CFD Modeling of Hydrodynamics of Fluidized Bed

The objective of this project is to simulate a gas-solid fluidized by applying CFD techniques in order to investigate hydrodynamics and heat transfer phenomena. Reactor model predictions will be compared with the corresponding experimental data reported in the literature to validate the model . To simulate a gas-solid fluidized bed we need to use the multiphase flow approach . First we have to write the equations for the different flow regimes and then different CFD techniques are applied for discretization of those equations. After that a code is written for calculating the values of volume fraction , velocity and temperature

Atomistic Mechanism of the Nucleation of Methylammonium Lead Iodide Perovskite from Solution

In the ongoing intense quest to increase the photoconversion efficiencies of lead halide perovskites, it has become evident that optimizing the morphology of the material is essential to achieve high peformance. Despite the fact that nucleation plays a key role in controlling the crystal morphology, very little is known about the nucleation and crystal growth processes. Here, we perform metadynamics simulations of nucleation of methylammonium lead triiodide (MAPI) in order to unravel the atomistic details of perovskite crystallization from a $\gamma$-butyrolactone solution. The metadynamics trajectories show that the nucleation process takes place in several stages. Initially, dense amorphous clusters mainly consisting of lead and iodide appear from the homogeneous solution. These clusters evolve into lead iodide (PbI$_{2}$) like structures. Subsequently, methylammonium (MA$^{+}$) ions diffuse into this PbI$_{2}$-like aggregates triggering the transformation into a perovskite crystal through a solid-solid transformation. Demonstrating the crucial role of the monovalent cations in crystallization, our simulations provide key insights into the evolution of the perovskite microstructure which is essential to make high-quality perovskite based solar cells and optoelectronics

Vapor-assisted deposition of highly efficient, stable black-phase FAPbI3 perovskite solar cells

Mixtures of cations or halides with FAPbI3 (where FA is formamidinium) lead to high efficiency in perovskite solar cells (PSCs) but also to blue-shifted absorption and long-term stability issues caused by loss of volatile methylammonium (MA) and phase segregation. We report a deposition method using MA thiocyanate (MASCN) or FASCN vapor treatment to convert yellow δ-FAPbI3 perovskite films to the desired pure α-phase. NMR quantifies MA incorporation into the framework. Molecular dynamics simulations show that SCN- anions promote the formation and stabilization of α-FAPbI3 below the thermodynamic phase-transition temperature. We used these low-defect-density α-FAPbI3 films to make PSCs with >23% power-conversion efficiency and long-term operational and thermal stability, as well as a low (330 millivolts) open-circuit voltage loss and a low (0.75 volt) turn-on voltage of electroluminescence

Modeling and Implementation of Simultaneous Double Gradient Chromatography

Polypeptides are becoming an important component of the antibiotic therapeutics. The production demand of therapeutic polypeptides is increasing and there is a significant interest in developing more efficient production processes. In pharmaceutical industries, polypeptides are produced as a crude mixture. Reverse phase high performance liquid chromatography (RP HPLC) is used as a typical separation technique to purify the target polypeptide from other impurities. Currently organic modifier gradients are used to elute product peptides separately from impurities. In this work, we add a second, simultaneous counter-ion gradient, in the hope of increasing separation performance and call it double gradient reverse phase chromatography. A general procedure of the model-based optimization of a polypeptide crude mixture purification process was followed to evaluate the effects of the double gradients on industrial chromatographic process. The target polypeptide elution profile was modeled with a bi-Langmuir adsorption equilibrium isotherm. The isotherm parameters of the target polypeptide were estimated by the inverse method. The model parameters of the impurities were regressed from experimental data. The variations of the isotherm parameters with the modifier concentration and counter-ion concentration were taken into account of the adsorption model. After model calibration and validation by comparison with suitable experimental data, Pareto optimization of the process were carried out to analyze the differences between single gradient chromatography and double gradient chromatography. It was observed that the additional linear gradient of counter-ion concentration did not improve the separation process. Conclusively we were able to demonstrate the concept of double gradient reverse phase chromatography within limited time and possible least experimental efforts

Understanding the formation of polytypes, stacking faults, and grain boundaries during crystallization of FAPbI3 perovskite

Control over morphological evolution is essential to make efficient, stable and reproducible perovskite electronics. In this letter, molecular dynamics simulations are performed to understand the crystallization of polytypes, stacking faults and grain boundaries of formamidinium lead iodide

Organic Spacers in 2D Perovskites: General Trends and Structure-Property Relationships from Computational Studies

Addition of large organic molecules to halide perovskites has been shown to provoke dimensionality reduction and formation of two-dimensional phases that demonstrate improved long-term stabilities. Optoelectronic properties of the resulting 2D layered perovskites are strongly influenced by the chemical nature of the additive molecules, which opens immense possibilities for preparation of materials with tailored properties. However, given the huge chemical space of possible organic spacers, a systematic and exhaustive search for optimal compounds is impossible and general structure-property relationships that could guide a rational design are still largely absent. Here, we provide an overview of a series of recent computational studies from our group on different types of spacers. We first develop a simplified universal monovalent cation model to map out approximate structural stability maps as a function of the van der Waals radius and the magnitude of dispersion interactions to monitor the possible emergence of 2D phases. We further provide structural and photophysical insights from classical and first-principles molecular dynamics simulations and density functional theory calculations on 2D hybrid perovskites based on a wide range of spacers with different chemical nature and varying conformational properties. Our computational predictions are validated through comparison with powder diffraction, conductivity and optical measurements. Such comparative study allows for providing some general structure-property correlations, which can serve as design guidelines in the search for optimal 2D and mixed 2D/3D perovskite photovoltaic materials

Atomistic Mechanism of the Nucleation of Methylammonium Lead Iodide Perovskite from Solution

In the ongoing intense quest to increase the performance of perovskite solar cells, optimizing the morphology of perovskite material has become imperative to achieve high power conversion efficiencies. Despite the fact that nucleation plays a key role in controlling the crystal morphology, very little is known about the nucleation and crystal growth processes. Here, we perform metadynamics simulations of nucleation of methylammonium lead triiodide (MAPI) in order to unravel the atomistic details of perovskite crystallization from a γ-butyrolactone solution. The metadynamics trajectories show that the nucleation process takes place in several stages. Initially, dense amorphous clusters mainly consisting of lead and iodide appear from the homogeneous solution. These clusters evolve into lead iodide (PbI2)-like structures. Subsequently, methylammonium (MA+) ions diffuse into these PbI2-like aggregates triggering the transformation into a perovskite crystal through a solid–solid transformation. These enticing results allowed us to design new experimental strategies to rationally control the dimensions of MAPI grains using the spin-coating technique and to engineer homogeneous nucleation and growth of MAPI single crystals. The experimental results amply support our unprecedented observations related to the critical role of monovalent cations in inducing the nucleation process in lead halide perovskites

Molecular Dynamics Simulations of Two-Step Process Enable Room-Temperature Synthesis of α-FAPbI3

It is well established that the lack of understanding the crystallization process in two-step sequential deposition has a direct impact on efficiency, stability and reproducibility of perovskite solar cells. Here, we try to understand the solid-solid phase transition occuring during two-step sequential deposition of methylammonium lead iodide and formamidinium lead iodide. Using metadynamics, X-ray diffraction and Raman spectroscopy, we reveal the microscopic details of this process. We find that the formation of perovskite proceeds through intermediate structures and report polymorphs found for methylammonium lead iodide and formamidinium lead iodide. From simulations, we discover a possible crystallization pathway for the highly efficient metastable α-phase of formamidinium lead iodide. Guided by these simulations, we perform experiments that results in the room temperature crystallization of α-formamidinium lead iodide

Unravelling the structural complexity and photophysical properties of adamantyl-based layered hybrid perovskites

Layered hybrid perovskites comprising adamantyl spacer (A) cations based on the A2FAn−1PbnI3n+1(n= 1-3, FA = formamidinium) compositions have recently been shown to act as promising materials for photovoltaic applications. While the corresponding perovskite solar cells show performances and stabilities that are superior in comparison to other layered two-dimensional formamidinium-based perovskite solar cells, the underlying reasons for their behaviour are not well understood. We provide a comprehensive investigation of the structural and photophysical properties of this unique class of materials, which is complemented by theoretical analysisviamolecular dynamics simulations and density functional theory calculations. We demonstrate the formation of well-defined structures of lower compositional representatives based onn= 1-2 formulations with (1-adamantyl)methanammonium spacer moieties, whereas higher compositional representatives (n> 2) are shown to consist of mixtures of low-dimensional phases evidenced by grazing incidence X-ray scattering. Furthermore, we reveal high photoconductivities of the corresponding hybrid perovskite materials, which is accompanied by long charge carrier lifetimes. This study thereby unravels features that are relevant for the performance of FA-based low-dimensional hybrid perovskites.ChemE/Opto-electronic MaterialsIndustrial Design EngineeringElectrical Engineering, Mathematics and Computer Scienc

Formamidinium-Based Dion-Jacobson Layered Hybrid Perovskites: Structural Complexity and Optoelectronic Properties

Layered hybrid perovskites have emerged as a promising alternative to stabilizing hybrid organic–inorganic perovskite materials, which are predominantly based on Ruddlesden-Popper structures. Formamidinium (FA)-based Dion-Jacobson perovskite analogs are developed that feature bifunctional organic spacers separating the hybrid perovskite slabs by introducing 1,4-phenylenedimethanammonium (PDMA) organic moieties. While these materials demonstrate competitive performances as compared to other FA-based low-dimensional perovskite solar cells, the underlying mechanisms for this behavior remain elusive. Here, the structural complexity and optoelectronic properties of materials featuring (PDMA)FAn–1PbnI3n+1 (n = 1–3) formulations are unraveled using a combination of techniques, including X-ray scattering measurements in conjunction with molecular dynamics simulations and density functional theory calculations. While theoretical calculations suggest that layered Dion-Jacobson perovskite structures are more prominent with the increasing number of inorganic layers (n), this is accompanied with an increase in formation energies that render n > 2 compositions difficult to obtain, in accordance with the experimental evidence. Moreover, the underlying intermolecular interactions and their templating effects on the Dion-Jacobson structure are elucidated, defining the optoelectronic properties. Consequently, despite the challenge to obtain phase-pure n > 1 compositions, time-resolved microwave conductivity measurements reveal high photoconductivities and long charge carrier lifetimes. This comprehensive analysis thereby reveals critical features for advancing layered hybrid perovskite optoelectronics.Accepted Author ManuscriptChemE/Opto-electronic Material