Dielectric Barrier Plasma Discharge Exsolution of Nanoparticles at Room Temperature and Atmospheric Pressure.

Exsolution of metal nanoparticles (NPs) on perovskite oxides has been demonstrated as a reliable strategy for producing catalyst-support systems. Conventional exsolution requires high temperatures for long periods of time, limiting the selection of support materials. Plasma direct exsolution is reported at room temperature and atmospheric pressure of Ni NPs from a model A-site deficient perovskite oxide (La0.43Ca0.37Ni0.06Ti0.94O2.955). Plasma exsolution is carried out within minutes (up to 15 min) using a dielectric barrier discharge configuration both with He-only gas as well as with He/H2 gas mixtures, yielding small NPs (<30 nm diameter). To prove the practical utility of exsolved NPs, various experiments aimed at assessing their catalytic performance for methanation from synthesis gas, CO, and CH4 oxidation are carried out. Low-temperature and atmospheric pressure plasma exsolution are successfully demonstrated and suggest that this approach could contribute to the practical deployment of exsolution-based stable catalyst systems.

Partial Exsolution Enables Superior Bifunctionality of Ir@SrIrO3 for Acidic Overall Water Splitting.

The pursuit of efficient and durable bifunctional electrocatalysts for overall water splitting in acidic media is highly desirable, albeit challenging. SrIrO3 based perovskites are electrochemically active for oxygen evolution reaction (OER), however, their inert activities toward hydrogen evolution reaction (HER) severely restrict the practical implementation in overall water splitting. Herein, an Ir@SrIrO3 heterojunction is newly developed by a partial exsolution approach, ensuring strong metal-support interaction for OER and HER. Notably, the Ir@SrIrO3-175 electrocatalyst, prepared by annealing SrIrO3 in 5% H2 atmosphere at 175 °C, delivers ultralow overpotentials of 229 mV at 10 mA cm-2 for OER and 28 mV at 10 mA cm-2 for HER, surpassing most recently reported bifunctional electrocatalysts. Moreover, the water electrolyzer using the Ir@SrIrO3-175 bifunctional electrocatalyst demonstrates the potential application prospect with high electrochemical performance and excellent durability in acidic environment. Theoretical calculations unveil that constructing Ir@SrIrO3 heterojunction regulates interfacial electronic redistribution, ultimately enabling low energy barriers for both OER and HER.

Ammonolysis-Driven Exsolution of Ru Nanoparticle Embedded in Conductive Metal Nitride Matrix to Boost Electrocatalyst Activity.

Exsolution is an effective method for synthesizing robust nanostructured metal-based functional materials. However, no studies have investigated the exsolution of metal nanoparticles into metal nitride substrates. In this study, a versatile nitridation-driven exsolution method is developed for embedding catalytically active metal nanoparticles in conductive metal nitride substrates via the ammonolysis of multimetallic oxides. Using this approach, Ti1-xRuxO2 nanowires are phase-transformed into holey TiN nanotubes embedded with exsolved Ru nanoparticles. These Ru-exsolved holey TiN nanotubes exhibit outstanding electrocatalytic activity for the hydrogen evolution reaction with excellent durability, which is significantly higher than that of Ru-deposited TiN nanotubes. The enhanced stability of the Ru-exsolved TiN nanotubes can be attributed to the Ru nanoparticles embedded in the robust metal nitride matrix and the formation of interfacial Ti3+─N─Ru4+ bonds. Density functional theory calculations reveal that the exsolved Ru nanoparticles have a lower d-band center position and optimized hydrogen affinity than deposited Ru nanoparticles, indicating the superior electrocatalyst performance of the former. In situ Raman spectroscopic analysis reveals that the electron transfer from TiN to Ru nanoparticles is enhanced during the electrocatalytic process. The proposed approach opens a new avenue for stabilizing diverse metal nanostructures in many conductive matrices like metal phosphides and chalcogenides.

SrMo0.9O3-δ Perovskite with Segregated Ru Nanoparticles Performing as Anode in Solid Oxide Fuel Cells.

A new anode material, Ru-SrMo0.9O3-δ, with a perovskite structure and segregated metallic Ru, has been tested in an intermediate-temperature solid oxide fuel cell (IT-SOFC) in an electrolyte-supported configuration giving substantial power densities as high as 840 mW/cm2 at 850 °C using pure H2 as fuel. This material has been prepared by the citrate method and structurally and microstructurally characterized at room temperature by different techniques such as X-ray diffraction (XRD), neutron powder diffraction (NPD), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). NPD was very useful to determine oxygen positions and vacancies, unveiling a cubic and oxygen-deficient perovskite SrMo0.9O3-δ oxide with a Pm-3m space group and potential ionic mobility. On the other hand, SEM and STEM studies have allowed to identify metallic segregated Ru nanoparticles providing the material with an excellent catalytic activity. Other properties such as the thermal expansion coefficient (TEC) and chemical compatibility with other cell components or electrical conductivity have also been studied to understand the excellent performance of this material as anode in IT-SOFC and correlate it with the crystallographic structure.

Ni-Substituted Sr2FeMoO6-δ as an Electrode Material for Symmetrical and Reversible Solid-Oxide Cells.

This work develops a novel perovskite Sr2FeNi0.35Mo0.65O6-δ (SFN0.35M) simultaneously using as a fuel electrode and oxygen electrode in a reversible solid oxide cell (RSOC). SFN0.35M shows outstanding electrocatalytic activity for hydrogen oxidation, hydrogen evolution, oxygen reduction, and oxygen evolution. In situ exsolution and dissolution of Fe-Ni alloy nanoparticles in SFN0.35M is revealed. In a reducing atmosphere, SFN0.35M shows in situ exsolution of Fe-Ni alloy nanoparticles, and then the Fe-Ni alloy is reoxidized into SFN0.35M while converting into an oxidizing atmosphere. The polarization resistances of SFN0.35M electrode are 0.043 Ω cm2 in 20% O2-N2 and 0.064 Ω cm2 in H2 at 850 °C. Moreover, symmetric fuel cells using the SFN0.35M electrode achieves a maximum power density of 0.501 W cm-2 at 850 °C in H2 fuel, while the symmetric electrolysis cell has an electrolysis current density of 0.794 A cm-2 at 1.29 V in 90% H2O-10% H2 at 850 °C. It is the first time we demonstrate that the cell voltage of symmetrical cell at 0.5 A cm-2 in the fuel cell mode and -0.5 A cm-2 in the electrolysis cell mode can be fully recovered in 10 electrode alternating cycles and therefore demonstrate the possibility that SFN0.35M can be used in a fully symmetric RSOC stack with electrode alternating functions.

Local Structures of Ex-Solved Nanoparticles Identified by Machine-Learned Potentials.

In this study, we identify the local structures of ex-solved nanoparticles using machine-learned potentials (MLPs). We develop a method for training machine-learned potentials by sampling local structures of heterointerface configurations as a training set with its efficacy tested on the Ni/MgO system, illustrating that the error in interface energy is only 0.004 eV/Å2. Using the developed scheme, we train an MLP for the Ni/La0.5Ca0.5TiO3 ex-solution system and identify the local structures for both exo- and endo-type particles. The established model aligns well with the experimental observations, accurately predicting a nucleation size of 0.45 nm. Lastly, the density functional theory calculations on the established atomistic model verify that the kinetic barrier for the dry reforming of methane are substantially reduced by 0.49 eV on the ex-solved catalysts compared to that on the impregnated catalysts. Our findings offer insights into the local structures, growth mechanisms, and underlying origin of the catalytic properties of ex-solved nanoparticles.

Recent Advances in Iridium-based Electrocatalysts for Acidic Electrolyte Oxidation.

Ongoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon-free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir-based OER catalysts. In this review, recent advances in Ir-based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir-based electrocatalysts, and common strategies for optimizing Ir-based catalysts. The future challenges and prospects of developing highly effective Ir-based catalysts are also discussed.

Comparative Study of Exsolved and Impregnated Ni Nanoparticles Supported on Nanoporous Perovskites for Low-Temperature CO Oxidation.

This study investigated the redox exsolution of Ni nanoparticles from a nanoporous La0.52Sr0.28Ti0.94Ni0.06O3 perovskite. The characteristics of exsolved Ni nanoparticles including their size, population, and surface concentration were deeply analyzed by environmental scanning electron microscopy (ESEM), transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) mapping, and hydrogen temperature-programmed reduction (H2-TPR). Ni exsolution was triggered in hydrogen as early as 400 °C, with the highest catalytic activity for low-temperature CO oxidation achieved after a reduction step at 500 °C, despite only a 10% fraction of Ni exsolved. The activity and stability of exsolved nanoparticles were compared with their impregnated counterparts on a perovskite material with a similar chemical composition (La0.65Sr0.35TiO3) and a comparable specific surface area and Ni loading. After an aging step at 800 °C, the catalytic activity of exsolved Ni nanoparticles at 300 °C was found to be 10 times higher than that of impregnated ones, emphasizing the thermal stability of Ni nanoparticles prepared by redox exsolution.

A Superior Catalytic Air Electrode with Temperature-Induced Exsolution toward Protonic Ceramic Cells.

Protonic ceramic cells merit extensive exploration, attributed to their innate capabilities for potent and environmentally benign energy conversion. In this work, a temperature-induced exsolution methodology to synthesize SrCo0.5Nb0.5O3-δ (SCN) nanoparticles (NPs) with notably elevated activity on the surface of PrSrCo1.8Nb0.2O6-δ (PSCN) is proposed, directly addressing the extant challenge of restrained catalytic activity prevalent in air electrode materials. In situ assessments reveal that SCN NPs commence exsolution from the matrix at temperatures surpassing 900 °C during straightforward calcination processes and maintain stability throughout annealing. Notably, the resultant SCN-PSCN interface facilitates vapor adsorption and protonation processes, which are poised to enhance surface reaction kinetics pertaining to the proton-involved oxygen reduction and evolution reaction (P-ORR and P-OER). A fuel-electrode-supported protonic ceramic cell leveraging SCN-PSCN as the air electrode manifests compelling performance, attaining a peak power density of 1.30 W·cm-2 in the fuel cell modality and a current density of 1.91 A·cm-2 at 1.3 V in the electrolysis mode, recorded at 650 °C. Furthermore, density functional theory calculations validate that the introduction of SCN NPs onto the PSCN surface conspicuously accelerates electrode reaction rates correlated with P-ORR and P-OER, by significantly mitigating energy barriers associated with surface oxygen and vapor dissociation.

A High-Entropy Layered Perovskite Coated with In Situ Exsolved Core-Shell CuFe@FeOx Nanoparticles for Efficient CO2 Electrolysis.

Solid oxide electrolysis cells (SOECs) are promising energy conversion devices capable of efficiently transforming CO2 into CO, reducing CO2 emissions, and alleviating the greenhouse effect. However, the development of a suitable cathode material remains a critical challenge. Here a new SOEC cathode is reported for CO2 electrolysis consisting of high-entropy Pr0.8 Sr1.2 (CuFe)0.4 Mo0.2 Mn0.2 Nb0.2 O4-δ (HE-PSCFMMN) layered perovskite uniformly coated with in situ exsolved core-shell structured CuFe alloy@FeOx (CFA@FeO) nanoparticles. Single cells with the HE-PSCFMMN-CFA@FeO cathode exhibit a consistently high current density of 1.95 A cm-2 for CO2 reduction at 1.5 V while maintaining excellent stability for up to 200 h under 0.75 A cm-2 at 800 °C in pure CO2 . In situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations confirm that the exsolution of CFA@FeO nanoparticles introduces additional oxygen vacancies within HE-PSCFMMN substrate, acting as active reaction sites. More importantly, the abundant oxygen vacancies in FeOx shell, in contrast to conventional in situ exsolved nanoparticles, enable the extension of the triple-phase boundary (TPB), thereby enhancing the kinetics of CO2 adsorption, dissociation, and reduction.

Improving the Oxygen Evolution Reaction: Exsolved Cobalt Nanoparticles on Titanate Perovskite Catalyst.

Perovskites are an important class of oxygen evolution reaction (OER) catalysts due to highly tunable compositions and adaptable characteristics. However, perovskite-based catalysts can have limited atom utilization efficiency due to large particle size, resulting in low mass activity. Herein, Cobalt nanoparticles are exsolved from La0.2+2x Ca0.7-2x Ti1-x Cox O3 perovskite and applied in OER. Upon reduction in the 5% H2 /N2 atmosphere at 800 °C for 2 h, the Co exsolved perovskite catalyst (R-LCTCo0.11) exhibits optimal OER performance. The mass activity of R-LCTCo0.11 reaches ≈1700 mA mg-1 at an overpotential of 450 mV, which is 17 times and 3 times higher than that of LCTCo0.11 (97 mA mg-1 ) and R-Mix (560 mA mg-1 ) catalysts respectively, surpassing the benchmark catalyst RuO2 (42.7 mA mg-1 of oxide at η = 470 mV). Electrochemical impedance spectroscopy (EIS) data reveals that R-LCTCo0.11 has the lowest charge transfer resistance (Rct  = 58 Ω), demonstrating the highest catalytic and kinetic activity for OER. Furthermore, this catalyst shows high stability during an accelerated durability test of 10 h electrolysis and 1000 cycles cyclic voltammetry (CV). This work demonstrates that nanoparticle exsolution from a doped perovskite is an effective strategy for improving the atom utilization efficiency in OER.

Fabrication of Heterostructural FeNi3-Loaded Perovskite Catalysts by Rapid Plasma for Highly Efficient Photothermal Reverse Water Gas Shift Reaction.

Metal-semiconductor heterostructured catalysts have attracted great attention because of their unique interfacial characteristics and superior catalytic performance. Exsolution of nanoparticles is one of the effective and simple ways for in-situ growth of metal nanoparticles embedded in oxide surfaces and their favorable dispersion and stability. However, both high-temperature and a reducing atmosphere are required simultaneously in conventional exsolution, which is time-consuming and costly, and particles often agglomerate during the process. In this work, Ca0.9Ti0.8Ni0.1Fe0.1O3-δ (CTNF) is exposed to dielectric blocking discharge (DBD) plasma at room temperature to fabricate alloying FeNi3 nanoparticles from CTNF perovskite. FeNi3-CTNF has outstanding catalytic activity for photothermal reverse water gas shift reaction (RWGS). At 350 °C under full-spectrum irradiation, the carbon monoxide (CO) yield of FeNi3-CTNF (10.78 mmol g-1 h-1) is 11 times that of pure CaTiO3(CTO), and the CO selectivity is 98.9%. This superior catalytic activity is attributed to the narrow band gap, photogenerated electron migration to alloy particles, and abundant surface oxygen vacancies. The carbene pathway reaction is also investigated through in-situ Raman spectroscopy. The present work presents a straightforward method for the exsolution of nanoalloys in metal-semiconductor heterostructures for photothermal CO2 reduction.

Smart Dual-Exsolved Self-Assembled Anode Enables Efficient and Robust Methane-Fueled Solid Oxide Fuel Cells.

Perovskite oxides have emerged as alternative anode materials for hydrocarbon-fueled solid oxide fuel cells (SOFCs). Nevertheless, the sluggish kinetics for hydrocarbon conversion hinder their commercial applications. Herein, a novel dual-exsolved self-assembled anode for CH4 -fueled SOFCs is developed. The designed Ru@Ru-Sr2 Fe1.5 Mo0.5 O6-δ (SFM)/Ru-Gd0.1 Ce0.9 O2-δ (GDC) anode exhibits a unique hierarchical structure of nano-heterointerfaces exsolved on submicron skeletons. As a result, the Ru@Ru-SFM/Ru-GDC anode-based single cell achieves high peak power densities of 1.03 and 0.63 W cm-2 at 800 °C under humidified H2 and CH4 , surpassing most reported perovskite-based anodes. Moreover, this anode demonstrates negligible degradation over 200 h in humidified CH4 , indicating high resistance to carbon deposition. Density functional theory calculations reveal that the created metal-oxide heterointerfaces of Ru@Ru-SFM and Ru@Ru-GDC have higher intrinsic activities for CH4 conversion compared to pristine SFM. These findings highlight a viable design of the dual-exsolved self-assembled anode for efficient and robust hydrocarbon-fueled SOFCs.

Maximizing Photoelectrochemical Performance in Metal-Oxide Hybrid Composites via Amorphous Exsolution-A New Exsolution Mechanism for Heterogeneous Catalysis.

Exsolution generates metal nanoparticles anchored within crystalline oxide supports, ensuring efficient exposure, uniform dispersion, and strong nanoparticle-perovskite interactions. Increased doping level in the perovskite is essential for further enhancing performance in renewable energy applications; however, this is constrained by limited surface exsolution, structural instability, and sluggish charge transfer. Here, hybrid composites are fabricated by vacuum-annealing a solution containing SrTiO3 photoanode and Co cocatalyst precursors for photoelectrochemical water-splitting. In situ transmission electron microscopy identifies uniform, high-density Co particles exsolving from amorphous SrTiO3 films, followed by film-crystallization at elevated temperatures. This unique process extracts entire Co dopants with complete structural stability, even at Co doping levels exceeding 30%, and upon air exposure, the Co particles embedded in the film oxidize to CoO, forming a Schottky junction at the interface. These conditions maximize photoelectrochemical activity and stability, surpassing those achieved by Co post-deposition and Co exsolution from crystalline oxides. Theoretical calculations demonstrate in the amorphous state, dopant─O bonds become weaker while Ti─O bonds remain strong, promoting selective exsolution. As expected from the calculations, nearly all of the 30% Fe dopants exsolve from SrTiO3 in an H2 environment, despite the strong Fe─O bond's low exsolution tendency. These analyses unravel the mechanisms driving the amorphous exsolution.

Strongly-Interacted NiSe2/NiFe2O4 Architectures Built Through Selective Atomic Migration as Catalysts for the Oxygen Evolution Reaction.

The interactions between the catalyst and support are widely used in many important catalytic reactions but the construction of strong interaction with definite microenvironments to understand the structure-activity relationship is still challenging. Here, strongly-interacted composites are prepared via selective exsolution of active NiSe2 from the host matrix of NiFe2O4 (S-NiSe2/NiFe2O4) taking advantage of the differences of migration energy, in which the NiSe2 possessed both high dispersion and small size. The characteristics of spatially resolved scanning transmission X-ray microscopy (STXM) coupled with analytical Mössbauer spectra for the surface and bulk electronic structures unveiled that this strongly interacted composite triggered more charge transfers from the NiSe2 to the host of NiFe2O4 while stabilizing the inherent atomic coordination of NiFe2O4. The obtained S-NiSe2/NiFe2O4 exhibits overpotentials of 290 mV at 10 mA cm-2 for oxygen evolution reaction (OER). This strategy is general and can be extended to other supported catalysts, providing a powerful tool for modulating the catalytic performance of strongly-interacted composites.

Enhancing the Electrochemical Performance in Symmetrical Solid Oxide Cells through Nanoengineered Redox-Stable Electrodes with Exsolved Nanoparticles.

Symmetrical solid oxide cells (SSOCs) have recently gained significant attention for their potential in energy conversion due to their simplified cell configuration, cost-effectiveness, and excellent reversibility. However, previous research efforts have mainly focused on improving the electrode performance of perovskite-type electrodes through different doping strategies, neglecting microstructural optimization. This work presents novel approaches for the nanostructural tailoring of (La0.8Sr0.2)0.95Fe1-xTixO3-δ (LSFTx, x = 0.2 and 0.4) electrodes using a single-step spray-pyrolysis deposition process. By incorporating these electrodes into a Ce0.9Gd0.1O1.95 (CGO) porous backbone or employing a nanocomposite architecture with nanoscale particle size, we achieved significant improvements in the polarization resistance (Rp) compared with traditional screen-printed electrodes. To further boost the fuel oxidation performance, a Ni-doping strategy, coupled with meticulous microstructural optimization, was implemented. The exsolution of Ni nanoparticles under reducing conditions resulted in remarkable Rp values as low as 0.34 and 0.11 Ω cm2 in air and wet H2 at 700 °C, respectively. Moreover, an electrolyte-supported cell with symmetrical electrodes demonstrated a stable maximum power density of 617 mW cm-2 at 800 °C. These findings highlight the importance of combining electrode composition optimization with advanced morphology control in the design of highly efficient and durable SSOCs.

Nanoparticle Exsolution on Perovskite Oxides: Insights into Mechanism, Characteristics and Novel Strategies.

Supported nanoparticles have attracted considerable attention as a promising catalyst for achieving unique properties in numerous applications, including fuel cells, chemical conversion, and batteries. Nanocatalysts demonstrate high activity by expanding the number of active sites, but they also intensify deactivation issues, such as agglomeration and poisoning, simultaneously. Exsolution for bottom-up synthesis of supported nanoparticles has emerged as a breakthrough technique to overcome limitations associated with conventional nanomaterials. Nanoparticles are uniformly exsolved from perovskite oxide supports and socketed into the oxide support by a one-step reduction process. Their uniformity and stability, resulting from the socketed structure, play a crucial role in the development of novel nanocatalysts. Recently, tremendous research efforts have been dedicated to further controlling exsolution particles. To effectively address exsolution at a more precise level, understanding the underlying mechanism is essential. This review presents a comprehensive overview of the exsolution mechanism, with a focus on its driving force, processes, properties, and synergetic strategies, as well as new pathways for optimizing nanocatalysts in diverse applications.

Microwave-Driven Exsolution of Ni Nanoparticles in A-Site Deficient Perovskites.

Exsolution has emerged as a promising method for generating metallic nanoparticles, whose robustness and stability outperform those of more conventional deposition methods, such as impregnation. In general, exsolution involves the migration of transition metal cations, typically perovskites, under reducing conditions, leading to the nucleation of well-anchored metallic nanoparticles on the oxide surface with particular properties. There is growing interest in exploring alternative methods for exsolution that do not rely on high-temperature reduction via hydrogen. For example, utilizing electrochemical potentials or plasma technologies has shown promising results in terms of faster exsolution, leading to better dispersion of nanoparticles under milder conditions. To avoid limitations in scaling up exhibited by electrochemical cells and plasma-generation devices, we proposed a method based on pulsed microwave (MW) radiation to drive the exsolution of metallic nanoparticles. Here, we demonstrate the H2-free MW-driven exsolution of Ni nanoparticles from lanthanum strontium titanates, characterizing the mechanism that provides control over nanoparticle size and dispersion and enhanced catalytic activity and stability for CO2 hydrogenation. The presented method will enable the production of metallic nanoparticles with a high potential for scalability, requiring short exposure times and low temperatures.

B-Site Super-Excess Design Sr2V0.4Fe0.9Mo0.7O6-δ-Ni0.4 as a Highly Active and Redox-Stable Solid Oxide Fuel Cell Anode.

In-situ exsolution type perovskites as solid oxide fuel cell (SOFCs) anode materials have received widespread attention because of their excellent catalytic activity. In this study, excessive NiO is introduced to the Sr2V0.4Fe0.9Mo0.7O6-δ (SVFMO) perovskite with the B-site excess design, and in-situ growth of FeNi3 alloy nanoparticles is induced in the reducing atmosphere to form the Sr2V0.4Fe0.9Mo0.7O6-δ-Ni0.4 (SVFMO-Ni0.4) composite anode. Here, with H2 or CH4 as SOFCs fuel gas, the formation of FeNi3 nanoparticles further enhances the catalytic ability. Compared with SVFMO, the maximum power density (Pmax) of Sr2V0.4Fe0.9Mo0.7O6-δ-Ni0.4 (SVFMO-Ni0.4) increases from 538 to 828 mW cm-2 at 850 °C with hydrogen as the fuel gas, and the total polarization resistance (RP) decreases from 0.23 to 0.17 Ω cm2. In addition, the long-term operational stability of the SVFMO-Ni0.4 anode shows no apparent performance degradation for more than 300 h. Compared with SVFMO, the Pmax of SVFMO-Ni0.4 increases from 138 to 464 mW cm-2 with methane as fuel gas, and the RP decreases from 1.21 to 0.29 Ω cm2.

Enhanced CO2 Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes.

In this study, perovskite oxides La0.3 Ca0.6 Ni0.05 Mnx Ti0.95- x O3- γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 - 3% H2 O. The performance of La0.3 Ca0.6 Ni0.05 Ti0.95 O3-γ is notably improved by co-doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3 ) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high-temperature operation, suggesting a reliable cathode material for CO2 electrolysis.