Study of the Hydrogen Evolution Reaction on Macroscopic Snse-Based Photoelectrodes
Authors: Ba Qianqian , Toth Peter , Janaky Csaba 
Published: February 2024

Conversion of solar energy to valuable chemicals by using photoelectrochemical (PEC) techniques such as water splitting, carbon dioxide reduction reaction (CO2RR) and nitrogen reduction reaction (N2RR), are promising methods to solve the issues of energy crisis and global warming [1-2]. Two-dimensional (2D) and layered semiconductors, for example, transition metal chalcogenides (TMCs), metal oxides and MXenes have attracted great attention for PEC applications because of their unique properties, such as high carrier mobility, tunable bandgap, anisotropic carrier transport, and high specific surface area [3]. Our review indicates that, i) 2D and layered semiconductors can be applied for different PEC applications, both in oxidation and reduction reactions, and have ability to give higher performance in water reduction (i.e., hydrogen evolution reaction, HER) than in the other ones. ii) TMCs have been the most studied material with higher performance than the others. However, high PEC performance was achieved only on single crystal TMCs or in microelectrochemical cells, implying a limitation in the scalability of this solar energy conversion approach [4]. There is a clear need to study macroelectrodes prepared from polycrystalline semiconductors and identify the opportunities and barriers for their applications.
In our study [5], tin(II) selenide (SnSe) was used as a photoelectrode for PEC HER since it has not been widely investigated for this PEC application. We fabricated SnSe macroscopic photocathodes by depositing SnSe flakes, made from commercial SnSe crystals using a liquid phase exfoliation (LPE) method, on glassy carbon. The as-received SnSe crystals were exfoliated in isopropanol/water mixtures (IPA/H2O) and pure IPA, respectively. Pure IPA was found to be the optimal solvent to prepare flakes and for achieving the highest PEC activity. An additional size separation to make three different size fractions of SnSe crystals served to further optimize the LPE process. Electrodes prepared from the largest flakes showed the highest photocurrent density of 2.44 ± 0.65 mA cm–2 at –0.74 V vs. RHE. The photodeposited Pt co-catalyst on SnSe surface further accelerated the PEC HER activity to 4.39 ± 0.15 mA cm–2. Intensity modulated photocurrent spectroscopy results manifested that the Pt co-catalyst enhanced the charge transfer process and suppressed charge carrier recombination. Overall, the solvent for exfoliation, the edge density of SnSe nanoflakes, immobilization method, and Pt co-catalyst affected the PEC HER performance of SnSe. These results indicate the merit of employing SnSe electrodes for PEC HER and inspire us to explore other photoelectrocatalytic reactions on the macroscopic exfoliated SnSe electrodes.
References
[1] Song H, Luo S, Huang H, et al. ACS Energy Lett., 2022, 7: 1043-1065.
[2] White JL, Baruch MF, Pander III JE, et al. Chem. Rev., 2015, 115: 12888-12935.
[3] Manzeli S, Ovchinnikov D, Pasquier D, et al. Nat. Rev. Mater., 2017, 2: 1-15.
[4] Tóth PS, Ba Q, Janáky C, J Solid State Electrochem, 2023, Accepted.
[5] Ba Q, Tóth PS, Vass Á, et al. Appl. Catal. A-Gen., 2023, under publication.