Abstract With a direct band gap, superior charge carrier mobility, and uniformly distributed pores, graphdiyne (GDY) has stimulated tremendous interest from the scientific community. However, its broad application is greatly limited by the complicated multistep synthesis process including complex deprotection of hexakis‐[(trimethylsilyl)ethynyl]benzene (HEB‐TMS) and peeling of GDY from the substrates. Here, we describe a deprotection‐free strategy to prepare GDY powder by directly using HEB‐TMS as the monomer. When CuCl was used as the catalysts in DMF solvent, the yield of GDY powder reached ≈100 %. More interestingly, uniformly dispersed CuO nanoparticles with an average diameter of ≈2.9 nm were in situ formed on GDY after the reaction. The prepared CuO/GDY was demonstrated an excellent co‐catalyst for photocatalytic hydrogen evolution, comparable to the state‐of‐art Pt co‐catalyst. The deprotection‐free approach will widen the use of GDY and facilitate its scaling up to industrial level.

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A Deprotection‐free Method for High‐yield Synthesis of Graphdiyne Powder with In Situ Formed CuO Nanoparticles

Graphdiyne-supported metal electrocatalysts: From nanoparticles and cluster to single atoms

Triple-atom catalysts 3TM-GYs (TM = Cu, Fe, and Co; GY = graphyne) for high-performance CO2 reduction reaction to C1 products

The interfacial interaction in supported catalysts is of great significance for heterogeneous catalysis because it can induce charge transfer, regulate electronic structure of active sites, influence reactant adsorption behavior, and eventually affect the catalytic performance. It has been theoretically and experimentally elucidated well in metal/oxide catalysts and oxide/metal inverse catalysts, but is rarely reported in carbon-supported catalysts due to the inertness of traditional carbon materials. Using an example of a graphdiyne-supported cuprous oxide nanocluster catalyst (Cu2O NCs/GDY), we herein demonstrate the strong electronic interaction between them and put forward a new type of electronic oxide-graphdiyne strong interaction, analogous to the concept of electronic oxide/metal strong interactions in oxide/metal inverse catalysts. Such electronic oxide-graphdiyne strong interaction can not only stabilize Cu2O NCs in a low-oxidation state without aggregation and oxidation under ambient conditions but also change their electronic structure, resulting in the optimized adsorption energy for reactants/intermediates and thus leading to improved catalytic activity in the Cu(I)-catalyzed azide-alkyne cycloaddition reaction. Our study will contribute to the comprehensive understanding of interfacial interactions in supported catalysts.

Electronic Oxide-Support Strong Interactions in the Graphdiyne-Supported Cuprous Oxide Nanocluster Catalyst.

With a direct band gap, superior charge carrier mobility, and uniformly distributed pores, graphdiyne (GDY) has stimulated tremendous interest from the scientific community. However, its broad application is greatly limited by the complicated multistep synthesis process including complex deprotection of hexakis-[(trimethylsilyl)ethynyl]benzene (HEB-TMS) and peeling of GDY from the substrates. Here, we describe a deprotection-free strategy to prepare GDY powder by directly using HEB-TMS as the monomer. When CuCl was used as the catalysts in DMF solvent, the yield of GDY powder reached ≈100 %. More interestingly, uniformly dispersed CuO nanoparticles with an average diameter of ≈2.9 nm were in situ formed on GDY after the reaction. The prepared CuO/GDY was demonstrated an excellent co-catalyst for photocatalytic hydrogen evolution, comparable to the state-of-art Pt co-catalyst. The deprotection-free approach will widen the use of GDY and facilitate its scaling up to industrial level. 

Yun-Nan Gong

Papers

Graphdiyne enables Cu nanoparticles for highly selective electroreduction of CO2 to formate