A-site Doping Research Articles

Promoting Charge-Carriers Dynamics by Relaxed Lattice Strain in A-site-doped Halide Perovskite for Photocatalytic H2 Evolution.

Because of the unique and superior optoelectronic properties, metal halide perovskites (MHPs) have attracted great interests in photocatalysis. Element doping strategy is adopted to modify perovskite materials to improve their photocatalytic performance. However, the contribution of bare doping-site onto photocatalytic efficiency, and the correlation between doping locations and activity have not yet to be demonstrated. Thispromoted us to explore the potential of A-site-doped MHPs for photocatalysis. Herein, we dope potassium (K+) into CsPbBr3 and first reveal that the occupied locations of K+ in CsPbBr3 is lattice incorporation rather than surface segregation, which would change from A-site substitution to interstitial site in lattice with the increase of K+ concentrations. Taking H2 evolution as a model reaction, photocatalytic activity of CsPbBr3 after K+ doping could be significantly improved ~11-fold with A-site substitution, which is superior to that of interstitial site doping. Moreover, other alkali metals including Li, Na, and Rb doping give the same results. The structure of photocatalysts during reaction confirmed the contribution of A-site doping onto enhanced photocatalytic activity. Mechanistic insights show it is a result of the relaxed residual lattice strain induced promoted charge-carriers dynamics and formed upward shifting of band after K+ A-site doping.

A-Site Doping Promotes CO2 Activation and Prolongs Charge Carrier Lifetimes in SrTiO3: Insight from Quantum Dynamics.

Using time-dependent density functional theory and nonadiabatic molecular dynamics, we systematically investigated the effect of A-site doping on the CO2 activation and charge carrier lifetimes in SrTiO3(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO2 on SrTiO3 surfaces, which is beneficial for promoting CO2 activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO2 near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO2 LUMO. Importantly, A-site doping causes a significant nonadiabatic coupling reduction and prolongs the charge recombination time by a factor of 1.86 compared to the pristine STO. Our study clarifies the influencing mechanism of A-site doping on CO2 activation and charge carrier lifetimes and suggests important principles for the design of high-performance photocatalytic semiconductors.

Effect of A-site cation doping on the catalytic oxidation of toluene over mullite catalyst GdMn2O5

Manganese-based mullite (AMn2O5) catalysts are promising for the catalytic oxidation of VOCs, with their oxidation reaction performance being tunable by modifying the composition of the A-site elements. In this work, various manganese-based mullite catalysts (Gd0.9X0.1Mn2O5, X =Sr, Ce, or Ca) with different A-site elements doping were prepared by the citric acid sol–gel method and applied to the catalytic oxidation of toluene. The activity tests indicated that the enhancement of catalytic performance by doping elements was in the order of Sr > Ce > Ca. Notably, the T90 of the Gd0.9Sr0.1Mn2O5 catalyst was 235.6 °C, a lower 37.8 °C than that of the GdMn2O5. Comprehensive characterization and density functional theory (DFT) simulations revealed that Sr doping facilitates the reduction of Mn4+ to Mn3+, increases the electron occupancy of the eg orbitals in octahedral Mn sites, and elevates the Mn-d band center, thus facilitating the adsorption and activation of O2. Additionally, the raised O-p band center caused by Sr doping enhances lattice oxygen mobility. In situ DRIFTS analysis indicated that the introduction of Sr at the A-site optimizes the toluene reaction pathway and accelerates the reaction rate. This work reveals that a simple A-site cation doping strategy can effectively regulate manganese-based mullite catalysts’ electronic structure and surface reaction activity, providing a feasible method for the large-scale preparation of manganese-based mullite catalysts with excellent catalytic performance.

Thermoelectric properties of A-site deficient reduced Sr0.775La0.15-xEuxTiO3-δ (0 ≤ x ≤ 0.15)

There are numerous different schemes to improve the figure of merit (ZT) in oxide thermoelectrics, including creating additional electrons using oxygen vacancies, chemical doping, and A-site nonstoichiometry. A-site deficient (Sr,La)0.925TiO3- δ has shown promise as an n-type oxide thermoelectric; herein, additional A-site substitutional doping with Eu was used to improve ZT, through a combination of A-site size mismatch and non-stoichiometry. A solid solution series Sr0.775La0.15-xEuxTiO3-δ (0 ≤ x ≤ 0.15) was synthesised, showing a modest improvement in thermoelectric properties for x = 0.05, with a ZT of 0.18 at 600 °C, vs a ZT of 0.16 in the end member composition. Upon full characterisation, the additional electrons provided by the formation of oxygen vacancies were being used up by reduction of the added europium dopants, leading to a drop in electrical conductivity, and correspondingly, ZT. This gives a useful perspective in choosing dopants for schemes such as these.

Dry reforming of toluene over Ni/pyrochlore catalysts with A-site Sr doping

Dry reforming with CO2 is one potential method for tar removal and further production of syngas in biomass gasification, but the crucial catalysts with good reaction characteristics are still being developed. In the work, Ni/pyrochlore was proposed to be utilized as catalysts in the dry reforming of tar, and thermodynamic calculation, reaction progress test, and materials characterization were conducted to reveal dry reforming characteristics over Ni/pyrochlore catalysts and the reaction mechanism behind. Results show that YS0.2C catalyst exhibits the best activity (toluene and CO2 conversion of 70.1% and 79.5%) and stability among all catalysts under the optimized conditions of 700 °C with a CO2/toluene molar ratio of 7. Analysis on physicochemical properties of the catalysts indicate Sr doping can effectively promote catalytic reforming by enhanced interaction between Ni and support, CO2 adsorption and oxygen mobility. The work offers a promising catalyst type in improving tar removal by dry reforming.

Fixed-Point Atomic Regulation Engineered Low-Thickness Wideband Microwave Absorption.

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8GHz, RLmin = -46dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

Pivotal Role of Modifiable A-Site Doping in Enhancing Valence Stability and Excited State Dynamics of MnO6.

The controlled regulation of A-site in rare earth manganate perovskites can orderly arrange the electronic states, leading to the emergence of unique transport properties. However, it is challenging to balance crystal structure stability and property variations during the multi-ion doping. In this study, a series of multivalent manganate perovskites are synthesized by hydrothermal method through the A-site multielement doping, which enables the manganese atoms with varying valence states to orderly arrange at the B site. Powder X-ray diffraction (PXRD) and X-ray absorption spectra (XAS) confirm that the splitting of the K─O hybrid orbitals in the crystal effectively prevents any distortion of the MnO6 octahedron, thereby facilitating the ordered arrangement of Mn (III) -Mn (IV) -Mn (V) at the B-site and promoting superstructure formation. The transient absorption spectra (TAS) reveals that the sequential arrangement of Mn (III) - Mn (IV) - Mn(V) better forms the charge transfer channels, and thereby makes the photodynamic properties of the sample composition-dependent. These photodynamic properties will facilitate the study of exciton-electron coupling behavior in LCKMO crystals during electrical transport.

A-site doping of cobalt-free Ba1-xAxFeO3-δ (A=Ca, Sr) as cathode for proton-conducting ceramic cells

A-site doping with Ca2+, Sr2+ for the cobalt-free BaFeO3-δ-based cathode materials for proton-conducting ceramic fuel cells (PCFCs) is studied. The composite Ba0·8Ca0·2FeO3-δ (BCF0.2)-BaZr0.1Ce0·7Y0.1Yb0.1O3-δ (BZCYYb) and Ba0·8Sr0·2FeO3-δ (BSF0.2)-BZCYYb electrode show polarization resistance (Rp) of 0.156 Ω cm2 and 0.308 Ω cm2 at 700 °C, respectively. It is found that the Ca or Sr doping not only benefits oxygen vacancy formation and ion migration but also optimizes the surface oxygen reduction reaction (ORR) process. The density functional theory (DFT) calculations show that the Gibbs energies of *OOH and *OH intermediates are decreased, indicating an enhanced surface ORR. The PCFC with BCF0.2-BZCYYb composite cathode achieves the maximum power density of 299.75 mW cm−2 at 700 °C and shows good stability at 650 °C for 65 h under a constant voltage of 0.75 V. These findings suggest that the BCF0.2-BZCYYb has the potential to serve as cobalt-free cathode materials for PCFCs.

Defect Control of Donor Doping on Dielectric Ceramics to Improve the Colossal Permittivity and Temperature Stability

As the demand for miniaturization of electronic devices increases, ceramics with an ABO3 structure require further improvement of the dielectric constant with high permittivity. In the present work, Ba1−1.5xBixTiO3 (BB100xT, x = 0.0025, 0.005, 0.0075, 0.01) ceramics were prepared via a solid-state reaction process. The effect of Bi doping on dielectric properties of lead-free relaxor ferroelectric BaTiO3-based ceramics was studied. The results showed that both colossal permittivity (37,174) and a temperature stability of TCC ≤ ±15% (−27–141 °C) were achieved in BB100xT ceramics at x = 0.5%. The A-site donor doping produces A-site vacancies, a larger space for Ti4+, and fluctuation of the component, which is partially responsible for the high permittivity and responsible for the temperature stability. Meanwhile, the contribution of defect dipoles, and IBLC and SBLC effects to polarization leads to the colossal permittivity. The formation of a liquid phase during sintering promotes mass transfer when the doping content is higher than 0.5%. This work benefits the exploration of novel multilayer ceramic capacitors with colossal permittivity and temperature stability via defect engineering.

Effects of K, Rb, and Br doping on Cs3Bi2I9 perovskites: A design of experiments approach

This work presents the effect of doping with different species on the structural sites of lead-free halide perovskites, aiming to evaluate the potential of the produced materials as photoabsorbing layers in 3rd generation solar cells. Lead-free perovskite films of Cs3Sb2I9, CsCu2I3, Cs3Bi2I9, and CsPbI3 were synthesized via the spin-coating method and characterized using X-ray diffraction, scanning electron microscopy with chemical microanalysis (SEM-EDS), and Uv-Vis spectroscopy. Computational models based on Density Functional Theory (DFT) were used to simulate the structures and properties of some of the perovskites synthesized in this study, in order to validate the experimentally obtained data. The Cs3Bi2I6Br3 perovskite was subjected to modification through A-site doping with K and Rb and X-site doping with Br, with a comprehensive study on the effects of processing variables, anti-solvent quantity, and crystallization temperature using a 23 experimental design. The outcomes highlighted the critical role of the anti-solvent quantity in structure formation and electronic properties. Toluene, as an anti-solvent, produced unique morphologies not commonly reported. Computational studies were performed using Density Functional Theory (DFT) to complement the experimental findings. The optimization process revealed that Cs3Bi2I9 structures mainly constituted [CsI12] and [BrI6] clusters, with Cs–I and Bi–I average bond lengths consistent with experimental results. X-site Br doping induced slight distortion, while A-site Rb/K doping showed minimal lattice parameter changes. Notably, K-induced morphological alterations suggested potential electronic transformations. From an electronic structure perspective, Cs3Bi2I9 had a band gap of 2.07 eV, slightly increased to 2.10 eV with Br doping. Rb maintained Br-doped structure, while K significantly reduced the band gap to 1.96 eV. These computational results align well with our experimental data, showcasing the accuracy of our calculations in predicting material properties. The results confirmed that the perovskites selected through experimental design and validated by computational simulation are promising semiconductor materials for photovoltaic applications, as well as being a lead-free photoabsorbing material option.

Effect of different donor dopants on the seed-free solid-state crystal growth of potassium sodium niobate

Seed-free solid-state crystal growth (SSCG) is a developing technique to produce lead-free potassium sodium niobate (KNN) single crystals with the advantage of expeditious growth rates. The fundamental mechanism for seed-free SSCG is abnormal grain growth, which can be promoted through the inclusion of a precise concentration of an A-site donor dopant in KNN. To date, Ba2+ and Bi3+ have been utilised to grow centimetre-sized KNN single crystals with piezoelectric properties equivalent to traditional melt growth techniques. This research explores a broad range of potential donor dopants in (K0.5Na0.5Li0.006Dx)NbO3 (where D = Ba2+, Ca2+, Sr2+, Pb2+, Bi3+, La3+, Ce3+,4+ and Pr3+,4+) to determine disparities in abnormal grain growth behaviour and the critical parameters that enable substantial single crystal growth. The incorporation of different donor dopants influences the grain growth behaviour, single crystal sizes and preferential crystallographic orientations. This inspires future research to explore different compositions and techniques to improve the KNN crystal sizes and piezoelectric properties and addressing other challenges. These efforts are essential to improve the maturity of seed-free SSCG, making it industrially viable and a genuine alternative to costly single crystal growth techniques.

A-site alkali metal-doped SrTi0.3Fe0.7O3-δ: A highly stable symmetrical electrode material for solid oxide electrochemical cells

To addresses the limitations in electrode performance observed at temperatures ≤700 °C, attributed to the low oxygen surface exchange coefficient primarily caused by high Sr surface segregation, we developed an electrode performance enhancement strategy involving A-site alkali metal doping to SrTi1-xFexO3-δ (STF)-based perovskite. Here, we present the symmetrical electrode material for solid oxide electrochemical cells (SOCs), Sr0.95Mg0.05Ti0.3Fe0.7O3-δ (SMTF), demonstrating a unique combination of excellent symmetrical electrode performance and long-term stability. A-site Mg doping reduces the Sr surface segregation and improves the conductivity but also significantly enhances its electrochemical performance. At 700 °C, the performance of SMTF symmetric cell in both fuel cell and electrolysis modes is 1.5 times higher than that of STF. Moreover, under air atmosphere, SMTF demonstrates stable performance (>1000 h) at 1 A cm−2, with no degradation observed after 400 h testing under humidified hydrogen conditions. Additionally, SMTF exhibits excellent CO2 tolerance in CO2-rich atmospheres.

Effect of A and B-site ion doping on the structure and properties of KNN-based ceramic coatings

K0.5Na0.5NbO3 (KNN) ceramics have been widely studied for high Curie temperature (Tc) and good electrical properties. The structural and electrical properties of KNN ceramics were significantly improved by A-site and B-site doping modifications. In this paper, KNN-based ceramic coatings doped with Mn, and Sb were prepared by supersonic plasma spraying. The effects of doping ions at A-site and B-site on the microstructure, phase structure, mechanical properties, and electrical properties of KNN-based ceramic coatings were mainly analyzed. The results show that the surface of the three coatings KNN, K0.5Na0.5Nb0.94Sb0.06O3 (KNNS), and K0.49Na0.49Mn0.02NbO3 (KNMN) is relatively flat, uniform distribution of the elements. The surface roughness (Sa) is 3.85 μm, 3.88 μm, and 3.66 μm, respectively. Pores and cracks are present within the coatings, but the KNNS ceramic coatings have significantly fewer pores and cracks compared to the KNN and KNMN ceramic coatings. XRD results show that KNN-based ceramic coatings exhibit single perovskite structure, and both Mn and Sb are successfully introduced into the KNN ceramics without the generation of a second phase. XPS results showed that the valence states of the elements in the KNN ceramic coatings did not change. In KNMN and KNNS ceramic coatings, the valence state of the doped elements did not change. The addition of Mn2+ and Sb3+ reduced the oxygen vacancy in KNN ceramic coatings. Among them, the KNMN ceramic coatings microhardness increased by 45.3 HV0.2, remnant polarization (Pr) increased by 8.1 μC/cm2, the dielectric constant (εr) increased by 107, and dielectric loss greatly reduced, reaching 0.005. The KNMN ceramic coatings microhardness increased by 90.8 HV0.2, dielectric constant increased by 195, Pr increased by 16.7 μC/cm2, dielectric loss is 0.007. These findings demonstrate that doping with Mn2+ and Sb3+ has a positive impact on the performance of KNN ceramic coatings, with Sb3+ having a greater effect.

Doping Up the Light: A Review of A/B-Site Doping in Metal Halide Perovskite Nanocrystals for Next-Generation LEDs.

All-inorganic metal halide perovskite nanocrystals (PeNCs) show great potential for the next generation of perovskite light-emitting diodes (PeLEDs). However, trap-assisted recombination negatively impacts the optoelectronic properties of PeNCs and prevents their widespread adoption for commercial exploitation. To mitigate trap-assisted recombination and further enhance the external quantum efficiency of PeLEDs, A/B-site doping has been widely investigated to tune the bandgap of PeNCs. The bandgap of PeNCs is adjustable within a small range (no more than 0.1 eV) by A-site cation doping, resulting in changes in the bond length of Pb-X and the angle of [PbX6]4. Nevertheless, B-site doping of PeNCs has a more significant impact on the bandgap level through modification of surface defect states. In this perspective, we delve into the synthesis of PeNCs with A/B-site doping and their impacts on the structural and optoelectronic properties, as well as their impacts on the performance of subsequent PeLEDs. Furthermore, we explore the A-site and B-site doping mechanisms and the impact of device architecture on doped PeNCs to maximize the performance and stability of PeLEDs. This work presents a comprehensive overview of the studies on A-site and B-site doping in PeNCs and approaches to unlock their full potential in the next generation of LEDs.

Innovative Design of BNKT-xSLZT Ceramics: Maximizing the Polarization Difference for Enhanced Energy Storage.

Lead-free relaxor ferroelectric ceramics with outstanding energy-storage (ES) density (Wrec) and high ES efficiency (η) are crucial for advanced pulse-power capacitors. This study introduces a strategic approach to maximizing the polarization difference (ΔP) by inducing a transition from the ferroelectric phase to the ergodic relaxor (ER) phase. By employing this strategy, a series of ceramics, (1 - x)(Bi0.5Na0.4K0.1)TiO3-x(Sr0.85La0.1)(Zr0.5Ti0.5)O3 (BNKT-xSLZT), with varying SLZT content (x = 0.05, 0.10, 0.15, and 0.20), were designed. The addition of SLZT enhances cationic disorder, induces vacancies at A sites, and disrupts long-range ferroelectric order, facilitating the formation of polar nanoregions and enhancing relaxor ferroelectric behavior. Furthermore, a viscous polymer process (VPP) technology is employed to optimize the ceramics' structure, aiming to increase the breakdown strength (Eb) and enhance ΔP. Ultimately, enhanced ES performance is demonstrated in BNKT-0.15SLZTVPP, achieving a remarkable Wrec of 6.85 J/cm3 and η of 84% under 470 kV/cm. This composition demonstrates excellent stability with minimal variations in Wrec (3.0%) and η (4.4%) over the temperature range of 20-110 °C. Additionally, BNKT-0.15SLZTVPP exhibits exceptional pulse charge-discharge properties, featuring a high discharge density of 3.72 J/cm3, a large power density of 164.2 MW/cm3, and a short discharge time (t0.9) of 193 ns under 300 kV/cm. The study validates the practicality of BNKT-0.15SLZTVPP for pulse capacitors and underscores the potential to enhance ES performance through A-site donor doping and VPP technology. This work provides a comprehensive understanding of the interplay among composition, structure, and ES properties in lead-free relaxor dielectric ceramics, laying the groundwork for innovative advancements in the field.

Effects of lanthanide doping on the electrode properties and exsolution behavior of A-site deficient Sr1.9Fe1.3Ni0.2Mo0.5O6-δ double perovskites

Double perovskite oxides of the Sr2Fe1.5Mo0.5O6-δ class are promising electrodes for Solid Oxide Fuel Cells (SOFCs) and Electrolyzers (SOECs) due to their outstanding electrochemical properties and durability. Additionally, their physicochemical properties can be tuned by B-site cation doping, namely, by partially substituting Fe cations with other transition metals such as Ni, Co, Mn, or Cu. This also allows the grain-surface functionalization with metallic alloyed nanocatalysts upon reduction driven by the exsolution phenomena, leading to higher electrocatalytic activity and resistance against sintering and coking. Traditionally, A-site deficiency has been employed to improve the amount of exsolved nanoparticles and, thereby, increase the number of Triple Phase Boundaries in the electrode. However, in Ni-doped non-stoichiometric double perovskite materials (e.g., Sr1.9Fe1.3Ni0.2Mo0.5O6-δ), A-site deficiency results in undesired NiO phase segregations. This, in turn, lowers the number of exsolvable cations, decreasing the number of metallic nanocatalysts compared to the stoichiometric compound. In this work, the impact of A-site doping with lanthanides (viz. Gd, La, Nd, and Pr) on the exsolution ability and electrochemical properties of non-stoichiometric Sr1.9Fe1.3Ni0.2Mo0.5O6-δ was evaluated. The results indicate that lanthanide doping enhances the conductivity of the double perovskites both in oxidizing and reducing atmospheres. In addition, lanthanide dopants that slightly destabilize the cubic structure also improve the exsolution dispersion, which decreases with increasing the double perovskite cell volume. These results illustrate how to design more efficient and durable electrocatalysts by modifying the double perovskite structure with A-site dopants.

Roles of the A-Site Ca Dopant in Modifying Surface Properties of a Co-Based Perovskite Catalyst for Selective Oxidation of Cyclohexane

Roles of the A-Site Ca Dopant in Modifying Surface Properties of a Co-Based Perovskite Catalyst for Selective Oxidation of Cyclohexane

Enhanced dielectric energy storage performance of Na0.5Bi0.5TiO3-LiTaO3-based lead-free relaxor ferroelectric ceramics through domain structural regulation and improved densification

Ceramic materials with relaxor dielectric properties, expressed as (1-x)(0.94Na0.5Bi0.5TiO3-0.06LiTaO3)-xCaTiO3 [(1-x)(NBT-LT)-xCT] with x values of 0.12, 0.15, 0.18, and 0.21, were synthesized through an A-site doping method to enhance energy storage capabilities. The linear dielectric CaTiO3 was chosen as the acceptor additive, and ceramic samples were prepared using conventional solid-phase and molding techniques. A comprehensive investigation evaluated the influence of different CT concentrations on the phase and energy storage/release characteristics of NBT-LT.Optimal performance was notably achieved with a 15% CT doping concentration, resulting in Wrec and η values of 2.16 J/cm³ and 70%, respectively, for a 100 μm thick sample under a 210 kV/cm voltage. When the film was rolled to a 60 μm thickness, the voltage strength increased to 330 kV/cm, leading to enhanced Wrec (5.33 J/cm³) and η (80%). Within the temperature range of 30 °C to 150 °C, only a marginal change in Wrec (less than 10%) was observed. Frequency conversion tests across the 1 Hz to 100 Hz range demonstrated the material's relative stability, with Wrec exhibiting minimal fluctuations. These findings emphasize the outstanding temperature and frequency stability of the material. During discharge, the material displayed a power density of up to 152 MW/cm³, coupled with a discharge time of 0.3 μs, showcasing remarkable pulse discharge capabilities. The experimental results affirm the promising potential of (NBT-LT)-0.15CT lead-free relaxor ferroelectric ceramics for application in commercial capacitors.

Boosting the catalytic activity of high-order Ruddlesden–Popper perovskite SrEu2Fe2O7-δ air electrode by A-site La doping for CO2 electrolysis in solid oxide electrolysis cells

Ruddlesden–Popper (R-P) oxides (An+1BnO3n+1) are potential air electrodes for solid oxide electrolysis cells (SOECs) because of their good electrochemical performance. Among them, SrEu2Fe2O7-δ (SEF) with n = 2 has received extensive attention because of its special structure and promising ionic–electronic conductivity. However, the SEF material is prone to degradation at high temperatures (600 °C–800 °C), and its long-term stability is easily affected. In this study, R-P oxide Sr1-xLaxEu2Fe2O7-δ (SLEFx; x = 0, 0.05, 0.1) was successfully synthesized using the sol–gel method. XRD results showed that La-doped SEF displayed good chemical and thermal compatibility with the gadolinia-doped ceria electrolyte. The SLEF0.05 electrode exhibited a polarization resistance of 0.075 Ω cm2 at 800 °C, which was 88.2 % lower than that of SEF. The half-cell based on the SLEF0.05 air electrode exhibited improved performance under the long-term stability test at a current density of − 0.5 A cm−2 for over 110 h at 800 °C, indicating excellent stability. Moreover, an electrolysis current density as high as 0.712 A cm−2 at 1.5 V was obtained for the full cell with the SLEF0.05 air electrode, which was 45.8 % higher than the SEF electrode when the temperature and feed gas were 800 °C and 50 % CO2–50 % CO, respectively. The XPS and cell testing results confirmed that La with high valance and small radius promoted the formation of oxygen vacancies and effectively enhanced the electrochemical performance and structural stability of the SEF material. Therefore, the R-P oxide SLEF0.05 is a promising air electrode material for SOECs.

Structure evolution and energy band modulation in Ba-doped BiFeO3 thin films

Bi1−xBaxFeO3 (BBFO, x = 0, 0.03, 0.1) thin films were epitaxially grown on SrRuO3-buffered SrTiO3 (001) substrates by pulsed laser deposition. With increasing Ba content, the BBFO thin films show significantly reduced leakage currents but suppressed ferroelectric polarization. X-ray diffraction reciprocal space mappings and Raman spectra indicate a structural evolution from a rhombohedral-like to tetragonal-like phase in the BBFO thin films. Optical absorption and photoelectron spectroscopy measurements demonstrate a modulation of energy band structures in the BBFO thin films. With A-site Ba acceptor doping, the BBFO thin films exhibit a blue-shift of optical bandgap and an increase in work function. The energy positions of conduction and valence bands of the BBFO thin films have been modulated, and the Fermi level shifts down to the center of the forbidden band, but acceptor-doped BFO thin films still show n-type conduction. The presence of extra oxygen vacancies by acceptor doping is supposed to make contribution to conduction behavior. This study provides a method to manipulate the functional properties and gives insights into the physics of Ba doping in BFO thin films.