Insights into Coke Formation and Removal under Operating Conditions with a Quantum Nanoreactor Approach.

The in situ formation and removal of coke is a critical problem in heterogeneous catalysis, but its mechanism is not well understood. This work investigates the mechanism of carbon deposition and hydrogenation on an Fe cluster under high-temperature conditions with the density functional tight-binding (DFTB) based nanoreactor molecular dynamics (NMD) method. Our study shows that successive formation of carbon chains, rings, and fused rings occurred during the carbon deposition on Fe clusters. Hydrogenation of activated carbon happens through direct C-H coupling, while the hydrogenation of graphitic carbon involves hydrogenation of the edge carbon, ring-opening reaction, and dealkylation reaction. The main function of the Fe catalyst is to provide the active sites for H2 dissociation and dissociated H spillover, while its activity toward C-C bond breaking is limited. These results highlight the role of the DFTB-NMD method as an effective tool to investigate reaction mechanisms under operating conditions in heterogeneous catalysis.

First-Principles Characterization and Experimental Validation of the Solid-Solid Interface in a Novel Organosulfur Cathode for the Li-S Battery.

Organosulfur silanes grafted on an aluminum current collector have been proposed and demonstrated to function as a sulfur source in the cathode for a lithium-sulfur (Li-S) battery. Bis[3-(triethoxysilyl)propyl]disulfide silane (TESPD) and bis[3-(triethoxysilyl)propyl]tetrasulfide silane (TESPT) are typical examples of organosulfur complexes used for the study. These organosulfur silanes act as an insulator. Formation of polysulfides (Li2Sx), which is a major bottleneck in the case of elemental sulfur, can be eliminated using this novel cathode. In the absence of charge-carrying polysulfide species, the role of insulating TESPD/TESPT in the charge conduction pathway is an open question. Insight into the interface between the Al current collector and grafted TESPD/TESPT at an atomic level is a prerequisite for addressing the charge conduction pathway. The systematic theoretical methodology is developed based on electronic structure calculations and ab initio molecular dynamics simulations to propose the realistic cathode model (hydration environment) for the Li-S battery. A cluster model is developed to predict the reduction potentials of TESPD/TESPT disclosing the reduction reaction with Li, resulting in the intramolecular S-S bond breaking which is validated by experimental cyclic voltammetry measurements. A realistic cathode model between the aluminum current collector and TESPD/TESPT is also proposed to mimic the experimental conditions where the Al surface was exposed to O2 and H2O. The top few layers of Al are transformed into α-Al2O3 and covered with H2O molecules in the vicinity of grafted TESPD/TESPT. The structural models are further validated by comparing simulated S 2p binding energies with experimental X-ray photoelectron spectroscopy studies.

Thermal Boundary Characteristics of Homo-/Heterogeneous Interfaces.

The interface of two solids in contact introduces a thermal boundary resistance (TBR), which is challenging to measure from experiments. Besides, if the interface is reactive, it can form an intermediate recrystallized or amorphous region, and extra influencing phenomena are introduced. Reactive force field Molecular Dynamics (ReaxFF MD) is used to study these interfacial phenomena at the (non-)reactive interface. The non-reactive interfaces are compared using a phenomenological theory (PT), predicting the temperature discontinuity at the interface. By connecting ReaxFF MD and PT we confirm a continuous temperature profile for the homogeneous non-reactive interface and a temperature jump in case of the heterogeneous non-reactive interface. ReaxFF MD is further used to understand the effect of chemical activity of two solids in contact. The selected Si/SiO 2 materials showed that the TBR of the reacted interface is two times larger than the non-reactive, going from 1 . 65 × 10 - 9 to 3 . 38 × 10 - 9 m 2 K/W. This is linked to the formation of an intermediate amorphous layer induced by heating, which remains stable when the system is cooled again. This provides the possibility to design multi-layered structures with a desired TBR.

Reactive force field development for magnesium chloride hydrates and its application for seasonal heat storage.

MgCl2 hydrates are considered as high-potential candidates for seasonal heat storage materials. These materials have high storage capacity and fast dehydration kinetics. However, as a side reaction to dehydration, hydrolysis may occur. Hydrolysis is an irreversible reaction, which produces HCl gas thus affecting the durability of heat storage systems. In this study, we present the parameterization of a reactive force field (ReaxFF) for MgCl2 hydrates to study the dehydration and hydrolysis kinetics of MgCl2·H2O and MgCl2·2H2O. The ReaxFF parameters have been derived by training against quantum mechanics data obtained from Density Functional Theory (DFT) calculations consisting of bond dissociation curves, angle bending curves, reaction enthalpies, and equation of state. A single-parameter search algorithm in combination with a Metropolis Monte Carlo algorithm is successfully used for this ReaxFF parameterization. The newly developed force field is validated by examining the elastic properties of MgCl2 hydrates and the proton transfer reaction barrier, which is important for the hydrolysis reaction. The bulk moduli of MgCl2·H2O and MgCl2·2H2O obtained from ReaxFF are in close agreement with the bulk moduli obtained from DFT. A barrier of 20.24 kcal mol(-1) for the proton transfer in MgCl2·2H2O is obtained, which is in good agreement with the barrier (19.55 kcal mol(-1)) obtained from DFT. Molecular dynamics simulations using the newly developed ReaxFF on 2D-periodic slabs of MgCl2·H2O and MgCl2·2H2O show that the dehydration rate increases more rapidly with temperature in MgCl2·H2O than in MgCl2·2H2O, in the temperature range 300-500 K. The onset temperature of HCl formation, a crucial design parameter in seasonal heat storage systems, is observed at 340 K for MgCl2·H2O, which is in agreement with experiments. The HCl formation is not observed for MgCl2·2H2O. The diffusion coefficient of H2O through MgCl2·H2O is lower than through MgCl2·2H2O, and can become a rate-limiting step. The diffusion coefficient increases with temperature and follows the Arrhenius law both for MgCl2·H2O and MgCl2·2H2O. These results indicate the validity of the ReaxFF approach for studying MgCl2 hydrates and provide important atomistic-scale insight of reaction kinetics and H2O transport in these materials.

A DFT-based comparative equilibrium study of thermal dehydration and hydrolysis of CaCl2 hydrates and MgCl2 hydrates for seasonal heat storage.

Salt hydrates store solar energy in chemical form via a reversible dehydration-hydration reaction. However, as a side reaction to dehydration, hydrolysis (HCl formation) may occur in chloride based salt hydrates (specially in MgCl2 hydrates), affecting the durability of the storage system. The mixture of CaCl2 and MgCl2 hydrates has been shown experimentally to have exceptional cycle stability and improved kinetics. However, the optimal operating conditions for the mixture are unknown. To understand the appropriate balance between dehydration and hydrolysis kinetics in the mixtures, it is essential to gain in-depth insight into the mixture components. We present a GGA-DFT level study to investigate the various gaseous structures of CaCl2 hydrates and to understand the relative stability of their conformers. The hydration strength and relative stability of conformers are dominated by electrostatic interactions. A wide network of intramolecular homonuclear and heteronuclear hydrogen bonds is observed in CaCl2 hydrates. Equilibrium product concentrations are obtained during dehydration and hydrolysis reactions under various temperature and pressure conditions. The trend of the dehydration curve with temperature in CaCl2 hydrates is similar to the experiments. Comparing these results to those of MgCl2 hydrates, we find that CaCl2 hydrates are more resistant towards hydrolysis in the temperature range of 273-800 K. Specifically, the present study reveals that the onset temperatures of HCl formation, a crucial design parameter for MgCl2 hydrates, are lower than for CaCl2 hydrates except for the mono-hydrate.

Methane and carbon dioxide adsorption on edge-functionalized graphene: a comparative DFT study.

With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO(2) and CH(4) to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH(2), H(2)PO(3), NO(2), and CH(3). Although different choices for the exchange-correlation functional lead to a spread of values for the binding energy, trends across the functional groups are largely preserved for each choice, as are the final orientations of the adsorbed gas molecules. We find binding of CO(2) to exceed that of CH(4) by roughly a factor of two. However, the two gases follow very similar trends with changes in the attached functional group, despite different molecular symmetries. Our results indicate that the presence of NH(2), H(2)PO(3), NO(2), and COOH functional groups can significantly enhance gas binding, making the edges potentially viable binding sites in materials with high concentrations of edge carbons. To first order, in-plane binding strength correlates with the larger permanent and induced dipole moments on these groups. Implications for tailoring carbon structures for increased gas uptake and improved CO(2)/CH(4) selectivity are discussed.