La0.5Sr0.5CoO3 Research Articles

Structure and ferroelectric photovoltaic effect modulation in the epitaxial BiFeO3/La0.5Sr0.5CO3 heterostructures

Square-shaped BiFeO3 (BFO) thin films were prepared on SrTiO3 (STO) substrates by off-axis magnetron sputtering using La0.5Sr0.5CoO3 (LSCO) as the bottom electrode, and both LSCO and BFO are perovskite structure. The BFO crystalline quality improves and the grain size becomes larger as the thickness H increases, and both have smaller mean square roughness. The effects of BFO thickness H, light intensity Ip and ambient temperature AT on the ferroelectric photovoltaic effect (FPE) for the Pt/BFO/LSCO heterostructures are significant. With the H increase, the open-circuit voltage Voc and short-circuit current Jsc increase linearly, with Voc up to 0.44 V. The short-circuit current modulation intensity ΔJsc follows the ΔJsc-300>ΔJsc-200>ΔJsc-100 rule. With the Ip increase, Pt/BFO(300nm)/LSCO' Jsc increases linearly, and Voc first increases and then tends to saturation, which satisfies Glass' law. With the AT increases, Voc is linearly decreasing and Jsc shows the law: decreasing→increasing→decreasing. The polarization-modulated FPE mechanism is investigated by analyzing the Pt/BFO/LSCO energy band structure, which is attributed to the coupling effect between the BFO depolarization field (Edp) and the built-in electric field at the interface (EPt/BFO & EBFO/LSCO), and the FPE mechanism is shifted from the interface barrier domination to the ferroelectric polarization domination as H increases.

Mesoporous La0.8Sr0.2CoO3/H-COK-12 catalyst synthesized by template method: Highly active for the complete oxidation of CO

Using cheap sodium silicate as a silica source and surfactant P123 as a soft template, an environment-friendly mesoporous material, COK-12, was prepared in a near-neutral environment. COK-12 was modified with n-hexane to obtain an H-COK-12 template with a compact and ordered pore structure. In this study, the modified mesoporous material H-COK-12 was used as the template for the first time, and the mesoporous La0.8Sr0.2CoO3 (LSC) catalyst was prepared by nano-casting method combined with sol–gel method. The results showed that the LSC-650 catalyst synthesized at 650 °C for 2 h possessed a large specific surface area (103.46 m2/g) and the highest surface Co4+/Co3+ and Oads/Olat molar ratio. In addition, the CO conversion with the LSC-T (T = 550, 600, 650, 700 °C) samples indicated that the LSC-650 sample had the best catalytic activity (T50 = 145 °C, T90 = 149 °C) and stability.

A comparative study on the electrical properties of Ba0.6Sr0.4TiO3 film capacitors with different top electrodes

Au/Ba0.6Sr0.4TiO3 (BST)/La0.5Sr0.5CoO3 (LSCO) and Pt/BST/LSCO ferroelectric capacitors were successfully constructed on (001) LaAlO3 substrates via off-axis magnetron sputtering. X-ray diffraction (XRD) and Phi scan patterns confirmed that the BST film was epitaxial with an out-of-plane tetragonal phase. The ferroelectric and dielectric measurements reveal that, compared with the Pt/BST/LSCO capacitor, the Au/BST/LSCO capacitor exhibits a larger coercive field (∼139.7 kV/cm), smaller permanent polarization (∼2.94 μC/cm2), and lower tunability (∼65.22 %), which may be attributed to the higher difference in work function and weaker depolarization field screen effect of the top electrode, as well as smaller interfacial capacitance of the Au/BST interface than those of the Pt/BST interface. Therefore, based on series capacitor model and leakage behavior analysis, the thickness and dielectric constant of interfacial layer are quantitatively determined to be 3.52 nm and 12.13 for Pt/BST, and 4.42 nm and 5.82 for Au/BST, respectively. Our results pave a way for improving the dielectric performance in electrically tunable microwave devices.

Physicochemical Properties of (La,Sr)CoO3 Thick Films on Fe-25Cr Steel under Exposure to SOFC Cathode Operating Conditions.

La0.6Sr0.4CoO3 (LSC) coatings with a thickness of 50-100 µm were deposited on Fe-25Cr ferritic stainless steel (DIN 50049) via screen printing. The required suspension had been prepared using fine LSC powders synthesised using EDTA gel processes. In its bulk form, the LSC consisted entirely of the rhombohedral phase with space group R-3c, and it exhibited high electrical conductivity (~144 S·cm-1). LSC-coated steel was oxidised in air at 1073 K, i.e., under conditions corresponding to SOFC cathode operation, for times of up to 144 h. The in situ electrical resistance of the steel/La0.6Sr0.4CoO3 layered system during oxidation was measured. The products formed on the samples after the oxidation reaction resulting from exposure to the corrosive medium were investigated using XRD, SEM-EDS, and TEM-SAD. The microstructural, nanostructural, phase, and chemical analysis of films was performed with a focus on the film/substrate interface. It was determined that the LSC coating interacts with the oxidised steel in the applied conditions, and a multi-layer interfacial zone is formed. Detailed TEM-SAD observations indicated the formation of a main layer consisting of SrCrO4, which was the reaction product of (La,Sr)CoO3, and the Cr2O3 scale formed on the metal surface. The formation of the SrCrO4 phase resulted in improved electrical conductivity of the investigated metal/ceramics layered composite material, as demonstrated by the low area-specific resistance values of 5 mΩ·cm2, thus making it potentially useful as a SOFC interconnect material operating at the tested temperature. In addition, the evaporation rate of chromium measured for the uncoated steel and the steel/La0.6Sr0.4CoO3 layered system likewise indicates that the coating is capable of acting as an effective barrier against the formation of volatile compounds of chromium.

The effects of crystal orientation on the ferroelectric and optoelectronic properties of Pt/Na0.5Bi0.5TiO3/La0.5Sr0.5CoO3 heterostructures

Due to their excellent ferroelectric, semiconducting, and optoelectronic properties, perovskite ferroelectric thin films have attracted increasing attention in the photovoltaic field. Using La0.5Sr0.5CoO3 (LSCO) as the bottom electrode, flake, strip and pyramidal Na0.5Bi0.5TiO3 (NBT) films were prepared on (001), (110) and (111) SrTiO3 (STO) substrates by off-axis magnetron sputtering and pulsed laser deposition, respectively. XRD and Phi scan results show that both LSCO and NBT are perovskite structures and satisfy the epitaxial growth along the substrate STO. NBT orientation has a significant effect on the ferroelectric properties of Pt/NBT/LSCO heterostructures. The remnant polarization 2Pr values for NBT(111), NBT(110) and NBT(001) are 87.5, 62.6 and 28.5 μC/cm2, respectively, and thus 2Pr(111)>2Pr(110)>2Pr(001). NBT(111) shows the best ferroelectric properties (Pr=41.3 μC/cm2), excellent fatigue-resisting (up to 1010 cycles) and retention performance (duration 104s). The 2Pr-T association 2 Pr=41.72+16.05*T0.35 for NBT(111) was obtained according to the curve fitting, it is found that the NBT orientation has a significant effect on the PV effect for PT/NBT/LSCO photovoltaics and the open-circuit voltage ∆Voc. The short-circuit current ∆Jsc of polarization regulate intensity follows the laws of ∆Voc-111>∆Voc-110>∆Voc-001 and ∆Jsc-111>∆Jsc-110>∆Jsc-001, the Jsc for Pt/NBT(111)/LSCO heterostructures increases linearly with the illumination Ip increasing, while the Voc decreases linearly. The ferroelectro-polarized modulation PV mechanism was investigated by analyzing band structure of the Pt/NBT/LSCO heterostructures, which is attributed to the coupling effect of the ferroelectric depolarization field and the interfacial Schottky barrier.

Sr and Fe substituted LaCoO3 nano perovskites: Electrochemical energy storage and sensing applications

Perovskite-type LaCoO3 (LCO), La0.8Sr0.2CoO3 (LSCO), and La0.8Sr0.2Co0.9Fe0.1O3 (LSCFO) were prepared though a sol gel assisted hydrothermal method for supercapacitors and electrochemical sensors for heavy metal ions detection applications. Rhombohedral crystal structure was confirmed using experimental and DFT based computational XRD pattern. LCO, LSCO and LSCFO based modified carbon paste electrodes were prepared for cyclic voltammetry, electrochemical impedance spectra and galvanostatic charge discharge measurements. Among all electrodes, LSCFO results with 715.5 Fg−1 specific capacitance with 97 % retention after 1500 cycles. Cyclic voltammetry measurements for the sensing and detection of heavy metal ions (chromium and mercury) were carried out using all three electrodes and observed that LSCFO showed better response comparatively to that of other two electrodes, thus can be claimed as a potential mixed metal oxide nanomaterial for the fabrication of electrodes for storage of energy and sensor applications.

The Multifunctionality of Lanthanum-Strontium Cobaltite Nanopowder: High-Pressure Magnetic Studies and Excellent Electrocatalytic Properties for OER.

Simultaneous study of magnetic and electrocatalytic properties of cobaltites under extreme conditions expands the understanding of physical and chemical processes proceeding in them with the possibility of their further practical application. Therefore, La0.6Sr0.4CoO3 (LSCO) nanopowders were synthesized at different annealing temperatures tann = 850-900 °C, and their multifunctional properties were studied comprehensively. As tann increases, the rhombohedral perovskite structure of the LSCO becomes more single-phase, whereas the average particle size and dispersion grow. Co3+ and Co4+ are the major components. It has been found that LSCO-900 shows two main Curie temperatures, TC1 and TC2, associated with a particle size distribution. As pressure P increases, average ⟨TC1⟩ and ⟨TC2⟩ increase from 253 and 175 K under ambient pressure to 268 and 180 K under P = 0.8 GPa, respectively. The increment of ⟨dTC/dP⟩ for the smaller and bigger particles is sufficiently high and equals 10 and 13 K/GPa, respectively. The magnetocaloric effect in the LSCO-900 nanopowder demonstrates an extremely wide peak δTfwhm > 50 K that can be used as one of the composite components, expanding its working temperature window. Moreover, all LSCO samples showed excellent electrocatalytic performance for the oxygen evolution reaction (OER) process (overpotentials of only 265-285 mV at a current density of 10 mA cm-2) with minimal η10 for LSCO-900. Based on the experimental data, it was concluded that the formation of a dense amorphous layer on the surface of the particles ensures high stability as a catalyst (at least 24 h) during electrolysis in 1 M KOH electrolyte.

Lanthanum strontium cobaltite-based perovskite as an electrocatalyst for zinc-air battery application

Developing a low-cost and highly efficient electrocatalyst for bifunctional oxygen electrocatalytic activity is crucial in the field of energy conversion and storage devices. In this study, we employed a doping strategy to finely tune the electronic structure of lanthanum strontium cobaltite-based perovskite. Furthermore, we introduce Mn, Ni, and Cu cations as dopants at the B-site of lanthanum strontium cobaltite, La0.5Sr0.5CoO3 (LSCO), to investigate oxygen electrocatalytic activity in alkaline electrolytes. Among the electrocatalysts we synthesized, La0.5Sr0.5Co0.8Ni0.2O3 (LSCNiO) exhibited the lowest OER overpotential (ηj=10) of 429 mV in 0.1 M KOH, surpassing LSCO by 71 mV and LCO by 204 mV, respectively. Additionally, LSCNiO demonstrated a positive potential of 0.68 V @ 1 mA cm−2 for ORR, which is 50 mV less for LSCO catalyst. The improved electrocatalytic activity was investigated using spectroscopic techniques, confirming the presence of oxygen vacancies and an elevated Co oxidation state. The synergistic interplay between Co and Ni cations enhanced the hybridization between Co/Ni 3d and O 2p bands, reducing energy barriers and improving oxygen reaction kinetics. Finally, LSCNiO oxide with a bifunctional index (ΔE) of 1.08 V is tested for zinc-air battery (ZAB) applications.

Magnetocaloric effect of nanostructured La0.6Sr0.4CoO3

In this study, we investigate the magnetic and magnetocaloric properties of nanostructured La0.6Sr0.4CoO3 (LSC) samples synthesized under confinement conditions within porous templates. Using this method, we obtained de-agglomerated nanoparticles, which provide us with the feasibility of applying them in nanoparticle films that can be tailored to intricate geometries. We specifically explored the impact of pore size of the template on key parameters including saturation magnetization (MS), Curie temperature (TC), maximum entropy change (ΔS), and relative cooling power (RCP). Our findings reveal enhancements in those quantities, that are likely to be related with the nanostructure of the samples, indicating the potential of nanostructured LSC as an active material for magnetic refrigeration devices. Our alternative approach of synthesizing magnetocaloric materials under confinement conditions presents an exciting prospect for future research and development in the field.

(High-Temperature Energy, Materials, & Processes Division Subhash Singhal Award) From Electrochemical to Mechanical Modeling of SOFCs and Their Experimental Validation

Due to the asymmetric structure with multiple materials, SOFCs are subjected to various modes of mechanical stress, resulting in a risk of failure. Of particular importance are thermal and chemical strains, which depend on the micro- and macroscopic distribution of electrochemical reaction sites. Therefore, SOFC modeling must include electrochemistry, mass and charge transport, thermo-fluid dynamics, and structural analysis. In addition, appropriate experiments must be performed to validate the modeling results. This research group is working to develop a comprehensive environment for modeling and validation in order to evaluate the mechanical reliability of SOFCs.Electrochemical modeling of cathode was made based on the defect chemistry and mass transport of (La,Sr)CoO3 (LSC) and (La,Sr)(Co,Fe)O3 (LSCF). An empirical equation for the surface reaction of the porous electrode was determined by electrochemical analysis of a dense film electrode taking into account the difference between the dense film and porous electrodes [1]. Anode reaction rate on a unit length of triple phase boundary of Ni-YSZ-gas was determined using circular Ni model electrodes of various size [2]. Evaluation of 3D oxygen potential distribution inside the constituent oxides was made using an in-house code called SIMUDEL where mixed ionic/electronic conduction and oxygen nonstoichiometry were taken into consideration [3,4]. It was combined with commercial software to make structural analysis. Mechanical properties used for calculation were obtained from measurements by the resonance method and the small punch method or collected from the literature. Non-linear stress-strain behaviors were observed with Ni-YSZ cermet [5] and inelastic behaviors were found in most nonstoichiometric oxide materials. Large ferro-elasticity emerged in the LSC and LSCF [6] and in Sc stabilized ZrO2 electrolyte at elevated temperatures. Chemical strain in vacancy formation was formulated with a linear function of the defect concentration as an independent factor from the thermal expansion. In the structural analysis, it was treated as the additional temperature change of the local material. Volume change of Ni-YSZ cermet on red-ox operation was a difficult factor to formulate because of its complex dependence on composition, temperature, and atmosphere. As expected, Ni-YSZ showed expansion when oxidized, but under certain conditions at an intermediate temperature range, it rather contracted on oxidation [7].In reality, the calculated stress distribution does not always match the actual behavior of the cell since there often are unconsidered factors. Thus, experimental validation is essential. For this purpose, we have developed methods for in-situ or operando measurements of cell shape and the residual stress. Long-focus laser profilometer was used to measure the warping of a planar cell during heating, operating, and cooling operations. For the change in the diameter of a tubular cell, the laser projection type dimension meter was employed. Residual stress measurements were made with a handy X-ray analyzer (μ-X360s, Pulstec Industrial. Co. Ltd.) combined with a newly developed one- or two-chamber cell holder [8,9]. Anode-supported cells from multiple sources were analyzed, showing different stress histories in red-ox operations depending on the microstructure of the anode support layer.Currently, we are developing a protocol for testing robustness of planar SOFCs. Here, temperature distribution is intentionally applied on a cell with segmented heater allays on the top and the bottom of the cell. Severe condition tests will be performed, and the results will be analyzed with the above-mentioned simulation.AcknowledgementThis study was supported by the New Energy and Industrial Technology Development Organization (NEDO) .[1] T. Kawada, Current Opinion in Electrochemistry, 21, 274-282 (2020) DOI: 10.1016/j.coelec.2020.03.016[2] M. Takeda, Master’s thesis, Graduate School of Environmental Studies, Tohoku University (2016) : M. Takeda, et al. Submitted to J. Electrochem. Soc.[3] K. Terada, et. al., ECS Trans. 35(2 part2), 923-933 DOI: 10.1149/1.3570073[4] M. Sato, et. al., Trans. Jpn. Soc. Comp. Eng. Sci. 2017, 14 (2017) DOI: 10.11421/jsces.2017.20170004[5] S. Watanabe et al., J. Mater. Sci. 55, 8679-8693 (2020) DOI: 10.1007/s10853-020-04624-4[6] Y. Kimura et al., J. Electrochem. Soc. 161(11), F3079- F3083 (2014) DOI: 10.1149/2.0131411jes[7] Y. Morishita et al. , ECS Trans., 91(1) 1979-1984 (2019). DOI: 10.1149/09101.1979ecst[8] K. Yashiro et al., submitted to J. Power Sources[9] K. Oshima et al.,ECS Trans. 103(1), 1251-1260 (2021) DOI: 10.1149/10301.1251ecst

Experimental Analysis of the Effect of Cathodic CO2 Supply to Industrial Solid Oxide Fuel Cells

The integration of Solid Oxide Fuel Cells (SOFCs) in hybrid power generation systems offers the opportunity to achieve higher electric efficiencies. In the SOS-CO2 cycle [1], a newly developed cycle for blue power production (i.e., power generated starting from natural gas while capturing CO2), the SOFC cathode is supplied with mixtures of CO2 and O2, up to 79% CO2 molar fraction, while the anode is supplied with a reformate feed, containing H2, CH4, CO, CO2, and water vapour. Aim of this work is to experimentally evaluate the performance and the durability of industrial 5x5 cm2 Ni-YSZ anode-supported SOFCs under the SOS-CO2 cycle conditions, focusing on the effects of the CO2-rich cathodic atmosphere. The cells mounted a LSCF-based (La0.6Sr0.4Co0.2Fe0.8O3) single phase cathode, coated by a current collection layer of LSC (La0.6Sr0.4CoO3). Laboratory tests were performed at 700°C, acquiring polarization (I/V) curves and EIS spectra by means of a Horiba – FuelCon C50 Evaluator test station. Initial investigations with 7% humidified H2 and 21/79 O2/CO2 cathodic mixture revealed 25% power loss compared to the base case with cathodic air. The test showed not only that the loss of performance was stable in time, but also that the power reduction was reversible since the initial performance in air was recovered. The EIS spectra showed an increase of the polarization resistance and of the ohmic resistance upon feeding CO2. This latter observation suggested a reduction of the electronic conductivity of the cathode, compatible with the formation of Sr carbonates on the perovskite surface [2–4]. To assess the performance of the SOFC under the operating conditions of the SOS-CO2 cycle, the anode was supplied with reformate. Compared to the base case with humidified hydrogen and air, the current density at 0.7 V decreased by 37% (490 mA/cm2). When supplying the 21/79 O2/CO2 mixture at the cathode, the current density stabilized at 420 mA/cm2 (Figure 1). Durability tests (over 300 h) at 700°C with reformate and 21/79 O2/CO2 mixture highlighted a moderate decrease of the current density at 0.7 V. After these tests, the cathode was characterized post-mortem with XRD, SEM and Raman to analyse the consequences of the prolonged exposure to CO2. To further quantify the effect of CO2 on the cathode, symmetric button cells were also characterized with EIS, measuring ohmic and polarization resistances. The results suggested that the adsorption of CO2 is reversible and indicated a better suitability of LSCF- compared to LSC-based cathodes for operations with CO2-rich mixtures. Experiments performed between 550 and 700°C at varying CO2 and O2 partial pressures allowed to describe the kinetics of the oxygen reduction reaction and extract its activation energy. Overall, the results provided key elements for the integration of SOFCs in the SOS-CO2 blue power technology.

Methane conversion to syngas by chemical looping on La0.8Sr0.2FexCo1-xO3 (x = 0, 0.25, 0.50, 0.75) perovskites with CO2 co-feeding

Partial oxidation of methane (POM) by chemical looping with CO2 co-feeding on La0.8Sr0.2FeO3 (LSF) perovskite catalyst yielded a highly selective operation and enabled to extend the duration of reduction cycle. In this work, the conversion of methane to syngas was studied on La0.8Sr0.2Fe(x)Co(1-x)O3 (x = 0, 0.25, 0.5, 0.75) perovskites in chemical-looping mode, co-feeding CO2 and methane. The reaction was conducted at 850 °C, 15 min reduction (10% methane in N2, 0–3% CO2), and 10 min oxidation (10% O2 in N2) cycles. The perovskites activity decreased with increasing Co content, in the absence of CO2, due to intensified coke deposition on the catalyst. Addition of CO2 during the reduction step (1–3%) reduced coke accumulation. A run conducted on La0.8Sr0.2CoO3 (LSC) with continuous feeding of CO2 and periodical (on–off) methane feeding indicated that CO2 reacts with the accumulated coke in reverse-Boudouard reaction, increasing CO selectivity without affecting the methane conversion. XRD analysis of reduced Co-containing perovskites indicates a decreasing perovskite content. Metallic Co and La2O3 phases increased as the Co content in the fresh perovskite increased, increasing coke deposition. As the Co content increased, the process shifts from POM with oxygen replenishment (LSF) to cracking followed by reverse-Boudouard reaction (LSC).

Chemical Compatibility and Electrochemical Performance of Ba7Ta3.7Mo1.3O20.15 Electrolytes for Solid Oxide Fuel Cells.

Hexagonal perovskite-related oxides Ba7Ta3.7Mo1.3O20.15 (BTM) have recently been reported as promising electrolyte materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). In this work, sintering properties, thermal expansion coefficient, and chemical stability of BTM were studied. In particular, the chemical compatibilities of (La0.75Sr0.25)0.95MnO3±δ (LSM), La0.6Sr0.4CoO3 (LSC), La0.6Sr0.4Co0.2Fe0.8O3+δ (LSCF), PrBaMn2O5+δ (PBM), Sr2Fe1.5Mo0.5O6-δ (SFM), BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY), and NiO electrode materials with the BTM electrolyte were evaluated. The results show that BTM is highly reactive with these electrodes, in particular, BTM tends to react with Ni, Co, Fe, Mn, Pr, Sr, and La elements in the electrodes to form resistive phases, thus deteriorating the electrochemical properties, which has not been reported before.

Beneficial Effects of La0.5Sr0.5CoO3 Coatings on Thin‐Film LiMn2O4 Cathodes for Lithium Ion Batteries

AbstractThe severe capacity loss of spinel LiMn2O4 (LMO) limits the utility of this otherwise promising lithium ion battery cathode material. One of the strategies to mitigate capacity fade is applying a coating on LMO particle surfaces. While this approach yields promising results, there is limited understanding of mechanisms whereby coatings improve LMO capacity retention. Herein, the effects of a new protective coating material, La0.5Sr0.5CoO3 (LSCO), in a thin‐film battery geometry that is amenable to fundamental studies of electrode processes, are reported. RF sputtering deposition is used to produce high quality 25–100 nm LMO cathodes on Al2O3 substrates with an intervening Pt/Ti back‐side contact layer. Cycling of the un‐coated cathodes results in capacity loss of 18% over 300 cycles. Adding a 2 nm LSCO layer reduces the capacity loss to 3%. While this may be due in part to reduced Mn dissolution, scanning transmission electron microscopy results indicate that the coating helps to preserve crystallinity and reduce lattice structure distortion due to inhibited formation of defect tetragonal spinel. Three‐electrode electrochemical impedance spectroscopy results reveal that the LSCO coating increases charge transfer and ohmic resistances, but the increases are generally too small to significantly impact cell performance even at high C‐rates.

Designing the nano-scale architecture of the air electrode for high-performance and robust reversible solid oxide cells

Herein, an innovative La0.6Sr0.4CoO3 (LSC) nanostructured air electrode, having superior catalytic activity and exceptional robustness against critical interfacial delamination-induced degradation, is reported. A ∼50 nm thin LSC air electrode decorated onto a porosity graded Gd0.1Ce0.9O2 backbone via ultrasonic-assisted infiltration showed significantly flourished ORR and OER kinetics with prolific electrochemical performance compared to the cell with conventional LSC air electrode. The SOC showed maximum power density of 2.24 W cm−2 in the fuel cell mode and maximum current density of 4.57 A cm−2 at an operating voltage of 1.6 V in the electrolysis mode at 750 °C. Results of the reversible cycling and galvanostatic stability tests indicate excellent durability, which is attributed to the elimination of detrimental O2 pressure evolved at the air electrode/electrolyte interface. Sited among the highest performances till date, this study provides a realization of a tremendously durable SOC design for the production of green hydrogen and electricity.

Simultaneous triple-effect on inhibiting the photogenerated carriers recombination of g-C3N4 for boosting solar H2 production at atmospheric pressure

Graphitic carbon nitride (g-C3N4) has been well known as one of the important organic semiconductor photocatalyst. However, its low photocatalytic activity greatly hampered its application, which relates to it fast recombination of photoexcited electrons and holes. In this work, conductive thermal oxidation catalysts with good photothermal property (Sm0.5Sr0.5CoO3 (SSC), La0.5Sr0.5CoO3 (LSC) and La0.5Sr0.5MnO3 (LSM)) were used to construct few-layer g-C3N4 based photocatalysts with simultaneously triple-effect on inhibiting the photogenerated carriers recombination. The stacking of g-C3N4 can be reduced by the thermal oxidation and the thickness of few-layer g-C3N4 nanosheets is about 1.5 nm on average, which shortens the migration distance of electrons. The heat converted by the photothermal effect of SSC can accelerate the migration of photogenerated electrons. In addition, the consumption of photogenerated holes can be transferred from g-C3N4 to SSC, further restraining the recombination of electron-hole pairs. The prepared few-layer g-C3N4 nanosheets with 1% addition of SSC exhibit a superior hydrogen evolution rate of 16,521.4 μmol g−1 h−1, which is 13.2 times higher than that of the bulk g-C3N4 at atmospheric pressure.

Crystal Facet and Electronic Structure Modulation of Perovskite Oxides for Water Oxidation

In water-splitting catalysts, exposing high-activity crystal facets with optimal electronic structures can significantly enhance the oxygen evolution reaction (OER) kinetics. In this work, we demonstrate a facile strategy for simultaneously modulating the preferential crystal facet and electronic structure of perovskite oxides for their use as water-electrolysis catalysts using a template-mediated growth approach. Experimental and computational analyses revealed that the preferred crystal facet of La0.5Sr0.5CoO3 (LSC) grown on MoReS2 was effectively modulated to the (110) plane, and the free energy barrier of the rate-determining step was lowered by such crystal facet engineering. Furthermore, the interfacial charge transfer between LSC and MoReS2 enabled the optimal electronic structure of the B-site cation in LSC. Consequently, LSC grown on MoReS2 exhibited an OER activity of 210 mV at 10 mA cm–2, surpassing the performance of state-of-the-art perovskite oxide-based catalysts. Our findings provide new insights into the design of efficient perovskite oxide-based electrocatalysts for water electrolysis.

Synergistic influence of plasmonic Ag nanoparticles/La0.6Sr0.4CoO3/TiO2 heterostructured photoanodes boosted solar energy harvesting by dye-sensitized photovoltaics

Several hybrid composite photoanodes composed of easily synthesizable and cost-effective La0.6Sr0.4CoO3 (LSCO) nanoparticles (obtained by the sol–gel method) combined with TiO2 nanoparticles were prepared and investigated for their light-harvesting properties in dye-sensitized solar cells (DSSCs). To develop these effective photoelectrode nanomaterials for DSSCs, the pure inorganic perovskite La0.6Sr0.4CoO3 (2, 4, 6 and 8 %) as well as plasmonic silver nanoparticles decorated La0.6Sr0.4CoO3 (6 % La0.6Sr0.4CoO3/x%Ag, x = 1, 2.5, 5, 7.5 and 10 %) nanomaterials were added into the TiO2 photoanodes. The XRD, FESEM, EDS, BET FT-IR, DRS, PL, and dye loading were used to study all nanostructured photoanodes' structural and morphological properties. Based on the photovoltaic tests, it was found that the DSSC fabricated with TiO2 + 6 % La0.6Sr0.4CoO3 achieved the most enhanced efficiency of 6.04 % among the TiO2 + La0.6Sr0.4CoO3 (2, 4, 6, and 8 %) containing devices. Furthermore, the power conversion efficiency (PCE) values were increased when Ag plasmonic nanoparticles were decorated on the La0.6Sr0.4CoO3 crystalline lattice. The greatest PCE = 7.34 % was attained for the optimized solar cell assembled by TiO2 + 6 % La0.6Sr0.4CoO3/7.5 %Ag photoanode which yielded ∼ 2.35 and 1.21 folds increase in PCE compared to the DSSCs containing pristine TiO2 nanoparticles and TiO2/6% La0.6Sr0.4CoO3 photoelectrodes, respectively. Based on the photoelectrochemical analysis, this structure exhibited the fastest electron transport rate, the most effective photo-induced charge separation, the greatest electron collection efficiency, the highest dye loading capacity, and the least photoluminescence intensity (charge recombination), which all contributed to increasing the DSSC device's efficiency.

Ferromagnetic exchange field stabilized antiferromagnetic ordering in a cuprate superconductor

We report experimental evidence of formation of antiferromagnetic clusters in composites made of a cuprate superconductor La1.85Sr0.15CuO4 (LCu) and a ferromagnet La0.6Sr0.4CoO3 (LCo). From linear and non-linear ac-susceptibility measurement on this composite material it is found that the exchange field of LCo suppress the dynamic antiferromagnetic spin fluctuation of LCu and convert it into the short range ordered superparamagnetic type antiferromagnetic (AFM) clusters at the cost of superconducting volume fraction. These shrank superconducting volume fraction shows quantum size effect (QSE) and follows DeGennes-Tinkham theory on finite size effect of superconductor.

Investigation of the necessity to apply a (Ce, Gd)O2 interlayer between the low-temperature processed (La, Sr)CoO3 electrode film and the (Zr, Y)O2 electrolyte in solid oxide fuel cells

Gadolinia doped ceria (GDC) interlayers have been widely used to avoid resistive phase formation at the mixed ionic electronic conductor (MIEC) (La,Sr)CoO3 (LSC) air electrode/ yttria stabilized zirconia (YSZ) electrolyte interfaces. Although MIEC electrodes fabricated by low-temperature metal organic precursor methods offer the highest electrochemical performance, no studies exist on the effect of GDC interlayer on their performance. In this work, we investigated the necessity for a GDC interlayer between the low-temperature processed LSC electrode and the YSZ electrolyte. Through x-ray diffraction, scanning transmission electron microscopy/energy-dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy analyses, we studied the impact of the GDC interlayer on i) the formation of resistive zirconate phases at the LSC/YSZ interface and ii) the overall phase and surface chemistry evolution. While no resistive zirconate phases formed in the LSC/YSZ system due to low processing temperatures, La leaching into the GDC layer altered the overall phase evolution, in addition to the resulting cation stoichiometry. This LSC/GDC/YSZ system showed a polarization resistance improved by an order of magnitude, attributable to the changes in phase composition.