Enhanced <i>p–d</i> Orbital Coupling in Unconventional Phase RhSb Alloy Nanoflowers for Efficient Ammonia Electrosynthesis in Neutral Media

Phase control provides a promising approach for physicochemical property modulation of metal/alloy nanomaterials toward various electrocatalytic applications. However, the controlled synthesis of alloy nanomaterials with unconventional phases remains challenging, especially for those containing both p- and d-block metals. Here, we report the one-pot synthesis of ultrathin RhSb alloy nanoflowers (NFs) with an unconventional 2H phase. Using 2H RhSb NFs as an electrocatalyst for nitrite reduction reaction in neutral media, the optimal NH<sub>3</sub> Faradaic efficiency and yield rate can reach up to 96.8% and 47.2 mg h<sup>-1</sup> mg<sub>cat</sub> <sup>-1</sup> at -0.3 and -0.6 V (vs. reversible hydrogen electrode), respectively. With 2H RhSb NFs as a bifunctional cathode catalyst, the as-assembled zinc-nitrite/methanol batteries deliver a high energy efficiency of 96.4% and improved rechargeability with 120-h stable running. Ex/in situ characterizations and theoretical calculations have demonstrated that the phase change of RhSb from face-centered cubic (fcc) to 2H has optimized the electronic structure through stronger interactions between Rh and Sb by p-d orbital couplings, which improves the adsorption of key intermediates and reduces the reaction barriers of nitrite reduction to guarantee the efficient electrocatalysis. This work offers a feasible strategy of boosting the electrocatalytic performance of alloy nanostructures by integrating phase control and p-d orbital coupling.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2025-04-07
DOI
https://doi.org/10.1002/anie.202504641
Citations
24
Primary Topic
Ammonia Synthesis and Nitrogen Reduction
Type
article
Field-Weighted Citation Impact
9.33

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article

Enhanced p–d Orbital Coupling in Unconventional Phase RhSb Alloy Nanoflowers for Efficient Ammonia Electrosynthesis in Neutral Media

Zhihang Xu, Yuecheng Xiong, Ye Zhu, Bolong Huang et al.
24 citations
Angewandte Chemie International Edition
Ammonia Synthesis and Nitrogen Reduction
9.33
article

Enhanced p–d Orbital Coupling in Unconventional Phase RhSb Alloy Nanoflowers for Efficient Ammonia Electrosynthesis in Neutral Media

Zhihang Xu, Yuecheng Xiong, Ye Zhu, Bolong Huang, Hsiao‐Chien Chen, Jingwen Zhou, Ning Yao, Fengkun Hao, Yunhao Wang, Zhanxi Fan, Hao Ming Chen, Mingzi Sun, Guozhi Wang, Qingbo Wa, Juan Wang, Xiang Meng, Chaohui Wang, Liang Guo, Helin Wang, Fu Liu, Mingzheng Shao
article en
24 citations

Abstract

Phase control provides a promising approach for physicochemical property modulation of metal/alloy nanomaterials toward various electrocatalytic applications. However, the controlled synthesis of alloy nanomaterials with unconventional phases remains challenging, especially for those containing both p- and d-block metals. Here, we report the one-pot synthesis of ultrathin RhSb alloy nanoflowers (NFs) with an unconventional 2H phase. Using 2H RhSb NFs as an electrocatalyst for nitrite reduction reaction in neutral media, the optimal NH<sub>3</sub> Faradaic efficiency and yield rate can reach up to 96.8% and 47.2 mg h<sup>-1</sup> mg<sub>cat</sub> <sup>-1</sup> at -0.3 and -0.6 V (vs. reversible hydrogen electrode), respectively. With 2H RhSb NFs as a bifunctional cathode catalyst, the as-assembled zinc-nitrite/methanol batteries deliver a high energy efficiency of 96.4% and improved rechargeability with 120-h stable running. Ex/in situ characterizations and theoretical calculations have demonstrated that the phase change of RhSb from face-centered cubic (fcc) to 2H has optimized the electronic structure through stronger interactions between Rh and Sb by p-d orbital couplings, which improves the adsorption of key intermediates and reduces the reaction barriers of nitrite reduction to guarantee the efficient electrocatalysis. This work offers a feasible strategy of boosting the electrocatalytic performance of alloy nanostructures by integrating phase control and p-d orbital coupling.

Angewandte Chemie International EditionVol. 64(23)
Chang Gung University of Science and Technology (TW), Hong Kong Polytechnic University (HK), National Taiwan University (TW), City University of Hong Kong (HK), Northwestern Polytechnical University (CN), Chang Gung University (TW), City University of Hong Kong, Shenzhen Research Institute (CN), Hubei University of Automotive Technology (CN)
City University of Hong Kong, National Natural Science Foundation of China, Natural Science Foundation of Guangdong Province, Hong Kong Polytechnic University
Affordable and clean energy
Openalex Percentile: Top 1%
Ammonia Synthesis and Nitrogen Reduction
9.33
DOIOpen Access PDFOpenAlex
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