Operando Studies Redirect Spatiotemporal Restructuration of Model Coordinated Oxides in Electrochemical Oxidation.

Tetrahedral, pyramidal, and octahedral metal-oxygen coordinated ligands are fundamental components in all metal-oxide structures. Understanding the impacts of their spatiotemporal behaviors during electrochemical oxidation is crucial for diverse applications, yet remains unsolved due to challenges in designing model oxides and conducting operando characterizations. Herein, combining a suite of advanced operando characterizations and systematic computations, a link between oxygen-evolving performance and operational structural properties is established on model oxides.

A Complex Oxide Containing Inherent Peroxide Ions for Catalyzing Oxygen Evolution Reactions in Acid.

Proton exchange membrane water electrolyzers powered by sustainable energy represent a cutting-edge technology for renewable hydrogen generation, while slow anodic oxygen evolution reaction (OER) kinetics still remains a formidable obstacle that necessitates basic comprehension for facilitating electrocatalysts' design. Here, we report a low-iridium complex oxide LaSrIrO with a unique hexagonal structure consisting of isolated Ir(V)O octahedra and true peroxide O groups as a highly active and stable OER electrocatalyst under acidic conditions. Remarkably, LaSrIrO, containing 59 wt % less iridium relative to the benchmark IrO, shows about an order of magnitude higher mass activity, 6-folds higher intrinsic activity than the latter, and also surpasses the state-of-the-art Ir-based oxides ever reported.

Synergistic Bulk and Surface Engineering for Expeditious and Durable Reversible Protonic Ceramic Electrochemical Cells Air Electrode.

Reversible protonic ceramic electrochemical cells (R-PCECs) offer the potential for high-efficiency power generation and green hydrogen production at intermediate temperatures. However, the commercial viability of R-PCECs is hampered by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) within conventional air electrodes operating at reduced temperatures. To address this challenge, this work introduces a novel approach based on the simultaneous optimization of bulk-phase metal-oxygen bonds and in-situ formation of a metal oxide nano-catalyst surface modification.

Synergistic dual-phase air electrode enables high and durable performance of reversible proton ceramic electrochemical cells.

Reversible proton ceramic electrochemical cells are promising solid-state ion devices for efficient power generation and energy storage, but necessitate effective air electrodes to accelerate the commercial application. Here, we construct a triple-conducting hybrid electrode through a stoichiometry tuning strategy, composed of a cubic phase BaSrCoFeO and a hexagonal phase BaSr(CoFe)O. Unlike the common method of creating self-assembled hybrids by breaking through material tolerance limits, the strategy of adjusting the stoichiometric ratio of the A-site/B-site not only achieves strong interactions between hybrid phases, but also can efficiently modifies the phase contents.

Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production.

Producing indispensable hydrogen and oxygen for social development via water electrolysis shows more prospects than other technologies. Although electrocatalysts have been explored for centuries, a universal activity descriptor for both hydrogen-evolution reaction (HER) and oxygen-evolution reaction (OER) is not yet developed. Moreover, a unifying concept is not yet established to simultaneously understand HER/OER mechanisms.

The bio-inspired heterogeneous single-cluster catalyst Ni100-FeS for enhanced electrochemical CO reduction to CH.

Electrochemical conversion of CO-to-CH is a process of converting the inert greenhouse gas into energy molecules. It offers great promise for the transformation of carbon-neutral economy. However, achieving high CH activity and selectivity remains a major challenge because the electrochemical reduction of CO-to-CH is accompanied by various C intermediates at the catalytic site, involving multiple proton-coupled electron transfer processes.

Exceptional Anisotropic Noncovalent Interactions in Ultrathin Nanorods: The Terminal σ-Hole.

Nanomaterial is the Holy Grail of material science, which has been widely applied in the fields of energy, environment, chemistry, and biomedicine. Its catalytic merits were usually ascribed to the advantages of size effect, strain effect, and covalent effect. Noncovalent interactions are critical in the catalysis processes but often overlooked.

New Undisputed Evidence and Strategy for Enhanced Lattice-Oxygen Participation of Perovskite Electrocatalyst through Cation Deficiency Manipulation.

Oxygen evolution reaction (OER) is a key half-reaction in many electrochemical transformations, and efficient electrocatalysts are critical to improve its kinetics which is typically sluggish due to its multielectron-transfer nature. Perovskite oxides are a popular category of OER catalysts, while their activity remains insufficient under the conventional adsorbate evolution reaction scheme where scaling relations limit activity enhancement. The lattice oxygen-mediated mechanism (LOM) has been recently reported to overcome such scaling relations and boost the OER catalysis over several doped perovskite catalysts.

Hydrogen spillover in complex oxide multifunctional sites improves acidic hydrogen evolution electrocatalysis.

Improving the catalytic efficiency of platinum for the hydrogen evolution reaction is valuable for water splitting technologies. Hydrogen spillover has emerged as a new strategy in designing binary-component Pt/support electrocatalysts. However, such binary catalysts often suffer from a long reaction pathway, undesirable interfacial barrier, and complicated synthetic processes.

A New Durable Surface Nanoparticles-Modified Perovskite Cathode for Protonic Ceramic Fuel Cells from Selective Cation Exsolution under Oxidizing Atmosphere.

A high-performance cathode of a protonic ceramic fuel cell (PCFC) should possess excellent oxygen reduction reactivity, high proton/oxygen-ion/electron conductivity, and sufficient operational stability, thus requiring a delicate tuning of both the bulk and surface properties of the electrode material. Although surface modification of perovskites with nanoparticles from reducing-atmosphere exsolution has been demonstrated effective at improving the electrochemical anodic oxidation, such nanoparticles would easily re-incorporate into the perovskite lattice causing a big challenge for their application as a cathode. Here, a durable perovskite-based nanocomposite cathode for PCFCs is reported, which is facilely prepared via the exsolution of nanoparticles in an oxidizing atmosphere.

One Pot-Synthesized Ag/Ag-Doped CeO Nanocomposite with Rich and Stable 3D Interfaces and Ce for Efficient Carbon Dioxide Electroreduction.

Electrochemical CO reduction (ECR) technology is promising to produce value-added chemicals and alleviate the climate deterioration. Interface engineering is demonstrated to improve the ECR performance for metal and oxide composite catalysts. However, the approach to form a substantial interface is still limited.

Exceptionally Robust Face-Sharing Motifs Enable Efficient and Durable Water Oxidation.

Corner-sharing oxides usually suffer from structural reconstruction during the bottleneck oxygen-evolution reaction (OER) in water electrolysis. Therefore, introducing dynamically stable active sites in an alternative structure is urgent but challenging. Here, 1D 5H-polytype Ba Bi Co FeO oxide with face-sharing motifs is identified as a highly active and stable candidate for alkaline OER.

High-Performance Perovskite Composite Electrocatalysts Enabled by Controllable Interface Engineering.

Single-phase perovskite oxides that contain nonprecious metals have long been pursued as candidates for catalyzing the oxygen evolution reaction, but their catalytic activity cannot meet the requirements for practical electrochemical energy conversion technologies. Here a cation deficiency-promoted phase separation strategy to design perovskite-based composites with significantly enhanced water oxidation kinetics compared to single-phase counterparts is reported. These composites, self-assembled from perovskite precursors, comprise strongly interacting perovskite and related phases, whose structure, composition, and concentration can be accurately controlled by tailoring the stoichiometry of the precursors.

Thermal-expansion offset for high-performance fuel cell cathodes.

One challenge for the commercial development of solid oxide fuel cells as efficient energy-conversion devices is thermo-mechanical instability. Large internal-strain gradients caused by the mismatch in thermal expansion behaviour between different fuel cell components are the main cause of this instability, which can lead to cell degradation, delamination or fracture. Here we demonstrate an approach to realizing full thermo-mechanical compatibility between the cathode and other cell components by introducing a thermal-expansion offset.

Fast operando spectroscopy tracking in situ generation of rich defects in silver nanocrystals for highly selective electrochemical CO reduction.

Electrochemical CO reduction (ECR) is highly attractive to curb global warming. The knowledge on the evolution of catalysts and identification of active sites during the reaction is important, but still limited. Here, we report an efficient catalyst (Ag-D) with suitable defect concentration operando formed during ECR within several minutes.

Efficient Water Splitting Actualized through an Electrochemistry-Induced Hetero-Structured Antiperovskite/(Oxy)Hydroxide Hybrid.

Exploring active, stable, and low-cost bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is crucial for water splitting technology associated with renewable energy storage in the form of hydrogen fuel. Here, a newly designed antiperovskite-based hybrid composed of a conductive InNNi core and amorphous InNi(oxy)hydroxide shell is first reported as promising OER/HER bifunctional electrocatalyst. Prepared by a facile electrochemical oxidation strategy, such unique hybrid (denoted as EO-InNNi ) exhibits excellent OER and HER activities in alkaline media, benefiting from the inherent high-efficiency HER catalytic nature of InNNi antiperovskite and the promoting role of OER-active InNi(oxy)hydroxide thin film, which is confirmed by theoretical simulations and in situ Raman studies.

Single-phase perovskite oxide with super-exchange induced atomic-scale synergistic active centers enables ultrafast hydrogen evolution.

The state-of-the-art active HER catalysts in acid media (e.g., Pt) generally lose considerable catalytic performance in alkaline media mainly due to the additional water dissociation step.

Utilizing ion leaching effects for achieving high oxygen-evolving performance on hybrid nanocomposite with self-optimized behaviors.

Ion leaching from pure-phase oxygen-evolving electrocatalysts generally exists, leading to the collapse and loss of catalyst crystalline matrix. Here, different from previous design methodologies of pure-phase perovskites, we introduce soluble BaCl and SrCl into perovskites through a self-assembly process aimed at simultaneously tuning dual cation/anion leaching effects and optimizing ion match in perovskites to protect the crystalline matrix. As a proof-of-concept, self-assembled hybrid BaSrCoFeO (BSCF) nanocomposite (with BaCl and SrCl) exhibits the low overpotential of 260 mV at 10 mA cm in 0.

Direct evidence of boosted oxygen evolution over perovskite by enhanced lattice oxygen participation.

The development of oxygen evolution reaction (OER) electrocatalysts remains a major challenge that requires significant advances in both mechanistic understanding and material design. Recent studies show that oxygen from the perovskite oxide lattice could participate in the OER via a lattice oxygen-mediated mechanism, providing possibilities for the development of alternative electrocatalysts that could overcome the scaling relations-induced limitations found in conventional catalysts utilizing the adsorbate evolution mechanism. Here we distinguish the extent to which the participation of lattice oxygen can contribute to the OER through the rational design of a model system of silicon-incorporated strontium cobaltite perovskite electrocatalysts with similar surface transition metal properties yet different oxygen diffusion rates.

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity.

Perovskite-based oxides have emerged as promising oxygen evolution reaction (OER) electrocatalysts. The performance is closely related to the lattice, electronic, and defect structure of the oxides, which determine surface and bulk properties and consequent catalytic activity and durability. Further, interfacial interactions between phases in a nanocomposite may affect bulk transportation and surface adsorption properties in a similar manner to phase doping except without solubility limits.

Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor.

Facile and reliable screening of cost-effective, high-performance and scalable electrocatalysts is key for energy conversion technologies such as water splitting. ABO perovskites, with rich constitutions and structures, have never been designed via activity descriptors for critical hydrogen evolution reaction (HER). Here, we apply coordination rationales to introduce A-site ionic electronegativity (AIE) as an efficient unifying descriptor to predict the HER activities of 13 cobalt-based perovskites.

Super-Exchange Interaction Induced Overall Optimization in Ferromagnetic Perovskite Oxides Enables Ultrafast Water Oxidation.

Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal-air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super-exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity.

New Phosphorus-Doped Perovskite Oxide as an Oxygen Reduction Reaction Electrocatalyst in an Alkaline Solution.

Because of their structural and compositional flexibility, perovskite oxides represent an attractive alternative electrocatalyst class to precious metals for the oxygen reduction reaction (ORR); an important reaction in fuel cells and metal-air batteries. Partial replacement of the original metal cation with another cation, namely, doping, can be used to tailor the ORR activity of perovskite, for which a metal has been exclusively used as the dopant component in the past. Herein, phosphorus is proposed as a non-metal dopant for the cation site to develop a new perovskite family with the formula of La Sr Mn P O (x=0, 0.

Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous BaSrCoFeO nanofilms with tunable oxidation state.

Perovskite oxides exhibit potential for use as electrocatalysts in the oxygen evolution reaction (OER). However, their low specific surface area is the main obstacle to realizing a high mass-specific activity that is required to be competitive against the state-of-the-art precious metal-based catalysts. We report the enhanced performance of BaSrCoFeO (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering.