Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen‐Evolution Reaction

Abstract A nickel(II) porphyrin Ni‐P (P=porphyrin) bearing four meso‐C6F5 groups to improve solubility and activity was used to explore different hydrogen‐evolution‐reaction (HER) mechanisms. Doubly reduced Ni‐P ([Ni‐P]2−) was involved in H2 production from acetic acid, whereas a singly reduced species ([Ni‐P]−) initiated HER with stronger trifluoroacetic acid (TFA). High activity and stability of Ni‐P were observed in catalysis, with a remarkable i c/i p value of 77 with TFA at a scan rate of 100 mV s−1 and 20 °C. Electrochemical, stopped‐flow, and theoretical studies indicated that a hydride species [H‐Ni‐P] is formed by oxidative protonation of [Ni‐P]−. Subsequent rapid bimetallic homolysis to give H2 and Ni‐P is probably involved in the catalytic cycle. HER cycling through this one‐electron‐reduction and homolysis mechanism has been proposed previously but rarely validated. The present results could thus have broad implications for the design of new exquisite cycles for H2 generation.

• Publication year

  2016

• Venue

  Angewandte Chemie

• Publication date

  2016-03-30

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1002/anie.201510001PMID 27028563PMCID 5071703
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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