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The Degree of Rate Control: A Powerful Tool for Catalysis Research

Charles T. Campbell*
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States

ABSTRACT: The “degree of rate control” (DRC) is a mathematical approach for analyzing multistep reaction mechanisms that
has proven very useful in catalysis research. It identifies the “rate-controlling transition states and intermediates” (i.e., those
whose DRCs are large in magnitude). Even in mechanisms with over 30 intermediates and transition states, these are generally
just a few distinct chemical species whose energies, if they could be independently changed, would achieve a faster net reaction
rate to the product of interest. For example, when there is a single “rate-determining step”, the DRC for its transition state (TS)
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is 1, which means (by definition) that if this TS’s energy could be decreased by kBT (where kB is Boltzmann’s constant and T is
temperature), the net rate would increase by a factor of e. Because the (relative) energies of these key adsorbed intermediates and
transition states can be adjusted by modifying the catalyst or solvent, or even a reactant’s molecular structure, the DRC values
provide important ideas for catalyst improvement. The species with large DRCs are also the ones whose energetics must be most
accurately measured or calculated to achieve an accurate kinetic model for any reaction mechanism. A tutorial on DRC analysis,
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the calculation of DRCs, and examples of the applications of DRCs in catalysis research is presented here. Applications of DRC
analysis include the following: clarifying reaction kinetics, improving the accuracy of computational models, improving reaction
conditions, improving choice of oxidant in selective oxidation, incorporation in algorithms which calculate net reaction rates of
multistep mechanisms without solving the differential equations involved, and high-throughput computational screening of
catalyst materials. Because DRC values can be determined experimentally, a full microkinetic model is not required to take
advantage of DRC analysis.

1. INTRODUCTION
In analyzing chemical kinetics involving multistep reaction
mechanisms, discussion of the rate-determining step (RDS) has
proven to be very powerful. When there is a single RDS and
one knows which step it is, one can often derive a simple rate
law for the net reaction’s rate involving only a few kinetic and
thermodynamic parameters, a common practice in textbooks on
kinetics. Furthermore, knowing the RDS gives fruitful ideas for
modifying the reaction conditions or catalyst to achieve a better
rate. The degree of rate control (DRC) is a tool for analyzing
reaction mechanisms and kinetics which serves a very similar
purpose to determining the RDS, but in a much broader and
more general way.
I conceived of and introduced the degree of rate control
initially in a paper in 1993, in response to a question by a
referee of an invited review paper I had submitted to the
proceedings of a symposium held in honor of Haldor Topsoe’s
80th birthday.1 I remain eternally grateful to that referee, who
wanted to know how I had determined which step was the
RDS, since I had mentioned the RDS for several catalytic
reactions in that paper. In response, I added a paragraph in
which I tried to articulate what had been going on in my mind
for a number of years when analyzing net reaction kinetics in
the context of some reasonably good knowledge of the
elementary-step kinetics involved. To explain this, I introduced
the “degree of rate control for elementary step i,” XRC,i, which I
defined as1
ki ⎛ ∂r ⎞ ⎛ ∂ln r ⎞
XRC, i = ⎜ ⎟ =⎜ ⎟
r ⎝ ∂ki ⎠ ⎝ ∂ln ki ⎠k
kj≠i , Ki j≠i , Ki
where r is the net reaction rate to the product of interest, and
the partial derivative is taken holding constant the rate
constants, kj, for all other steps j ≠ i and the equilibrium
constant, Ki, for step i (and all other steps too, since their
forward and reverse rate constants are held fixed). Note that
keeping Ki constant means that the forward and reverse rate
constants for step i, ki and k−i, both must be varied by equal
factors so that their ratio remains constant. The reaction
conditions (e.g., temperature, concentrations) are also held
constant here.
By this definition above, XRC,i equals the relative increase in
the net rate per relative increase in the rate constant for step i
(differentially). The larger the numeric value of XRC,i is for a
given step, the bigger is the influence of its rate constant on the
overall reaction rate r. A positive value indicates that increasing
ki will increase the net rate r; such steps are termed rate-limiting
steps (RLS). A negative value indicates the opposite; such steps
are termed inhibition steps. It turns out that for typical
textbook cases of reaction mechanisms where there is a single
RDS, XRC,i = 1 for the RDS and zero for all other steps.2
To my knowledge, no other method had been developed
which so unambiguously defines the rate-determining step.
However, it is much more powerful than just doing that, as
shown below. Without my knowledge until recently, a quantity
with the same definition as XRC,i had already been introduced
by K. J. Laidler in the Journal of Chemical Education in 19883
(which he attributed there to a personal communication from
W. J. Ray), where he called it instead the “control function” (or
“control factor”) for step i, “CFi.” To my knowledge, neither
Received: January 12, 2017
(1) Published: March 3, 2017

© 2017 American Chemical Society 2770 DOI: 10.1021/acscatal.7b00115

ACS Catal. 2017, 7, 2770−2779
ACS Catalysis Viewpoint

concept was used to a significant extent, probably due to the

fact that its real applications awaited modern computational
power for theoretical rate predictions. While eq 1 looks much
like equations used in standard differential sensitivity analyses
by engineers to ascertain the sensitivity of outputs of a model to
one input parameter, it also represents quite an advance
compared to that, since the entities that are held constant in
this partial derivative ensure thermodynamic and kinetic
consistency. As we show next, these are held constant because
XRC,i is a conceptualization of the effect of changing the
potential energy surface upon which the reaction proceeds, so
that DRC has a deeper physical meaning than any such usual
“sensitivity” for a parameter in a model.
Within transition state theory, the rate constant ki is given
by4
ki = (kBT /h)exp( −ΔGi 0,TS/RT ) (2) Figure 1. Schematic standard-state free-energy diagram for the
reaction AC(g) + B(g) → AB(g) + C(g), showing an incremental
where h is Planck’s constant, ΔGi0,TS
is the difference in
decrease in the standard-state free energy of one transition state TS3,
standard-state molar free energy between the transition state as implied by the definition of the degree of rate control for that step
and the reactants for step i, R is the universal gas constant, and (XRC,TS3) in eq 5. Also shown is the change implied by the definition
T is the absolute temperature. (Sometimes a transmission of the degree of rate control for one reaction intermediate, AB*
coefficient κ is added in front, and for second-order reactions (XRC,AB*), as defined in eq 6, ref 2. Note that such reaction energy
this must be divided by the standard-state concentration.) diagrams require element balance at each step, so that the same
Taking the logarithm of both sides gives number of atoms of each element must be present at each energy
minimum and maximum as in the reactants and products. Thus, some
ln ki = ln(kBT /h) − (ΔGi 0,TS/RT ) (3) species are necessarily carried along as spectators in individual steps, as
is C* in the step across TS3.
Taking the derivative of both sides (holding temperature
constant) gives
already pointed this out in a 2001 paper where I showed the
d(ln ki) = d(ln(kBT /h)) − d(ΔGi 0,TS/RT ) advantages of DRC analysis compared to analysis of DeDonder
Relations for identifying the RDS.5 There, I wrote that the
= −d(ΔGi 0,TS/RT ) (4)
mathematical operation associated with finding the DRC for a
Thus, eq 1, which defines XRC,i, can be rewritten in terms of step “is analogous to finding an additive which somehow
the standard-state free energy of activation for step i (ΔGi0,TS), magically stabilizes the transition state to that one elementary
and the standard-state free energy for its transition state, Gi0,TS, step without affecting the energies of any other adsorbed
as species.”
When the DRC is defined in this way as the change in net
ki ⎛ ∂r ⎞ ⎛ ∂ln r ⎞ rate due to the decrease in energy of one of the maxima in the
XRC, i = ⎜ ⎟ =⎜ ⎟ reaction energy diagram, it suggests that one can extend this
r ⎝ ∂ki ⎠ ⎝ ∂ln ki ⎠k
kj≠i , Ki j≠i , Ki concept to the minima in reaction energy diagrams too. Two
⎛ ⎞ ⎛ ⎞ engineers from Denmark, Drs. Carsten Stegelmann and Anders
⎜ ∂ln r ⎟ ⎜ ∂ln r ⎟ Andreasen, realized this and asked for my help in developing a
=⎜ ⎟ =⎜ ⎟ degree of rate control that applies instead to intermediates
⎜ ∂ −ΔGi ⎟ ⎜ ∂ −Gi ⎟
0,TS 0,TS

⎝ (
RT ) ⎠k
j≠i , Ki
⎝ ( )
RT ⎠G0,TS , G 0
j≠i m (5)
rather than transition states. We thus developed an equivalent
definition for the degree of rate control of any intermediate, n,
in a reaction mechanism, XTRC,n, as:2
The partial derivative in the final equality here is taken
holding the Gibbs free energy of all other transition states j ≠ i ⎛ ⎞ ⎛ ⎞
and all intermediates m constant, which is the same as holding 1 ⎜ ∂r ⎟ ⎜ ∂ln r ⎟
the rate constants, kj, of all other steps j ≠ i and the equilibrium X TRC, n = ⎜ ⎟ =⎜ ⎟
r ⎜ ∂ −Gn0 ⎟
0
⎜ ∂ −Gn ⎟
constant, Kj, of all steps j constant. This is best understood by ⎝ ( )
RT ⎠G 0
m ≠ n , Gi
0,TS ⎝ ( )
RT ⎠G 0
m ≠ n , Gi
0,TS
inspection of the standard-state free-energy diagram for a
typical reaction shown in Figure 1, recognizing that this (6)
requires holding the equilibrium constant for all steps i and j where the partial derivative is taken holding constant the
constant, and that the equilibrium constant for any step n, Kn, standard-state free energy of all other intermediates m ≠ n
equals exp(−ΔGn0,rxn/RT), where ΔGn0,rxn is the difference in (Gm0), all reactants, all products, and all transition states i
standard-state molar free energy between the products and the (Gi0,TS). Since the free energy of intermediates is inherently a
reactants for step n. This final equality in eq 5 shows that XRC,i thermodynamic quantity, whereas that for a transition state is a
can be equivalently defined as the relative increase in the net kinetic quantity, we initially referred to this is as the degree of
rate to the product of interest due to a (differential) decrease in thermodynamic rate control of intermediate n, hence the added
the standard-state free energy for the transition state for step i “T” in the subscript XTRC,n. By definition, it is the relative
(divided by RT), while holding constant the standard-state free increase in the net rate to the product of interest per
energy for all other transition states and all intermediates. I had (differential) decrease in the standard-state free energy for
2771 DOI: 10.1021/acscatal.7b00115
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ACS Catalysis
intermediate n (divided by RT), while holding constant the
standard-state free energy for all other intermediates and all
transition states. We did not realize at that time that a very
similar extension of my degree of rate control concept had
already been made by Kozuch and Shaik in 2006,6 who
introduced the “degree of turnover frequency control of each
intermediate” specifically defined only for analyzing multistep
catalytic mechanisms, so that the intermediates they consider
are always bound to a catalyst (see also ref 7). Kozuch and
Shaik also had presented many useful applications of this
concept, as well as ideas that evolve from it.8−10 Our XTRC,n
concept is more general than this, in that it is not intended to
be limited to catalytic reactions and is generally appropriate for
any multistep reaction mechanism with any type of
intermediates, whether bound to a catalyst or not.
Because of the extreme similarity between the definitions
above for XRC,i and XTRC,n, we now most commonly express
these same concepts in terms of a more general definition for
the degree of rate control that applies to any species i, whether
it be a transition state or intermediate. We define this
generalized degree of rate control for species i (DRCi or
simply Xi) as
⎛ ⎞ ⎛ ⎞
1 ⎜ ∂r ⎟ ⎜ ∂ln r ⎟
DRCi = Xi = ⎜ ⎟ =⎜ ⎟
r ⎜ ∂ −Gi0 ⎟ ⎜ ∂ −Gi
0
⎟ would this increase the net rate?
⎝ RT ( ) ⎠G0
j≠i
⎝ RT( ) ⎠G0
j≠i
⎛ ⎞
⎜ −∂ln r ⎟ EXPRESSION
=⎜ 0
⎟
⎜ ∂ Gi ⎟
⎝ RT ( ) ⎠G0
j≠i (7)
where the partial derivative is now taken holding constant the
standard-state free energy of all other species (intermediates,
transition states, reactants, and products), j. Its value describes
the relative increase in net rate due to the (differential)
stabilization of the standard-state free energy for species i,
holding all the other species’ energies constant. Thus, eq 7
probes the importance of one species’ free energy in the full
standard-state free-energy surface for the full reaction. It gives
the same value for the DRCi (or Xi) as XRC,i in eq 5 and XTRC,i
in eq 6. Although the final expression in eq 7 is mathematically
equivalent to the middle expression, the final expression is
recommended for practical implementation. This is because it is
impossible to stabilize the transition state for elementary steps
that have no real standard-state free-energy barrier between
reactants and products (as is common in molecular adsorption
and desorption, for example) without also stabilizing either the
reactant or the product. That is, it is physically impossible to
perform the mathematical operation as written in the middle
expression. In such cases, one must instead destabilize the
transition state (i.e., introduce a small free-energy barrier) and
change the sign on the resulting change in relative rate, as done
in the final expression here.
The beauty of eq 7 is thus that it directly connects the net
rate with individual energies that one can hope to control to
advantage. If we take the reactants as the reference state of zero
standard-state free energy and enthalpy, each standard-state
(molar) free energy Gi0 breaks up into a sum of an enthalpy
contribution (ΔHi0) and an entropy contribution (−TΔSi0) as
Gi0 = ΔGi0 = ΔHi0 − TΔSi0, where Δ refers to differences
relative to the reactants. Note that ΔHi0 = ΔUi0 + P(ΔVi0),
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where U is the molar internal energy, P is the standard pressure
(1 bar), and V is molar volume. If one modifies the catalyst or
solvent in some way, it is usually the case that the molar
entropy and molar volume of all species i change so little that
TΔΔSi0 and P(ΔΔVi0) are negligible compared to ΔΔUi0, in
which case the change in Gi0 due to this modification is
essentially given by ΔGi0 = ΔUi0, where Δ now refers to
differences induced by the modification. Because calculations
(like density functional theory, DFT) and experiments allow us
to estimate the effect of such modifications on ΔUi0, eq 7
provides a route to quantitatively estimate the effects of such
modifications on the net rate and selectivity, if one knows DRCi
before modification (see below).
The degree of rate control for a transition state (or
elementary step) answers the question: Suppose one could
change the catalyst with a modifier that differentially lowered
the energy (i.e., standard-state free energy) of the transition
state for that one elementary step, without changing any other
such energy. By what relative amount would this increase the
net rate, per unit change in energy (in units of RT)? Similarly,
the degree of rate control of an intermediate answers the
closely related question: Suppose one could introduce a catalyst
or catalyst modifier that differentially lowered the energy (i.e.,
standard-state free energy) of one intermediate, without
changing any other such energy. By what relative amount
2. AN EXAMPLE OF DRC ANALYSIS OF A SIMPLE
MECHANISM WITH AN ANALYTICAL RATE
To demonstrate the use of eq 7, consider a simple Langmuir−
Hinshelwood mechanism with one rate-determining step
(RDS) and all other steps quasi-equilibrated:
A + * ⇌ A* (fast to equilibrium) (reaction 1)
B + * ⇌ B* (fast to equilibrium) (reaction 2)
A* + B* ⇌ AB* + * (RDS) (reaction 3)
AB* ⇌ AB + * (fast to equilibrium) (reaction 4)
where * denotes a free surface site, X is a gas phase species, and
X* is a surface-bound intermediate. By applying the quasi-
equilibrium approximation under conditions where step 3 is
irreversible and the surface is almost saturated with A*, we have
shown that this gives a simple rate law for the rate to make AB2:
K p
r = k3 2 B
K1 pA (8)
where pX is the partial pressure of X. Using the above
expressions for the rate constant for step i (ki = (kBT/h)
exp(−ΔGi0,TS/RT)), and the equilibrium constants for step n
(Kn), equals exp(−ΔGn0,rxn/RT)), and remembering that the
gaseous reactants are taken as the reference of zero free energy,
this can be written as
Performing the partial derivative in eq 7 using this rate
expression to calculate the degrees of rate control gives that
DOI: 10.1021/acscatal.7b00115
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DRCTS3 = 1, DRCA* = −2 and DRCi = 0 for all other transition
states and adsorbates. The RDS has a DRC of +1 as expected.
The DRC of A* is −2, which is minus 1 times the number of
times GA*0 enters the rate eq (eqs 8 and 9) via rate constants
and equilibrium constants (= 2 here) times the fractional
coverage of sites by A* (= ∼1.0 here). In general, we f ind that
the DRC for adsorbed intermediates is some small negative integer
times the f ractional coverage of sites by that adsorbate, so that it is
essentially zero for adsorbates at low coverage and a small negative
integer for adsorbates that saturate the surface.2,11 It is not yet
clear how to predict the value of that integer when there is not
a single RDS.
This analysis reveals that the key to catalyst improvement
and design is to stabilize key transition states (those with large
positive DRCs) without stabilizing key intermediates (those
with large negative DRCs) too much, or to destabilize those
key intermediates without destabilizing related key transition
states too much. This is similar to the well-known Sabatier
Principle, as has been shown beautifully by Dumesic.12
However, DRCs are more quantitative in their applicability,
and they are more general because they can include multiple
species of each type. One could also improve the catalysts by
destabilizing the transition states of inhibition steps (those with
large negative DRCs).
While we have calculated the DRCs above using rigorous
math to take the partial derivatives of an analytical rate
expression, in practice the DRCs are usually determined instead
numerically, by using a computer and finite-difference methods
to take the numerical derivative of a rate that is typically
determined from a numerical solution to the systems of
differential equations defined by the microkinetic model and all
of its parameters.
It is important to recognize that DRCs can also be estimated
experimentally. This is easiest to see for the DRCs for
adsorbates, which are just proportional to their fractional
coverages, which can be measured by a wide variety of
experimental methods. However, it is also common to
determine the rate-determining step (RDS) for a reaction
from a variety of experimental measurements (e.g., reaction
orders in reactant concentrations, comparing the activation
energy of the net reaction to that for isolated elementary steps,
etc.). The transition state for the RDS has a DRC of 1, leaving
the DRCs for the other steps near zero (unless the mechanism
has branching). There are many situations, however, where
there is not a single RDS, most commonly when two steps have
large DRCs that sum to nearly 1. This is more challenging
experimentally but is sometimes seen by increasing or
decreasing a reactant concentration or temperature, which
can tune the system between conditions where one of these
steps is the RDS, and then the other becomes the RDS, with a
mixture of two strongly rate-controlling steps in between (and
often a rate maximum).
3. PROPERTIES OF THE DEGREE OF RATE CONTROL
(DRCI)
We have shown that for previously analyzed mechanisms at
reaction conditions where there is a single rate-determining
step (e.g., in numerous textbook examples where an analytical
rate expression was derived for a mechanism), the degree of
rate control is equal to one for the transition state for that step,
and zero for all other steps,2 as also shown for one example
above. There are many studies of multistep mechanisms which
have shown that the degree of rate control is nearly zero for the
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Viewpoint
vast majority of steps. For example, Agarwal, Sanchez-Castillo,
Madon, Dumesic et al.13 showed that in 2-methylhexane
conversion over USY zeolite for ∼30% conversion at 773 K,
only 5 of the 36 steps in the simplified mechanism have DRCs
that exceed 0.06, with one step most dominant (DRC near 0.5).
They also analyzed a 371-step model for conversion of
isobutane over USY zeolite, and they found only 20 steps
that had DRCs that exceeded 0.1 even when their individual-
product DRCs were summed over all the seven different
products.14
The degree of rate control of transition states (for the rate to
produce any one product or to consume any one reactant)
seems to be conserved when summed over all steps i (i.e., all
transition states) in the mechanism:
∑ XRC,i= ∑ DRCi = 1
steps TSs (10)
Baranski has proven this rule for parallel (series) reaction
mechanisms,15 and Dumesic has proven this rule more
generally for any reaction scheme that leads to a single net
reaction.12 This has also been found in a wide range of studies
where microkinetic models were analyzed for their DRCs (for
example, see refs 2,11,13−24), including cases where branching
leads to more than one net reaction and selectivity becomes an
issue.
In collaboration with Per Stoltze’s group at Aalborg
University and N.C. Schiødt at Haldor Topsøe, we performed
a study of the selective oxidation of ethylene with O2 to
ethylene epoxide over metallic Ag catalysts which provides an
excellent example of the power of DRC analysis for such
branching reactions.23 In this case, the alternate reaction
produces the thermodynamically favored product, CO2 + H2O.
We used a modified version of the mechanism first put forth by
Linic and Barteau,16 who identified the key intermediate as an
oxametallacycle (*CH2CH2O*) based on DFT calculations. In
our model, the kinetic parameters for the 17 elementary steps
in forward and reverse were determined experimentally, some
by fitting this microkinetic model to the net reaction rate data.
The degrees of rate control are shown in Figure 2 versus
temperature. This common intermediate is produced via steps
2 and 5 (that are rate-controlling for both ethylene
consumption and ethylene epoxide production) before the
branching steps 7 and 8 that determine selectivity. Step 7 is
oxametallacycle ring closure, leading to the desired epoxide,
whereas step 8 is H migration on theh oxametallacycle, which
leads to complete combustion products. Note that the DRCs
for these branching steps mirror each other exactly, with
opposite signs. The negative DRC for step 8 indicates that it
inhibits epoxide production (by consuming the oxametallacycle
to make CO2 before it can make the epoxide). This occurs
whenever the selectivity is determined in a branching
competition that occurs after the steps that control the rate
of reactant consumption. That this occurs here after the steps
that control the rate of ethylene consumption is consistent with
our earlier experiments on Ag(110), which showed that the
activation energies and reaction orders in both reactants for the
rates to both products varied with the coverage of chlorine
adatoms in very similar ways, over the same range of chlorine
coverage where selectivity improved dramatically up to
80%.25,26 In more complex mechanisms, the DRCs for such
branching steps do not always mirror each other with opposite
signs as in this simple example.
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ACS Catalysis Viewpoint

sum to a number exceeding 1 here only because CO* and C*

occupy different types of sites in this microkinetic model.

4. THE DEGREE OF SELECTIVITY CONTROL (XSC,i)

We previously extended the definition of the degree of rate
control in eq 1 to similarly define the degree of selectivity
control for step i, whereby the net rate r was just replaced
throughout eq 1 with the selectivity to the desired product P
from the most valuable reactant R, S = rP/rR, where rP is the
rate of production of P and rR is the rate of consumption of R
(scaled by the stoichiometric ratio of P:R).27 We now extend
the definition of the more generalized degree of rate control for
species i in eq 7 to define the degree of selectivity control for
species i (DSCi) as follows:

Figure 2. Degrees of rate control for the rate of producing ethylene ⎛ ⎞ ⎛ ⎞ ⎛ ⎞

epoxide for the rate-controlling elementary steps (transition states) 1 ⎜⎜ ∂S ⎟⎟ ⎜ ∂ln S ⎟
⎜ ⎟
⎜ −∂ln S ⎟
⎜ ⎟
DSCi = = =
versus temperature at industrial reaction conditions (pO2 = pC2H4 = 100 S ⎜⎜ ⎜⎛ −Gi0 ⎟⎞ ⎟⎟ ⎜⎜ ⎜⎛ −Gi0 ⎟⎞ ⎟⎟ ⎜⎜ ⎜⎛ Gi0 ⎟⎞ ⎟⎟
∂ RT ∂ RT ∂ RT
⎝ ⎝ ⎠⎠ 0 ⎝ ⎝ ⎠⎠ 0 ⎝ ⎝ ⎠ ⎠G0
kPa). Values for the 12 other elementary steps are very close to zero, G j≠i G j≠i j≠i
so they are not shown. The dashed curves for branching steps 7 and 8 ⎛ ⎞ ⎛ ⎞ ⎛ ⎞
would be at zero too if the degree of rate control for the rate of ⎜ −∂ln(r /r ) ⎟ ⎜ −∂ln r ⎟ ⎜ −∂ln r ⎟
consumption of ethylene were plotted here instead. Step 13 is the RDS =⎜ P R ⎟
=⎜ P⎟
−⎜ R⎟
⎜⎜ ⎛ G0 ⎞ ⎟ ⎜⎜ ⎜⎛ Gi0 ⎟⎞ ⎟⎟ ⎜⎜ ⎜⎛ Gi0 ⎟⎞ ⎟⎟
for a separate parallel pathway for ethylene combustion that makes a ∂⎜ RTi ⎟ ⎟ ∂ RT ∂ RT
⎝ ⎝ ⎠ ⎠ ⎝ ⎝ ⎠ ⎠G0 ⎝ ⎝ ⎠ ⎠G0
very minor contribution to the rate of combustion and whose nature is Gj0≠ i j≠i j≠i
poorly understood. Modified from ref 23. = DRCi ,P − DRCi ,R (11)

where DRCi,P and DRCi,R are the degees of rate control of

species i for the rates of making P and consuming R,
As noted above, the DRC for adsorbed intermediates is
respectively. The value of DSCi (= DRCi,P − DRCi,R) describes
generally a negative integer times the fractional coverage of sites
the relative increase in net selectivity to P from R due to the
by that adsorbate, so that it is essentially zero for adsorbates at
(differential) stabilization of the standard-state free energy for
low coverage and a large negative integer for adsorbates that
species i (either one transition state or one stable adsorbed
saturate the surface,2,11 unless there is a branching competition.
intermediate) holding all other species’ energies constant.
Table 1 shows an example set of DRC values for steady-state
methane steam reforming over Rh(211) computed using a
microkinetic model based on DFT energies.11 Note that the 5. USING THE DEGREES OF RATE CONTROL TO
DRCs are nearly zero for all but four species. The DRCs for the IMPROVE MICROKINETIC MODELS
TSs sum up to 1.0 as expected. The DRCs for adsorbates are Thanks to successes of density functional theory with periodic
equal to their factional coverages times − 1. These coverages boundary conditions (DFT) in calculating relatively accurate
reaction energy diagrams for catalytic reactions on surfaces,
Table 1. Degrees of Rate Control for All Intermediates and microkinetic models for reaction mechanisms involving many
Transition States Computed for Methane Steam Reforming elementary steps have become very common in the past 20
over Rh(211)a years.2,11,13−24,28−43 Because these highly efficient computa-
tional codes for calculating the energies of adsorbed
species Xi species Xi
intermediates and transition states still have some problems
intermediates transition states with energy accuracy,44 one would prefer to use more accurate
CO*s −0.76 C−O* 0.87 (and computationally more expensive and time-demanding)
C*f −0.54 H−CH3* 0.11 quantum mechanical methods when possible. Greeley’s group
CH*f −0.01 H−OH* 0.01 has shown that DRCs provide a highly efficient way to
H*h −0.01 CO-H* 0.00 approach such improvements in energy accuracy. By first
O*s 0.00 H−C* 0.00 calculating the DRCs from a microkinetic model based on a
OH*s 0.00 H−CH* 0.00 lower-accuracy but much faster version of DFT, they identified
CH3*t 0.00 H−CH2* 0.00 the few adsorbates and adsorbed transition states with large
CH2*t 0.00 H−CO* 0.00 DRCs. Since these are the only species whose energies affect
HCO*s 0.00 C−OH* 0.00 the net rate, they then recalculated their energies with a more
COH*s 0.00 O−CH* 0.00 accurate but much more computationally demanding method,
H−H* 0.00 HSE06.45,46 This clever approach has great potential for
O−H* 0.00 markedly improving rate predictions based on DFT with only
moderate increases in computational costs.
a
Reaction conditions are T = 773 K, PCO = 0.050 bar, PH2 = 0.15 bar, The degree of rate control is similarly a powerful aid to the
PCH4 = PH2O = 0.40 bar. Superscripts on adsorbates correspond to development of more accurate microkinetic models based on
different types of sites. Dashes in transition states correspond to the experimental measurements of elementary-step energetics,
bonds that are being broken/formed in the adsorbed species. From ref since its values identify which intermediate and transition
11. state energies are most important to measure with high
2774 DOI: 10.1021/acscatal.7b00115
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ACS Catalysis
accuracy. It offers many opportunities for theory and
experiment to synergistically interact.
6. A NOTE REGARDING STANDARD STATE
CONCENTRATIONS AND ENTROPIES
Note that the definition of DRC in eq 7 refers to “standard
state” free energies. Indeed, knowing the free energies (or
energies and entropies) of the standard states for all the
adsorbates and transition states is really required for micro-
kinetic modeling, whether or not DRC analysis is involved.
Here we use the usual definition of standard state in
thermodynamics, so that for each species, a specific reference
condition must be defined, which includes in its choice a
specific standard-state concentration value (which affects the
entropy). For example, for ideal gases in mixtures, that is
typically taken to be the pure gas at one bar pressure and the
same temperature. The standard state of a solute in a liquid
solution is often taken to be unit mole fraction if the solution
resembles an ideal solution, but for other solutions where the
solute−solvent interactions are quite different than solute−
solute interactions, it is better to use some ideally dilute
solution reference state, a hypothetical state where the solute’s
concentration is either unit mole fraction or one molar
concentration, but where its energy is the same as if it were
ideally dilute (surrounded by solvent only). For adsorbates, the
situation can be rather complicated. They are often treated with
the 2D ideal gas (or free translator) model or the 2D ideal
lattice gas (or localized oscillator) model. These represent two
limiting behaviors of the real situation for adsorbates on solid
surfaces, which are more accurately described as hindered
translators since there are periodic energy barriers for adsorbate
translation parallel to the surface.4,47 We recently described a
simple extension of the ideal 2D gas model to a more realistic
ideal hindered translator model, which enables easy but much
more accurate estimations of the partition function and entropy
of adsorbates.47 Depending on the mechanism, it is sometimes
necessary to intermix these different adsorbate models (ideal
2D gas, ideal 2D lattice gas and ideal hindered translator)
within the same equilibrium constant or rate constant
expression. This requires great care to ensure that consistent
choices of standard-state concentrations are used throughout.
We recently derived expressions for equilibrium constants and
rate constants within transition state theory (TST) using both
partition functions and standard-state entropies, in a self-
consistent way that can treat all three models simultaneously.4
That formalism enables the mixing of these models, using
activities instead of concentrations to do so. We showed there
that a standard state for 2D (and 1D) ideal gases defined such
that their translational entropy is 2/3 (or 1/3) that for the
corresponding ideal 3D gas offers intuitive advantages for
estimating equilibrium and rate constants for adsorbates. This
standard-state concentration of the ideal 2D gas is approx-
imately the 2/3 power of the standard state concentration of
the corresponding 3D ideal gas (i.e., the concentration at the
standard pressure of 1 bar at that temperature).4
7. WEB-ACCESSIBLE, OPEN-SOURCE CODE FOR DRC
ANALYSIS AND ESTIMATION OF ENTROPY
Medford, Shi, Hoffmann, Lausche, Fitzgibbon, and Bligaard in
Jens Nørskov’s group have developed a powerful, open-source
catalytic (and electro-catalytic) kinetics code called “Cat-
MAP”.48 It is accessible for free online (https://github.com/
2775
Viewpoint
SUNCAT-Center/catmap), and it includes a tool for DRC
analysis of microkinetic models. The code is used quite
extensively in academia and industry. It is now being modified
to also include methods for calculating standard-state entropies
of adsorbates (and adsorbed transition states) using the
hindered translator approximation mentioned above.
8. A NOTE REGARDING BEP RELATIONS AND OTHER
SCALING RELATIONS
One would like to alter a catalyst or the solvent with the aim of
changing the energy of a specific transition state or intermediate
to achieve a higher rate or selectivity, chosen based on
knowledge of the degrees of rate control. However, one should
recognize that stabilizing a transition state will generally also
stabilize the reactant and/or product of that step, and vice
versa. These energies (or free energies) are connected through
the Brønsted-Evans−Polanyi (BEP) relations24 (or linear free-
energy relations49,50), which state that the change in the
activation (free) energy for an elementary step (in this case, due
to changing the material) are proportional to the change in its
net reaction (free) energy, with a slope between zero and unity.
Depending on the values of this slope and the values of the
DRCs, one can find cases where real gains can be achieved in
the net reaction rate or selectivity, but BEP relations generally
make it more difficult. For example, whenever there is a single
rate-determining transition state and a single rate-controlling
adsorbate, changing the catalyst to make it less noble will
stabilize this transition (increasing the rate) while simulta-
neously stabilizing this adsorbate (decreasing the rate). This
trade-off suggests an optimum catalyst that is neither too
aggressive nor too noble, just as expected based on the Sabatier
Principle.24
Bligaard, Norskøv, and co-workers have discovered BEP and
many other linear scaling relations among the energies of
adsorbed intermediates and transition states as estimated with
DFT calculations, which even enabled them to estimate net
catalytic reaction rates on different materials using only two
descriptors for each material (typically its adsorption energies
to C, O, N, or H atoms).24,28,29,51−56 This was possible due to
the fact that the energy of every adsorbate and transition state
in the mechanism could be estimated as a linear combination of
these two descriptors.
When such linear scaling relations are used in microkinetic
models, it means that there are fewer independent variables in
rate predictions for different materials than the energies of each
adsorbate and transition state on each material, since many of
these are coupled by their scaling relations. Nørskov, Bligaard,
and Kleis 55 therefore introduced an extension of the
generalized DRC concept to define the “degree of catalyst
control for descriptor i,” XCC,i, in terms of the materials’ mutually
independent underlying descriptors, where the definition of
XCC,i has the exact same form as eqs 5, 6, and 7, except now the
Gi0 in the denominators in these equations is the value of
descriptor i (energy of descriptor i).
This concept of the “degree of catalyst control” makes it
quickly obvious that when materials strictly follow such linear
scaling relations, there must be serious constraints on our
ability to find better catalysts. Bligaard et al.56 pointed out that
“the mere existence of linear scaling relationships within a
certain class of materials severely limits our ability to find better
catalysts within that class. The activity of even the best material
is inevitably constrained, as dictated by the scaling relation-
ships.” This was recognized previously by Nørskov’s group,
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ACS Catalysis
who further pointed out the advantages of finding new classes
of materials that break the limitations of linear scaling for
conventional classes of materials, and even offered suggestions
on how one might “break the scaling relations.”57−59
Phillip Christopher’s group has included BEP and other
linear scaling relationships in DRC analysis, and they developed
an approach to identify the relevant rate- or selectivity-
controlling steps that are tunable within the conf ines of such
linear relations between kinetic parameters.60 They also extended
that approach to the degree of selectivity control.61
9. APPLICATIONS OF DRC ANALYSIS
Analyses of DRCs have been used on many occasions to gain
insights into reaction mechanisms and ways to improve
catalysts (including electrocatalysts) or catalytic processes. Its
power in such applications has been discussed in some detail by
Nørskov, Bligaard, and Kleis.55 DRC analysis is even included
in some undergraduate Chemical Engineering classes, as
pioneered by James Dumesic at the University of Wisconsin.
In 2011, Kozuch and Shaik8 developed an “Energy Span
Model” based on DRCs in a paper which has already been cited
over 250 times, mainly in the context of homogeneous catalysis.
It neglects entropic differences between species, which is easier
to do when all the species are in liquid solution and the choice
of standard-state concentration can be the same. Care should
be taken when applying it to adsorbed species where very
different statistical mechanical models are often used to
describe different classes of adsorbates (see above), and these
can have large standard-state entropy differences that arise only
from differences in choices of standard-state concentrations.
The analysis of DRCs has also been used to improve reaction
conditions to get better yields and selectivity over the same
catalyst material. For example, together with Rachel Getman’s
group, we used DRC analysis to discover reaction conditions
that dramatically improve the regio-selectivity to 1-butanol in a
computational model for n-butane oxidation over model MOF-
encapsulated Ag3Pd catalysts.62 Metal nanoparticles encapsu-
lated within metal organic frameworks (MOFs) offer steric
restrictions near the catalytic metal that can improve selectivity,
much like in enzymes. We first developed a microkinetic model
for the oxidation of n-butane to 1-butanol with O2 over a model
for MOF-encapsulated Ag3Pd nanoparticles. The model
consisted of a Ag3Pd(111) surface decorated with a 2-atom-
thick ring of (immobile) helium atoms that creates an artificial
pore of similar size to that in common MOFs, which sterically
constrains the adsorbed reaction intermediates. The kinetic
parameters for the elementary steps were calculated on the
basis of energies from DFT. The microkinetic model was
analyzed at 423 K in a mixture of butane and O2 to determine
the dominant pathways and which species (adsorbed
intermediates and transition states in the reaction mechanism)
have energies that most sensitively affect the reaction rates to
the different products, using DRC analysis. This analysis
provided evidence which suggested to (1) add water to produce
more OH*, thus inhibiting certain undesired steps which
produce OH*, and (2) eliminate most of the O2 pressure to
reduce the O* coverage, thus also inhibiting these steps. When
combined with an increase in butane pressure, these changes in
H2O and O2 pressure led to dramatic improvements in both the
1-butanol selectivity (from 0 to 95%) and the rate (to 2
molecules site−1 s−1).62 At these optimum conditions, the net
reaction was found to be approximately:62
2776
Viewpoint
2O2 + 3H 2O + 7n−C4 H10 → 7C4 H 9OH + 3H 2
Thus, ∼43% of the oxygen is supplied by water, and only
57% by O2, clearly demonstrating that one can sometimes
achieve high selectivity in oxidation reactions by using a mixture
of H2O with O2 as the oxidant. This idea may be applicable in
many selective oxidations. Indeed, a recent paper reviews other
studies which indicate that the catalytic activity and selectivity
of selective oxidation reactions may be tuned by judiciously
controlling the water content during the reaction.63 These
results demonstrate that the careful analysis of DRCs is a
powerful way to optimize catalytic process conditions and even
to improve upon the choices of reactants.
10. DUMESIC’S METHOD USING DRCS WITHIN HIS
MAXIMUM RATE ANALYSIS TO BYPASS SOLVING
DIFFERENTIAL EQUATIONS TO CALCULATE
RATES IN MICROKINETIC MODELING
DRCs have also found use in analytical solutions to kinetic
equations. Motagamwala and Dumesic64 have shown that the
defining equations for DRCs can be combined with simple
equations for the maximum rate of each step to provide
excellent estimates of the net catalytic reaction rate, thus
bypassing the need to solve the many coupled differential
equations that define the full microkinetic model. They showed
that the steady-state kinetics of a chemical reaction can be
analyzed analytically in terms of proposed reaction schemes
composed of a series of steps by calculating the “maximum
rates” of the constituent steps, rmax,i (the rate assuming that the
TS for step i is equilibrated with the gas-phase reactants). They
derived analytical expressions in terms of rmax,i to calculate
DRCs for each step to determine the extent to which each step
controls the rate of the net reaction. The values of rmax,i can be
used to estimate the rate of the net reaction, thus making it
possible to estimate the net reaction rate without solving the
differential equations as usual. This approach gives the exact
rate for reaction mechanisms where the stoichiometric
coefficients of the constituent steps are equal to unity, and
the most abundant adsorbed species are in quasi-equilibrium
with the gas phase and can be used as an approximation with
good accuracy for many other types of reaction mechanisms.
This allows one to identify the best mechanism among several
possible mechanisms, which can then be followed by a more
detailed analysis of the full microkinetic model of the best
mechanism to determine the surface coverages and DRCs of
adsorbed species and the DRCs of the elementary steps.
11. A METHOD FOR FAST COMPUTATIONAL
SCREENING OF CATALYSTS BASED ON DRCS
Because of the rapid evolution of computational methods that
predict reaction rates for different catalyst materials with ever-
increasing speed and accuracy,28 it is likely that the computa-
tional screening of materials for catalytic activity and/or
selectivity will play an ever increasing role in catalysis research.
There have been many successes already in high-throughput
computational screening to accelerate the discovery of new
catalyst materials.33,34,37,52,65−67 The most successful and
commonly used method for computational screening of solid
catalysts has been the descriptor-based, linear-scaling approach
developed by Nørskov, Bligaard, and co-workers,24,28,29,51−54
referred to below as the “NB” (for Nørskov−Bligaard) method.
It uses linear scaling relationships (including BEP relations) to
estimate the energies of all adsorbed intermediates and
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transition states based on a few key “descriptors”, typically the
binding energy of the catalyst surface to two selected atoms (C,
O, or N).
We recently introduced a new method capable of high-
throughput computational screening of catalyst materials that is
based on the use of DRCs.11 It starts with a reference material
(typically the best known catalyst) for which a full mechanism
and microkinetic model is developed. These are then used to
determine the DRCs of the species in the mechanism (i.e., all
adsorbed intermediates and transition states) at the reaction
conditions of interest. The few species with the highest DRCs
for this reference material are chosen, and their energies on
different materials are used as the key descriptors needed to
estimate their rates and thus screen materials for their activity.
A derivation of the needed equations is provided in detail
elsewhere.11 Here we just give a summary of the main steps.
Rearranging eq 7 gives
⎛ −G ⎞
Xi*d⎜ i ⎟ = d(ln r )
⎝ RT ⎠
where we have dropped the superscript “0” on G0i to simplify
typing, but we still recognize that Gi refers to the standard-state
free energy of species i. We can now integrate this over some
change in Gi, from its value Gi,o for some reference catalyst,
denoted by a small o subscript, to its value Gi,n for some new
catalyst, n. Assuming that Xi remains constant over the range of
interest, at constant temperature this gives
⎛ −Gi , n − ( −Gi , o) ⎞ rn
Xi*⎜
⎝ RT
⎟=
⎠
∫r d(ln r ) = ln
o (13)
Equation 13 shows the change in the total rate to the product
of interest, in moving from catalyst o to catalyst n, due only to
the change in the standard-state free energy of species i, Gi, and
its degree of rate control Xi. This is only true if all other Xi = 0
in the reaction. If there are N different adsorbates and transition
states in the mechanism, then the total change in ln(rate) is the
sum of terms of identical form to the left-hand side of eq 13:
N ⎛ −Gi , n − ( −Gi , o) ⎞ r
∑ Xi*⎜ ⎟ = ln n
i=1 ⎝ RT ⎠ ro
Taking the exponent of both sides of this equation and
assuming that the standard-state entropy of the same adsorbed
species or transition state is similar on different surfaces, so that
changes in standard-state free energies approximately equal
changes in the electronic potential energy (i.e., the internal
energy at 0 K, Ei,n), gives
rn N −Ei , n − (−Ei , o)
= e∑i=1 Xi * ( RT
)
ro
One may use this equation to estimate rn/ro for new (but
similar) materials to the reference material. Since Xi is near zero
for most species, one need only to execute this sum over those
few species with non-negligible Xi, so one only needs to
computationally estimate the internal energies (on both
materials) for those few intermediates and transition states.
In our first application of eq 15,11 DFT was used to calculate
these internal energies. In principle, one could estimate these
by any other electronic structure method, by experiments, or by
semiempirical methods.
Viewpoint
To assess the accuracy of eq 15, we compared its predictions
to those of the NB method for the relative rates of the (211)
surfaces of 12 late transition metals for methane steam
reforming (at T = 773 K, PCO = 0.050 bar, PH2 = 0.15 bar,
PCH4 = PH2O = 0.40 bar).11 We used the Rh(211) surface as the
reference catalyst to get the Xi values used in eq 15. We found it
to be slightly more accurate (relative to a full DFT-based
calculation of the rate for each metal) than the NB approach
when the metals are similar to the reference metal (<0.5 eV
different on the NB descriptor plot where the axes are the bond
energies to C and O adatoms), clearly attributable to the errors
in the linear scaling approximations intrinsic to the NB
approach. In private communication, Jens Nørskov has argued
that those linear scaling relations may provide more accurate
estimates of the species’ energies than the raw DFT energies.
When the metals are very different from the reference (>1 eV
away on the NB-type descriptor plot), eq 15 is much less
accurate than the NB approach. This is due to the fact that the
DRCs change too much (from those of the reference metal
(12)
Rh), so that the approximation in eq 15 of DRCs equal to those
for the reference material breaks down. Different species
become rate-controlling for these distant metals.11
To assess the validity of this “constant DRC approximation”
used for eq 15, the DRCs for adsorbed species and transition
states were calculated by the NB approach across descriptor
space, for this same methane steam reforming reaction and
same conditions as above.11 The results are summarized in
Figure 3, where the colors correspond to the species with the
rn
ro
(14) Figure 3. (a) Coverages (or −DRCs) of adsorbed species and (b) the
DRCs of transition states for methane steam reforming, computed
using the NB approach, plotted as a function of the two NB
descriptors (the adsorption energies of O and C atoms). Reaction
conditions are the same as in Table 1. The colors in the legend labels
on the bottom left represent values of absolute magnitude 1.0, with
lighter coloring being smaller coverages down to 0.0 (white). The
coverages are equal to the absolute magnitude of the degree of rate
control for adsorbed species, and the color map for coverages is
created by letting the red, green, and blue channels be weighted by the
coverage of O*, C*, and CO* respectively. The color map for
(15) transition states is created similarly, with the color corresponding to
each transition-state given to the bottom right corresponding to that
DRC = 1.0. From ref 11.
dominant DRC. It is clear that the DRCs change drastically
throughout this (EC*, EO*) two-descriptor plane. However, there
are large areas where the DRCs are constant, and these cover the
vast majority of descriptor space. Within each of these regions, the
approximations in eq 15 are valid. Thus, if a new class of catalyst
is discovered for some reaction, and it has not yet been
optimized, it is most likely to fall in such an area with constant
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ACS Catalysis
DRCs where eq 15 is valid. It thus could prove excellent for
computationally optimizing such new catalyst materials.
The fact that Rh falls on the border of several such areas for
methane steam reforming is due to the fact that Rh was nearly
the optimum metal for these reaction conditions already.
Optimizing a catalyst material generally means moving on
descriptor space to such a border area where there is no longer
a single adsorbate and single transition state that dominate the
DRCs. The fact that eq 15 is still more accurate than the NB
method within 0.5 eV of Rh on this plot indicates that this
DRC method is reasonably robust even when the DRCs are
changing near the reference material. To bypass the issue of
changing DRCs for the key species, one could adapt this DRC
method by moving only small distances in descriptor space
using constant DRC values, and then, when a better material is
found, recalculate the DRC values by using full DFT for that
new reference material, tiling out descriptor space with small
steps in that way.11
Note that one could improve the accuracy of the NB method
for catalyst screening by using full DFT instead of linear scaling
to calculate the energies for all species with large DRCs but
retain most of the speed by using linear scaling for all species
with small DRCs.
This DRC-based approach to catalyst screening in eq 15 is
computationally faster than the NB method when screening
less than 100 new catalysts, thus adding a valuable approach
that is complementary to the Nørskov−Bligaard method. It can
be implemented without a microkinetic model if the DRCs of
the dominant species are known approximately (e.g., from
experiments).
In computational catalyst screening, one is often more
interested to optimize selectivity than activity. A simple
derivation11 shows that the selectivity ratio equivalent of the
activity ratio in eq 15 above (i.e., the selectivity to the desired
product P from reactant R for a new material n relative to
reference material o) can be estimated by
Sn −Ei , n − (−Ei , o)
N (12) Dumesic, J. A.; Huber, G. W.; Boudart, M. In Handbook of
= e∑i=1(XP,i − XR,i) * ( RT
)
So (16)
Note the similarity of this to the right-hand side of eq 15: Xi
is simply replaced with XP,i − XR,I, which is the difference in
DRCs for species i in the rate of making the desired product P
and the rate of consuming the most valuable reactant R. Thus,
eq 16 is almost as easy to apply as eq 15 except that it uses two
DRCs instead of one.
These DRC-based methods for catalyst improvement are
somewhat related to a mathematical optimization technique
known as the “steepest descent” or “gradient descent” method.
12. DEGREES OF RATE CONTROL UNDER TRANSIENT
REACTION CONDITIONS
The analysis of DRC values had mainly been applied to kinetics
where a steady-state or quasi-steady-state rate has been
established, as, for example, in a flow reactor, or for low
conversion rates in batch reactors. However, it can be applied
to transient kinetics within some microkinetic models. To do
this, one must follow a careful procedure that is a bit tricky, as
described previously.5 Basically, one must recognize that the
DRCs vary with time (just as they do with reactant and product
concentrations, even at steady state). Thus, one must propagate
the transient kinetics up to the time of interest using the
unperturbed energies of the microkinetic model being analyzed.
2778
Viewpoint
One then changes each energy slightly to numerically
determine its DRC using only a tiny time step beyond that,
making sure (numerically) that any changes in coverages are
tiny on a relative (i.e., %) basis and that a true differential
response in relative rate to that energy change is approached.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: charliec@uw.edu.
ORCID
Charles T. Campbell: 0000-0002-5024-8210
Notes
The author declares no competing financial interest.
■ ACKNOWLEDGMENTS
The authors would like to acknowledge the Department of
Energy, Office of Basic Energy Sciences, Chemical Sciences
Division grant number DE-FG02-96ER14630, for support of
this work, and the reviewers for helpful suggestions.
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2779 DOI: 10.1021/acscatal.7b00115

ACS Catal. 2017, 7, 2770−2779