Effects of Coverage,Water, and Defects on Catechol/TiO2 Interface

Catechol adsorbed on TiO₂ is one of the simplest models to explore the relevant properties of dye-sensitized solar cells. However, the effects of water and defects on the electronic levels and the excitonic properties of the catechol/TiO₂ interface have been rarely explored. Here, we investigate four catechol/TiO₂ interfaces aiming to study the influence of coverage, water, and defects on the electronic levels and the excitonic properties of the catechol/TiO₂ interface through the first-principles many-body Green's function theory. We find that the adsorption of catechol on the rutile (110) surface increases the energies of both the TiO₂ valence band maximum and conduction band minimum by approximately 0.7 eV. The increasing coverage and the presence of water can reduce the optical absorption of charge-transfer excitons with maximum oscillator strength. Regarding the reduced hydroxylated TiO₂ substrate, the conduction band minimum decreases greatly, resulting in a sub-bandgap of 2.51 eV. The exciton distributions in the four investigated interfaces can spread across several unit cells, especially for the hydroxylated TiO₂ substrate. Although the hydroxylated TiO₂ substrate leads to a lower open-circuit voltage, it may increase the separation between photogenerated electrons and holes and may therefore be beneficial for improving the photovoltaic efficiency by controlling its concentration. Our results may provide guidance for the design of highly efficient solar cells in future.     

Adatom Defect Induced Spin Polarization of Asymmetric Structures

The spin polarization of carbon nanomaterials is crucial to design spintronic devices. In this paper, the first-principles is used to study the electronic properties of two defect asymmetric structures, Cap-(9, 0)-Def [6, 6] and Cap-(9, 0)-Def [5, 6]. We found that the ground state of Cap-(9, 0)-Def [6, 6] is sextet and the ground state of Cap-(9, 0)-Def [5, 6] is quartet, and the former has a lower energy. In addition, compared with Cap-(9, 0) CNTs, the C adatom on C₃₀ causes spin polarization phenomenon and Cap-(9, 0)-Def [6, 6] has more spin electrons than Cap-(9, 0)-Def [5, 6] structure. Moreover, different adsorb defects reveal different electron accumulation. This finding shows that spin polarization of the asymmetric structure can be adjusted by introducing adatom defects.     

Effect of selected dopants on conductivity and moisture stability of Li3PS4 sulfide solid electrolyte: a first-principles study

The first principle computational screening was performed to investigate the effect of selected dopants for Li₃PS₄ sulfide solid electrolyte on its ionic conductivity and stability toward moisture. The results suggest that substitution P⁵⁺ using isovalent cations whose electronegativity (EN) value is closer to the value of S has more significant effects on the ionic conductivity, whereby W⁵⁺ and Sb⁵⁺ can improve most. Similarly, aliovalent cation substitutions with compensating changes in the lithium-ion concentration, particularly those with a lower oxidation state and higher EN, such as Cu²⁺, effectively enhance the lithium-ion conductivity in this structure. For cation dopants, it is found that ionic conductivity improvement of Li₃PS₄ is the synergetic effect of EN and oxidation number of the dopant as well as the material's lattice parameter change. Oxides of the considered cation dopants can also improve the ionic conductivity of the material but have much lower lithium-ion conductivity than the cases of cation dopants. However, the metal oxide dopants, particularly those derived from soft Lewis' acid cations, show a marginal improvement in moisture stability of the Li₃PS₄ electrolyte. The effect of halides and metal halide dopants on the lithium-ion conductivity and moisture stability of Li₃PS₄ electrolyte are also studied. It is found that metal halides are more effective than any other dopants in improving the ionic conductivity of Li₃PS₄.     

Adsorption of Volatile Organic Compounds (VOCs) on Oxygen-rich Porous Carbon Materials Obtained from Glucose/Potassium Oxalate

To investigate the effects of oxygen-containing functional groups on the adsorption of volatile organic compounds (VOCs) with different polarity, oxygen-rich porous carbon materials (OPCs) were synthesized by heat treatment of glucose/potassium oxalate material. The carbon material had a large specific surface area (1697 m² g⁻¹) and a high oxygen content (18.95 at.%). OPC exhibited high adsorption capacity of toluene (309 mg g⁻¹) and methanol (447 mg g⁻¹). The specific surface area and total pore volume determined the adsorption capacity of toluene and methanol at the high-pressure range, while the oxygen-containing groups became the main factor affecting the methanol adsorption at the low-pressure range due to the hydrogen bond interaction through the density functional theory (DFT) calculations. This study provides an important hint for developing a novel O-doped adsorbent for the VOCs adsorption applications and analyzing the role of oxygen-containing groups in the VOCs adsorption under the low-pressure range.     

Phosphorene Supported Single-Atom Catalysts for CO Oxidation: A Computational Study

Single-atom catalysts (SACs) have attracted extensive attention owing to their high catalytic activity. The development of efficient SACs is crucial for applications in heterogeneous catalysis. In this article, the geometric configuration, electronic structure, stabilitiy and catalytic performance of phosphorene (Pn) supported single metal atoms (M=Ru, Rh, Pd, Ir, Pt, and Au) have been systematically investigated using density functional theory calculations and ab initio molecular dynamics simulations. The single atoms are found to occupy the hollow site of phosphorene. Among the catalysts studied, Ru-decorated phosphorene is determined to be a potential catalyst by evaluating adsorption energies of gaseous molecules. Various mechanisms including the Eley-Rideal (ER), Langmuir-Hinshelwood (LH) and trimolecular Eley-Rideal (TER) mechanisms are considered to validate the most favourable reaction pathway. Our results reveal that Ru−Pn exhibits outstanding catalytic activity toward CO oxidation reaction via TER mechanism with the corresponding rate-determining energy barrier of 0.44 eV, making it a very promising SAC for CO oxidation under mild conditions. Overall, this work may provide a new avenue for the design and fabrication of two-dimensional materials supported SACs for low-temperature CO oxidation.     

Monolayer 1T and 1T′ MoSO as Promising Electrocatalyst for Hydrogen Evolution based on First Principle Calculations

Molybdenum disulfide (MoS₂) has been regarded as one of the most promising candidates for replacing Pt group noble metals as an efficient electrocatalyst to enhance the hydrogen evolution reaction (HER) in consideration of its relatively high earth abundance. Recent studies show that the catalytic efficiency of MoS₂ for HER can be promoted by the presence of 1T-phase MoS₂. It is hard to precisely control the formation of 1T-MoS₂, however, due to its metastability relative to 2H-MoS₂. Elevating the stability of 1T phase allotrope is therefore of great importance and could be realized by replacing divalent S with monovalent elements or groups according to crystal field theory, which has been demonstrated through our first-principles density functional theory (DFT) calculation results. Differential Gibbs free energy analysis for hydrogen adsorption (ΔG_H*) suggest that 1T and 1T′ MoSO (O doped MoS₂) might be taken as potential candidate catalysts for HER process with better performance than 1T and 1T′ MoS₂. We also propose a probable approach to synthesize 1T and 1T′ MoSO under oxidation circumstance environment of graphene oxide.     

Reduction of Dimerization Tendency Due to the Decrease in Hybridization Index by Inclusion of 4s and 4p Semicore States as Valence States in Mon (n=2-18) Clusters: A First-Principles Study

Owing to the unique structural, electronic, and physico-chemical properties, molybdenum clusters are expected to play an important role in future nanotechnologies. However, their ground states are still under debate. In this study, the crystal structure analysis by particle swarm optimization (CALYPSO) approach is used for the global minimum search, which is followed by first-principles calculations, to detect an obvious dimerization tendency in Mo\begin{document}$ _n $\end{document} (\begin{document}$ n $\end{document} = 2\begin{document}$ - $\end{document}18) clusters when the 4s and 4p semicore states are not regarded as the valence states. Further, the clusters with even number of atoms are usually magic clusters with high stability. However, after including the 4s and 4p electrons as valence electrons, the dimerization tendency exhibits a drastic reduction because the average hybridization indices \begin{document}$ H_{ \rm{sp}} $\end{document}, \begin{document}$ H_{ \rm{sd}} $\end{document}, and \begin{document}$ H_{ \rm{pd}} $\end{document} are reduced significantly. Overall, this work reports new ground states of Mo\begin{document}$ _n $\end{document} (\begin{document}$ n $\end{document} = 11, 14, 15) clusters and proves that semicore states are essential for Mo\begin{document}$ _n $\end{document}     

Monitoring of the Pre-Equilibrium Step in the Alkyne Hydration Reaction Catalyzed by Au(III) Complexes: A Computational Study Based on Experimental Evidences

The coordination ability of the [(ppy)Au(IPr)]²⁺ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl⁻, BF₄⁻, OTf⁻, H₂O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF₄⁻ and OTf⁻ have very similar coordination ability towards [(ppy)Au(IPr)]²⁺ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]²⁺ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]²⁺ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf⁻ and BF₄⁻, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H₂O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts.