Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO<sub>3</sub> electrocatalyst

Tian, Han; Cui, Xiangzhi; Zeng, Liming; Su, Liang; Song, Yiling; Shi, Jianlin

doi:10.1039/c8ta12219a

Cited by 163 publications

(134 citation statements)

References 38 publications

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“…For a comparison, the In‐CoO/CoP nanosheets (In‐CoO/CoP NS) were also prepared by the phosphorization of In 2 O 3 /CoO precursor. From the ESR spectra shown in Figure c, In‐CoO/CoP FNS and In‐CoO/CoP NS all display the obvious signals at the position of g = 2.002, indicating the existence of oxygen vacancies in both samples . It should be noted that In‐CoO/CoP FNS exhibits the significantly increased ESR intensity relative to In‐CoO/CoP NS, demonstrating a higher oxygen vacancy concentration of In‐CoO/CoP FNS owing to the effect of in situ formed •OH free radicals …”

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confidence: 92%

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

Jin

Chen

et al. 2019

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An efficient and low‐cost electrocatalyst for reversible oxygen electrocatalysis is crucial for improving the performance of rechargeable metal−air batteries. Herein, a novel oxygen vacancy–rich 2D porous In‐doped CoO/CoP heterostructure (In‐CoO/CoP FNS) is designed and developed by a facile free radicals–induced strategy as an effective bifunctional electrocatalyst for rechargeable Zn–air batteries. The electron spin resonance and X‐ray absorption near edge spectroscopy provide clear evidence that abundant oxygen vacancies are formed in the interface of In‐CoO/CoP FNS. Owing to abundant oxygen vacancies, porous heterostructure, and multiple components, In‐CoO/CoP FNS exhibits excellent oxygen reduction reaction activity with a positive half‐wave potential of 0.81 V and superior oxygen evolution reaction activity with a low overpotential of 365 mV at 10 mA cm−2. Moreover, a home‐made Zn–air battery with In‐CoO/CoP FNS as an air cathode delivers a large power density of 139.4 mW cm−2, a high energy density of 938 Wh kgZn−1, and can be steadily cycled over 130 h at 10 mA cm−2, demonstrating great application potential in rechargeable metal–air batteries.

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confidence: 92%

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

Jin

Chen

et al. 2019

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“…[11] Among all other transition metal oxides, being excellent corrosion resistant, WO 3 stands apart due to its stability in aqueous and acidic electrolytic solution. [12,13] However, the intrinsic electronic structures of WO 3 hinders the electrolysis of water and in acidic medium electrochemical activities is very less due to the adsorption energy of the atomic hydrogen on W-site is undesirable, [14] leading to the poor activity of WO 3 for HER in acidic media. As explained from the volcano plot [15] (which is plot of Gibbs free energy (~G H ) against the current density) the hydrogen binding energy to the surface should be optimal which means Gibbs free energy should be around~G~0 KJ/mol.…”

Section: Introductionmentioning

confidence: 99%

“…Among the transition metal oxides (TMO's), tungsten oxide (WO 3 ) had received much attention due to the applications in the various fields, such as in lithium‐ion batteries, gas sensors and as electrochromic films utilizing in smart windows . Among all other transition metal oxides, being excellent corrosion resistant, WO 3 stands apart due to its stability in aqueous and acidic electrolytic solution . However, the intrinsic electronic structures of WO 3 hinders the electrolysis of water and in acidic medium electrochemical activities is very less due to the adsorption energy of the atomic hydrogen on W‐site is undesirable, leading to the poor activity of WO 3 for HER in acidic media.…”

Section: Introductionmentioning

confidence: 99%

Phase and Vacancy Modulation in Tungsten Oxide: Electrochemical Hydrogen Evolution

2019

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Defects in crystal structures often contribute to an increase in the number of catalytically active sites and, in turn, enhance the electrochemical performances. In the present work, we modulate the phase transition of tungsten oxide from hexagonal to the monoclinic by tuning annealing conditions in vacuum environment. This phase transition also accompanies the incorporation of oxygen vacancies in crystal structures. WO3‐x annealed at 550 °C (Vac‐550) shows a transition from heaxagonal to monoclinic with superior hydrogen evolution activity, exhibiting a Tafel slope of only 30 mV/dec, which is comparable that of commercial Pt/C. XRD, in situ TEM, EPR, and XPS analysis provide detailed insights into the structural transition as well as oxygen vacancy concentration of the annealed WO3‐x samples in a vacuum environment. This work paves the way towards a generalized methodology for enhancing electrochemical activity by the vacancy modulation in transition‐metal oxides.

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“…[13] In contrast, the Pt SA/m-WO 3Àx mainly contains Pt 2+ species (Supporting Information, Figure S5), suggesting the formation of ahigher coordination number with the PtÀOb onds than the PtÀPt bonds. [14] Thed econvoluted W4fp eaks correspond to the binding energy of two Woxidation states,W 6+ (4f 7/2 ,35.5 eV) and W 5+ (4f 7/2 ,34.4 eV; Figure 2b-d). Theratio of W 5+ species in the WO 3Àx with Pt was higher than that of pristine WO 3Àx (Figure 2e).…”

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Investigation of the Support Effect in Atomically Dispersed Pt on WO_3−x for Utilization of Pt in the Hydrogen Evolution Reaction

et al. 2019

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Single-atom catalysts (SACs) have attracted growing attention because they maximizet he number of active sites, with unpredictable catalytic activity.Despite numerous studies on SACs,t here is little researcho nt he support, which is essential to understanding SAC. Herein, we systematically investigated the influence of the support on the performance of the SACb yc omparing with single-atom Pt supported on carbon (Pt SA/C) and Pt nanoparticles supported on WO 3Àx (Pt NP/WO 3Àx ). The results revealed that the support effect was maximized for atomically dispersed Pt supported on WO 3Àx (Pt SA/WO 3Àx ). The Pt SA/WO 3Àx exhibited ahigher degree of hydrogen spillover from Pt atoms to WO 3Àx at the interface, compared with Pt NP/WO 3Àx ,w hichd rastically enhanced Pt mass activity for hydrogen evolution (up to 10 times). This strategy provides an ew framework for enhancing catalytic activity for HER, by reducing noble metal usage in the field of SACs.Hydrogen is being pursued as af uture alternative to fossil fuels and an ideal energy carrier for renewable energy, because it has the highest energy density per mass without any pollutants.Currently,hydrogen production is primarily based on the steam reforming of fossil fuels,w hich is accompanied by environmental issues,s uch as as ubstantial increase in atmospheric CO 2 .Accordingly,itisnecessary to find sustainable and clean alternatives. [1] Electrochemical water splitting is considered ap otentially cost-effective and promising approach for clean hydrogen production. [2] Fort he cathodic hydrogen evolution reaction (HER), platinum (Pt)-based materials are known to the most active electrocatalysts,b ut the high cost and scarcity of Pt are key obstacles to commercial applications of water electrolyzers. [3] Hitherto,n umerous design strategies have been developed for nanostructured electrocatalysts to obtain outstanding electrochemical performance. [4] These strategies are shown to improve the utilization of Pt, and thereby to reduce the use of Pt. Fore xamples,c ore-shell [5] and hollow structures [6] can significantly improve Pt utilization by diminishing the buried non-active Pt atoms inside the particles. From this point of view,single-atom catalysts (SACs), where all metal species are individually dispersed on ad esired support, could be the best candidates to meet this goal, because they offer the maximum number of surface exposed Pt atoms.S everal studies have also demonstrated that Pt SACs show greatly boosted Pt mass activity compared to commercial Pt/C.However,research that considers the effect of the support on SACs performance for the HER is rarely found. [3,7] Thec hoice of support material is one of the most promising strategies for improving (electro)catalysis because interactions between the metal and support can drastically tune the electronic structure of the supported metal, and enhance performance. [8] Furthermore,i th as been recently reported that HER performance can be improved by not only changing the electronic structure of the supported m...

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Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO₃ electrocatalyst

Abstract: Oxygen vacancy creation in WO3 induces a synergetic catalytic effect between Pt atoms and def-WO3, thus bestowing excellent HER performances.

Cited by 163 publications

References 38 publications

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

Phase and Vacancy Modulation in Tungsten Oxide: Electrochemical Hydrogen Evolution

Investigation of the Support Effect in Atomically Dispersed Pt on WO_3−x for Utilization of Pt in the Hydrogen Evolution Reaction

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Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO3 electrocatalyst

Abstract: Oxygen vacancy creation in WO3 induces a synergetic catalytic effect between Pt atoms and def-WO3, thus bestowing excellent HER performances.

Cited by 163 publications

References 38 publications

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

Oxygen Vacancy–Rich In‐Doped CoO/CoP Heterostructure as an Effective Air Cathode for Rechargeable Zn–Air Batteries

Phase and Vacancy Modulation in Tungsten Oxide: Electrochemical Hydrogen Evolution

Investigation of the Support Effect in Atomically Dispersed Pt on WO3−x for Utilization of Pt in the Hydrogen Evolution Reaction

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Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO₃ electrocatalyst

Investigation of the Support Effect in Atomically Dispersed Pt on WO_3−x for Utilization of Pt in the Hydrogen Evolution Reaction