Engineering kesterite based photocathode for photoelectrochemical ammonia synthesis from NOx reduction

Shujie Zhou; Kaiwen Sun; Cui Ying Toe; Jun Yin; Jialiang Huang; Yiyu Zeng; Doudou Zhang; Weijian Chen; Omar F. Mohammed; Xiaojing Hao; Rose Amal

doi:10.1002/adma.202201670

Engineering kesterite based photocathode for photoelectrochemical ammonia synthesis from NOx reduction

Shujie Zhou, Kaiwen Sun, Cui Ying Toe, Jun Yin, Jialiang Huang, Yiyu Zeng, Doudou Zhang, Weijian Chen, Omar F. Mohammed, Xiaojing Hao, Rose Amal

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

23 Scopus citations

Abstract

Ammonia is a key chemical feedstock for industry as well as future carbon-free fuel and transportable vector for renewable energy. Photoelectrochemical (PEC) ammonia synthesis from NOx reduction reaction (NOx RR) provides not only a promising alternative to the energy-intensive Haber-Bosch process through direct solar-to-ammonia conversion, but a sustainable solution for balancing the global nitrogen cycle by restoring ammonia from wastewater. In this work, we, for the first time, demonstrated selective ammonia synthesis from PEC NOx RR by kesterite (Cu2 ZnSnS4 (CZTS)) photocathode through loading defect-engineered TiOx cocatalyst on CdS/CZTS photocathode (TiOx /CdS/CZTS). The uniquely designed photocathode enables selective ammonia production from NOx RR, yielding up to 89.1% faradaic efficiency (0.1 V versus reversible hydrogen electrode (RHE)) with a remarkable positive onset potential (0.38 V versus RHE). By tailoring the amount of surface defective Ti3+ species, the adsorption of reactant NO3- and * NO2 intermediate is significantly promoted while the full coverage of TiOx also suppresses NO2- liberation as a by-product, contributing to high ammonia selectivity. Our further attempted PEC ammonia synthesis from simulated wastewater shows good faradaic efficiency of 64.9%, unveiling the potential of using kesterite based photocathode for sustainably restoring ammonia from nitrate-rich wastewater.

Original language	English (US)
Pages (from-to)	2201670
Journal	Advanced Materials
DOIs	https://doi.org/10.1002/adma.202201670
State	Published - May 23 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-05-26
Acknowledgements: The authors acknowledge the facilities and the scientific and technical assistance of Microscopy Australia at the Electron Microscope Unit (EMU)and other characterization facilitates within the Mark Wainwright Analytical Centre (MWAC) at UNSW Sydney. The work was supported by the Australian Research Council (ARC) Training Centre for the Global Hydrogen Economy (IC200100023).X.H. acknowledges the Australian Research Council (ARC) Future Fellowship Programme (FT190100756). K.S. acknowledges the Australian Centre for Advanced Photovoltaics (ACAP) postdoctoral fellowship programme (RG172864-B). Responsibility for the views, information or advice expressed herein is not accepted by the Australian Government. The authors acknowledge Dr. BingqiaoXie for the valuable discussion on the reaction mechanism,Dr. Zhipeng Ma, Jing Sun and Chen Han for the assistance of calibration process.

ASJC Scopus subject areas

Mechanics of Materials
General Materials Science
Mechanical Engineering

UN SDGs

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

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https://repository.kaust.edu.sa/bitstream/10754/678235/1/Advanced%20Materials%20-%202022%20-%20Zhou%20-%20Engineering%20kesterite%20based%20photocathode%20for%20photoelectrochemical%20ammonia%20synthesis%20from_removed.pdf

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title = "Engineering kesterite based photocathode for photoelectrochemical ammonia synthesis from NOx reduction",

abstract = "Ammonia is a key chemical feedstock for industry as well as future carbon-free fuel and transportable vector for renewable energy. Photoelectrochemical (PEC) ammonia synthesis from NOx reduction reaction (NOx RR) provides not only a promising alternative to the energy-intensive Haber-Bosch process through direct solar-to-ammonia conversion, but a sustainable solution for balancing the global nitrogen cycle by restoring ammonia from wastewater. In this work, we, for the first time, demonstrated selective ammonia synthesis from PEC NOx RR by kesterite (Cu2 ZnSnS4 (CZTS)) photocathode through loading defect-engineered TiOx cocatalyst on CdS/CZTS photocathode (TiOx /CdS/CZTS). The uniquely designed photocathode enables selective ammonia production from NOx RR, yielding up to 89.1% faradaic efficiency (0.1 V versus reversible hydrogen electrode (RHE)) with a remarkable positive onset potential (0.38 V versus RHE). By tailoring the amount of surface defective Ti3+ species, the adsorption of reactant NO3- and * NO2 intermediate is significantly promoted while the full coverage of TiOx also suppresses NO2- liberation as a by-product, contributing to high ammonia selectivity. Our further attempted PEC ammonia synthesis from simulated wastewater shows good faradaic efficiency of 64.9%, unveiling the potential of using kesterite based photocathode for sustainably restoring ammonia from nitrate-rich wastewater.",

author = "Shujie Zhou and Kaiwen Sun and Toe, {Cui Ying} and Jun Yin and Jialiang Huang and Yiyu Zeng and Doudou Zhang and Weijian Chen and Mohammed, {Omar F.} and Xiaojing Hao and Rose Amal",

note = "KAUST Repository Item: Exported on 2022-05-26 Acknowledgements: The authors acknowledge the facilities and the scientific and technical assistance of Microscopy Australia at the Electron Microscope Unit (EMU)and other characterization facilitates within the Mark Wainwright Analytical Centre (MWAC) at UNSW Sydney. The work was supported by the Australian Research Council (ARC) Training Centre for the Global Hydrogen Economy (IC200100023).X.H. acknowledges the Australian Research Council (ARC) Future Fellowship Programme (FT190100756). K.S. acknowledges the Australian Centre for Advanced Photovoltaics (ACAP) postdoctoral fellowship programme (RG172864-B). Responsibility for the views, information or advice expressed herein is not accepted by the Australian Government. The authors acknowledge Dr. BingqiaoXie for the valuable discussion on the reaction mechanism,Dr. Zhipeng Ma, Jing Sun and Chen Han for the assistance of calibration process.",

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month = may,

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doi = "10.1002/adma.202201670",

language = "English (US)",

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T1 - Engineering kesterite based photocathode for photoelectrochemical ammonia synthesis from NOx reduction

AU - Zhou, Shujie

AU - Sun, Kaiwen

AU - Toe, Cui Ying

AU - Yin, Jun

AU - Huang, Jialiang

AU - Zeng, Yiyu

AU - Zhang, Doudou

AU - Chen, Weijian

AU - Mohammed, Omar F.

AU - Hao, Xiaojing

AU - Amal, Rose

N1 - KAUST Repository Item: Exported on 2022-05-26 Acknowledgements: The authors acknowledge the facilities and the scientific and technical assistance of Microscopy Australia at the Electron Microscope Unit (EMU)and other characterization facilitates within the Mark Wainwright Analytical Centre (MWAC) at UNSW Sydney. The work was supported by the Australian Research Council (ARC) Training Centre for the Global Hydrogen Economy (IC200100023).X.H. acknowledges the Australian Research Council (ARC) Future Fellowship Programme (FT190100756). K.S. acknowledges the Australian Centre for Advanced Photovoltaics (ACAP) postdoctoral fellowship programme (RG172864-B). Responsibility for the views, information or advice expressed herein is not accepted by the Australian Government. The authors acknowledge Dr. BingqiaoXie for the valuable discussion on the reaction mechanism,Dr. Zhipeng Ma, Jing Sun and Chen Han for the assistance of calibration process.

PY - 2022/5/23

Y1 - 2022/5/23

N2 - Ammonia is a key chemical feedstock for industry as well as future carbon-free fuel and transportable vector for renewable energy. Photoelectrochemical (PEC) ammonia synthesis from NOx reduction reaction (NOx RR) provides not only a promising alternative to the energy-intensive Haber-Bosch process through direct solar-to-ammonia conversion, but a sustainable solution for balancing the global nitrogen cycle by restoring ammonia from wastewater. In this work, we, for the first time, demonstrated selective ammonia synthesis from PEC NOx RR by kesterite (Cu2 ZnSnS4 (CZTS)) photocathode through loading defect-engineered TiOx cocatalyst on CdS/CZTS photocathode (TiOx /CdS/CZTS). The uniquely designed photocathode enables selective ammonia production from NOx RR, yielding up to 89.1% faradaic efficiency (0.1 V versus reversible hydrogen electrode (RHE)) with a remarkable positive onset potential (0.38 V versus RHE). By tailoring the amount of surface defective Ti3+ species, the adsorption of reactant NO3- and * NO2 intermediate is significantly promoted while the full coverage of TiOx also suppresses NO2- liberation as a by-product, contributing to high ammonia selectivity. Our further attempted PEC ammonia synthesis from simulated wastewater shows good faradaic efficiency of 64.9%, unveiling the potential of using kesterite based photocathode for sustainably restoring ammonia from nitrate-rich wastewater.

AB - Ammonia is a key chemical feedstock for industry as well as future carbon-free fuel and transportable vector for renewable energy. Photoelectrochemical (PEC) ammonia synthesis from NOx reduction reaction (NOx RR) provides not only a promising alternative to the energy-intensive Haber-Bosch process through direct solar-to-ammonia conversion, but a sustainable solution for balancing the global nitrogen cycle by restoring ammonia from wastewater. In this work, we, for the first time, demonstrated selective ammonia synthesis from PEC NOx RR by kesterite (Cu2 ZnSnS4 (CZTS)) photocathode through loading defect-engineered TiOx cocatalyst on CdS/CZTS photocathode (TiOx /CdS/CZTS). The uniquely designed photocathode enables selective ammonia production from NOx RR, yielding up to 89.1% faradaic efficiency (0.1 V versus reversible hydrogen electrode (RHE)) with a remarkable positive onset potential (0.38 V versus RHE). By tailoring the amount of surface defective Ti3+ species, the adsorption of reactant NO3- and * NO2 intermediate is significantly promoted while the full coverage of TiOx also suppresses NO2- liberation as a by-product, contributing to high ammonia selectivity. Our further attempted PEC ammonia synthesis from simulated wastewater shows good faradaic efficiency of 64.9%, unveiling the potential of using kesterite based photocathode for sustainably restoring ammonia from nitrate-rich wastewater.

UR - http://hdl.handle.net/10754/678235

UR - https://onlinelibrary.wiley.com/doi/10.1002/adma.202201670

U2 - 10.1002/adma.202201670

DO - 10.1002/adma.202201670

M3 - Article

C2 - 35606154

SN - 0935-9648

SP - 2201670

JO - Advanced Materials

JF - Advanced Materials

ER -

Engineering kesterite based photocathode for photoelectrochemical ammonia synthesis from NOx reduction

Abstract

Bibliographical note

ASJC Scopus subject areas

UN SDGs

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