Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia

Yunhao Wang; Fengkun Hao; Mingzi Sun; Meng-Ting Liu; Jingwen Zhou; Yuecheng Xiong; Chenliang Ye; Xixi Wang; Fu Liu; Juan Wang; Pengyi Lu; Yangbo Ma; Jinwen Yin; Hsiao-Chien Chen; Qinghua Zhang; Lin Gu; Hao Ming Chen; Bolong Huang; Zhanxi Fan

doi:10.1002/adma.202313548

Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia

Adv Mater. 2024 Apr;36(14):e2313548. doi: 10.1002/adma.202313548. Epub 2024 Jan 26.

Authors

Yunhao Wang¹, Fengkun Hao¹, Mingzi Sun², Meng-Ting Liu³, Jingwen Zhou^{1

4}, Yuecheng Xiong^{1

4}, Chenliang Ye⁵, Xixi Wang¹, Fu Liu¹, Juan Wang¹, Pengyi Lu^{1

4}, Yangbo Ma¹, Jinwen Yin¹, Hsiao-Chien Chen⁶, Qinghua Zhang⁷, Lin Gu⁸, Hao Ming Chen^{3

9}, Bolong Huang², Zhanxi Fan^{1

4

10}

Affiliations

¹ Department of Chemistry, City University of Hong Kong, Hong Kong, 999077, China.
² Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, 999077, China.
³ Department of Chemistry and Center for Emerging Materials and Advanced Devices, National Taiwan University, Taipei, 10617, Taiwan.
⁴ Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Hong Kong, 999077, China.
⁵ Department of Power Engineering, North China Electric Power University, Baoding, Hebei, 071003, China.
⁶ Center for Reliability Science and Technologies, Chang Gung University, Taoyuan, 33302, Taiwan.
⁷ Institute of Physics, Beijing National Laboratory for Condensed Matter Physics, Chinese Academy of Sciences, Beijing, 100190, China.
⁸ Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China.
⁹ Graduate Institute of Nanomedicine and Medical Engineering, College of Biomedical Engineering, Taipei Medical University, Taipei, 11031, Taiwan.
¹⁰ City University of Hong Kong Shenzhen Research Institute, Shenzhen, 518057, China.

PMID: 38279631
DOI: 10.1002/adma.202313548

Abstract

Electrocatalytic nitrate reduction reaction (NO₃RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains a great challenge to achieve highly efficient ammonia production due to the complex proton-coupled electron transfer process in NO₃RR. Here, the controlled synthesis of RuMo alloy nanoflowers (NFs) with unconventional face-centered cubic (fcc) phase and hexagonal close-packed/fcc heterophase for highly efficient NO₃RR is reported. Significantly, fcc RuMo NFs demonstrate high Faradaic efficiency of 95.2% and a large yield rate of 32.7 mg h^-1 mg_cat ^-1 toward ammonia production at 0 and -0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations and theoretical calculations have unraveled that fcc RuMo NFs possess the highest d-band center with superior electroactivity, which originates from the strong Ru─Mo interactions and the high intrinsic activity of the unconventional fcc phase. The optimal electronic structures of fcc RuMo NFs supply strong adsorption of key intermediates with suppression of the competitive hydrogen evolution, which further determines the remarkable NO₃RR performance. The successful demonstration of high-performance zinc-nitrate batteries with fcc RuMo NFs suggests their substantial application potential in electrochemical energy supply systems.

Keywords: ammonia; crystal phase engineering; electrocatalysis; nitrate reduction reaction; ultrathin alloy nanostructures.

Abstract

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