Bioinspired acetate-mediated proton shuttling toward robust oxygen evolution

doi:10.1016/S1872-2067(26)65072-3

Abstract

Abstract:

Persistent proton accumulation from extensive reactant deprotonation during oxygen evolution reaction (OER) induces severe local acidification at electrode-electrolyte interface, accelerating catalyst degradation and performance decay. Employing NiFe layered double hydroxide (NiFe-LDH) as a model, we present a bioinspired strategy wherein Lewis-basic acetate anion (CH₃COO^-, Ac^-) functions as dynamic proton shuttle to regulate interfacial microenvironment (Ac^--LDH). Ac^- undergoes reversible -COO^-/-COOH cycle upon protonation, promoting efficient proton transfer and reinforcing hydrogen-bond networks that expedite OH^- delivery to LDH surface. Simultaneously, Ac^- lone pairs selectively coordinate with Fe centers in LDH framework, tuning electronic structure and enhancing intrinsic activity. In-situ Raman and infrared spectroscopy capture transient CH₃COOH formation, while differential electrochemical mass spectrometry evidences proton shuttling via CH₃COOD detection. Theoretical calculations reveal that Ac^- coordination stabilizes active site and reduces OER energy barrier. Leveraging this dual functionality, Ac^--LDH exhibits superior activity with 213 mV overpotential at 10 mA cm^-2 and remarkable durability, maintaining 50 mA cm^-2 for over 1200 h in anion-exchange membrane electrolyzer. This work establishes bioinspired molecular shuttles for interfacial microenvironment engineering as versatile paradigm for developing OER catalysts with high activity and durability.

Key words: Layered double hydroxide, Biomimetic, Proton shuttling, Proton migration, Oxygen evolution reaction

Jianping Zhang, Kun Zhang, Yinglong Weng, Nannan Li, Tingting Huang, Yitong Lu, Tingyu Sun, Xiaotong Han, Jieshan Qiu. Bioinspired acetate-mediated proton shuttling toward robust oxygen evolution[J]. Chinese Journal of Catalysis, 2026, 87: 282-294.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65072-3

https://www.cjcatal.com/EN/Y2026/V87/I8/282

Figures/Tables 8

Fig. 1. (a) Schematic of proton accumulation-induced NiFe-LDH dissolution. (b) Schematic of carrier proteins transporting ions and small molecules to maintain intracellular homeostasis (illustration created using Figdraw). (c) Schematic of Ac- and SO42- modulated NiFe-LDH.

Fig. 2. Structural characterization of Ac--LDH. XRD patterns (a) and FT-IR spectra (b) of Ac--LDH and SO42--LDH. (c) Contact-angle measurements for Ac--LDH and SO42--LDH. TEM (d) and HR-TEM (e) images of Ac--LDH (inset: SAED pattern). (f) HR-TEM image and corresponding 3D intensity map of Ac--LDH. (g) Elemental mapping of Ac--LDH.

Fig. 3. Local structure analysis of Ac--LDH and SO42--LDH. XPS spectra of Fe 2p (a) and Ni 2p (b) for Ac--LDH and SO42--LDH. (c) Content of specific species in Ac--LDH and SO42--LDH. (d) EPR spectra of Ac--LDH and SO42--LDH. Normalized XANES spectra at Fe (e) and Ni (f) K-edges. Fourier-transformed EXAFS spectra at Fe (g) and Ni (h) K-edges. Wavelet-transformed spectra at Fe (i) and Ni (j) K-edges for Ac--LDH. Wavelet-transformed spectra at Fe (k) and Ni (l) K-edges for SO42--LDH.

Fig. 4. OER activity evaluation of the catalysts. (a) CV curves of Ac--LDH and SO42--LDH. LSV curves (b) and Tafel plots (c) of Ac--LDH, SO42--LDH, and RuO2. Cdl plots (d) and Nyquist plots (e) of Ac--LDH and SO42--LDH. (f) Comparison of comprehensive electrochemical properties. (g) Durability test curves (insets: SEM images of Ac--LDH and SO42--LDH after stability testing). (h) Comparison of OER performance between Ac--LDH and reported catalysts.

Fig. 5. Enhancement mechanism of OER activity. In-situ Bode plots of Ac--LDH (a) and SO42--LDH (b). (c) Histogram of phase-angle changes with applied potential. (d) Schematic of equivalent circuit and correlations of equivalent resistances. (e) Charge-transfer resistance at different potentials. (f) Open-circuit potential measured in 1.0 mol L-1 KOH before and after injection of 6.0 mol L-1 KOH. (g) Zeta potential in 1.0 mol L-1 KOH. (h) Schematic of GCS model and OH- enrichment at electrode-electrolyte interface for Ac--LDH.

Fig. 6. Reaction mechanism investigation of Ac--LDH catalyst. In-situ Raman spectra of Ac--LDH (a) and SO42--LDH (b). Potential-dependent (c) and time-dependent (d) Raman intensity ratio for Ac--LDH and SO42--LDH. (e) In-situ infrared spectra of Ac--LDH. (f) DEMS signals for 32O2 and 61CH3COOD of Ac--LDH. (g) Proposed OER pathways for Ac--LDH and SO42--LDH.

Fig. 7. Theoretical calculations of the OER activity of Ac--LDH electrocatalyst. (a) Electrostatic potential maps of HAc, H2SO4, Ac-, and SO42-. 2D differential electron density maps of Ac--LDH (front (b), top (d), and side (f) views) and SO42--LDH (front(c), top (e), and side (g) views). 3D differential electron density maps of Ac--LDH (h) and SO42--LDH (i). DOS (j) and PDOS (k) curves of Ac--LDH and SO42--LDH. (l) Schematic of p- and d-band center alignment for Ac--LDH and SO42--LDH. (m) Gibbs free energy profiles of Ac--LDH and SO42--LDH.

Fig. 8. Performance tests of Ac--LDH catalyst in AEMWE. (a) LSV curves for overall water electrolysis. (b) Comparison of voltage at 10 and 50 mA cm-2. (c) The measured O2 amount of of Ac--LDH. (d) Durability test curves. (e) Schematic of AEMWE device. (f) Polarization curves of Ac--LDH in AEMWE. (g) Durability test curves in AEMWE.

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