A Surfactant-Free and General Strategy for the Synthesis of Bimetallic Core-Shell Nanocrystals on Reduced Graphene Oxide through Targeted Photodeposition

Yidan Liu; Yali Ji; Qian Li; Yi Zhu; Jianchao Peng; Rongrong Jia; Zhuangchai Lai; Liyi Shi; Fengtao Fan; Gengfeng Zheng; Lei Huang; Can Li

doi:10.1021/acsnano.3c04281

A Surfactant-Free and General Strategy for the Synthesis of Bimetallic Core-Shell Nanocrystals on Reduced Graphene Oxide through Targeted Photodeposition

ACS Nano. 2023 Aug 8;17(15):15085-15096. doi: 10.1021/acsnano.3c04281. Epub 2023 Jul 27.

Authors

Yidan Liu^{1

2}, Yali Ji³, Qian Li⁴, Yi Zhu¹, Jianchao Peng⁵, Rongrong Jia¹, Zhuangchai Lai⁶, Liyi Shi¹, Fengtao Fan⁴, Gengfeng Zheng³, Lei Huang¹, Can Li⁴

Affiliations

¹ Research Center of Nano Science and Technology, College of Sciences, Shanghai University, Shanghai 200444, People's Republic of China.
² School of Materials Science and Engineering, Shanghai University, Shanghai 200444, People's Republic of China.
³ Laboratory of Advanced Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, People's Republic of China.
⁴ State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
⁵ Laboratory for Microstructures, Shanghai University, Shanghai 200444, People's Republic of China.
⁶ Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong SAR, People's Republic of China.

PMID: 37497875
DOI: 10.1021/acsnano.3c04281

Abstract

Tunable physicochemical properties of bimetallic core-shell heterostructured nanocrystals (HNCs) have shown enormous potential in electrocatalytic reactions. In many cases, HNCs are required to load on supports to inhibit catalyst aggregation. However, the introduction of supports during the process of growing core-shell HNCs makes the synthesis much more complicated and difficult to control precisely. Herein, we reported a universal photochemical synthetic strategy for the controlled synthesis of well-defined surfactant-free core-shell metal HNCs on a reduced graphene oxide (rGO) support, which was assisted by the fine control of photogenerated electrons directly transferring to the targeted metal seeds via rGO and the precisely tuned adsorption capacity of the added second metal precursors. The surface photovoltage microscopy (SPVM) platform proved that photogenerated electrons flowed through rGO to Pd particles under illumination. We have successfully synthesized 24 different core-shell metal HNCs, i.,e., M_A@M_B (M_A = Pd, Au, and Pt; M_B = Au, Ag, Pt, Pd, Ir, Ru, Rh, Ni and Cu), on the rGO supports. The as-prepared Pd@Cu core-shell HNCs showed outstanding performance in the electrocatalytic reduction of CO₂ to CH₄. This work could shed light on the controlled synthesis of more functional bimetallic nanostructured materials on diverse supports for various applications.

Keywords: bimetallic core−shell heterostructure nanocrystals; electrochemical CO2 reduction reaction; electron transfer; photodeposition; reduced graphene oxide.