Enhanced p–d Orbital Coupling in Unconventional Phase RhSb Alloy Nanoflowers for Efficient Ammonia Electrosynthesis in Neutral Media
Journal
Angewandte Chemie International Edition
ISSN
1433-7851
1521-3773
Date Issued
2025-04-11
Author(s)
Fu Liu
Jingwen Zhou
Mingzi Sun
Zhihang Xu
Helin Wang
Ning Yao
Yunhao Wang
Fengkun Hao
Yuecheng Xiong
Juan Wang
Liang Guo
Qingbo Wa
Guozhi Wang
Xiang Meng
Mingzheng Shao
Chaohui Wang
Hsiao‐Chien Chen
Ye Zhu
Bolong Huang
Zhanxi Fan
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 NH3 Faradaic efficiency and yield rate can reach up to 96.8% and 47.2 mg h−1 mgcat−1 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.
Subjects
Alloy nanostructures
Ammonia electrosynthesis
Electrocatalysis
Phase control
p–d Orbital coupling
SDGs
Publisher
Wiley
Type
journal article