Unconventional chemical graphitization and functionalization of graphene oxide toward nanocomposites by degradation of ZnSe[DETA]0.5 hybrid nanobelts

基于ZnSe[DETA]0.5有机无机杂化纳米带的不稳定性实现氧化石墨烯非常规化学石墨化和功能化

Abstract

The high surface energy of nanomaterials endows them a metastable nature, which greatly limits their application. However, in some cases, the degradation process derived from the poor stability of nanomaterials offers an unconventional approach to design and obtain functional nanomaterials. Herein, based on the poor stability of ZnSe-[DETA]0.5 hybrid nanobelts, we developed a new strategy to chemically graphitize and functionalize graphene oxide (GO). When ZnSe[DETA]0.5 hybrid nanobelts encountered a strong acid, they were attacked by H+ cations and could release highly reactive Se2− anions into the reaction solution. Like other common reductants (such as N2H4·H2O), these Se2− anions exhibited an excellent ability to restore the structure of GO. The structural restoration of GO was greatly affected by the reaction time, the volume of HCl, and the mass ratio between GO and ZnSe[DETA]0.5 nanobelts. By carefully controlling the reaction process and the post-processing process, we finally obtained several Se-based reduced GO (RGO) nanocomposites (such as ZnSe/Se-RGO, ZnSe-RGO, and Se-RGO) and various selenide/metal-RGO nanocomposites (such as Ag2Se-RGO, Cu2Se-RGO, and Pt-RGO). Although the original structure and composition of ZnSe[DETA]0.5 nanobelts are destroyed, the procedure presents an unconventional way to chemically graphitize and functionalize GO and thus provides a new material synthesis platform for nanocomposites.

摘要

与宏观块材不同, 纳米材料高的表面能赋予其亚稳态特性, 使其对外界变化十分敏感. 当纳米颗粒与外界发生强烈相互作用(溶解、酸解等)时, 这些高度不稳定的纳米颗粒将通过一系列持续的调整过程(结构重组、化学转化等)来达到一个新的稳态, 而合理地利用这些调整过程可实现功能纳米材料的非常规设计和制备. 本文基于ZnSe[DETA]0.5有机无机杂化纳米带的低稳定性提出了一种氧化石墨烯非常规化学石墨化和功能化新策略. 在强酸作用下, H+离子会质子化ZnSe[DETA]0.5纳米带中的DETA分子, 使得原本被DETA分子所稳定的ZnSe无机片层变得极为不稳定, 释放出高还原性的Se2−阴离子. 这些高还原性的Se2−阴离子与溶液中的氧化石墨烯纳米片相互作用, 在室温条件下即可对其进行非常规化学还原和掺杂. 此外, 由于Se2−/Se较低的还原电势(−0.924V), 通过控制Se2−阴离子的氧化过程和后处理过程, 可分别得到Se/(Se+ZnSe)/ZnSe与还原石墨烯的三种不同复合材料; 其中, Se-还原石墨烯复合材料又可作为前驱体进一步通过物理/化学过程形成Se纳米线/Cu2Se/Ag2Se/Pt与还原石墨烯复合材料. 显然, 合理地利用纳米材料的不稳定过程可以为构建各种功能纳米材料提供一个非常规设计和制备平台.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21431006, 51732011, 21761132008 and 21805189), the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (21521001), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (CAS) (QYZDJ-SSW-SLH036), the National Basic Research Program of China (2014CB931800), and the Excellence and Scientific Research Grant from Hefei Science Center of CAS (2015HSC-UE007). This work was partially carried out at the Center for Micro and Nanoscale Research and Fabrication, USTC. Xu L is grateful for the funding support from China Postdoctoral Science Foundation (2018M630711 and 2019T120540), and the Natural Science Foundation of Guangdong (2018A030310617). Author contributions Yu SH and He C conceived and supervised the project. Xu L, Hu ZW and Wang LL conducted the experiments, analyzed the results and wrote the paper. Yu SH and He C revised the manuscript. All authors contributed to the general discussion. Conflict of interest The authors declare no conflict of interest. Supplementary information Supporting data are available in the online version of the paper.

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Yu SH and He C conceived and supervised the project. Xu L, Hu ZW and Wang LL conducted the experiments, analyzed the results and wrote the paper. Yu SH and He C revised the manuscript. All authors contributed to the general discussion.

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Correspondence to Chuanxin He 何传新 or Shu-Hong Yu 俞书宏.

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Additional information

Liang Xu received his Bachelor’s degree from Lanzhou University in 2011 and his PhD in 2016 from the University of Science and Technology of China (USTC) under the supervision of Prof. Shu-Hong Yu. Now, he is a postdoctor at Shenzhen University, and his current research focuses on the stability and reactivity of nanomaterials.

Chuanxin He received his PhD in polymer chemistry and physics from USTC in 2010 and now is an Assistant Dean of the College of Chemistry and Environmental Engineering, Shenzhen University. His current research interest is to design and synthesize novel nanostructure materials for fuel cells, water splitting and electrochemical reduction of carbon dioxide.

Shu-Hong Yu completed PhD in inorganic chemistry in 1998 from USTC. Currently, he is leading the Division of Nanomaterials & Chemistry, Hefei National Research center for Physical Sciences at the Microscale, USTC. He was elected as an academician of the Chinese Academy of Sciences in 2019. His research interests include bio-inspired synthesis of nanoscale building blocks, self-assembly and macroscopic assemblies, nanocomposites, and their functions and applications.

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Xu, L., Hu, Z., Wang, L. et al. Unconventional chemical graphitization and functionalization of graphene oxide toward nanocomposites by degradation of ZnSe[DETA]0.5 hybrid nanobelts. Sci. China Mater. (2020). https://doi.org/10.1007/s40843-020-1341-1

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Keywords

  • stability
  • degradation
  • unconventional chemical graphitization
  • hybrid nanobelt
  • graphene oxide