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Why is bulk thermochemistry a good descriptor for the electrocatalytic activity of transition metal oxides? Federico Calle-Vallejo, Oscar Diaz-Morales, Manuel Kolb, and Marc T.M. Koper ACS Catal., Just Accepted Manuscript • Publication Date (Web): 19 Dec 2014 Downloaded from http://pubs.acs.org on December 20, 2014

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Why is bulk thermochemistry a good descriptor for the electrocatalytic activity of transition metal oxides? Federico Calle-Vallejo1,*, Oscar A. Díaz-Morales2, Manuel J. Kolb2, Marc T. M. Koper2,*

1

Université de Lyon, CNRS, Laboratoire de Chimie, ENS Lyon, 46 Allée d’Italie, 69364

Lyon Cedex 07, France. 2

Leiden Institute of Chemistry, Leiden University, 2300 RA, Leiden, The Netherlands.

* Address correspondence to: [email protected], [email protected]

ABSTRACT It is well known that transition metal oxides can efficiently catalyze electrochemical reactions of interest in electrolyzers and fuel cells. The question is how to describe and rationalize the variations in catalytic activity among a given class of oxides, so that known materials can be improved and new active materials be predicted. In this context, descriptor-based analyses are a powerful tool, as they help to rationalize the trends in catalytic activity through correlations with other properties of the material. Particularly, bulk thermochemistry has long been used to describe the trends in catalytic activity of oxide surfaces. Here we explain the reason for the apparent success of this descriptor on the basis of perovskite oxides and monoxidesand the oxygen evolution reaction:essentially, bulk thermochemistry and surface adsorption

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energeticsdepend similarly on the number of outer electrons of the transition metal in the oxide. This correspondence applies to a wide number of transition metals and is responsible for the linear relationship between bulk and surface properties that enables the construction of volcano-type activity plots.

KEYWORDS Perovskite oxides; monoxides; outer electrons; oxygen evolution reaction; bulk energy of formation; volcano plot.

Due to the scarceness of fossil fuels and their related environmental concerns, society needs to trigger and sustainably propel the so-called hydrogen economy.1This paradigm requires the widespread use of devices such as electrolyzers and fuel cells. These utilize catalysts for the capture and transformation of solar energy into electricity and fuels with null or reduced carbon footprints. The interconversionbetween chemical and electrical energy is currently far from being energetically efficient and cost-effective, which hinders the commercialization of these technologies.2 Therefore, better catalysts made from earth-abundant elements are required. In this respect, transition metal oxides (and related compounds such as hydroxides and oxy-hydroxides) offer good tradeoffs between catalytic activity and total costs, as they are not necessarily made of noble metals.3Some of these oxides have been thoroughly studied for the past thirty years4 and new materials have been discovered recently through systematic experimental and theoretical routines.3a, 5Among those routines, descriptor-based analysis has proved successful inrationalizingthe trends in reactivity of transition metal oxides3a, 6. This analysis correlates experimental or theoretical estimations of the catalytic activity with a descriptor, in such way that several catalysts can be directly compared and smooth (often linear) trends are observed. The challenge lies in finding the appropriate descriptor for a specific reaction and class of materials. Among the large number of theoretical descriptors for


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the catalytic activityof oxides, we highlight the binding energies of key intermediates,6b, 7the average energies of the p-band of lattice oxygen atoms at the surface,8and the number of outer electrons of the transition metal in the oxide.6aOn the other hand, experimentalelectrocatalysis has traditionally resorted to bulk thermochemistry to describe activity trends,4b, c and only recently alternative descriptors such as orbital occupations have come into play.3a In this article, we will show that the simple concept of outer electrons is able to explain why bulk thermochemistry is an excellent descriptor for the electrocatalytic activity of a wide range of transition metal oxides.Thus, we aimto provide a link between theoretical and experimental descriptors by establishingenergetic scaling relations between bulk and surface properties. Our case study is the oxygen evolution reaction (OER), which takes place at the anode of electrolyzers. We will analyze the trends for two families of perovskite oxides, namely AMO3, where A is either La or Sr and M is a metal from Sc to Ge. This rangeincludes not only the previous range of oxides from Ti to Cu,6b, 9 but also coversSc, Zn, Gaand Ge at the M site. Additionally, we will consider the case of monoxides (MO) in the range between Ca and Cu. We will start by assuming that the OER proceeds in acid media through the following series of reaction steps6b, 10:

* + H 2O(l ) → *OH + ( H + + e− ) , *OH → *O + ( H + + e− ) ,

∆G1 = ∆GOH

(1)

∆G2 = ∆GO − ∆GOH

(2)

*O + H 2O(l ) → *OOH + ( H + + e− ) , *OOH → * + O2( g ) + ( H + + e− ) ,

∆G3 = ∆GOOH − ∆GO

∆G4 = ∆GO2 − ∆GOOH

(3)

(4)

Where * denotes an active M site at a(001)MO2-terminated surface in AMO3,or an M site at the (001) surface of MO. According to these equations, the adsorbed intermediates of the


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OER are *O, *OH and *OOH, the adsorption energies of which are ∆GO , ∆GOH , and ∆GOOH , respectively. The energetics of proton-electron pairs in solution is estimated through the computational hydrogen electrode (CHE, see further details in the Supporting Information).11 Within this scale, the formation energy of O2( ∆GO2 ) is 4.92 eV (that is 1.23 V × 4 e-), whereas that of H2O is zero.On the other hand, the free energies of formation of the bulk perovskites were calculated at 298.15 K from the A and M components and water, protons and electrons (making use of the CHE), in the following way:

(

A + M + 3H 2O(l ) → AMO3 + 6 ( H + + e− ) , ∆G form, bulk = GAMO3 − GA − GM + 3 GH2 − GH2O

)

(5)

The formation energies of MO were calculated analogously through CHE approach: M + H 2O( l ) → MO + 2 ( H + + e− )

(6)

In Figures 1 and 2we summarize the trends in bulk formation energies and in the adsorption energies of *O, *OH and *OOH for LaMO3 and SrMO3and MO.


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Figure 1. Trends in surface adsorption and bulk thermochemistry ofSrMO3(squares) and LaMO3 (circles) as a function of the number of outer electrons of M. The adsorption energies of *O (blue), *OH (red), and *OOH (green) are given for (a) SrMO3 and (b) LaMO3.(c) Formation energies of LaMO3 (violet) and SrMO3 (orange) from La/Sr, M and H2O. The metal at the M site is given in each case. The parameters of the linear fits are provided in the Supporting Information. Data in a) and b) was taken from refs6; data in c) was adapted from ref9. Triangles correspond to the materials for which the bulk-surface correlation does not apply.


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Figure 2.Trends in surface adsorption and bulk thermochemistry of MO as a function of the number of outer electrons of M, with M ranging between Ca and Cu. (a) Adsorption energies of *O (blue), *OH (red), and *OOH (green), taken from refs6. (b) Formation energies of bulk MO from M and H2O, adapted from ref9. The parameters of the linear fits are provided in the Supporting Information. Triangles correspond to the materials for which the bulk-surface correlation does not apply.

In Figures 1 and 2the trends in bulk thermochemistry and surface adsorption energies are smoothly described by the number of outer electrons of the transition metal at the M site in AMO3 in the ranges from 0 to 7 for SrMO3, 0 to 8 for LaMO3, and 0 to 9 for MO. The number of outer electrons is equivalent to the number of valence electrons for a pure element, and in ionic compounds it is calculated as the resultingnumber of valence electrons in an ion upon oxidation or reduction.6a For instance, Cr possesses 6 valence electrons, as its electronic


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distribution ends in 4s1 3d5. Hence, Cr2+, as in CrO, has 4 outer electrons; Cr3+, as in LaCrO3, has 3 outer electrons; while Cr4+, as in SrCrO3, has 2 outer electrons. The trends in Figures 1.cand 2.bhave been observed both experimentally and theoretically (see9 and references therein) and have also been extended to other families of perovskite oxides.12 Besides, the trends in formation energies of other classes of oxides such as rutiles are also known to follow similar electron-counting rules.13It is important to note that althoughthe trends in formation energies are well captured for LaMO3, SrMO3and MOby RPBE,a constant shift exists between theoretical predictions and experimental values of the formation energies.9Such error is largely or totally suppressed when only oxides take part in the chemical reactions, and the GGA + U method is known to improve the overall description of oxides.14 The linear trends in the range of outer electrons between 1 to 7-8-9 (depending on the oxide family)in Figures 1.a, 1.b and 2.a are extensible to pure metals (M)and adsorption energy grids can be created, as the slopes of the lines are nearly the same and the separation between them is also a constant.6aThisdemonstrates the wide range of applicability of outer electrons as descriptors in adsorption processes.Moreover, the theoretical activity predictions for the OER based on those trends reproduce the experimental ones,4d, 6b and the catalytic activity of transition metal hydroxides has also been shown to follow similar trends.15 Clearly, for the range of outer electrons between 1 and 7-8-9since both bulk and surface energetics depend linearly on the same parameter (the number of outer electrons), it is expected that, by transitivity, bulk and surface energetics will also scale linearly with each other,as shown in Figure 3.The similar dependence on the number of outer electrons of both surface and bulk properties allows for the use of the latter to describe trends in surface reactivity. This apparently simple result is the underlying chemical justificationfor the use of bulk data to rationalize surface catalytic activity not only in electrocatalysis4b, c but also in


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heterogeneous catalysis.16It is also important to note that the energetics of materials with zero outer electrons, namely CaO,LaScO3 and SrTiO3, deviate significantly from the main trends in Figure 3.6a This is because the electronic structure of these compounds is optimal, as all of their components possess noble gas configurations. This implies that the bulk exhibits the most stable energies of formationpossible within a given family of compounds, while the surface is quite noble, as the binding of adsorbates implies electron covalence with already filled bands. Similar arguments justify the existence of the observed minima at 10 outer electrons in Figure 1for SrGeO3 and LaGaO3, as this value implies a full d-band for M and noble gas configurations for A and O. Clearly, the deviations from the linear trends in Figure 3 originate from the mismatch between the bulk and surface energetics in Figures 1and 2. This kind of mismatch is well known to cause deviations in energetic scaling relationships and is most prominent for the adsorption energies of *O in Figure 3.17

Figure 3. Scaling relationships between the energies of formation of the bulk and the adsorption energies of *O

(blue), *OH (red) and *OOH (green) for(a) MO,(b) LaMO3 and (b) SrMO3. The Figure shows that for the range between Ti to Cu, bulk thermochemistry is an excellent descriptor of surface adsorption energies. The parameters of the linear fits are provided in the Supporting Information. Triangles represent the data for which the linear relationships do not apply.


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Note in the linear regions in Figure 3 that for a given M, the binding energies of OER adsorbates on MO are typically stronger than those of LaMO3 and those are, in turn, stronger than those of SrMO3. This is because M2+ is less oxidized than M3+ and M4+, and increasing oxidation states correspond to weaker adsorption energies.6aWith the bulk-surfacescaling relationships in Figure 3 one can generate activity plots for the OER. To do so, we follow Rossmeisl and coworkers,6b, 10 who found that, generally, steps 2 (with ∆G2) and 3 (with ∆G3) are the possible potential-limiting steps of the OER. In Figure 4 we have takenthe highest energies among ∆G1, ∆G2, ∆G3, and ∆G4 for each perovskite and monoxideand subtracted them from 1.23 V, in order to obtain a first estimation of the OER overpotential in identical conditions for all oxides. The volcano plots in Figure 4 resemble previous activity plots that used surface adsorption energiesas descriptors.6b, 10 Note, however, that volcano plots based on scaling relationships are more robust than the one in Figure 4, as only theyonly require two lines to represent the activity trends (see Figure S1 in the Supporting Information, where the scaling relations between the adsorption energies of the OER intermediates are providedfor all oxides in this study). Conversely,the activity plot in Figure 4needs two lines per family of oxide compounds. Volcano plots exclusively based on adsorptive scaling relations are also advantageous because they tend to have little deviations from the main trends. However, the kind of volcano plot in Figure 4 possesses a unique feature: it simultaneously provides an estimation of the catalytic activity and the chemical stability of materials. This is because the formation energy of the bulk as defined in Equations 5 and 6 is a measure of the stability of the oxide in aqueous solution. Evidently, these initial stability estimations for MO and AMO3require further analysis of other (electro)chemical reactions, such as oxide-phase changes and dissolution of A and/or M,in order to provide a thorough estimation of


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thestability of the oxideunder OER conditions.9, 18Note than an additional advantage of the volcano plot in Figure 4 is the large availability of bulk energetics data for most oxides. In any case, it is possible to say that, according to the volcano plots in Figure 4, the most active compounds tend to be the least stable ones, as the majority of the oxides on the volcano curves lie on their left legs (that is, on the lines with positive slopes in Figure 4). Asactivity and stability follow opposite trends,high pH values are recommended to enhance the chemical stability of perovskite oxides. Note in passing that LaMO3perovskites are always more stable than their SrMO3and MO counterparts, and that for a given metal M, Sr-doped perovskites have intermediate formation energies between LaMO3 and SrMO3(see ref.9 and references therein).Therefore, Sr-doping seems to be beneficial for the enhancement of the OER activity of La-perovskite oxides located on the left leg of the volcano plot.Similarly, La-doping might enhance the OER activity of perovskites on the right leg of the volcano plot, granting additional stability, as well.

Figure 4.Volcano-type activity plot for LaMO3 (violet circles), SrMO3 (orange squares), and MO (brown rhombs). The descriptor is the formation energy of the oxide in the bulk, while the additive inverse of the


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overpotential is estimated from reaction energetics at surfaces. According to this plot, the most active catalysts in this study are NiO, LaNiO3SrCoO3. Triangles represent the data for which the linear relationships do not apply.

In summary, we haveillustrated the correlation between bulk and surface energetics on the basis of the OER electrocatalysis on transition-metal perovskites and monoxides. This correlation is responsible for the existence of volcano plots that rationalize trends in catalytic activity through variations in bulk thermochemistry. Additionally, such volcano plots provide direct estimations of the chemical stability of the oxides, which is paramount in the search for catalysts with good tradeoffs between activity and stability under reaction conditions. The boundaries of applicability of themethod are from SrVO3 to SrCuO3 in Sr-perovskites;from LaTiO3 to LaCuO3 in La-perovskites; and from TiO to CuO in monoxides. The method cannot be extrapolated to include compounds with zero outer electrons at the M site, namely CaO,SrTiO3 and LaScO3,while Zn, Ga and Ge are to be added cautiously. We have previously shown that the concept of outer electrons explains the existence of scaling relationships between chemisorbates on transition metals, their monoxides and ternary oxides in the perovskite phase,6a,

17

and in functionalized graphitic materials and metalloporphyrinswith

transition-metal centers.19Here, we have shown that the intimate relationship between bulk thermochemistry and surface adsorption is also captured by the same concept for monoxides andtwo families of perovskite oxides. Generally speaking, outer electrons are, thus, able to add generality and simplicity to the description of activity trends in the broad field of catalysis.

COMPUTATIONAL METHODS All DFT calculations of bulk and surface systems were performed with Dacapo, a plane-wave code, theRPBE exchange-correlation functionaland ultrasoft pseudopotentials. Spin


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unrestricted calculations were carried out when necessary. Further details of these calculations can be found elsewhere.6a, 9

Notes The authors declare no competing financial interests

Supporting Information Available:Parameters of the linear fits in Figures 1-3,definition of adsorption energies, computational hydrogen electrode. This material is available free of charge via the Internet http://pubs.acs.org.

ACKNOWLEDGMENT FCV acknowledgesfunding from the EU’s FP7/2007-2013program, call FCH-JU-20111under grant agreement n°303419 (PUMA MIND). This work was also supported by the Netherlands Organization for Scientific Research (NWO) and in part by the BioSolar Cells open innovation consortium, supported by the Dutch Ministry of Economic Affairs, Agriculture and Innovation.

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