Small Cations Research Articles

Carbons prepared by microwave co-pyrolysis of waste scrap tyres and corn cob: Effect of cation size and charge on xylene adsorption

Carbons prepared by pyrolysis of waste corn cobs or scrap tyres using different microwave power (200, 400, 600 W) are compared with carbons prepared by co-pyrolysis of corn:tyre mixtures in various mass ratios without/with activator (KOH, ZnCl2, K2CO3, NaOH in solid or liquid phase). Activation and co-pyrolysis of corn:tyre mixture was proved to be advantageous, prepared activated carbons showed enhanced xylene adsorption compared to non-activated. Activated carbons prepared from corn:tyre mixture at mass ratio of 4:1 and using ZnCl2 in liquid and ZnCl2 and K2CO3 in solid phase showed the highest adsorption capacities (∼171, 139 and 104 mgxylene·g−1, respectively) despite the opposite trend in their microporosity. Molecular modeling proved a preferential interaction of xylene with activated carbons porous structure through Zn2+, K+ and Na+ ions. The smallest cation with the highest positive charge, Zn2+, interacts the most strongly with xylene. The strength of cation-xylene interaction decreases as follows: Zn2+ > Na+ > K+. As the strongest were proved xylene interactions with Pore (5.2 Å)_Zn2+ > Pore (8.5 Å)_Zn2+ > Surface_Zn2+ > Pore (5.2 Å)_Na+ ∼ Pore (5.2 Å)_K+, which explains the highest adsorption capacities of ZnCl2-activated carbons despite of their lower microporosity compared to carbon activated by using K2CO3(s).

NaZr2(PO4)3 - a cubic langbeinite-type sodium-ion solid conductor.

The synthesis of langbeinite-type phosphates with small cations such as Li+ or Na+via a high-temperature solid-state reaction is a challenging task due to the predominant formation of a related NaSICON-type phase. This work reports on the synthesis route, crystal structure, thermal behavior, and Na-conductive properties of the langbeinite-type NaZr2(PO4)3 prepared by a mechanochemically activated ion-exchange reaction between hydrothermally prepared NH4Zr2(PO4)3 and NaNO3. The crystal structure of NaZr2(PO4)3 is refined based on X-ray diffraction data and validated by Fourier-transformed infrared spectroscopy. NaZr2(PO4)3 is found to be stable up to 730 °C, undergoing a transformation into the NaSICON phase with further heating. Notably, in the 25-500 °C range, the material shows negative thermal expansion. The Na+ conductivity within the range of 50-225 °C amounts to 1.7 × 10-8 S cm-1 at 50 °C and 1 × 10-6 S cm-1 at 225 °C with an activation energy of 0.44 eV, accompanied by a sufficiently low (∼10-12 S cm-1) electronic conductivity. The bandgap of 4.44 eV and the electrochemical stability window covering the 1.39-4.18 V vs. Na/Na+ range are calculated using density functional theory. The obtained results open up opportunities for designing langbeinite-structured phosphates as potential solid electrolytes for Na-ion batteries.

Unveiling the generation of mesoporous MFI zeolites with one-dimensional fins in the assistance from small quaternary ammonium cation and its application in propane aromatization

In this work, a kind of ZSM-5 zeolite with one-dimensional fins growing along the [010] direction has been successfully synthesized utilizing both tetrapropylammonium hydroxide (TPAOH) and tetramethylammonium hydroxide (TMAOH) as co-templates. With the aid of molecular dynamic simulations and a series of experimental evidences, the formation mechanism of the one-dimensional feature is determined to arise from the synergic effects between TPA+ and TMA+. Two TPA+ and three TMA+ would co-exist in a unit MFI cell at a certain crystallization period depending on the composition of zeolite and precursor, and this configuration ensures a minimum stabilization energy required for the growth along [010] direction. Investigations manifest these needle-like fins with diameters of ca. 60 nm could function as pseudo nano crystals and introduce additional pores ranging from 10 to 90 nm, which effectively promotes the diffusion capability and substantially improves the catalytic performance in propane aromatization.

Enhancing the X-ray Sensitivity of Cs2AgBiBr6 Double Perovskite Single Crystals through Cation Engineering.

Owing to their outstanding optoelectronic properties, halide perovskite (HP) materials have been employed in a wide range of applications, including solar cells, light-emitting devices, and X-ray detectors. Among them, lead-free double HPs are characterized by enhanced stability and reduced toxicity compared with lead-based alternatives. Cs2AgBiBr6, in particular, has emerged as a promising candidate for direct X-ray detection. The detection sensitivity, on the other hand, cannot yet compete with that of lead-containing perovskites. Developing schemes to improve X-ray detection efficiency is critical for reducing radiation exposure in medical imaging applications. Here, we investigate the potential of controlled doping and cation substitution with either lanthanides or small organic cations to improve the X-ray detection performance of Cs2AgBiBr6. Our findings reveal that by growing the perovskite in a slightly Bi-poor and Eu-rich environment, the X-ray sensitivity significantly increases 7-fold (from 17 to 120 μC Gyair -1 cm-2) and simultaneously improves the phototo-dark current ratio (from 2.5 to 29). Additionally, Cs-site substitution with imidazolium remarkably enhances the sensitivity over 10-fold (180 μC Gyair -1 cm-2), and ammonium enhances the phototo-dark current ratio to 37. Terahertz photoconductivity measurements reveal a positive correlation between enhanced X-ray sensitivity and improved charge transport properties (e.g., increased scattering time and, thus, carrier mobility) by doping. This study outlines straightforward strategies for boosting X-ray detection and fundamental photoconductivity in lead-free double HP, with potential implications for broader optoelectronic applications.

A DFT Computational Study of Type-I Clathrates A8Sn46-x (A = Cs or NH4, x = 0 or 2).

Semiconducting clathrates have attracted considerable interest in the field of thermoelectric materials. We report here a computational study on the crystal structure, the enthalpy of formation, and the physical properties of the following type-I clathrates: (a) experimentally studied Cs8Sn44 and hypothetical Cs8Sn46 and (b) hypothetical (NH4)8Sn46-x (x = 0 or 2). The ab initio VASP calculations for the nominal stoichiometries include the geometry optimization of the initial structural models, enthalpies of formation, and the electronic and phonon density of states. Comparison of the chemical bonding of the structural models is performed via the electron localization function. The results show that the presence and distribution of defects in the Sn framework for both Cs8Sn46-x and (NH4)8Sn46-x systems significantly alters the formation energy and its electrical properties, ranging from metallic to semiconducting behavior. In particular, one defect per six-membered Sn ring in a 3D spiro-network is the thermodynamically preferred configuration that results in the Cs8Sn44 and (NH4)8Sn44 stoichiometries with narrow-band gap semiconducting behavior. Moreover, the rotation of the ammonium cation in the polyhedral cavities is an interesting feature that may promote the use of ammonium or other small molecular cations as guests in clathrates for thermoelectric applications; this is due to the decrease in the lattice thermal conductivity.

Gas-Phase Structures of Fucosylated Oligosaccharides: Alkali Metal and Halogen Influences.

Fucosylated carbohydrate antigens play critical roles in physiology and pathology with function linked to their structural details. However, the separation and structural characterization of isomeric fucosylated epitopes remain challenging analytically. Here, we report for the first time the influence of alkali metal cations (Li+, Na+, K+, Rb+, and Cs+) and halogen anions (Cl-, Br-, and I-) on the gas-phase conformational landscapes of common fucosylated trisaccharides (Lewis A, X, and H types 1 and 2) and tetrasaccharides (Lewis B and Y) using trapped ion mobility spectrometry coupled to mass spectrometry and theoretical calculations. Inspection of the mobility profiles of individual standards showed a dependence on the number of mobility bands with the oligosaccharide and the alkali metal and halogen; collision cross sections are reported for all of the observed species. Results showed that trisaccharides (Lewis A, X, and H types 1 and 2) can be best mobility resolved in the positive mode using the [M + Li]+ molecular ion form (baseline resolution r ≈ 2.88 between Lewis X and A); tetrasaccharides can be best mobility resolved in the negative mode using the [M + I]- molecular ion form (baseline separation r ≈ 1.35 between Lewis B and Y). The correlation between the number of oligosaccharide conformers as a function of the molecular ion adduct was studied using density functional theory. Theoretical calculations revealed that smaller cations can form more stable structures based on the number of coordinations, while larger cations induced greater oligosaccharide reorganizations; candidate structures are proposed to better understand the gas-phase oligosaccharide rearrangement trends. Inspection of the candidate structures suggests that the interplay between ion size/charge density and molecular structure dictated the conformational preferences and, consequently, the number of mobility bands and the mobility separation across isomers. This work provides a fundamental understanding of the gas-phase structural dynamics of fucosylated oligosaccharides and their interaction with alkali metals and halogens.

Size sieving and electrostatic exclusion synergetic strategy for high efficiency recovery of superbase-derived ionic liquids via nanofiltration from the spinning process

Superbase-derived ionic liquids (SILs) as the promising green solvents for cellulose spinning process should be urgently and deeply evaluated with respect to their recyclability. Herein, size sieving and electrostatic exclusion synergetic strategy was adopted for recycling four SILs ([DBUH][CH3CH2OCH2COO], [DBUH][CH3OCH2COO], [DBNH][CH3CH2OCH2COO], and [DBNH][CH3OCH2COO]) from aqueous solutions by the nanofiltration membranes (NF270 and NF90) at the first time. NF270 with larger pore and more negative charge was conducive to recycle SIL on account of a higher volume flux and the remarkably high IL rejection (＞95 %) compared to NF90. Rising the pressure and temperature played the positive role in the permeate flux of the membranes, whereas the elevated SIL concentration markedly decreased the electrostatic exclusion, leading to a decline in the recovery efficiency. Benefiting from the size sieving effect, the [DBNH][CH3OCH2COO] with small cation and anion structure could be recovered efficiently due to the high energy gap and big IL aggregates. Conversely, the strong electrostatic attraction was appeared between [DBUH][CH3CH2OCH2COO] (low energy gap and high positive charge density) and the membranes, leading to a decline in recovery efficiency. Furthermore, the combination of nanofiltration and evaporation to recover SIL from spinning wastewater effectively reduced the total recovery cost (1.51 $/Kg) in comparison with the evaporation only. Insight gained from this work suggested a high-efficiency and economical approach could be used in the recovery of SILs with small cations and anions size via large pore nanofiltration membranes during the industrialized cellulose spinning process.

A novel and efficient method for synthesizing reduced charge montmorillonite

Layer charge (LC), a paramount physiochemical characteristic of montmorillonite (Mt), has been garnered considerable attention on its regulating and impact on modified Mt products. Incorporating small cations such as Li+ into the tetrahedral/octahedral sheets of Mt, or employing acid treatment, are feasible methods to reduce its LC. However, conventional techniques for producing reduced charge Mt (RC-Mt) often suffer from prolonged processing times, complex procedures, and high consumption of water and energy. Moreover, the formation mechanisms of RC-Mt remain inadequately understood. To address these challenges, this study proposes a novel and efficient method combining dry lithiation and microwave irradiation to prepare RC-Mt, and compares it with a conventional acid treatment. The research also explores the applications of RC-Mt, focusing on organic modification and the evaluation of adsorption performance. It was found that the cation exchange capacity (CEC) of RC-Mt diminished with increasing microwave power and time, LiCl dosage, HCl concentration, acidification duration and temperature. It has been demonstrated that the dry lithiation & microwave method significantly reduces the total preparation time of RC-Mt to 12 min while eliminating the generation of wastewater. The pivotal advantages of this approach include its efficiency, time-saving, and minimal environmental impact. Analytical techniques such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance spectroscopy (SSNMR) revealed that microwave irradiation facilitates the migration of Li+ into the hexagonal cavities and octahedral vacancies of the Mt tetrahedral sheets. Additionally, acid treatment results in the dissolution of octahedral cations from Mt. The modified products of RC-Mt with lower CEC, exhibited enhanced adsorption of perchlorate ions (ClO4−). These findings offer significant insights into the modification of Mt and its potential for advanced technological applications, presenting a promising avenue for future research.

Two serial filters control P2X7 cation selectivity, Ser342 in the central pore and lateral acidic residues at the cytoplasmic interface.

The human P2X7 receptor (hP2X7R) is a homotrimeric cell surface receptor gated by extracellular ATP4- with two transmembrane helices per subunit, TM1 and TM2. A ring of three S342 residues, one from each pore-forming TM2 helix, located halfway across the membrane bilayer, functions to close and open the gate in the apo and ATP4--bound open states, respectively. The hP2X7R is selective for small inorganic cations, but can also conduct larger organic cations such as Tris+. Here, we show by voltage-clamp electrophysiology in Xenopus laevis oocytes that mutation of S342 residues to positively charged lysines decreases the selectivity for Na+ over Tris+, but maintains cation selectivity. Deep in the membrane, laterally below the S342 ring are nine acidic residues arranged as an isosceles triangle consisting of residues E14, D352, and D356 on each side, which do not move significantly during gating. When the E14K mutation is combined with lysine substitutions of D352 and/or D356, cation selectivity is lost and permeation of the small anion Cl- is allowed. Lysine substitutions of S342 together with D352 or E14 plus D356 in the acidic triangle convert the hP2X7R mutant to a fully Cl--selective ATP4--gated receptor. We conclude that the ion selectivity of wild-type hP2X7R is determined by two sequential filters in one single pathway: (i) a primary size filter, S342, in the membrane center and (ii) three cation filters lateral to the channel axis, one per subunit interface, consisting of a total of nine acidic residues at the cytoplasmic interface.

A New Type of Acidic OH-Groups in the LTL Zeolite

Acidic properties of ion-exchanged LTL zeolites have been studied using FTIR spectroscopy, complemented by X-ray powder diffraction, SEM-EDX, XRF and N2 physisorption. Infrared spectra of the ion-exchanged zeolites show the presence of two intense bands of the bridging OH-groups: a narrow band at ~3640 cm−1 that is attributed to Si(OH)Al groups freely vibrating in 12 MR and a broad, intense band at ~3250 cm−1 that is assigned to bridging OH groups forming hydrogen bond with neighbouring oxygen atoms, e.g., in six-membered rings. The former can be selectively removed by caesium or rubidium cations with up to 3 Cs+ or Rb+ per unit cell readily ion-exchanged into the LTL zeolite, replacing an equivalent number of acidic OH-groups or K+ cations within the structure. The cation migration of the larger cation, evaluated by the Rietveld refinement method, occurs mostly via the main 12 MR channels. By contrast, less than 1 Li+ or Na+ cation per unit cell can be introduced under similar conditions. Accordingly, the concentration of Si(OH)Al groups in back-exchanged NH4-K-LTL with smaller cations (Li+, Na+) does not differ considerably from the concentration of Brønsted acid sites in the original NH4-K-LTL. Lower concentrations of acid sites have been detected in the samples back-exchanged with Cs+, Rb+ and K+. In addition, the acidic properties of NH4-LTL samples have been compared with a structurally related NH4-MAZ zeolite.

The Effect of the Tetraalkylammonium Cation in the Electrochemical CO2 Reduction Reaction on Copper Electrode.

Aprotic organic solvents such as acetonitrile offer a potential solution to promote electrochemical CO2 reduction over the competing hydrogen evolution reaction. Tetraalkylammonium cations (TAA+) are widely used as supporting electrolytes in organic media due to their high solubility and conductivity. The alkyl chain length of TAA+ cations is known to influence electron transfer processes in electrochemical systems by the adsorption of TAA+, causing modifications of the double layer. In this work, we elucidate the influence of the cation chain length on the mechanism and selectivity of the CO2RR reaction under controlled dry and wet acetonitrile conditions on copper cathodes. We find that the hydrophobic hydration character of the cation, which can be tuned by the chain length, has an effect on product distribution, altering the reaction pathway. Under dry conditions, smaller cations (TEA+) preferentially promote oxalate production via dimerization of the CO2 ·- intermediate, whereas formate is favored in the presence of water via protonation reaction. Larger cations (TBA+ > TPA+ > TEA+) favor the generation of CO regardless of water content. In situ FTIR analysis showed that TBA+ cations are able to stabilize adsorbed CO more effectively than TEA+, explaining why larger cations generate a higher proportion of CO. Our findings also suggest that higher cation concentrations suppress hydrogen evolution, particularly with larger cations, highlighting the role of cation chain length size and hydrophobic hydration shell.

Electrochemical Amalgamation Optimization as Part of the Development of the OREATE Process

Oxide reduction by electrochemical amalgamation and thermal extraction (OREATE) is an electrochemical process in which metal oxides are converted to highly pure metals. This process that is currently being developed at LANL involves the dissolution and chlorination of the metal oxide into an acidic medium. This metal cation is then electrochemically amalgamated via reduction using a mercury pool cathode. Finally, mercury's high vapor pressure allows an easy thermal extraction process to obtain the metal. In addition to its ability to electrochemically form amalgams, mercury is used because it has a high hydrogen evolution overpotential, allowing for a higher current efficiency for reduction of the metals in acidic solution. As a critical step of the OREATE process, the electrochemical amalgamation reaction must be optimized in order to advance the overall performance.In this work, we studied the electrochemical amalgamation of cerium through anodic stripping voltammetry (ASV) experiments using a silver-based mercury film electrode (SBMFE). The SBMFE allows for the electrochemical amalgamation to be optimized at a smaller scale than the mercury pool, which not only minimizes the amount of mercury needed, but also drastically reduces the experiment time. This study included several different experimental parameters such as the pH of the buffered solution, concentration of cerium, reduction potential, and temperature. For each parameter, the reaction rate and current efficiency were evaluated to determine the optimal conditions for the electrochemical amalgamation reaction.The results showed that the pH of the buffered solution must be 3.5 or lower to avoid the formation of cerium hydroxides, which can passivate the surface of the mercury electrode. However, an increasingly acidic solution promotes the hydrogen evolution reaction, which directly competes with the electrochemical reduction of cerium, decreasing the overall current efficiency. Likewise, it has been demonstrated that an increase of the cerium concentration in solution drops the current efficiency of the electrochemical amalgamation reaction. This effect can be explained by the fact that cerium is a small cation with a +3 charge that leads to a high degree of solvation. Therefore, as the cerium concentration in solution increases, more water molecules are brought to the electrode surface during electrochemical amalgamation. This favors the water reduction reaction that increases hydrogen evolution and lowers current efficiency. However, increasing the concentration of cerium enhances the reaction rate of the electrochemical amalgamation, resulting in more cerium entering the mercury film. Furthermore, as the reduction potential is moved towards more negative potentials, the reaction rate increases. However, a more negative reduction potential promotes a faster hydrogen evolution reaction, which diminishes the current efficiency. Finally, it has been demonstrated that temperature increases the reaction rate, though it does not have a significant effect on the current efficiency.In conclusion, a variety of system parameters were explored for their effect on current efficiency and reaction rate of the electrochemical amalgamation reaction. This allowed for the determination of the optimal parameters to be used during the electrochemical amalgamation in the large-scale OREATE process.

Interfacial Phase Separation Governs the Chemomechanics of Polymer Electrolytes in High-Voltage, Solid-State Lithium Batteries

Polymer electrolytes hold great promise for safe and high-energy solid-state batteries. Multiphase polymer electrolytes, consisting of mobile and rigid phases, exhibit fast ion conduction and desired mechanical properties. However, fundamental challenges exist in understanding and regulating intricate chemomechanical interactions at the electrode-electrolyte interface, especially when using a high-voltage layered cathode. Here, we report that depletion of the mobile conductive phase at the interface contributes to battery performance degradation. Molecular ionic composite electrolytes, composed of a rigid-rod ionic polymer with small mobile cations and anions, serve as a multiphase platform to investigate the evolution of conductive domains at the interface. Synchrotron chemical and structural analyses enable the direct visualization of concentration polarization and spatially resolve the interfacial chemical states over a statistically significant field of view for buried interfaces. We discover that concentration and chemical heterogeneities prevail at electrode-electrolyte interfaces, leading to interfacial chemomechanical degradation. We further demonstrate an interphase tailoring strategy based on electrolyte additives to mitigate such interfacial heterogeneity and improve battery stability. While polymer electrolytes have been considered “deformable” for conformal interfaces, our work shows the hidden roles of interfacial chemomechanics in polymer electrolytes and provides an effective mitigation approach.

Synergy Between Dynamic Behavior of Hydrogen Defects and Non-Radiative Recombination in Metal-Halide Perovskites.

In organic-inorganic hybrid perovskite solar cells (PSCs), hydrogen defects introduce deep-level trap states, significantly influencing non-radiative recombination processes. Those defects are primarily observed in MA-PSCs rather than FA-PSCs. As a result, MA-PSCs demonstrated a lower efficiency of 23.6% compared to 26.1% of FA-PSCs. In this work, both hydrogen vacancy (VH -) and hydrogen interstitial (Hi -) defects in MAPbI3 bulk and on surfaces, respectively are investigated. i) Bulk VH - defects have dramatic impact on non-radiative recombination, with lifetime varying from 67 to 8ns, depending on whether deprotonated MA0 are ion-bonded or not. ii) Surface H-defects exhibited an inherent self-healing mechanism through a chemical bond between MA0 and Pb2+, indicating a self-passivation effect. iii) Both VH - and Hi - defects can be mitigated by alkali cation passivation; while large cations are preferable for VH - passivation, given strong binding energy of cation/perovskite, as well as, weak band edge non-adiabatic couplings; and small cations are suited for Hi - passivation, considering the steric hindrance effect. The dual passivation strategy addressed diverse experimental outcomes, particularly in enhancing performance associated with cation selections. The dynamic connection between hydrogen defects and non-radiative recombination is elucidated, providing insights into hydrogen defect passivation essential for high-performance PSCs fabrication.

Adaptation of the BaAl4 Type to Small Cations: The Case of NaGa4.

Single-phase NaGa4 samples were prepared by annealing stoichiometric element mixtures at 200 °C, 300 °C, and 450 °C in closed tantalum ampoules. No compositional homogeneity range was detected. While single crystals annealed at 200 °C feature a fully ordered crystal structure, a crystal annealed at 300 °C reveals a defect with mutual exchange of Na atoms and Ga2 dumbbells. The structure motif caused by the violation of translational symmetry resembles the CeMg2Si2 type of structure. The NaGa4 structure constitutes a branch of the BaAl4 type distinguished by a notably high c/a ratio (space group I4/mmm; a=4.2261(1) Å, c=11.2633(6) Å, c/a=2.67). This distortion enables the adaption of the BaAl4-type to small cations, when the further shortening of the apical-apical distance d(Ga-Ga) is not possible any more. Therefore, NaGa4 offers an adaption alternative to the monoclinic distortion observed in CaGa4 and YbGa4. Conductivity measurements validate the metallic behavior anticipated by NMR measurements in earlier studies.

Enhancement of electrochemical stability by molecular cation vacancies of the electrode material CH3NH3NiCl3 for lithium-ion batteries

At present, efforts are being made to find new low-cost materials for photovoltaic, optoelectronic and energy storage applications. In this regard, compounds of the halide perovskite type have been increasingly studied over the past few years. The incorporation of small cations in these compounds and their possible use in rechargeable batteries can be achieved by the electrochemical reversibility technique, where perovskites with large cations are used to obtain a new isostructural compound with smaller cations and large interstitial space or free vacancies for ionic transport. The present work studied the electrochemical reversibility of lithium-ion into CH3NH3NiCl3 (MANiCl3) active material, after the formation of MA+ vacancies or interstitial spaces, taking both experimental and theoretical approaches. The material displayed an anodic behavior and an initial capacity of discharge of ca. 170 mAhg−1 at 0.2C (0.1 mA), a full capacity retention up to the first 25 cycles of charge–discharge, and even reached a retention of up to 80 % of initial capacity at the 80th cycle. First-principles density functional theory calculations show that the shape of the crystal lattice and volume changes of all the different phases involved in the electrochemical process are tiny, at about 3 Å3 per cell. In addition, there are no appreciable elastic contributions to the energy variation during the de-lithiation/lithiation process, indicating that memory effects are not an issue. The calculated formation energies of the lithiated structures and the open circuit voltages are −2.91 eV and 1.33 V for LinMA1-nNiCl3 and −1.41 eV and 2.91 V for Li2nMA1-nNiCl3, respectively. These findings suggest that incorporating one or, at most, to two lithium atoms is favorable for the overall stability and electrochemical performance.

Crystal structure and Hirshfeld surface analysis of 2-bromo-ethyl-ammonium bromide - a possible side product upon synthesis of hybrid perovskites.

This study presents the synthesis, characterization and Hirshfeld surface analysis of a small organic ammonium salt, C2H7BrN+·Br-. Small cations like the one in the title compound are considered promising components of hybrid perovskites, crucial for optoelectronic and photovoltaic applications. While the incorporation of this organic cation into various hybrid perovskite structures has been explored, its halide salt counterpart remains largely uninvestigated. The obtained structural results are valuable for the synthesis and phase analysis of hybrid perovskites. The title compound crystallizes in the solvent-free form in the centrosymmetric monoclinic space group P21/c, featuring one organic cation and one bromide anion in its asymmetric unit, with a torsion angle of -64.8 (2)° between the ammonium group and the bromine substituent, positioned in a gauche conformation. The crystal packing is predominantly governed by Br⋯H inter-actions, which constitute 62.6% of the overall close atom contacts.

Ca2+ induced highly fluorescent CsPb(Br/Cl)3 perovskite quantum dots via fast Anion-Exchange & Cation-Doping Inter-Promotion strategy for efficient deep-blue light-emitting diodes

Despite the impressive development of perovskite light-emitting diodes (PeLEDs), it is still challenging to achieve high-efficiency deep-blue PeLEDs using colloid perovskite quantum dots (PQDs). The efficiency of PQDs with a wavelength below 460 nm, which meets the requirements for deep-blue emission in the Telecommunication Union UHD television standard (ITU REC. 2020), lags far behind those of their sky-blue counterparts. To address this issue, a novel strategy of fast anion-exchange & cation-doping inter-promotion (FAECDIP) is proposed to achieve highly efficient deep-blue PQDs by introducing CaBr2 into the CsPbCl3 PQDs. Owing to the presence of Ca2+, the speed of ion exchange is increased, driven by the smaller cation, Ca2+, improving the preparation efficiency. Additionally, Ca2+ was doped on the surface of PQDs. Based on studies of fast anion-exchange and theoretical calculations, Ca2+ improves the optical performance by decreasing the number of traps and increasing the crystallinity of target PQDs, facilitating the stability of treated films and PeLEDs by enhancing the formation energy of halogen vacancies. Here, a high PLQY of 80.3 % CaBr2-induced CsPb(Cl/Br)3 deep-blue PQDs (∼446 nm) was achieved. The correspondent PeLEDs (∼447 nm) achieved a superior EQE of 5.88 %, which is the state-of-the-art among the reported deep-blue PeLEDs. Our strategy provides a potential route to achieve deep-blue PeLEDs, which differs from the previous tedious-complex methods.

Designing high-efficiency red-emitting Mg2In1-zSczSbO6:Mn4+,Li+ phosphors for plant growth lighting

In this work, a synergistic strategy of small cation substitution and charge compensation to realize efficient red luminescence has been developed, which greatly improves the luminescence performance of Mg2InSbO6:Mn4+ by modulating the degree of distortion of the Mn4+ lattice site. The doping Mn ion is stabilized in the tetravalent state and occupies the Sb5+ site. After the Sc3+-In3+ substitution, the emission characteristic of the original Mg2InSbO6:Mn4+ is regulated and effectively red-shifted, and the extruded [MnO6] octahedron present distorted due to the aberration of the near-neighboring lattice sites of Mn4+. Through the Sc3+-In3+ substitution and Li+ compensation, the optimal thermal stability at 423 K is enhanced by 19.1% compared with that of Mg2InSbO6:Mn4+. Surprisingly, the designed Mg2In0.3Sc0.7SbO6:0.003Mn4+,Li+ phosphor exhibits excellent quantum yield (82.02%) and high color purity (97.3%), which is higher than most of the reported Mn4+-doped phosphors. Moreover, the growth of sweet potatoes by combining the plant growth illumination device encapsulated by the phosphor is implemented. The relevant growth parameters further confirm that the designed phosphors have a great potential application in the field of plant growth lighting.

The Influence of Ions on the Electrochemical Stability of Aqueous Electrolytes.

The electrochemical stability window of water is known to vary with the type and concentration of dissolved salts. However, the underlying influence of ions on the thermodynamic stability of aqueous solutions has not been fully understood. Here, we investigated the electrolytic behaviors of aqueous electrolytes as a function of different ions. Our findings indicate that ions with high ionic potentials, i.e., charge density, promote the formation of their respective hydration structures, enhancing electrolytic reactions via an inductive effect, particularly for small cations. Conversely, ions with lower ionic potentials increase the proportion of free water molecules-those not engaged in hydration shells or hydrogen-bonding networks-leading to greater electrolytic stability. Furthermore, we observe that the chemical environment created by bulky ions with lower ionic potentials impedes electrolytic reactions by frustrating the solvation of protons and hydroxide ions, the products of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. We found that the solvation of protons plays a more substantial role than that of hydroxide, which explains a greater shift for OER than for HER, a puzzle that cannot be rationalized by the notion of varying O-H bond strengths of water. These insights will help the design of aqueous systems.