Perovskite Metal Oxides Research Articles

Comparison of Single Atoms vs. Sub-Nanoclusters as Co-Catalysts in Perovskites and Metal Oxides for Photocatalytic Technologies

Adatoms as co-catalysts may play a key role in photocatalysis, yet control of their exact configuration remains challenging. Specifically, there is converging evidence that ultra-small structures may be optimal as co-catalysts; however, a comprehensive distinction between single atoms (SAs), sub-nanoclusters (SNCs), and quantum-sized small particles (QSSPs) has yet to be established. Herein, we present a critical review addressing these distinctions, along with challenges related to the controlled synthesis of SAs, SNCs, and QSSPs; their detection methods; and their functional benefits in photocatalysis. Our discussion focuses on perovskite oxides (e.g., such as ABO3, where A and B are cations) and metal oxides (MxOy, where M is a metal) decorated with adatoms, which demonstrate superior photocatalytic performance compared to their unmodified counterparts. Finally, we highlight cases of misinterpretation between SA, SNC, and QSSP configurations emerging from limitations in high-resolution detection techniques and synthesis methods.

Recent progress of gas sensors based on perovskites.

Gas sensors convert gas-related information into usable data by monitoring changes in conductivity and chemical reactions resulting from the adsorption of gas molecules. Recently, perovskites have emerged as promising candidate materials for gas sensors, owing to their polar reactivity, chemical responsiveness, and sensitivity. These characteristics enable the detection of the presence and concentration of various gases. This article provides a concise review of recent advancements in perovskite-based gas sensors. First, the chemical composition, structure, and preparation methods of perovskites, as well as the effects of their structure on gas sensing performance, are examined. The key performance parameters of the sensor and the sensing mechanism of the perovskite-based gas sensor are discussed. Then the development of gas sensors based on different structural types of perovskites, including single-component perovskites, mixed-component perovskites, and metal-oxide perovskites, is discussed. Finally, the challenges and opportunities for gas sensors based on perovskites are summarized and prospected.

Exploring the role of nonlocal Coulomb interactions in perovskite transition metal oxides

Employing the density functional theory incorporating on-site and inter-site Coulomb interactions (DFT + U + V), we have investigated the role of the nonlocal interactions on the electronic structures of the transition metal oxide perovskites. Using constrained random phase approximation calculations, we derived screened Coulomb interaction parameters and revealed a competition between localization and screening effects, which results in nonmonotonic behavior with d-orbital occupation. We highlight the significant role and nonlocality of inter-site Coulomb interactions, V, comparable in magnitude to the local interaction, U. Our DFT + U + V results exemplarily show the representative band renormalization, and deviations from ideal extended Hubbard models due to increased hybridization between transition metal d and oxygen p orbitals as occupation increases. We further demonstrate that the inclusion of the inter-site V is essential for accurately reproducing the experimental magnetic order in transition metal oxides.

Irreversible oxygen uptake and thermal expansion in the solid electrolyte oxygen-deficient perovskite Ca(Ti0.8Fe0.2)O3−δ

The efficient operation of solid oxide fuel cells for renewable energy generation requires solid electrolytes with high ionic conductivity, thermal stability, and chemical durability. Metal oxide perovskites of the form ABO3 are promising candidates, especially when doped with cations that incorporate interstitial oxygen or oxygen vacancies to enhance ionic conductivity. However, doping can lead to complex and poorly understood crystallographic structures. In this study, we investigate the effects of Fe3+ doping on the orthorhombic Pbnm CaTiO3 perovskite, forming Ca(Ti0.8Fe0.2)O3−δ, and demonstrate the complexity of its phase transitions at operational temperatures. Using synchrotron X-ray diffraction and thermogravimetric analysis, we show that this material undergoes significant oxygen uptake at elevated temperatures, leading to an irreversible expansion of the unit cell and changes in polyhedral coordination upon cooling. These structural modifications are attributed to the partial oxidation of Fe3+ to Fe4+, providing insight into the inconsistencies observed in previous studies of oxygen-deficient perovskites. Our findings highlight the critical role of thermal history and oxygen availability in determining the structural stability and long-term performance of perovskite-based solid electrolytes in solid oxide fuel cells.

Proton Solubilities in Candidate Protonic Ceramic Fuel Cell Air Electrode Materials from First Principles

Using a mixed protonic-electronic conducting oxide as the air electrode of protonic ceramic fuel cells is one strategy for increasing their electrical efficiency, as this should enable a larger particle surface area to participate in the oxygen reduction reaction. However, because of their complex defect chemistry, few studies have focused on proton solubility in electrode materials, and hence little is known about which materials are able to absorb sufficient protons to support high conductivity. To help identify materials likely to have both high protonic and electronic conductivity, we performed first-principles calculations of 3d transition metal oxide perovskites LnMO3 (Ln = La, Pr, Nd, Sm, Gd; M = Sc, V–Ni), focusing on their hydration enthalpies calculated according toH2O+v O ⋅⋅+OO ×→2OHO ⋅, where v O ⋅⋅ is an oxide-ion vacancy and the proton bonds to an O atom to form a hydroxide ion, OHO ⋅.We found that hydration becomes less favorable as the number of 3d electrons increases, i.e., as the M-O bonds become less basic. In contrast, electronic conductivity, as assessed from band structure plots and effective masses, generally increases. By comparing the hydration enthalpy to that of prototypical proton electrolyte BaZrO3, good mixed proton-hole conducting oxides are thus likely to be found using transition metals from the middle of the period (M = Cr–Co) when Ln = La. Smaller lanthanides favor easier hydration, however, so that good mixed conducting perovskites containing Fe, Co, and/or Ni may be achievable using lanthanides Pr, Nd or Sm.AcknowledgmentThis work was performed as part of the Development of Ultra-High Efficiency Protonic Ceramic Fuel Cell Devices project (JPNP20003), commissioned by the New Energy and Industrial Technology Development Organization.

Recent Progress on Perovskite Materials for VOC Gas Sensing.

Volatile organic compound (VOC) gases are highly hazardous to human health, and their presence in the human breath plays an indispensable role for the early diagnosis of various diseases (cancer, renal failure, etc.). In recent times, perovskite materials have shown notable performance in the detection of VOC gases with high accuracy, fast response, recovery time, selectivity, and sensitivity, owing to their unique crystallographic structures and excellent optoelectronic properties. In this Review, we look at recent reports on perovskite-based sensors and their sensing performance toward VOC gases. Here, we focus on the sensing mechanisms of two types of perovskite materials, metal halide and metal oxide perovskites, and explain the differences in their crystal structures. We also discuss the common preparation methods used by researchers for the synthesis of these perovskite materials. Further, we elucidate various important factors influencing the sensing performance of perovskite-based sensors, such as doping, defects, morphology, temperature, humidity, and light. We conclude with the future prospects and challenges related to these perovskite-based sensors toward the detection of VOC gases.

Interfacial stability and electronic properties of YBCO/ABO3 heterostructures: A comparative DFT study

In this study, we utilized density functional theory (DFT) to analyze the interfacial properties of YBa2Cu3O7 (YBCO) with perovskite metal oxides LaAlO3 (LAO), KTaO3 (KTO), and SrTiO3 (STO). We focused on surface energies, lattice mismatches, strain energies, and adhesion energies to gauge the stability and compatibility of these interfaces. Our findings indicate that KTO exhibits the highest surface preference due to its lowest surface energy (0.054 eV/Å 2), suggesting superior surface stability. Moreover, LAO and STO show minor lattice mismatches with YBCO, implying effective interface integration, while YBCO/KTO interfaces experience significant strain due to extensive lattice mismatches. STO is distinguished by the lowest strain energy (0.07 eV), indicating minimal energy requirement for lattice mismatch accommodation, unlike KTO, which demonstrates high strain energy (0.42 eV) and potential structural distortions. The strongest interfacial bond, as indicated by an adhesion energy of −2.16 eV, was observed at YBCO/LAO, while the weakest was found at the YBCO/KTO interface, with an adhesion energy of −0.56 eV. Additionally, charge density difference (CDD) analysis highlighted electron density redistribution at the interfaces, predominantly around interfacial oxygen atoms, indicating a mix of ionic and covalent bonding. This study provides comparative insights into the interfacial characteristics of YBCO/ABO3 heterostructures, suggesting pathways for optimizing their design and performance.

Eco-Friendly Mechanochemical Synthesis of Bifunctional Metal Oxide Electrocatalysts for Zn-Air Batteries.

The development of green and environmentally friendly synthesis methods of electrocatalysts is a crucial aspect in decarbonizing energy generation. In this study, eco-friendly mechanochemical synthesis of perovskite metal oxide-carbon black composites is proposed using different conditions and additives such as KOH. Furthermore, the optimization of ball milling conditions, including time and rotational speed, is studied. The mechanochemical synthesis in solid-state conditions without additives produces electrocatalysts that exhibit the highest bifunctional electrochemical activity towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Moreover, this synthesis demonstrates a lower Environmental Impact Factor (E-factor), indicating its greener nature, and due to its simplicity, it has a great potential for scalability. The obtained bifunctional electrocatalysts have been tested in a rechargeable zinc-air battery (ZAB) for 22 h with similar performance compared to the commercial catalyst (Pt/C) at significantly lower cost. These promising findings are attributed to the enhanced interaction between the perovskite metal oxide and carbon material and the improved dispersion of the perovskite metal oxide on the carbon materials.

Redox Stability Analysis of Co-Doped Barium Niobate Thin Films Via Cyclic Voltammetry

The electrochemical oxidative coupling of methane (E-OCM) to higher hydrocarbons, requires anodes that are stable under reducing conditions. We have previously demonstrated high activity with long term stability/durability for the perovskite anode BaMg0.33Nb0.67-xFexO3-δ (BMNF) while performing E-OCM1. Our group has also improved the total conductivity and activity of barium niobate perovskites via exchange of Mg for Ca (from 18 mS/cm-1 to 41 mS/cm-1), while also decreasing the Goldschmidt tolerance factor below 1 for increased cubic perovskite structural stability2. Perovskite metal oxide thin films can be produced with well-defined thicknesses and stoichiometries through pulsed laser deposition (PLD)3. These thin films are utilized in cyclic voltammetry experiments on YSZ substrates to further elucidate the chemical stability and oxygen sub-stoichiometry of high temperature SOFC/SOEC electrodes. Through application of reducing potentials to the electrode of interest, the voltage and current responses can be correlated to effective oxygen activities in which reduction of the electrode may occur. Usage of this technique with calcium and iron doped barium niobate perovskites (BaCa0.33Nb0.67-xFexO3-δ - BCNF) provides insights into the thermochemical stability and iron doping effects under highly reducing environments. The BCNF thin film electrodes were characterized via grazing incidence XRD and XRF for crystal structure and chemical composition. After initial characterization, cyclic voltammetry experiments were performed in a novel cell setup. These BCNF thin films show promise for evaluating stability mechanisms for E-OCM operation while providing details on compositional changes and oxygen loss of BCNF in reducing environments.

Porous hollow sphere structure PrFeO3 as an efficient sensing material for n-butanol detection

N-butanol is a harmful volatile gas, so creating an appropriate n-butanol sensor is critical for preserving human health and the manufacturing environment. In contrast to single metal oxide semiconductors, multicomponent metal oxides, especially perovskite ternary metal oxides with the ABO3 structure, exhibit significant potential for development owing to their precise structures and diverse physicochemical properties. In this paper, three-dimensional porous hollow spheres PrFeO3 were synthesized by combining air annealing and hydrothermal techniques. The crystal structure, surface composition, chemical state, and morphology of PrFeO3 materials were evaluated using several kinds of characterization approaches. The gas sensitivity of PrFeO3 materials was also thoroughly explored. The results show that at the optimal working temperature of 280 ℃, the PrFeO3 material excels in n-butanol gas sensing, with a response of 85 for 100 ppm n-butanol. Additionally, the sensor demonstrates high selectivity for n-butanol gases, low concentration detection capability, outstanding repeatability, rapid reaction recovery time (18 s/13 s), long-term stability, and exceptional reproducibility. The unique morphology and high oxygen vacancy content of PrFeO3 provide numerous active sites on its surface, promoting the adsorption and desorption of n-butanol gas molecules and enhancing its gas-sensitive properties.

Highly confined epsilon-near-zero and surface phonon polaritons in SrTiO3 membranes

Recent theoretical studies have suggested that transition metal perovskite oxide membranes can enable surface phonon polaritons in the infrared range with low loss and much stronger subwavelength confinement than bulk crystals. Such modes, however, have not been experimentally observed so far. Here, using a combination of far-field Fourier-transform infrared (FTIR) spectroscopy and near-field synchrotron infrared nanospectroscopy (SINS) imaging, we study the phonon polaritons in a 100 nm thick freestanding crystalline membrane of SrTiO3 transferred on metallic and dielectric substrates. We observe a symmetric-antisymmetric mode splitting giving rise to epsilon-near-zero and Berreman modes as well as highly confined (by a factor of 10) propagating phonon polaritons, both of which result from the deep-subwavelength thickness of the membranes. Theoretical modeling based on the analytical finite-dipole model and numerical finite-difference methods fully corroborate the experimental results. Our work reveals the potential of oxide membranes as a promising platform for infrared photonics and polaritonics.

A Versatile Synthesis Platform Based on Polymer Cubosomes for a Library of Highly Ordered Nanoporous Metal Oxides Particles.

Polymer cubosomes (PCs) have well-defined inverse bicontinuous cubic mesophases formed by amphiphilic block copolymer bilayers. The open hydrophilic channels, large periods, and robust physical properties of PCs are advantageous to many host-guest interactions and yet not fully exploited, especially in the fields of functional nanomaterials. Here, the self-assembly of poly(ethylene oxide)-block-polystyrene block copolymers is systematically investigated and a series of robust PCs is developed via a cosolvent method. Ordered nanoporous metal oxide particles are obtained by selectively filling the hydrophilic channels of PCs via an impregnation strategy, followed by a two-step thermal treatment. Based on this versatile PC platform, the general synthesis of a library of ordered porous particles with different pore structures , tunable large pore size (18-78nm), high specific surface areas (up to 123.3m2g-1 for WO3) and diverse framework compositions, such as transition and non-transition metal oxides, rare earth chloride oxides, perovskite, pyrochlore, and high-entropy metal oxides is demonstrated. As typical materials obtained via this method, ordered porous WO3 particles have the advantages of open continuous structure and semiconducting properties, thus showing superior gas sensing performances toward hydrogen sulfide.

Catalytic Oxidation of BTX (Benzene, Toluene, and Xylene) Using Metal Oxide Perovskites

AbstractThe high toxicity, volatility, and dispersion of the light aromatics, benzene, toluene, and xylene (BTX) pose a serious threat to the environment and human health. Compared to incineration, catalytic oxidation technologies for BTX removal offer benefits such as low energy consumption, high efficiency, and low pollution. ABO3–type perovskite catalysts (ABO3–PCs) are particularly promising materials for the catalytic oxidation of BTX due to their high activity and thermal stability, as well as their adjustable elemental composition and flexible structure allowing their properties to be improved. Nonetheless, the full potential of ABO3–PCs for the oxidation of BTX has yet to be reached. This review systematically and critically analyses progress in the catalytic oxidation of BTX by ABO3–PCs. Catalytic performance is assessed for each category of perovskite, including non–doped, doped (A–, B–, or A/B–site doped), and loading type (noble metal, metal oxide, and matrix composite), with structure–activity relationships are established. A kinetic model and proposed mechanism for the catalytic oxidation of BTX are also presented. Finally, the challenges and opportunities of ABO3–PCs applied to BTX oxidation and other reactions are highlighted.

High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 with tailored eg occupancy and transition metal-oxygen bond properties for oxygen reduction reaction

Forming high entropy oxide provides a feasible approach to finding a balance among moderate eg occupancy, high transition metal-oxygen (TM-O) covalency, and lattice energy, which is essential to ensure efficient and durable oxygen reduction reaction (ORR) process for perovskite lanthanide-transition metal oxides (LaTMO3). However, due to the compositional complexity, clarifying the relevance among the high entropy components, eg occupancy, TM-O properties, and ORR performance still remains a challenge. Herein, adopting the B site entropy-driven strategy, a series of LaTMO3 (TM = Cr, Mn, Fe, Co, Ni) with tunable eg occupancy and TM-O bond properties are synthesized, and the correlations between high entropy elements, eg occupancy, TM-O properties, and ORR performances are revealed quantitively based on the crystal field theory and the Phillips–Van Vechten–Levine (P–V–L) valence bond theory. High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 delivers a low overpotential of 493 mV (vs. 503 mV for LaMnO3) and a minuscule decline by only 1.7% (vs. 4.4% for LaMnO3) in half wave potential after 10,000 cycles, which can be associated with the tailored eg occupancy (1.06) and the significant enhancement in both TM-O covalency (4%) and lattice energy (691.75 kJ mol–1). This work not only demonstrates the prospects of high entropy LaTMO3 in the ORR field but also provides a new perspective for the quantitative analysis of the structure-activity relationship for high entropy oxide ORR catalysts.

Zinc stannate oxide perovskite nanomaterial based electrochemical detection of ammonia

Metal oxide perovskites are promising for sensing harmful chemicals at room temperature with high accuracy, sensitivity, selectivity, and ultra-low detection limit. There is a need for material that can have high sensitivity toward hazardous chemicals like ammonia. In this paper, a one-step hydrothermal process has been successfully used for the synthesis of ZnSnO3 nanopowder. With the presence of ample oxygen vacancies and a large surface area, ZnSnO3 nanopowder facilitates excellent electrochemical sensing properties. Here, the electrochemical ammonia sensing was investigated in potentiometric and amperometric modes. At room temperature, ammonia was detected within a linear concentration range from 10 nM to 60 nM, utilizing a low potential of 20 mV. The fabricated ammonia sensor based on ZnSnO3 nanopowder can detect at an ultra-low detection limit of 0.851 pM with a high sensitivity value of 4.548 mAcm−2nM−1. The reproducibility, repeatability, and stability of the ammonia sensor are also reported.

Metal(Pt, Pd)-Perovskite Oxide(Ba0.5Sr0.5Co0.8Fe0.2O3-δ) Hybrid Material As a Bifunctional Electrocatalyst for Lithium-Air Battery

The rapid depletion of fossil fuel resources and growing concerns over climate change have made the development of next-generation batteries a top priority. Among these, Li-O2 batteries have attracted significant interest due to their potential for much higher gravimetric energy storage density compared to other chemical batteries. However, efficient and cost-effective catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical for the efficient functioning of these batteries.In recent years, complex perovskite oxides, such as Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), have been identified as promising candidates for bifunctional catalysts due to their defective structures and excellent oxygen mobility. However, while BSCF exhibits high OER activity, its ORR performance is poor. To address this issue, researchers have turned to metal-oxide composite catalysts, where nanosized metals are deposited on the surface of perovskite oxides, to increase activity and stability towards ORR due to the synergistic effect between metal and oxide support.In this study, we report the development of bifunctional electrocatalysts with highly electrocatalytic activity for ORR and OER. We used a simple wet-chemical processing technique to deposit metal catalysts with superior ORR activity on perovskite oxide-based catalysts with high OER activity. The direct deposition method is an effective way to create a good distribution of metal catalysts, intimate contact between metal catalysts and BSCF perovskite oxide, which may contribute to the creation of a synergistic effect between them. Our results showed that the metal catalysts deposited on perovskite oxides of Pd@BSCF and Pt@BSCF exhibited better ORR activity than others and higher OER activity than the perovskite oxides alone, resulting in much-enhanced bifunctionality through a synergistic effect between the metal catalysts and perovskite oxides.We further investigated the enhanced bifunctional electrocatalytic activity of the metal catalysts deposited perovskite oxides for Li-O2 batteries. The assembled Li-O2 batteries with Pd@BSCF cathode demonstrated lower discharge/charge overpotential (0.8 V at the cutoff capacity of 500 mAh gcat -1) and improved cycling stability (over 70 cycles), indicating the effectiveness of our approach in enhancing the bifunctional activities of ORR and OER for application in electrochemical energy storage and conversion systems. The encouraging results obtained from this study might have been attributed to two mechanisms, namely, the synergistic effect of electronic transfer and RDS/spillover. Our study suggests that the deposition of metal catalysts on the surface of perovskite oxides (Pd@BSCF and Pt@BSCF) is an effective approach to enhance bifunctional activities of ORR and OER, making it a promising strategy for the development of next-generation batteries. Figure 1

Improvement of oxygen reduction activity and stability on a perovskite oxide surface by electrochemical potential

The instability of the surface chemistry in transition metal oxide perovskites is the main factor hindering the long-term durability of oxygen electrodes in solid oxide electrochemical cells. The instability of surface chemistry is mainly due to the segregation of A-site dopants from the lattice to the surface. Here we report that cathodic potential can remarkably improve the stability in oxygen reduction reaction and electrochemical activity, by decomposing the near-surface region of the perovskite phase in a porous electrode made of La1-xSrxCo1-xFexO3 mixed with Sm0.2Ce0.8O1.9. Our approach combines X-ray photoelectron spectroscopy and secondary ion mass spectrometry for surface and sub-surface analysis. Formation of Ruddlesden-Popper phase is accompanied by suppression of the A-site dopant segregation, and exsolution of catalytically active Co particles onto the surface. These findings reveal the chemical and structural elements that maintain an active surface for oxygen reduction, and the cathodic potential is one way to generate these desirable chemistries.

Freestanding Perovskite Oxide Membranes: A New Playground for Novel Ferroic Properties and Applications

AbstractTransition metal perovskite oxide membranes and their unique properties have attracted great attention recently and have been developed into one of the research frontiers in condensed matter physics and materials science. Free of constraint imposed by the underlying substrate, freestanding membranes exhibit extraordinary structural tunability and flexibility far exceeding the bulk materials and epitaxial films clamped on substrates, which substantially extends the explorable regime in the phase diagrams. Moreover, high‐quality oxide membranes, even down to a single unit cell, can be synthesized and stacked/integrated with any materials for novel artificial heterostructures and electronic applications. The exceptional structural tunability and stacking ability in oxide membranes provide new knobs to explore the spontaneous symmetry breaking in oxides, providing a fertile playground for emergent primary ferroic/multiferroic properties and electronic applications. Here, the recent progress is briefly reviewed and the promising outlook for future research in ferroic perovskite oxide membranes and their applications is discussed.

Understanding double perovskite oxides capabilities to improve photocatalytic contaminants degradation performances in water treatment processes: A review

Clean energy and environmental technologies are essential for a sustainable future. Photocatalysts are at the core of these technologies, increasing the efficiency of key chemical reactions and improving their selectivity. Metal oxides like perovskite oxides are long recognized as active photocatalysts of rather simple ionic arrangements. Double perovskites are alternatives to single perovskites, which are known as cation ordered perovskites. Double perovskite oxides such as A2B'B“O6 are emerging compounds with various optoelectronic properties that are suitable for optics, photonics, electronics, and catalysis applications. A, B', and B” are cations with varying degrees of chemical flexibility, leading to multiple combinations, which make them excellent candidates as advanced materials. Herein, we comprehensively screened stable A2B'B“O6 double perovskite metal oxides arranged based on Sr, La, K, Gd, Ba, Na, Ca, Dy, Tb, Sm, Eu, and Bi cations ordered at A sites that have been used in photocatalytic pollutant degradation and water treatment processes. Also, we examined recent developments of double perovskites oxides as photocatalysts through discussion on how their chemistries could be tailored to improve their performances. Also, photocatalytic process was explained along with its characteristics, milestones, mechanisms, modes of operation, and double perovskites materials used in this field indicating unique photocatalytic properties.

Modulating surface electron structure of LaMnO3 nanocatalysts for peroxymonosulfate activation by quenching-induced near-surface modification

Modifying the surface structure of catalysts is critical for facilitating peroxymonosulfate (PMS) activation. Here, we present a quenching approach to effectively modify the surface chemistry of LaMnO3 nanocatalysts, in which the optimal catalyst obtained by quenching displays higher catalytic degradation performance for levofloxacin (LEVO). The experimental results demonstrates that the increased intrinsic catalytic activity is directly connected to the quenching-induced exposed facets transition and synergistic effect of Cu/Co ions. Meanwhile, density functional theory calculations (DFT) further reveal the aforementioned modifications to surface structure result in an upward shift of d-band centre, which optimizes the adsorption of PMS and makes it easier for the transfer of electron between Mn sites and PMS, thereby facilitating the reduction of Mn4+ and enhancing catalytic activity for PMS activation and LEVO degradation. This study presents new ideas for controlling surface structure of perovskite metal oxide catalysts and broadens applicability of quenching chemistry in heterogeneous catalysis.