Perspective

pubs.acs.org/acscatalysis

Reaction Pathways of Hydrogen-Evolving Electrocatalysts:

Electrochemical and Spectroscopic Studies of Proton-Coupled
Electron Transfer Processes
Noémie Elgrishi,‡ Brian D. McCarthy,‡ Eric S. Rountree, and Jillian L. Dempsey*
Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, United States

ABSTRACT: Proton-coupled electron transfer (PCET) re-

actions are at the heart of the catalytic processes involved in
hydrogen evolution. In this Perspective, the state-of-the-art
spectroscopic and electrochemical methods available to
elucidate the mechanisms of PCET reactions of fuel-forming
catalysts are presented. Through examples of our recent work,
the applications of these methods are discussed with a focus on
the type of information and the accuracy that can be obtained
from each. Three case studies are presented to illustrate
different possible origins for peak shifts observed in cyclic
voltammograms.

KEYWORDS: PCET, electrocatalysis, cyclic voltammetry, stopped-flow, solar fuels

1. INTRODUCTION Scheme 1. Square Scheme Representation of a Homogeneous

Development of cost-effective solar energy storage technology is
paramount for realizing the transition away from fossil fuel
energy.1−3 In terms of chemical fuels, chemical bonds in energy-
poor molecules must be rearranged to yield energy-rich fuels.
Frequently, these rearrangements involve the movement of
multiple protons and electrons such as in H2 evolution, CO2
reduction, and water oxidation.4−6 Minimizing energy loss
during these rearrangements is imperative for practical large-
scale fuel production. As energy losses are intricately related to
the kinetics of elementary chemical steps, careful modulation of
the pathway taken from energy-poor reactants to energy-rich
products is critical. It is particularly attractive to mediate these
complex transformations using molecular transition metal
catalysts. As such, opportunities exist to modulate reaction
mechanism and perturb reaction kinetics through systematic
changes to catalyst structure and electronics, as well as reaction
conditions.
A common motivation for understanding reaction mechanisms
of catalytic transformations is the hope that this insight can lead
to modification and improvement of a catalyst. For example, if
the hydrogen evolution mechanism for a specific catalyst is
understood, a second generation catalyst can be rationally
designed. An elegant example is the evolution and improvement
of the [Ni(PR2 NR2 ′)2]2+ family of hydrogen evolution catalysts.7
Notably, within the context of hydrogen evolution, the catalyst
orchestrates the union of two electrons and two protons, and
elementary steps are frequently proton-coupled electron transfer
(PCET) reactions. PCET is traditionally viewed in terms of a
square scheme (Scheme 1) where concerted and stepwise routes
are possible. Reactions that proceed via the stepwise routes
PCET Reaction Where Species M Receives One Electron and
One Proton To Form MHa
a
H−A represents an acid molecule, and ET, PT, and CPET indicate
electron transfer, proton transfer, and concerted proton−electron
transfer, respectively.
necessarily proceed through high-energy intermediates. Con-
sequently, mechanistic study of PCET reactions involving
transition-metal complexes is an important step toward design-
ing more efficient catalysts for hydrogen evolution reactions.
Further, as PCET reactions are additionally relevant outside the
subfield of fuel formation reactions, the quest to understand
PCET in hydrogen evolution catalysts simultaneously contrib-
utes more broadly useful fundamental knowledge.
Our group has focused on understanding PCET processes in
matters relevant to energy conversion and storage processes;
specifically, in the context of homogeneous electrochemical
catalysts for the hydrogen evolution reaction (HER). As noted
above, it has become increasingly clear that an understanding of
Received: March 16, 2016
Revised: April 21, 2016

© XXXX American Chemical Society 3644 DOI: 10.1021/acscatal.6b00778

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electrochemical PCET processes are crucial for advancing HER
and other catalytic processes. Studies of PCET reaction
mechanisms to date have primarily involved organic substrates
relevant to biological charge transport pathways, with only a few
examples of transition metal-based systems.8−11 Further, while a
rich literature exists for the study of homogeneous-based PCET,
where electron and proton transfers occur between discrete
molecules (Figure 1A),9,12−16 there are fewer reports which
Figure 1. Cartoon depictions of (A) homogeneous termolecular PCET
(case for two donors and one acceptor shown; more partners are
possible) and (B) electrochemical PCET.
detail individual electrochemical PCET steps (specifically where
the electrode is a partner in the electron transfer reaction, Figure
1B).11,17−24 This is not due to a lack of methodology or theory
extensive information and experimental examples exist for the
study of electrochemical mechanism.21,22,25−32 In addition,
detailed theoretical analyses for mechanism-dependent electro-
chemical PCET rate expressions have been reported.33−35
However, only recently have these methods received more use
in the study of PCET processes relevant to energy
storage.21,23,24,27,31,36
In the study of electrochemical mechanisms, elementary steps
are generally divided into two categories: electrochemical (E)
steps and chemical (C) steps. An E step involves the movement
of an electron to/from the electrode, whereas any other
homogeneous chemical transformation corresponds to a C
step. Additional subscripts may designate reversibility (subscript
r) or irreversibility (subscript i) of individual steps, while the term
(EC) indicates a concerted E and C step. This classic
electrochemical nomenclature is readily paired with traditional
homogeneous PCET terminology. For example, an electron
transfer followed by a proton transfer, referred to as ET-PT in
PCET literature, is designated more generally as an EC
electrochemical mechanism. Meanwhile, the concerted-proton
electron transfer (i.e., CPET) pathway would be designated
(EC).
Proton transfer generally occurs between discrete molecular
proton donors and proton acceptors; however, electron transfer
may occur between solution species or, as considered more
frequently, to and from the electrode directly. As electron
transfer occurs between solution and an electrode, two
interesting and, as of yet, incompletely explored influences on
the PCET mechanism arise.
First, the kinetic barrier of the CPET pathway is impacted. In
purely homogeneous systems, PCET may involve three discrete
molecules which must encounter one another in a ternary
3645
Perspective
reaction for a CPET process (Figure 1A). Although the
formation of high-energy, charged intermediates are circum-
vented, this termolecular reaction can give rise to a high kinetic
barrier. As such, stepwise ET-PT or PT-ET mechanisms are
often favored kinetically.37,38 Conversely, for electrochemical
PCET, the reaction between the PCET substrate and the proton
donor/acceptor occurs at an essentially infinite electrode surface
(Figure 1B). As such, the kinetic barriers for an electrochemical
CPET process will be different than the termolecular
homogeneous example.
Second, the electron transfer driving force changes during a
potential-sweep electrochemical experiment. It has been
demonstrated that via careful selection of chemical oxidants,
the PCET oxidation of a tungsten-hydride bond can be induced
to undergo a CPET mechanism.10 In an electrochemical
experiment such as cyclic voltammetry, the driving force for
electron transfer changes as a function of time. This suggests that
the PCET mechanism may change during a single experiment as
the potential is swept (Figure 2). It has already been
Figure 2. As applied potential changes throughout a variable-potential
experiment, the PCET mechanism accessed may change as the driving
force changes.
demonstrated that mechanisms for hydrogen evolution can in
some cases switch from ECEC to EECC as the applied potential
is scanned cathodically.24,39 This strongly suggests that a change
of potential may promote a change in the mechanism of an
individual PCET event.
In this Perspective, the methods available to chemists for the
study of PCET reactions in organic solvents will be introduced,
with a focus on recent developments in electrochemical methods
and their applications in acetonitrile. Our efforts in applying
these methods to the elucidation of PCET mechanisms of
hydrogen-evolving catalysts will then be discussed, highlighting
the role of each method in building a broad mechanistic picture.
Finally, three case studies of model systems relevant to hydrogen
production will be presented to reflect upon different origins of
peak shifts observed in cyclic voltammograms and their
mechanistic implications.
2. METHODS FOR ELUCIDATING REACTION
MECHANISMS AND EXPERIMENTAL
CONSIDERATIONS
In this section, methodology for the elucidation of PCET
mechanisms, particularly PCET reactions in catalysis, will be
discussed. The primary methods utilized in our laboratory and
others will be described, along with the information that can be
gained from their application. Care will be taken to highlight
factors influencing the quality of the data and analysis, as well as
potential pitfalls.
2.1. Time-Resolved Spectroscopy. Two additional spec-
troscopic techniques have found utility in the study of PCET
reactionstopped-flow spectroscopy and transient absorption
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spectroscopy. Both techniques take advantage of changes in the
absorption profiles during a reaction to gain mechanistic and
kinetic information; specific details are discussed below.
2.1.1. Stopped-Flow Spectroscopy. Stopped-flow spectros-
copy is a powerful tool for extracting kinetic information and has
been used to examine PCET in various systems.10,40−43 Stopped-
flow has been applied to the study of both catalytic cycles and
elementary reaction steps where the reaction is accompanied by
clear spectral changes. In a typical stopped-flow experiment, the
contents of two syringes are rapidly mixed and the absorbance of
the system recorded over time, either as full spectra at designated
time delays or as single-wavelength kinetics traces (absorbance vs
time). A general-purpose UV−vis absorption spectrometer may
be used in cases where reaction kinetics are slow.44
Stopped-flow methods are amendable to monitoring the
reaction between many reagent types or even combinations of
reagents. For PCET studies, these may be chemical reductants,
oxidants, hydride donors, acid, or base, for example. Once the
two solutions have been rapidly mixed, the absorbance is
recorded as a function of time. When monitoring a single
elementary step, pseudo-first-order conditions are often
employed, enabling the reaction kinetics to be fit to a single
exponential to extract an observed rate constant kobs. For
complex reactions, the kinetics traces can be fit using a kinetics
model based on a series of differential equations describing the
concentrations of each reactant, intermediate, and product as a
function of time. Obtaining rate constants through stopped-flow
measurements has been shown to corroborate electrochemically
derived rate constants.24,40,41
2.1.2. Transient Absorption Spectroscopy. Time-resolved
optical monitoring techniques can also be coupled to photo-
triggering methods to initiate PCET reactions. In traditional laser
flash-photolysis methods, excited-state reductants (including
ruthenium, rhenium, iridium, and copper polypyridyl com-
plexes) are employed to initiate the one-electron reduction of a
redox-active molecule upon excitation by a pulsed laser.8,45−53 In
the presence of a proton source, reduction will often be
accompanied by a protonation reaction.12,54,55 As in stopped-
flow spectroscopy, the distinct optical signatures of the different
redox forms of the catalysts, as well as the protonated species,
allow the reaction intermediates and products to be spectroscopi-
cally detected and monitored. However, in these phototriggered
transient absorption experiments, it is the change in the sample
absorbance (as opposed to the absolute absorbance) that is
monitored as a function of time. Data can be recorded as
difference spectra at designated time delays or as single-
wavelength kinetics traces, depending upon experimental setup.
While phototriggered reactions typically involve the initiation
of electron transfer, proton transfer reactions may be photo-
initiated as well using photoacids.12 Photoacids are species that
become powerful proton donors in their electronic excited states,
allowing in situ generation of a proton donor upon pulsed laser
excitation.56,57 Beginning with the reduced metal species,
photoexcitation of the photoacid will promote proton transfer
to yield a PCET reaction intermediate. Like photoinduced
electron transfer reactions, proton transfer reactions can also be
monitored optically if protonation is accompanied by a distinct
change in absorption. While identifying the conditions to
phototrigger an electron transfer or proton transfer reaction
for a laser flash-photolysis experiment may be challenging,
especially when other reactive substrates are present in solution,
this time-resolved spectroscopy allows much faster reactions to
be optically monitored. Compared to stopped-flow spectrosco-
3646
Perspective
py, which has a time resolution of microseconds due to the
necessary mixing time, transient absorption spectroscopy allows
investigation of kinetics in the pico- to nanosecond regime.
2.2. Electrochemistry. Electrochemical methods have vast
precedent in the study of reaction mechanisms,25,26 and
consequently, electrochemistry has been increasingly utilized in
the study of PCET reactions. One key benefit of electrochemistry
is the dynamic control over the energy of electrons. Of the
multitude of electrochemical techniques, cyclic voltammetry has
emerged as the favorite tool for uncovering reaction mechanisms
and determining rate constants due to the rich information
available from current−potential responses and the extensive
analytical methods established for interpreting resulting data.
Additionally, cyclic voltammetry is a nondestructive technique;
only the minute volume of reactants immediately next to the
working electrode (the reaction layer) is involved in a
measurement. Finally, over the last 5 years, great strides have
been made in the development of mathematical models to extract
quantitative kinetic information from cyclic voltammograms of
multielectron, multisubstrate reactions. Presented here is a brief
summary of the electrochemical tools most commonly used in
our laboratory; more extensive discussions are available.26,32
2.2.1. Kinetic Analysis Using Catalytic Plateau Current and
Half-Wave Potential. In the case of electrochemical catalysis
under ideal conditions with no limiting side phenomena or
substrate depletion, an S-shaped response with superimposable
forward and reverse traces is obtained by cyclic voltammetry.32
An observed rate constant kobs can be extracted using the
experimental catalytic plateau current (ipl, which is independent
of scan rate) and the potential at which half the catalytic current is
reached (Ecat/2). For a two-electron catalytic process and
assuming that both electron transfers occur at the electrode
with the second reduction being easier than the first, the catalytic
plateau current is given by eq 1 where [Cat]0 is the bulk solution
catalyst concentration, D is the catalyst diffusion coefficient, F the
Faraday constant, and A is the electrochemically accessible
electrode surface area.
i pl = 2FA[Cat]0 D kobs (1)
eq 1 is often divided by the one-electron peak current in the
absence of substrate, i0p, given by the Randles−Sevcik equation
(eq 2, where F is the Faraday constant, T is temperature, and υ is
scan rate) to yield eq 3, which eliminates the need for the
diffusion coefficient and electrode surface area to be
independently determined:
DυF
i p0 = 0.446FA[Cat]0
RT (2)
i pl kobsRT
= 0.448
i p0 υF (3)
Expressions for kobs as a function of the rate constants for the
first and second chemical steps, k1 and k2 respectively, can be
derived for specific mechanisms.28 For the mechanisms ECEC
and EECC, assuming S-shaped catalytic responses, expressions
for kobs as well as Ecat/2, the potential at which half of the plateau
current is reached, are given in Table 1 as a function of k1, k2, and
E1/2, the potential of the electrochemical event triggering
catalysis. In many cases, either k1 or k2 is rate limiting, resulting
in a collapse of the equations in Table 1 simpler expressions.
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Table 1. Values of kobs and Ecat/2 as a Function of the Rate
Constants of the Two Chemical Steps Considered28,39
ECEC EECC
k1
k1
kobs k1 1+
k1
⎛ k2 ⎞
1+
k2 k2 ⎜⎜1 +
⎝
⎟⎟
k1 ⎠
⎛ ⎞
RT ⎛ k1⎞ RT ⎜
ln⎜1
Ecat/2 E1/2 + ln⎜1 + ⎟ E1/2 + +
F ⎝ k2 ⎠ F
⎜
⎛
k 2 ⎜1 +
⎝ ⎝
kobs collapses to k rate limiting for both cases, while Ecat/2
collapses to E1/2 only when k1 is rate limiting.
2.2.2. Foot-of-the-Wave Analysis (FOWA) for Kinetic
Evaluation. Experimentally, S-shaped cyclic voltammograms
and consequently accurate plateau currents may not be accessible
due to substrate consumption, catalyst degradation, or other side
phenomena.27,32 This prohibits the analysis of the plateau
current to extract kinetic information. As the influence of these
side reactions increase throughout a cyclic voltammetry
experiment, the plateau current becomes inaccessible. Costentin
and Savéant recently recognized that in these cases, the current
(i) vs applied potential (E) plot of nonideal catalytic cyclic
voltammograms overlays with the idealized cyclic voltammogram
near the beginning of the catalytic scan.27 Consequently, kinetic
information can still be gleaned using data recorded near the foot
of the wave where the influence of such phenomena is minimized
in a method coined foot-of-the-wave analysis (FOWA).27 The
generic expression of the current near the foot of the wave,
assuming fast electron transfers occurring only at the electrode, is
i i pl /i p0
=
1 + exp⎡⎣ RT (E − Ecat/2)⎤⎦
i p0 F nature and choice of acid source is of paramount importance in
where the specific definition of ipl and Ecat/2 varies with
mechanism (see eq 1 and Table 1).28,32 FOWA has rapidly
proven extremely valuable with successful application to the
study of a number of electrocatalytic PCET reactions including
H2 evolution, CO2 reduction, and water oxidation.24,27,39,58−63
Recently, the influence of the heterogeneous electron transfer
rate and the percentage of the current response used in FOWA
on the kinetic results were reported.39 It was found that utilizing
larger percentages of the catalytic wave for FOWA resulted in
larger errors; additionally, the linear portion of the wave
decreased with smaller (and more realistic) values of the
heterogeneous electron transfer rate constant. This study
emphasizes the importance of only using the linear portion of
the data for FOWA.
Finally, obtaining accurate values from FOWA is only possible
when an accurate value is known for the potential of the catalysis-
initiating redox process (E1/2). The potential of an electro-
chemical event in the absence of substrate is often used, but care
must be taken to ensure that this redox process is indeed the
initiating event for catalysis. This can be difficult to obtain in
some cases, especially when the solvent is the substrate.
2.2.3. Catalytic Tafel Plots and Standard States. To
benchmark catalysts studied in different conditions, in the
presence of different acids and at different overpotentials,
Savéant and co-workers proposed the use of catalytic Tafel plots.
These plots, of the log of the turnover frequency (TOF) as a
function of overpotential (η) (the log plot of eq 5), showcase the
Perspective
figures of merits of different homogeneous catalysts by
illustrating the trade-off between activity and overpotential.
The turnover frequency is defined as the moles of product
generated per unit of time divided by the moles of the active form
of the catalyst present in the reaction-diffusion layer, and the
expression of the maximal turnover frequency TOFmax is
dependent upon the mechanism considered.28,32
TOFmax
k1 ⎟ TOF =
⎟ ⎡ − η − Ecat/2)⎤⎦
k2 ⎞
⎟⎟
F Solv
1 + exp⎣ RT (E HA/H
k1 ⎠ ⎠ 2 (5)
The overpotential η is defined as the difference between the
applied potential at the electrode (E) and the apparent standard
potential of the reduction of protons to hydrogen in the
conditions of acid and solvent studied ESolv HA/H2: η = EHA/H2 − E.
Solv
The catalytic Tafel plots are generated using TOFmax, Ecat/2,
HA/H2 at a fixed stated acid concentration. Determination of
and ESolv
the value of ESolv
HA/H2 is discussed in section 2.3.1. Savéant and
Artero suggest using the standard concentration of 1 M to
generate the catalytic Tafel plots. Practically, researchers
experimentally determine the rate constants for the trans-
formations studied using the methods described above, and they
generate catalytic Tafel plots by calculating at each overpotential
the expected turnover frequency. The aim of this tool is to
provide a simple visual representation of the activity of different
catalysts at different overpotentials.
Recent concerns have emerged over the usefulness of this tool
as the activity reported is necessarily idealized. One such concern
was over the actual acid concentration in the medium, as well as
turning on catalyst-dependent side reactions and deactivation
pathways at such high hypothetical acid concentrations.39
2.3. Considerations for Choosing an Acid Source. The
(4) PCET processes. Several key parameters should be considered
when choosing an acid, including acid pKa, structure, standard
reduction potential for H2 production, potential of background
reduction at the electrode, and solution thermal equilibrium
processes. This section will briefly touch on the influence of each
parameter, focusing on practical guidelines to be mindful of
during PCET studies. A case study of the impact of these
parameters on reactivity is presented in section 3.3.
2.3.1. Acid pKa, Thermodynamic Potential for Reduction,
and Structure. Acid strength, quantified through pKa, is the
parameter most commonly used in the choice of acid for the
study of PCET reactions. Extensive tabulation of acid pKa values
in acetonitrile is available; this existing data spans a wide range of
acid types, including phenols, carboxylic acids, anilinium and
pyridinium derivatives, among others.64−67
The pKa of the chosen acid directly relates to the overpotential
for the specific electrochemical PCET reaction. The required
overpotential for a catalytic reaction has implications for the
comparison of catalysts as discussed in the context of catalytic
Tafel plots and for analyzing catalytic thermochemical cycles. For
the example of hydrogen evolution, evaluation of the over-
potential η as a function of the applied potential E, necessitates
knowledge of two parameters: the standard reduction potential
of H+ to H2 in the solvent (E0,Solv
H+/H2) and the pKa of the acid (HA)
in the solvent (Solv):68
Solv
η = E HA/H − E = E H0,Solv − 0.059 × pK a Solv − E
+
2 /H 2 (6)
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Recently, a methodology was outlined for the direct
electrochemical determination of ESolv HA/H2 via measurement of
the open circuit potential of an electrochemical cell containing
the respective acid and 1 atm of H2 gas at equilibrium in the
solvent studied.69 To date, the experimental complexity of the
measurement has limited its use.
A recent report investigating the kinetics of the CPET reaction
between acids and gold electrodes in acetonitrile shed light on
the influence of acid structure in terms of steric hindrance.70
Faster kinetics of the CPET process to the electrode were
measured for triethylammonium compared to diisopropylethy-
lammonium. This effect was attributed to the increased Tolman
cone angle of 200° for the diisopropylethylammonium cation
compared to 150° for triethylammonium.
The possibility of interactions between catalysts and conjugate
bases is another parameter to be considered in the choice of acid/
base pairs for mechanistic studies. The influence of base structure
has recently been highlighted in our study of catalytic proton
reduction by cobaloxime complexes with substituted aniliniums
as an acid source (see below). It has been shown that during the
course of catalysis, as conjugate base aniline is generated, the
aniline molecules can bind to the cobalt center, influencing what
the active catalyst is and so altering the cyclic voltammetry
responses.71 This effect is readily apparent in the cyclic
voltammetry of Co(dmgBF2)2(CH3CN)2 (dmgBF2 = difluor-
oboryldimethylglyoxime) with and without added 4-MeO-
aniline (Figure 3). Upon base addition, the CoIII/II wave
Figure 3. Cyclic voltammograms recorded at 100 mV/s in 0.25 M
[Bu4N][PF6] of 0.38 mM of Co(dmgBF2)2(CH3CN)2 in the absence
(a) and presence (b) of 2 mM 4-methoxyaniline. Reprinted with
permission from reference 71. Copyright 2016 American Chemical
Society.
reversibility and potential is modified, without apparent changes
to the CoII/I wave. Separate UV−vis titration experiments
demonstrated that one and two aniline molecules can reversibly
coordinate to the catalyst.71
2.3.2. Acid Homoconjugation, Heteroconjugation, and
Dimerization. Acid and base molecules are well-known to
interact in solution via the processes of homoconjugation,
heteroconjugation, and dimerization. These three processes,
depicted in eqs 7 to 9, have a varying degree of importance
3648
Perspective
depending on the acid structure, concentration, and the nature of
the solvent.
homoconjugation: BH+ + B → BHB+ (7)
dimerization: 2BH → (BH)2 (8)
heteroconjugation: BH+ + H 2O → BH3O+ (9)
Homoconjugation is particularly strong for phenols and
carboxylic acids. For example, phenolate is reported to have a
homoconjugation constant close to 16 000 M−1, while benzoate
has a constant of almost 4000 M−1.64 By contrast, aniline has a
much lower homoconjugation constants of 4 M−1;64 it is often
assumed that most aniline derivatives have low homoconjugation
constants.72 As was recently demonstrated in the study of
[Ni(PR2 NR2 ′)2]2+ hydrogen evolution catalysts, failure to account
for homoconjugation when determining rate constants from
cyclic voltammetry data can lead to misinterpretations of the
influence of added base as well as errors in the determination of
rate constants. However, careful consideration of homoconjuga-
tion can permit accurate determination of kobs and mechanistic
assignment.39
Acid dimerization is another process to consider, especially
when the acid dimer has a lower pKa than the parent acid. The
presence of an acidic species with a different pKa than the parent
acid may result in multiple PCET mechanisms, complicating
kinetic and mechanistic analysis. Dimerization can occur in
aprotic organic solvents when interaction between two acid
molecules yields a stabilization greater than solvation by the
aprotic organic solvent. Dimerization has been found to
influence the reactivity of carboxylic acids in acetonitrile.73
Heteroconjugation arises between acids and bases of a
different species; for example, the interaction of a carboxylic
acid with water. In the context of electrochemical studies in
acetonitrile, the effect of heteroconjugation has only been
considered when water is added to the organic solvent.73
2.3.3. Reduction of Acids at Electrode Surfaces. For
solutions containing protic species, an important control
experiment to keep in mind is at what potential these protic
species are directly reduced at the electrode. In other words,
control experiments for each individual component of an
electrochemical system are crucial. Glassy carbon electrodes
have long been used in the study of fuel-forming catalysts,
especially hydrogen evolution, due to their low background
activity for direct, heterogeneous acid reduction. While the
background activity is less significant than on other electrode
materials such as platinum, direct acid reduction at glassy carbon
electrodes still occurs. Our group recently published a systematic
study of the direct reduction of 20 acids in acetonitrile on glassy
carbon electrodes.74 These acids spanned over 35 pKa units in
acetonitrile, with the experimental direct acid reduction
potential, reported as the current inflection potential (Einf),
covering a range of over 2 V.
These results are visually summarized in Figure 4, where the
color intensity reflects the current intensity observed as a
percentage of the current observed at Einf. This study
underscored four factors influencing the observed voltammo-
grams: electrode fouling, irreproducibility from scan to scan,
curve crossing, and acids with erratic backgrounds. The influence
of adding water to each acid was also studied. While no significant
peak shifts were observed with water addition, the current
increased for a number of acids known to have a high
homoconjugation constants. The current increase was proposed
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Figure 4. Acid reduction potentials in acetonitrile (25 mM acid, 100
mV/s) depicting the range between the direct reduction potential Einf.
and the approximate thermodynamic potential for hydrogen evolution.
Caveats for three acids are listed. Adapted with permission from ref 74.
Copyright 2014 American Chemical Society.
Figure 5. Kinetic zone diagram and simulated CV waveforms for the
catalytic EC′ mechanism of the one electron reduction of a substrate via
a redox catalyst mediator. Reprinted with permission from ref 32.
Copyright 2014 American Chemical Society.
to be the result of the added water stabilizing the in situ generated
conjugate bases and so freeing additional acid molecules tied up
in homoconjugation for direct electrode reduction. Overall, this
study allows for easier and mindful selection of a suitable acid for
electrochemical PCET reactions.
2.4. Homogeneous to Heterogeneous Transformation
of Catalysts. The past decade has witnessed increased
awareness of the possibility of transformation from a
homogeneous precatalyst to heterogeneous catalyst.75−78
There has been a recent surge in the identification of molecular
species which decompose to heterogeneous material deposited
on the electrode surface; known examples are depicted in Table
2.11,79−88
3649
Perspective
As the number of reports grows, some key structural motifs
have emerged as susceptible to decomposition. Cobalt and nickel
compounds containing CN and N−O bonds were reported by
a number of groups80,81,83,84,89 to decompose in acidic and
reducing conditions to Co- and Ni-containing nanoparticles,
respectively. Firm experimental evidence that CN bonds can
predispose a complex to decomposition was provided by our
group via direct comparison of two complexes either with or
without CN bonds.87
The presence of Ni−S bonds also appears to render
compounds lacking CN or N−O bonds susceptible to
decompositions, as discussed by Roberts85 and by our group.11
In these cases, it appears that cleavage of adjacent S−C bonds
with concomitant ligand destructionis favored by Ni−S
bonds.11,85 Finally, we recently demonstrated with an Fe
complex that protic conditions are not required for decom-
position.88
2.5. Digital Simulations. The modeling of electroanalytical
experiments has advanced to a level of great accuracy over the last
half century. Two general approaches have been used:
(1) The semianalytical solutions to the diffusion equations
have been obtained through the integral equation method
in order to describe the voltammetric response of specific
mechanisms (e.g., equations presented in section 2.2.1).
These solutions are often applied directly or used to
generate working curves based on dimensionless param-
eters.26
(2) Finite difference or finite element numerical methods have
been used to solve the diffusion equations in conjunction
with the kinetic equations describing the chemical reaction
of interest (known as digital simulation).
Both methods are very valuable, but digital simulation is
generally found to be more accessible to most researchers.
Digital simulation software can be used to generate simulated
voltammograms that can be directly compared with experimental
voltammograms. However, successful simulation of experimental
data requires accurate assessment of a large number of
parameters, and the sensitivity of electroanalytical techniques
to environmental factors that cannot be emulated in simulation
often prevents satisfactory fitting. In our experience, we have
found digital simulation to be most valuable in addressing “what
if” questions and to test if the already derived equations can be
extended to a proposed mechanism. Both of these cases are
highlighted below in our mechanistic studies of cobaloxime.71
2.6. Traversing the Zone Diagram To Access S-Shaped
Voltammograms. Zone diagrams pictorially depict the
voltammetric waveform shapes expected as a function of
dimensionless parameters;91 the zone diagram for an EC′
mechanism is shown in Figure 5. For an EC′ reaction, the kinetic
(λ) and excess factors (γ) describe how waveforms will evolve as
a function of parameters such as ke (the rate constant for the
reaction of the reduced catalyst and the substrate), υ (the scan
rate), and [Cat]0 and [CA]0 (the bulk concentration of catalyst
and substrate A, respectively):26,91
⎛ RT ⎞⎛ ke[Cat]0 ⎞
λ= ⎜ ⎟⎜ ⎟
⎝ F ⎠⎝ υ ⎠ (10)
[CA ]0
γ=
[Cat]0 (11)
By changing these experimental parameters, waveforms
conforming to different zones can be accessed.32
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Table 2. Metal Complexes Known to Electrochemically Degrade in Organic Solventsa under Catalytic Conditions To Form
Electrode-Adsorbed Heterogeneous Materialsb

a
All examples were in either acetonitrile or dimethylformamide. bThis table does not include examples where the homogeneous catalyst only
degrades after harsh prolonged catalysis; e.g., ref 90.

Until recently, it was not clear if the EC′ Zone Diagram could
be directly extended to the more complex multielectron,
multisubstrate reactions associated with fuel production.92
However, voltammograms have now been reported for the
catalytic reduction of protons from a series of eight para-
substituted aniliniums to hydrogen by the catalyst Co-
(dmgBF2)2(CH3CN)2. Notably, the voltammetric responses
recorded for varying kinetic and excess factors apparently
spanned all of the waveform shapes associated with the EC′ Zone
Diagram. Detailed analysis confirmed that the EC′ Zone
3650
Diagram could be qualitatively extended to multielectron,
multisubstrate reactions.92 In addition to υ, [CA]0, and [Cat]0,
the pKa of added acids could also be used to traverse the zone
diagram as it was found that the observed rate constant is linearly
dependent on acid strength.71,92
Using the methods detailed above in section 2.2.1, global rate
constants can be extracted from the plateau region of S-shaped
voltammograms of Zone KS (and the related Zone KD) for both
EC′ and various multielectron, multisubstrate reactions, such as
the ECEC pathway.26,28 Further, it has long been known that
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kinetic information can also be extracted from waveforms in the
“total catalysis” region (Zone KT2) for a simple EC′
reaction.32,91 The catalytic peak potential of a total catalysis
voltammogram varies as a function of ke, υ, [CA]0, and [Cat]0 (see
section 4.1).32 More recently, peak shift analysis has been
extended to the ECEC mechanism and demonstrated, under
limiting conditions, to provide information about the rate
constant k1.71 Ultimately, the primary utility of a multielectron,
multisubstrate zone diagram is its use as a navigational tool to
modify experimental conditions in order to enter either the zones
in which kinetic information can be extracted.
3. CASE STUDIES: REACTION MECHANISMS AND
KINETICS OF H2-EVOLVING CATALYSTS
The electrochemical and spectroscopic methods discussed in
section 2 have been applied in concert to elucidate the reaction
pathways of catalysts for hydrogen evolution. Recent work has
focused on two highly active catalysts, Co(dmgBF2)2(CH3CN)2
(dmgBF 2 = difluoroboryldimethylglyoxime) and [Ni-
(P2PhN2Ph)2]2+ (P2PhN2Ph = 1,3,5,7-tetraphenyl-1,5-diaza-3,7-di-
phosphacyclooctane) (Scheme 2). In addition to identifying
Scheme 2. Co(dmgBF2)2(CH3CN)2 (left) and
[Ni(PPh Ph 2+
2 N2 )2] (right)
dominant PCET reaction pathways, these studies have yielded
new insight into the kinetics of elementary reaction steps and
revealed linear free energy relationships between rate constants
for these individual steps and acid pKa. The complexities of
proton source reactivity in acetonitrile have also been established
through the investigation of reaction kinetics as a function of
various acid parameters.
3.1. Mechanistic Study of Electrocatalytic H2 Evolution
by a Cobaloxime. Cobaloximes and their derivatives have been
incorporated as catalysts in both electrochemical and photo-
chemical H2 production cycles.93−123 While their operating
mechanisms have been explored in depth under certain
conditions using both experimental and theoretical meth-
ods,54,93,94,96−98,124−126 electroanalytical methods were recently
applied to explore the reaction pathways and kinetics of
Co(dmgBF2)2(CH3CN)2 (dmgBF2 = difluoroboryldimethyl-
glyoxime) as a function of acid strength.71,92 Through the use
of a series of analogous acids, specifically para-substituted
aniliniums, complicating factors resulting from different
homoconjugation constants across dissimilar acids were reduced,
allowing studies to focus on the direct effect of acid pKa on
reaction kinetics and mechanism. It should be noted that
Co(dmgBF2)2(CH3CN)2 decomposes in the presence of strong
acids; in the extreme case of strong acid and reducing conditions
cobalt-containing nanoparticles form, as noted in Table 2 above.
In our studies of Co(dmgBF2)2(CH3CN)2, great care was taken
to limit the extent of decomposition.71
Cyclic voltammograms of Co(dmgBF2)2(CH3CN)2 recorded
in acetonitrile in the presence of para-substituted aniliniums
exhibit an increase in cathodic current and loss of reversibility at
3651
Perspective
the [Co(dmgBF2)2(CH3CN)2]0/− couple. Notably, the Ecat/2
(the half-wave potential of the sigmoidal response) shifts to
values positive of E°′([Co(dmgBF2)2(CH3CN)2]0/−). For acids
of pKa > ca. 9.5, the catalytic response currents approach a
plateau shape as the acid concentration is increased; these
catalytic plateau currents (ipl) were found to be first-order in both
acid concentration and catalyst concentration, consistent with
prior results.97
These three observations provide evidence to support
assignment of the reaction mechanism (Figure 6A). Specifically,
the shifting Ecat/2 indicates that the first chemical step (C1,
protonation of [Co(dmgBF2)2(CH3CN)2]− to form a putative
CoIII-hydride intermediate) is rapid, and the subsequent
chemical step(s) is(are) rate-limiting. Previously, two independ-
ent theoretical124,126 and one experimental125 study have shown
that the CoIII-hydride intermediate is more readily reduced than
the parent CoII species, indicating that this intermediate will be
spontaneously reduced. Further, based on the influence of acid
and catalyst concentration on the catalytic plateau current, the
rate-limiting step for catalysis is also first-order in both acid and
catalyst, indicating a second (rate-limiting) protonation step
(C2) and an overall heterolytic route for hydrogen production.
Together, these data support a heterolytic ECEC pathway for H2
evolution from anilinium acids in acetonitrile. Notably, this
assignment is consistent with that from theoretical work54,124 as
well as conclusions from photocatalysis and laser flash photolysis
experiments.112,125
Of note, a homolytic route involving the bimetallic reaction of
two CoIII-hydride species has previously been recognized as a
viable pathway for H2 production by both computational
studies124,126 and thermochemical analysis.54 While clear
evidence diagnosing a homolytic pathway for hydrogen
production has not yet been reported, 29 recent work
investigating the cleavage of H2 by Co(dmgBF2)2(CH3CN)2
under high H2 pressures suggests this reaction proceeds via a
homolytic cleavage route.127−129 As such, a homolytic reaction
pathway for hydrogen production may be accessible under
alternative experimental conditions, or could be occurring as a
minor parallel pathway.
With this mechanistic assignment, kinetic details for
elementary steps can be elucidated through analysis of the
voltammograms. The second-order global rate constants for
catalysis were determined from the analysis of the acid
concentration-dependent plateau currents for acids with pKa >
ca. 9.5 (Figure 6B). As the plateau current reflects the observed
rate constant, kinetic details of the rate-limiting step can be
gleaned directly. As described above, the second protonation is
the rate-limiting step under these conditions and described by
rate constant k2. Across the series of aniliniums with pKa > ca. 9.5,
catalysis was found to accelerate as the strength of acid increased
and a linear correlation is observed between log(k2) and acid pKa
(slope = −0.77). For acids with pKa < ca. 9.5, catalytic
voltammograms remained peaked and the catalytic responses
were determined to be controlled by diffusion of the acid to the
reaction layer. As such, second-order rate constants could not be
determined for these acids; however, extrapolation of the linear
relationship determined for weaker acids allows these rate
constants to be estimated.
Rate constants for the first protonation step (k1) were
determined from foot-of-the-wave (FOWA) analysis. Like k2, a
linear correlation between log(k1) and pKa was observed (slope =
−0.97). Values for k1 are ca. 3 orders of magnitude greater than
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Figure 6. (A) Reaction mechanism for hydrogen evolution catalyzed by
Co(dmgBF2)2(CH3CN)2 as supported by detailed analysis of catalytic
CVs. (B) Rate constants k1 and k2 determined from FOWA and plateau
current analysis, respectively, of acid concentration-dependent catalytic
voltammograms of Co(dmgBF2)2(CH3CN)2 and a series of para-
substituted aniliniums. k2 values for acids 6, 7, and 8 were extrapolated
from the linear relationship established at higher pKa values. kΩ
represents an acid-independent step and was determined from catalytic
voltammograms recorded at high acid concentrations in which the
voltammetric responses were acid concentration and pKa-independent.
Acids identity: (1) 4-methoxyanilinium, (2) 4-t-butylanilinium, (3)
anilinium, (4) 4-chloroanilinium, (5) 4-trifluoromethoxyanilinium, (6)
4-(methylbenzoate)anilinium, (7) 4-trifluoromethylanilinium, and (8)
4-cyanoanilinium. Adapted with permission from ref 71. Copyright 2016
American Chemical Society.
those of k2, consistent with the interpretation of an ECEC
pathway with a rate-limiting second chemical step.
At high acid concentrations, the plateau currents reach a
limiting value that is acid concentration and pKa-independent.
This observation extends to both the weaker acids and the
stronger acids described above which exhibit only peak-shaped
voltammograms in their acid-dependent region. Across the range
of acids explored, this limiting plateau current is constant, though
the concentration of the acid required to reach this limiting value
increases as acid strength decreases. The first-order rate constant
3652
Perspective
determined from this limiting current value (ca. 125 s−1) likely
reflects either an H−H bond formation step or H2 release.
Kinetic and mechanistic insight gained from comprehensive
analysis of the catalytic voltammograms contributes to a more
detailed picture of hydrogen evolution from cobaloximes.
Specifically, it was learned that upon reduction of the CoII
species, rapid protonation (k1) yields a CoIII-hydride species
(that may undergo tautomerization128−130). This intermediate is
readily reduced to form a CoII-hydride (k2). The subsequent
second protonation step is 3 orders of magnitude slower than the
first step. The resulting CoII−H2 species releases H2 to close the
catalytic cycle via an acid-independent step with a first-order rate
constant of 125 s−1.
3.2. Mechanistic Study of Electrocatalytic H2 Evolution
by [Ni(P2PhN2Ph)2]2+. [Ni(P2PhN2Ph)2]2+ (P2PhN2Ph = 1,3,5,7-
tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane) and its family
of hydrogen production/oxidation catalysts have been thor-
oughly studied over the past decade, with the notable result of
clearly demonstrating the importance of the secondary
coordination sphere in catalytic reactions.131−136 While original
reports assumed a single catalytic mechanism, the possibility of
multiple catalytic routes has been recently examined.24,39,137
Two generic pathways have been identified: an ECEC pathway,
whereby the first protonation occurs on the NiI species after a
single reduction, and an EECC pathway, where double reduction
to form a Ni0 species occurs prior to both protonations.
Two recent experimental studies probing these parallel
reaction pathways approached the problem very differently.
Wiedner and co-workers examined the reactivity of [Ni-
(PPh Ph
2 N2 )2]
2+
using dimethylformamidium (DMFH+) as the
proton source.39 DMFH+ is a relatively strong acid in acetonitrile
with a pKa of 6.1, resulting in cyclic voltammograms with both
the ECEC and EECC pathways readily apparent. Using a mixture
of electrochemical techniques, primarily based around FOWA,
the overall contributions of the two different pathways were
deconvoluted. In work in our lab, we utilized a weaker acid
(anilinium, pKa = 10.6) to isolate the EECC mechanism and then
used several of the previously discussed methods to determine
the individual rate constants of the elementary reaction steps.24
3.2.1. Electrochemical Studies To Elucidate Kinetics of Ni0
Protonation and Subsequent Reactivity. While analysis of
cyclic voltammograms under pseudo-first-order conditions is
useful for extracting kinetic information, experiments carried out
under more stoichiometric catalyst:substrate conditions can
provide additional information on how the reaction proceeds. In
the analysis of [Ni(PPh Ph 2+
2 N2 )2] , stoichiometric addition of
anilinium confirmed rapid reactivity of acid with the Ni0 species
by a signature kinetic peak shift (discussed further in section 4.2)
and the appearance of a new oxidation feature on the return trace.
Given that two electrons and a single proton had been
transferred to the catalyst, it was natural to assume hydride
formation. Independent synthesis and cyclic voltammetric
analysis of a NiII-hydride confirmed that the new oxidation
feature observed did correspond to the hydride species (Figure
7).24
With the first chemical step established as hydride formation,
we next examined the details of this elementary step under
catalytic conditions. First, a rate constant was determined by
analyzing the kinetic peak shift of the NiI/0 wave in the presence
of acid. Conveniently, catalytic turnover could be prevented on
the electrochemical time scale, even under pseudo-first-order
conditions, by the addition of excess base. This rate constant was
corroborated with FOWA. FOWA uniquely provides the rate
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chemical step of H2 productionshould control the overall

Figure 7. Cyclic voltammograms of 1.5 mM [Ni(PPh Ph 2+
2 N2 ) 2] and
approximately 1 equiv of anilinium (blue) compared with the cyclic
voltammogram of 0.6 mM of the independently synthesized NiII-
hydride (black) in CH3CN. The new oxidation observed at −0.4 V for
[Ni(P2PhN2Ph)2]2+ in the presence of acid matches that of the
independently synthesized hydride. Voltammograms recorded at 100
mV/s in 200 mM [NBu4][PF6] CH3CN solutions. Reprinted with
permission from ref 24. Copyright 2015 American Chemical Society.
reaction kinetics. If this is the case, the plateau currents should
directly reflect this reactivity and spectroscopic monitoring of the
reaction of NiII-hydride with anilinium should result in a similar
observed rate constant.
The NiII-hydride is a stable complex with a distinct absorption
spectrum from [Ni(PPh Ph 2+
2 N2 )2] , allowing us to observe its
reactivity with anilinium directly, using stopped-flow spectros-
copy. As stopped-flow spectroscopy is a time-resolved technique
compared to the steady-state nature of electrochemical methods,
complementary chemical reactivity information can be gathered
by employing this experimental technique. Reaction of the NiII-
hydride with anilinium affords a kinetic trace with two distinct
regions: a fast component on the order of seconds, and a slow
component on the order of minutes (Figure 9). Under pseudo-

constant for only the first step in the catalytic reaction.

Reasonable agreement (1.2 × 106 M−1 s−1 for peak shift analysis,
and 6.5 × 106 M−1 s−1 for FOWA) was found between the
resulting values.24
Subsequent reactivity of the NiII-hydride was then inves-
tigated. Comparison of the value estimated for kobs from the
catalytic plateau currents and the value determined for rate
constant k1 indicates that the overall rate of catalysis is not
governed by hydride formation. As such, kinetic information
obtained from the plateau current represents steps subsequent to
the first protonation. At low acid concentrations the reaction is Figure 9. Stopped-flow kinetics trace for a solution 0.39 mM NiII-
hydride and 100 mM anilinium. 88% of the change in absorbance is
approximately first-order in acid; however, at higher acid
accounted for in the “fast” kinetics (shown in inset), which occurs over 2
concentrations, an acid concentration-independent region is s followed by a “slow” process occurring over the course of 5 min.
reached (with anilinium the maximum rate constant was ∼20 s−1
as measured by the ECEC plateau equation, Figure 8).24
3.2.2. Investigation of Hydride Reactivity with Acid via first-order conditions, the fast component was fit to single
Stopped-Flow Spectroscopy. The cyclic voltammetry studies exponential kinetics. The rate constant obtained was found to be
described above establish that the formation of the hydride is first-order with respect to the anilinium concentration.24
rapid and these kinetics do not affect the overall catalytic rate At first glance, the first-order response with anilinium
described by kobs. With this assumption, it was asserted that the appeared to be in conflict with the acid-independent response
reactivity of the hydride with the proton sourcethe second obtained from cyclic voltammetry at higher acid concentrations.

Figure 8. Observed rate constants obtained from the current plateau (blue circles) for the reaction of [Ni(PPh Ph 2+
2 N2 )2] and anilinium, and from stopped-
flow kinetics traces (red circles) for the reaction of NiII-hydride and anilinium. Black circles represent the fit for the mechanism shown in the right panel,
and the appropriate kinetics models are shown for the time-resolved (red) and steady-state (blue) kinetics. Data from ref 24.

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However, the discrepancy was reconciled by considering the
possibility of an off-cycle intermediate, which has been
extensively explored in several previous studies.39,136,138−142
These works reveal that the [Ni(PR2 NR2 ′)2]2+ molecules can be
protonated in an “exo” position on the pendant amine which
prohibits catalytic turnover. This effectively inactivates the
catalyst prior to catalytic turnover. The “exo” position proton
must be removed, followed by protonation in the “endo” position
for productive catalysis to occur. Under the conditions accessed
in cyclic voltammetry, an increase in the acid concentration
results in an increase in the concentration of the inactive catalyst,
reducing the apparent rate constant and giving the appearance of
acid concentration independence. The time-resolved (stopped-
flow) kinetics do not exhibit acid independence because no
equilibrium can be established between the inactive and active
forms of the catalyst. However, the generation of the inactive
catalyst affects the kinetics analysis of the fast component and the
slow component observed corresponds conversion of the
inactive species to the active species followed by hydrogen
release.24
3.3. Reactivity of NiIIH with Various Proton Sources. As
the reaction of the NiII-hydride with acid was established to be
the rate-limiting step for hydrogen production, this elementary
reaction step provided a convenient platform to take a deeper
look at the influence of the proton source on reaction
mechanisms in acetonitrile. Reactivity of the NiII-hydride with
a series of acids were examined using the same stopped-flow
procedure described for the reaction with anilinium (section
3.2.2). The effect of various parameters, including pKa, presence
of base, molecular association, and interaction with water, were
explored.73
3.3.1. Acid pKa. As discussed above, pKa is the most commonly
considered parameter for acids in PCET studies. In the reaction
of NiII−hydride with acid, the anticipated linear free energy
relationship is obtained between the log of the reaction rate and
the acid pKa (Figure 10). With a sufficiently strong driving force
for proton transfer the reaction rate constant becomes substrate
pKa independent (pKa < 8.6). The data in Figure 10 is limited to a
series of structurally related para-substituted aniline derivatives.
Figure 10. Second-order rate constants vs acid pKa for the reaction of
NiII-hydride with para-substituted aniliniums. The linear region between
pKa 12 to 8.6 has a slope of −0.7. Reprinted with permission from ref 73.
Copyright 2016 American Chemical Society.
3654
Perspective
Changing the proton source structure significantly affects its
reactivity (as will be shown in the following sections).
The effect of added base on reaction kinetics was explored.
When base is added to solution, the reaction kinetics were
observed to slow. A trend between amount of base necessary to
slow the reaction and acid pKa was observed. The higher the pKa,
the less base required to lower the observed reaction rate (when
pKa is greater than 8.6, reactivity of acids below a pKa of 8.6 do
not have a pKa dependence as illustrated in Figure 10).
3.3.2. Molecular Association. Two different forms of
molecular association were examined, homoconjugation and
dimerization (aggregation and heteroconjugation were also
considered for studies involving water). The list of proton
sources with recorded homoconjugation constants in the
working range of [Ni(PPh Ph
2 N2 )2]
2+
(pKa < 12) is limited, but
the effect could be examined through the comparison of 4-
cyanoanilinium (pKa = 7, log(KHC) = 0.1),73 p-toluenesulfonic
acid (pKa = 8.6, log(KHC) = 3),74 and dimethylformamidium
(pKa = 8.6, log(KHC) = 1.7).74 While this series of acids had only
small differences in their pKa values, the reaction rate constants
were found to be highly dependent on the homoconjugation
constants, with fast reaction rate constants observed for the acids
with larger homoconjugation constants (p-toluenesulfonic acid
(130 000 M−1 s−1) > dimethylformamidium (12 750 M−1 s−1) >
p-cyanoanilinium (750 M−1 s−1 )).73 In past work, the
acceleration of acid−base reactivity for acids with large
homoconjugation constants has been attributed to a lowering
of the “effective” pKa as a result of stabilization of generated
conjugate base via homoconjugation with acid.69,72,136,143−145
However, rate constants for this series span more than 2 orders of
magnitude, and this span is too large to be accounted for simply
by homoconjugation. Likely, larger homoconjugation constant
correlate with increased hydrogen bonding abilities, and these
acids may better stabilize the proton transfer transition state.
To our knowledge, proton source dimerization has yet to be
considered in the PCET fuel forming literature. While there are
no recorded dimerization constants for proton sources with a pKa
less than 12, carboxylic acids are known to dimerize in
acetonitrile and this generally results in a pKa for the dimerized
species that is ∼3.5 units lower than the monomer.64 No
dimerization constants are recorded for trifluoroacetic acid (pKa
= 12.6) and trichloroacetic acid (pKa = 10.8). However, the
reaction of trifluoroacetic and trichloroacetic acid with the NiII-
hydride is second-order in acid, as would be expected for a highly
reactive acid dimer with a very low dimerization constant. This is
an important finding as trifluoroacetic acid is often used in
electrocatalytic studies; indeed, many studies report second-
order kinetics with trifluoroacetic acid.136,146−151
3.3.3. Addition of Water to Acetonitrile Solutions. Because
the target for most H2 evolution electrocatalytic systems is to
operate in water, water is often intentionally added to acetonitrile
solutions during catalysis to probe catalyst water stability and
performance.140,152 Consequently, it is important to understand
how the addition of water affects the proton source being
employed. Two cases are considered here: (1) water becomes
protonated and thereby hydronium is available to act as a proton
source, or (2) water heteroconjugates with the proton source,
affecting its reactivity. Hydronium has a very low pKa in
acetonitrile (2.2), but the ability of water to form large aggregates
with concurrent stabilization of the hydronium ion significantly
increases its effective pKa with increasing water concentration.
Figure 11 demonstrates the influence of water on the rate
constant of reaction with NiII-hydride and acid over a range of
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Figure 11. Concentration of water versus observed rate constant for
1.25 mM triflic acid (pKa = 2.6), 1.3 mM dimethylformamidium
(DMFH+, pKa = 6.1), and 2.5 mM 4-cyanoanilinium (4-CN, pKa = 7).
Observed rate constants obtained from reaction with NiII-hydride to
form hydrogen. Reprinted with permission from ref 73. Copyright 2016
American Chemical Society.
water concentrations for three acids. triflic acid (pKa = 2.6),
dimethylformamidium (pKa = 6.1), and 4-cyanonanilinium (pKa
= 7) were compared; in each case, addition of water resulted in
hydronium formation, which showed a higher reaction rate than
the original proton source. Eventually, further increases in water
concentration began to shut down the reaction, as the excess
water reacts as a base in solution to hinder turnover, as discussed
above.73
Heteroconjugation of water to proton sources with higher pKa
values was investigated through the addition of water to solutions
of trifluoroacetic acid. The reaction rate decreased exponentially
with the concentration of water, suggesting the acid hetero-
conjugates to water. This chaotropic activity breaks up the
dimerization of trifluoroacetic acid.
3.4. Linear Free Energy Relationships in H2 Evolution.
For both the Co(dmgBF2)2(CH3CN)2 and [Ni(PPh Ph
2 N2 ) 2 ]
2+
catalysts, linear free energy relationships have been observed
between rate constants for elementary proton transfer steps and
acid pKa in acetonitrile, with larger rate constants observed for
stronger acids. Plots of log(k) vs pKa for these catalysts have
slopes that span −0.7 to −0.97. The physical interpretation of
these correlations is still under investigation, but the differences
likely reflect the nature of the proton transfer transition state. As
such, differences between the nucleophilic species reacting in
these proton transfer steps are reflected in these relationships.
As the thermodynamic potential for reduction of an acid to
hydrogen in acetonitrile depends linearly on the pKa of the acid
for structurally comparable acids,69,153 the larger rate constants
observed for stronger acids also correspond to larger over-
potentials for catalytic hydrogen production. As such, the linear
free energy relationships observed provide an experimentally
based visual representation of the catalytic activity in different
conditions. These relationships could prove useful in bench-
marking catalysts, and illustrate the power of detailed kinetic and
mechanistic studies.
3655
Perspective
4. CASE STUDIES: MODEL SYSTEMS TO INVESTIGATE
ELEMENTARY PCET REACTION STEPS
As detailed above, catalysis involves elementary steps whose
kinetics may be investigated by a variety of spectroscopic and
electrochemical methods. A key question for driving the design
of more energy-efficient catalysts is whether the elementary steps
may be controlled through rational design of catalysts or
experimental conditions. Toward this, efforts in our group have
focused on furthering cyclic voltammetry techniques for the
study of PCET systems.
Shifts in the applied potential at which reactivity is observed
are common in PCET systems (or all catalytic systems for that
matter), yet the reason for potential shifts can differ greatly.
Three separate factors, all dependent upon proton addition, are
presented herein: First, the appearance of total-catalysis
responses;71,92 second, a kinetic shift in the reduction potential
and loss of reversibility;24 and third, a thermodynamic shift in the
reduction potential.11 Distinguishing between these cases is not
always straightforward; we hope that presentation of these three
case studies can help aid researchers in elucidating the factors
that perturb peak location. Special emphasis is placed on the
thermodynamic potential shift, which in this case was found to
correspond to a concerted proton electron transfer
4.1. Total Catalysis Gives Rise to a Second Peak. As
noted above, cobaloxime has been reported to yield total catalysis
responses under specific conditions (Figure 12). This occurs
Figure 12. Example of a total catalysis waveform for the electrochemical
hydrogen evolution with 5 mM catalyst Co(dmgBF2)2(CH3CN)2 and 5
mM 4-cyanoanilinium in acetonitrile at 100 mV/s with 0.25 M
[Bu4N][PF6]. All of the acid is consumed near the reaction layer,
resulting in the appearance of initial catalytic current followed by the
CoII/I redox wave.
when the kinetics of catalysis are fast enough such that prior to
the primary redox wave the small amount of reduced catalyst (as
governed by the Nernst equation) consumes all of the available
substrate to produce product and regenerate the catalyst.
Consequently, the normal redox wave of the catalyst is observed
after the catalytic peak. Extracting accurate kinetic information
from the catalytic peak position in this case is possible but is
significantly restricted to a small parameter range; therefore,
more versatile methods like foot-of-the-wave analysis are
generally preferred.24,71 Assignment of a feature as total catalysis
can be confirmed via observation of the suspected catalytic peak
location as a function of acid concentration, catalyst concen-
tration, and scan rate.71
4.2. Kinetic Control over Peak Location. The mechanism
for the first elementary steps for the [Ni(PPh Ph
2 N2 )2]
2+
catalyst
discussed above was probed by cyclic voltammetry. While
[Ni(PPh Ph
2 N2 )2]
2+
is a catalyst for hydrogen evolution, catalytic
turnover can be shut off by the addition of excess conjugate base,
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ACS Catalysis Perspective

permitting investigation of the first proton transfer event.24 As Scheme 3. NiP2S2

shown in Figure 13, increasing acid concentration results in a

Figure 13. (A) Titration of a solution of 1 mM [Ni(PPh Ph 2+

2 N2 )2] and 1 M
aniline with increasing concentrations of anilinium results in a positive
kinetic shift of the reduction wave. (B) Plotting the shift versus
log[anilinium] gives a line with a slope of 33 mV/decade, consistent with
the theoretical slope of 30 mV/decade for an EC mechanism. Data taken
from ref 24.

positive shift of the NiI/0 reduction event due to the subsequent

chemical step: protonation of the Ni0 species. Plotting log[BH+]
vs the difference in peak potential yields a slope of 33 mV/
decade. This observation supports a stepwise bimolecular EC
reaction with initial Nernstian electron transfer to the Ni species
followed by irreversible reaction with solution acid BH+; the peak
location potential as a function of [BH+] can be described as25,154
RT ⎛ k1[BH ]RT ⎞
+
RT
Epeak = EI0/0 − (0.78) + ln⎜ ⎟
F 2F ⎝ Fυ ⎠ (12)
where E0I/0is the potential of electron transfer in the absence of
BH+, R is the gas constant, F is the Faraday constant, T
temperature, k1 is the rate of reaction of BH+ with reduced
catalyst, and υ is the scan rate. Analysis of the resulting shift vs
[anilinium] permitted evaluation of the protonation rate
constant as 1.2 × 106 M−1 s−1.24 Importantly, the slope of plots
of log([BH+]) vs the difference in peak potential is predicted by
eq 12 to be 30 mV/decadea close match for the experimentally
observed slope of 33 mV/decade. Analysis of experimental plots
of log([acid]) vs the difference in peak potential provides an
experimental means of testing if an EC mechanism is operative.
As the rate of the chemical step directly corresponds to the
magnitude of the peak shift, this type of potential shift is often
referred to as a kinetic shift.
4.3. Thermodynamic Control of Peak Location. The last
example discussed here is that of thermodynamically controlled
PCET. For a solution of a nickel bisphosphine dithiolate complex
(NiP2S2, Scheme 3) with stoichiometric triethylammonium,
reduction occurs at potentials much more positive and the
magnitude of current passed doubles (Figure 14A,B).11
Assuming no nickel−nickel interactions, two electrons and one
proton are added to each nickel molecule in this redox event. As
two-electron transfer is not observed in the absence of acid, the
3656
Figure 14. Analysis of reactivity of NiP2S2 with triethylammonium in
acetonitrile; data taken from reference.11 (A) Cyclic voltammograms at
100 mV/s of solutions of NiP2S2 with and without one equivalent of
triethylammonium. (B) Theoretical peak shift analysis based on a
stepwise ECE mechanism compared with real peak shift; current
integrations demonstrating two electron and one proton reactivity. (C)
Observation of a kinetic isotope effect upon addition of either 0.24 M
H2O or D2O to a solution of NiP2S2 with substoichiometric
triethylammonium.
stepwise EEC mechanism was ruled out. Three possible
mechanisms were then consideredECE, CEE, or the
concerted (EC)E. No protonation or association between the
nickel complex and acid was detected by either UV−vis or 1H
NMR spectroscopy, suggesting that a CEE mechanism was not
operative.
A ECE mechanism with an irreversible chemical step could
result in a large kinetic shift of the reduction event, especially with
a fast kinetic step. A kinetic shift was observed for the second case
study above with [Ni(PPh Ph 2+
2 N2 )2] . Digital simulations of an ECE
mechanism demonstrated that the magnitude of a reasonable
kinetic shift was lower than that observed experimentally (Figure
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ACS Catalysis
14B). This left the (EC)E mechanism as a plausible candidate
where the first proton and electron transfer together at a unique
potentialin other words, a thermodynamic effect. In the
literature, evidence for electrochemical CPET has been
supported by observation of a kinetic isotope effect where a
small amount of a protic solvent in the proteo or deutero form
was added to the solution.20,155−159 Comparison of the cyclic
voltammograms of solutions of NiP2S2 with either H2O or D2O
showed a small but clear KIE (Figure 14C), supporting a (EC)E
mechanism. It should be noted that while observation of an
electrochemical KIE supports a concerted mechanism, the lack of
a KIE does not rule out a concerted mechanism.
5. OUTLOOK: FUTURE DIRECTIONS FOR THE
ELUCIDATION OF PCET PROCESSES IN MOLECULAR
CATALYSTS
It is our hope that with increased accessibility to tools for
studying PCET processes, a greater research effort will be
directed at investigating the PCET pathways involved in the
catalytic transformations associated with fuel production. Both
electrochemical and spectroscopic methods were presented, with
a focus on applications of these methods and potential pitfalls.
The case studies briefly discussed above illustrate the range of
PCET mechanisms thus far explored by our group. Observation
of apparent CPET in the reactivity of NiP2S2 has provided
interesting directions for our future researchcan CPET be
intentionally promoted by varying catalyst electronics or acid
strength? As the CPET pathway circumvents high energy
intermediates, inducing CPET may result in catalysts with
decreased required operating potentials and thus higher
efficiencies. Current work seeks to gain control over PCET
reaction mechanisms through experimental parameters.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: dempseyj@email.unc.edu.
Author Contributions
‡ (27) Costentin, C.; Drouet, S.; Robert, M.; Savéant, J. M. J. Am. Chem.
These authors contributed equally (N.E. and B.D.M).
Funding
This work was supported by the University of North Carolina at
Chapel Hill and the David and Lucile Packard Foundation.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the University of North Carolina at
Chapel Hill. J.L.D. acknowledges support from a Packard
Fellowship for Science and Engineering.
■
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DOI: 10.1021/acscatal.6b00778
ACS Catal. 2016, 6, 3644−3659