Szczegóły publikacji
Opis bibliograficzny
Processing-induced differences in hydrogen evolution activity of $Fe_{3−x}Ni_{x}Se_{4}$ selenides: theoretically assisted analysis / Miłosz KOŻUSZNIK, Mathias Smialkowski, Tomasz KUREK, Krzysztof MARS, Jakub CIEŚLAK, Ulf-Peter Apfel, Andrzej MIKUŁA // Catalysis Science & Technology ; ISSN 2044-4753 . — 2026 — vol. 16 iss. 18, s. 6233–6247. — Bibliogr. s. 6245–6247, Abstr. — Publikacja dostępna online od: 2026-08-17
Autorzy (7)
- AGHKożusznik Miłosz
- Smialkowski Mathias
- AGHKurek Tomasz
- AGHMars Krzysztof
- AGHCieślak Jakub
- Apfel Ulf-Peter
- AGHMikuła Andrzej
Dane bibliometryczne
| ID BaDAP | 170184 |
|---|---|
| Data dodania do BaDAP | 2026-09-28 |
| Tekst źródłowy | URL |
| DOI | 10.1039/d6cy00721j |
| Rok publikacji | 2026 |
| Typ publikacji | artykuł w czasopiśmie |
| Otwarty dostęp |  |
| Czasopismo/seria | Catalysis Science & Technology |
Abstract
Monoclinic bimetallic selenides (Fe,Ni)3Se4 represent promising cobalt-free electrocatalysts for the hydrogen evolution reaction (HER), yet their electrocatalytic performance is governed by a complex interplay between synthesis pathways and electrode architectures. Herein, we systematically compare two synthesis approaches – a top-down route (solid-state reaction followed by high-energy milling) and a bottom-up mechanochemical route (mechanical alloying), across two electrode architectures: freestanding bulk sintered pellets and drop-cast catalyst inks. Mechanochemically alloyed samples demonstrate superior initial HER activity, achieving overpotentials as low as 222 ± 10 mV at −10 mA cm−2 This enhanced performance is associated, at least in part, with the mechanochemical formation of a coexisting, highly active cubic perselenide phase (Fe,Ni)Se2 alongside the target monoclinic matrix. Conversely, bulk pellet electrodes exhibit electrochemical activation, characterized by a progressive decrease in overpotential during extended electrolysis, reaching an overpotential of 325 ± 25 mV. Combined XPS and ICP-OES analyses confirm that this activation is driven by preferential Fe dissolution, which induces dynamic surface restructuring. Density functional theory (DFT) calculations elucidate these experimental observations by mapping hydrogen adsorption free energies (ΔGH*). While Fe-rich environments, particularly μ2(Fe–Ni) bridge sites, bind hydrogen too strongly (ΔGH* ≪ 0), μ2(Ni–Se) motifs provide optimal, near-thermoneutral binding kinetics. Consequently, electrochemically induced Fe leaching in bulk architectures triggers a beneficial surface transformation, shifting the interface from strongly binding Fe-rich states toward catalytically optimal and stable Ni–Se active sites. These results demonstrate that the catalytic output of Fe–Ni selenides is dictated by a dynamic trade-off where Fe enhances the initial HER activity, while Ni–Se motifs govern the sustained catalytic performance, underscoring the critical role of synthesis choice and electrode architecture in designing non-precious electrocatalysts.
