利用表面配位层钝化铜的氧化反应，这一成果由厦门大学Nanfeng Zheng、Lan-Sun Zheng和北京大学Ying Jiang研究小组合作取得。 这一研究成果于2020年10月14日发表在国际顶尖学术期刊《自然》上。

课题组曾经报道使用溶剂热合成法，以甲酸为还原剂制备高空气稳定的铜纳米片。研究人员报告，在甲酸钠的存在下，溶剂热法处理铜会导致铜表面的晶体学重建和一个超薄表面配位层的形成。小组揭示表面改性不影响铜的热/电导率，但引入了在空气、盐雾以及碱性条件的抗氧化性能。研究人员也开发一种快速室温电化学合成方法，由此产生的材料证明同样强大的钝化性能。

研究组通过引入烷硫醇配体与未被钝化层保护的缺陷位点进行配位，进一步提高铜表面的抗氧化性。研究组证明，温和的处理条件使这项技术适用于制备各种形式的空气稳定的铜材料，包括箔，纳米线，纳米颗粒和块状浆料。该研究组预期这项工作中所开发的技术将有助于扩大铜的工业应用。

据了解，由于铜具有高热/电导率、好的延展性和整体无毒性的特点，被广泛用于日常应用和工业中，尤其在抗氧化技术方面。然而，许多广泛使用的抗氧化技术，例如合金和电镀，通常会影响一些物理特性(例如热/电导率和颜色）和引入有害元素，如铬和镍。尽管已努力开发以有机分子，无机材料或碳基材料为抗氧化剂的表面钝化技术，其大规模使用仍未成功。

附：英文原文

Title: Surface coordination layer passivates oxidation of copper

Author: 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, Nanfeng Zheng

Issue&Volume: 2020-10-14

Abstract: Owing to its high thermal and electrical conductivities, its ductility and its overall non-toxicity, 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 electroplating, 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 inhibitors, 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 agent. 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. 

DOI: 10.1038/s41586-020-2783-x

Source: https://www.nature.com/articles/s41586-020-2783-x