浙江大学黄宁团队设计并合成了稳定的双金属聚酞菁共价有机框架作为优良的电催化剂。相关研究成果发表在2021年10月12日出版的《美国化学会杂志》。

高度稳定的共价有机框架（COF）的开发对于其在实际应用中的实现是具有非常重要的意义。

该文中，研究人员合理地设计和合成了新型超稳定双金属聚酞菁COFs，该COFs通过八羟基苯酞菁和十六氟酞菁之间的亲核芳香取代以二恶英键构建。得到的双金属CuPcF8-CoPc-COF和CuPcF8-CoNPc-COF在恶劣条件下表现出很强的鲁棒性。金属酞菁单元的重叠叠加模式为电子转移提供了高速通道。由于具有这些结构优势，两种COF在水系统中都表现出相当高的电催化CO₂还原活性、选择性和稳定性。值得注意的是，CuPcF8-CoNPc-COF表现出97%的法拉第效率和2.87 s^–1的超高的转换频率，优于大多数基于COF的电催化剂。此外，通过理论计算很好地证明了催化机理。

该研究工作不仅扩大了二恶英连接COF的种类，而且为其在碳循环中的实际应用迈出了新的一步。

附：英文原文

Title: Stable Bimetallic Polyphthalocyanine Covalent Organic Frameworks as Superior Electrocatalysts

Author: Yan Yue, Peiyu Cai, Kai Xu, Hanying Li, Hongzheng Chen, Hong-Cai Zhou, Ning Huang

Issue&Volume: October 12, 2021

Abstract: The development of highly stable covalent organic frameworks (COFs) is extremely compelling for their implementation in practical application. In this work, we rationally designed and synthesized new kinds of ultrastable bimetallic polyphthalocyanine COFs, which are constructed with the dioxin linkage through the nucleophilic aromatic substitution between octahydroxylphthalocyanine and hexadecafluorophthalocyanine. The resulting bimetallic CuPcF8-CoPc-COF and CuPcF8-CoNPc-COF exhibited strong robustness under harsh conditions. The eclipsed stacking mode of metallophthalocyanine units supplies a high-speed pathway for electron transfer. With these structural advantages, both COFs displayed considerable activity, selectivity, and stability toward electrocatalytic CO2 reduction in an aqueous system. Notably, CuPcF8-CoNPc-COF showed a faradaic efficiency of 97% and an exceptionally high turnover frequency of 2.87 s–1, which is superior to most COF-based electrocatalysts. Furthermore, the catalytic mechanism was well demonstrated by using a theoretical calculation. This work not only expanded the variety of dioxin-linked COFs, but also constituted a new step toward their practical use in carbon cycle.

DOI: 10.1021/jacs.1c06238

Source: https://pubs.acs.org/doi/10.1021/jacs.1c06238