Activity and Stability Boosting of an Oxygen‐Vacancy‐Rich BiVO<sub>4</sub> Photoanode by NiFe‐MOFs Thin Layer for Water Oxidation

Pan, Jinbo; Wang, Binghao; Wang, Jinbo; Ding, Hongzhi; Zhou, Wei; Li, Xuan; Zhang, Jinrong; Shen, Sheng; Guo, Jinsong; Chen, Lang; Au, Chak Tong; Jiang, Lilong; Yin, Shuang‐Feng

doi:10.1002/anie.202012550

Cited by 250 publications

(127 citation statements)

References 55 publications

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“…In order to further explore the role of SO 4 2− groups and bulk S v , DFT calculations were employed to estimate the energy barrier of each OER pathway on ZIS, ZIS‐O, and ZIS‐O‐S photoanodes. [ 38,39 ] The Gibbs free energy diagrams calculated on the surface of ZIS, ZIS‐O, and ZIS‐O‐S photoanodes are shown in Figure 4d–f. The detailed Gibbs free energy of each step is presented in Table S3, Supporting Information.…”

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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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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“…Density Functional Theory (DFT) and X‐ray photoelectron spectroscopy (XPS) confirm the strong coordination between CA and Ov‐BiVO 4 . [ 94 ] The charge redistribution through the interface endowed the Ni and Fe sites with enhanced OER activity, leading to boosted photocurrent and stability.…”

Section: Strategies For the Construction Of Core–shell Photoanodementioning

confidence: 99%

Core–Shell Photoanodes for Photoelectrochemical Water Oxidation

Pan

Shen

Chen

et al. 2021

Adv Funct Materials

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Photoelectrochemical (PEC) water splitting into hydrogen and oxygen is a promising solution for the conversion and storage of solar energy. Because sluggish water oxidation is the bottleneck of water splitting, the design and preparation of an efficient photoanode is intensively investigated. Currently, all known photoanode materials suffer from at least one of the following drawbacks: ① low carriers separation efficiency; ② sluggish surface water oxidation reaction; ③ poor long‐term stability; ④ insufficient water adsorption and gas desorption. Core–shell configurations can endow a photoanode with improved activity and stability by coating an overlayer that plays energetic, catalytic, and/or protective roles. The construction strategy has an important effect on the activity of a core–shell photoanode. Nonetheless, the mechanism for the improvement of performance is still ambiguous and is worthy of a closer examination. In this review, the successes and challenges of core–shell photoanodes for water oxidation, focusing on synthesis strategies as well as functionalities (facilitating carrier separation, surface reaction promotion, corrosion prevention, and bubble detachment) are explored. Finally, the perspectives of this class of materials in terms of new opportunities and efforts are discussed.

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“…This structure significantly increases the number of reaction sites because the nanogeometry CoNi‐MOFs participates in water oxidation reactions thus improve the PEC performance (Figure 2b). Very recently, a remarkable photocurrent density of BiVO 4 ‐based photoanode was achieved by Pan's group [76] . The NiFe‐MOF was coated on oxygen‐vacancy‐rich BiVO 4 (O v ‐BiVO 4 ) through a hydrothermal method to form a core‐shell structure (Figure 2c).…”

Section: Mofs and Their Derivatives‐modified Semiconductorsmentioning

confidence: 99%

Semiconductor‐based Photoanodes Modified with Metal‐Organic Frameworks and Molecular Catalysts as Cocatalysts for Enhanced Photoelectrochemical Water Oxidation Reaction

et al. 2021

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Photoelectrochemical (PEC) water splitting is a promising approach to convert inexhaustible solar energy to hydrogen energy. In this system, the semiconductor is a crucial part as photoelectrode to harvest the solar light and achieve water splitting on the surface. For the surface modification of semiconductor, cocatalyst loading is an effective method to improve the sluggish reaction kinetics. Due to the specific structure of their organic ligands, the metal‐organic frameworks (MOFs) or molecular catalysts as cocatalysts can provide more reaction sites and overcome the interface recombination between semiconductors and cocatalyst layers. The inorganic metal species derived from the MOFs or molecular catalysts also possess porous structures. This review summarizes the recent developments of MOFs and molecular catalysts as well as their derivatives modifying several representative semiconductors for PEC water oxidation reaction. The synthesis methods and performance enhancements are discussed. Finally, this review addresses remarks on current existing changes and perspectives for the further development.

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Activity and Stability Boosting of an Oxygen‐Vacancy‐Rich BiVO₄ Photoanode by NiFe‐MOFs Thin Layer for Water Oxidation

Cited by 250 publications

References 55 publications

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

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

Core–Shell Photoanodes for Photoelectrochemical Water Oxidation

Semiconductor‐based Photoanodes Modified with Metal‐Organic Frameworks and Molecular Catalysts as Cocatalysts for Enhanced Photoelectrochemical Water Oxidation Reaction

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Activity and Stability Boosting of an Oxygen‐Vacancy‐Rich BiVO4 Photoanode by NiFe‐MOFs Thin Layer for Water Oxidation

Cited by 250 publications

References 55 publications

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

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

Core–Shell Photoanodes for Photoelectrochemical Water Oxidation

Semiconductor‐based Photoanodes Modified with Metal‐Organic Frameworks and Molecular Catalysts as Cocatalysts for Enhanced Photoelectrochemical Water Oxidation Reaction

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Product

Resources

About

Activity and Stability Boosting of an Oxygen‐Vacancy‐Rich BiVO₄ Photoanode by NiFe‐MOFs Thin Layer for Water Oxidation

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

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