Halides Research Articles

Breaking dielectric dilemma via polymer functionalized perovskite piezocomposite with large current density output

Organometal halide perovskite (OHP) composites are flexible and easy to synthesize, making them ideal for ambient mechanical energy harvesting. Yet, the output current density from the piezoelectric nanogenerators (PENGs) remains orders of magnitude lower than their ceramic counterparts. In prior composites, high permittivity nanoparticles enhance the dielectric constant (ϵr) but reduce the dielectric strength (Eb). This guides our design: increase the dielectric constant by the high ϵr nanoparticle while enhancing the Eb by optimizing the perovskite structure. Therefore, we chemically functionalize the nanoparticles to suppress their electrically triggered ion migration for an improved piezoelectric response. The polystyrene functionalizes with FAPbBr2I enlarges the grains, homogenizes the halide ions, and maintains their structural integrity inside a polymer. Consequently, the PENG produces a current density of 2.6 µAcm−2N−1. The intercalated electrodes boost the current density to 25 µAcm−2N−1, an order of magnitude enhancement for OHP composites, and higher than ceramic composites.

White Light Emission in Europium‐Doped Inorganic Perovskite Single Matrix

AbstractThe realization of stable single‐component white light emission in metal halide perovskites is still challenging due to the fast halide ion migration and narrow luminescence bands. In this work, all‐inorganic single CsPbClxBr3−x perovskite microplates with stable red‐blue‐green triple color light emission are prepared by introducing europium ions Eu3+ as dopants. Eu doping effectively suppresses ion migration and enables two spatially separated halide phases with stable dual‐wavelength emissions. Furthermore, the incorporation of Eu3+ compensates for the absence of red‐light emission, thereby yielding a superior white emission with exceptional quality. The color rendering index of triple‐color‐emitting perovskites can be tuned successfully by controlling the halogen ratios, and the optimal microplate achieved a Commissions Internationale de l’Eclairage (CIE) coordinates of (0.32, 0.32). The results present a new enlightenment for the preparation of low‐cost single‐component white light materials.

Study on the sorption and desorption behavior of La3+ and Bi3+ by bis(2-ethylhexyl)phosphate modified activated carbon.

The separation of 213Bi from its parent radionuclide 225Ac via radionuclide generators has proven to be a challenge due to the limited performance of the current sorbents. This study evaluated the separation performance of La3+ (as a surrogate for 225Ac) and Bi3+ using bis(2-ethylhexyl)phosphate monofunctionalized activated carbon (HDEHP/AC). The potential applications of phosphate groups as active sites and the carbon structure as a sorbent support were confirmed and validated. Various factors, including pH values, salt concentration, halide ions, contact time, solid-to-liquid ratio, initial La3+/Bi3+ concentration, and gamma irradiation were examined through batch sorption experiments in both single and binary systems. HDEHP/AC had a high sorption capacity for La3+ via electrostatic attraction, with the sorption data fitting well to the pseudo-second-order kinetic equation and Langmuir model. The sorption performance of La3+ on HDEHP/AC was minimally affected as the NaCl/NaI concentrations increased at pH = 2, whereas the sorption capacity for Bi3+ decreased significantly. Additionally, selective desorption of La3+ and Bi3+ was achieved using HNO3 and NaI solutions, respectively. These results backed up by a conceptual separation process point toward a potential use of these materials in a direct/inverse 225Ac/213Bi radionuclide generator. Further optimization of the material and separation process will be required to bring this class of promising materials into an actual generator for medical applications.

Air and Water Stable Bicyclic (Alkyl)(Amino)Carbene Stabilized Phosphenium Cation: Reactivity and Selective Fluoride Ion Affinity.

The synthesis and reactivity of an air and water stable Bicyclic (alkyl)(amino)carbene (BICAAC) stabilized phosphenium cation (1) is reported. Air and water stable phosphenium cation are rare in the literature. Compound 1 is obtained by reaction of BICAAC with Ph2PCl in THF followed by anion exchange with LiOTf. The reduction and oxidation of 1 yielded corresponding α-radical phosphine species (2) and BICAAC stabilized phosphenium oxide (3) respectively. All compounds are well characterized by single crystal X-ray diffraction studies. The Lewis acidity of compounds 1 and 3 are determined by conducting fluoride ion affinity experiments using UV-Vis spectrophotometry and multinuclei NMR spectroscopy. Compounds 1 and 3 exhibited selective binding to fluoride anion but did not interact with other halides (Cl- and Br-). Quantum chemical calculations were performed to understand the structure and nature of bonding interactions in these compounds, as well as to comprehend the specific bonding affinity to fluoride over other halide ions.

Post-Synthetic Modification of Porous Organic Cages for Enhanced Iodine Adsorption Performance.

The capture of radioactive iodine species from nuclear waste is crucial for environmental protection and human health. Porous organic cages (POCs), an emerging porous material, have showed potential in iodine adsorption due to the advantages of tunable pores and processibility. However, integrating multiple desirable characteristics into a single POC through bottom-up assembly of pre-designed building blocks remains challenging. Post-synthetic modification (PSM) offers an alternative approach, enabling the introduction of various functions into a single POC. Herein, a viable and highly efficient three-step PSM strategy to modify a representative POC (CC3), is presented. The modified POC, OFT-RCC36+6Br-, features a charged confined space, electron-rich heteroatom, and halide ions, exhibiting significantly enhanced iodine vapor uptake compared to the parental cage. The universality of the PSM strategy has been verified by successfully modifying two other POCs. The iodine adsorption behaviors of three modified cage adsorbents in organic solvent and aqueous solution have also been investigated, all of which exhibited improved performance, especially in comparison to ionic cages modified through direct protonation. This work provides an effective PSM strategy for POCs to facilitate iodine adsorption. More importantly, the introduction of a new PSM strategy enriches the functional diversity of POCs, potentially broadening their future applications.

Customizing Aniline-Derived Molecular Structures to Attain beyond 22 % Efficient Inorganic Perovskite Solar Cells.

The characteristics of the soft component and the ionic-electronic nature in all-inorganic CsPbI3-xBrx perovskite typically lead to a significant number of halide vacancy defects and ions migration, resulting in a reduction in both photovoltaic efficiency and stability. Herein, we present a tailored approach in which both anion-fixation and undercoordinated-Pb passivation are achieved in situ during crystallization by employing a molecule derived from aniline, specifically 2-methoxy-5-trifluoromethylaniline (MFA), to address the above challenges. The incorporation of MFA into the perovskite film results in a pronounced inhibition of ion migration, a significant reduction in trap density, an enhancement in grain size, an extension of charge carrier lifetime, and a more favorable alignment of energy levels. These advantageous characteristics contribute to achieving a champion power conversion efficiency (PCE) of 22.14 % for the MFA-based CsPbI3-xBrx perovskite solar cells (PSCs), representing the highest efficiency reported thus far for this type of inorganic metal halide perovskite solar cells, to the best of our knowledge. Moreover, the resultant PSCs exhibits higher environmental stability and photostability. This strategy is anticipated to offer significant advantages for large-area fabrication, particularly in terms of simplicity.

Hetero-Nucleation Induced [111]-Oriented Mixed Halide Perovskite for Stable Pure Red Light-Emitting Diodes.

Mixed halide 3D perovskites are promising for bright, efficient, and wide-color gamut light-emitting diodes (LEDs) due to their excellent carrier transport, high luminescence, and easily tunable bandgaps. However, serious halide ion migration inside mixed halide 3D perovskite results in poor operational and spectral stability of the as-fabricated LEDs. Here, a hetero-nucleation crystallization strategy is reported to grow [111]-orientationpreferred mixed halide 3D perovskite CsPbI3-xBrx thin films for stable pure red LEDs. This hetero-nucleation crystallization is enabled by the addition of phosphoric acid (H3PO4) complexation, which promotes the growth of small perovskite grains into large grains with uniform [111]-orientation. The obtained [111]-orientation preferred film exhibits excellent stability under light or electric field stimulus as revealed by model analysis and experimental results compared to that of [001]-orientation preferred film. Thus, based on the [111]-orientationpreferred film, the fabricated LED exhibits an external quantum efficiency of 22.8%, a maximum brightness of 12000cdm-2, and a half-life time of 4080min under 1.5mA cm-2. More importantly, the electroluminescence spectrum of the device remains stable during the continuous operation of 4080min, showcasing the significant spectral stability improvement enabled by the hetero-nucleation induced [111]-orientation strategy.

Two mercury(II) halide coordination polymers with efficient photoluminescence

Two coordination polymers (CPs), [Hg(Bpbp)X2]n (X = Br (1), I (2), Bpbp = 4,4′-bis(4-pyridyl)-biphenyl), were synthesized via solvothermal synthesis methods, and were further fully characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, FT-IR spectroscopy, and thermogravimetric analyses. The two CPs exhibit similar one-dimensional zigzag chain structures constructed by Bpbp ligand connecting Hg(II) cations with halide ions as terminal ligands, while the zigzag chains show different configurations, symmetries and packing modes. The results of photoluminescence experiments and DFT calculations indicate that both the halide anions and conjugated Bpbp ligands show important roles in the emission process of CPs, and halide anions may tune the luminescence properties of CPs.

Nanometer-Resolved Mapping of Organic Cation Migration Behavior in Methylammonium Lead Halide Perovskites.

The performance and stability of organic metal halide perovskite (OMHP) optoelectronic devices have been associated with ion migration. Understanding of nanoscale resolved organic cation migration mechanism would facilitate structure engineering and commercialization of OMHP. Here, we report a three-dimensional approach for in situ nanoscale infrared imaging of organic ion migration behavior in OMHPs, enabling to distinguish migrations along grain boundary and in crystal lattice. Our results reveal that organic cation migration along OMHP film surface and grain boundaries (GBs) occurs at lower biases than in crystal lattice. We visualize the transition of organic cation migration channels from GBs to volume upon increasing electric field. The temporal resolved results demonstrate the fast MA+ migration kinetics at GBs, which is comparable to diffusivity of halide ions. Our findings help understand the role of organic cations in the performance of OMHP devices, and the proposed approach holds broad applicability for revealing migration mechanisms of organic ions in OMHPs based optoelectronic devices.

Tetrapyrrolic macrocycles self-organization into floating layers and sensory properties of their Langmuir-Schaefer films

The influence of the chemical structure of the 5,10,15,20-tetraphenylporphyrin (I) and 2-aza-21-carba-5,10,15,20-tetraphenylporphyrin (II) on their supramolecular organization in floating layers at the air/water interface and sensor properties in Langmuir-Schaefer films has been investigated. It was shown that a minor change in the macrocycle structure (namely, the replacement of a single nitrogen atom from the center to the periphery of macrocycle) has a considerable effect on the surface properties and hysteresis processes of the floating layers. Using the Bruster angle microscopy, it was established that both porphyrins aggregate even before the compression of their floating layers begins. The aggregation is more pronounced in porphyrin I. The analysis of hysteresis loops showed that the formation of a floating layer by the modified porphyrin II requires approximately 100 times more energy than for the unmodified porphyrin I. Using the Langmuir-Schaefer (LS) method, the floating layers were transferred onto solid substrates and the resulting thin films were analyzed by atomic force microscopy, scanning electron microscopy, polarization optical microscopy, and spectrophotometry. The combination of these methods revealed a general tendency of the porphyrins to form 3D structures on the surface of LS-films. The study of the basic properties of the porphyrin's LS-films showed that both porphyrins are diprotonated. The protonation process in porphyrin II occurs at a concentration of HClO4 that is 1000 times lower than that observed in porphyrin I. The greater tendency to protonation of porphyrin II is caused by the availability of both nitrogen atoms (the external nitrogen atom located at the macrocycle periphery and the internal nitrogen atom, which becomes more assesible to interactions due to the distortion of the macrocycle). As for the sensor properties of LS-films for iodide ion in aqueous solutions, it was observed that the diprotonated form of porphyrin I exhibited higher sensitivity due to a more developed film surface because of the presence of a greater number of 3D aggregates. The data obtained can be used in the development of efficient pH-controlled thin-film sensor materials for halide ions.

Effect of Halide Ions on the TiO2-mediated Photocatalysis of Carbendazim in Aqueous Medium Under Near-ultraviolet Light Irradiation

The degradation of carbendazim (CBZ) through TiO2 photocatalysis, in the presence of halide ions and under near-UV light irradiation, was investigated. HPLC–MS technique was used to characterize the photoproducts. Spectrophotometric analysis showed that CBZ degraded slowly in TiO2 aqueous dispersions containing no salt (CBZ conversion of 6% after ca. 5 h of irradiation). The photodegradation efficiency increased particularly by addition of bromide salts. Indeed, CBZ reached complete degradation after ca. 30 min at the maximum concentration of NaBr used (0.05 M). Two significant aspects have emerged from the data analysis: the bromide role is to cause inhibition of the electron–hole recombination, a reaction known to be competitive with the reactive process; CBZ photodegradation is especially initiated by direct hole transfer pathway, whereas the OH• role is crucial in the catalyst regeneration process. Degradation attempts under sunlight appeared promising for a more sustainable photocatalytic process.

A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals.

Electrochemical CO2 reduction reaction (eCO2RR) has been explored extensively for mitigation of noxious CO2 gas generating C1 and C2+ hydrocarbons and oxygenates as value-added fuels and chemicals with remarkable selectivity. The source of CO2 being a pure CO2 feed, it does not fully satisfy the real-time digestion of industrial exhausts. Besides the detrimental effect of noxious gas mixture leading to global warming, there is a huge capital investment in purifying the flue gas mixtures from industries. The presence of other impurity gases affects the eCO2RR mechanism and its activity and selectivity toward C2+ products dwindle drastically. Impurities like NOx, SOx, O2, N2, and halide ions present in flue gas mixture reduce the conversion and selectivity of eCO2RR significantly. Instead of wiping out these impurities via separation processes, new strategies from material chemistry and electrochemistry can open new avenues for turning foes to friends! In this perspective, the co-electroreduction will vividly discussed and supporting role of different heteroatom-containing impurity gases with CO2, generating highly stable C─N, C─S, C─X bonds, and highlight the existing limitations and providing probable solutions for attaining further success in this field and translating this to industrial exhaust streams.

Anodic Dissolution and Electropolishing of Titanium in an Amide-Type Ionic Liquid Containing Halide Ions

Anodic dissolution of titanium was investigated in an amide-type ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl-sulfonyl)amide (BMPTFSA) in the presence of halide ions, Cl– and Br–. Electropolishing of Ti was possible in the presence of Cl– at 353 K, suggesting that the surface of a Ti electrode with the native oxide layer was activated by Cl–. The dissolved species of Ti after anodic dissolution of Ti at 0 V vs. Ag|Ag(I) was found to be tetravalent [TiCl6]2–, because the applied potential was more positive than the redox potential of [TiCl6]2–/[TiCl6]3–. The morphology of a Ti electrode changed after potentiostatic anodic oxidation at –0.5 V in BMPTFSA containing BMPBr, indicating that anodic dissolution of Ti was possible in the presence of Br–.

Ion specificity on cysteine tripeptides in aqueous environments revealed by molecular simulation

Molecular dynamics simulations were conducted to investigate the interactions of cysteine tripeptides with ions and water molecules in solutions of salts (MA, M = Li+ and Cs+, A = halide ions). The results revealed that as the anion size increases, cations aggregate more easily around the tripeptide, irrespective of capping. Radial distribution function (RDF) analysis showed direct interactions between F− and tricysteine, whereas Cl−, Br−, and I− exhibited indirect binding. Comparison between Li+ and Cs+ systems indicated that the smaller Li+ ions tend to distribute more around the tripeptide, engaging in direct interactions, whereas Cs+ ions interact indirectly, mediated by water molecules. Interaction energy analysis demonstrated that in lithium salt solutions, the total energy of anions with tricysteine decreased with anion size for both capped and uncapped systems. In cesium salt solutions, the anionic I− had the strongest interaction with cysteine tripeptides, and the cationic Cs+ interaction with tripeptides peaked in the CsI solution. The results highlight differences in ionic interactions depending on the anion-cation correlations of different salts.

Design of novel copper(I) metallomesogens with benzoylthiourea ligands having peripherally connected cyano or fluoro groups

A new set of liquid crystals based on copper(I) complexes with a cyano or fluoro group attached at the para position of an aromatic ring in a benzoyl thiourea ligand was prepared and studied for their liquid crystalline properties. Incorporating electron-withdrawing fluoro or cyano groups into the structural matrix can enhance their thermal stability, phase transition temperatures, and optical properties. The prepared Cu(Ln)2X compounds, where X = Cl, Br, or I, and 4-(dodecyloxy)-N-((4-fluorophenyl)carbamothioyl)benzamide (L1), N-((4-cyanophenyl)carbamothioyl)-4-(dodecyloxy)benzamide (L2), N-((4-fluorophenyl)carbamothioyl)-3,4-bis(octyloxy)benzamide (L3), and N-((4-cyanophenyl)carbamothioyl)-3,4-bis(octyloxy)benzamide (L4) displayed a SmA mesophase depending on the type of the attached terminal group (F or CN), number of alkoxy chains (one or two) and the nature of the halide ion coordinated to the metal center (Cl, Br or I). The structures of the compounds were characterized by 1H and 13C NMR, ESI-MS and IR studies, and their mesomorphic properties were investigated via a combination of polarising optical microscopy (POM), differential scanning calorimetry (DSC), and powder X-ray diffraction studies. These compounds were stable throughout the temperature range of the mesophases. This study further reiterates the consequential effect of incorporating cyano or fluoro groups on the mesomorphic and the size of the halide ions of the studied compounds.

In-Situ Surface Repair of FAPbBr3 Quantum Dots toward High-Performance Pure-Green Perovskite Light-Emitting Diodes.

Metal halide perovskite light-emitting diodes (PeLEDs) are ideal for high-resolution displays due to their tunable emission, narrow spectra, and low-cost processing. Colloidal FAPbBr3 perovskite quantum dots (PeQDs) enhance radiative recombination, making them efficient for pure-green PeLEDs. However, their low stability and surface defects limit their practical application. Here, we address these challenges by proposing an in situ surface repair strategy using benzhydroxamic acid (BHA) as a modifier. We demonstrated that BHA can coordinate with Pb2+ ions and form hydrogen bonds with FA+ and halide ions, effectively reducing nonradiative recombination and maintaining the integrity of the PeQDs. High-quality FAPbBr3 PeQDs with a photoluminescence quantum yield (PLQY) of up to 92.5% were achieved, leading to pure-green PeLEDs with an external quantum efficiency (EQE) of 24.8% and a maximum luminance of 40,231 cd m-2, providing a feasible and promising perspective for advanced solid-state lighting and displays.

Efficient and Stable Blue Perovskite Light‐Emitting Diodes Enabled by Effective Hydrolysis of Dichloride

AbstractDespite the substantial progress in sky‐blue (480−495 nm) perovskite light‐emitting diodes (PeLEDs), the pure‐blue PeLEDs (<480 nm) merely show moderate performances. As a straightforward and effective facile way to obtain pure‐blue emission, the bromide‐chloride mixed perovskites have received considerable attention. However, the tricky issue of halide migration in the mixed halide perovskites makes a tough challenge to achieve efficient PeLEDs with stable electroluminescence (EL) spectra. Herein, the in situ treatment of Cl‐rich benzene phosphorus oxydichloride (BPOD) is proposed to achieve high‐quality pure‐blue perovskites by simultaneously enlarging the perovskite bandgap, passivating the halide vacancy defects, and immobilizing the halide ions through the hydrolysis products of chloride ions and phenylphosphonic acid. As a result, highly‐performed pure‐blue PeLEDs with a maximum external quantum efficiency (EQE) of 9.3% at 477 nm, an impressive lifetime of 34.7 min at 104 cd m−2, and very stable EL spectra are achieved, which are superior to the conventional mixed halide PeLEDs based on lead‐chloride precursor, representing one of the best performances for mixed halide pure‐blue PeLEDs. Therefore, this work contributes a feasible and effective method for efficient and stable pure‐blue PeLEDs.

High-Performance Thermally Evaporated Blue Perovskite Light-Emitting Diodes Enabled by Post-Evaporation Passivation

Thermally evaporated perovskite light-emitting diodes (PeLEDs) are promising for next-generation displays, yet process-compatible passivation strategies for performance enhancement are still lacking. Herein, an effective in-situ surface passivation strategy using post-evaporated metformin hydrochloride (MFCl) is introduced in co-evaporated PeLEDs. MFCl post-deposited onto the perovskite film induces surface reconstruction, improving surface uniformity and healing grain boundaries. Additionally, MFCl penetrates deeply into the perovskite film, passivating both undercoordinated Pb and halide ions at grain boundaries. By employing this strategy, we achieve thermally evaporated blue PeLEDs with a peak external quantum efficiency (EQE) of 9.2 % and a maximum luminance of 1820 cd/m−2(−|-), emitting at a peak wavelength of 488 nm. Furthermore, this strategy effectively suppresses ion migration, significantly enhancing the spectral stability and device lifetime of the blue PeLEDs. This work provides a process-compatible defect passivation strategy for thermally evaporated PeLEDs, laying the foundation for further advancements in this field.

Chemical Synergic Stabilization of High Br-Content Mixed-Halide Wide-Bandgap Perovskites for Durable Multi-Terminal Tandem Solar Cells with Minimized Pb Leakage.

High Br-content mixed-halide perovskites with wide-bandgap (WBG) of 1.6-2.0 eV have showcased vast potential to be used in tandem solar cells. However, they often suffer from severe halide segregation, phase separation and ion migration issues, which would accelerate the decomposition of perovskites films,deteriorate the photovoltaic performance and even aggravate the lead leakage from damaged devices. Here, we report a novel chemical synergic interaction strategy to mitigate the abovementioned issues. A small amount of cationic β-cyclodextrin, composed of multiple ammonium cations, chlorine ions and abundant hydroxyl functional groups, was introduced into WBG perovskites, which effectively stabilized the halide ions and homogenized the phase distribution, comprehensively passivated the defects,and efficiently immobilized the Pb2+ ions. Encouragingly, the cationic β-cyclodextrin was universal and useful for different WBG perovskites, which favorably boosted the efficiencies by 10%-36% and extended the device operational stability to 2680 h. The integrated four-terminal orsix-terminal all-perovskite tandem solar cells exhibited efficiencies up to 24.39% and 22.42%, respectively. We demonstrated the cationic β-cyclodextrin-assisted internal chemical encapsulation effectively prevented the Pb leakage from severely damaged devices with only 5.63 ppb Pb leaching out. The target tandem solar cells with cationic β-cyclodextrin modification also realized a Pb sequestration efficiency of 93.4%.

Chemical Synergic Stabilization of High Br‐Content Mixed‐Halide Wide‐Bandgap Perovskites for Durable Multi‐Terminal Tandem Solar Cells with Minimized Pb Leakage

High Br‐content mixed‐halide perovskites with wide‐bandgap (WBG) of 1.6‐2.0 eV have showcased vast potential to be used in tandem solar cells. However, they often suffer from severe halide segregation, phase separation and ion migration issues, which would accelerate the decomposition of perovskites films, deteriorate the photovoltaic performance and even aggravate the lead leakage from damaged devices. Here, we report a novel chemical synergic interaction strategy to mitigate the abovementioned issues. A small amount of cationic β‐cyclodextrin, composed of multiple ammonium cations, chlorine ions and abundant hydroxyl functional groups, was introduced into WBG perovskites, which effectively stabilized the halide ions and homogenized the phase distribution, comprehensively passivated the defects,and efficiently immobilized the Pb2+ ions. Encouragingly, the cationic β‐cyclodextrin was universal and useful for different WBG perovskites, which favorably boosted the efficiencies by 10%‐36% and extended the device operational stability to 2680 h. The integrated four‐terminal or six‐terminal all‐perovskite tandem solar cells exhibited efficiencies up to 24.39% and 22.42%, respectively. We demonstrated the cationic β‐cyclodextrin‐assisted internal chemical encapsulation effectively prevented the Pb leakage from severely damaged devices with only 5.63 ppb Pb leaching out. The target tandem solar cells with cationic β‐cyclodextrin modification also realized a Pb sequestration efficiency of 93.4%.