Interfacial Engineering Enhances the Electroactivity of Frame‐Like Concave RhCu Bimetallic Nanocubes for Nitrate Reduction

• Published in: Advanced energy materials Vol. 12; no. 15
• Main Authors: Ge, Zi‐Xin, Wang, Tian‐Jiao, Ding, Yu, Yin, Shi‐Bin, Li, Fu‐Min, Chen, Pei, Chen, Yu
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.04.2022
• Subjects: Ammonia; bimetallic nanocubes; Bimetals; Catalysis; Density functional theory; Electroactivity; Electrocatalysts; interfacial engineering; Mass transfer; nitrate reduction reaction; Organic chemistry; Reduction; RhCu alloys; Rhodium
• ISSN: 1614-6832; 1614-6840
• DOI: 10.1002/aenm.202103916

Ammonia is a crucial chemical in agriculture, industry, and emerging energy industries, so high‐efficient, energy‐saving, sustainable, and environmentally‐friendly NH3 synthesis strategies are highly desired. Here polyallylamine (PA) functionalized frame‐like concave RhCu bimetallic nanocubes (PA‐RhCu cNCs) are reported with an electrochemically active surface area of 72.8 m2 g−1 as a robust electrocatalyst for the 8e reduction of nitrate (NO3−) to NH3. PA‐RhCu cNCs show a remarkable NH3 production yield of 2.40 mg h−1 mgcat−1 and a high faradaic efficiency of 93.7% at +0.05 V potential. Density functional theory calculations and experimental results indicate that Cu and PA (adsorbed amino) coregulate the Rh d‐band center, which slightly weakens the adsorption energy of reaction‐related species on Rh. In addition, the electrochemical interface mass transfer accelerated by the surface PA further determines the notable performance of PA‐RhCu cNCs for electroreduction of NO3− to NH3. These findings may open an avenue to construct other advanced catalysts based on organic molecule‐mediated interfacial engineering in various catalysis/electrocatalysis fields. Polyallylamine functionalized frame‐like concave RhCu bimetallic nanocubes are synthesized by a facile wet chemical method, which achieve a remarkable NH3 production yield of 2.40 mg h–1 mgcat–1 and a high Faradaic efficiency of 93.7% at +0.05 V for NO3− electroreduction thanks to abundant active sites, Cu and polyallylamine coregulated Rh electronic structure and accelerated mass transfer induced by polyallylamine.