Synthesis and characterization of a family of layered trichalcogenides for assisted hydrogen photogeneration

Three layered trisulfides (TiS₃, ZrS₃, HfS₃) have been synthesized by solid–gas reaction between metal and sulfur in a vacuum sealed ampoule at 550 °C during 60 h. The samples used in this work were prepared from a colloidal suspension of powder of each one of the metal trisulfides (MS₃, M = Ti, Zr, Hf) in ethanol and deposited on titanium disks and quartz substrates by ”drop coating” technique. These samples have been characterized by X‐ray diffraction, energy dispersive analysis of X‐ray and scanning electron microscopy. The obtained direct optical band gaps are 1.0 ± 0.1 eV, 2.0 ± 0.1 eV and 2.2 ± 0.1 eV for TiS₃, ZrS₃ and HfS₃, respectively. Photoelectrochemical measurements in 0.5 M Na₂SO₃ have been carried out to characterize the MS₃/electrolyte interface. The flat‐band potentials (V_fb) vs. Ag/AgCl measured by electrochemical impedance spectroscopy (EIS) are –0.84 ± 0.02 V (TiS₃), –0.93 ± 0.02 V (ZrS₃) and –0.92 ± 0.02 V (HfS₃). Hydrogen generation was investigated in a photoelectrochemical cell (PEC) with MS₃ as photoanodes under white light illumination of 200 ± 20 mW/cm² at external bias potentials of 0.3 V vs. Ag/AgCl. Hydrogen evolution flows have been quantified by quadrupole mass spectrometry (QMS) reaching instantaneous values up to 19 ± 2 nmol H₂/min cm² with TiS₃ as photoanode.