“d‐Electron Complementation” Induced V‐Co Phosphide for Efficient Overall Water Splitting

Zhang, Rui; Wei, Ziyu; Ye, Gaoyang; Chen, Guanjie; Miao, Jiaojiao; Zhou, Xuehua; Zhu, Xiangwei; Cao, Xiaoqun; Sun, Xiangnan

doi:10.1002/aenm.202101758

Cited by 114 publications

(91 citation statements)

References 63 publications

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“…Meanwhile, the binding energy of P reduces by 0.4 eV after V incorporation, indicating the increased electron cloud density around P sites in VÀ CoP 2 . [40] There observations can be ascribed to the fact that V with multiple valences can manipulate the valence state and electronic structure of Co element, [41,42] making electron-rich Co transfer electrons to P. In consequence, Co loses electrons leading to higher binding energy, whereas P acquires electrons generating lower binding energy. The above results indicate that V incorporation alters the crystal environment and electronic structure of CoP 2 , which could regulate the adsorption behavior of reactive intermediates, thus promoting catalytic activity.…”

Section: Resultsmentioning

confidence: 99%

Vanadium‐Incorporated CoP₂ with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Wang

Jiao

et al. 2022

Angewandte Chemie

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Proton exchange membrane water electrolyzer (PEMWE) in acidic media is a hopeful scenario for hydrogen production by using renewable energy sources, but the grand challenge lies in substituting active and stable noble-metal catalysts. Herein, a robust electrocatalyst of V-CoP2 porous nanowires arranged on carbon cloth is successfully fabricated via incorporating vanadium into CoP2 lattice. Structural characterizations and theoretical analysis indicate that lattice expansion of CoP2 caused by V incorporation results in the upshift of d-band center, which is conducive to hydrogen adsorption for boosting HER activity. Besides, V promotes surface reconstruction to generate a thicker Co3O4 layer that enhances acid-corrosion resistance and optimizes the adsorption of water and oxygen-containing species, thus improving OER activity and stability. Accordingly, it presents a superior acidic overall water splitting activity (1.47 V@10 mA cm -2 ) over Pt-C/CC||RuO2/CC, and remarkable stability. This work proposes a new route to design efficient electrocatalysts via lattice engineering for PEMWE.

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Section: Resultsmentioning

confidence: 99%

Vanadium‐Incorporated CoP₂ with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Wang

Jiao

et al. 2022

Angewandte Chemie

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“…The adsorption free energies of H 2 O (ΔG(*H 2 O)) and H (ΔG(*H)) on the obtained CoP surfaces were studied using DFT calculations (Figures S13 and S14, Supporting Information). The H 2 O absorption process in a neutral solution involves several major steps, as indicated below: 23] H 2 O underwent a 4-step process to complete the entire HER, including: H 2 O + *, H* + OH*, H* + OH -, and ½ H 2 + * + OH -. [24] The ΔG(*H 2 O) value of CoP decreased from −0.16 to −0.83 eV after doping with N and Cu, which can be attributed to the enhancement of the electric positivity of the metal sites, which favors the adsorption of negative O in H 2 O molecules, as described above (Figure 3e).…”

Section: Resultsmentioning

confidence: 99%

Self‐Co‐Electrolysis for Co‐Production of Phosphate and Hydrogen in Neutral Phosphate Buffer Electrolyte

Chen

et al. 2022

Advanced Materials

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and environmental problems caused by the consumption of fossil fuels. [2] Conventional electrocatalytic systems, which are usually driven by an external electric supply and focus on producing a singletarget chemical, cannot meet the current demands of human society. [3] Therefore, novel electrocatalytic systems, especially co-electrocatalysis and self-powered electrocatalysis, have been designed to produce higher-value-added chemicals yields with a lower consumption of energy.Our group has previously reported the co-electrocatalytic conversions of H 2 O and glycerol, [4] and CO 2 and methanol, [5] which require an external power supply; however, their electrical energy consumption is significantly reduced, and the final products are value-added compounds. Comparatively, self-powered systems such as lithium-carbon, [6] Zn-H 2 O, [7] Zn-NO 3 -, [8] and hydrazine-H 2 O, [9] have also been reported using sacrificial metal anodes. Although self-powered systems have been considered an efficient method to produce high-value chemicals, two major drawbacks are associated with the applications of currently available SPSs: i) strong acidic and/or alkaline electrolytes are used, thus posing a safety risk to the operators, and ii) anodes are consumed without any value-added chemicals being produced. [10] Herein, we report a general and efficient self-co-electrolysis system (SCES) for the co-production of high-value chemicals at both electrodes in a neutral phosphate buffer solution (PBS) that does not require external power. This method assimilates the favorable chemical production by co-electrocatalysis and the self-energy supply of SPSs in one system. Additionally, it minimizes both safety and environmental concerns. We have chosen to use Zn as the anode in our system.Zn is abundant in the earth and is relatively inexpensive. It has a moderate equilibrium potential (−0.76 V), which features both high safety and high electrochemical performance under aqueous conditions. H 2 can be easily generated by sacrificing Zn in acidic or alkaline solutions; however, neutral media pose fewer safety risks; nonetheless, the reaction remains challenging owing to its sluggish kinetics and the low-value counterpart product of ZnO. To the best of our knowledge, there are no reports based on electrochemical Zn-H 2 O assemblies that employ neutral electrolytes. We hypothesized that a commercial Zn-H 2 O electrochemical configuration for efficient HER using neutral electrolytes under ambient conditions should meet twoThe spontaneous reaction between Zn and H 2 O is of critical importance and could plausibly be used to produce H 2 gas, especially under neutral conditions. However, this reaction has long been overlooked owing to its sluggish kinetics and Zn consumption. Herein, a unique self-co-electrolysis system (SCES) is reported, which uses a Zn anode, a CoP-based catalytic cathode, and a neutral phosphate buffer solution (PBS) as the electrolyte. In this SCES, Zn is not only a sacrificial anode but also an important precursor of highvalue...

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“…6 b and Additional file 1 : Table S4). The smaller energy gap between E Y3d3/2 and E Y3d5/2 suggest it is easier to reduce Y(III) by the oxidation of Ru(IV), favoring a high OER kinetics [ 53 ].…”

Section: Resultsmentioning

confidence: 99%

Regulating the electronic structures of mixed B-site pyrochlore to enhance the turnover frequency in water oxidation

et al. 2022

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This paper describes the development of mixed B-site pyrochlore Y2MnRuO7 electrocatalyst for oxygen evolution reaction (OER) in acidic media, a challenge for the development of low-temperature electrolyzer for green hydrogen production. Recently, several theories have been developed to understand the reaction mechanism for OER, though there is an uncertainty in most of the cases, due to the complex surface structures. Several key factors such as lattice oxygen, defect, electronic structure, oxidation state, hydroxyl group and conductivity were identified and shown to be important to the OER activity. The contribution of each factor to the performance however is often not well understood, limiting their impact in guiding the design of OER electrocatalysts. In this work, we showed mixed B-site pyrochlore Y2MnRuO7 catalyst exhibits 14 times higher turnover frequency (TOF) than RuO2 while maintaining a low overpotential of ~ 300 mV for the entire testing period of 24 h in acidic electrolyte. X-ray photoelectron spectroscopy (XPS) analysis reveals that this B-site mixed pyrochlore Y2MnRuO7 has a higher oxidation state of Ru than those of Y2Ru2O7, which could be crucial for improving OER performance as the broadened and lowered Ru 4d band resulted from the B-site substitution by Mn is beneficial to the OER kinetics.

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“d‐Electron Complementation” Induced V‐Co Phosphide for Efficient Overall Water Splitting

Cited by 114 publications

References 63 publications

Vanadium‐Incorporated CoP₂ with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Vanadium‐Incorporated CoP₂ with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Self‐Co‐Electrolysis for Co‐Production of Phosphate and Hydrogen in Neutral Phosphate Buffer Electrolyte

Regulating the electronic structures of mixed B-site pyrochlore to enhance the turnover frequency in water oxidation

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“d‐Electron Complementation” Induced V‐Co Phosphide for Efficient Overall Water Splitting

Cited by 114 publications

References 63 publications

Vanadium‐Incorporated CoP2 with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Vanadium‐Incorporated CoP2 with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Self‐Co‐Electrolysis for Co‐Production of Phosphate and Hydrogen in Neutral Phosphate Buffer Electrolyte

Regulating the electronic structures of mixed B-site pyrochlore to enhance the turnover frequency in water oxidation

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Vanadium‐Incorporated CoP₂ with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting

Vanadium‐Incorporated CoP₂ with Lattice Expansion for Highly Efficient Acidic Overall Water Splitting