First-principles study of catalytic activity of W-doped cobalt phosphide toward the hydrogen evolution reaction

Fu, Cehuang; Yan, Xiaohui; Yang, Lijun; Shen, Shuiyun; Luo, Liuxuan; Wei, Guanghua; Zhang, Junliang

doi:10.1016/s1872-2067(20)63622-1

Cited by 19 publications

(11 citation statements)

References 30 publications

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“…Δ G H* of all doped structures are shown in Tables S3–S6. According to our work before, Δ G H* is related to the d band center of metal atoms on the surface as shown in Figure . The H atom is hardly adsorbed on an invalid site as per the bridge style.…”

Section: Discussionmentioning

confidence: 83%

“…In this calculation, Δ G NRR max and Δ G HER max , which are the maximum energy requests in NRR and HER, are used to evaluate the competition in reaction thermodynamics. There are two kinds of metal sites on the (101) facet of CoP, which are marked as valid and invalid sites (Co1 and Co2) according to different adsorption energies of H* (Δ G H* ) as shown in Figure S1 . We use Co1 bri or Co1 top to mark the adsorption styles where the intermediate takes up two Co1 sites or one Co1 site.…”

Section: Calculation Methodsmentioning

confidence: 99%

“…3d-transition metal is cheap and abundant. What is more, 3d-transition-metal-doped CoP, such as Mn-/Fe-/Ni-/Cu-doped CoP, have been synthesized successfully in many experiments. − In our preliminary research of the W-doped CoP, the (101) plane of the CoP is the main active facet and its activity could be adjusted by changing the d band center during the metal-doping process. , Herein, the HER process, the NRR process, and the competition between HER and NRR on the M-doped CoP (101) plane (M = Mn, Fe, Ni, and Cu) are studied by density functional theory (DFT) further in this work. It is found that the doping changes the d band centers greatly, which influences adsorptions on CoP. , NRR and HER prefer to occur on metal active sites and the site with a greater Δ G H* often contains a larger .…”

Section: Introductionmentioning

confidence: 99%

“…16−20 In our preliminary research of the W-doped CoP, the (101) plane of the CoP is the main active facet and its activity could be adjusted by changing the d band center during the metal-doping process. 16,21 Herein, the HER process, the NRR process, and the competition between A lower ΔG NRR max and a higher ΔG HER max indicate better NRR performance. When the d band center decreases and the adsorption is weakened, ΔG NRR max is higher and ΔG HER max is lower, which promotes the HER process.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Exploration of the Thermodynamic Process Competition between NRR and HER on Transition-Metal-Doped CoP (101) Facets

Luo

Yang

et al. 2021

J. Phys. Chem. C

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Transition-metal phosphides are a series of potential electrocatalysts in many electrochemical processes, among which CoP attracts the most attention because of its high stability, abundance, and low cost. In this article, we calculate both the hydrogen evolution reaction (HER) and the nitrogen reduction reaction (NRR) processes on a series of (101) facets of M-doped CoP (M = Mn, Fe, Ni, and Cu). Mn and Fe doping leads to higher d band centers of metal sites on the surface, in which all of the adsorptions are stronger than those on nondoped CoP. Ni and Cu doping causes lower d band centers of metal sites and weakens all of the adsorptions on the CoP surface. The competition of reaction thermodynamics between HER and NRR could be understood by the theoretical onset potential, which is evaluated by the maximum energy request in the electrochemical process. In our calculations, there is a linear relationship between the adsorption energy of H* and energy requirement of the NRR’s potential-limiting step. It is revealed that when CoP is doped with metals which show weaker electronegativity, N2 adsorption is intensified and more electrons are injected into N2 during NRR, for which the NN triple bond is weakened and the catalyst performs better NRR activity and selectivity. Therefore, Mn and Fe perform better in promoting NRR. This theoretical exploration helps understand the relationship between the HER and NRR processes on the CoP (101) plane and gives a guide to design improved CoP with greater HER or NRR catalytic activity by transition-metal doping.

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Section: Discussionmentioning

confidence: 83%

Section: Calculation Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Theoretical Exploration of the Thermodynamic Process Competition between NRR and HER on Transition-Metal-Doped CoP (101) Facets

Luo

Yang

et al. 2021

J. Phys. Chem. C

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“…[1][2][3][4][5][6] Electrocatalytic water splitting has been supposed to be a green and effective avenue for large-scale production of hydrogen fuels via the hydrogen evolution reaction (HER). [7][8][9][10][11] To achieve large-scale H 2 generation from HER, an efficient HER catalyst for HER and exhibited the Pt-like electrocatalytic activity under the all pH spectrum. [33,34] Very Recently, electrocatalysts with rich Ru/RuPx interfaces have been studied for the enhanced HER activities owing to the great catalytic activity of Ru for water dissociation for forming the adsorbed -OH.…”

Section: Introductionmentioning

confidence: 99%

Heterostructure of RuO₂‐RuP₂/Ru Derived from HMT‐based Coordination Polymers as Superior pH‐Universal Electrocatalyst for Hydrogen Evolution Reaction

Zhao

Zhang

Gao

et al. 2022

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is often required with minimal overpotential and fast kinetics. [12] At present, platinum (Pt) is commonly regarded as the most active catalyst toward HER because of its high exchange current density and small Tafel slope. [13][14][15] However, the high cost, scarcity and low stability of Pt metal in non-acidic media hindered their application in practical large-scale H 2 production. [16][17][18] Accordingly, it is highly desirable to develop effective, durable, inexpensive, and readily available catalysts that could work well for HER regardless of electrolyte pH values.Earth-abundant transition metal compounds, such as metal phosphates (MP x ) and metal oxides (MO x ), have been extensively investigated to develop cost-effective catalysts for HER. [19][20][21][22][23][24] However, the catalytic performance of these electrocatalysts are still far from comparable to commercial Pt/C, especially under alkaline or neutral conditions. [25,26] Recently, Ru-based materials attract great attention as advanced substitutes for HER electrocatalysis due to their relatively low cost (≈4% of Pt), high activity and excellent stability. [27][28][29] Many efforts have been made in this regard in recent years, ruthenium phosphides (RuP x ) compounds were proved to have superior HER catalytic performance that could be comparable with commercial Pt/C catalysts from both theoretical calculations and experimental points. [30][31][32] As reported by Mu et al. that RuP 2 nanoparticles embedded into a N, P codoped carbon (RuP 2 @NPC) could be employed as a catalyst Searching for Pt-like activity, stable and economic electrocatalysts that can function at various pH values for the hydrogen evolution reaction (HER) is under increasing interest for the scientific community as H2 is a very promising energy carrier with great potential development value for renewable energy conversion. Herein, a unique self-supported heterostructure of RuO 2 -RuP 2 /Ru on the N, P co-doped carbon matrix (Ru-HMT-MP-7) is demonstrated, which is derived from HMT-based coordination polymers as superior pH-universal electrocatalysts. In the strategy, pyrolysis and phosphating processes are simultaneously proceeded that can produce the unique heterostructure containing three phases of RuO 2 , RuP 2, and Ru, at the same time the generated RuO 2 -RuP 2 /Ru can be highly dispersed on the self-assembly N, P co-doped carbon substrates. The resulting heterostructure Ru-HMT-MP-7 exhibits excellent activity superior to that of benchmark Pt/C with low overpotentials at 10 mA cm −2 (33 mV for 1.0 M KOH, 29 mV for 0.5 M H 2 SO 4 and 86 mV for 1.0 M PBS) and long-term electrocatalysis durability toward HER at various pH values. The rational construction strategy paves a novel avenue for obtaining superior pH-universal catalysts for electrochemical energy storage and conversion.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202105168.

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Surface Design Strategy of Catalysts for Water Electrolysis

Zhou

Gao

Zou

et al. 2022

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consumption leads to a range of environmental problems such as air pollution, thermal pollution, global warming, and resource shortage. [1,2] Therefore, the development of clean, renewable, and new energy that can replace traditional fossil fuels is the top priority of energy development. [3] Hydrogen energy is the most promising clean energy, with high combustion calorific value (4.5 times coke). [4] Hydrogen produces water when converting chemical energy, contributing to recycling resources. [5] There are three kinds of techniques for hydrogen production: photocatalysis, water electrolysis, and biomass reforming. Global generate electricity by using renewable energy such as wind, water, and solar energy, but the storage problem of electricity leads to incomplete utilization of electricity. [6][7][8] Water electrolysis only needs renewable electric power to drive the reaction, and it has attracted wide attention due to pollution-free and low cost. [9] As a result, water electrolysis has very broad prospects in solving energy and environmental problems.Water electrolysis technology gets hydrogen by converting electrical energy into chemical energy, oxygen is obtained on the anode via the oxygen evolution reaction (OER), and hydrogen is obtained on the cathode via the hydrogen evolution reaction (HER). [10] As commercial electrocatalysts on the anode side of electrolyzer, Ir-based catalysts can not only survive under high corrosion conditions but also show efficient catalytic performance. Noble metal materials (Ir-based OER catalysts and Pt-based HER catalysts) are the best catalysts, but the high price and rare reserves limit their long-term commercial applications. [11,12] Therefore, catalysts with high activity and low cost are the ongoing research targets. The exposure of OER catalysts to highly corrosive and oxidative conditions cause severe inactivation and instability, which is one of bottlenecks for largescale application of water electrolysis. The most stable catalyst is the corroded Fe foam, which maintains a current density of 1000 mA cm −2 at 5000 h. [13] Co 3 O 4 @CoO can maintain a steady current of >1000 h without showing significant decay. [14] However, the short-term stability of some catalysts does not meet the requirements of practical applications.This review presents the recent progress of OER and HER catalysts. Through a summary of the reaction mechanisms of OER and HER, it is clear about the specific steps in the occurrence of OER and HER. The rate-determining steps of OER and HER can indicate a specific direction for the design of the catalysts. And then focus on the recent progress on surface design of various OER and HER catalysts and find that the catalyst surface regulation plays an important role in the catalyst design.Hydrogen, a new energy carrier that can replace traditional fossil fuels, is seen as one of the most promising clean energy sources. The use of renewable electricity to drive hydrogen production has very broad prospects for addressing energy and environmental problems. T...

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First-principles study of catalytic activity of W-doped cobalt phosphide toward the hydrogen evolution reaction

Cited by 19 publications

References 30 publications

Theoretical Exploration of the Thermodynamic Process Competition between NRR and HER on Transition-Metal-Doped CoP (101) Facets

Theoretical Exploration of the Thermodynamic Process Competition between NRR and HER on Transition-Metal-Doped CoP (101) Facets

Heterostructure of RuO₂‐RuP₂/Ru Derived from HMT‐based Coordination Polymers as Superior pH‐Universal Electrocatalyst for Hydrogen Evolution Reaction

Surface Design Strategy of Catalysts for Water Electrolysis

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First-principles study of catalytic activity of W-doped cobalt phosphide toward the hydrogen evolution reaction

Cited by 19 publications

References 30 publications

Theoretical Exploration of the Thermodynamic Process Competition between NRR and HER on Transition-Metal-Doped CoP (101) Facets

Theoretical Exploration of the Thermodynamic Process Competition between NRR and HER on Transition-Metal-Doped CoP (101) Facets

Heterostructure of RuO2‐RuP2/Ru Derived from HMT‐based Coordination Polymers as Superior pH‐Universal Electrocatalyst for Hydrogen Evolution Reaction

Surface Design Strategy of Catalysts for Water Electrolysis

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Heterostructure of RuO₂‐RuP₂/Ru Derived from HMT‐based Coordination Polymers as Superior pH‐Universal Electrocatalyst for Hydrogen Evolution Reaction