Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations

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Abstract

Photoelectrochemical (PEC) organic transformations occurring at anodes are a promising strategy for circumventing the sluggish kinetics of the oxygen evolution reaction. Here, we report a free radical-mediated reaction instead of direct hole transfer occurring at the solid/liquid interface for PEC oxidation of benzyl alcohol (BA) to benzaldehyde (BAD) with high selectivity. A bismuth vanadate (BiVO ₄) photoanode coated with a 2,2′-bipyridine–based covalent organic framework bearing single Ni sites (Ni-TpBpy) was developed to drive the transformation. Experimental studies reveal that the reaction at the Ni-TpBpy/BiVO ₄ photoanode followed first-order reaction kinetics, boosting the formation of surface-bound ·OH radicals, which suppressed further BAD oxidation and provided a nearly 100% selectivity and a rate of 80.63 μmol hour ⁻¹ for the BA-to-BAD conversion. Because alcohol-to-aldehyde conversions are involved in the valorizations of biomass and plastics, this work is expected to open distinct avenues for producing key intermediates of great value.

Abstract

OH radicals formed at semiconductor/liquid interface for solar-driven organic transformation.

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Nanoporous BiVO4 photoanodes with dual-layer oxygen evolution catalysts for solar water splitting.

Tae-Woo Kim, Kyoung-Shin Choi (2014)

Bismuth vanadate (BiVO4) has a band structure that is well-suited for potential use as a photoanode in solar water splitting, but it suffers from poor electron-hole separation. Here, we demonstrate that a nanoporous morphology (specific surface area of 31.8 square meters per gram) effectively suppresses bulk carrier recombination without additional doping, manifesting an electron-hole separation yield of 0.90 at 1.23 volts (V) versus the reversible hydrogen electrode (RHE). We enhanced the propensity for surface-reaching holes to instigate water-splitting chemistry by serially applying two different oxygen evolution catalyst (OEC) layers, FeOOH and NiOOH, which reduces interface recombination at the BiVO4/OEC junction while creating a more favorable Helmholtz layer potential drop at the OEC/electrolyte junction. The resulting BiVO4/FeOOH/NiOOH photoanode achieves a photocurrent density of 2.73 milliamps per square centimenter at a potential as low as 0.6 V versus RHE.

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A Covalent Organic Framework Bearing Single Ni Sites as a Synergistic Photocatalyst for Selective Photoreduction of CO2 to CO

Wanfu Zhong, Rongjian Sa, Liuyi Li … (2019)

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Water oxidation at hematite photoelectrodes: the role of surface states.

Benjamin Klahr, Sixto Giménez, Francisco Fabregat-Santiago … (2012)

Hematite (α-Fe(2)O(3)) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical-chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement.

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Author and article information

Contributors

Cheng Lin:

ORCID: https://orcid.org/0000-0001-7076-2826

Role: ConceptualizationRole: Data curationRole: Formal analysisRole: InvestigationRole: MethodologyRole: Project administrationRole: ResourcesRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Zhen Shan:

ORCID: https://orcid.org/0000-0003-0399-5552

Role: ConceptualizationRole: InvestigationRole: MethodologyRole: ResourcesRole: Validation

Chaoran Dong:

ORCID: https://orcid.org/0009-0007-5708-6457

Role: ConceptualizationRole: InvestigationRole: MethodologyRole: Resources

Yuan Lu:

ORCID: https://orcid.org/0009-0009-3678-535X

Role: ConceptualizationRole: Data curationRole: Formal analysisRole: InvestigationRole: MethodologyRole: ResourcesRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Weikun Meng: Role: Data curationRole: Formal analysisRole: InvestigationRole: ResourcesRole: ValidationRole: Visualization

Gen Zhang:

ORCID: https://orcid.org/0000-0001-5948-8635

Role: ConceptualizationRole: Data curationRole: Formal analysisRole: Funding acquisitionRole: InvestigationRole: MethodologyRole: Project administrationRole: ResourcesRole: SoftwareRole: SupervisionRole: ValidationRole: VisualizationRole: Writing - original draftRole: Writing - review & editing

Bo Cai:

ORCID: https://orcid.org/0000-0002-6605-5931

Role: Formal analysisRole: Software

Guanyong Su:

ORCID: https://orcid.org/0000-0003-4356-5194

Role: Formal analysisRole: InvestigationRole: MethodologyRole: ResourcesRole: Visualization

Jong Hyeok Park:

ORCID: https://orcid.org/0000-0002-6629-3147

Kan Zhang:

ORCID: https://orcid.org/0000-0003-1121-3426

Role: ConceptualizationRole: Funding acquisitionRole: Project administrationRole: SupervisionRole: Writing - review & editing

Journal

Journal ID (nlm-ta): Sci Adv

Journal ID (iso-abbrev): Sci Adv

Journal ID (publisher-id): sciadv

Journal ID (hwp): advances

Title: Science Advances

Publisher: American Association for the Advancement of Science

ISSN (Electronic): 2375-2548

Publication date Collection: 10 November 2023

Publication date (Electronic, pub): 08 November 2023

Volume: 9

Issue: 45

Electronic Location Identifier: eadi9442

Affiliations

[ ¹ ]Nanjing University of Science and Technology, Nanjing 210094, China.

[ ² ]Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749, Republic of Korea.

[ ³ ]Institute of Advanced Materials, Nanjing University of Posts and Telecommunications, Nanjing 210023, China.

Author notes

[* ]Corresponding author. Email: zhanggen@ 123456njust.edu.cn (G.Z.); sugy@ 123456njust.edu.cn (G.S.); lutts@ 123456yonsei.ac.kr (J.H.P.); zhangkan@ 123456njust.edu.cn (K.Z.)

[†]

These authors contributed equally to this work.

Author information

Cheng Lin https://orcid.org/0000-0001-7076-2826

Zhen Shan https://orcid.org/0000-0003-0399-5552

Chaoran Dong https://orcid.org/0009-0007-5708-6457

Yuan Lu https://orcid.org/0009-0009-3678-535X

Gen Zhang https://orcid.org/0000-0001-5948-8635

Bo Cai https://orcid.org/0000-0002-6605-5931

Guanyong Su https://orcid.org/0000-0003-4356-5194

Jong Hyeok Park https://orcid.org/0000-0002-6629-3147

Kan Zhang https://orcid.org/0000-0003-1121-3426

Article

Publisher ID: adi9442

DOI: 10.1126/sciadv.adi9442

PMC ID: 10631720

PubMed ID: 37939175

SO-VID: 813fef33-61cd-4f2d-b884-c47893cbd750

Copyright © Copyright © 2023 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

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This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

History

Date received : 27 May 2023

Date accepted : 05 October 2023

Funding

Funded by: FundRef http://dx.doi.org/10.13039/501100001809, National Natural Science Foundation of China;

Award ID: 22172077

Funded by: FundRef http://dx.doi.org/10.13039/501100002949, Government of Jiangsu Province;

Award ID: BK 20211573

Funded by: FundRef http://dx.doi.org/10.13039/501100002949, Government of Jiangsu Province;

Award ID: BZ2020063

Funded by: FundRef http://dx.doi.org/10.13039/501100002949, Government of Jiangsu Province;

Award ID: 30921011216

Funded by: NRF Korea;

Award ID: 2022H1D3A3A01077254

Funded by: NRF Korea;

Award ID: NRF-2019R1A2C3010479

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Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations

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Most cited references 55

Nanoporous BiVO4 photoanodes with dual-layer oxygen evolution catalysts for solar water splitting.

A Covalent Organic Framework Bearing Single Ni Sites as a Synergistic Photocatalyst for Selective Photoreduction of CO2 to CO

Water oxidation at hematite photoelectrodes: the role of surface states.

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