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Open AccessDOI: 10.1007/s40843-026-4239-2Original Research

Amino Acid Intercalated Iron-Rich NiFe-LDHs with Low-Spin Fe3+ for Oxygen Evolution Reaction Electrocatalysis

Donghua University, College of Materials Science and Engineering

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Amino Acid Intercalated Iron-Rich NiFe-LDHs with Low-Spin Fe3+ for Oxygen Evolution Reaction Electrocatalysis
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SCIENCE CHINA Materials
Published:January 15, 2026Edition:Vol. 32, Issue 1 • pp. 100-112Citation:CHEN Tingting et al. (2026), SCIENCE CHINA Materials
Impact Factor3.5 (Q2 Scopus)
Source Journal中国科学: 材料
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Water Electrolysis for Green Hydrogen: Low-Iridium PEM & High-Pressure Alkaline Systems
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Key Takeaways & Executive Findings

  • • • Glycine-intercalated NiFe-LDH achieves an overpotential of 240 mV at 10 mA cm−2 in 1.0 M KOH, a 40 mV improvement over pristine NiFe-LDH (280 mV), directly lowering the energy input required for hydrogen production. • • The Tafel slope is reduced to 38 mV dec−1 from 52 mV dec−1, indicating faster reaction kinetics and more favorable charge transfer, which is critical for high-current-density industrial electrolyzers. • • The electrochemically active surface area increases by 2.3-fold, and charge transfer resistance drops from 12.5 Ω to 4.8 Ω, enhancing catalytic site accessibility and electron transport, thereby improving overall electrode efficiency. • • Long-term stability is demonstrated with 95% activity retention after 24 h of continuous operation at 10 mA cm−2, addressing durability concerns for practical water splitting applications.

Abstract

The sluggish kinetics of the oxygen evolution reaction (OER) remains a bottleneck for efficient water splitting. NiFe-layered double hydroxides (LDHs) are promising OER catalysts, but their performance is often limited by the high-spin state of Fe3+ and poor structural stability. Here, we report a series of amino acid-intercalated iron-rich NiFe-LDHs (AA-NiFe-LDHs) synthesized via a facile one-step coprecipitation method. Intercalation of glycine, alanine, and valine into the interlayer galleries expands the interlayer spacing and induces a partial transition of Fe3+ from high-spin to low-spin state, as confirmed by X-ray absorption spectroscopy and Mössbauer spectroscopy. The low-spin Fe3+ enhances the intrinsic catalytic activity by optimizing the adsorption energy of oxygen intermediates. Among the series, the glycine-intercalated sample (Gly-NiFe-LDH) exhibits the best OER performance in 1.0 M KOH, with an overpotential of 240 mV at 10 mA cm−2 and a Tafel slope of 38 mV dec−1, significantly outperforming the pristine NiFe-LDH (280 mV, 52 mV dec−1). Moreover, Gly-NiFe-LDH shows excellent long-term stability, retaining 95% of its initial activity after 24 h of chronopotentiometry at 10 mA cm−2. The intercalation also increases the electrochemically active surface area by 2.3-fold and reduces the charge transfer resistance from 12.5 Ω to 4.8 Ω. This work demonstrates that amino acid intercalation is an effective strategy to modulate the spin state of Fe3+ and enhance the OER performance of NiFe-LDHs, providing a new avenue for designing high-efficiency, low-cost electrocatalysts.

1. Introduction

Electrochemical water splitting is a cornerstone of green hydrogen production, yet its efficiency is severely hampered by the oxygen evolution reaction (OER) at the anode. The OER involves a four-electron transfer process with sluggish kinetics, requiring high overpotentials to drive the reaction at meaningful rates. Precious metal oxides such as IrO2 and RuO2 are the benchmark catalysts, but their high cost and scarcity limit large-scale deployment. Transition metal-based catalysts, particularly NiFe-layered double hydroxides (LDHs), have emerged as promising alternatives due to their low cost, high activity, and tunable composition. However, the intrinsic activity of NiFe-LDHs is often constrained by the electronic structure of Fe3+, which typically resides in a high-spin state, leading to suboptimal adsorption energies for reaction intermediates.

To overcome this bottleneck, researchers have explored various strategies including defect engineering, heteroatom doping, and interlayer anion modification. Among these, intercalation of organic molecules into the LDH interlayer galleries offers a unique opportunity to modulate the local coordination environment and electronic configuration of metal centers. In this work, we introduce amino acids as intercalants to induce a spin-state transition of Fe3+ from high-spin to low-spin, thereby enhancing the intrinsic OER activity. This approach not only improves catalytic performance but also provides a simple, scalable synthesis route, addressing the critical need for cost-effective and durable OER catalysts for industrial water electrolysis.

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Cite This Research Paper
CHEN Tingting, ZHANG Jiaqi, YIN Taishan, TAN Zhicheng, CHEN Long, PANG Huan, HUANG Zhongjie (2026). Amino Acid Intercalated Iron-Rich NiFe-LDHs with Low-Spin Fe3+ for Oxygen Evolution Reaction Electrocatalysis. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-026-4239-2
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Frequently Asked Questions

What is the specific mechanism by which amino acid intercalation induces the low-spin state of Fe3+ and how does this affect the OER activity?

Amino acid intercalation expands the interlayer spacing and alters the ligand field around Fe3+ ions, promoting a transition from high-spin to low-spin configuration. This is confirmed by XAS and Mössbauer spectroscopy. The low-spin Fe3+ optimizes the d-band center, leading to more favorable adsorption energies for OER intermediates, thereby reducing the overpotential by 40 mV compared to pristine NiFe-LDH.

How does the intercalation affect the electrochemical surface area and charge transfer resistance, and what are the implications for high-rate operation?

Intercalation increases the electrochemically active surface area by 2.3-fold, providing more accessible active sites. Additionally, the charge transfer resistance decreases from 12.5 Ω to 4.8 Ω, facilitating faster electron transfer. These improvements are critical for maintaining low overpotentials at high current densities, which is essential for industrial electrolyzers operating at 200-500 mA cm−2.

What is the long-term stability of the glycine-intercalated NiFe-LDH under continuous operation, and what degradation mechanisms are observed?

The catalyst retains 95% of its initial activity after 24 h of chronopotentiometry at 10 mA cm−2, indicating excellent stability. Post-analysis suggests minimal structural changes, with no significant Fe leaching or phase transformation, likely due to the stabilizing effect of the intercalated amino acids.

How does the performance of the amino acid-intercalated NiFe-LDH compare to state-of-the-art OER catalysts, and what is the cost advantage?

The overpotential of 240 mV at 10 mA cm−2 is competitive with many noble metal-based catalysts (e.g., IrO2 ~300 mV) and other non-noble metal catalysts. The synthesis uses inexpensive iron and nickel salts and amino acids, making it significantly cheaper than IrO2 or RuO2, with potential for scalable production.

What is the role of the specific amino acid (glycine vs. alanine vs. valine) in determining the catalytic performance, and is there an optimal chain length or functional group?

Glycine, the smallest amino acid, provides the highest interlayer expansion and most effective spin-state transition, leading to the best OER performance. Larger amino acids like alanine and valine also improve activity but to a lesser extent, likely due to steric hindrance and less efficient interaction with the metal centers. This suggests that smaller intercalants with simple structures are more effective.

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