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使用高价路易斯酸稳定镍铁活性位点用于选择性海水氧化。

Stabilizing NiFe active sites using a high-valent Lewis acid for selective seawater oxidation.

作者信息

Liu Chenxi, Teng Zefeng, Liu Xu, Zhang Rui, Chi Jingqi, Zhu Jiawei, Qin Junfeng, Liu Xiaobin, Wu Zexing, Wang Lei

机构信息

Key Laboratory of Eco-chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Environment and Safety Engineering, Qingdao University of Science and Technology Qingdao 266042 China.

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University Nanjing 2111189 China

出版信息

Chem Sci. 2025 Aug 15. doi: 10.1039/d5sc02818c.

DOI:10.1039/d5sc02818c
PMID:40822099
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12355219/
Abstract

Seawater electrolysis for hydrogen production harnesses renewable energy sources, contributing to sustainable development. However, competing anodic reactions, such as the chloride oxidation reaction (ClOR), can adversely affect the activity and stability of the oxygen evolution reaction (OER). In this study, we propose a strategy that significantly enhances the OER activity and selectivity of NiFe-layered double hydroxides (LDHs) by incorporating chromium (Cr) (Cr-NiFeLDHs). The Cr-NiFeLDH anode demonstrates an impressive overpotential of only 349 mV at a current density of 1000 mA cm, outperforming RuO in industrial applications and maintaining stability for over 140 h in anion exchange membrane (AEM) electrolyzer tests. Quasi characterization reveals that Cr doping activates the high valence states of Ni, Fe and Cr, enhancing the electron transfer and activity of OER performance. Furthermore, the high selectivity for OH due to the hard Cr Lewis acid effectively mitigates the competitive ClOR, a critical challenge in seawater electrolysis. This synergistic stabilization effect of high valence states fundamentally enhances the activity, selectivity, and stability of Cr-NiFeLDH anodes.

摘要

用于制氢的海水电解利用可再生能源,有助于可持续发展。然而,诸如氯离子氧化反应(ClOR)等竞争性阳极反应会对析氧反应(OER)的活性和稳定性产生不利影响。在本研究中,我们提出了一种策略,即通过掺入铬(Cr)(Cr-NiFeLDHs)来显著提高镍铁层状双氢氧化物(LDHs)的OER活性和选择性。Cr-NiFeLDH阳极在电流密度为1000 mA cm时表现出仅349 mV的令人印象深刻的过电位,在工业应用中优于RuO,并在阴离子交换膜(AEM)电解槽测试中保持超过140小时的稳定性。准表征表明,Cr掺杂激活了Ni、Fe和Cr的高价态,增强了OER性能的电子转移和活性。此外,由于硬Cr路易斯酸对OH的高选择性有效地减轻了竞争性ClOR,这是海水电解中的一个关键挑战。这种高价态的协同稳定作用从根本上提高了Cr-NiFeLDH阳极的活性、选择性和稳定性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/4aef3aa2764a/d5sc02818c-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/ce3e4f84b093/d5sc02818c-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/0d84f02e8db3/d5sc02818c-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/17fe21255049/d5sc02818c-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/d99b51f57ffd/d5sc02818c-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/4aef3aa2764a/d5sc02818c-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/ce3e4f84b093/d5sc02818c-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/0d84f02e8db3/d5sc02818c-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/17fe21255049/d5sc02818c-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/d99b51f57ffd/d5sc02818c-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4381/12422307/4aef3aa2764a/d5sc02818c-f5.jpg

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Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414721. doi: 10.1002/anie.202414721. Epub 2024 Nov 9.
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Fe-S dually modulated adsorbate evolution and lattice oxygen compatible mechanism for water oxidation.
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Boosting Oxygen Evolution Reaction Performance on NiFe-Based Catalysts Through d-Orbital Hybridization.通过d轨道杂化提高镍铁基催化剂上的析氧反应性能
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