Search Results (51)

Two-dimensional lead halide perovskites are of significant interest for a variety of practical applications. However, the relationships between their composition and properties are not fully clear. Here we investigated photoluminescence from 2D Ruddlesden–Popper perovskites with different bulky spacer cations. Significant differences in their optical properties and stability are observed, and perovskites with benzylammonium (BZA) and phenethylammonium (PEA) were selected for more detailed investigation of the observed stability differences due to their similar structure. We find that PEA₂PbI₄ exhibits more narrow emission and increased stability compared to BZA₂PbI₄. In addition, PEA₂PbI₄ exhibits self-healing of defects evident from PL enhancement, which is absent for BZA₂PbI₄. The observed differences between perovskites with BZA and PEA spacer cations can be attributed to differences in the formation of spacer cation vacancies. Full article

Solid oxide fuel cells (SOFCs) represent a pivotal technology in renewable energy due to their clean and efficient power generation capabilities. Their role in potential carbon mitigation enhances their viability. SOFCs can operate via a variety of alternative fuels, including hydrocarbons, alcohols, solid carbon, and ammonia. However, several solutions have been proposed to overcome various technical issues and to allow for stable operation in dry methane, without coking in the anode layer. To avoid coke formation thermodynamically, methane is typically reformed, contributing to an increased degradation rate through the addition of oxygen-containing gases into the fuel gas to increase the O/C ratio. The performance achieved by reforming catalytic materials, comprising active sites, supports, and electrochemical testing, significantly influences catalyst performance, showing relatively high open-circuit voltages and coking-resistance of the CH₄ reforming catalysts. In the next step, the operating principles and thermodynamics of methane reforming are explored, including their traditional catalyst materials and their accompanying challenges. This work explores the components and functions of SOFCs, particularly focusing on anode materials such as perovskites, Ruddlesden–Popper oxides, and spinels, along with their structure–property relationships, including their ionic and electronic conductivity, thermal expansion coefficients, and acidity/basicity. Mechanistic and kinetic studies of common reforming processes, including steam reforming, partial oxidation, CO₂ reforming, and the mixed steam and dry reforming of methane, are analyzed. Furthermore, this review examines catalyst deactivation mechanisms, specifically carbon and metal sulfide formation, and the performance of methane reforming and partial oxidation catalysts in SOFCs. Single-cell performance, including that of various perovskite and related oxides, activity/stability enhancement by infiltration, and the simulation and modeling of electrochemical performance, is discussed. This review also addresses research challenges in regards to methane reforming and partial oxidation within SOFCs, such as gas composition changes and large thermal gradients in stack systems. Finally, this review investigates the modeling of catalytic and non-catalytic processes using different dimension and segment simulations of steam methane reforming, presenting new engineering designs, material developments, and the latest knowledge to guide the development of and the driving force behind an oxygen concentration gradient through the external circuit to the cathode. Full article

Using reduced-dimensional halide perovskites is emerging as a promising strategy for enhancing the stability of optoelectronic devices such as solar cells, even if their performances remain a step below those of the 3D halide perovskites. Two-dimensional Ruddlesden–Popper (2D-RP) structures are characterized by the n parameter that represents the number of PbI₆ layers in the spacer-separated perovskite slabs. The present study focuses on formamidinium (FA)-based 2D-RP type perovskites denoted as PMA₂FA_n−1Pb_nI_3n+1 (PMA = Phenylmethylammonium or benzylammonium). We investigate the effect of n on the one step growth mechanism and the film morphology, microstructure, phase purity, and optoelectronic properties. Our findings demonstrate that the average n is not only determined by the initial spacer content in the precursor solution but also by the thermal annealing process that leads to a partial spacer loss. Depending on n, perovskite solar cells achieving a power conversion efficiency up to 21%, coupled with enhanced film stability compared to 3D perovskites have been prepared. By using MACl additive and an excess of PbI₂ in the perovskite precursor solution, we have been able to achieve high efficiency and to stabilize the n = 5 perovskite solar cells. This research represents a significant stride in comprehending the formation of FA-based layered perovskites through one-step sequential deposition, enabling control over their phase distribution, composition, and orientation. Full article

As one of the representative transparent conducting oxides, perovskite-typed La-doped BaSnO₃ (LBSO) films could be integrated with other perovskite materials to create all-perovskite oxide devices exhibiting exotic physical properties. To overcome the intricate trade-off between conductivity and transmittance in LBSO-based devices, understanding the structural modulating mechanisms of transmittance is definitely crucial. In this paper, the influences of the prevailing Ruddlesden–Popper faults (RP faults) on the transmittance of LBSO films were systematically illuminated, whose density were regulated by the oxygen partial pressures during film growth. High-angle annular dark field (HAADF) STEM and X-ray diffraction (XRD) were employed to characterize the microstructures of the films growing under various oxygen partial pressures and annealing under different oxygen partial pressures. A decrease in RP fault density was observed in the films grown and annealed at high oxygen partial pressures, which displayed improved visible light transmittance. Atomic-scale energy-dispersive spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) analyses revealed the different electronic structure at RP faults compared with the bulk material, including the double concentration of La and increased M5/M4 white line ratio, which is modulative by the oxygen deficiency in LBSO film. It is revealed that the RP defaults in LBSO films annealed at low oxygen pressures displayed larger changes in electronic structure compared with the counterparts with low oxygen deficiency. This work suggests that the oxygen deficiency in LSBO films plays a crucial role in changing the density of RP faults and their electronic structures, thereby regulating the transmittance of LBSO films, which would provide guidance for fabricating high-performance LBSO films. Full article

Metallic Pd/Ni gauzes, located downstream of the Pt/Rh ammonia oxidation catalyst nets in the Ostwald process, is the current technology for capturing volatile gas phase platinum and rhodium species lost from the Pt/Rh combustion catalyst through evaporation. In this screening study, we explore four oxide families, ABO₃ perovskites, (ABO₃)_n(AO) Ruddlesden–Popper (RP) phases, AO rock salt, and A₂O₃ sesquioxide type oxides, as alternative materials for platinum capture. It was found that all the tested nickelates, LaNiO₃, NdNiO₃, La₂NiO₄, and La₄Ni₃O₁₀, captured platinum well and formed A₂NiPtO₆. In contrast, La_0.85Sr_0.15FeO₃, LaFeO₃, and LaCoO₃ did not capture platinum. CaO, SrO, and Nd₂O₃ formed low-dimensional platinates such as Ca_xPt₃O₄, Sr₄PtO₆, and a newly discovered neodymium platinate, Nd_10.67Pt₄O₂₄. Gd₂O₃ did not capture platinum in bench-scale experiments in dry air, but did, however, seem to capture platinum under pilot plant conditions, likely due to the co-capture of Co lost from the N₂O abatement catalyst. The catalytic activity of both oxides and platinum-containing products were studied, toward NO_x and N₂O decomposition. None of the oxides showed significant activity toward NO_x decomposition, and all showed activity toward N₂O decomposition, but to different extents. An overall assessment of the screened oxides with respect to potential use in industrial Ostwald conditions is provided. All tested oxides except CaO and SrO withstood industrial conditions. From our assessments, the nickelates and A₂O₃ (A = Nd, Gd) stand out as superior oxides for platinum capture. Full article

Sr₂TiO₄, a prominent member of the Ruddlesden–Popper (RP) perovskite family, has garnered significant interest in photocatalysis, primarily owing to its distinctive two-dimensional (2D) layered structure. In this review, we provide an insightful and concise summary of the intrinsic properties of Sr₂TiO₄, focusing on the electronic, optical, and structural characteristics that render it a promising candidate for photocatalytic applications. Moreover, we delve into the innovative strategies that have been developed to optimize the structural attributes of Sr₂TiO₄. These strategies aim to maximize light absorption, improve charge separation, and accelerate the photocatalytic reaction rates. By highlighting these unique approaches, we strive to contribute to a more profound understanding of the material’s potential and stimulate further advancements in developing Sr₂TiO₄-based photocatalytic systems. The review not only synthesizes the existing knowledge but also offers a perspective in future directions for research and application. As the field of photocatalysis continues to evolve, Sr₂TiO₄ stands poised to play a pivotal role in the quest for more efficient and sustainable solar energy conversion technology. Full article

In this work, the recent achievements in the application of solid oxides fuel cells (SOFCs) are discussed. This paper summarizes the progress in two major topics: the materials for the electrolytes, anode, and cathode, and the fuels used, such as hydrocarbon, alcohol, and solid carbon fuels. Various aspects related to the development of new materials for the main components of the materials for electrocatalysts and for solid electrolytes (e.g., pure metals, metal alloys, high entropy oxides, cermets, perovskite oxides, Ruddlesden–Popper phase materials, scandia-stabilized-zirconia, perovskite oxides, and ceria-based solid electrolytes) are reported in a coherent and explanatory way. The selection of appropriate material for electrocatalysts and for solid electrolyte is crucial to achieve successful commercialization of the SOFC technology, since enhanced efficiency and increased life span is desirable. Based on the recent advancements, tests were conducted in a biogas-fueled Ni-YSZ/YSZ/GDC/LSC commercial cell, to elucidate the suitability of the LSC as an anode. Results obtained encourage the application of LSC as an anode in actual SOFC and SOFEC systems. Thus, H₂-SOFC demonstrated a satisfying ASR value, while, for biogas-assisted electrolysis, the current values slightly increased compared to the methane-SOFEC, and for a 50/50 biogas mixture of methane and carbon dioxide, the corresponding value presented the higher increase. Full article

Layered A_n+1B_nO_3n+1 (n = 1…∞) Ruddlesden–Popper (RP) phases are a promising system for a variety of applications. Within the RP family, the thermodynamic properties of the phases are essentially additive with variation in the n value, but at present, there are no general approaches that would allow one to evaluate the individual stability of the RP phases and the possibility of their interconversion. The aim of this paper is to present a novel concept for performing a thermodynamic analysis of RP phases using the reciprocal values of the index n. We present an empirical equation ΔG_1/n = ΔG_P + B₁/n + B₂/n², where ΔG_1/n and ΔG_P are the molar Gibbs energies of formation of the Ruddlesden–Popper (RP) phase (AO)_1/nABO₃ and the parent ABO₃ perovskite, respectively, and n is a stoichiometry index of A_n+1B_nO_3n+1 RP phase. The correlation was validated using available thermodynamic data for the systems Sr-Ti-O, Ca-Ti-O, Sr-Zr-O, La-Ni-O, and La-Co-O. For all A-B combinations, the equation quantitatively describes the Gibbs energy of RP phase formation. Predicted values for the non-linear approximation lie within the experimental uncertainty in determining ΔG_1/n. The proposed correlation was used to analyze the relative stability of the RP phases and to determine the feasibility of synthesizing new compounds. Full article

We report on the use of 2D Ruddlesden–Popper (RP) perovskites as optoelectronic materials in building-integrated applications, addressing the challenge of balancing transparency, photoluminescence, and stability. With the addition of polyvinylpyrrolidone (PVP), the 2D RP films exhibit superior transparency compared to their 3D counterparts with an average visible transmittance (AVT) greater than 50% and photoluminescence stability under continuous illumination and 85 °C heat for up to 100 h as bare, unencapsulated films. Structural investigations show a stress relaxation in the 3D perovskite films after degradation from thermal aging that is not observed in the 2D RP films, which retain their phase after thermal and light aging. We also demonstrate ultrasmooth, wide-bandgap 2D Dion–Jacobson (DJ) films with PVP incorporation up to 2.95 eV, an AVT above 70%, and roughnesses of ~2 nm. These findings contribute to the development of next-generation solar materials, paving the way for their integration into built structures. Full article

In this work, evidence of isothermal magnetic entropy change ($∆S_M$) over a broad temperature region is presented in a series of La_1.4Sr_1.6Mn_2−xNb_xO₇ Ruddlesden–Popper compounds with niobium modification (Nb) (0.0 ≤ x ≤ 0.15) at the manganese (Mn) site. The ceramic samples were obtained through a solid-state sintering method in optimized conditions. All compounds predominantly possessed Ruddlesden–Popper phase while a few additional reflections were resolved in Nb-doped compounds which indicates the separation of structural phases. These peaks are assigned to a separate layered perovskite and single perovskite with tetragonal symmetry and hexagonal symmetry, respectively. The microstructure of the pure sample reveals uniform grain morphology but in Nb-doped specimens chiefly three types of grains were found. It was assumed that the inter-connected large particles were of R-P phase which is dominant in both parent and x = 0.05 compounds, while the hexagonal and polygonal morphology of grains in higher concentrations of dopants directly corroborates with the symmetry of single perovskite and additional layered perovskite phases, respectively. The parent compound exhibits a single $∆S_M$ curve, whereas all Nb-substituted samples display bifurcated $∆S_M$ curves. This indicated two transition regions with multiple magnetic components, attributed to distinct structural phases. The highest ${∆S}_M$ values obtained for components corresponding to the R-P phase are 2.32 Jkg⁻¹k⁻¹, 0.75 Jkg⁻¹k⁻¹, 0.58 Jkg⁻¹k⁻¹ and 0.43 Jkg⁻¹k⁻¹ and for the second component located around room temperature are 0.0 Jkg⁻¹k⁻¹, 0.2 Jkg⁻¹k⁻¹, 0.28 Jkg⁻¹k⁻¹ and 0.35 Jkg⁻¹k⁻¹ for x = 0.0, 0.05, 0.10 and 0.15 compositions, respectively, at 2.5 T. Due to the collective participation of both components the $∆S_M$ was expanded through a broad temperature range upon Nb doping. Full article

The growth of epitaxial thin films from the Ruddlesden–Popper series of strontium iridates by magnetron sputtering is analyzed. It was found that, even using a non-stoichiometric target, the films formed under various conditions were consistently of the perovskite-like n = ∞ SrIrO₃ phase, with no evidence of other RP series phases. A detailed inspection of the temperature–oxygen phase diagram underscored that kinetics mechanisms prevail over thermodynamics considerations. The analysis of the angular distribution of sputtered iridium and strontium species indicated clearly different spatial distribution patterns. Additionally, significant backsputtering was detected at elevated temperatures. Thus, it is assumed that the interplay between these two kinetic phenomena is at the origin of the preferential nucleation of the SrIrO₃ phase. In addition, strategies for controlling cation stoichiometry off-axis have also been explored. Finally, the long-term stability of the films has been demonstrated. Full article

Nanosheets of layered perovskite-like oxides attract researchers as building blocks for the creation of a wide range of demanded nanomaterials. However, Ruddlesden–Popper phases are difficult to separate into nanosheets quantitatively via the conventional liquid-phase exfoliation procedure in aqueous solutions of bulky organic bases. The present study has considered systematically a relatively novel and efficient approach to a high-yield preparation of concentrated suspensions of perovskite nanosheets. For this, the Ruddlesden–Popper titanates HLnTiO₄ and H₂Ln₂Ti₃O₁₀ (Ln = La, Nd) have been intercalated by n-alkylamines with various chain lengths, exposed to sonication in aqueous tetrabutylammonium hydroxide (TBAOH) and centrifuged to separate the nanosheet-containing supernatant. The experiments included variations of a wide range of conditions, which allowed for the achievement of impressive nanosheet concentrations in suspensions up to 2.1 g/L and yields up to 95%. The latter were found to strongly depend on the length of intercalated n-alkylamines. Despite the less expanded interlayer space, the titanates modified with short-chain amines demonstrated a much higher completeness of liquid-phase exfoliation as compared to those with long-chain ones. It was also shown that the exfoliation efficiency depends more on the sample stirring time in the TBAOH solution than on the sonication duration. Analysis of the titanate nanosheets obtained by means of dynamic light scattering, electron and atomic force microscopy revealed their lateral sizes of 30–250 nm and thickness of 2–4 nm. The investigated exfoliation strategy appears to be convenient for the high-yield production of perovskite nanosheet-based materials for photocatalytic hydrogen production, environmental remediation and other applications. Full article

Perovskite solar cells (PSCs) have driven improvements in photovoltaic technology as a promising post-silicon photovoltaic technology. However, their decency in providing efficiency is quite intriguing but remains poor in stability. Advancement in lower dimensional technology indicates the shortcomings of 3D perovskite materials, which can be overcome by the introduction of 2D perovskites in an appropriate manner. Two-dimensional perovskites have piqued researchers’ interest in photovoltaic technology because of their remarkable structural and electrical properties which yield an increase in stability and enhance its light absorption properties. Therefore, 2D/3D multi-dimensional perovskite solar cells are expected to provide substantial stability and higher efficiency. In this study, 2D perovskite materials such as BA₂MA₂Pb₃I₁₀ and BA₂MA₂Pb₄I₁₃ were used as the capping layer on a 3D MAGeI₃ layer to fulfil the mixed-dimensionality. The band alignments of both 2D and 3D perovskite were matched decently and other properties like defect tolerance and other IV characteristics on varying defect densities are provided in this study. Mixed-dimensional perovskite with n = 4 showed increased efficiency with respect to single 3D perovskite in decimals, yet is more stable in harsh environments. Full article

The conventional Ni–YSZ (yttria-stabilized zirconia) fuel electrode experiences severe degradation due to Ni- agglomeration and migration away from the electrolyte. Therefore, herein, we have considered Ni free electrodes, i.e., La_0.6Sr_0.4MnO_3-δ (LSM)-based perovskite oxides as fuel electrodes. The LSM perovskite phase transforms into a Ruddlesden–Popper LSM (RP-LSM) phase with exsolved MnO_x under reducing atmospheres. The RP-LSM is mainly interesting due to its good electrical conductivity, redox stability, and acceptable electrochemical behaviour. In this work, we synthesized the LSM powder and characterized it using several methods including X-ray diffraction (XRD), thermogravimetry analyses (TGA), four-probe conductivity, and scanning electron microscope with energy-dispersive X-ray spectroscopy (SEM-EDX). Finally, the electrolyte-supported single cells were fabricated and electrochemically characterized using AC and DC techniques under electrolysis conditions. In addition to pure LSM fuel electrodes, we have also investigated the electrochemical behaviour of LSM + YSZ (50:50) and LSM + GDC (50:50) composite fuel electrodes. The single cells containing LSM and LSM + GDC fuel electrodes show higher cell performance than LSM + YSZ. For instance, current densities of 1, 1.03, and 0.51 A·cm⁻² at 1.5 V are obtained for LSM, LSM + GDC, and LSM + YSZ fuel electrodes containing single cells, respectively, with a 50% N₂ and 50% H₂O feed gas mixture. Moreover, the performance of the cell was also investigated under co-electrolysis with 50% CO₂ and 50% H₂O and under direct CO₂ electrolysis conditions with 100% CO₂ fuel gas. Full article