Understanding homogeneous hydrogen evolution reactivity and deactivation pathways of molecular molybdenum sulfide catalysts. Issue 5 (7th March 2018)

• Record Type: Journal Article
• Authors: Dave, M.; Rajagopal, A.; Damm-Ruttensperger, M.; Schwarz, B.; Nägele, F.; Daccache, L.; Fantauzzi, D.; Jacob, T.; Streb, C.
• Is Part Of: Sustainable energy & fuels. Volume 2:Issue 5(2018)
• Page Start: 1020
• Page End: 1026
• Publication Date: 2018-03-07
• Subjects: Renewable energy sources -- Periodicals; Fuel cells -- Periodicals; Electric batteries -- Periodicals; Electrochemistry -- Periodicals; 660.297
• DOI: 10.1039/c7se00599g
• Languages: English
• ISSNs: 2398-4902

Abstract

Abstract : The first example of light driven, homogeneous hydrogen evolution reactivity of a molecular molybdenum sulfide is presented together with experimental and theoretical insights into the reasons for the unusually high activity. Abstract : Molybdenum sulfides are highly active hydrogen evolution reaction (HER) catalysts based on earth abundant elements. Here, the molybdenum sulfide anion [Mo3 S13 ] 2− is used as a molecular model to rationalize HER reactivity of Mo–S-catalysts. For the first time, homogeneous, visible light-driven HER activity of [Mo3 S13 ] 2− is reported and high reactivity is observed (turnover number TON ∼23 000, maximum turnover frequency TOFmax ∼156 min −1 ). Experimental and theoretical studies shed light on the catalytic role of terminal disulfide ligands (S2 2− ) and show that these ligands modulate catalyst redox-activity and electron transfer in solution. Partial substitution of the terminal disulfides with water ligands leads to the most active catalytic species, e.g. [Mo3 S11 (H2 O)2 ]. In contrast, complete substitution of the terminal disulfides results in a significant loss of reactivity. These results could lay the foundations for the knowledge-based development of homogeneous and heterogeneous molybdenum sulfide catalysts.