Zhao Qian, Zhang Qingxin, Xu Yuhan, Han Anhao, He Haowen, Zheng Haoquan, Zhang Wei, Lei Haitao, Apfel Ulf-Peter, Cao Rui
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China.
Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie, Activation of Small Molecules/Technical Electrochemistry, Universitätsstrasse 150, 44801, Bochum, Germany.
Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202414104. doi: 10.1002/anie.202414104. Epub 2024 Oct 14.
Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist proton transfer in channels, few studies are dedicated to improving proton transfer at the local environments of active sites in porous materials. Herein, we report on new Co-corrole-based porous organic polymers (POPs) with improved proton transfer for electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). By tuning the pore sizes and installing proton relays at Co corrole sites, we designed and synthesized POP-2-OH with improved proton transfer both in channels and at local Co active sites. This POP shows remarkable activity for both electrocatalytic ORR with E=0.91 V vs RHE and OER with η=255 mV. Therefore, this work is significant to present a strategy to improve active site local proton transfer in porous materials and highlight the key role of such structural functionalization in boosting oxygen electrocatalysis.
改善质子转移对于多孔材料的电催化至关重要。尽管已报道了几种策略来辅助通道中的质子转移，但很少有研究致力于改善多孔材料中活性位点局部环境下的质子转移。在此，我们报道了新型基于钴卟啉的多孔有机聚合物（POPs），其具有改善的质子转移性能，可用于电催化氧还原反应（ORR）和析氧反应（OER）。通过调节孔径并在钴卟啉位点安装质子中继体，我们设计并合成了在通道和局部钴活性位点均具有改善质子转移性能的POP-2-OH。这种POP对于电催化ORR（相对于可逆氢电极，E = 0.91 V）和OER（η = 255 mV）均表现出显著活性。因此，这项工作对于提出一种改善多孔材料中活性位点局部质子转移的策略具有重要意义，并突出了这种结构功能化在促进氧电催化中的关键作用。
