上海大学张登松团队报道了通过Cu -联吡啶二维共价有机框架膜，增强传质促进电催化硝酸还原。相关研究成果发表在2024年12月24日出版的《德国应用化学》。

电催化硝酸盐还原（NO₃RR）是一种有前景的污染物去除和氨合成方法，涉及8个电子和9个质子的转移。因此，合理设计具有增强传质的催化界面，对于实现高氨收率和法拉第效率（FE）至关重要。

该文中，研究人员引入了铜联吡啶催化界面，并制备了具有明显暴露催化位点的结晶2D共价有机框架薄膜，与块状催化剂相比，提高了FE和氨的收率（在0.5M硝酸盐中，FE=92.7%，NH₃收率=14.9mg·h^-1cm^-2），并优于大多数报道的NO₃RR电催化剂。

薄膜状形态增强了铜-联吡啶界面上的传质，从而获得了优异的催化性能。研究人员通过原位表征和理论计算证实了反应途径和机理。Cu位点充当吸附和活化的主要中心，而联吡啶位点促进水的吸附和解离，提供足够的H*并加速质子耦合电子转移动力学。

该研究提供了一种可行的策略，通过合理的形态控制来增强催化界面处的传质，提高NO₃RR过程中催化剂的固有活性。

附：英文原文

Title: Boosting Electrocatalytic Nitrate Reduction through Enhanced Mass Transfer in Cu-Bipyridine 2D Covalent Organic Framework Films

Author: Ying Zhu, Haiyan Duan, Christoph G. Gruber, Wenqiang Qu, Hui Zhang, Zhenlin Wang, Jian Zhong, Xinhe Zhang, Lupeng Han, Danhong Cheng, Dana D. Medina, Emiliano Cortes, Dengsong Zhang

Issue&Volume: 2024-12-24

Abstract: Electrocatalytic nitrate reduction (NO3RR) is a promising method for pollutant removal and ammonia synthesis and involves the transfer of eight electrons and nine protons. As such, the rational design of catalytic interfaces with enhanced mass transfer is crucial for achieving high ammonia yield rates and Faradaic efficiency (FE). In this work, we incorporated a Cu-bipyridine catalytic interface and fabricated crystalline 2D covalent organic framework films with significantly exposed catalytic sites, leading to improved FE and ammonia yield (FE = 92.7%, NH3 yield rate = 14.9 mg·h-1cm-2 in 0.5 M nitrate) compared to bulk catalysts and outperforming most reported NO3RR electrocatalysts. The film-like morphology enhances mass transfer across the Cu-bipyridine interface, resulting in superior catalytic performance. We confirmed the reaction pathway and mechanism through in-situ characterizations and theoretical calculations. The Cu sites act as primary centers for adsorption and activation, while the bipyridine sites facilitate water adsorption and dissociation, supplying sufficient H* and accelerating proton-coupled electron transfer kinetics. This study provides a viable strategy to enhance mass transfer at the catalytic interface through rational morphology control, boosting the intrinsic activity of catalysts in the NO3RR process.

DOI: 10.1002/anie.202421821

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202421821