Ligand-assisted Reprecipitation Research Articles

Stability and photocatalytic performance enhancement of sodium-doped CsPbBr3/Cs4PbBr6 nanocomposites for dye wastewater degradation

The extremely poor stability of lead halide perovskites has always been a challenge. In this paper, CsPbBr3 nanocrystals, CsPbBr3/Cs4PbBr6 nanocomposites and Na-CsPbBr3/Cs4PbBr6 nanocomposites were prepared by thermal injection and ligand-assisted reprecipitation method. The photocatalytic effect and stability of CsPbBr3 in aqueous systems were significantly improved by sodium ions doping and complexation with Cs4PbBr6. The results showed that the photocatalytic degradation rate of 5% Na-CsPbBr3 for Sudan red (III) was 57.8% within 180 min, while that of pure CsPbBr3 was only 14.47%. In the CsPbBr3/Cs4PbBr6 nanocomposites, Na-CsPbBr3/Cs4PbBr6 nanocomposites photocatalyzed nearly 94% of Sudan red (III) in 120 min, while CsPbBr3/Cs4PbBr6 photocatalyzed only 56% of organic dyes in the same time. Cs4PbBr6 can passivate CsPbBr3 in situ to enhance the stability of the perovskite material. In the four cyclic degradation experimental tests in aqueous systems, the nanocomposites maintained good stability performance. This study provides a new way to improve the catalytic performance and stability of perovskite materials.

Light-induced transformation of all-inorganic mixed-halide perovskite nanoplatelets: ion migration and coalescence

When exposed to light, the colloidal perovskite nanoplatelets (NPLs) in the film can fuse into larger grains, and this phenomenon was thought to be closely related to ion migration. However, the available CsPbBr3 NPLs are not conducive to directly distinguishing this hypothesis. Herein, we prepare mixed-halide perovskite CsPbBr2.7I0.3 NPLs by a ligand-assisted reprecipitation method and investigate the photoluminescence evolution of NPLs under laser irradiation. At a low-irradiation intensity, 4.5-monolayer NPLs exhibit blue-shifted photoluminescence peaks due to the migration of iodide ions. Under higher laser fluence, a new photoluminescence component appears in the long wavelength region after the spectral blue shift, which is attributed to the coalescence of NPLs according to transmission electron microscopy analysis. A similar spectral evolution is also observed in 8-monolayer NPLs, while only the spectral blue shift caused by ion migration is detected in cuboidal CsPbBr2.7I0.3 nanocrystals. The use of strong bonding ligands can inhibit the fusion process of the NPLs, but not to impede ion migration, suggesting that fusion requires ligand detachment rather than ion migration. Similar suppression effects can be achieved in a vacuum atmosphere. Moreover, we demonstrate that mixed-halide NPLs can be used to realize anti-counterfeiting applications with superior photosensitivity.

Sensitive detection of bilirubin using highly luminescent benzylamine capped CH3NH3PbBr3 perovskite quantum dots

Luminescent organic–inorganic metal halide hybrid perovskite quantum dots (PQDs) as a new class of fluorophores are finding increasing attention towards chemical and biological sensing due to their exceptional photophysical properties. Herein, we synthesized highly fluorescent CH3NH3PbBr3 perovskite quantum dots (B-PQDs) through the ligand assisted reprecipitation method (LARP), using benzylamine as the surface capping ligand. Morphological and opto-structural properties of the as-synthesized B-PQDs were thoroughly investigated using high resolution transmission electron microscopy (HR-TEM), X-Ray diffraction (XRD), Fourier transform infra-red spectroscopy (FT-IR), UV–Vis absorption, and fluorescence spectroscopy. The as-synthesized electron-rich amine-capped B-PQDs were employed to study their sensing response towards bilirubin (BL). The aromatic amine capped B-PQDs enhance the sensory response towards BL due to the π-π interaction with BL’s conjugated system. The B-PQDs were found to be highly sensitive towards BL with a stern–volmer constant value ≈ 4.3 × 104 M−1 and limit of detection of 0.42 μM. A panel of characterizations were carried out to investigate the detailed sensing mechanism where resonance energy transfer was found to be the dominant quenching mechanism for BL detection. Our results demonstrated the potential for utilizing organic–inorganic halide perovskite quantum dots for sensing applications, through surface ligand modification tailored for detecting specific analytes.

Nitrogen Configuration Effects on Charge Carrier Dynamics in CsPbBr3/Carbon Dots S-Scheme Heterojunction for Photocatalytic CO2 Reduction.

Nitrogen-doped carbon dots (NCDs) featuring primary pyrrolic N and pyridinic N dominated configurations were prepared using hydrothermal (H-NCDs) and microwave (M-NCDs) methods, respectively. These H-NCDs and M-NCDs were subsequently applied to decorate CsPbBr3 nanocrystals (CPB NCs) individually, using a ligand-assisted reprecipitation process. Both CPB/M-NCDs and CPB/H-NCDs nanoheterostructures (NHSs) exhibited S-scheme charge transfer behavior, which enhanced their performance in photocatalytic CO2 reduction and selectivity of CO2-to-CH4 conversion, compared to pristine CPB NCs. The presence of pyrrolic N configuration at the heterojunction of CPB/H-NCDs facilitated efficient S-scheme charge transfer, leading to a remarkable 43-fold increase in photoactivity. In contrast, CPB/M-NCDs showed only a modest 3-fold enhancement in photoactivity, which was attributed to electron trapping by pyridinic N at the heterojunction. The study offers crucial insights into charge carrier dynamics within perovskite/carbon NHSs at the molecular level to advance the understanding of solar fuel generation.

Novel room-temperature synthesis of pioneering CsPbX3@(Ce)UiO-66-Y hybrid nanomaterials for boosted photocatalytic hydrogen evolution

Perovskites are attractive structures for photocatalytic hydrogen generation, but also are limited by low stability, which can be improved by combination with other materials. Perovskite structures have potential for photocatalytic hydrogen generation; however, their practical application is hindered by inherent low stability. This limitation can be effectively mitigated through strategic combinations with complementary materials. Therefore, hybrids consisting of the perovskite CsPbX3 (X = Br, I) and the metal–organic framework (Ce)UiO-66-Y (Y = H, Br, NH2) were successfully synthesized for the first time, using a straightforward ligand-assisted reprecipitation synthesis at room temperature. To develop a room temperature synthesis for CsPbX3@(Ce)UiO-66-Y hybrid nanomaterials, herein, we optimized the synthesis of perovskite firstly (considering factors such as the choice of solvents, the drying of stabilizers, and the purification) and then developed an efficient way to combine both materials. Six types of hybrid materials, differing in the type of perovskite and functional group in the MOFs linker, were synthesized by the introduction of MOFs powder into a solution containing perovskite precursors (CsX and PbX2 in DMF stabilized by oleyamine and oleic acid) followed by antisolvent addition. We demonstrated that the hybrids containing perovskite in combination with MOF (Ce)UiO-66-NH2 in a molar ratio of 13:1 exhibited significantly higher activity and twice as long reaction stability time compared to the individual components of the hybrids when tested separately. This outcome underscores the presence of a synergistic effect, highlighting the potential of these hybrid materials in catalyzing hydrogen generation.

Efficient nanostructured Cs2CuBr2Cl2 perovskite as a fluorescent sensor for the selective “Switch Off” detection of nitrobenzene

Lead halide nanostructured perovskites are well known for their excellent photoluminescence and optoelectronic properties. However, lead toxicity and instability in moisture impedes its suitability for material use. Here we synthesized a highly efficient, lead free, economical, stable Cs2CuBr2Cl2 perovskite nanocrystals (PNCs) via Ligand Assisted Re-Precipitation (LARP) method which is less explored. The sensing application of the synthesized PNCs towards nitro explosives and other small organic compounds were studied. The probe exhibited high selectivity towards nitrobenzene with a lowest detection limit of 57.64 nM. The fluorescent emission intensity was drastically quenched upon the addition of 32 µM nitrobenzene. A Stern-Volmer plot was utilized for the quantification of fluorescence quenching. Further to investigate the quenching mechanism, time correlated single photon counting spectroscopy and other photoluminescence studies were performed pointing out the possibility of fluorescence resonance energy transfer. The work has been further extended to test the capability of the probe to detect nitrobenzene in real water samples and a good recovery percentage ranging from 93-98 % was obtained. Further, a paper strip assay was designed which successfully detected nitrobenzene and can be clearly noticed even with our naked eye making the probe an excellent sensor for nitrobenzene detection.

Enhanced photoluminescence emission intensity and stability of deep blue-emissive (Et3NH)PbBr3 perovskite nanocrystals by using metal-organic frameworks

The primary obstacle faced by researchers in the field of luminescent metal-halide perovskites is their inherent instability, prompting a shift in focus towards enhancing the stability of perovskite nanocrystals (PNCs). One of the promising approaches to address this challenge involves the utilization of metal-organic frameworks (MOFs) to fabricate PNCs@MOF composites. The present study reports a facile and low-cost colloidal strategy to prepare (Et3NH)PbBr3 PNCs followed by their encapsulation within UiO-67 to enhance their photoluminescence (PL) emission stability. The PNCs and modified UiO-67 were prepared separately via simple and efficient ligand-assisted reprecipitation (LARP) and hydrothermal methods, respectively. After modification of the UiO-67, the pore sizes experienced a substantial increase from 1.90 to 28.84 nm which significantly facilitated the localization of PNCs within the porous matrix. Under a full survey of experimental conditions, the resulting (Et3NH)PbBr3@UiO-67 composite exhibited a bright deep-blue emission at around 410 nm with an emission quantum yield of 52 %. The emission durability of the fabricated PNCs@MOF composites was assessed against temperature and long-time of storage, confirming the superior advantages of MOF even at elevated temperatures of up to 100 °C. The stable and luminous deep-blue emission displayed by the PNCs@MOF composites in this investigation, offers a promising advancement in materials development for optoelectronic applications.

Visual and rapid fluorescence sensing for hexavalent chromium by hydroxypropyl chitosan passivated bismuth-based perovskite quantum dots.

Hydroxypropyl chitosan-Cs3Bi2Cl9 perovskite quantum dots (HPCS-PQDs) weresynthesized by a simple ligand-assisted reprecipitation method via green hydroxypropyl chitosan as the ligand and used as the specific signal of a fluorescence probe to achieve the highly sensitive detection of hexavalent chromium(Cr(VI)) and compared with chitosan-Cs3Bi2Cl9 QDs (CS-PQDs). HPCS-PQDs with multiple active hydroxyl passivations were found to enhance the photoluminescence quantum yield (PLQY) by 90%. After being placed in aqueous solution and irradiated with ultraviolet light for 96h the fluorescence intensity of HPCS-PQDs remained above 60%. The blue emission ofHPCS-PQDs hasa good selectivity and short response time (30s) for Cr(VI). Agood linear relationship is established between the fluorescence quenching rate of the HPCS-PQDs and concentration of Cr(VI) from 0.8 to 400µM, with a limit of detection (LOD) of 0.27µM. Thefluorescence quenching mechanism is the static quenching and internal filtration effect caused by HPCS-PQDs forming a non-fluorescent ground-state complex with Cr(VI). Thesensor cannot only be used to detectCr(VI) in water samples with high accuracy but canalso be prepared as a test paper for the detection for Cr(VI).

Eu3+ doped Cs–Bi–Cl perovskite quantum dots with diverse crystal structures for metal ion detection

The accumulation of heavy metal ions in the human body sharply affects health, drawing global attention. Consequently, there is an urgent need to develop environmentally-friendly and non-toxic metal ion fluorescent sensing probes. Herein, two fluorescent probes based on Cs–Bi–Cl perovskite quantum dots (PeQDs) with distinct structures, namely Cs3BiCl6:Eu3+ (3-1-6-E) and Cs3Bi2Cl9:Eu3+ (3-2-9-E), were successfully synthesized by using the ligand-assisted re-precipitation (LARP) method for detecting Cu2+ and Fe3+ ions in ethanol. Both PeQDs exhibit polychromatic emission, including feature emission around 505 nm and distinctive emission from Eu3+ ions in the long-wavelength region, making them suitable for ratiometric fluorescent probes. Significantly, both probes displayed excellent linear relationship with correlation coefficients of 0.998 (3-1-6-E) and 0.985 (3-2-9-E), respectively. The limit of detection (LOD) reached 6.23 μM (3-1-6-E) and 4.55 μM (3-2-9-E). Notably, the 3-2-9-E quantum dots (QDs) successfully detected Fe3+ ions in ethanol, owing to their unique photo-quenching and photo-recovery phenomena. The detection results exhibited excellent linear fitting, with a correlation coefficient of 0.996 and a low LOD of 3.6 μM. Furthermore, compared to undoped PeQDs, Eu3+ ion-doped PeQDs demonstrate strongly enhanced luminescence intensity and excellent photo-stability. This work expands the potential applications of lead-free PeQDs while simultaneously improving their luminescent properties.

One-step synthesis of highly fluorescent perovskite nanocrystals in antisolvent for bioimaging

All inorganic perovskite nanocrystals (CsPbX3 NCs) have excellent optical properties with high quantum yield, size tunable absorption and emission spectra which makes them popular for a wide variety of applications. All the commonly used synthesis techniques, such as hot injection and ligand assisted reprecipitation method (LARP), use ‘good’ solvent such as dimethyl formamide, dimethyl sulfoxide or octadecene to dissolve the precursor salts. The CsPbX3 NCs formation is triggered either by rapid injection of the dissolved precursor salt in hot mixture (hot injection) or by adding a ‘good’ solvent into a ‘poor’ solvent (LARP) that induces crystallization. Here, we present an alternative synthesis of CsPbX3 perovskite nanocrystals in an antisolvent system, instead of a ‘good’ solvent. Crystallization in the antisolvent is induced by adding a trace amount of water, leading to the formation of highly bright CsPbX3 nanocrystals. This method resulted in a maximum photoluminescent quantum yield of ∼91%. Furthermore, these CsPbBr3 NCs can be modified to create core–shell structures with polymers such as silica, in the same pot. Encapsulating the NCs within a protective silica shell resulted in vastly superior water stability compared to the bare NCs. The silica coated CsPbBr3 NCs showed strong fluorescence in water were used to label breast cancer cells, thereby demonstrating its potential as an optical contrast agent for advanced bioimaging applications. Overall, this synthesis approach requires minimal steps and time, and can be carried out in an ambient atmosphere, thereby increasing its versatility and practicality, which is particularly attractive in low-resource settings.

Improved photoluminescence stability and defect passivation in SbBr3 post-treated CsPbBr3 quantum dots under ambient conditions.

Inorganic cesium lead halide perovskites have evoked wide popularity because of their excellent optoelectronic properties, high photoluminescence (PL) quantum yield (PLQY), and narrowband emission. Here, cesium lead bromide (CsPbBr3 ) quantum dots (QDs) were synthesized via the ligand-assisted re-precipitation method. Post-synthesis treatment of CsPbBr3 QDs using antimony tribromide improved the PL stability and optoelectronic properties of the QDs. In addition, the PLQY of the post-treated sample was enhanced to 91% via post-treatment, and the luminescence observed was maintained for 8 days. The post-synthesis treatment ensured defect passivation and improved the stability of CsPbBr3 perovskite QDs. High-resolution transmission electron microscopy revealed the presence of more ordered, uniform-sized CsPbBr3 QDs after post-synthesis treatment, and the uniformity of the sample improved as the day passed. The formation of a mixed crystal phase was observed from X-ray diffraction in both as-synthesized, as well as post-treated QDs samples with the possibility of a polycrystalline nature in the post-treated CsPbBr3 QDs as per the selected area electron diffraction pattern. The X-ray photoelectron spectroscopy spectra confirmed the presence of antimony and the possibility of defect passivation in the post-treated samples. These QDs can act as potential candidates in various optoelectronic applications such as photodetectors and light-emitting diodes due to their high PLQY and longer lifetime.

Phase composition and luminescent properties of cesium lead bromide perovskite nanopowders

Halide perovskite nanopowders were synthesized by ligand-assisted re-precipitation technique with different volume ratios of mixture solution to antisolvent (toluene). It was found that with an increase in the proportion of toluene, the phase formed as a result of recrystallization changes predominantly from Cs4PbBr6 to the CsPbBr3, while less stable CsPb2Br5 phase was also discovered. The change in the phase composition of powders obtained with different volume ratios of mixture solution to toluene is explained by the salting out effect of slightly soluble compounds. The phase composition had a correlation with the crystal size distribution, as well as with the photoluminescence quantum yield. Optical properties, including absorption spectra, photoluminescence excitation and luminescence spectra were investigated. Nanopowders obtained with a ratio of the mixture of solution to toluene of about 1:0.9 had the maximum quantum efficiency. The following was associated with the formation of low-dimensional CsPbBr3 “slabbed” crystals sticked on rhombohedral Cs4PbBr6 crystals. The composite film based on nanocrystals and thermoplastic polyurethane was made by hot pressing, the potential of its use as a phosphor coating for an ultraviolet LED was shown.

Scintillation Properties of CsPbBr3 Nanocrystals Prepared by Ligand-Assisted Reprecipitation and Dual Effect of Polyacrylate Encapsulation toward Scalable Ultrafast Radiation Detectors.

Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymeric hosts are gaining attention as scalable and low-cost scintillation detectors for technologically relevant applications. Despite rapid progress, little is currently known about the scintillation properties and stability of LHP-NCs prepared by the ligand assisted reprecipitation (LARP) method, which allows mass scalability at room temperature unmatched by any other type of nanostructure, and the implications of incorporating LHP-NCs into polyacrylate hosts are still largely debated. Here, we show that LARP-synthesized CsPbBr3 NCs are comparable to particles from hot-injection routes and unravel the dual effect of polyacrylate incorporation, where the partial degradation of LHP-NCs luminescence is counterbalanced by the passivation of electron-poor defects by the host acrylic groups. Experiments on NCs with tailored surface defects show that the balance between such antithetical effects of polymer embedding is determined by the surface defect density of the NCs and provide guidelines for further material optimization.

Photoluminescence and photovoltaic properties of cesium lead bromide nanocrystals with linoleic acid ligand

Cesium lead bromide (CsPbBr3) nanocrystals (NCs) were synthesized using the ligand-assisted reprecipitation (LARP) method, with linoleic acid (LA) and oleylamine (OlAm) as ligands. The crystal structures of the samples depend on the ligand used in the synthesis. Sample-1, with LA-OlAm as the ligand, showed an orthorhombic crystal structure, whereas Sample-2, with OlAm only, showed a tetragonal crystal structure. These samples exhibited slightly different photoluminescence (PL) characteristics, where the PL peak of Sample-1 appeared at 521.4 nm, whereas the PL peak of Sample-2 appeared at 524.1 nm. Sample-1 showed brighter PL than that of Sample-2. These differences are strongly related to their crystal structures and degree of crystallization, which is also evident from the differences in the chemical states of the Br and Pb ions on the NCs surface, as depicted by the X-Ray Photoelectron Spectroscopy (XPS) spectra. In addition, despite exhibiting PL characteristics, these CsPbBr3 NCs also exhibit photovoltaic properties.

Influence of arylalkyl amines on the formation of hybrid CsPbBr3 nanocrystals via a modified LARP method.

Perovskite nanocrystals have attracted much attention in the last ten years due to their different applications, especially in the photovoltaic domain and LED performance. In this large family of perovskite nanocrystals, CsPbBr3 nanocrystals are attractive nanomaterials because they are good candidates for obtaining green emissions and exploring new synthesis routes. In this context, controlling the nanometric scale's morphology, particularly the size and monodispersity, is fundamental for exploring their photophysical properties and final applications. Currently, the nanometric size of nanocrystals is ensured by the presence of oleic acid and oleylamine molecules, in using Hot Injection (HI) or ligand-assisted reprecipitation (LARP) methods. If oleic acid plays a fundamental role, oleylamine can be easily substituted by other amino molecules, opening the way for the functionalization of CsPbBr3 nanocrystals and the obtention of new hybrid perovskite nanocrystal families. In this article, we describe the synthesis, by soft chemistry, of a new family of hybrid organic-inorganic CsPbBr3 nanocrystals, functionalized by aryl-alkylamine (AAA) molecules, through the modified LARP method. We highlight the mechanism for cutting submicron crystals into nanocrystals, using aryl-alkylamine molecules like scissors. The impact of these amino molecules on the final nanocrystals leads to different nanocrystal morphologies (nanocubes, nanosheets, or nanorods) and structures (monoclinic, rhombohedral, or tetragonal). In addition, this modified LARP method highlights, under certain experimental conditions, an unexpected formation of PbO ribbons.

Understanding the Effect of the Synthetic Method and Surface Chemistry on the Properties of CsPbBr3 Nanoparticles.

Over the last decade, the attractive properties of CsPbBr3 nanoparticles (NPs) have driven ever-increasing progress in the development of synthetic procedures to obtain high-quality NPs at high concentrations. Understanding how the properties of NPs are influenced by the composition of the reaction mixture in combination with the specific synthetic methodology is crucial, both for further elucidating the fundamental characteristics of this class of materials and for their manufacturing towards technological applications. This work aims to shed light on this aspect by synthesizing CsPbBr3 NPs by means of two well-assessed synthetic procedures, namely, hot injection (HI) and ligand-assisted reprecipitation (LARP) in non-polar solvents, using PbBr2 and Cs2CO3 as precursors in the presence of already widely investigated ligands. The overall goal is to study and compare the properties of the NPs to understand how each synthetic method influences the NPs' size and/or the optical properties. Reaction composition and conditions are purposely tuned towards the production of nanocubes with narrow size distribution, high emission properties, and the highest achievable concentration. As a result, the formation of bulk crystals as precipitate in LARP limits the achievement of a highly concentrated NP solution. The size of the NPs obtained by LARP seems to be poorly affected by the ligands' nature and the excess bromide, as consequence of bromide-rich solvation agents, effectively results in NPs with excellent emission properties. In contrast, NPs synthesized by HI exhibit high reaction yield, diffusion growth-controlled size, and less striking emission properties, probably ascribed to a bromide-deficient condition.

Crystal structures and photoluminescence characteristics of cesium lead bromide perovskite nanoplatelets depending on the antisolvent and ligand used in their syntheses

Cesium lead bromide (CsPbBr3) nanocrystals (NCs) with nanoplatelet shapes and different crystal structures were synthesized via the ligand-assisted reprecipitation (LARP) method using different pairs of ligands and antisolvents, namely oleic acid (OA) or linoleic acid (LA) as the ligand and toluene or chloroform as the antisolvent. The XRD data revealed that the obtained CsPbBr3 NCs have different crystal structures, namely orthorhombic, tetragonal, and cubic, depending on the ligand and antisolvent pair, which exhibited significantly different photoluminescence (PL) characteristics. From the XPS data, these CsPbBr3 nanoplatelets showed two doublet peaks of the Br-3d orbital at different binding energies, representing two different chemical environments of the Br bonds. The doublet peak apparent at a higher binding energy was associated with the Br chemical states at the crystal surface, which appeared because of the distorted crystal structure resulting from the interaction of the solvent and ligand with Br ions. The PL emission consists of three luminescence centers: a PL band peaked at 520 nm (A band), a PL band peaked at 540 nm (B band), and a PL band tail, which can be discussed in terms of exciton models. Stable and intense luminescence was observed in CsPbBr3 nanoplatelets synthesized using a pair of toluene antisolvent and LA ligand, namely CsPbBr3#(Tl/LA). The orthorhombic crystal structure and distorted crystal surface in this sample may lead to confinement of the photogenerated small exciton-polaron and weak phonon interactions, which effectively hinder exciton dissociation, particularly at the crystal surface, resulting in intense PL. The results of this study may provide additional important insights into the role of the antisolvent and ligand in the formation of CsPbBr3 NCs and the exciton behavior in their PL characteristics, which may also be found in other types of halide perovskites.

Unveiling non-radiative center control in CsPbBr3 nanocrystals: A comprehensive comparative analysis of hot injection and ligand-assisted reprecipitation approaches

Unveiling non-radiative center control in CsPbBr3 nanocrystals: A comprehensive comparative analysis of hot injection and ligand-assisted reprecipitation approaches

Analysis of the Heat Treatment Effect of CsPbBr<sub>3</sub> Photoanode on the Photoelectrochemical Performance: Preliminary Results

The perovskite CsPbBr3 possesses good photoelectrochemical properties, making it a potential candidate for use as a photoanode. The commonly used photoanode is the FTO/TiO2/CsPbBr3 photoanode in water splitting applications. However, there has been no research conducted on the FTO/TiO2/CsPbBr3 photoanode for the oxidation of glucose derived from abundant biomass sources. This study aims to analyze the influence of heat treatment and glucose concentration on the performance of glucose oxidation, as well as the efficiency of glucose conversion and electricity production. First, CsPbBr3 solution is prepared under vacuum conditions using the Ligand Assisted Reprecipitation (LARP) method. Subsequently, the fabrication process of the FTO/TiO2/CsPbBr3 photoanode is carried out with variations including no heat treatment, heat treatment at a temperature of 110°C, and variations in glucose solution concentrations of 0.2 M and 0.5 M. XRD and SEM tests are conducted to determine the formed phases and morphology of CsPbBr3. The XRD and SEM results confirm the presence of CsPbBr3 phase and the formation of CsPb2Br5 phase due to the heat treatment process. The EIS testing reveals that the heat treatment process induces an oxidation process in the CsPbBr3 perovskite, which can decrease the glucose oxidation performance of the FTO/TiO2/CsPbBr3 photoanode. Based on HPLC analysis, the highest conversion efficiency of glucose is 97.37%, respectively under 110 oC heat treatment and with 0.5 M glucose.

Experimental analysis of methylammonium and Formamidinium-based halide perovskite properties for optoelectronic applications

Nowadays, the toxicity of lead in metal-halide perovskites is the most precarious obstruction in the commercialization of perovskite-based optoelectronic devices. However, Pb-free metal halide perovskites as environment-friendly materials because of their exceptional properties, such as band-gap tunability, narrow emission spectra, low toxicity and easy solution-processability, are potential candidates for optoelectronic applications. Recently, literature reported the poor structural stability and low-emission intensity of Bi-based perovskite NCs. Still, this paper focuses on the fabrication of Formamidinium (FA)-based Bi mixed halide and Methylammonium(MA)-based Bi-pure halide perovskites using Ligand-Assisted Reprecipitation Technique (LARP) technique. XRD diffraction patterns of FA-based perovskites were slightly broad, signifying the nanocrystalline form and limited size of perovskite nanocrystals. While the XRD diffraction patterns of MA3Bi2X9 (X = Cl/Br/I) perovskites were narrow, signifying the amorphous nature and larger size of perovskite nanocrystals. The peak positions were varied in MA-based bismuth halide perovskites with respect to the halide variation from Br to Cl to I ions. The optical study shows the variation in band gap and average lifetime with respect to halide variation leading to enhanced optical properties for device applications. The band-gap of FA3Bi2BrxCl1-x & FA3Bi2IxCl1-x perovskites was calculated to be around 3.7 & 3.8 eV, respectively, while in MA-halide perovskites the band-gap was calculated to be 2.8 eV, 3.1 eV & 3.4 eV with respect to halide variation from I to Cl to Br in perovskite samples using Tauc's plot respectively. Moreover, simulation is carried out using the SCAPS-1D software to study the various parameters in MA & FA-based Bi-pure or mixed halide perovskites. Here, we discussed the variation in efficiency with respect to the thickness variation from 100 to 500 nm for MA3Bi2I9 halide perovskites. These MA3Bi2I9 halide perovskites show minimum efficiency of 4.65 % at 100 nm thickness, while the perovskite sample exhibits maximum efficiency of 10.32 % at 500 nm thickness. Thus, the results stated that the thickness of absorber layers directly affects the device characteristics for optoelectronic applications.