Photoelectrocatalytic N2 fixation and C-H oxyfunctionalization driven by H2O oxidation

Chang Hyun Kim; Jinhyun Kim; Frank Hollmann; Chan Beum Park

doi:10.1016/j.apcatb.2023.122925

Photoelectrocatalytic N₂ fixation and C-H oxyfunctionalization driven by H₂O oxidation

Chang Hyun Kim, Jinhyun Kim, Frank Hollmann, Chan Beum Park^*

^*Corresponding author for this work

BT/Biocatalysis

Research output: Contribution to journal › Article › Scientific › peer-review

2 Citations (Scopus)

44 Downloads (Pure)

Abstract

Solar-driven N₂ fixation offers a green alternative to the highly energy-intensive Haber-Bosch process that releases more than 300 million metric tons of CO₂ annually to form NH₃. However, N₂-reducing photoelectrochemical (PEC) studies have not elucidated how an oxidation reaction affects the N₂ reduction reaction (NRR). Here, we report a bias-free PEC platform for N₂ reduction to NH₃ and H₂O oxidation to O₂ and H₂O₂. Under solar light, the molybdenum-doped bismuth vanadate-based photoanodes extract electrons from H₂O and transfer them to the silicon photovoltaic-wired hematite photocathode. The light-absorbing cathode receives the electrons to drive the NRR, which is influenced by the H₂O oxidation reaction's conditions. Furthermore, the integration of PEC NRR with H₂O₂-dependent biocatalytic oxyfunctionalization achieves simultaneous synthesis of valuable chemicals on both electrodes. This work presents the first example of a PEC NRR platform coupled with H₂O oxidation and H₂O₂-dependent oxygenation for unbiased chemical synthesis using N₂, H₂O, and sunlight.

Original language	English
Article number	122925
Journal	Applied Catalysis B: Environmental
Volume	336
DOIs	https://doi.org/10.1016/j.apcatb.2023.122925
Publication status	Published - 2023

Bibliographical note

Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.

Keywords

Biocatalysis
Nitrogen fixation
Oxygenation
Photoelectrocatalysis
Solar fuel

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.apcatb.2023.122925

1-s2.0-S0926337323005684-mainFinal published version, 5.13 MB

Cite this

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title = "Photoelectrocatalytic N2 fixation and C-H oxyfunctionalization driven by H2O oxidation",

abstract = "Solar-driven N2 fixation offers a green alternative to the highly energy-intensive Haber-Bosch process that releases more than 300 million metric tons of CO2 annually to form NH3. However, N2-reducing photoelectrochemical (PEC) studies have not elucidated how an oxidation reaction affects the N2 reduction reaction (NRR). Here, we report a bias-free PEC platform for N2 reduction to NH3 and H2O oxidation to O2 and H2O2. Under solar light, the molybdenum-doped bismuth vanadate-based photoanodes extract electrons from H2O and transfer them to the silicon photovoltaic-wired hematite photocathode. The light-absorbing cathode receives the electrons to drive the NRR, which is influenced by the H2O oxidation reaction's conditions. Furthermore, the integration of PEC NRR with H2O2-dependent biocatalytic oxyfunctionalization achieves simultaneous synthesis of valuable chemicals on both electrodes. This work presents the first example of a PEC NRR platform coupled with H2O oxidation and H2O2-dependent oxygenation for unbiased chemical synthesis using N2, H2O, and sunlight.",

keywords = "Biocatalysis, Nitrogen fixation, Oxygenation, Photoelectrocatalysis, Solar fuel",

author = "Kim, {Chang Hyun} and Jinhyun Kim and Frank Hollmann and Park, {Chan Beum}",

note = "Green Open Access added to TU Delft Institutional Repository {\textquoteleft}You share, we take care!{\textquoteright} – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.",

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doi = "10.1016/j.apcatb.2023.122925",

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AU - Kim, Chang Hyun

AU - Kim, Jinhyun

AU - Hollmann, Frank

AU - Park, Chan Beum

N1 - Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.

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Y1 - 2023

N2 - Solar-driven N2 fixation offers a green alternative to the highly energy-intensive Haber-Bosch process that releases more than 300 million metric tons of CO2 annually to form NH3. However, N2-reducing photoelectrochemical (PEC) studies have not elucidated how an oxidation reaction affects the N2 reduction reaction (NRR). Here, we report a bias-free PEC platform for N2 reduction to NH3 and H2O oxidation to O2 and H2O2. Under solar light, the molybdenum-doped bismuth vanadate-based photoanodes extract electrons from H2O and transfer them to the silicon photovoltaic-wired hematite photocathode. The light-absorbing cathode receives the electrons to drive the NRR, which is influenced by the H2O oxidation reaction's conditions. Furthermore, the integration of PEC NRR with H2O2-dependent biocatalytic oxyfunctionalization achieves simultaneous synthesis of valuable chemicals on both electrodes. This work presents the first example of a PEC NRR platform coupled with H2O oxidation and H2O2-dependent oxygenation for unbiased chemical synthesis using N2, H2O, and sunlight.

AB - Solar-driven N2 fixation offers a green alternative to the highly energy-intensive Haber-Bosch process that releases more than 300 million metric tons of CO2 annually to form NH3. However, N2-reducing photoelectrochemical (PEC) studies have not elucidated how an oxidation reaction affects the N2 reduction reaction (NRR). Here, we report a bias-free PEC platform for N2 reduction to NH3 and H2O oxidation to O2 and H2O2. Under solar light, the molybdenum-doped bismuth vanadate-based photoanodes extract electrons from H2O and transfer them to the silicon photovoltaic-wired hematite photocathode. The light-absorbing cathode receives the electrons to drive the NRR, which is influenced by the H2O oxidation reaction's conditions. Furthermore, the integration of PEC NRR with H2O2-dependent biocatalytic oxyfunctionalization achieves simultaneous synthesis of valuable chemicals on both electrodes. This work presents the first example of a PEC NRR platform coupled with H2O oxidation and H2O2-dependent oxygenation for unbiased chemical synthesis using N2, H2O, and sunlight.

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