Topotactic Phase Research Articles

Memristive Artificial Synapses Based on Brownmillerite for Endurable Weight Modulation.

Exploring a computing paradigm that blends memory and computation functions is essential for artificial synapses. While memristors for artificial synapses are widely studied due to their energy-efficient structures, random filament conduction in general memristors makes them less preferred for endurability in long-term synaptic modulation. Herein, the topotactic phase transition (TPT) in brownmillerite-phased (110)-SrCoO2.5 (SCO2.5) is harnessed to enhance the reversibility of oxygen ion migration through 1-D oxygen vacancy channels. By employing a heteroepitaxial structured 2-terminal configuration of Au/SCO2.5/SrRuO3/SrTiO3, the brownmillerite SCO2.5-based synapse artificial synapses are exploited. Demonstration of the TPT behavior is corroborated by comparing oxygen migration energy by density-functional theory calculations and experimental results, and by monitoring the voltage pulse-induced peak shift in the Raman spectra of SCO2.5. With the voltage pulse-driven TPT behaviors, it is reliably characterized by linear, symmetric, and endurable long-term potentiation and depression performances. Notably, the durability of the TPT-based weight control mechanism is demonstrated by achieving consistent and noise-free weight updates over 32 000 iterations across 640 cycles. Furthermore, learning performances based on deep neural networks and convolutional neural networks on various image datasets yielded very high recognition accuracy. The work offers valuable insights into designing memristive synapses that enable reliable weight updates in neural networks.

Oxygen vacancy order–disorder transition process during topotactic filament formation in a perovskite oxide tracked by Raman microscopy and transmission electron microscopy

Vacancy-ordered perovskite oxides are attracting attention due to their diverse functions such as resistive switching, electrocatalytic activity, oxygen diffusivity, and ferroelectricity. It is important to clarify the chemical lattice strains arising from compositional changes and the associated vacancy order–disorder phase transitions at the atomic scale. Here, we elucidate the intermediate process of a topotactic phase transition in Ca-doped bismuth ferrite films consisting of alternating stacks of oxygen perovskite layers and a brownmillerite-type oxygen vacancy layer. We use Raman spectroscopy and transmission electron microscopy to closely examine the evolution of local strains exerted on the constituent sub-layers by electrochemical oxidation. A negative Raman chemical shift is observed during oxidation, which is linearly correlated with the local negative chemical expansivity of the oxygen layer. It seemingly contradicts with the general trend that oxides undergo lattice contraction upon oxidation. Oxygen vacancies initially confined in the vacancy layers can be understood to diffuse into the oxygen layers during melting of the ordered structure. The finding deepens our understanding of the electro-chemo-mechanical coupling of vacancy-ordered oxides.

Facile synthesis of multifunctional zeolitic imidazolate framework-8 coatings on diverse bare substrates using a one-step strategy

Rational growth of metal–organic frameworks (MOFs) with controllable morphology and surface properties has been challenging. In this study, facile synthesis of zeolitic imidazolate framework-8 (ZIF-8) in solutions as well as direct in-situ growth of ZIF-8 on various untreated substrates was studied systematically. ZIF crystals with controllable morphology and size were prepared by simply adjusting the ethanol content in the co-solvent system, achieving a rational synthesis of ZIFs in controlled environments. More importantly, co-solvent content was proved to be crucial in the inter-dimensional topotactic phase transformation from a 2-dimensional ZIF-L to a three-dimensional ZIF-8. Then, the facile in-situ crystallization of ZIF-8 on a variety of untreated substrates was studied. With the use of co-solvents, ZIF-8 crystals were formed uniformly and continuously on all substrates regardless of the nature of the support material, including organic supports such as nylon membranes, 3D printed meshes, melamine sponges, mask filter layers, fabric, metallic support stainless-steel meshes, and ceramic pellet. This facile coating strategy provided controllable crystal coating morphology, size, and coating density, without surface modification/pre-treatment steps which are commonly used in the synthesis of high-quality ZIF coatings/membranes. The ZIF-8 coated substrates prepared in a co-solvent system displayed superior performance in some environmental remediation and biomedical applications. For example, the ZIF-8-coated nylon membrane achieved an impressive 96 ∼ 98 % small oil droplet removal from emulsions while maintaining a high water flux of ∼ 1200 L m−2h−1 bar−1. The superhydrophobic ZIF-8-coated melamine sponges were effective for fast oil adsorption. Last but not least, the ZIF-8-coated masks demonstrated greatly improved antibacterial activities. Overall, the co-solvent synthesis method reported in this work has enabled a one-step universal strategy for the direct growth of zeolitic imidazolate framework coating on diverse bare substrates with controlled surface properties and thus showed significant commercial potential in environmental and biological applications.

Hydrogen-Induced Topotactic Phase Transformations of Cobaltite Thin Films.

Manipulating physical properties through ion migration in complex oxide thin films is an emerging research direction to achieve tunable materials for advanced applications. While the reduction of complex oxides has been widely reported, few reports exist on the modulation of physical properties through a direct hydrogenation process. Here, we report an unusual mechanism for hydrogen-induced topotactic phase transitions in perovskite La0.7Sr0.3CoO3 thin films. Hydrogenation is performed upon annealing in a pure hydrogen gas environment, offering a direct understanding of the role that hydrogen plays at the atomic scale in these transitions. Topotactic phase transformations from the perovskite (P) to hydrogenated-brownmillerite (H-BM) phase can be induced at temperatures as low as 220 °C, while at higher hydrogenation temperatures (320-400 °C), the progression toward more reduced phases is hindered. Density functional theory calculations suggest that hydroxyl bonds are formed with the introduction of hydrogen ions, which lower the formation energy of oxygen vacancies of the neighboring oxygen, enabling the transition from the P to H-BM phase at low temperatures. Furthermore, the impact on the magnetic and electronic properties of the hydrogenation temperature is investigated. Our research provides a potential pathway for utilizing hydrogen as a basis for low-temperature modulation of complex oxide thin films, with potential applications in neuromorphic computing.

Strain-oxygen vacancies coupling in topotactic (La,Sr)CoO3-δ thin films

Oxygen defect engineering is a widely used approach for tuning physical properties in oxides. Multivalent transition metal oxide La0.7Sr0.3CoO3-δ (LSCO) shows oxygen vacancy-driven metal-to-insulator transition (MIT) due to topotactic phase transition and its high oxygen vacancy tolerance. Here, we introduce strain as a new degree of freedom to study the strain-oxygen vacancy coupling effects and elucidate its impact on the electronic property in oxygen-deficient LSCO epitaxial thin films grown on SrTiO3 (100) single crystal. By combining the experimental results with density functional theory plus U (DFT+U) calculations, we reveal that 2.1 % in-plane tensile strain can stabilize the insulating state of LSCO with a surprisingly low concentration of oxygen vacancies, <0.5 %. This study reveals that the MIT in LSCO is governed by the combination of oxygen vacancies and strain, offering the potential for additional tuning knob of the material's electronic properties.

Validation of van der Waals Interface for Enhanced Resistive Switching Performance in Memristor by Using Topotactic Phase Transition Material

Validation of van der Waals Interface for Enhanced Resistive Switching Performance in Memristor by Using Topotactic Phase Transition Material

Two-dimensional confined topotactic transformation to produce Co-Pi/Co3O4 hybrid porous nanosheets for promoted water oxidation

Exploring advanced electrocatalyst for the oxygen evolution reaction (OER) is of great importance in pursuing efficient and sustainable hydrogen production via electrolytic water splitting. Considering the structure–activity-stability relationship for designing advanced OER catalysts, two-dimensional (2D) porous catalyst with single crystallinity is deemed to be an ideal platform which could simultaneously endow enriched active sites, facile mass and charge transport ability as well as robust structural stability. Herein, we proposed a facile 2D confined topotactic phase transformation approach, which realizes the fabrication of highly porous single-crystalline Co3O4 nanosheets with in-situ surface modification of amorphous Co-Pi active species. Benefitted from the highly exposed undercoordinated cobalt sites, facilitated mass transport and facile 2D charge transfer pathway, the Co-Pi/Co3O4 hybrid porous nanosheets display enhanced OER activity with obvious pre-oxidation-induced activation. In addition, the operational stability was significantly improved owing to the strengthened structural stability which effectively buffers the internal strains and avoids the structural collapse during the electrochemical process. This work proposed a facile and mild method for the synthesis of amorphous/single-crystalline hybrid porous materials, and the achievement of synergistic modulation of active site density and charge transfer ability via targeted microstructural construction will shed light on catalyst design in the future.

Deterministic Orientation Control of Ferroelectric HfO2 Thin Film Growth by a Topotactic Phase Transition of an Oxide Electrode.

The scale-free ferroelectricity with superior Si compatibility of HfO2 has reawakened the feasibility of scaled-down nonvolatile devices and beyond the complementary metal-oxide-semiconductor (CMOS) architecture based on ferroelectric materials. However, despite the rapid development, fundamental understanding, and control of the metastable ferroelectric phase in terms of oxygen ion movement of HfO2 remain ambiguous. In this study, we have deterministically controlled the orientation of a single-crystalline ferroelectric phase HfO2 thin film via oxygen ion movement. We induced a topotactic phase transition of the metal electrode accompanied by the stabilization of the differently oriented ferroelectric phase HfO2 through the migration of oxygen ions between the oxygen-reactive metal electrode and the HfO2 layer. By stabilizing different polarization directions of HfO2 through oxygen ion migration, we can gain a profound understanding of the oxygen ion-relevant unclear phenomena of ferroelectric HfO2.

Transparent conducting oxides SrNbO3 thin film with record high figure of merit

Transparent conducting oxides are crucial in the field of optoelectronics, and SrNbO3 has emerged as a promising candidate because it can outperform commonly used indium tin oxides due to its novel functionality. However, experimental investigations of SrNbO3 are challenging because it undergoes topotactic phase transition to exhibit insulating behavior. Here, we investigate the pivotal role of SrNbO3 stoichiometry to enhance its performance as a transparent conducting oxide. Results indicate the optoelectronic properties of SrNbO3 are highly dependent on its intrinsic lattice parameters and stoichiometry. Films with lattice parameters close to those of pure SrNbO3 exhibit excellent conductivity and transmittance in the visible range, while off-stoichiometry diminishes optoelectronic properties. Our stoichiometric sample demonstrates a record-high figure of merit for SrNbO3, considerably surpassing that of indium tin oxide by an order of magnitude. Thus, this study paves the way for production of high-quality SrNbO3 and leveraging its novel functionalities in optoelectronic applications.

Atomic‐Scale Phase Transformation in Perovskite LaCoOx Resistive Switching Memristive Devices

Resistive random‐access memory (RRAM) is considered the next‐generation nonvolatile memory owing to its simplicity, low power consumption, and high storage density. Resistive switching (RS) occurs in a wide range of materials among the transition metal oxides. Herein, an epitaxial ternary metal oxide layer, LaCoOx (LCO), grown on Nb‐doped SrTiO3 substrates, is utilized as an RRAM device. When voltage is applied, it exhibits excellent RS behavior. More than 900 cycles are obtained, and the retention time reaches up to 104 s. To investigate the RS behavior, high‐resolution transmission electron microscopy and atomic‐scale scanning transmission electron microscopy are used to observe the structural evolution and oxygen ion migration in LCO. The structure exhibits a perovskite–brownmillerite topotactic phase transformation from LaCoO2.5 or LaCoO2.67 to the LaCoO3 conductive regions. The reversible transition between the low‐resistance states and high‐resistance states enables the RS mechanism. Additionally, the valence states are confirmed using high‐resolution X‐ray photoelectron spectroscopy. This study not only illustrates the oxygen‐ion migration mechanism of LCO but also demonstrates its suitability for RRAM applications.

La0.6Sr0.4CoO3−δ Films Under Deoxygenation: Magnetic And Electronic Transitions Are Apart from The Structural Phase Transition

AbstractTopotactic phase transitions induced by changes in the oxygen vacancy concentration can largely alter the physical properties of complex oxides, including electronic and magnetic phases, while maintaining the structural integrity of the crystal lattice. An oxygen‐vacancy‐induced topotactic phase transition from perovskite (PV) to brownmillerite (BM) is achieved in epitaxial La0.6Sr0.4CoO3−δ (LSCO) thin films. Two novel intermediate states with different oxygen content are identified by X‐ray diffraction, which involves a single‐phase reduced PV state and a mixed state of co‐existing PV and BM. The combination of depth‐sensitive polarized neutron reflectometry (PNR) and Rutherford backscattering (RBS) allows a quantitative determination of magnetization and the mean oxygen content in all states, revealing a continuous transition from La0.6Sr0.4CoO2.97 to La0.6Sr0.4CoO2.5. BM formation is observed for an LSCO layer with an oxygen content of 2.67, while the magnetic and electronic transition already occurs for a layer with a higher oxygen content of 2.77 (and above) and in the absence of a BM signature. These results demonstrate that the physics of electronic metal‐to‐insulator transition (MIT), magnetic ferromagnet‐to‐non‐ferromagnet transition (FM‐to‐non‐FM), and structural PV‐to‐BM phase transition should be considered within the framework of separate but interrelated processes.

Organic Species-Intercalated Vanadium Oxide for Sodium-Ion Battery: Mixed-Anion Coordination Effect, Enhanced d-p Orbital Hybridization, and Topotactic Phase Conversion Induced by N-Substitution.

Sodium-ion battery (SIB) is a reasonable alternative to lithium-ion battery (LIB) in the field of grid-scale energy storage systems. Unfortunately, the development of appropriate cathode material is a bottleneck in the field of SIB. In the present work, (p-TQ)-VO, formulated as (p-TQ)0.2V2O5·0.38H2O, was synthesized based on a facile hydrothermal reaction of V2O5 and methylhydroquinone (p-HTQ). And when V2O5 was replaced by VN, (p-TQ)-VN, formulated as (p-TQ)0.22V2(O/N)5, was prepared instead. The (p-TQ)-VO sample displays good electrochemical performance as the SIB cathode. And (p-TQ)-VN shows a much higher capacity at a small current density, and it can maintain structural integrity with partial topotactic phase transformation into NaxV2O5 during the discharge/charge process. A series of characterizations of (p-TQ)-VO and (p-TQ)-VN reveals the successful intercalation of p-TQ into the layered V2O5 with a (001) lattice spacing of 13.7 and 10.7 Å, respectively. In (p-TQ)-VN, partial terminal oxygen (Ot) atoms from the V-O-V layer have been substituted by N atoms, which can boost the orbital hybridization of V 3d and Ot 2p, shorten the V-Ot bonds in the c-axial direction, and elongate the V-O bonds in the ab plane with compressed {VO4N2} octahedra, giving rise to mixed-anion coordination effect. As a result, the enhanced electron densities around the Ot atoms of the V-O-V layer can facilitate the affinity toward the inserted Na+ ions, leading to partial phase conversion into NaNO2/NaNO3. Moreover, density functional density (DFT) calculations reveal that the N-incorporation can improve electron conductivity with richer molecular orbital energy levels, resulting in multistep redox reactions and enhanced capacity.

Mitigating the P2–O2 phase transition of Ni–Co–Mn based layered oxide for improved sodium-ion batteries via interlayered structural modulation

Mn-based layered oxides are promising cathode materials for sodium-ion batteries owing to their high reversible capacities. However, P2–O2 phase transition and Jahn–Teller distortion of Mn3+ frequently occur at the end of the discharging process, resulting in low cycling stability and severe capacity degradation during the cycling processes. In this study, we proposed an effective strategy to inhibit the harmful phase transition and suppress the Jahn–Teller distortion using Al substitution. The proposed method was validated via in situ and ex situ X-ray diffraction. Furthermore, the Al-substituted P2-Na0.7Ni0.2Co0.2Mn0.58Al0.02O2(NCMA2) electrode exhibited only a topotactic phase transition from P2 to OP4 and excellent cycling stability (80% retention of the initial capacity at 170 mAh/g after 50 cycles at 0.1 C within 1.50–4.50 V). X-ray photoelectron spectroscopy analysis showed that the Mn4+ content of the Al-substituted electrode was higher than the bare NCM (Na0.7Ni0.2Co0.2Mn0.6O2) electrode in both the charge and discharge states. This confirms that Al substitution can improve the electrochemical performance by mitigating the irreversible P2–O2 phase transition and suppressing Jahn–Teller distortion. This study provides a new perspective for effectively mitigating the P2–O2 phase transition in Mn-based layered oxide cathodes via interlayered structural modulation.

Heterointerface manipulation in the architecture of Co-Mo2C@NC boosts water electrolysis

Heterostructures with tunable electronic properties have shown great potential in water electrolysis for the replacement of current benchmark precious metals. However, constructing heterostructures with sufficient interfaces to strengthen the synergistic effect of multiple species still remains a challenge due to phase separation. Herein, an efficient electrocatalyst composed of a nanosized cobalt/Mo2C heterostructure anchored on N−doped carbon (Co−Mo2C@NC) was achieved by in situ topotactic phase transformation. With the merits of high conductivity, hierarchical pores, and strong electronic interaction between Co and Mo2C, the Co−Mo2C@5NC−4 catalyst shows excellent activity with a low overpotential for the hydrogen evolution reaction (HER, 89 mV@10 mA cm−2 in alkaline medium; 143 mV@10 mA cm−2 in acidic medium) and oxygen evolution reaction (OER, 356 mV@10 mA cm−2 in alkaline medium), as well as high stability. Furthermore, this catalyst in an electrolyzer shows efficient activity for overall water splitting and long−term durability. Theoretical calculations reveal the optimized adsorption−desorption behaviour of hydrogen intermediates on the generated cobalt layered hydroxide (Co LDH)/Mo2C interfaces, resulting in boosting alkaline water electrolysis. This work proposes a new interface−engineering perspective for the construction of high−activity heterostructures for electrochemical conversion.

Graphene Quantum Dots as an Oxygen Reservoir for Topotactic Phase Transition‐Based Memristive Devices

AbstractA novel class of transition metal oxides, capable of reversible topotactic phase transition between the oxygen‐deficient brownmillerite and oxygen‐rich perovskite, has emerged as a promising material for memristive and magnetoelectric devices. However, the absence of a local oxygen source in the device structure necessitates an oxygen exchange process between the surrounding atmosphere and the switching layer during operation, which can lead to unreliable device performance. In this study, graphene quantum dots (GQDs) are introduced into a SrFe0.5Co0.5Ox memristive device as an oxygen reservoir for the nanoscale topotactic redox process. The SrFe0.5Co0.5Ox memristive devices with GQDs exhibit reliable resistive switching performance compared to SrFe0.5Co0.5Ox devices without GQDs. To understand the effect of GQDs on the device structure, a pulse endurance test is carried out in a high vacuum. The devices with GQDs show rather good endurance behavior, while devices without GQDs exhibit endurance failure. These results provide a deeper understanding of the potential use of GQDs in enhancing the performance of SrFe0.5Co0.5Ox memristive devices, with implications for tuning nanoscale topotactic phase transition for multi‐functional properties.

Nanoscale multistate resistive switching in WO3 through scanning probe induced proton evolution

Multistate resistive switching device emerges as a promising electronic unit for energy-efficient neuromorphic computing. Electric-field induced topotactic phase transition with ionic evolution represents an important pathway for this purpose, which, however, faces significant challenges in device scaling. This work demonstrates a convenient scanning-probe-induced proton evolution within WO3, driving a reversible insulator-to-metal transition (IMT) at nanoscale. Specifically, the Pt-coated scanning probe serves as an efficient hydrogen catalysis probe, leading to a hydrogen spillover across the nano junction between the probe and sample surface. A positively biased voltage drives protons into the sample, while a negative voltage extracts protons out, giving rise to a reversible manipulation on hydrogenation-induced electron doping, accompanied by a dramatic resistive switching. The precise control of the scanning probe offers the opportunity to manipulate the local conductivity at nanoscale, which is further visualized through a printed portrait encoded by local conductivity. Notably, multistate resistive switching is successfully demonstrated via successive set and reset processes. Our work highlights the probe-induced hydrogen evolution as a new direction to engineer memristor at nanoscale.

Wide-range continuous tuning of the thermal conductivity of La0.5Sr0.5CoO3-δ films via room-temperature ion-gel gating

Solid-state control of the thermal conductivity of materials is of exceptional interest for novel devices such as thermal diodes and switches. Here, we demonstrate the ability to continuously tune the thermal conductivity of nanoscale films of La0.5Sr0.5CoO3-δ (LSCO) by a factor of over 5, via a room-temperature electrolyte-gate-induced non-volatile topotactic phase transformation from perovskite (with δ ≈ 0.1) to an oxygen-vacancy-ordered brownmillerite phase (with δ = 0.5), accompanied by a metal-insulator transition. Combining time-domain thermoreflectance and electronic transport measurements, model analyses based on molecular dynamics and Boltzmann transport equation, and structural characterization by X-ray diffraction, we uncover and deconvolve the effects of these transitions on heat carriers, including electrons and lattice vibrations. The wide-range continuous tunability of LSCO thermal conductivity enabled by low-voltage (below 4 V) room-temperature electrolyte gating opens the door to non-volatile dynamic control of thermal transport in perovskite-based functional materials, for thermal regulation and management in device applications.

Strain-driven formation of epitaxial nanostructures in brownmillerite strontium cobaltite thin films

Nanostructured materials can display unique physical properties and are of particular interest for their new functionalities. Epitaxial growth is a promising approach for the controlled synthesis of nanostructures with desired structures and crystallinity. SrCoOx is a particularly intriguing material owing to a topotactic phase transition between an antiferromagnetic insulating brownmillerite SrCoO2.5 (BM-SCO) phase and a ferromagnetic metallic perovskite SrCoO3-δ (P-SCO) phase depending on the oxygen concentration. Here, we present the formation and control of epitaxial BM-SCO nanostructures by substrate-induced anisotropic strain. Perovskite substrates with a (110)-orientation and which allow for compressive strain result in the creation of BM-SCO nanobars, while (111)-oriented substrates give rise to the formation of BM-SCO nanoislands. We have found that substrate-induced anisotropic strain coupled with the orientation of crystalline domains determines the shape and facet of the nanostructures, while their size can be tuned by the degree of strain. Moreover, the nanostructures can be transformed between antiferromagnetic BM-SCO and ferromagnetic P-SCO via ionic liquid gating. Thus, this study provides insights into the design of epitaxial nanostructures whose structure and physical properties can be readily controlled.

Decoding Li+/Na+ Exchange Route Toward High‐Performance Mn‐Based Layered Cathodes for Li‐Ion Batteries

AbstractLi+/Na+ exchange has been extensively explored as an effective method to prepare high‐performance Mn‐based layered cathodes for Li‐ion batteries, since the first report in 1996 by P. G. Bruce (Nature, 1996. 381, 499–500). Understanding the detailed structural changes during the ion‐exchange process is crucial to implement the synthetic control of high‐performance layered Mn‐based cathodes, but less studied. Herein, in situ synchrotron X‐ray diffraction, density functional theory calculations, and electrochemical tests are combined to conduct the systemic studies into the structural changes during the ion‐exchange process of an Mn‐only layered cathode O3‐type Li0.67[Li0.22Mn0.78]O2 (LLMO) from the corresponding counterpart P3‐type Na0.67[Li0.22Mn0.78]O2 (NLMO). The temperature‐resolved observations combined with theoretical calculations reveal that the Li+/Na+ exchange is favorable thermodynamically and composited with two tandem topotactic phase transitions: 1) from NLMO to a layered intermediate through ≈60% of Li+/Na+ exchange. 2) then to the final layered product LLMO through further Li insertion. Moreover, the intermediate‐dominate composite is obtained by slowing down the exchange kinetics below room temperature, showing better electrochemical performance than LLMO obtained by the traditional molten‐salt method. The findings provide guides for the synthetic control of high‐performance Mn‐based cathodes under mild conditions.

Coordination Tailoring of Epitaxial Perovskite-Derived Iron Oxide Films for Efficient Water Oxidation Electrocatalysis

Cost-effective perovskite oxides have recently offered intriguing promise for electrochemical energy storage and conversion systems. Despite the breadth of previously studied electronic structures and properties, the sluggish kinetics of the oxygen evolution reaction (OER) of perovskite oxides basically restrict their applications in metal–air batteries and electrolytic cells. In this work, we report on a highly efficient OER activity of perovskite-derived SrFeO3−δ (0.0 ≤ δ ≤ 1.0) single-crystal films by selectively tuning the Fe–O coordination structure and film orientation. Our findings show that the facile anionic oxygen-induced topotactic brownmillerite phase of the SrFeO2.5 film possesses superior electrocatalytic performance with a small overpotential and Tafel slope, which is mainly attributed to the peculiar Fe–O coordination framework along with ordered oxygen vacancy channels. Moreover, the low adsorption free energy and small charge transfer resistance could further boost the electrocatalytic OER performance of the (111)-oriented BM-SrFeO2.5 films. This delicate tailoring of the epitaxial SrFeO3−δ films enables the tunable catalytic reaction pathways and concomitantly efficient OER kinetics, which has significant implications for the rational design of cost-effective and high-performance perovskite-based electrocatalysts.