Fully π-conjugated organic frameworks (π-COFs) have attracted considerable attention due to their enhanced stability and conductivity compared to conventional covalent organic frameworks (COFs). Here, we report the synthesis of a crystalline and stable hierarchical porous π-COF (polyphthalocyanine, HPPc) and demonstrate its potential as an ideal electrosynthesis platform. The as-synthesized crystalline HPPc possesses a high surface area (∼324 m² g^–1), plentiful inherent micropores (1.4 nm), along with hard-template-induced, uniform, and interconnected mesopores (35 nm). This dual-porosity design can lead to improved active site dispersion and mass diffusion. Moreover, the long-range ordering brought by high crystallinity enables the precise customization of active sites as needed. Anchored with nickel and cobalt atoms, the optimized catalyst exhibits an outstanding oxygen evolution reaction performance, including a competitive overpotential of 305 mV at 10 mA cm^–2 and a low Tafel slope of 40 mV dec^–1, significantly surpassing commercial RuO₂. This work opens a new avenue for the rational design and synthesis of chemically stable and crystalline hierarchical porous π-COFs for various applications.

中文翻译：

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结晶稳定的多级多孔共轭有机框架作为电合成的理想平台

与传统的共价有机框架 （COF） 相比，全π共轭有机框架 （π-COF） 因其增强的稳定性和导电性而受到广泛关注。在这里，我们报道了结晶稳定的多级多孔 π-COF（聚酞菁，HPPc）的合成，并展示了其作为理想电合成平台的潜力。合成的结晶 HPPc 具有高表面积 （∼324 m² g^–1）、丰富的固有微孔 （1.4 nm） 以及硬模板诱导的均匀和互连的介孔 （35 nm）。这种双孔隙率设计可以改善活性位点分散和质量扩散。此外，高结晶度带来的长距离有序性使活动位点的需要能够根据需要进行精确定制。以镍和钴原子为锚定物，优化的催化剂表现出出色的析氧反应性能，包括在 10 mA cm^–2 时 305 mV 的竞争性过电位和 40 mV dec^–1 的低塔菲尔斜率，明显超过商用 RuO₂。这项工作为合理设计和合成化学稳定和结晶多级多孔 π-COF 开辟了一条新的途径，用于各种应用。