Scalable synthesis of 2D hydrogen-substituted graphdiyne on Zn substrate for high-yield N2 fixation. (December 2020)

• Record Type: Journal Article
• Authors: Yang, Qi; Guo, Ying; Gu, Jinxing; Li, Na; Wang, Changda; Liu, Zhuoxin; Li, Xinliang; Huang, Zhaodong; Wei, Shiqiang; Xu, Suying; Song, Li; Fan, Jun; Chen, Zhongfang; Qiu, Jieshan; Zhi, Chunyi
• Is Part Of: Nano energy. Volume 78(2020)
• Publication Date: 2020-12
• Subjects: Graphdiyne -- Zinc substrate -- Two dimensional materials -- N2 fixation -- Metal-free electrocatalysts; Nanoscience -- Periodicals; Nanotechnology -- Periodicals; Nanostructured materials -- Periodicals; Power resources -- Technological innovations -- Periodicals; Nanoscience; Nanostructured materials; Nanotechnology; Power resources -- Technological innovations; Periodicals; 621.042
• DOI: 10.1016/j.nanoen.2020.105283
• Languages: English
• ISSNs: 2211-2855

Abstract

Abstract: Hydrogen-substituted graphdiyne (HsGDY), as a new rising star of carbon materials family, demonstrates high conjugation, robust chemical stability, and versatility for modification. However, grand challenges, including low production rate, disordered topology, and amorphous structure, greatly hinder its large-scale applications. Herein, we report, for the first time, the scalable synthesis (up to gram-level) of two-dimensional (2D) crystalline HsGDY nanosheets with Zn as a substrate. Moreover, as a metal-free catalyst for electrochemical N2 fixation, 2D HsGDY achieves an ultrahigh yield of 103 μg h −1 mg −1 cat. with a potential of −0.2 V vs reversible hydrogen electrode (RHE), which is comparable with that of noble metals and single-atom catalysts. Different from the heteroatom active sites in carbon-based catalysts reported before, the inner alkynyl C itself in 2D HsGDY was identified as the active site, which adsorbs and activates NN due to the positive charge and high spin density triggered by the slight O doping in the form of CO at the outer alkynyl C. We believe that this Zn-templated scalable production of high-quality HsGDY paves the way for its large-scale production and provides a new playground for the multiple research fields. Graphical abstract: This work reports, for the first time, the scalable synthesis (up to gram-level) of two-dimensional crystalline hydrogen-substituted graphdiyne (HsGDY) nanosheets with Zn as a substrate. The novel interface polymerization substrate and the as-generated scalable synthesis method pave the way for the high-quality preparation of HsGDY and its analogues. Image 1 Highlights: This work uncovers the potential of zinc substrate for synthesizing 2D HsGDY, due to restraining the monomer distortion. Using Zn as substrate, we obtained up to 0.5 g-level HsGDY, which accelerates the large-scale applications. As a metal-free catalyst for NRR, 2D HsGDY achieved a high yield of 103 μg h-1 mg −1 cat. at −0.2 V vs RHE. We further identified the alkynyl carbon atom directly connecting to the benzene ring as the active site for NRR.