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Title: Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo- Protonation Sites

A new Ni(II) complex, [Ni(7PPh2NH)2]2+ (7PPh2NH = 3,6-triphenyl-1-aza-3,6-diphosphacycloheptane) has been synthesized, and its electrochemical properties are reported. The 7PPh2NH ligand features an NH, ensuring properly positioned protonated amine groups (Nā€“H+) for electrocatalysis, regardless of whether protonation occurs exo- or endo- to the metal center. The compound is an electrocatalyst for H2 production in the presence of organic acids (pKa range 10ā€“13 in CH3CN) with turnover frequencies ranging from 160ā€“770 s-1 at overpotentials between 320ā€“470 mV, as measured at the half peak potential of the catalytic wave. In stark contrast to [Ni(PR2NR'2)2]2+ and other [Ni(7PPh2NR')]2+ complexes, catalytic turnover frequencies for H2 production by [Ni(7PPh2NH)2]2+ do not show catalytic rate enhancement upon the addition of H2O. This finding supports the assertion that [Ni(7PPh2NH)2]2+ eliminates the distinction between the endo- and exo-protonation isomers. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.
Authors:
; ; ; ;
Publication Date:
OSTI Identifier:
1182863
Report Number(s):
PNNL-SA-104339
KC0307010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis, 5(4):2116-2123
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
nickel phosphine; electrocatalyst; proton movement; hydrogen production