Effects of oxygen pressure on the morphology and surface energetics of ß-PbO2: insight from DFT calculations.

For over a century, lead dioxide (PbO2) has been investigated in lead-acid batteries and extensively utilized in a variety of applications. Identifying the surface properties and equilibrium morphology of ß-PbO2 (rutile phase) particles is mandatory for industrial utilization and surface engineering. Using density-functional calculations within the generalized gradient approximation revised for solids (PBEsol), we investigate a variety of surface properties of ß-PbO2. The surface energies of low-Miller-index stoichiometric surfaces are firstly determined, and the (110) surface is found to be the most thermodynamically stable. The relative energetics of these surfaces are represented by a Wulff construction which shows an acicular shape, mostly dominated by the (110) and (100) surfaces. Besides, we investigate the surface chemistry of ß-PbO2 under reduction and oxidation conditions as a function of oxygen pressure, finding that most surfaces except for (100) and (110) are likely to be oxidized. Under oxygen pressure at 1 atm and oxygen-rich limit, the (101) surface is the most thermodynamically stable, dominating the Wulff construction with pyramidal shapes. Our results indicate that the growth conditions that cause non-stoichiometry of the surface could modify the equilibrium Wulff shape of ß-PbO2. Our predicted Wulff shapes and dominant facets agree with the experimental results in which the pyramidal shape of the ß-PbO2 grains has often been observed with the (101) preferred orientation.

The role of native point defects and donor impurities in the electrical properties of ZnSb2O4: a hybrid density-functional study.

The ceramic material zinc antimony oxide ZnSb2O4 has promising electrical and magnetic properties, making it suitable for various applications such as electrochemical and energy storage. However, the effects of point defects and impurities on its electrical properties have never been revealed. Here, we employ hybrid density-functional calculations to investigate the energetics and electronic properties of native point defects and donor impurities in ZnSb2O4. The energetically favorable configurations of native point defects under selected growth conditions (O-rich and O-poor) are identified based on the calculated formation energies. The study finds no shallow donor and shallow acceptor defects with low formation energies. Still, the oxygen vacancy (VO) has the lowest formation energy among the donor-type defects under O-rich and O-poor conditions. However, it acts as a very deep acceptor, making it unlikely to provide free electron carriers to the conduction band. Moreover, electron carriers are likely to be compensated by the formation of zinc vacancies (VZn) and the zinc substituted for antimony (ZnSb), which behave as dominant acceptors. Our analysis of the charge neutrality conditions estimates that the Fermi level of undoped ZnSb2O4 would be pinned in a range that is 2.60 eV to 3.12 eV above the VBM for O-rich to O-poor growth conditions, respectively, suggesting that this material is semi-insulating. The possibility of enhancing free electron carriers by doping with Al, Ga, In, and F impurities is also investigated. Our results, however, indicate that high n-type conductivity is hindered by self-compensation in which the impurities additionally act as electron killers. Our results suggest that other impurity candidates and approaches may need to be considered to efficiently dope this material into n-type. Overall, this work paves the way for point defect engineering in this class of ternary oxides.

Towards a new packing pattern of Li adsorption in two-dimensional pentagonal BCN.

Two-dimensional (2D) materials with a penta-atomic-configuration, such as penta-graphene and penta-B2C, have received great attention as anodes in Li-ion batteries (LIBs). Recently, penta-BCN has been demonstrated to exhibit the highest theoretical capacity to date of 2183 mA h g-1, corresponding to the composition Li3BCN. Herein, we study the layer-by-layer Li adsorption on penta-BCN by explicitly and comprehensively considering its structure. We discover a new, more energetically favorable Li adsorption site that is distinct from the latest report by Chen et al. (Phys. Chem. Chem. Phys., 2021, 23, 17693). The possible migration pathway and the accompanying activation energy are also investigated. Full lithium adsorption leads to the formula Li2BCN and the reduced theoretical capacity of 1455 mA h g-1. Still, penta-BCN exhibits metallic conductivity during Li adsorption, and has a low open-circuit voltage, and a low ion-diffusion barrier, all being beneficial for anode materials. These observations imply that penta-BCN remains one of the most effective anode materials for LIBs with a quick charge/discharge rate.

Potential usage of biosynthesized zinc oxide nanoparticles from mangosteen peel ethanol extract to inhibit Xanthomonas oryzae and promote rice growth.

In recent decades, the biosynthesis of nanoparticles using biological agents, such as plant extracts, has grown in popularity due to their environmental and economic benefits. Therefore, this study investigated into utilizing ethanol crude extract sourced from mangosteen peel for the synthesis of zinc oxide nanoparticles (ZnO NPs) and assessing their efficacy against the rice blight pathogen (Xanthomonas oryzae pv. oryzae) through antibacterial evaluations. Additionally, the effects of the synthesized ZnO NPs on rice plant growth was investigated. The X-ray diffraction analysis revealed the production of wurtzite ZnO NPs under specific synthesis conditions, exhibiting a crystallite size of 38.71 nm (or 387.122 Å) without any contamination. Analysis of the ultraviolet-visible optical absorption spectrum indicated a characteristic absorption peak at 363 nm, suggesting a calculated band gap energy of 2.88 eV for the ZnO NPs. Furthermore, Fourier transform infrared spectroscopy analysis confirmed the presence of active compounds functional groups from mangosteen peel in the synthesized ZnO NPs. These biosynthesized ZnO NPs demonstrated significant inhibition of X. oryzae pv. oryzae growth, exhibiting an in vitro 50 % inhibitory concentration (IC50) value of 1.895 mg/mL and a minimum inhibitory concentration (MIC) value of 4 mg/mL. The ZnO NPs treatments at two-fold IC50 values significantly enhanced root length, dry biomass, and chlorophyll a content in rice plants. Consequently, the results demonstrated the potential application of biosynthesized ZnO NPs from mangosteen peel extract in green agriculture, as an alternative to excessive antibiotic use, for combating bacterial plant diseases, and for enhancing plant growth.

Ternary pentagonal BXN (X = C, Si, Ge, and Sn) sheets with high piezoelectricity.

The discovery of new and stable two-dimensional pentagonal materials with piezoelectric properties is essential for technological advancement. Inspired by recently reported piezoelectric materials penta-BCN and penta-BSiN, we proposed penta-BGeN and penta-BSnN as new members of the penta-family based on first-principles calculations. Comprehensive analyses indicated that both penta-BGeN and penta-BSnN are thermodynamically, dynamically, mechanically, and thermally stable. In terms of mechanical stability, the elastic constant decreased as lower elements in group 4A of the periodic table were used. Therefore, penta-BGeN and penta-BSnN are softer than penta-BCN and penta-BSiN. In terms of piezoelectric properties, piezoelectric stress and strain tensors increase following the same pattern. In group 4A, penta-BSnN had the highest intrinsic piezoelectricity, especially the e 22 piezoelectric stress. Typically, the piezoelectric strain d ij coefficient increases with material softness; penta-BSnN possessed the highest d ij . Thus, due to its inherent piezoelectricity, penta-BSnN has tremendous potential as a nanoscale piezoelectric material.

XAS study on copper red in ancient glass beads from Thailand.

Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.

Structure of the hydrated Ca(2+) and Cl(-): Combined X-ray absorption measurements and QM/MM MD simulations study.

A combination of X-ray absorption spectroscopy (XAS) measurements and quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations has been applied to elucidate detailed information on the hydration structures of Ca(2+) and Cl(-). The XAS spectra (extended X-ray absorption fine structure, EXAFS, and X-ray absorption near-edge structure, XANES) measured from aqueous CaCl(2) solution were analyzed and compared to those generated from snapshots of QM/MM MD simulations of Ca(2+) and Cl(-) in water. With regard to this scheme, the simulated QM/MM-EXAFS and QM/MM-XANES spectra, which correspond to the local structure and geometrical arrangement of the hydrated Ca(2+) and Cl(-) at molecular level show good agreement with the experimentally observed EXAFS and XANES spectra. From the analyses of the simulated QM/MM-EXAFS spectra, the hydration numbers for Ca(2+) and Cl(-) were found to be 7.1 +/- 0.7 and 5.1 +/- 1.3, respectively, compared to the corresponding values of 6.9 +/- 0.7 and 6.0 +/- 1.7 derived from the measured EXAFS data. In particular for XANES results, it is found that ensemble averages derived from the QM/MM MD simulations can provide reliable QM/MM-XANES spectra, which are strongly related to the shape of the experimental XANES spectra. Since there is no direct way to convert the measured XANES spectrum into details relating to geometrical arrangement of the hydrated ions, it is demonstrated that such a combined technique of XAS experiments and QM/MM MD simulations is well-suited for the structural verification of aqueous ionic solutions.

Author Correction: Stacking stability of C2N bilayer nanosheet.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Energetics and optical properties of carbon impurities in rutile TiO2.

Titanium dioxide is one of the most promising materials for many applications such as photovoltaics and photocatalysis. Non-metal doping of TiO2 is widely used to improve the photoconversion efficiency by shifting the absorption edge from the UV to visible-light region. Here, we employ hybrid density-functional calculations to investigate the energetics and optical properties of carbon (C) impurities in rutile TiO2. The predominant configurations of the C impurities are identified through the calculated formation energies under O-poor and O-rich growth conditions. Under the O-poor condition, we find that C occupying the oxygen site (CO) is energetically favorable for Fermi-level values near the conduction band minimum (n-type TiO2), and acts as a double acceptor. Under the O-rich condition, the Ci-VTi complex is energetically favorable, and is exclusively stable in the neutral charge state. We also find that interstitial hydrogen (Hi) can bind to CO, forming a CO-Hi complex. Our results suggest that CO and CO-Hi are a cause of visible-light absorption under oxygen deficient growth conditions.

Utilization of Cratoxylum formosum crude extract for synthesis of ZnO nanosheets: Characterization, biological activities and effects on gene expression of nonmelanoma skin cancer cell.

Cratoxylum formosum Dyer is a medicinal plant widely found in Asia and commonly consumed for food and folk medicine. It is rich in phenolic compounds. The present study utilized water crude extract of C. formosum leaves to synthesize zinc oxide nanoparticles (ZnO NPs) by green synthesis. The synthesized ZnO NPs with the average electronic band gap ∼3  eV were obtained and found to either have spherical shape or sheet-like structures depending on synthesis process and concentration of crude extract. Higher concentration of C. formosum extract also eliminates impurity of Zn(OH)2 during the synthesis. Results from an agar disk diffusion assay demonstrated that all synthesized ZnO samples inhibited growth of Gram-positive bacteria, Bacillus subtilis and Staphylococcus epidermidis and Gram-negative bacterium, Escherichia coli. Furthermore, all synthesized ZnO demonstrated potent anti-cancer activity against non-melanoma skin cancer cells (A431) and the intermediary of cancerous keratinocytes (HaCaT) without affecting normal cell lines (Vero). In addition, we observed that the ZnO nanosheet offered stronger cytotoxicity effects against A431 than spherical shaped ZnO particles. Analysis of RNA-sequencing data revealed that synthesized ZnO nanosheets altered the number of genes in pathways involved in cancer and MAPK signaling pathways in A431 cells. Several isoforms of metallothionein transcripts were upregulated including transcripts involved in inflammatory responses whereas transcripts promoted cell proliferation and apoptosis were downregulated. Therefore, these studies firstly reported potential usage of the green-synthesized ZnO nanosheets from C. formosum extract for development of antibacterial substances or anticancer drugs.

Stacking stability of C2N bilayer nanosheet.

In recent years, a 2D graphene-like sheet: monolayer C2N was synthesized via a simple wet-chemical reaction. Here, we studied the stability and electronic properties of bilayer C2N. According to a previous study, a bilayer may exist in one of three highly symmetric stacking configurations, namely as AA, AB and AB'-stacking. For the AA-stacking, the top layer is directly stacked on the bottom layer. Furthermore, AB- and AB'-stacking can be obtained by shifting the top layer of AA-stacking by a/3-b/3 along zigzag direction and by a/2 along armchair direction, respectively, where a and b are translation vectors of the unit cell. By using first-principles calculations, we calculated the stability of AA, AB and AB'-stacking C2N and their electronic band structure. We found that the AB-stacking is the most favorable structure and has the highest band gap, which appeared to agree with previous study. Nevertheless, we furthermore examine the energy landscape and translation sliding barriers between stacking layers. From energy profiles, we interestingly found that the most stable positions are shifted from the high symmetry AB-stacking. In electronic band structure details, band characteristic can be modified according to the shift. The interlayer shear mode close to local minimum point was determined to be roughly 2.02 × 1012 rad/s.