Tunable charge transfer efficiency in HxMoO3@ZnIn2S4 hierarchical direct Z-scheme heterojunction toward efficient visible-light-driven hydrogen evolution

Xing, Fangshu; Cheng, Chu Yong; Zhang, Jingwen; Liu, Min; Chen, Cheng; Huang, Caijin

doi:10.1016/j.apcatb.2020.119818

Cited by 101 publications

(32 citation statements)

References 59 publications

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“…The surface phases of the Ru–Mo–oxides have been further probed by Raman, which is more surface sensitive than XRD . In situ Raman measurements (Figure c) show that the signals from the MoO 3 phase in 1.9 wt % Ru–Mo–O x decrease largely in their intensity upon exposure to the reaction gas at 250 °C, which is due to hydrogen intercalation and high carrier density in the formed H x MoO 3 phase . Above 300 °C Raman peaks at 197, 221, 340, 485, 557, and 717 cm –1 become the main signals, which are from the defective MoO 3– x (0 < x < 1) phase with rich oxygen vacancies. , Both Raman and XRD results confirm that the 1.9 wt % Ru–Mo–O x catalyst in reaction gas and at temperatures above 300 °C consists of the MoO 3– x surface phase and MoO 2 bulk phase.…”

Section: Resultsmentioning

confidence: 99%

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

et al. 2022

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Encapsulation of metal nanoparticles by support-derived materials known as the classical strong metal–support interaction (SMSI) often happens upon thermal treatment of supported metal catalysts at high temperatures (≥500 °C) and consequently lowers the catalytic performance due to blockage of metal active sites. Here, we show that this SMSI state can be constructed in a Ru–MoO3 catalyst using CO2 hydrogenation reaction gas and at a low temperature of 250 °C, which favors the selective CO2 hydrogenation to CO. During the reaction, Ru nanoparticles facilitate reduction of MoO3 to generate active MoO3–x overlayers with oxygen vacancies, which migrate onto Ru nanoparticles’ surface and form the encapsulated structure, that is, Ru@MoO3–x . The formed SMSI state changes 100% CH4 selectivity on fresh Ru particle surfaces to above 99.0% CO selectivity with excellent activity and long-term catalytic stability. The encapsulating oxide layers can be removed via O2 treatment, switching back completely to the methanation. This work suggests that the encapsulation of metal nanocatalysts can be dynamically generated in real reactions, which helps to gain the target products with high activity.

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Section: Resultsmentioning

confidence: 99%

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

et al. 2022

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“…[25] Raman peaks located at 242, 308, and 353 cm −1 can be ascribed to the F 2g , F 1u , A 1g modes of ZIS, respectively. [26,27] After annealing in air, the ZIS-O sample exhibits an additional peak located at 990 cm −1 compared with ZIS, which can be ascribed to the SO stretch of SO 4 2− . Besides, ZIS-O-S with eliminated excessive surface S v shows a peak located at 990 cm −1 as well, implying that Na 2 S treatment has no effect on SO 4 2− groups.…”

Section: Resultsmentioning

confidence: 99%

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Gao

Meng

et al. 2021

Advanced Energy Materials

116

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friendly properties. [6] However, due to its severe bulk carrier recombination, unfavorable carrier transportation, and sluggish surface OER dynamics, the PEC performance of bare ZnIn 2 S 4 photoanode is still not satisfactory.Various strategies have been developed to enhance the PEC performance of ZnIn 2 S 4 , such as morphology engineering, constructing heterojunctions, and coating surface co-catalysts, etc. [7][8][9] Among them, decorating surface cocatalysts has been considered as an effective strategy to promote surface water oxidation kinetics of pristine ZnIn 2 S 4 . However, the integration of water-oxidation cocatalysts with PEC photoanodes has been limited to metal-based materials, such Co-Pi, FeCoO x , and FeOOH. [10][11][12][13][14][15] The cocatalysts containing metallic ions tend to be toxic and expensive, which could limit their further applications. In addition, these cocatalysts may cause light absorption attenuation and increased charge recombination due to the large thickness/dimension of cocatalysts and additional interface defects between cocatalysts and photo anodes. Recently, nonmetallic anionic groups, such as phosphate (PO 4 3− ), selenate (SeO 4 2− ), and sulfate (SO 4 2− ), have emerged as alternatives to boost water oxidation ability. [16][17][18] These nonmetallic groups could optimize the electronic structure of active sites, regulate the adsorption of intermediates to reduce OER overpotential, and promote the surface carrier transfer. Particularly, the SO 4 2− group can break the adsorption-energy scaling relation between OH* and OOH* (reaction intermediates) and decrease the OER overpotential. [17] Accordingly, engineering ZnIn 2 S 4 with SO 4 2− groups is a promising strategy to improve its surface reaction kinetics. However, the introduction of nonmetallic anionic groups usually relies on a direct mixing method or external addition, which leads to weak chemical interaction and thus decreases the effectiveness and durability of the resultant materials. [17] In contrast, in situ introducing SO 4 2− anionic groups into ZnIn 2 S 4 to induce strong bonding between anions and metal atoms is expected to remarkably facilitate solar water oxidation.As a kind of intrinsic defect for metal sulfide, sulfur vacancies (S v ) have the ability to adjust the electronic structure of metal sulfide, leading to optimization of the adsorption free energy and also improvement of the conductivity. [19,20] S v can be divided into bulk S v and surface S v according to their spatial Severe charge recombination and slow surface water oxidation kinetics seriously limit the practical application of ZnIn 2 S 4 photoanodes for photo electrochemical water splitting. Herein, an in situ strategy to introduce sulfate (SO 4 2− ) anions and controlled bulk sulfur vacancies (S v ) into a ZnIn 2 S 4 photoanode is developed, and its PEC performance is remarkably enhanced, achieving a photocurrent density of 3.52 mA cm −2 at 1.23 V versus reversible hydrogen electrode (V RHE ) and negatively shifted onset potential of 0....

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“…1-647) [19] and hexagonal phase of ZnIn 2 S 4 (JCPDS No. 65-2023), [24] respectively. For XRD pattern of ZIS/CS, not only peaks corresponding to CdS but also the ZnIn 2 S 4 could be observed, respectively, suggesting the successful synthesis of heterojunction.…”

Section: Characterization Of Morphology and Structurementioning

confidence: 97%

Constructing Direct Z‐Scheme Heterostructure by Enwrapping ZnIn₂S₄ on CdS Hollow Cube for Efficient Photocatalytic H₂ Generation

Jiang

et al. 2022

Advanced Science

111

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Rational design hybrid nanostructure photocatalysts with efficient charge separation and transfer, and good solar light harvesting ability have critical significance for achieving high solar-to-chemical conversion efficiency. Here a highly active and stable composite photocatalyst is reported by integrating ultrathin ZnIn 2 S 4 nanosheets on surface of hollow CdS cube to form the cube-in-cube structure. Experimental results combined with density functional theory calculations confirm that the Z-scheme ZnIn 2 S 4 /CdS heterojunction is formed, which highly boosts the charge separation and transfer under the local-electric-field at semiconductor/semiconductor interface, and thus prolongs their lifetimes. Moreover, such a structure affords the highly enhanced light-harvesting property. The optimized ZnIn 2 S 4 /CdS nanohybrids exhibit superior H 2 generation rate under visible-light irradiation (𝝀 ≥ 420 nm) with excellent photochemical stability during 20 h continuous operation.

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Tunable charge transfer efficiency in HxMoO3@ZnIn2S4 hierarchical direct Z-scheme heterojunction toward efficient visible-light-driven hydrogen evolution

Cited by 101 publications

References 59 publications

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Constructing Direct Z‐Scheme Heterostructure by Enwrapping ZnIn₂S₄ on CdS Hollow Cube for Efficient Photocatalytic H₂ Generation

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Tunable charge transfer efficiency in HxMoO3@ZnIn2S4 hierarchical direct Z-scheme heterojunction toward efficient visible-light-driven hydrogen evolution

Cited by 101 publications

References 59 publications

Overturning CO2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Overturning CO2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn2S4 Photoanode for Enhanced Photoelectrochemical Water Splitting

Constructing Direct Z‐Scheme Heterostructure by Enwrapping ZnIn2S4 on CdS Hollow Cube for Efficient Photocatalytic H2 Generation

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About

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Constructing Direct Z‐Scheme Heterostructure by Enwrapping ZnIn₂S₄ on CdS Hollow Cube for Efficient Photocatalytic H₂ Generation