DFT Investigations of Aun Nano-Clusters Supported on TiO2 Nanotubes: Structures and Electronic Properties.

TiO2 nanotubes (TiO2NTs) are beneficial for photogenerated electron separation in photocatalysis. In order to improve the utilization rate of TiO2NTs in the visible light region, an effective method is to use Aun cluster deposition-modified TiO2NTs. It is of great significance to investigate the mechanism of Aun clusters supported on TiO2NTs to strengthen its visible-light response. In this work, the structures, electronic properties, Mulliken atomic charge, density of states, band structure, and deformation density of Aun (n = 1, 8, 13) clusters supported on TiO2NTs were investigated by DMOL3. Based on published research results, the most stable adsorption configurations of Aun (n = 1, 8, 13) clusters supported with TiO2NTs were obtained. The adsorption energy increased as the number of Au adatoms increased linearly. The Aun clusters supported on TiO2NTs carry a negative charge. The band gaps of the three most stable structures of each adsorption system decreased compared to TiO2NTs; the valence top and the conduction bottom of the Fermi level come mainly from the contribution of 5d and 6s-Au. The electronic properties of the 5d and 6s impurity orbitals cause valence widening and band gap narrowing.

An Unsymmetric Salamo-like Chemosensor for Fuorescent Recognition of Zn2.

A new unsymmetric tetradentate salamo-like chemical sensor H2L for fluorescent recognition of Zn2+ has been designed and synthesized. The sensor can recognize Zn2+ from other metal ions examined with selectivity, anti-interference, reliability and high sensitivity (LOD = 1.89 × 10-6 M) in ethanol/H2O solution. The results of UV-Vis and fluorescent spectra analyses, X-ray crystallographic study and DMol3 simulation and calculation (on Materials Studio) indicate that the chelation-enhanced fluorescence (CHEF) recognition mechanism of the sensor H2L for Zn2+ is of its hindered PET process. The sensor H2L for Zn2+ has excellent fluorescence characteristics and has potential application value in biological and environmental systems.

Molecular level unveils anion exchange membrane fouling induced by natural organic matter via XDLVO and molecular simulation.

Membrane fouling, critically determined by the interplay of interfacial interaction between foulant and membrane, is a critical impediment that limits application extension of electrodialysis (ED) process. In this study, the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) model and molecular simulation were performed to quantify the interaction energy barrier for revealing anion exchange membranes (AEMs) fouling mechanisms of calcium ions coexisted with natural organic matter (NOM) (sodium alginate, humic acid, and bovine serum albumin). The insight gained from DMol3 module was also utilized to interpret the adhesion process of NOM at the molecular level. The interaction energy suggested that the presence of Ca-NOM complex magnify the adhesion on the surface cavities of AEMs structures. The molecular simulation and XDLVO presented a good agreement in predicting the fouling trajectory based on the experimental findings. The short-path acid-base interaction exerted a predominant influence on exploring the fouling formation process. In addition, the sodium alginate displayed more stable adhesion behavior through calcium ions bridges stimuli than humic acid and bovine serum albumin. In particular, the molecular simulation calculations exhibited a superior level of concurrence with colloid growth of membrane fouling. Combined XDLVO theory with DMol3 model proposed a new approach to understand membrane fouling mechanisms in ED process.

Study of the structural characteristics, optical properties, and electrical conductivity of doped [P(An-MMa)/ZrO2]TF nanofiber composite using experimental data and TD-DFT/DMol3 computations.

The powder form of the new nanofiber composite of poly(acrylonitrile-co-methylmethacrylate) (P(An-MMa)) with zirconium dioxide (ZrO2) was synthesized using the sol-gel method and subsequently converted to a thin film [P(An-MMa)/ZrO2]TF via the physical vapor deposition (PVD) technique. Numerous characterization techniques, including Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and ultraviolet-visible (UV-Vis) optical spectroscopy, were used to characterize [P(An-MMa)/ZrO2]TF. Additionally, using density functional theory (DFT), optimization via time-dependent density functional theory (TD-DFT/DMol3) and Cambridge Serial Total Energy Bundle (TD-DFT/CASTEP) was developed. The TD-DFT calculations accurately matched the observed XRD and Raman spectra and validated the molecular structure of the examined materials. The average crystallite size of [P(An-MMa)/ZrO2]TF, as determined by XRD calculations, is 171.04 nm. The SEM image depicts a one-dimensional morphological structure made up of tightly packed fibrous nanowires or brushes. The optical properties of the films were determined using optical absorbance spectrophotometric results in the 200-850-nm wavelength range. The optical energy bandgaps computed using Tauc's equation for [P(An-MMa)/ZrO2]TF are 2.352 and 2.253 eV, respectively, whereas the isolated molecule of the composite [P(An-MMa)/ZrO2]Iso has a bandgap of 2.415 eV as determined by TD-DFT/DMol3. The optical characteristics predicted by CASTEP in TD-DFT are in good agreement with the experimental values. The investigated large optical energy bandgap nanofiber composite is advantageous for some energy storage applications.

Formation of a Key Intermediate Complex Species in Catalytic Hydrolysis of NH3BH3 by Bimetal Clusters: Metal-Dihydride and Boron-Multihydroxy.

The hydrolysis of AB (AB, NH3BH3) with the help of transition metal catalysts has been identified as one of the promising strategies for the dehydrogenation in numerous experiments. Although great progress has been achieved in experiments, evaluation of the B-N bond cleavage channel as well as the hydrogen transfer channel has not been performed to gain a deep understanding of the kinetic route. Based on the density functional theory (DFT) calculation, we presented a clear mechanistic study on the hydrolytic reaction of AB by choosing the smallest NiCu cluster as a catalyst model. Two attacking types of water molecules were considered for the hydrolytic reaction of AB: stepwise and simultaneous adsorption on the catalyst. The Ni and Cu metal atoms play the distinctive roles in catalytic activity, i.e., Ni atom takes reactions for the H2O decomposition with the formation of [OH]- group whereas Cu atom takes reactions for the hydride transfer with the formation of metal-dihydride complex. The formation of Cu-dihydride and B-multihydroxy complex is the prerequisite for the effectively hydrolytic dehydrogenation of AB. By analyzing the maximum barrier height of the pathways which determines the kinetic rates, we found that the hydride hydrogen transferring rather than the N-B bond breaking is responsible to the experimentally measured activation energy barrier.

Insight into the gas phase dissociation of CF3CH2I and its reactions with H and OH by first principles.

The Arrhenius kinetic parameters of dissociation reactions and reactions of CF3CH2I with radicals like H, O, and OH are determined using highly accurate first principles calculations. Thermophysical properties like molar heat capacity (Cp), thermal stability index, and the bond dissociation energies are also determined for the CF3CH2I molecule under the PBE/DNP formalism. Since, there are no theoretical study or experimental investigation reports available regarding the dissociation reactions of CF3CH2I and reactions of this molecule with the H and OH radical, a parallel comparative analysis is done with similar iodoalkanes to ascertain the precision of the results obtained. The atmospheric lifetime of 0.54 years is obtained for this molecule.

Vibrational spectroscopy of the double complex salt Pd(NH3)4(ReO4)2, a bimetallic catalyst precursor.

Tetraamminepalladium(II) perrhenate, a double complex salt, has significant utility in PdRe catalyst preparation; however, the vibrational spectra of this readily prepared compound have not been described in the literature. Herein, we present the infrared (IR) and Raman spectra of tetraamminepalladium(II) perrhenate and several related compounds. The experimental spectra are complemented by an analysis of normal vibrational modes that compares the experimentally obtained spectra with spectra calculated using DFT (DMol3). The spectra are dominated by features due to the ammine groups and the ReO stretch in Td ReO4-; lattice vibrations due to the D4h Pd(NH3)42+ are also observed in the Raman spectrum. Generally, we observe good agreement between ab initio calculations and experimental spectra. The calculated IR spectrum closely matches experimental results for peak positions and their relative intensities. The methods for calculating resonance Raman intensities are implemented using the time correlator formalism using two methods to obtain the excited state displacements and electron-vibration coupling constants, which are the needed inputs in addition to the normal mode wave numbers. Calculated excited state energy surfaces of Raman-active modes correctly predict relative intensities of the peaks and Franck-Condon activity; however, the position of Raman bands are predicted at lower frequencies than observed. Factor group splitting of Raman peaks observed in spectra of pure compounds is not predicted by DFT.

Theoretical Study on Free Fatty Acid Elimination Mechanism for Waste Cooking Oils to Biodiesel over Acid Catalyst.

A theoretical investigation on the esterification mechanism of free fatty acid (FFA) in waste cooking oils (WCOs) has been carried out using DMol(3) module based on the density functional theory (DFT). Three potential pathways of FFA esterification reaction are designed to achieve the formation of fatty acid methyl ester (FAME), and calculated results show that the energy barrier can be efficiently reduced from 88.597kcal/mol to 15.318kcal/mol by acid catalyst. The molar enthalpy changes (ΔrHm°) of designed pathways are negative, indicating that FFA esterification reaction is an exothermic process. The obtained favorable energy pathway is: H(+) firstly activates FFA, then the intermediate combines with methanol to form a tetrahedral structure, and finally, producing FAME after removing a water molecule. The rate-determining step is the combination of the activated FFA with methanol, and the activation energy is about 11.513kcal/mol at 298.15K. Our results should provide basic and reliable theoretical data for further understanding the elimination mechanism of FFA over acid catalyst in the conversion of WCOs to biodiesel products.