Augmented photoelectrochemical water reduction: influence of copper vacancies and hole-transport layer on CuBi<sub>2</sub>O<sub>4</sub> photocathode

Gopannagari, Madhusudana; Reddy, D. Amaranatha; Hong, Da; Reddy, K. Arun Joshi; Kumar, D. Praveen; Ahn, Hyun S.; Kim, Tae Kyu

doi:10.1039/d1ta09956f

Cited by 15 publications

(7 citation statements)

References 67 publications

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“…Based on the CB band potentials, the photogenerated holes easily transfer from the IO-CBO-3 photocathodes to externally connected Pt electrodes, where the holes are oxidized to form oxygen. The photogenerated electrons contribute to hydrogen production on the surface of the IO-CBO-3 nanostructures. − The interconnected porous structures contribute toward a reduced recombination rate and promote the charge-carrier’s transportation rate, resulting in high stability and an enhanced hydrogen evolution rate.…”

Section: Resultsmentioning

confidence: 99%

Inverse Opal CuBi₂O₄ Photocathodes for Robust Photoelectrochemical Water Splitting

Kim

2022

ACS Appl. Energy Mater.

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In general, p-type CuBi2O4 (CBO) photocathodes demonstrate excellent solar-to-hydrogen conversion efficiencies but have low quantum yields near the band-edge region (i.e., above 600 nm), which substantially impedes achieving photocurrent densities that match the theoretical values. This is the main obstacle in the construction of photoelectrochemical (PEC) water-splitting cells. To overcome this difficulty, we fabricated inverse opal-like structured CBO (IO-CBO) photocathodes using a layered self-assembly approach. The fabricated photocathodes have an interconnected macroporous structure that supports enhanced visible-light-harvesting capabilities and improves intrinsic charge-carrier transport properties. Optimized IO-CBO cathodes exhibit a high photocurrent density of 2.95 mA cm–2 at 0.6 V versus a reversible hydrogen electrode with stability over 2 h of operation. Furthermore, IO-CBO cathodes have exceptional near-band-edge photon harvesting and quantum yields of 15% at 600 nm, which is unprecedented for CuBi2O4-type photocathodes. We believe that the present work promotes the application of ternary-based nanostructures in solar-driven hydrogen production.

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Section: Resultsmentioning

confidence: 99%

Inverse Opal CuBi₂O₄ Photocathodes for Robust Photoelectrochemical Water Splitting

Kim

2022

ACS Appl. Energy Mater.

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“…Gopannagari et al attached Fe-doped NiO x thin layer onto the copper vacancyinduced CuBi 2 O 4 (CBOÀ O 2 ) back-interface for photoelectrochemical water reduction. [53] The CBOÀ O 2 photocathode exhibited a higher hole-concentration and the Fe : NiO x layer acted as an efficient hole-transport layer at the back interface (Figure 8e). Fe : NiO x À HTL effectively extracted the photogenerated holes from the CBOÀ O 2 photocathode with high a hole concentration.…”

Section: Hole Transport/storage/blocking Layermentioning

confidence: 99%

Stability of Photocathodes: A Review on Principles, Design, and Strategies

Wang

Liu

et al. 2023

ChemSusChem

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Photoelectrochemical devices based on semiconductor photoelectrode can directly convert and store solar energy into chemical fuels. Although the efficient photoelectrodes with commercially valuable solar‐to‐fuel energy conversion efficiency have been reported over past decades, one of the most enormous challenges is the stability of the photoelectrode due to corrosion during operation. Thus, it is of paramount importance for developing a stable photoelectrode to deploy solar‐fuel production. This Review commences with a fundamental understanding of thermodynamics for photoelectrochemical reactions and the fundamentals of photocathodes. Then, the commercial application of photoelectrochemical technology is prospected. We specifically focus on recent strategies for designing photocathodes with long‐term stability, including energy band alignment, hole transport/storage/blocking layer, spatial decoupling, grafting molecular catalysts, protective/passivation layer, surface element reconstruction, and solvent effects. Based on the insights gained from these effective strategies, we propose an outlook of key aspects that address the challenges for development of stable photoelectrodes in future work.

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“…Many studies on metal oxides consider their vacancy properties due to the interaction between gaseous oxygen and oxide lattice. [ 164 ] It has been shown that metal oxide photocathode with Cu vacancies can enhance the kinetics of interface reactions between electrode and electrolyte. However, the role of vacancies in preventing charge recombination has not been addressed.…”

Section: Applications Of Defective Photocathode In Energy Conversionmentioning

confidence: 99%

“…[180] In addition, the possible products of nitrogen reduction are NO 2 , N 2 , NH 3 , and H 2 , and increasing the FE of NO 3 to NH 3 remains a challenge. [181] [164] Copyright 2022, Royal Society of Chemistry. g) Kinetic model showing two competitive pathways for the decay of the excited charge-transfer state.…”

Section: N 2 Fixationmentioning

confidence: 99%

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Defective Photocathode: Fundamentals, Construction, and Catalytic Energy Conversion

Huang

2023

Adv Funct Materials

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The development of a long‐term and sustainable energy economy is one of the most significant technological challenges facing humanity. Photoelectrochemical (PEC) technology is considered as the most attractive route for converting solar energy into chemical energy. However, the slow reaction kinetics of PEC oxidation and reduction greatly hinder its practical application. To address this issue, engineering photoelectrodes with various defects can significantly improve their catalytic performance, which can not only regulate catalyst electronic structure but also promote charge transfer/separation by serving as an active/adsorption/energy storage site. Herein, the defect engineering strategies for photoelectrodes are systematically summarized, focusing on the latest progress in defective photocathode for energy conversion. First, an overview of defect types, basic principles of photocathode, and the positive role of defects in the photocathode are provided. Second, the construction strategies and characterization methods of defective photocathode are summarized. Then, the progress of typical energy conversion applications, including hydrogen production, CO2 reduction, and nitrogen reduction over defective photocathode, is reviewed, highlighting the crucial role of defects in high catalytic performance. Finally, the challenges and future prospects of defective photocathode are discussed, aiming to bring new opportunities for the development of photocathode through defect engineering.

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Augmented photoelectrochemical water reduction: influence of copper vacancies and hole-transport layer on CuBi₂O₄ photocathode

Abstract: A ternary metal oxide CuBi2O4 has received immense attention in the research field of photoelectrochemical(PEC) for water or CO2 reduction owing to its ideal optical bandgap and positive photocurrent onset...

Cited by 15 publications

References 67 publications

Inverse Opal CuBi₂O₄ Photocathodes for Robust Photoelectrochemical Water Splitting

Inverse Opal CuBi₂O₄ Photocathodes for Robust Photoelectrochemical Water Splitting

Stability of Photocathodes: A Review on Principles, Design, and Strategies

Defective Photocathode: Fundamentals, Construction, and Catalytic Energy Conversion

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Augmented photoelectrochemical water reduction: influence of copper vacancies and hole-transport layer on CuBi2O4 photocathode

Abstract: A ternary metal oxide CuBi2O4 has received immense attention in the research field of photoelectrochemical(PEC) for water or CO2 reduction owing to its ideal optical bandgap and positive photocurrent onset...

Cited by 15 publications

References 67 publications

Inverse Opal CuBi2O4 Photocathodes for Robust Photoelectrochemical Water Splitting

Inverse Opal CuBi2O4 Photocathodes for Robust Photoelectrochemical Water Splitting

Stability of Photocathodes: A Review on Principles, Design, and Strategies

Defective Photocathode: Fundamentals, Construction, and Catalytic Energy Conversion

Contact Info

Product

Resources

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Augmented photoelectrochemical water reduction: influence of copper vacancies and hole-transport layer on CuBi₂O₄ photocathode

Inverse Opal CuBi₂O₄ Photocathodes for Robust Photoelectrochemical Water Splitting

Inverse Opal CuBi₂O₄ Photocathodes for Robust Photoelectrochemical Water Splitting