100 = −35/−123 mV vs. RHE) and shows durable HMFOR/HER stability. In particular, Co-NiMoO/NF maintains high FDCA selectivity (~99.2%) and Faradaic efficiency (~95.7%) for 40 successive cycles at 1.36 V vs. RHE for HMFOR. Conversely, Co-NiMoO/NF maintains stable operation at −200 mA•cm −2 for 50 h with no significant activity attenuation for HER. When coupled as a bifunctional electrode for overall HMF splitting, Co-NiMoO/NF reaches an electric flux of 50 mA•cm −2 at 1.48 V, which is 290 mV lower than that of the overall water splitting. This confirms that the HMFOR-assisted H2 production over Co-NiMoO/NF significantly reduces the energy consumption. Moreover, the two-electrode system maintains good FDCA selectivity (97.6%) for 10 cycles at 1.45 V, implying good stability of HMFOR-assisted H2 evolution. The remarkable catalytic performance of Co-NiMoO/NF could be due to the introduction of Co, which optimizes the electronic structure of Ni-Mo-O and adsorption behaviors of the reactants, thereby enhancing the intrinsic activity and stability of the catalyst. Meanwhile, the porous nanorod structure enhanced the mass transport of substrates and desorption of bubbles, thereby elevating the HMFOR/HER kinetics. This study provides useful insights for designing efficient and durable bifunctional catalysts for HMFOR and HER.

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“…124 The electrocatalytic OER influenced by residual or adsorbed anionic species, such as P, S, and Se, was investigated in alkaline media. 126,127 Thus, as shown in Figure 9d, the Wang group grew different oxyanions on commercial nickel foams to study its effects toward MOR by anionic species. And then followed by the in situ electrochemical oxidation in the alkaline, the different coordination environment of these oxyanions (NiOOH-TO x , T= P, S, and Se) of Ni sites were formed (Figure 9e).…”

Section: Ni-basedmentioning

confidence: 99%

Boosting Hydrogen Evolution by Methanol Oxidation Reaction on Ni-Based Electrocatalysts: From Fundamental Electrochemistry to Perspectives

Li,

Wang

et al. 2024

ACS Energy Lett.

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Hydrogen production via electrocatalytic water splitting is hampered by the slow kinetics of the anodic oxygen evolution reaction (OER). To address this limitation, the electrochemical hydrogen evolution reaction (HER) can be boosted with the more favorable oxidation of small organic molecules ideally driven by renewable energies, producing valuable chemicals. In this context, coupling hydrogen production with the methanol oxidation reaction (MOR) with simultaneous formate production has garnered significant interest. Such a cost-effective electrocatalytic process, meeting the growing demand for energy storage and fuel production, requires developing cheap and efficient electrocatalysts. Given the knowledge gap between precious and nonprecious metal electrocatalysts, exemplified by nickel and its derived compounds, this review focuses on MOR from fundamental electrochemistry, materials design and synthesis, and activity-composition/structure relations. Despite significant advances, we still face formidable challenges in deciphering the intricate catalytic mechanism, elevating the activity and selectivity to new heights, and pioneering the development of scalable prototypes.

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Surface-confined self-reconstruction to sulfate-terminated ultrathin layers on NiMo3S4 toward biomass molecule electro-oxidation

Cited by 39 publications

References 55 publications

S‐Species‐Evoked High‐Valence Ni²⁺^δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

S‐Species‐Evoked High‐Valence Ni²⁺^δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

Electronic Modulation of Ni-Mo-O Porous Nanorods by Co Doping for Selective Oxidation of 5-Hydroxymethylfurfural Coupled with Hydrogen Evolution

Boosting Hydrogen Evolution by Methanol Oxidation Reaction on Ni-Based Electrocatalysts: From Fundamental Electrochemistry to Perspectives

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Surface-confined self-reconstruction to sulfate-terminated ultrathin layers on NiMo3S4 toward biomass molecule electro-oxidation

Cited by 39 publications

References 55 publications

S‐Species‐Evoked High‐Valence Ni2+δ of the Evolved β‐Ni(OH)2 Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

S‐Species‐Evoked High‐Valence Ni2+δ of the Evolved β‐Ni(OH)2 Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

Electronic Modulation of Ni-Mo-O Porous Nanorods by Co Doping for Selective Oxidation of 5-Hydroxymethylfurfural Coupled with Hydrogen Evolution

Boosting Hydrogen Evolution by Methanol Oxidation Reaction on Ni-Based Electrocatalysts: From Fundamental Electrochemistry to Perspectives

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S‐Species‐Evoked High‐Valence Ni²⁺^δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

S‐Species‐Evoked High‐Valence Ni²⁺^δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural