Add like
Add dislike
Add to saved papers

Bond Activation and Hydrogen Evolution from Water through Reactions with M 3 S 4 (M = Mo, W) and W 3 S 3 Anionic Clusters.

Transition metal sulfides (TMS) are being investigated with increased frequency because of their ability to efficiently catalyze the hydrogen evolution reaction. We have studied the trimetallic TMS cluster ions, Mo3 S4 - , W3 S4 - , and W3 S3 - , and probed their efficiency for bond activation and hydrogen evolution from water. These clusters have geometries that are related to the edge sites on bulk MoS2 surfaces that are known to play a role in hydrogen evolution. Using density functional theory, the electronic structures of these clusters and their chemical reactivity with water have been investigated. The reaction mechanism involves the initial formation of hydroxyl and thiol groups, hydrogen migration to form an intermediate with a metal hydride bond, and finally, combination of a hydride and a proton to eliminate H2 . Using this mechanism, free energy profiles of the reactions of the three metal clusters with water have been constructed. Unlike previous reactivity studies of other related cluster systems, there is no overall energy barrier in the reactions involving the M3 S4 systems. The energy required for the rate-determining step of the reaction (the initial addition of the cluster by water) is lower than the separated reactants (-0.8 kcal/mol for Mo and -5.1 kcal/mol for W). They confirm the M3 S4 - cluster's ability to efficiently activate the chemical bonds in water to release H2. Though the W3 S3 - cluster is not as efficient at bond activation, it provides insights into the factors that contribute to the success of the M3 S4 anionic systems in hydrogen evolution.

Full text links

We have located links that may give you full text access.
Can't access the paper?
Try logging in through your university/institutional subscription. For a smoother one-click institutional access experience, please use our mobile app.

For the best experience, use the Read mobile app

Mobile app image

Get seemless 1-tap access through your institution/university

For the best experience, use the Read mobile app

All material on this website is protected by copyright, Copyright © 1994-2024 by WebMD LLC.
This website also contains material copyrighted by 3rd parties.

By using this service, you agree to our terms of use and privacy policy.

Your Privacy Choices Toggle icon

You can now claim free CME credits for this literature searchClaim now

Get seemless 1-tap access through your institution/university

For the best experience, use the Read mobile app