journal article·2023-05Open access

Photoelectrochemical N2‐to‐NH3 Fixation with High Efficiency and Rates via Optimized Si‐Based System at Positive Potential versus Li0/+

Xiaoran Zhang, Yanhong Lyu, Huaijuan Zhou, Jianyun Zheng, Aibin Huang, Jingjing Ding, Chao Xie, Roland De Marco, Nataliya Tsud, Viacheslav Kalinovych, San Ping Jiang, Liming Dai, Shuangyin Wang

Advanced Materials· Volume 35· Issue 21

Abstract

Abstract As a widely used commodity chemical, ammonia is critical for producing nitrogen‐containing fertilizers and serving as the promising zero‐carbon energy carrier. Photoelectrochemical nitrogen reduction reaction (PEC NRR) can provide a solar‐powered green and sustainable route for synthesis of ammonia (NH3). Herein, an optimum PEC system is reported with an Si‐based hierarchically‐structured PdCu/TiO2/Si photocathode and well‐thought‐out trifluoroethanol as the proton source for lithium‐mediated PEC NRR, achieving a record high NH3 yield of 43.09 µg cm−2 h−1 and an excellent faradaic efficiency of 46.15% under 0.12 MPa O2 and 3.88 MPa N2 at 0.07 V versus lithium(0/+) redox couple (vs Li0/+). PEC measurements coupled with operando characterization reveal that the PdCu/TiO2/Si photocathode under N2 pressures facilitate the reduction of N2 to form lithium nitride (Li3N), which reacts with active protons to produce NH3 while releasing the Li+ to reinitiate the cycle of the PEC NRR. The Li‐mediated PEC NRR process is further enhanced by introducing small amount of O2 or CO2 under pressure by accelerating the decomposition of Li3N. For the first time, this work provides mechanistic understanding of the lithium‐mediated PEC NRR process and opens new avenues for efficient solar‐powered green conversion of N2‐to‐NH3.
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Research context

OpenAlex topics: Ammonia Synthesis and Nitrogen Reduction · Advanced Photocatalysis Techniques · Chemical Synthesis and Characterization

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

State Key Laboratory of Chem/Bio‐Sensing and Chemometrics College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P. R. China

Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory Foshan 528216 China

Advanced Research Institute of Multidisciplinary Sciences Beijing Institute of Technology Beijing 100081 China

State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of Ceramics Chinese Academy of Sciences Shanghai 200050 China

Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences Beijing 100049 China

School of Chemistry and Molecular Biosciences The University of Queensland Brisbane QLD 4072 Australia

Department of Chemistry School of Pure Science College of Engineering Science and Technology Fiji National University Samabula, P.O. Box 3722 Suva Fiji

Charles University Faculty of Mathematics and Physics Department of Surface and Plasma Science Holešovičkách 2 Prague 18000 Czech Republic

WA School of Mines: Minerals Energy and Chemical Engineering Curtin University Perth WA 6102 Australia

Australian Carbon Materials Centre (A‐CMC) School of Chemical Engineering University of New South Wales Sydney NSW 2052 Australia

Funding

National Natural Science Foundation of China · Australian Research Council

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