Controllable electrochemical construction of highly dual porous Co-Mn-S@Ni-Co heterojunction for boosting energy-saving hydrogen production assisted by urea oxidation reaction

Maedeh Akbari Kenari; Alireza Sabour Rouh Aghdam; Danial Iravani; Abdolvahab Seif; Ehsan Allahyari; Ghasem Barati Darband

doi:10.1016/j.jcis.2025.139649

Controllable electrochemical construction of highly dual porous Co-Mn-S@Ni-Co heterojunction for boosting energy-saving hydrogen production assisted by urea oxidation reaction

J Colloid Interface Sci. 2026 Apr:707:139649. doi: 10.1016/j.jcis.2025.139649. Epub 2025 Dec 7.

Authors

Maedeh Akbari Kenari¹, Alireza Sabour Rouh Aghdam¹, Danial Iravani², Abdolvahab Seif³, Ehsan Allahyari⁴, Ghasem Barati Darband⁵

Affiliations

¹ Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University (TMU), P.O. Box: 14115-143, Tehran, Iran.
² Department of Chemical Engineering, Faculty of Engineering, Ferdowsi University of Mashhad (FUM), P.O. Box: 9177948944, Azadi Square, Pardis Campus, Mashhad, Iran.
³ Department of Chemistry, University of Turin, Via Pietro Giuria 7, 10125 Torino, Italy. Electronic address: abdolvahabseif@gmail.com.
⁴ Department of Materials Science and Engineering, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad, Iran.
⁵ Department of Materials Science and Engineering, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad, Iran. Electronic address: baratidarband@um.ac.ir.

PMID: 41397356
DOI: 10.1016/j.jcis.2025.139649

Abstract

The slow process of oxygen evolution reaction (OER) and the high cost of noble metal oxide catalysts have hindered the widespread application of environmentally friendly electrochemical water splitting for hydrogen production. Therefore, the emergence of effective transition metal-based electrocatalysts for the hydrogen evolution reaction (HER) and urea oxidation reaction (UOR, as an alternative to OER) is crucial for large-scale sustainable electrochemical hydrogen production. In this study, an active, effective, and stable CoMnS@NiCo/NF electrode was synthesized using a binder-free and efficient two-step electrodeposition method as a multifunctional electrode for HER and UOR. Taking advantage of the large active surface area, interconnected pores and porosity, the synergistic effect between elements, accelerated charge, and mass transfer, the synthesized CoMnS@NiCo/NF electrode showed unique electrochemical activity over 5 cycles. This electrode exhibited excellent HER activity with 138 mV overpotential at 100 mA.cm^-2. In addition, for the UOR process, the required voltage in 100 mA.cm^-2 was 1.37 V vs. RHE. Also, the bi-functional activity of this electrode in the HER/UOR process was also outstanding, with 1.55 V cell voltage at 100 mA.cm^-2. To evaluate its industrial performance, the electrocatalytic stability tests showed satisfactory results. Spin-polarized density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations demonstrate that sulfur incorporation leads to local amorphization and electronic redistribution, effectively tuning the d-band position of Co/Mn active sites. This enhanced activation-desorption balance markedly increases HER and UOR catalytic performance. This study provides new strategies and insights for the synthesis of active and stable electrocatalysts in energy conversion systems.

Keywords: Ab initio molecular dynamics; Density functional theory; Electrocatalyst; Electrodeposition; Hydrogen evolution reaction; Urea oxidation reaction.