Ultrafine Core@Shell Cu1Au1@Cu1Pd3 Nanodots Synergized with 3D Porous N-Doped Graphene Nanosheets as a High-Performance Multifunctional Electrocatalyst

Liuxuan Luo; Cehuang Fu; Yangge Guo; Xiyang Cai; Xiashuang Luo; Zehao Tan; Rui Xue; Xiaojing Cheng; Shuiyun Shen; Junliang Zhang

doi:10.1021/acsnano.2c11627

Ultrafine Core@Shell Cu₁Au₁@Cu₁Pd₃ Nanodots Synergized with 3D Porous N-Doped Graphene Nanosheets as a High-Performance Multifunctional Electrocatalyst

ACS Nano. 2023 Feb 14;17(3):2992-3006. doi: 10.1021/acsnano.2c11627. Epub 2023 Jan 27.

Authors

Affiliation

¹ Institute of Fuel Cells, Key Laboratory for Power Machinery and Engineering of MOE, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai200240, People's Republic of China.

PMID: 36706226
DOI: 10.1021/acsnano.2c11627

Abstract

Rationally combining designed supports and metal-based nanomaterials is effective to synergize their respective physicochemical and electrochemical properties for developing highly active and stable/durable electrocatalysts. Accordingly, in this work, sub-5 nm and monodispersed nanodots (NDs) with the special nanostructure of an ultrafine Cu₁Au₁ core and a 2-3-atomic-layer Cu₁Pd₃ shell are synthesized by a facile solvothermal method, which are further evenly and firmly anchored onto 3D porous N-doped graphene nanosheets (NGS) via a simple annealing (A) process. The as-obtained Cu₁Au₁@Cu₁Pd₃ NDs/NGS-A exhibits exceptional electrocatalytic activity and noble-metal utilization toward the alkaline oxygen reduction, methanol oxidation, and ethanol oxidation reactions, showing dozens-fold enhancements compared with commercial Pd/C and Pt/C. Besides, it also has excellent long-term electrochemical stability and electrocatalytic durability. Advanced and comprehensive experimental and theoretical analyses unveil the synthetic mechanism of the special core@shell nanostructure and further reveal the origins of the significantly enhanced electrocatalytic performance: (1) the prominent structural properties of NGS, (2) the ultrasmall and monodispersed size as well as the highly uniform morphology of the NDs-A, (3) the special Cu-Au-Pd alloy nanostructure with an ultrafine core and a subnanometer shell, and (4) the strong metal-support interaction. This work not only develops a facile method for fabricating the special metal-based ultrafine-core@ultrathin-shell nanostructure but also proposes an effective and practical design paradigm of comprehensively and rationally considering both supports and metal-based nanomaterials for realizing high-performance multifunctional electrocatalysts, which can be further expanded to other supports and metal-based nanomaterials for other energy-conversion or environmental (electro)catalytic applications.

Keywords: core@shell nanostructure; ethanol oxidation reaction; gold; metal−support interaction; methanol oxidation reaction; oxygen reduction reaction; palladium.