Cobalt induced electronic and defect structure modulation in nickel iron layered double hydroxides for electrochemical, photo-electrochemical and photocatalytic water splitting.
- 1African Sustainable Agriculture Research Institute (ASARI), College of Agriculture and Environmental Sciences (CAES), Mohammed VI Polytechnic University (UM6P) Laayoune Morocco [email protected] [email protected].
- 2National Centre for Nanoscience and Nanotechnology, University of Madras Chennai India.
- 3Catalysis Laboratory, Centre of Advanced Study in Crystallography & Biophysics, University of Madras Chennai India.
Abstract
Multifunctional materials capable of meeting the growing demand for clean energy are being actively pursued as sustainable alternatives to fossil-fuel-based resources. Subtle modifications to the crystal structure can significantly alter the electronic configurations of such materials, enabling enhanced performance across multiple catalytic processes. In this context, we report the optimal incorporation of Co into the NiFe LDH nanostructure to achieve versatile catalytic functionality. Structural analysis reveals the formation of hierarchical architectures while offering redox-active hydroxyl-rich interfaces beneficial for electrocatalytic and photocatalytic reactions. Furthermore, the substitution of Co ions in the LDH layers promotes Co 3d-O 2p hybridized intermediate states, leading to electronic band structure modulation characterized by the optical band gap narrowing from 2.36 eV to 1.88 eV and formation of a plausible p-n heterojunction as evidenced from UV-vis diffuse reflectance spectroscopy and Mott-Schottky (MS) analysis, respectively. Owing to these synergistic structural and electronic effects, the optimized NiCoFe (1 : 2 : 1) configuration exhibits enhanced photoelectrocatalytic hydrogen evolution (HER) and oxygen evolution (OER) activities, delivering low overpotentials of 155 mV for the HER and 350 mV for the OER, with Tafel slope values of 270 and 26.4 mV dec⁻¹, respectively. Overall, for electrocatalytic water splitting, the same catalyst achieves an overpotential of 234 mV for the HER and 50 mV for the OER, accompanied by favourable Tafel slopes of 114 and 285.6 mV dec⁻¹, respectively. Photocatalytic hydrogen evolution measurements using NiCoFe (1 : 2 : 1) LDH further revealed an average H₂ evolution rate of 925 µmol h⁻¹ g⁻¹ in comparison with bare (NiFe LDH), which only had a rate of about 752 µmol h⁻¹ g⁻¹. These results demonstrate that cobalt-induced electronic and structural modulation in NiFe LDHs provides a promising platform for efficient multimodal water-splitting applications.
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BibTeX
@article{kamalakkannan2026cobalt,
title = {{Cobalt induced electronic and defect structure modulation in nickel iron layered double hydroxides for electrochemical, photo-electrochemical and photocatalytic water splitting.}},
author = {Annamalai Kamalakkannan and Salma Machiche and Balakumar Subramanian and Sasirekha N R and Mohamed Essalhi and Otman Abida},
journal = {RSC advances},
year = {2026},
month = oct,
doi = {10.1039/d6ra08160f},
url = {https://europepmc.org/article/MED/42948613},
note = {CC BY},
}
RIS
TY - JOUR
TI - Cobalt induced electronic and defect structure modulation in nickel iron layered double hydroxides for electrochemical, photo-electrochemical and photocatalytic water splitting.
AU - Annamalai Kamalakkannan
AU - Salma Machiche
AU - Balakumar Subramanian
AU - Sasirekha N R
AU - Mohamed Essalhi
AU - Otman Abida
PY - 2026
DA - 2026/10/27
JO - RSC advances
DO - 10.1039/d6ra08160f
UR - https://europepmc.org/article/MED/42948613
AB - Multifunctional materials capable of meeting the growing demand for clean energy are being actively pursued as sustainable alternatives to fossil-fuel-based resources. Subtle modifications to the crystal structure can significantly alter the electronic configurations of such materials, enabling enhanced performance across multiple catalytic processes. In this context, we report the optimal incorporation of Co into the NiFe LDH nanostructure to achieve versatile catalytic functionality. Structural analysis reveals the formation of hierarchical architectures while offering redox-active hydroxyl-rich interfaces beneficial for electrocatalytic and photocatalytic reactions. Furthermore, the substitution of Co ions in the LDH layers promotes Co 3d-O 2p hybridized intermediate states, leading to electronic band structure modulation characterized by the optical band gap narrowing from 2.36 eV to 1.88 eV and formation of a plausible p-n heterojunction as evidenced from UV-vis diffuse reflectance spectroscopy and Mott-Schottky (MS) analysis, respectively. Owing to these synergistic structural and electronic effects, the optimized NiCoFe (1 : 2 : 1) configuration exhibits enhanced photoelectrocatalytic hydrogen evolution (HER) and oxygen evolution (OER) activities, delivering low overpotentials of 155 mV for the HER and 350 mV for the OER, with Tafel slope values of 270 and 26.4 mV dec⁻¹, respectively. Overall, for electrocatalytic water splitting, the same catalyst achieves an overpotential of 234 mV for the HER and 50 mV for the OER, accompanied by favourable Tafel slopes of 114 and 285.6 mV dec⁻¹, respectively. Photocatalytic hydrogen evolution measurements using NiCoFe (1 : 2 : 1) LDH further revealed an average H₂ evolution rate of 925 µmol h⁻¹ g⁻¹ in comparison with bare (NiFe LDH), which only had a rate of about 752 µmol h⁻¹ g⁻¹. These results demonstrate that cobalt-induced electronic and structural modulation in NiFe LDHs provides a promising platform for efficient multimodal water-splitting applications.
SN - 2046-2069
ER -