Binary-doped metal-free carbon materials are promising bifunctional catalysts for rechargeable zinc–air batteries (ZABs) due to their synergetic effect. However, the fabrication of co-doped carbon materials with a well-defined structure, elemental composition and homogeneous distribution of doping elements is highly challenging, creating demand for novel designs and synthesis methods. Herein, a supramolecular strategy is proposed to precisely fabricate binary-doped metal-free graphdiyne. Specifically, trifluoro-substituted graphdiynes with guest molecules (melamine or 1,3,5-triaminobenzene) assembled via hydrogen bonding (N–H⋯F) are synthesized. The introduction of guest molecules into the pore structure of trifluoro-graphdiyne achieves defined non-metal binary doping (N and F atoms) of graphdiyne. The electron transport and charge distribution of the supramolecular-system-based trifluoro-graphdiyne can be tuned by altering the guest molecules. ZABs constructed by the as-prepared trifluoro-graphdiyne supramolecular systems exhibit impressive electrochemical performances, with a low voltage gap of 0.83 V and long-term stability of over 1000 cycles. The peak power density of the ZABs is up to 94.1 mW cm⁻² with a high specific capacity of 707.8 mA h g⁻¹ and energy density of 700.3 W h kg⁻¹ (current density: 25 mA cm⁻²). The proposed supramolecular strategy creates a new route to non-metal multi-doped carbon materials for efficient bifunctional oxygen electrocatalysis and high-performance ZABs, expanding new applications of graphdiyne for ZABs.

中文翻译：

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一种超分子策略来精确制造用于高性能锌空气电池的二元掺杂无金属石墨二炔

由于其协同效应，二元掺杂无金属碳材料是用于可充电锌空气电池（ZAB）的有前途的双功能催化剂。然而，制造具有明确结构、元素组成和掺杂元素均匀分布的共掺杂碳材料极具挑战性，这就产生了对新颖设计和合成方法的需求。在此，提出了一种超分子策略来精确制造二元掺杂的无金属石墨炔。具体来说，合成了通过氢键（N-H⋯F）组装客体分子（三聚氰胺或1,3,5-三氨基苯）的三氟取代石墨二炔。将客体分子引入三氟石墨二炔的孔结构中，实现了石墨二炔的特定非金属二元掺杂（N和F原子）。基于超分子系统的三氟石墨二炔的电子传输和电荷分布可以通过改变客体分子来调节。由所制备的三氟石墨二炔超分子体系构建的ZAB表现出令人印象深刻的电化学性能，具有0.83 V的低电压间隙和超过1000次循环的长期稳定性。ZAB的峰值功率密度高达94.1 mW cm ^{-2 ，具有707.8 mA hg -1}的高比容量和700.3 W h kg ^-1的能量密度（电流密度：25 mA cm ^-2）。所提出的超分子策略为用于高效双功能氧电催化和高性能ZAB的非金属多掺杂碳材料开辟了一条新途径，扩大了石墨二炔在ZAB中的新应用。