3 research outputs found
Kinetic Analysis of Competitive Electrocatalytic Pathways: New Insights into Hydrogen Production with Nickel Electrocatalysts
The
hydrogen production electrocatalyst NiÂ(P<sup>Ph</sup><sub>2</sub>N<sup>Ph</sup><sub>2</sub>)<sub>2</sub><sup>2+</sup> (<b>1</b>) is
capable of traversing multiple electrocatalytic pathways. When
using dimethylformamidium, DMFÂ(H)<sup>+</sup>, the mechanism of H<sub>2</sub> formation by <b>1</b> changes from an ECEC to an EECC
mechanism as the potential approaches the NiÂ(I/0) couple. Two electrochemical
methods, current–potential analysis and foot-of-the-wave analysis
(FOWA), were performed on <b>1</b> to measure detailed kinetics
of the competing ECEC and EECC pathways. A sensitivity analysis was
performed on the methods using digital simulations to understand their
strengths and limitations. Chemical rate constants were significantly
underestimated when not accounting for electron-transfer kinetics,
even when electron transfer was fast enough to afford a reversible
noncatalytic wave. The EECC pathway of <b>1</b> was faster than
the ECEC pathway under all conditions studied. Buffered DMF:DMFÂ(H)<sup>+</sup> mixtures afforded an increase in the catalytic rate constant
(<i>k</i><sub>obs</sub>) of the EECC pathway, but <i>k</i><sub>obs</sub> for the ECEC pathway did not change when
using buffered acid. Further kinetic analysis of the ECEC path revealed
that base increases the rate of isomerization from exo-protonated Ni(0)
isomers to the catalytically active endo-isomers, but decreases the
rate of protonation of NiÂ(I). FOWA did not provide accurate rate constants,
but FOWA was used to estimate the reduction potential of the previously
undetected exo-protonated NiÂ(I) intermediate. Comparison of catalytic
Tafel plots for <b>1</b> under different conditions reveals
substantial inaccuracies in the turnover frequency at zero overpotential
when the kinetic and thermodynamic effects of the conjugate base are
not accounted for properly
Electrocatalytic Hydrogen Production by [Ni(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>]<sup>2+</sup>: Removing the Distinction Between Endo- and Exo-Protonation Sites
A new NiÂ(II) complex, [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>H]<sup>3+</sup> (7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup> = 3,6-diphenyl-1-aza-3,6-diphosphacycloheptane),
has been synthesized, and its electrochemical properties have been
reported. The 7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup> ligand features
an NH, ensuring properly positioned protonated amine groups (N–H<sup>+</sup>) for electrocatalysis, regardless of whether protonation
occurs exo or endo to the metal center. The compound is an electrocatalyst
for H<sub>2</sub> production in the presence of organic acids (p<i>K</i><sub>a</sub> range 10–13 in CH<sub>3</sub>CN), with
turnover frequencies ranging from 160 to 780 s<sup>–1</sup> at overpotentials between 320 and 470 mV, as measured at the potential
of the catalytic wave. In stark contrast to [NiÂ(P<sup>Ph</sup><sub>2</sub>N<sup>R<sup>′</sup></sup><sub>2</sub>)<sub>2</sub>]<sup>2+</sup> (P<sup>Ph</sup><sub>2</sub>N<sup>R<sup>′</sup></sup><sub>2</sub> = 3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)
and other [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>R<sup>′</sup></sup>)<sub>2</sub>]<sup>2+</sup> complexes, catalytic turnover frequencies for H<sub>2</sub> production by [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>]<sup>2+</sup> do not show catalytic rate enhancement upon
the addition of H<sub>2</sub>O. This finding supports the assertion
that [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>]<sup>2+</sup> eliminates the distinction between the endo- and exo-protonation
isomers
Electrocatalytic Hydrogen Production by [Ni(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>]<sup>2+</sup>: Removing the Distinction Between Endo- and Exo-Protonation Sites
A new NiÂ(II) complex, [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>H]<sup>3+</sup> (7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup> = 3,6-diphenyl-1-aza-3,6-diphosphacycloheptane),
has been synthesized, and its electrochemical properties have been
reported. The 7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup> ligand features
an NH, ensuring properly positioned protonated amine groups (N–H<sup>+</sup>) for electrocatalysis, regardless of whether protonation
occurs exo or endo to the metal center. The compound is an electrocatalyst
for H<sub>2</sub> production in the presence of organic acids (p<i>K</i><sub>a</sub> range 10–13 in CH<sub>3</sub>CN), with
turnover frequencies ranging from 160 to 780 s<sup>–1</sup> at overpotentials between 320 and 470 mV, as measured at the potential
of the catalytic wave. In stark contrast to [NiÂ(P<sup>Ph</sup><sub>2</sub>N<sup>R<sup>′</sup></sup><sub>2</sub>)<sub>2</sub>]<sup>2+</sup> (P<sup>Ph</sup><sub>2</sub>N<sup>R<sup>′</sup></sup><sub>2</sub> = 3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane)
and other [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>R<sup>′</sup></sup>)<sub>2</sub>]<sup>2+</sup> complexes, catalytic turnover frequencies for H<sub>2</sub> production by [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>]<sup>2+</sup> do not show catalytic rate enhancement upon
the addition of H<sub>2</sub>O. This finding supports the assertion
that [NiÂ(7P<sup>Ph</sup><sub>2</sub>N<sup>H</sup>)<sub>2</sub>]<sup>2+</sup> eliminates the distinction between the endo- and exo-protonation
isomers