Surface coordination layer passivates oxidation of copper

Jian Peng, Bili Chen, Zhichang Wang, Jing Guo, Binghui Wu, Shuqiang Hao, Qinghua Zhang, Lin Gu, Qin Zhou, Zhi Liu, Shuqin Hong, Sifan You, Ang Fu, Zaifa Shi, Hao Xie, Duanyun Cao, Chang-Jian Lin, Gang Fu (), Lan-Sun Zheng, Ying Jiang () and Nanfeng Zheng ()
Additional contact information
Jian Peng: Xiamen University
Bili Chen: Xiamen University
Zhichang Wang: Xiamen University
Jing Guo: Beijing Normal University
Binghui Wu: Xiamen University
Shuqiang Hao: Xiamen University
Qinghua Zhang: Chinese Academy of Sciences
Lin Gu: Chinese Academy of Sciences
Qin Zhou: Shanghai Tech University
Zhi Liu: Shanghai Tech University
Shuqin Hong: Xiamen University
Sifan You: Peking University
Ang Fu: Xiamen University
Zaifa Shi: Xiamen University
Hao Xie: Xiamen University
Duanyun Cao: Peking University
Chang-Jian Lin: Xiamen University
Gang Fu: Xiamen University
Lan-Sun Zheng: Xiamen University
Ying Jiang: Peking University
Nanfeng Zheng: Xiamen University

Nature, 2020, vol. 586, issue 7829, 390-394

Abstract: Abstract Owing to its high thermal and electrical conductivities, its ductility and its overall non-toxicity1–3, copper is widely used in daily applications and in industry, particularly in anti-oxidation technologies. However, many widespread anti-oxidation techniques, such as alloying and electroplating1,2, often degrade some physical properties (for example, thermal and electrical conductivities and colour) and introduce harmful elements such as chromium and nickel. Although efforts have been made to develop surface passivation technologies using organic molecules, inorganic materials or carbon-based materials as oxidation inhibitors4–12, their large-scale application has had limited success. We have previously reported the solvothermal synthesis of highly air-stable copper nanosheets using formate as a reducing agent13. Here we report that a solvothermal treatment of copper in the presence of sodium formate leads to crystallographic reconstruction of the copper surface and formation of an ultrathin surface coordination layer. We reveal that the surface modification does not affect the electrical or thermal conductivities of the bulk copper, but introduces high oxidation resistance in air, salt spray and alkaline conditions. We also develop a rapid room-temperature electrochemical synthesis protocol, with the resulting materials demonstrating similarly strong passivation performance. We further improve the oxidation resistance of the copper surfaces by introducing alkanethiol ligands to coordinate with steps or defect sites that are not protected by the passivation layer. We demonstrate that the mild treatment conditions make this technology applicable to the preparation of air-stable copper materials in different forms, including foils, nanowires, nanoparticles and bulk pastes. We expect that the technology developed in this work will help to expand the industrial applications of copper.

Date: 2020
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DOI: 10.1038/s41586-020-2783-x

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