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Enhanced Electrocatalytic Activity in GaSe and InSe Nanosheets: The Role of Surface Oxides
Author(s) -
D'Olimpio Gianluca,
Nappini Silvia,
Vorokhta Mykhailo,
Lozzi Luca,
Genuzio Francesca,
Menteş Tevfik Onur,
Paolucci Valentina,
Gürbulak Bekir,
Duman Songül,
Ottaviano Luca,
Locatelli Andrea,
Bondino Federica,
Boukhvalov Danil W.,
Politano Antonio
Publication year - 2020
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.202005466
Subject(s) - materials science , exfoliation joint , selenide , semiconductor , catalysis , density functional theory , band gap , indium , van der waals force , chemical physics , water splitting , photocatalysis , electrochemistry , nanotechnology , gallium , stoichiometry , chemical engineering , chemistry , computational chemistry , optoelectronics , graphene , molecule , electrode , organic chemistry , selenium , engineering , metallurgy
Gallium selenide (GaSe) is a van der Waals semiconductor widely used for optoelectronic devices, whose performances are dictated by bulk properties, including band‐gap energy. However, recent experimental observations that the exfoliation of GaSe into atomically thin layers enhances performances in electrochemistry and photocatalysis have opened new avenues for its applications in the fields of energy and catalysis. Here, it is demonstrated by surface‐science experiments and density functional theory (DFT) that the oxidation of GaSe into Ga 2 O 3 , driven by Se vacancies and edge sites created in the exfoliation process, plays a pivotal role in catalytic processes. Specifically, both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are energetically unfavorable in pristine GaSe, due to energy barriers of 1.9 and 5.7–7.4 eV, respectively. On the contrary, energy barriers are reduced concurrently with surface oxidation. Especially, the Heyrovsky step ( H ads + H + + e − → H 2 ) of HER becomes energetically favorable only in sub‐stoichiometric Ga 2 O 2.97 (−0.3 eV/H + ). It is also discovered that the same mechanisms occur for the case of the parental compound indium selenide (InSe), thus ensuring the validity of the model for the broad class of III‐VI layered semiconductors.