Proceedings of nanoGe Fall Meeting 2018 (NFM18)
Publication date: 6th July 2018
Hydrogen (H2) is a highly important feedstock in the chemical industry and a promising fuel for mobile applications, not only because of its high energy density, but also its potential to replace fossil fuels avoiding further release of CO2[1]. Among others, solar water splitting is a method of great potential capacity, which has attracted interest since 1972[2]. To realize it in a large scale, environmental friendly, earth abundant and cheap catalysts are in demand to replace costly platinum with the aim to lower overpotential in the hydrogen evolving reaction (HER).
One of these catalysts is the ammonium thiomolybdate (NH4)2Mo3S13, which was first synthesized and structurally characterized by Müller in 1978 [3]. In 2014, Kibsgaard et al. [1] demonstrated its promising properties as HER catalyst. In our study, (NH4)2Mo3S13 is used as co-catalyst deposited on highly (001)-textured p-typed WSe2 photocathodes, which were grown by an amorphous solid-liquid crystallization process (see Bozheyev et al. [4]). Furthermore, (NH4)2Mo3S13 is a semiconductor which is able to form a hetero-junction with WSe2 and to passivate surface states as evident from a suppression of surface recombination in our intensity-modulated photocurrent spectroscopy (IMPS) measurements. As a result, a significant improvement of the photocurrent in 0.5M sulfuric acid electrolyte (pH 0) up to 5.6mA/cm2 could be achieved from after the deposition of a thin (NH4)2Mo3S13 layer on WSe2. In this contribution, the semiconducting and electrochemical properties of (NH4)2Mo3S13 will be discussed [5].
1. Kibsgaard, J., T.F. Jaramillo, et al, Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate Mo3S13 (2-) clusters. Nature Chemistry, 2014. 6(3): p. 248-253.
2. Fujishima Akira, H.K., Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature, 1972. 238(5358): p. 37-38.
3. Prof. Dr. Achim Müller, et al., Directed Synthesis of [Mo3S13] 2−, an Isolated Cluster Containing Sulfur Atoms in Three Different States of Bonding. Angewandte Chemie, 1978. 17(7): p. 535.
4. Bozheyev, F., et al., Preparation of highly (001)-oriented photoactive tungsten diselenide (WSe2) films by an amorphous solid-liquid-crystalline solid (aSLcS) rapid-crystallization process. physica status solidi (a), 2014. 211(9): p. 2013-2019.
5. Xi F., Fiechter S, et al. On the photoelectrochemical properties of ammonium thiomolybdate layers. in preparation.
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