A Caltech Library Service

Intra-​molecular proton transfer and hydrogen evolution mechanism in cobalt catalysts

Huo, Pengfei and Uyeda, Christopher and Goodpaster, Jason D. and Peters, Jonas C. and Miller, Thomas F. (2014) Intra-​molecular proton transfer and hydrogen evolution mechanism in cobalt catalysts. In: 248th American Chemical Society National Meeting & Exposition, 10-14 August 2014, San Francisco, CA.

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item:


Hydrogen generation through catalytic water splitting is a promising strategy for solar energy storage and clean renewable energy generation. In most hydrogen evolution catalysts, external energetic costs to initiate the reaction are anti-correlated with the overall turnover frequency for the catalyst. This has been a limitation for designing more efficient catalysts that evolve hydrogen with both a high reactive rate and a low energetic cost. Here, we report the synthesis and characterization of cobalt-based (pyridine-diimine-dioime) catalysts for hydrogen evolution. A combination of theor. and exptl. anal. suggests that the complex can facilitate an intra-mol. proton transfer reaction from protonated pyridine to cobalt. This process produces CoIII hydride as the key intermediate for hydrogen evolution. Our calcns. indicate a significantly lower energetic barrier for hydrogen generation process with a CoII hydride intermediate compared to the corresponding CoIII hydride intermediate, suggesting that the CoII hydride is the key reactive species for hydrogen generation. Using these insights, we propose a strategy to decouple the anti-correlation between external energetic costs and the catalytic turnover frequency, which provides a promising design principle for more efficient hydrogen evolution catalysts.

Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription Website
Huo, Pengfei0000-0002-8639-9299
Uyeda, Christopher0000-0001-9396-915X
Goodpaster, Jason D.0000-0001-6461-4501
Peters, Jonas C.0000-0002-6610-4414
Miller, Thomas F.0000-0002-1882-5380
Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20140811-133647033
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:48325
Deposited By: Tony Diaz
Deposited On:11 Aug 2014 20:46
Last Modified:20 Feb 2020 22:23

Repository Staff Only: item control page