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Dynamic Alkaline Microenvironment Engineering enables 14,000h stable operation of anion exchange membrane electrolyzer

Prof. Licheng Sun’s group has published their work in the Angewandte Chemie International Edition, highlighting the crucial role of a zwitterion-modified NiFe catalyst that has demonstrated stable performance for over 14000 h at ampere-scale current density in anion exchange membrane water electrolysis device.

Prof. Licheng Sun’s group in the Department of Chemistry at Westlake University recently published a research paper in the Angewandte Chemie International Edition. The paper is titled “Zwitterion-Modified NiFe OER Catalyst Achieving Ultra-Stable Anion Exchange Membrane Water Electrolysis via Dynamic Alkaline Microenvironment Engineering.

Anion exchange membrane water electrolysis (AEM-WE) has emerged as a promising strategy for hydrogen generation, combining the advantages of alkaline water electrolysis (AWE) with low costs and proton exchange membrane water electrolysis (PEM-WE) with high efficiency. However, the oxygen evolution reaction (OER) on the anode in AEM-WE suffers from sluggish kinetics and poor chemical stability hindering its industrial application. In particular, under industrial current densities, rapid accumulation of a large amount of H+ at the anode catalyst surface, coupled with insufficient hydroxide ion (OH) transport kinetics at the membrane-catalyst interface, leads to a localized decrease in pH, triggering chemical corrosion of the catalyst and significantly deteriorating device performance and long-term stability.

Recently, Prof. Licheng Sun's group at Westlake University developed a zwitterion-modified NiFe-LDH catalyst (z-NiFe) synthesized through simple gradient soaking for highly effective and ultrastable alkaline water oxidation. z-NiFe exhibits a high OER activity (overpotential of 190 mV at 1000 mA cm−2) and stability (over 12600 h at 1000 mA cm−2) in 1 M KOH. Moreover, z-NiFe demonstrates an AEM-WE device activity of 7860 mA cm−2 at a cell voltage of 2.00 V and maintains long-term stability for over 14000 h at 1000 mA cm−2.

In-situ Raman, zeta potential and OH conductivity data indicate that the presence of zwitterion creates a local alkaline enriched environment around active sites by accelerating OH transfer from AEM to the catalyst, which can rapidly neutralize the H+ produced during the OER. DFT studies indicate that the O− from the carboxylate group of the z-TCQ ion replaces the lattice oxygen (O2−) between Ni and Fe sites, establishing a local hydrogen bond network that helps stabilize the adsorbed O*.

Our work demonstrates that the zwitterions modulation strategy enables accelerated directional migration of OH from the membrane and electrolyte to active sites, thereby establishing an alkaline sustained microenvironment at the catalytic interface. The dynamically maintained alkaline microenvironment at the reaction interface spontaneously neutralizes generated H+, effectively suppressing chemical corrosion while enhancing catalytic performance through pH regulation. This strategy offers an in-depth study of the interfacial properties between AEM and catalysts, providing novel insights into the design of anode catalysts and their interactions with membranes.

Dr. Li Wen-Long, Postdoctoral Researcher at Westlake University, Dr. Ding Yun-Xuan, Assistant Researcher at Westlake University, and Dr. Zhao Yi-Long, Postdoctoral Researcher at Westlake University, are co-first authors of the study. The corresponding author is Prof. Licheng Sun, chair professor of chemistry and director of the Center of Artificial Photosynthesis for Solar Fuels at Westlake University.