Carbonate formation lowers the electrocatalytic activity of perovskite oxides for water electrolysis

Baeumer, Christoph; Liang, Allen Yu-Lun; Trstenjak, Urška; Lu, Qiyang; Waser, Rainer; Mefford, J. Tyler; Gunkel, Felix; Nemšák, Slavomír; Chueh, William C.

doi:10.1039/d1ta03205d

Cited by 14 publications

(8 citation statements)

References 34 publications

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“…[16,39] Thus, when too many oxyanions are present, they will block the OER active sites. [23,40,41] This competition is consistent with the observation that the addition of oxyanions to the electrolyte first leads to an improvement of the OER activity (see following paragraphs), but after a certain concentration (in the order of magnitude of 0.1 M) the overpotential increases. [15,16] In this regard, it is worth mentioning that anodic potentials can increase the local concentration of (oxy)anions in the (near-)surface area of the electrode, as oxyanion migration into the double-layer can take place to compensate the build-up positive charge on the electrode surface.…”

Section: àsupporting

confidence: 88%

“…Density functional theory (DFT) calculations revealed that the adsorption energy is often negative (e.g., −1.9 eV for SeO 4 2− on NiOOH) [15] and occurs at the same transition metal sites where the OER intermediates are adsorbed (Ni preferred to Fe) [16, 39] . Thus, when too many oxyanions are present, they will block the OER active sites [23, 40, 41] . This competition is consistent with the observation that the addition of oxyanions to the electrolyte first leads to an improvement of the OER activity (see following paragraphs), but after a certain concentration (in the order of magnitude of 0.1 M) the overpotential increases [15, 16] .…”

Section: The Effect Of Surface‐adsorbed Oxyanionssupporting

confidence: 73%

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Effect of Surface‐Adsorbed and Intercalated (Oxy)anions on the Oxygen Evolution Reaction

Hausmann

Menezes

2022

Angewandte Chemie

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As the kinetically demanding oxygen evolution reaction (OER) is crucial for the decarbonization of our society, a wide range of (pre)catalysts with various non‐active‐site elements (e.g., Mo, S, Se, N, P, C, Si…) have been investigated. Thermodynamics dictate that these elements oxidize during industrial operation. The formed oxyanions are water soluble and thus predominantly leach in a reconstruction process. Nevertheless, recently, it was unveiled that these thermodynamically stable (oxy)anions can adsorb on the surface or intercalate in the interlayer space of the active catalyst. There, they tune the electronic properties of the active sites and can interact with the reaction intermediates, changing the OER kinetics and potentially breaking the persisting OER *OH/*OOH scaling relations. Thus, the addition of (oxy)anions to the electrolyte opens a new design dimension for OER catalysis and the herein discussed observations deepen the understanding of the role of anions in the OER.

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Section: àsupporting

confidence: 88%

Section: The Effect Of Surface‐adsorbed Oxyanionssupporting

confidence: 73%

Effect of Surface‐Adsorbed and Intercalated (Oxy)anions on the Oxygen Evolution Reaction

Hausmann

Menezes

2022

Angewandte Chemie

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“…This enhanced material control with atomically smooth catalyst surfaces comes at the cost of a minimized contact area between catalyst and electrolyte, limiting the technological relevance of epitaxial systems. But such atomically controlled model systems have emerged as an ideal platform to identify structure-function-relationships at the atomic level, a prerequisite for advanced design rules ( Risch et al, 2013 ; May et al, 2015 ; Scholz et al, 2016 ; Gunkel et al, 2017 ; Eom et al, 2018 ; Bak et al, 2019 ; Liu et al, 2019 ; Weber et al, 2019 ; Baeumer et al, 2021a ; Baeumer, 2021 ; Baeumer et al, 2021b ; Wan et al, 2021 ) and offering to finally overcome the materials challenge imposed by the activity-stability dilemma.…”

Section: Atomistic Understanding Of Activity and Degradation Relies O...mentioning

confidence: 99%

Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysis

et al. 2022

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The oxygen evolution reaction (OER) is one of the key kinetically limiting half reactions in electrochemical energy conversion. Model epitaxial catalysts have emerged as a platform to identify structure-function-relationships at the atomic level, a prerequisite to establish advanced catalyst design rules. Previous work identified an inverse relationship between activity and the stability of noble metal and oxide OER catalysts in both acidic and alkaline environments: The most active catalysts for the anodic OER are chemically unstable under reaction conditions leading to fast catalyst dissolution or amorphization, while the most stable catalysts lack sufficient activity. In this perspective, we discuss the role that epitaxial catalysts play in identifying this activity-stability-dilemma and introduce examples of how they can help overcome it. After a brief review of previously observed activity-stability-relationships, we will investigate the dependence of both activity and stability as a function of crystal facet. Our experiments reveal that the inverse relationship is not universal and does not hold for all perovskite oxides in the same manner. In fact, we find that facet-controlled epitaxial La0.6Sr0.4CoO3-δ catalysts follow the inverse relationship, while for LaNiO3-δ, the (111) facet is both the most active and the most stable. In addition, we show that both activity and stability can be enhanced simultaneously by moving from La-rich to Ni-rich termination layers. These examples show that the previously observed inverse activity-stability-relationship can be overcome for select materials and through careful control of the atomic arrangement at the solid-liquid interface. This realization re-opens the search for active and stable catalysts for water electrolysis that are made from earth-abundant elements. At the same time, these results showcase that additional stabilization via material design strategies will be required to induce a general departure from inverse stability-activity relationships among the transition metal oxide catalysts to ultimately grant access to the full range of available oxides for OER catalysis.

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“…241 In case of OER, the presence of carbonate was found to decrease the catalytic activity of LaNiO 3 by formation of carbonates which altered the chemical environment of active sites. 242 This may be generally applicable to other transition metal based OER catalysts.…”

Section: Impact Of Impurities In Awes and Aemwesmentioning

confidence: 98%

Impact of impurities on water electrolysis: a review

Becker

Murawski

Shinde

et al. 2023

Sustainable Energy Fuels

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Carbonate formation lowers the electrocatalytic activity of perovskite oxides for water electrolysis

Abstract: The study of oxide electrocatalysts is often complicated by the formation of complex and unknown surface species as well as the interaction between the catalysts and common support materials. Because...

Cited by 14 publications

References 34 publications

Effect of Surface‐Adsorbed and Intercalated (Oxy)anions on the Oxygen Evolution Reaction

Effect of Surface‐Adsorbed and Intercalated (Oxy)anions on the Oxygen Evolution Reaction

Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysis

Impact of impurities on water electrolysis: a review

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