Large Cations Research Articles

Band gap tailoring with octahedral distortion and bader charge analysis for 2D-Ruddlesden–Popper monolayer tin halide perovskites

Intercalation of large organic spacer cations with inorganic layers of octahedral metal halide cages in 2D-Ruddlesden–Popper (RP) monolayer perovskites (R–NH3)2An−1BnX3n+1 by using a rational design approach has shown structural versatility and energetic stability. A systematic theoretical investigation of the structural, electronic, and mechanical properties was conducted with and without spin-orbit coupling (SOC) under the influence of a range of organic monovalent spacer cations [R–NH3]+ with different inorganic halide anions. This resulted in 12 compositions. Lattice distortion and octahedral tilting provided gradient band gaps that displayed a good linear relationship with equatorial Sn–X–Sn angles in debt of larger halide anions. By fixing halide ions, larger spacer cations reduce the band gap further. The halides function as acceptors, whereas Sn and N function as donors. Intermingled N-atoms of spacer cations incorporate additional charges to axial halide ions of [SnX6]4- with state-of-the-art features of defect tolerance, quantum and dielectric confinement, low effective masses, and high mobility.

Low Dimensional, Metal-Free, Hydrazinium Halide Perovskite-Related Single Crystals and Their Use as X-Ray Detectors.

Metal-free halide perovskites (MFHaPs) have garnered significant attention in recent years due to their desirable properties, such as low toxicity, light weight, chemical versatility, and potential for optoelectronics. MFHaPs with the formula A2+ B+ X-3 (where A is a large organic divalent cation, B+ is typically NH4 + , and X is a halide) have been studied extensively, but few studies have examined alternative cations at the B position. This paper reports the synthesis of three MFHaP-related single crystals, DABCO-N2 H5 -X3 (DABCO = N-N-diazabicyclo[2.2.2]octonium, X = Br and I) and (DABCO)3 -N2 H5 (NH4 )2 Cl9 , which feature hydrazinium (N2 H5 ) at the B position. The crystals have a perovskite-like, one-dimensional, edge-connected structure and exhibit optical and band structure properties. The crystalswerethen tested as X-ray detectors, where they showed excellent photoresponsivity, stability, and low background noise, owing to the large semi-gap that dictates long lifetimes. The detectors exhibited sensitivity as high as 1143 ± 10 µC Gyair -1 cm-2 and a low detection limit of 2.68 µGy s-1 at 10V. The researchers suggest that the stronger hydrogen bonding in N2 H5 + compounds compared to NH4 + MFHaPs may contribute to the detectors' enhanced stability.

Improving the stability and performance of hybrid perovskite solar cells based on 1D/3D mixed-dimensional structure by multiple cation doping

1D-structure perovskite materials have gradually attracted people's attention due to the flexibility of their crystal structures and their strong stability to environments such as water and humidity. In this work, 1D/3D mixed-dimensional perovskite materials were achieved by adding large cation tBA+. The Cs+ doped high quality perovskite films (CstBAMAFA) were prepared by a two-step solution method, and the photoelectrical properties and stability of perovskite solar cells (PSCs) were systematically analyzed. The photoelectric conversion efficiency (PCE) of the champion Cs+ doped 1D/3D PSCs reached 17.08%, and the stability was significantly improved compared with the control group. The PCE of unencapsulated PSCs could retain 80% of the initial value after 197 days of storage in Ar glove box, and 69.3% of the initial value after 20 days of storage at 30 °C with a relative humidity of 50–60%. The improved efficiency and stability of Cs+ doped 1D/3D PSCs are attributed to the filling of the grain boundaries by the 1D phase.

Large Cation Engineering in Organic Antimony Halides for Low‐Loss Active Waveguide

AbstractActive waveguides have attracted growing attention as a basic component of miniaturized and integrated photonic devices. However, most optical waveguide materials suffer from severe self‐absorption, which greatly increases the optical loss. Therefore, developing highly efficient red‐emitting materials with large Stokes shift and negligible self‐absorption is of great interest. Herein, this work proposes a strategy to achieve both large Stokes shifts and high photoluminescence quantum yield (PLQY) in organic metal halide via large cation engineering. Two zero‐dimensional antimony(III) chlorides, (TMA)2SbCl5 and (TMAA)2SbCl5, are designed and synthesized by screening the ligands with different cationic volumes. Experimental and theoretical results reveal that the large cation can promote the self‐trapped excitons emission and improve stability. Benefiting from the large Stokes shift (291 nm) and high PLQY (98.3%), the as‐prepared (TMAA)2SbCl5 microplate exhibits efficient active waveguide with low loss coefficient of 6.07 × 10−3 dB µm−1. This work not only develops a novel active waveguide material, but also provides insights into the role of organic cation, which will provide new inspiration for the exploitation of excellent luminescent metal halides and photonic devices.

Mass and Charge Transfer in a Polymeric NiSalen Complex at Subzero Temperatures

Electrochemical energy storage systems have a wide range of commercial applications. They keep energy and power even at temperatures up to +60 °C. However, the capacity and power of such energy storage systems reduce sharply at negative temperatures due to the difficulty of counterion injection into the electrode material. The application of organic electrode materials based on salen-type polymers is a prospective approach to the development of materials for low-temperature energy sources. Poly[Ni(CH3Salen)]-based electrode materials synthesized from different electrolytes were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and quartz crystal microgravimetry at temperatures from -40 °C to 20 °C. By analyzing data obtained in various electrolyte solutions, it was shown that at subzero temperatures, the process of injection into the polymer film, together with slow diffusion within the film, predominantly limit the electrochemical performance of electrode materials based on poly[Ni(CH3Salen)]. It was shown that the deposition of the polymer from solutions with larger cations allow the enhancement of the charge transfer due to the formation of porous structures facilitating the counter-ion diffusion.

Enhancing cation storage performance of layered double hydroxides by increasing the interlayer distance.

Layered double hydroxides (LDH) can be transformed from alkaline supercapacitor material into metal-cation storage cathode working in neutral electrolytes through electrochemical activation. However, the rate performance for storing large cations is restricted by the small interlayer distance of LDH. Herein, the interlayer distance of NiCo-LDH is expanded by replacing the interlayer nitrate ions with 1,4-benzenedicarboxylic anions (BDC), leading to the enhanced rate performance for storing large cations (Na+, Mg2+, and Zn2+), whereas almost the unchanged one for storing small-radius Li+ ions. The improved rate performance of the BDC-pillared LDH (LDH-BDC) stems from the reduced charge-transfer and Warburg resistances during charge/discharge due to the increased interlayer distance, as revealed by in situ electrochemical impedance spectra. The asymmetric zinc-ion supercapacitor assembled with LDH-BDC and activated carbon presents high energy density and cycling stability. This study demonstrates an effective strategy to improve the large cation storage performance of LDH electrodes by increasing the interlayer distance.

Efficiency enhancement of dye-sensitized solar cell with PVdF-HFP:MPII:NaI quasi-solid-state electrolyte

Quasi-solid-state polymer electrolyte (QSSPE) based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) was prepared using sodium iodide (NaI) salt, 1-methyl-3-propylimidazolium iodide (MPII) ionic liquid, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) plasticizers. This paper discusses the effects of using a binary mixture of large (MPII) and small (NaI) cation alkaline salts on enhancing the performance of DSSCs with gel polymer electrolytes. The amount of NaI was varied while the other components were kept constant to study the dependence of dye-sensitized solar cell (DSSC) performance on NaI amount. The incorporation of NaI in PVdF-HFP-MPII-PC-DME has enhanced the efficiency of DSSC. DSSC with 0.6 M MPII and 0.4 M NaI showed the highest efficiency of 4.16 % and short circuit current density (J sc) of 13.63 mAcm−2. Additionally, the roles of TBP and GuSCN as co-additives in the electrolytes were also discussed in this paper. The presence of 4-tert-butylpyridine (TBP) and guanidine thiocyanate (GuSCN) further enhanced the efficiency from 4.16 to 6.95 %.

Competition and Neutralization: Thermally Induced Crystallization and Phase Evolution of Amorphous Calcium Phosphate with Cosubstitution of Larger and Smaller Divalent Cations.

The presented study evaluated the effect of cosubstitution of larger and smaller divalent cations on the thermally induced crystallization of amorphous calcium phosphate (ACP). The predesigned combinations of larger (Sr2+ and Ba2+) and smaller (Mg2+, Cu2+, and Co2+) divalent cations were carried out and their effects on the thermodynamic equilibrium between α/β-tricalcium phosphate (TCP) were outlined. The coexistence of larger and smaller divalent cations shielded the formation of α-TCP and shifted the thermodynamic equilibrium toward the β-TCP, which implied that the smaller cations dominated the crystalline phase. However, the retarded crystallization induced by the larger cations still remained and allowed ACP to maintain its amorphous nature partly or completely until a higher temperature.

High-Efficiency Intrinsic Yellow-Orange Emission in Hybrid Indium Bromide with Double Octahedral Configuration

Zero-dimensional (0D) In-based organic-inorganic metal halides (OIMHs) have received growing interest in recent years as promising luminescent materials. However, the high efficiencies of 0D In-based OIMHs are all dependent on Sb doping in the existing literature. Here, we report a novel 0D In-based OIMH (C10H22N2)2In2Br10, which exhibits intrinsic broadband emission (610 nm), and the photoluminescence quantum yield (PLQY) can reach 70% without Sb doping. (C10H22N2)2In2Br10 shows a typical 0D structure with three different In-Br polyhedra (two octahedra and one tetrahedron) separated by large organic cations. Based on the optical property measurements and theoretical calculations, we demonstrate that (C10H22N2)2In2Br10 is an indirect semiconductor with a band gap of 3.74 eV, and the In-Br inorganic moiety is primarily responsible for the intense emission of (C10H22N2)2In2Br10. Interestingly, the unique double octahedral configuration in (C10H22N2)2In2Br10 may enhance the structural distortion and stimulate the self-trapped excitons (STEs), leading to the related high PLQY. Our work provides a novel 0D In-based OIMH with high-efficiency intrinsic emission, which is helpful for understanding the structure-PL relationships of hybrid halides.

A2Zr2O7 (A=La/Gd/Yb): Grain growth effect on phase stability properties at 1300°C

The present study aims to investigate the influence of grain growth during heat treatment on the phase stability of AZO: A2Zr2O7 compounds at 1300°C. To this end, three cations of La3+, Gd3+, and Yb3+ (corresponding to large, medium and small cations, respectively) were placed in the A-site of the AZO compounds through co-precipitation–calcination technique at 1000°C for 3 h to achieve LaZO: La2Zr2O7, GdZO: Gd2Zr2O7, and YbZO: Yb2Zr2O7, respectively. The phase stability of LaZO, GdZO, and YbZO was assessed under 50 h of heat treatment at 1300°C. Characterization techniques such as conventional and high-temperature XRD, Raman and Fourier transform infrared (FTIR) spectroscopies, simultaneous thermal analysis (DTA/TG), and field-emission scanning electron microscopy (FESEM) were employed to assess the synthesized compounds. FESEM results of LaZO, GdZO and YbZO calcinated powders indicated orderly particles, uniform in shape and size, with a relative tendency of agglomeration and with an average particle size of less than ∼100 nm. XRD results of LaZO and YbZO powders after calcination indicated the formation of pyrochlore and defect fluorite structures, respectively. The placement of Gd3+ (GdZO) led to the formation of a dual pyrochlore-defect fluorite structure. The current research also indicated an enhancement in the tendency to form pyrochlore structure in GdZO and YbZO compounds along with the growth of the grains after 20 (mean grain size of ∼250 nm) and 50 h (mean grain size of ∼800 nm) of exposure to the temperature of 1300°C, respectively.

Improving the brightness of quasi-2D perovskite light-emitting diode by controlling stoichiometric ratio of perovskite emission layer

The quasi-two-dimensional (quasi-2D) perovskite possesses good film coverage and high photoluminescence quantum efficiency, and exhibits a characteristic of high-level radiation recombination. However, the charge transferring from quasi-2D perovskites is not comparable to that of three-dimensional perovskites due to the insulating nature of large organic cations, thus limits the brightness of quasi-2D perovskite light-emitting diodes (PLEDs). In this work, phenylethylammonium bromide (PEABr) and formamidine hydrobromide (FABr) were strategically introduced as two spacer cations to form quasi-2D perovskite phase, thus weakened the van der Waals gap between individual perovskite layers. The enhanced coupling strength between each layer promoted the energy transfer efficiency and led to an increasing radiative recombination rate of the perovskite films. Meanwhile, an optimized molar ratio of PEABr: FABr: PbBr2 improved perovskite film morphology and passivated its defects, which reduced the nonradiative recombination loss of quasi-2D PLEDs. As a result, a maximum brightness of 32,368 cd m − 2 can be obtained for this kind of devices.

Biodiesel Additives Synthesis Using Solid Heteropolyacid Catalysts

Fossil additives are a primary energy source and their contribution is around 80% in the world. Therefore, bioadditives that reduce their impact are each very important. This article discusses the chemical transformation of glycerol to carbonate, ethers, esters, ketals, and acetals, compounds with high technological applications, especially in the fuel sector as bioadditives. Mainly, heterogeneous catalysts are important in the production of more than 80% of chemicals in the word. The focus is on demonstrating how the Keggin heteropolyacids (HPAs) are efficient catalysts in the reactions of syntheses of glycerol-derived bioadditives, either in homogeneous or heterogeneous phases. Although solid, HPAs have a low surface area and are soluble in polar solvents, hampering their use as heterogeneous catalysts. Alternatively, they have been successfully used supported on solid matrixes with a high surface area. Another option is converting the Keggin HPAs to insoluble salts simply by exchanging their protons with large cations like potassium, cesium, or ammonium-derivatives. Therefore, solid heteropoly salts have reduced the cost and the environmental impact of bioadditive synthesis processes, being an alternative to traditional mineral acids or solid-supported catalysts. This review describes the most recent advances achieved in the processes of synthesis of glycerol-derived bioadditives over solid-supported HPAs or their solid heteropoly salts.

Temperature-Dependent Reversible Optical Properties of Mn-Based Organic–Inorganic Hybrid (C8H20N)2MnCl4 Metal Halides

Organic-inorganic metal halides (OIMHs) have abundant optical properties and potential applications, such as light-emitting diodes, displays, solar cells, and photodetectors. Herein, we report zero-dimensional Mn-based OIMH (C8H20N)2MnCl4 single crystals synthesized by a simple slow evaporation method, which exhibit intense green emission at 520 nm originating from 4T1-6A1 transition of Mn2+ ions. Large organic cations in the crystal structure result in the isolated [MnCl4]2- tetrahedrons, and the closest Mn-Mn distance reaches 9.07 Å, which effectively inhibits the migration of excitation energy between adjacent Mn2+ emission centers, thus achieving a high quantum yield (∼87%) and a long photoluminescence (PL) lifetime (3.42 ms). The different optical and structural properties at low and high temperatures are revealed by temperature-dependent PL and X-ray diffraction spectra. The PL spectra and lifetimes under the heating and cooling processes indicate that the optical property transitions are reversible at 220/240 K. Our work provides a promising strategy for building multifunctional optoelectronic materials and insights into the understanding convertible photophysical properties from isomers of metal halides.

Large ammonium cation-induced controlled mixed-phase of CsPbBr3 perovskites for color tunable perovskite light-emitting diodes

Color tunability is a unique advantage of perovskite light-emitters for next-generation display technologies because controlled dimension and phase of metal halide perovskites can vary the optoelectronic properties of perovskite light-emitting diodes (PeLEDs). Herein, we demonstrate a color tuning of green-emitting CsPbBr3–based PeLEDs to sky-blue by employing n-butylammonium bromide (BABr). The incorporation of BABr, a large ammonium cation, in CsPbBr3 facilitates the formation of 2-dimensional (2D) perovskite structure with band-gap widening that corresponds to fluorescence peak shift from 513 to 406 nm. In addition, the incorporation of BABr is found to restrict the quick nucleation and rapid growth of CsPbBr3 crystals to allow subsequent growth of 2D structure with lower n-phases, affording a smooth and uniform film surface. As a result, the optoelectronic properties of the CsPbBr3-based PeLEDs were significantly improved by BABr with a brightness of 5260 cd m–2, peak external quantum efficiency of 6.72 % and a maximum current efficiency of 27.78 cd A–1. Moreover, the BABr addition also induced a facile color conversion from green to sky-blue, suggesting remarkable potential toward high-performance PeLEDs with tunable emission colors for next-generation display technologies.

Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway.

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from IrxCly precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts─IrCl3, IrCl4, H2IrCl6, or Na2IrCl6─colloidal nanoparticles as small as Ir∼55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic (fcc) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl3 or IrCl4, metallic iridium nanoparticles form rapidly from IrxClyn- complexes, whereas using H2IrCl6 or Na2IrCl6, the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H2IrCl6, the formation of different Irn (n = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. The results show that the synthesis of iridium nanoparticles from IrxCly is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

Highly Efficient, Flexible, and Eco-Friendly Manganese(II) Halide Nanocrystal Membrane with Low Light Scattering for High-Resolution X-ray Imaging.

Scintillators enable invisible X-ray to be converted into ultraviolet (UV)/visible light that can be collected using a sensor array and is the core component of the X-ray imaging system. However, combining the excellent properties of high light output, high spatial resolution, flexibility, non-toxicity, and cost effectiveness into a single X-ray scintillator remains a great challenge. Herein, a novel scintillator based on benzyltriphenylphosphonium manganese(II) bromide (BTP2MnBr4) nanocrystal (NC) membranes was developed by the in situ fabrication strategy. The long Mn-Mn distance provided by the large BTP cation allows the nonradiative energy dissipation in this manganese(II) halide to be significantly suppressed. As a result, the flexible BTP2MnBr4 NC scintillator shows an excellent linear response to the X-ray dose rate, a high light yield of ∼71,000 photon/MeV, a low detection limit of 86.2 nGyair/s at a signal-to-noise ratio of 3, a strong radiation hardness, and a long-term thermal stability. Thanks to the low Rayleigh scattering associated with the dense distribution of nanometer-scale emitters, light cross-talk in X-ray imaging is greatly suppressed. The impressively high-spatial resolution X-ray imaging (23.8 lp/mm at modulation transfer function = 0.2 and >20 lp/mm for a standard pattern chart) was achieved on this scintillator. Moreover, well-resolved 3D dynamic rendering X-ray projections were also successfully demonstrated using this scintillator. These results shed light on designing efficient, flexible, and eco-friendly scintillators for high-resolution X-ray imaging.

LaCo1-x-yCuxTiyO3/KIT-6 perovskites: synthesis and catalytic behavior in syngas conversion to higher alcohols.

Highly dispersed LaCo1-x-yCuxTiyO3/KIT-6 perovskites were synthesized by the citrate method with inert mesoporous KIT-6 addition. The KIT-6 matrix was removed by dissolution in 7% NaOH aqueous solution. The dispersity of perovskites probably varies depending on the largest cation and its content at the B position of the perovskite ABO3 structure. The CoS=23+/CoS=03+ ratio increases with the increase in copper content and in the presence of Ti4+. It may be explained by the compensation of the distortion of the perovskite structure. The maximum syngas conversion is achieved at nCo/nCu = 7/3. At a higher copper content, the activity of the samples decreases due to the formation of large copper particles (up to 40 nm) in the course of the reduction. The selectivity for alcohols increases with an increase in the proportion of copper and reaches maximum values at a ratio of nCo/nCu close to 1. The distribution of alcohols is the same for all samples, except for LaCo0.35Cu0.35Ti0.3O3/KIT-6. It can be assumed that the synthesis of alcohols proceeds on bimetallic CoCu particles 3 nm in size and cobalt particles 4-6 nm in size, most likely enriched with copper on the surface.

Solvent-controlled formation of alkali and alkali-earth-secured cucurbituril/guest trimers.

Cucurbit[7]uril (CB[7]) encapsulates adamantyl and trimethylsilyl substituents of positively charged guests in dimethyl sulfoxide (DMSO). Unlike in water or deuterium oxide, addition of a selection of alkali and alkali-earth cations with van der Waals radii between 1.0 and 1.4 Å (Na+, K+, Ca2+, Sr2+, Ba2+ and Eu3+) to the CB[7]/guest complexes triggers their cation-mediated trimerization, a process that is very slow on the nuclear magnetic resonance (NMR) time scale. Smaller (Li+, Mg2+) or larger cations (Rb+, Cs+ or NH4+) are inert. The trimers display extensive CH-O interactions between the equatorial and pseudo-equatorial hydrogens of CB[7] and the carbonyl rim of the neighboring CB[7] unit in the trimer, and a deeply nested cation between the three interacting carbonylated CB[7] rims; a counteranion is likely perched in the shallow cavity formed by the three outer walls of CB[7] in the trimer. Remarkably, a guest must occupy the cavity of CB[7] for trimerization to take place. Using a combination of semi-empirical and density functional theory techniques in conjunction with continuum solvation models, we showed that trimerization is favored in DMSO, and not in water, because the penalty for the partial desolvation of three of the six CB[7] portals upon aggregation into a trimer is less unfavorable in DMSO compared to water.

Efficient lead sorption by ammonium phosphomolybdate: experimental and density functional theory (DFT) studies

Ammonium phosphomolybdate is a versatile inorganic compound and displays high adsorption capacity for large metal cations (e.g. Pb) due to its negatively charged cage-like structure with hollow cavities.

Local density changes and carbonate rotation enable Ba incorporation in amorphous calcium carbonate.

Incorporation of a Ba impurity in amorphous calcium carbonate (ACC) is shown with ab initio molecular dynamics simulations to have a long-range effect on its atomic-level structure and to be energetically favoured relative to incorporation in crystalline calcium carbonate polymorphs. The ability of carbonate ions to rotate and of ACC to undergo local density changes explain ACC's propensity for incorporating divalent metal impurities with a wide range of ionic radii. These findings provide an atomic-level basis for understanding the significant effects of low concentrations of impurities on the structure of ACC.