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疏氯型亚磷酸铁氢作为阴离子交换膜(海)水电解中的析氧反应活性电催化剂。

Chlorophobic Iron Hydrogen Phosphite as OER-Active Electrocatalyst in Anion Exchange Membrane (Sea)Water Electrolysis.

作者信息

Das Chandni, Sinha Nibedita, Nair Aathira, Pal Santanu, Joshi Kavita, Roy Poulomi

机构信息

Physical & Materials Chemistry Division, CSIR-National Chemical Laboratory (NCL), Dr. Homi Bhabha Road, Pune, Maharashtra, 411008, India.

CSIR-Central Mechanical Engineering Research Institute (CMERI), Mahatma Gandhi Avenue, Durgapur, West Bengal, 713209, India.

出版信息

Small. 2025 Aug;21(34):e2505781. doi: 10.1002/smll.202505781. Epub 2025 Jul 1.

DOI:10.1002/smll.202505781
PMID:40589403
Abstract

Seawater electrolysis is recognized as a promising technology to cater to the worldwide drive for sustainable hydrogen production; however, its practical viability is often hindered by the inevitable anode corrosion arising from the electrode side reactions owing to the presence of high chloride content which eventually degrade the electrode performance eventually. Herein, the design of unprecedented ammonium iron hydrogen phosphite (FeHPhi) along with a trace amount of Cu, is reported as the unique and much desired electrode material for seawater electrolysis due to its special chloride repellant nature along with great electrocatalytic activity toward water oxidation. The [HPO] oxoanion as Lewis base in the structure effectively restricts chloride ions, while the Fe center acts as Lewis acid offering an active site for water oxidation, also well-supported theoretically. Leveraging this frustrated Lewis pair combination, the electrocatalyst achieves a high current density of 500 mA cm at 344 mV overpotential in alkaline real seawater with impressive robustness to sustain for 200 h when operated under chlorine evolution reaction dominating region (>2 V). The electrocatalyst also demonstrates superior performance in anion exchange membrane freshwater and seawater electrolysis, demonstrating its potential applicability.

摘要

海水电解被认为是一种很有前景的技术,可满足全球对可持续制氢的需求;然而,由于高氯含量导致电极侧反应不可避免地产生阳极腐蚀,最终降低电极性能,其实际可行性常常受到阻碍。在此,本文报道了前所未有的亚磷酸氢铵铁(FeHPhi)与痕量铜的设计,由于其特殊的抗氯性质以及对水氧化具有出色的电催化活性,它是海水电解中独特且备受期待的电极材料。结构中的[HPO]含氧阴离子作为路易斯碱有效地限制了氯离子,而铁中心作为路易斯酸为水氧化提供了活性位点,这在理论上也得到了很好的支持。利用这种受阻路易斯酸碱对组合,该电催化剂在碱性实际海水中,在344 mV过电位下实现了500 mA cm的高电流密度,并且在析氯反应主导区域(>2 V)运行时具有令人印象深刻的稳健性,可持续200小时。该电催化剂在阴离子交换膜淡水和海水电解中也表现出优异的性能,证明了其潜在的适用性。

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