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Influence of the proton relay spacer on hydrogen electrocatalysis by cobalt hangman porphyrins

Journal Article · · Journal of Porphyrins and Phthalocyanines
 [1];  [2];  [3];  [3]
  1. Harvard University, Cambridge, MA (United States); Harvard University Department of Chemistry and Chemical Biology
  2. Harvard University, Cambridge, MA (United States); University of California, Berkeley, CA (United States)
  3. Harvard University, Cambridge, MA (United States)
+ Show Author Affiliations
A cobalt hangman porphyrin system with a phenyl spacer between the porphyrin ring and an internal carboxylic acid group as well as its non-hangman analogue were synthesized and utilized for the study of the proton-coupled electron transfer (PCET) kinetics attendant to electrocatalytic hydrogen evolution. Cyclic voltammetry (CV) together with simulations show that a short distance between the proton relay and the redox active cobalt center as well as the increased proton donating strength results in superior catalytic activity. Here, the mechanism of hydrogen generation is at the nexus of proton transfer–electron transfer (PTET) and concerted proton–electron transfer (CPET), as opposed to an ETPT mechanism that is characteristic of hangman systems with longer proton relay networks.
Research Organization:
Harvard University, Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)
Grant/Contract Number:
SC0017619
OSTI ID:
1992659
Alternate ID(s):
OSTI ID: 1852378
Journal Information:
Journal of Porphyrins and Phthalocyanines, Journal Name: Journal of Porphyrins and Phthalocyanines Journal Issue: 07n08 Vol. 25; ISSN 1088-4246
Publisher:
World ScientificCopyright Statement
Country of Publication:
United States
Language:
English

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Influence of the proton relay spacer on hydrogen electrocatalysis by cobalt hangman porphyrins
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalysis
hangman porphyrin
hydrogen evolution reaction
proton-coupled electron transfer
solar fuels
trumpet plot