Sequential self-reconstruction of localized Mo species in hierarchical carbon/Co–Mo oxide heterostructures for boosting alkaline hydrogen evolution kinetics and durability

Quan, Quan; Bu, Xiuming; Chen, Dong; Wang, Fei; Kang, Xiaolin; Wang, Wei; Meng, You; Yip, SenPo; Liu, Chuntai; Ho, Johnny C.

doi:10.1039/d1ta09010k

Cited by 15 publications

(13 citation statements)

References 51 publications

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“…The high-resolution Mo 3d XPS spectrum of P-Mo-Co 3 O 4 @CC is disassembled into three sets of peaks (Figure 4A), which can be attributed to Mo 4+ , Mo 5+ , and Mo 6+ species. 56,57 High-resolution Co 2p spectrum of P-Mo-Co 3 O 4 @CC in Figure 4B can be well indexed to Co 2+ (780.72 and 796.23 eV) and Co 3+ (782.43 and 798.38 eV) with corresponding satellite peaks. The introduction of Mo element with different electronegativity (χ) can spontaneously lead to the electron migration between Mo and Co, 3,58 which significantly remodels the electronic structure (i.e., charge redistribution) of the surrounding Co atoms.…”

Section: Oer Improvement Mechanismsmentioning

confidence: 94%

Plasma‐induced Mo‐doped Co₃O₄ with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Huang

Pan

et al. 2022

Carbon Energy

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Heteroatomic substitution and vacancy engineering of spinel oxides can theoretically optimize the oxygen evolution reaction (OER) through charge redistribution and d‐band center modification but still remain a great challenge in both the preparation and catalytic mechanism. Herein, we proposed a novel and efficient Ar‐plasma (P)‐assisted strategy to construct heteroatom Mo‐substituted and oxygen vacancies enriched hierarchical spinel Co3O4 porous nanoneedle arrays in situ grown on carbon cloth (denoted P‐Mo‐Co3O4@CC) to improve the OER performance. Ar‐plasma technology can efficiently generate vacancy sites at the surface of hydroxide, which induces the anchoring of Mo anion salts through electrostatic interaction, finally facilitating the substitution of Mo atoms and the formation of oxygen vacancies on the Co3O4 surface. The P‐Mo‐Co3O4@CC affords a low overpotential of only 276 mV at 10 mA cm−2 for the OER, which is 58 mV superior to that of Mo‐free Co3O4@CC and surpasses commercial RuO2 catalyst. The robust stability and satisfactory selectivity (nearly 100% Faradic efficiency) of P‐Mo‐Co3O4@CC for the OER are also demonstrated. Theoretical studies demonstrate that Mo with variable valance states can efficiently regulates the atomic ratio of Co3+/Co2+ and increases the number of oxygen vacancies, thereby inducing charge redistribution and tuning the d‐band center of Co3O4, which improve the adsorption energy of oxygen intermediates (e.g., *OOH) on P‐Mo‐Co3O4@CC during OER. Furthermore, the two‐electrode OER//HER electrolyzer equipped with P‐Mo‐Co3O4@CC as anode displays a low operation potential of 1.54 V to deliver a current density of 10 mA cm−2, and also exhibits good reversibility and anticurrent fluctuation ability under simulated real energy supply conditions, demonstrating the great potential of P‐Mo‐Co3O4@CC in water electrolysis.

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Section: Oer Improvement Mechanismsmentioning

confidence: 94%

Plasma‐induced Mo‐doped Co₃O₄ with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Huang

Pan

et al. 2022

Carbon Energy

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“…Currently, non-noble metal HER catalysts mainly include transition metal phosphates, , sulfides, , oxides, , nitrides, , etc. Transition metal nitrides (TMNs) are potential catalysts for HER .…”

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confidence: 99%

Substitutional Doping Engineering toward W₂N Nanorod for Hydrogen Evolution Reaction at High Current Density

Dan

Liang

Gong

et al. 2022

ACS Materials Lett.

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Transition metal nitrides and elemental doping are effective methods to enhance the catalytic activity of hydrogen evolution reaction (HER) at a high current density. Herein, Ni-W2N@NF was synthesized to exhibit excellent HER performance in an alkaline environment. Not only theoretical but also experimental analyses prove that Ni enters the W2N lattice in the form of substitutional doping. Ni-doped W2N optimizes the free energy of hydrogen adsorption and hydroxide adsorption. Thus, the HER kinetics are accelerated. Therefore, the synthesized Ni-W2N@NF achieved an industrial high current density of 2000 mA cm–2 in 1 M KOH with a small overpotential of 317 mV. The HER activity of Ni-W2N@NF is superior to those of most reports. What is more, the obtained catalyst achieves a current density of 1500 mA cm–2 in an alkaline seawater solution with an overpotential of only 345 mV and exhibits excellent cycling stability. This work will offer a feasible idea for a designing platinum group metals free metal as an effective catalyst for HER reaction under an industrial large current in an alkaline solution.

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“…At the same time, the peak at ∼460 cm –1 assigned to Ni 2+ -SOH appeared and maintained from the open-circuit potential to 100th CV cycle, which indicated the reconstruction free of Ni 2+ -SOH during the short-period CV tests. After the final 100th CV cycle, there is no Raman single assigned to Mo–O–Mo (263, 476, and 706 cm –1 ) bonds and t-S 2 2– /b-S 2 2– (∼500–600 cm –1 ) ligands, suggesting that there is no polymerization of Mo during the HER process in the alkaline electrolyte on the surface of Mo–NT@NF. ,, This phenomenon was in contrast to many molybdenum-based materials that have been reported in the literature for HER processes. Subsequently, a series of negative potentials were applied on the initial NT@NF (Figure S41) and Mo–NT@NF (Figure c).…”

Section: Her Performancementioning

confidence: 72%

N, S Co-Coordinated Mo Defect Sites in Metal Coordination Polymers for Boosting Perdurable and High-Efficiency Alkaline Hydrogen Evolution

Liu

Zou

Cong

et al. 2023

ACS Sustainable Chem. Eng.

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In the area of water electrolysis, molybdenum sulfide (MoS x ) materials have attracted a lot of interest and investigation due to their platinum-like catalytic activity. Herein, this work describes the synthesis of a novel molybdenum-based coordination metal polymer (CMP) by adding s-triazine-2,4,6-trithiol (C3H3N3S3) ligands under mild conditions, which addresses the issues of poor electrical conductivity and limited exposure of active sites in conventional MoS x materials. Combination of X-ray absorption near-edge spectroscopy, X-ray photoelectron spectroscopy, and in situ Raman spectroscopy identifies the key role of N, S co-coordinated Mo defect site [MoV(O)S x N y ] moieties as active sites in alkaline hydrogen evolution reaction (HER) processes. Benefitting from the good electrical conductivity of the CMP network, the efficient dispersion, and anchoring of the oxygenated molybdenum sites by N and S, the optimized Mo-based CMP exhibits a high-efficiency alkaline HER (η10: 87 mV) with 30,000 CV times cycle stability. This good HER catalyst also shows well durability at 100 mA cm–2 for 80 h in alkaline simulated seawater (1 M KOH + 0.5 M NaCl). This work inspires new ideas to design N, S co-coordinated molybdenum-based CMP electrocatalysts for hydrogen production by commercial alkaline water splitting.

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Sequential self-reconstruction of localized Mo species in hierarchical carbon/Co–Mo oxide heterostructures for boosting alkaline hydrogen evolution kinetics and durability

Abstract: Surface self-reconstruction processes in alkaline hydrogen evolution reaction (HER), especially regarding the explicit structure-activity relationships, remain elusive. Here, we first design a hierarchical Co@NCNT/CoMoOx precatalyst constituted by the defective CoMoOx...

Cited by 15 publications

References 51 publications

Plasma‐induced Mo‐doped Co₃O₄ with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Plasma‐induced Mo‐doped Co₃O₄ with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Substitutional Doping Engineering toward W₂N Nanorod for Hydrogen Evolution Reaction at High Current Density

N, S Co-Coordinated Mo Defect Sites in Metal Coordination Polymers for Boosting Perdurable and High-Efficiency Alkaline Hydrogen Evolution

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Sequential self-reconstruction of localized Mo species in hierarchical carbon/Co–Mo oxide heterostructures for boosting alkaline hydrogen evolution kinetics and durability

Abstract: Surface self-reconstruction processes in alkaline hydrogen evolution reaction (HER), especially regarding the explicit structure-activity relationships, remain elusive. Here, we first design a hierarchical Co@NCNT/CoMoOx precatalyst constituted by the defective CoMoOx...

Cited by 15 publications

References 51 publications

Plasma‐induced Mo‐doped Co3O4 with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Plasma‐induced Mo‐doped Co3O4 with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Substitutional Doping Engineering toward W2N Nanorod for Hydrogen Evolution Reaction at High Current Density

N, S Co-Coordinated Mo Defect Sites in Metal Coordination Polymers for Boosting Perdurable and High-Efficiency Alkaline Hydrogen Evolution

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Plasma‐induced Mo‐doped Co₃O₄ with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Plasma‐induced Mo‐doped Co₃O₄ with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting

Substitutional Doping Engineering toward W₂N Nanorod for Hydrogen Evolution Reaction at High Current Density