Surface Functionalization of a γ‐Graphyne‐like Carbon Material via Click Chemistry

Xiong, Huatian; Zou, Haiyuan; Liu, Hong; Wang, Mei; Duan, Lele

doi:10.1002/asia.202100125

“…The peaks located at around 1394 cm -1 and 1577 cm -1 are attributed to the defects/edges of the as-prepared samples (D band) and the stretching vibration of sp 2 -hybridized carbon in aromatic rings (G band), respectively [40,41]. The weak peaks at ca 2023 cm -1 and 2168 cm -1 are ascribed to the sp-hybridized carbon in conjugated diyne linkages [42]. Furthermore, the carbon species and the valence states of metals were investigated by XPS (figures 3, S7, and S12).…”

Section: Resultsmentioning

confidence: 99%

A single-step strategy for general construction of metal sub-nanoclusters on graphdiyne

Xiong¹,

Zou²,

Rong³

et al. 2021

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Metal sub-nanoclusters (SNCs) inherit the metrics of unsaturated active sites and ultrahigh metal utilization from single-atom catalysts (SACs), and they can drive the reactions involving multiple adsorbates by their enriched metal cofactors that beyond SACs. However, the current synthetic strategy offers limited versatility to prepare SNCs due to their subnanometric feature and high active surface. Herein, we demonstrate a universal and facile one-pot reaction to construct wide assortments of metal SNCs with the size of 2 to 3 nm on graphdiyne (GDY), denoted as M-SNCs/GDY (M = Co, Ni, Cu, Ag, Pd, Rh, Au, Ir, and Pt). Systematic investigations reveal that the correlated metal SNCs formation undergone the nucleation and growth process, during which the metal single-atoms were first anchored and then served as nuclei to grow SNCs confined on GDY. The electrochemical CO2 reduction reaction (eCO2RR) catalyzed by Cu-SNC/GDY and a Cu single-atom catalyst on GDY (Cu-SAC/GDY) was investigated to demonstrate the advantages of SNCs over SACs in manipulating the multicomponent reaction. Cu-SNC/GDY exhibited promoted Faradic efficiency (FE) of carbon products and suppressed competing hydrogen evolution reaction compared to the Cu-SAC/GDY. Benefiting from the function of multiple active centers, a C2+ FE of 31.6% was achieved over the Cu-SNC/GDY at −0.7 V versus reversible hydrogen electrode, which is 11-fold higher than that of Cu-SAC/GDY. In situ infrared spectroelectrochemistry confirmed that Cu-SNC/GDY could adsorb more eCO2RR intermediates over Cu-SAC/GDY. This study delivers a single-step strategy for preparing metal SNCs on GDY and expands the scope of SNCs.

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Metal‐Free Wet Chemistry for the Fast Gram‐Scale Synthesis of γ‐Graphyne and its Derivatives

Song,

Liu,

Zou

et al. 2024

Angewandte Chemie

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γ‐Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal‐free nucleophilic crosslinking method using wet chemistry for fast gram‐scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro‐(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as‐prepared GY reveals a layered structure, characterized by the presence of the C(sp)‐C(sp2) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F‐/N‐rich GY derivatives, using electron‐deficient fluoro‐substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal‐free, scalable, and cost‐effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials.

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Metal‐Free Wet Chemistry for the Fast Gram‐Scale Synthesis of γ‐Graphyne and its Derivatives

Song,

Liu,

Zou

et al. 2024

Angew Chem Int Ed

0

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γ‐Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal‐free nucleophilic crosslinking method using wet chemistry for fast gram‐scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro‐(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as‐prepared GY reveals a layered structure, characterized by the presence of the C(sp)‐C(sp2) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F‐/N‐rich GY derivatives, using electron‐deficient fluoro‐substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal‐free, scalable, and cost‐effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials.

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Surface Functionalization of a γ‐Graphyne‐like Carbon Material via Click Chemistry

Cited by 9 publications

References 47 publications

A single-step strategy for general construction of metal sub-nanoclusters on graphdiyne

A single-step strategy for general construction of metal sub-nanoclusters on graphdiyne

Metal‐Free Wet Chemistry for the Fast Gram‐Scale Synthesis of γ‐Graphyne and its Derivatives

Metal‐Free Wet Chemistry for the Fast Gram‐Scale Synthesis of γ‐Graphyne and its Derivatives

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