pubs.acs.

org/accounts Article

Electronic Structure-Based Descriptors for Oxide Properties and

Functions
Livia Giordano,*,‡ Karthik Akkiraju,‡ Ryan Jacobs,* Daniele Vivona, Dane Morgan,
and Yang Shao-Horn*
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CONSPECTUS: The transition from fossil fuels to renewable energy requires

the development of efficient and cost-effective energy storage technologies. A
Downloaded via DONGHUA UNIV LIB on June 24, 2024 at 13:58:58 (UTC).

promising way forward is to harness the energy of intermittent renewable

sources, such as solar and wind, to perform (electro)catalytic reactions to
generate fuels, thus storing energy in the form of chemical bonds. However,
current catalysts rely on the use of expensive, rare, or geographically localized
elements, such as platinum. Widespread adoption of new (electro)catalytic
technologies hinges on the discovery and development of materials containing
earth-abundant elements, which can efficiently catalyze an array of (electro)-
chemical reactions.
In the context of catalysis, descriptors provide correlations between fundamental
physical properties, such as the electronic structure, and the resulting catalytic
activity. The use of easily accessible descriptors has proven to be a powerful
method to advance and accelerate discovery and design of new catalyst
materials. The position of the oxygen electronic 2p band center has been
proposed to capture the basic physical properties of oxides, including oxygen
vacancy formation energy, diffusion barrier of oxygen ions, and work function.
Moreover, the adsorption strength of relevant reaction intermediates at the surface of oxides can be strongly correlated with the
energy of the oxygen 2p states, which affects the catalytic activity of reactions, such as oxygen electrocatalysis, and oxidative
dehydrogenation of organic molecules. Such descriptors for catalytic activity can be used to predict the activity of new catalysts and
understand trends and behavior among different catalysts.
In this Account, we discuss how the energy of the oxygen 2p states can be used as a descriptor for oxide bulk and surface chemical
properties. We show how the oxide redox properties vary linearly with the position of the oxygen 2p band center with respect to the
Fermi level, and we discuss how this descriptor can be expanded across different materials and structural families, including possible
generalizations to compounds outside oxides. We highlight the power of the oxygen 2p band center to predict the catalytic activity of
oxides. We conclude with an outlook examining under which conditions this descriptor can be applied to predict oxide properties
and possible opportunities for further refining and accelerating property predictions of oxides by leveraging material databases and
machine learning.

■ KEY REFERENCES
• Lee, Y.-L.; Kleis, J.; Rossmeisl, J.; Shao-Horn, Y.;
emission spectroscopy oxygen 2p-band center and
multiple measures of catalytic activity, including high-
temperature oxygen reduction surface exchange rates,
Morgan, D. Prediction of solid oxide fuel cell cathode aqueous oxygen evolution current densities, and binding
activity with first-principles descriptors. Energy Environ. energies of oxygen evolution intermediate species.
Sci. 2011, 4, 3966−3970.1 Experimentally measured area
specific resistance and oxygen surface exchange of solid • Giordano, L.; Østergaard, T. M.; Muy, S.; Yu, Y.;
oxide fuel cell cathode perovskites are correlated with Charles, N.; Kim, S.; Zhang, Y.; Maglia, F.; Jung, R.;
DFT calculated oxygen 2p-band center.
• Jacobs, R., Hwang, J., Shao-Horn, Y.; Morgan, D. Received: August 13, 2021
Assessing Correlations of Perovskite Catalytic Perform- Published: January 20, 2022
ance with Electronic Structure Descriptors. Chem. Mater.
2019, 31, 785−797.2 Analyzed correlations of the
calculated oxygen 2p-band center for different DFT
functionals with the experimentally measured X-ray

© 2022 American Chemical Society https://doi.org/10.1021/acs.accounts.1c00509

298 Acc. Chem. Res. 2022, 55, 298−308
Accounts of Chemical Research
Figure 1. Electronic structure of perovskites. (a) Contributions to the band structure of an oxide. Orbital figures adapted with permission from ref
46. Copyright 2015, Ebrahim Hassani. (b, c) Schematic representation of properties or reaction energies trends for oxide oxidation and reduction
with the O 2p-band center vs EFermi, with corresponding charge transfers. The specific processes noted (e.g., O adsorption) are representative
canonical examples. Oxygen, red; transition metal, gray; rare earth metal, green.
Lund, I.; Rossmeisl, J.; Shao-Horn, Y. Ligand-Dependent
Energetics for Dehydrogenation: Implications in Li-Ion
Battery Electrolyte Stability and Selective Oxidation
Catalysis of Hydrogen-Containing Molecules. Chem.
Mater. 2019, 31, 5464−5474.3 Computed hydrogen
adsorption energetics on insulating, semiconducting, and
metallic oxides, phosphates, fluorides, and sulfides were
correlated with the ligand p-band center.
• Hwang, J.; Rao, R. R.; Giordano, L.; Akkiraju, K.; Wang,
X. R.; Crumlin, E. J.; Bluhm, H.; Shao-Horn, Y.
Regulating oxygen activity of perovskites to promote
NOx oxidation and reduction kinetics. Nat. Catal. 2021,
4, 663−673.4 Surface oxygen activity, defined as the
oxygen 2p-band center relative to the Fermi level,
dictates the adsorption and surface coverage of NOx
species and the kinetics of NO oxidation for
La1−xSrxCoO3 perovskites.
■
INTRODUCTION
Addressing human pollution and climate change challenges of
the 21st century relies on the transition from fossil fuels to
renewable energy sources, such as solar and wind, which need
to be coupled with technologies to store and reconvert their
intermittent energy production.5−7 A promising path forward
is the use of (electro)catalytic reactions to generate fuels, thus
storing energy in chemical bonds. In this context, the
development of stable and active (electro)catalysts based on
inexpensive and earth abundant elements is key. Descriptor-
based approaches have been shown to be powerful to
accelerate the search for novel (electro)catalysts. A descriptor
is a numerical representation of a material used to form a
correlation with a property of interest.8 Useful descriptors
correlate strongly to the property of interest, while being
significantly faster and easier to obtain than explicitly
measuring the property of interest, and are applicable to a
wide composition space within a particular materials family
and ideally beyond it. Descriptors obtained from first-
principles calculations can be used to rapidly screen a large
number of materials. In catalysis, descriptors were first
introduced by Balanin in 19699 and gained momentum with
the pioneering work of Trasatti,10,11 Bockris, and Otagawa,12
299
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which demonstrated the correlations of the oxygen evolution
activity of ABO3 perovskites with the formation enthalpy of
transition metal hydroxides. First-principles-based descriptors
have become increasingly useful over the past two decades, as
pioneered by Norskov and colleagues, who demonstrated how
metal electronic structure features, such as metal d-band
center, correlate with the binding energy of surface
adsorbates.13−16 The metal d-band center correlation can be
used to predict the catalytic activity of numerous reactions,
including N2 dissociation,16 CO adsorption,17 hydrogen
evolution,18 and oxygen reduction reactions.19,20 Subsequently,
some of us have extended this concept to oxides,1,21 where the
bulk O 2p-band center relative to the Fermi level (EFermi) was
found to linearly correlate with bulk and surface oxygen
vacancy (Ovac) formation energies and experimental oxygen
surface exchange rates for perovskites used in solid oxide fuel
cells.1 In addition, other descriptors have been reported to
describe the catalytic activity of oxides, including surface
transition metal eg filling,22,23 charge transfer energy24 and
formation energy of bulk oxides.25
The bulk O 2p-band center of oxides can be straightfor-
wardly obtained from density functional theory (DFT)
calculations.26,27 For trends in O 2p-band center for a set of
materials to be viable, the O 2p-band center needs to be
calculated using the same DFT methodology for all the
materials under study. In addition, the O 2p-band center can
be experimentally obtained by valence band X-ray photo-
emission (XPS) and X-ray emission (XES) spectroscopy.24,28,2
More specifically, XES spectra aligned with valence-band XPS
measurements yield O 2p-band spectra relative to the oxide
Fermi level.29 The computed bulk O 2p-band center value can
then be validated against experimental values. Moreover, it has
been shown that the O 2p-band center correlates well with the
charge transfer energy (of charge transfer insulators)24 and the
surface O 2p-band center.1 This latter point of the bulk and
surface O 2p-band centers correlating well together is
important from the standpoint of using the easier to obtain
bulk O 2p-band center to correlate to surface-specific
properties, as will be discussed more later. Although DFT+U
and more computationally demanding hybrid DFT are
typically required for accurate descriptions of oxide electronic
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Figure 2. Bulk and surface properties as a function of O 2p-band center for perovskite oxides. (a) Bulk and (001) surface Ovac formation energies as
a function of bulk and surface O 2p-band centers, respectively, computed with PBE+U for ABO3 perovskites (slopes −2.24/−1.59 for bulk/surface
Ovac). Data from refs 30 and 49. (b) OH and O binding energy on transition metal site of ABO3(001) perovskites as a function of the surface O 2p-
band center computed with PBE (filled circle) and PBE+U (empty circles). Data from ref 2. (c) H, CH3, CO2, O, and OH binding energies on
oxygen site of ABO3(001) perovskites as a function of bulk (O−Ooxide and HO−Ooxide) and surface (H−Ooxide, H3C−Ooxide, and O2C−Ooxide) O
2p-band centers computed with PBE (O−Ooxide and HO−Ooxide) and PBE+U (H−Ooxide, H3C−Ooxide, and O2C−Ooxide). Data from refs 49 and 51.
Details of reactions, oxide compositions, and statistical metrics for Figure 2a−c can be found in Figures S1−3 and Tables S1−8 and S18.
Abbreviations: BTO, BaTiO3; STO, SrTiO3; PTO, PrTiO3; BCO, BaCoO3; BWO, BaWO3; BNBO, BaNbO3; LCUO, LaCuO3; LCRO, LaCrO3;
LNO, LaNiO3; LVO, LaVO3; SCO, SrCoO3; LCO, LaCoO3; STAO, SrTaO3; SNO, SrNiO3.

structure, the O 2p-band center computed with simple DFT
methods (i.e., PBE functional) do not necessarily result in less
robust linear correlations with experimental data.2 The bulk O
2p-band center descriptor has been used extensively to infer
correlations with catalytically relevant properties and functions,
including oxygen ion migration,30,31 oxygen evolution catalytic
activity in basic solution,32 oxide work function,33 oxidative
dehydrogenation of carbonate solvents at positive electrodes in
Li-ion batteries.34,3
In this Account, we review how the O 2p-band center
controls M−O bond characteristics and redox of oxides, and
how it correlates with binding energies of reaction
intermediates and other oxide properties, and catalytic activity.
We discuss how bulk, surface, and adsorbate p band descriptors
can be used to generalize these trends to other classes of
materials beyond oxides.
density of states (DOS), typically including both occupied and
unoccupied states, and conventionally it is referenced to EFermi.
The O 2p-band center can be tuned by the electronegativity
of the cations, the cation first-shell coordination environments
(e.g., tetrahedral and octahedral coordination),1,41 inductive
effects from the second-shell coordination,42 and strain.43,44
Specifically, oxides with more electronegative cations tend to
have shallower O 2p-band centers24 (i.e., less negative, closer
to EFermi). Moving across a row on the periodic table from left
to right increases the nuclear charge, increasing the number of
d electrons and, correspondingly, increases electronegativity.
Increasing cation oxidation state decreases the number of d
electrons (e.g., Mn3+ to Mn4+) and increases the metal ion
electronegativity due to reduced electron shielding. As
hybridization and metal−oxygen covalency scale with cation
electronegativity,45 the O 2p-band center has been shown to

■ OXIDE ELECTRONIC STRUCTURE AND

CONNECTION TO OXIDE PROPERTIES
We begin by reviewing cation-oxygen bonding in transition
metal oxides. When isolated metal and oxygen atoms are
brought together to form an oxide, electrons are transferred
from metal (M) to oxygen, resulting in positively charged
cations surrounded by oxygen anions (Figure 1a). Metal and
oxygen states split into multiple states due to crystal field
splitting associated with the coordination environment. For
example, a MO6 octahedral environment has metal dz2 and
dx2−y2 orbitals strongly overlapping with adjacent O 2p orbitals,
forming σ-bonding and σ*-antibonding states. The remaining
metal dxy, dyz, and dxz orbitals have weaker spatial overlap with
adjacent O 2p-orbitals, forming π-bonding and π*-antibonding
states. The translational symmetry of the oxide crystal results
in separate M d bands and O 2p bands (Figure 1a),35,36 where
the hybridization of these bands, due to spatial overlap and
similar energy scale, determines the degree of covalency in the
M−O bond. The position of the O 2p states is then closely
related with the other electronic properties of the oxide,37−39
such as charge transfer energy, covalency, and presence of a
band gap.40 The O 2p-band center descriptor is calculated as
the centroid of the O component of the projected electronic
300
correlate with charge transfer energy for perovskites of late
transition metal oxides.24
Throughout this Account, we focus mainly on the
correlations and understanding of the O 2p-band center for
metallic oxides, where EFermi is given approximately by the
highest energy electrons. Semiconducting and insulating oxides
with significant band gap represent a more complex situation
as EFermi can be anywhere in the gap depending on dopants and
carrier/defect concentrations. These gap effects introduce
another potentially large energy into the oxidation/reduction
processes, complicating the use of O 2p-band center
correlations. In case of materials with a nonzero band gap,
alternative descriptors such as the charge transfer energy, may
be more appropriate to predict the oxide properties.24
The O 2p-band center can influence the energetics of redox
processes for oxide bulk and surfaces, such as Ovac formation
and filling, and adsorption energies on oxide surfaces. The
effectiveness of the O 2p-band center descriptor on the
energetics can be qualitatively understood in terms of a rigid
band model,47 which has been successfully used to describe
late transition metal perovskites.48 In this model, oxidation of
oxides, for example, through filling of Ovac, involves moving
electrons from EFermi to O 2p-band, resulting in an upshift of O
2p-band center toward EFermi. This upshift in O 2p-band center
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is both the result of EFermi moving down due to electron
depletion from EFermi to the newly added oxygen and an
increase in the total oxygen DOS relative to the transition
metal DOS (Figure 1b). Thus, the energetics for Ovac filling
becomes less negative (i.e., less favorable) with shallower O 2p-
band center. Similarly, adsorption of O and OH on oxide
surfaces can also oxidize the system, where adsorption
energetics should become less favorable with shallower O
2p-band center (Figure 1b). The opposite trends occur with
reduction of the system, for example, by creation of Ovac on
metal oxide surfaces (Figure 1c), where electrons are
transferred from O 2p-band to EFermi, resulting in a downshift
of O 2p-band center away from EFermi. This downshift of O 2p-
band center is the result of adding electrons to EFermi and
reduction in the oxygen DOS relative to the transition metal
DOS. Therefore, reduction of oxides involving Ovac formation
become easier with shallower O 2p-band center (Figure 1c).
These trends of oxidative and reductive energetics persist also
when the oxidation and reduction proceeds through non-
oxygen adsorbates (e.g., adsorption of H, Figure 1c).
Specifically, the adsorbate moves electrons to/from EFermi,
whose absolute position relative to vacuum is given with a
reasonable accuracy by its position relative to the O 2p-band
center, as demonstrated experimentally for a number of
perovskites.24 This absolute referencing effect also allows O
2p-band center to correlate with work function, as discussed
further below.
■ CORRELATING OXYGEN 2P-BAND CENTER TO
BOND STRENGTH AND BINDING ENERGIES
The first oxide property shown to correlate with the O 2p-band
center1 was the Ovac formation energy, which decreases with
shallower O 2p-band center, as shown for bulk30 and surface49
of perovskite oxides in Figure 2a. Increasing number of d
electrons for metal cations and increasing oxidation state (e.g.,
from Vx+ to Nix+ and from M3+ to M4+)34 is associated with
shifting EFermi closer to the centroid of oxygen DOS, making
the O 2p center shallower, which coincides with reduced Ovac
formation energy (Figure S1). This trend derives from the
charge compensation for the formation of Ovac, which largely
takes place through the reduction of two M ions for these
reducible oxides.50 In addition, the energy penalty for the
formation of bulk and surface oxygen vacancies shows similar
slopes with respect to the respective O 2p-band center (slopes
−2.24 and −1.59, respectively), close to −2 expected for two
electrons transferred per Ovac.3
Besides oxygen vacancies, the O 2p-band center of oxides
has been shown to correlate with the binding energy of
adsorbates on the oxide surface. For example, the binding
energy of electronegative adsorbates, such as OH and O,
adsorbed on the metal sites of the (100) surface of perovskites
have a positive slope with the O 2p-band center (Figure 2b),1
indicative of the oxide being oxidized. As expected, the slope
for HO−Moxide (1.06 at PBE level, and 1.29 at PBE+U level) is
lower than the slope of O−Moxide (2.13 at PBE level),1 in
agreement with greater oxidation of the surface upon
adsorption of O (ideally 2 electron transfer) than OH (ideally
1 electron transfer) on the metal sites. On the other hand, a
negative slope with the O 2p-band center is observed when
OH and O are adsorbed on the surface oxygen sites of BO2-
terminated (001) perovskites (Figure 2c), indicating oxide
reduction upon the formation of HO−Ooxide51 and O−Ooxide.51
Similarly, adsorption of hydrogen (H−Ooxide)49 or C-
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containing species (O2C−Ooxide and H3C−Ooxide)49 on surface
oxygen sites of (001) perovskites, shows a strong dependency
on the O 2p-band center (Figure 2c), with slopes of −0.97 and
−0.98 for H−Ooxide and H3C−Ooxide, respectively. Adsorption
of a hydrogen atom on the surface oxygen site of perovskites is
accompanied by transfer of one electron and the reduction of a
transition metal cation, which is similar to that upon
adsorption of C-containing species with formation of C−Ooxide
bonds.3,34,49
Making the O 2p-band center shallower using late transition
metal cations and increasing cation oxidation state, associated
with greater metal−oxygen covalency, can facilitate adsorption
of species, such as CO252 and NO4 on surface oxygen sites
instead of surface metal sites. For example, the adsorption of
NO and NO2 on oxygen sites of (001) La1−xSrxCoO3, forming
NO−Ooxide4 and NO2−Ooxide, is energetically more favorable
than that adsorption on metal sites and shows a negative slope
with the surface O 2p-band center, indicative of surface oxide
reduction. This trend is consistent with increased signal
associated with NOx species measured by X-ray photoemission
spectroscopy (XPS) when increasing Sr in La1−xSrxCoO3.4
Similarly, the energetics of CO2−Ooxide (surface carbonate)
formation becomes more favorable with shallower O 2p-band
center, indicative of more reactive oxygens on oxide surfaces,
which agrees with the observation of more (bi)carbonate
species using XPS.52
The O 2p-band-dependent energetics discussed for perov-
skites hold true for other oxide crystal families and ligands. For
example, the O 2p-band center of Ruddlesden−Popper
((LaxSr1−x)2MO4, with M = Co, Ni, Cu) correlates with the
formation energies of interstitial oxygen in the structure
(Figure 3a).53 The formation energy of interstitial oxygen
species trends with the O 2p-band center of (LaxSr1−x)2MO4
with positive slopes, indicative of oxide oxidation, opposite to
Ovac formation energies in perovskites with a negative slope,
indicative of oxide reduction. The peroxide interstitial has a
slope of +0.28 while the oxygen ion interstitial has a slope of
+1.71, which difference can be attributed to reduced charge
transfer from (LaxSr1−x)2MO4 to peroxide-forming interstitials
compared to oxide ion interstitials. In addition, the energetics
for hydrogen adsorption on surface oxygen sites of LixMO2 (M
= V, Cr, Mn, Fe, Co, and Ni; x = 0, 0.5, and 1), as well as
surface Ovac formation, have negative slopes with the O 2p-
band center (Figure 3b), indicative of greater driving force for
oxide reduction with shallower O 2p-band center, in agreement
with trends found for perovskites (Figure 2a). Hydrogen
adsorption on surface oxygen sites becomes increasingly
energetically favorable with shallower O 2p-band center
compared to hydrogen adsorption on surface metal sites.
Like perovskites, the more active surface oxygen sites come
from highly covalent oxides with late transition metals (i.e.,
Ni), and transition metals in high oxidation states (x = 0.5
(M3+/M4+) or x = 0.0 (M4+), Figures 3b and S4). Moreover,
similar correlations are observed between the energetics of
surface Ovac formation and H−Ooxide and O 2p-band center for
a larger library of oxides with different crystal structures,
including layered oxides, rocksalts, and rutiles (Figure 3c). For
oxides in Figure 3c with high band gaps, the O 2p-band center
is referenced to the conduction band minimum, to account for
the extra energy needed to reduce an insulator. Notably, these
trends hold even when different ligands (S2−, F−, PO43−,
AsO43) are considered (Figure S5), where the ligand vacancy
formation energy and hydrogen adsorption correlate with the
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Figure 3. Bulk and surface properties as a function of O 2p-band
center across different material families. (a) Defect formation energies
as a function of O 2p-band center for Ruddlesden−Popper phases
((LaxSr1−x)2MO4±δ) with M = Co, Ni, Cu), Data from ref 53. (b)
Hydrogen binding energy at metal (H−Moxide) and oxygen (H−
Ooxide) site and Ovac formation energy on the LixMO2 (101̅4) surface
of layered compounds (M = V, Cr, Mn, Fe, Co, and Ni) as a function
of the surface O 2p-band center computed with RPBE, where H−
Moxide shows a small positive slope (0.14), while H−Ooxide and Ovac
have negative slopes (−1.36 and −1.61, respectively). Data from ref
56. (c) Hydrogen binding energy at oxygen site (H−Ooxide), and Ovac
formation energy on the surface of different oxide crystal families,
including layered compounds, rocksalt, rutile oxides, as a function of
the surface O 2p-band center with respect to the conduction band
minimum (CBM) computed with PBE where H−Ooxide and Ovac have
slopes −0.84 and −1.13, respectively. Data from ref 3. (d) Energy
required to create adsorbed O as a function of O 2p-band center of
adsorbed O computed for rutile, perovskite oxides, and metal surfaces.
Data from ref 54. Details of the oxide compositions and statistical
metric for Figure 3a−c can be found in Figures S4−S8 and Tables
S9−S12 and S18. Abbreviations: LIMO, LiMnO3; LI0.5IMO,
Li0.5MnO2; MO2, MnO2; HFO, HfO2; LMGP, LiMGP; NB, Nb;
PT, Pt; AU, Au; LCAO, LaCaO3; SSBO, SrSbO3.
ligand p-band center suggesting that a more general “anion p-
band center” quantity may describe the energetics of
oxidation/reduction, metal-anion bond strength, and resulting
catalytic activity trends for systems beyond oxides, for example,
sulfides, fluorides,3 and possibly more. A multivariable
statistical analysis has indicated that developing multivariate
models including O 2p-band center, band gap, and metal−
ligand distance can greatly increase the predictive power of the
more general ligand p-band correlation.3
It should be noted, here, that while the bulk O 2p-band
center is a unique value for the material at fixed composition,
the surface O 2p-band center depends on the surface
orientation and termination. Thus, one material can have
many surface O 2p-band center values, depending on the
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surface orientation and termination considered. The reported
surface O 2p-band centers have been computed by taking the
most stable surface orientation of the compound (i.e., (001)
surface for perovskite oxides), and were computed for the
ABO3 perovskite AO and BO2-terminated surfaces. As shown
in Figures 2b and S2c, there is a dependence of the O 2p-band
center on the surface termination. We expect this change of the
local surface O 2p-band center (vs the bulk value) to reflect a
change in the adsorption properties and catalytic activity for
the specific surface or site. This concept has been further
extended beyond the band center of oxide bulk and surface to
the O 2p-band center of surface adsorbates themselves. For
example, oxygen adsorption energy is correlated with the O 2p-
band center of adsorbed O on the surface of oxides (rutiles and
perovskites) and metals (Figure 3d).54 Similarly, differently
coordinated surface oxygens of RuO2 crystal orientations have
different O 2p-band centers due to their specific coordination,
local environment, and bond angles, resulting in modified O
binding energies on surface Ru site.55 This concept of local O
2p-band can be combined with the idea of a general anion p-
band center to open the possibility of a generalized form of this
electronic structure descriptor to predict adsorbate energetics
on different materials, beyond oxides, and O-containing
adsorbates.
■ CORRELATING OXYGEN 2P-BAND CENTER TO
(ELECTRO)CATALYTIC ACTIVITY
The O 2p-band center has been proposed as a descriptor for
the (electro)catalytic activity of oxides. The role of the O 2p-
band center in oxygen electrocatalysis has been studied
extensively.1,2,24,57 The surface oxygen exchange kinetics,
which measures the rate of oxygen incorporation/release
into/from oxides (O2 + 4e− → 2O2−),1 central to the efficiency
of solid oxide fuel cells, increases over many orders of
magnitude with shallower/deeper O 2p-band center (Figure
4a).1 The enhanced rate can be attributed to reduced energy
for Ovac formation in oxides with shallow O 2p-band center,
where oxygen vacancies serve as active sites for adsorption and
dissociation of molecular oxygen (Figure 4a bottom). On the
other hand, the surface exchange kinetics of Ruddlesden−
Popper ((LaxSr1−x)2MO4, with M = Co, Ni, Cu)31 decreases
with higher O 2p-band center, which can be attributed to
increasing formation energy of oxide and peroxide intersti-
tials.53 The observed opposite slopes of surface exchange rates
between perovskites and Ruddlesden−Popper oxides is a direct
consequence of different active sites and catalytic mechanisms
which involve vacancy- and interstitial-mediated processes for
perovskites and Ruddlesden−Poppers, respectively. In addi-
tion, having higher O 2p-band center (e.g., Hf0.5Ba0.5CoO3 and
Pr0.5Ba0.5CoO3) correlates with greater catalytic activity of
oxygen evolution reaction (OER) for perovskites in basic
solution (Figure 4b).32 In the conventional reaction mecha-
nism, the enhanced OER kinetics found for these perovskites
can be attributed to reduced barrier from O to OOH as the
rate-limiting step (Figure 4b bottom), associated with reduced
binding energy of oxygenated species, such as O and
OH21,24,58 on surface metal sites.32,59 More recently, it was
shown that the enhanced activity can also result from (1)
reduced electron transfer energy barrier for water oxidation
associated with the energy for unoccupied states residing closer
to the redox energy potential of H2O/O2 for oxides with higher
O 2p-band centers24 and (2) reduced barrier for the rate-
limiting step in the OER associated with the OER having
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Figure 4. Surface catalytic properties as a function of O 2p-band center for perovskite oxides. (a) Oxygen surface exchange coefficient as a function
of the bulk O 2p-band center relative to EFermi computed with PBE+U for ABO3 perovskite oxides. Data from ref 1. (b) OER activities measured at
0.5 mA/cm2ox as a function of the bulk O 2p-band center relative to EFermi computed with PBE+U for ABO3 perovskites. Data from ref 32. (c) NO
oxidation turnover frequency for LaxSr1−xCoO3 perovskites as a function of the surface O 2p-band center relative to EFermi computed with PBE+U.
Data from ref 4. Details of the oxide compositions and statistical metrics for Figure 4a and b can be found in Figure S10 and Tables S13−S14 and
S18. Abbreviations: LMO, LaMnO3; LCO, LaCoO3; LSMO25, La0.75Sr0.25MnO3; BSCF, Ba0.5Sr0.5Co0.75Fe0.25O3; SCN10, SrCo0.9Nb0.1O3δ−; PBFO,
Pr0.5Ba0.5FeO6; LSC82, La0.8Sr0.2CoO3; LSC64, La0.6Sr0.4CoO3; LSC46, La0.4Sr0.6CoO3; GBCO, Gd0.5Ba0.5CoO3; SBCO, Sr0.5Ba0.5CoO3; HBCO,
Hf0.5Ba0.5CoO3; PBCO, Pr0.5Ba0.5CoO3.

decoupled electron and proton transfer steps.60 Moreover,
most active perovskites with high O 2p-band center can have
surface oxygen sites that are as active as surface metal sites.60
This comparably high metal- and oxygen-site activity can be
attributed to comparable binding energy of oxygenated species
on surface oxygen and metal sites59 as well as the lowered
energy penalty for Ovac formation for these oxides (Figure 2a−
c), where the formation of Ovac is a reaction intermediate at
surface oxygen sites.60 Unfortunately, a shallower O 2p-band
center is accompanied by decreased oxide stability during the
OER, which can be attributed to reduced M−O bond
strength.57,61 For example, some perovskites, such as BSCF,
undergo dissolution during OER in basic solution.62,63
oxidation is limited by NO adsorption on oxygen sites to form
NO−Ooxide for the left-hand side of the volcano (LaCoO3),
and by NO2 removal or Ovac refilling for the right-hand side of
the volcano (La1−xSrxCoO3 with x > 0.2) (Figure 4c bottom),4
in agreement with lower Ovac formation energy (i.e., more
difficult Ovac filling) for high O 2p-band center (Figure 2a).
Similarly, the kinetics for propane66 and methane oxidation67
show a volcano trend with the surface O 2p-band center for
perovskites (Figure S9). We hypothesize the volcano depend-
ence by considering that the left-hand side of the volcano is
limited by the activation of the C−H bond in the alkanes,
while the right-hand side of the volcano is limited by H2O
desorption or Ovac refilling.

The O 2p-band center also serves as an effective descriptor
for other electrocatalytic reactions and heterogeneous catalysis
on oxide surfaces. The O 2p-band descriptor is correlated with
the hydrogen evolution reaction (HER) activity of A-site
modified Co-based perovskites,64 and Co-based double
perovskites, where a volcano-type relationship was observed
for the HER activity with respect to the O 2p-band center.65
NO oxidation kinetics exhibit a volcano trend with the O 2p-
band center of La1−xSrxCoO3, where the most active
composition is found for x = 0.2.4 This volcano trend with
O 2p-band center can be understood by considering that NO
303
■
CORRELATING OXYGEN 2P-BAND CENTER TO
OXIDE PROPERTIES
In this section, we show how the O 2p-band center correlates
with other oxide properties, not directly related to energetics of
adsorption and defect formation. The migration barrier for
oxygen ion diffusion in a number of perovskites decreases as
the value of O 2p-band center increases30 (Figure 5a). This
trend can be attributed to two factors. The first factor is the
reduced energy penalty for Ovac formation (Figure 2a),
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Acc. Chem. Res. 2022, 55, 298−308
Accounts of Chemical Research
Figure 5. Dependence of oxide physical properties on oxygen
electronic structure. (a) Oxygen diffusion barrier as a function of bulk
O 2p-band center computed with PBE for ABO3 and AA′BB′O3
perovskites, experimental (data from ref 31) and computed with
charge compensation (data from ref 30). The slopes of experimental
and computed diffusion barriers are −2.21 and −0.26, respectively.
(b) Work function for AO and BO2-terminated (100) surfaces of
ABO3 perovskites as a function of bulk O 2p-band center computed
with HSE for insulating (empty circles) and metallic (filled circles)
oxides. Data from ref 72. For insulating compounds, EFermi is
considered as located at the valence band maximum (p-type limit of
the work function). Details of the oxide compositions and statistical
metrics for Figure 4a and b can be found in Figure S8 and Tables
S15−S17 and S18. Abbreviations: PTO, PrTiO3; STO, SrTiO3; LTO,
LaTiO3; LSMO82, La0.8Sr0.2MnO3; LSCO55, La0.5Sr0.5CoO3; BSCF,
Ba0.5Sr0.5Co0.75Fe0.25O3; LRO, LaRuO3; LSMO375,
La0.625Sr0.375MnO3.
allowing oxygen ions to diffuse faster in the perovskite
structure. The second factor is high O 2p-band center results
in a reduced M−O framework bond strength, where weaker,
more flexible, M−O bonds enable more facile diffusion of
oxygen ions. The migration barrier shown in Figure 5a was
computed by removing O2− ions (i.e., the O and its 2
electrons, making the calculation charge-compensated) when
creating Ovac, preventing the local oxidation state to change.30
Experimental activation energy for perovskites shows a
correlation with a higher slope than the computed one,31
which can be attributed to interactions between the diffusing
oxygen ion and localized electronic charge in perovskites with
transition metal ions.68,69 A positive slope for the migration
activation energy with O 2p-band has been found for
Ruddlesden−Popper phases.31 This change in the sign of the
slope in the Ruddlesden−Popper phases relative to perovskites
occurs for the same reasons discussed previously for surface
exchange coefficient, where defect-mediated diffusion is
reductive in perovskites (O vacancies) and oxidative in
Ruddlesden−Popper phases (O interstitials).
The O 2p-band center also correlates with the work
function, which is the energy required to move an electron
from the EFermi of a solid to the vacuum. Knowing the work
function allows one to establish the relative energies of oxide
electrons to key redox levels of interest (e.g., water splitting24
and CO2 reduction59,70). More specifically, EFermi can be
written relative to the standard hydrogen electrode (SHE) as
work function −4.4 eV, being the vacuum energy level 4.4 eV
above the H+/H2 redox couple that defines the SHE.71 Jacobs
et al.72 have analyzed the work function of BO2- and AO-
terminated surfaces on ABO3 (100) perovskites by hybrid
functional (HSE) DFT (Figure 5b). They found a linear
304
pubs.acs.org/accounts Article
correlation of the work function with the O 2p-band center.
The trend derives from the relatively fixed position of the O
2p-band center with respect to the vacuum level,24 which
implies that the difference between the O 2p band-center and
EFermi correlates with the change in work function. Three broad
classes of perovskite materials were categorized in this work:
(a) highly ionic materials with large band gap and empty d
states (i.e., LaScO3) with high work function, (b) materials
with half or mostly filled d states and lower ionicity (i.e.,
LaNiO3) with intermediate work function, and (c) materials
with barely filled d states, medium ionicity (i.e., SrVO3) with
low work function. Interestingly, the slope of the linear trend
with the O 2p-band center is larger for the BO2 surface (slope
between 0.7 and 1), suggesting that the work function is
controlled by the band position, compared to the AO surface
(slope between 0.2 and 0.6), where the effect of surface dipole
on the work function is larger as the electrons at EFermi
participating in the emission originate from the subsurface
BO2 layer.72 These relationships between O 2p-band center
and work function and the role of band positions versus surface
dipoles in setting the work function for BO2 and AO perovskite
surfaces are also in agreement with the work of Xiong et al.73
Such trends can in turn be used to tune work functions to
design new materials specifically tailored to catalyze a
particular reaction on a specific surface orientation and
termination, potentially informing new materials composition
or processing routes, for example, through targeting thin film
growth of a certain surface orientation.
■
CONCLUSIONS AND PERSPECTIVES
The O 2p-band center provides a proxy measurement of the
overall M−O bond strength of the oxide material, the nature of
the M−O bonding (e.g., degree of hybridization), and the
position of band levels relevant for materials redox. The results
summarized in this work suggest that the descriptor could be
generalized to other anions as a more widely applicable “anion
p-band center”. The anion p-band center of either a bulk,
surface, or adsorbate might play a parallel role to the oxygen
2p-band center, correlating with defect, migration, adsorption,
redox, and work function energies, and overall catalytic
processes. If such a generalization is successful, the anion p-
band center could be used to understand trends of material
properties and functions not only in different oxide structural
families but for different materials chemistries beyond oxides,
for example fluorides, sulfides, phosphides, and more. We
expect the use of the anion p-band center to find relevance in
numerous materials design applications and to provide new
insights relating trends in materials properties and functions to
the underlying materials chemistry outside of oxides and
oxygen adsorbates.
The use of descriptors, such as the O 2p-band center,
provides a powerful method for the accelerated discovery and
design of new catalyst materials. Given these correlations, high-
throughput density functional theory calculation studies can be
conducted, and the predicted quantities of interest can be
obtained from calculation of the O 2p-band center for each
screened material.74 These correlations also enable improved
understanding of materials trends, which, coupled with
domain-specific knowledge, can be used to guide new efforts
by proposing sensible composition or structure spaces to focus
a materials search, or provide rational strategies toward
targeted design spaces of interest.
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Acc. Chem. Res. 2022, 55, 298−308
Accounts of Chemical Research
In this Account, we focused on discussing the bulk O 2p-
band center descriptor, where a single value is used to
represent a given material composition. It is worth pointing out
the potential limitations of this approach when implementing
the descriptor approach in practice. A specific limitation of the
bulk O 2p-band center and bulk descriptor approach more
generally is related to predicting surface termination-sensitive
phenomena. If a property of a material measured for two
different surface orientations is shown to differ markedly
(which, for example, is the case with work function), then this
single bulk descriptor cannot accurately capture both surface
properties for the same material with a single trend. The reason
the bulk descriptor provides a robust trend with surface-
sensitive phenomena is because the bulk and surface O 2p-
band center are directly correlated with each other. In the limit
of the surface and bulk electronic structure not being directly
correlated, the use of the bulk O 2p-band center to form
correlations would be expected to fail. We speculate this may
occur if, for example, there is a near-surface phase change to a
different material than the bulk, which surface phase may have
electronic structure and properties that differ significantly from
the bulk material being represented with the bulk O 2p-band
descriptor. Moreover, the bulk O 2p-band descriptor may fail
to capture the specificity of local environments in highly
substituted compounds, or on heterogeneous surface struc-
tures. As discussed in this account, for such situations the use
of a local ligand 2p-band can overcome the limitation of the
bulk O 2p-band descriptor, while providing a single-feature
measure of the local electronic structure to inform the search
of materials with specific binding energy or catalytic properties.
The acceleration of such materials discovery and design
efforts are enabled by the fact that the O 2p-band center can be
obtained from a single bulk DFT calculation,1 typically
requiring less than 1 day of combined human and computer
time per system. This time scale of obtaining at least a
qualitative sense of whether a material is of interest for a
particular application is likely 1−3 orders of magnitude faster
than explicitly synthesizing the material, confirming its
structure and composition, and then measuring the quantity
of interest. Given the increased prevalence of large materials
databases of computed data, together with rapidly increased
adoption of machine learning methods in materials science,
there is an opportunity to further develop the descriptor-based
approach of catalyst discovery and design with the aid of
modern data science and machine learning techniques.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.accounts.1c00509.
Supporting data, figures, and table containing all data
reported in this manuscript, including material compo-
sition and details of the linear fitting (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Livia Giordano − Research Laboratory of Electronics,
Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States; Present
Address: Department of Materials Science, University of
Milano-Bicocca, Milano, Italy; orcid.org/0000-0002-
6879-9424; Email: lgiordan@mit.edu
305
pubs.acs.org/accounts Article
Ryan Jacobs − Department of Materials Science and
Engineering, University of Wisconsin−Madison, Madison,
Wisconsin 53706, United States; orcid.org/0000-0003-
2229-6730; Email: rjacobs3@wisc.edu
Yang Shao-Horn − Research Laboratory of Electronics,
Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States; Department of
Materials Science and Engineering and Department of
Mechanical Engineering, Massachusetts Institute of
Technology, Cambridge, Massachusetts 02139, United
States; orcid.org/0000-0001-8714-2121;
Email: shaohorn@mit.edu
Authors
Karthik Akkiraju − Department of Materials Science and
Engineering, Massachusetts Institute of Technology,
Cambridge, Massachusetts 02139, United States
Daniele Vivona − Department of Mechanical Engineering,
Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States
Dane Morgan − Department of Materials Science and
Engineering, University of Wisconsin−Madison, Madison,
Wisconsin 53706, United States; orcid.org/0000-0002-
4911-0046
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.accounts.1c00509
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Author Contributions
‡
These authors contributed equally.
Funding
R.J. and D.M. were supported by the Department of Energy
(DOE) Award No. DE-SC0020419. L.G. and Y.S.-H. thank
Toyota Research Institute (TRI) and their Accelerated
Materials Design and Discovery (AMDD) program for
financial support of this work.
Notes
The authors declare no competing financial interest.
Biographies
Livia Giordano is associate professor at the University of Milano-
Bicocca, Italy, after having been a Research Scientist at the
Massachusetts Institute of Technology. She studies interfacial
phenomena and reaction mechanisms to inform material design in
electrochemistry and heterogeneous catalysis.
Karthik Akkiraju is a Ph.D. candidate under the guidance of
Professor Shao-Horn at the Massachusetts Institute of Technology.
His research focuses on understanding reaction mechanisms for clean
air applications and chemical production using a descriptor approach.
Ryan Jacobs is Research Scientist at the University of Wisconsin-
Madison. His research combines molecular simulations, data science,
and machine learning to understand, discover, and design materials
for fuel cells, batteries, and electron emitters.
Daniele Vivona is a Ph.D. candidate under the supervision of
Professor Shao-Horn at the Massachusetts Institute of Technology.
His research focuses on developing design principles for solid state
https://doi.org/10.1021/acs.accounts.1c00509
Acc. Chem. Res. 2022, 55, 298−308
Accounts of Chemical Research
ionic conductors and accelerating materials discovery for clean energy
applications.
Dane Morgan is Professor in Materials Science and Engineering at
the University of Wisconsin, Madison. His work combines thermo-
statistics, thermokinetics, and informatics analysis with atomic scale
calculations to understand and predict materials properties.
Yang Shao-Horn is professor at Massachusetts Institute of
Technology. Her work applies fundamental understanding in reaction
mechanisms to design new materials for electrocatalysis of oxygen
reduction, water splitting, lithium storage, methanol oxidation, and
CO2 reduction.
■
ABBREVIATIONS
DFT, density functional theory
DOS, density of states
EFermi, Fermi energy
Ovac, oxygen vacancy
■
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