Structural, electronic, optical, elastic, thermodynamic and thermal transport properties of Cs2AgInCl6 and Cs2AgSbCl6 double perovskite semiconductors using a first-principles study.

In this study, we employ the framework of first-principles density functional theory (DFT) computations to investigate the physical, electrical, bandgap and thermal conductivity of Cs2AgInCl6-CAIC (type I) and Cs2AgSbCl6-CASC (type II) using the GGA-PBE method. CAIC possesses a direct band gap energy of 1.812 eV, while CASC demonstrates an indirect band gap energy of 0.926 eV. The CAIC and CASC exhibit intriguingly reduced thermal conductivity, which can be attributed to the notable reduction in their respective Debye temperatures, measuring 182 K and 135 K, respectively. The Raman active modes computed under ambient conditions have been compared with real-world data, showing excellent agreement. The thermal conductivity values of CAIC and CASC compounds exhibit quantum mechanical characteristics, with values of 0.075 and 0.25 W m-1 K-1, respectively, at 300 K. It is foreseen that these outcomes will generate investigations concerning phosphors and diodes that rely on single emitters, with the aim of advancing lighting and display technologies in the forthcoming generations.

Correction: Structural, electronic, optical, elastic, thermodynamic and thermal transport properties of Cs2AgInCl6 and Cs2AgSbCl6 double perovskite semiconductors using a first-principles study.

Correction for 'Structural, electronic, optical, elastic, thermodynamic and thermal transport properties of Cs2AgInCl6 and Cs2AgSbCl6 double perovskite semiconductors using a first-principles study' by Keqing Zhang et al., Phys. Chem. Chem. Phys., 2023, 25, 31848-31868, https://doi.org/10.1039/d3cp03795a.

Large area, one step synthesis of NiSe2 films on cellulose paper for glucose monitoring in bio-mimicking samples for clinical diagnostics.

There is an urgent need to develop low cost electrochemical sensors wherein the sensor can be disposed after recording data, thereby eliminating the issue of inaccuracy arising from repeated sensing measurements, which plagues most conventional electrochemical sensors. This work is the first demonstration of a NiSe2 based disposable, one time use electrochemical glucose sensor in bio-mimicking real samples wherein NiSe2 was hydrothermally grown NiSe2 on a biodegradable cellulose paper. Both physicochemical (x-ray diffraction, x-ray photoelectron spectroscopy, field emission scanning electron microscope) and electrochemical (impedance spectroscopy and cyclic voltammetry (CV)) characterization techniques confirmed the growth and presence of NiSe2 on a cellulose paper. Electrochemical techniques like CV and amperometric (i-t) were utilized for the selective and sensitive oxidation of glucose. The results suggests that the proposed NiSe2 sensor is effective in a linear range of 0.1-1 mM with fast response time (3.9 s), low detection limit (24.8 ± 0.1 µM) and high sensitivity (0.25 A M-1 cm-2) at a potential applied (E app = 0.55 V versus Ag∣AgCl). Prior to the real sample analyses i.e. glucose detection in human urine, the fabricated NiSe2 sensor was tested for selectivity towards glucose in co-existing interferences (dopamine, ascorbic acid, uric acid, urea, sodium chloride, fructose, lactose and cysteine). Finally, glucose in artificial blood serum and urine samples was demonstrated with the fabricated NiSe2 sensor and the results are comparable to the conventional laboratory methods. The present methodology presents a novel possibility towards the design of next generation, affordable point-of-care devices for a broad range of clinical diagnostics.

Binary Diffusion Coefficients of Platinum(II) Acetylacetonate in Supercritical Carbon Dioxide.

Binary diffusion coefficients (D12) and retention factors (k) of platinum(II) acetylacetonate at infinitesimal concentration in supercritical (sc) carbon dioxide (CO2) were measured by the chromatographic impulse response method with a poly(ethylene glycol) coated capillary column at temperatures from (308.15 to 343.15) K and pressures from (8.5 to 40.0) MPa, and D12 in liquid ethanol at temperatures from (298.15 to 333.15) K and atmospheric pressure by the Taylor dispersion method. As has been seen for our previously reported data on other metal complexes measured in sc CO2 and organic solvents, the D12 data in sc CO2 and liquid ethanol were represented by a function of temperature and solvent viscosity. The D12 values for metal complexes were not related to the solute molecular weights. The k values in sc CO2 were expressed by a function of temperature and CO2 density.

One-Step Synthesis of Fragment-Reduced Graphene Oxide as an Electrode Material for Supercapacitors.

We herein report for the first time a simple environmentally friendly hydrothermal method for one-step synthesis of fragment-reduced graphene oxide (FrGO) under mild conditions without the addition of reducing agents, and we applied it as an electrode material for a supercapacitor. The characterization results show that the introduction of Al2O3 as a spacer and HCl as an etchant results in a macroporous/mesoporous structure, increases the fragmentation of the FrGO microtopography, shortens the electron/ion transport path, and increases the contact between the electrode material and the electrolyte. Compared to the traditional hydrothermal reduced graphene materials, FrGO shows a larger specific capacitance. The results indicate that suitable hydrothermal temperature and time can effectively promote the retention of more oxygen-containing functional groups on the graphene surface. The first-principles density functional theory (DFT) calculation results show that the electrostatic potential in carbonyl group graphene is more negative, favored by the H+ adsorption, and provides the system with a pseudocapacitive effect. Under optimized conditions, FrGO (1:4, 180 °C, 3 h) exhibits 417 F/g at 1 A/g with an outstanding capacitance retention of 78.51% at 50 A/g and exhibits remarkable stability over 20 000 charge/discharge cycles. The proposed FrGO-based synthesis method can be used to guide the development of electrode materials for various supercapacitor devices.

One-step solvothermal synthesis of nanoflake-nanorod WS2 hybrid for non-enzymatic detection of uric acid and quercetin in blood serum.

Herein, we report a novel, one-step solvothermal assisted thermal decomposition synthesis of nanoflake-nanorod tungsten disulphide (WS2) nanomaterial and its application for non-enzymatic electrochemical sensing of uric acid (UA) and quercetin. The as-synthesised WS2 was characterized using X-ray diffraction (XRD), Raman spectrometer, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). SEM analysis revealed the growth of 2D-1D nanoflake-nanorod hybrid nanostructure of 2H phase WS2 with greater defects and metal edges. Under optimized conditions, the WS2 modified glassy carbon electrode (WS2/GCE) facilitated the effective sensing of UA and quercetin which was measured using differential pulse voltammetry (DPV) technique. The sensor exhibited a low limit of detection (LoD) of 1.2 µM, the sensitivity of 312 nA/µM.cm2 for the dynamic range from 5 µM to 1 mM towards UA while an even lower of 2.4 nM and sensitivity of 258 nA/nM cm2 in the dynamic range of 10 nM-50 µM for quercetin. The enhanced sensing ability of the sensor attributed towards the synergetic effect of 2D-1D hybrid structure of WS2, wherein the 2D nanoflakes enhance the electrocatalytic property of WS2 with shorter diffusion length and 1D nanorods offer large surface area which provides greater number of active sites for sensing. Further, the sensor showed a remarkable selectivity towards UA and quercetin in the presence of ascorbic acid (AA), dopamine (DA), sodium (Na+), chloride (Cl-), calcium (Ca2+) and glucose. The sensor was further employed in successful detection of UA and quercetin in the simulated blood serum sample with excellent recovery percentages. The proposed synthesis route can be used to develop WS2 based electrochemical sensing platforms useful for various bioanalytical applications.

Simultaneous determination of binary diffusion coefficients from multiple response curves by chromatographic measurements.

The chromatographic impulse response technique with a polymer coated capillary column was applied to measurements of infinite dilution binary diffusion coefficients D and retention factors k in supercritical carbon dioxide by injecting a hexane solution dissolving a mixture of three unsaturated fatty acids such as alpha-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid. The coefficients were simultaneously estimated by the curve fitting analysis even from partially overlapping response curves with the resolution of 0.8. The D and k values for each solute were able to be so obtained as accurately as those determined by individually injecting a single component solution. Almost no effect of the interaction among the components in the mixture was found from various approaching ways for curve fitting and the consecutive injection of the mixture at a certain interval.

Density dependence of retention factors of trans-stilbene oxide for chiral separation by supercritical fluid chromatography.

Retention factors for two enantiomers of trans-stilbene oxide, k1 and k2, were measured with a chiral AD-H column using two syringe pumps to feed CO2 and methanol as a co-solvent at various temperatures, pressures and co-solvent mole fractions to determine the effects of these operating conditions on the retention factors. The retention factors k1 and k2 are for the (R,R)- and (S,S)-forms, respectively. When the isothermal compressibilities of a mixture of CO2 and MeOH were lower than 0.01, far from the critical locus of the CO2 and methanol mixture, both retention factors were well expressed with the solvent density and temperature with an average absolute relative deviation of 1-2%. In the vicinity of the critical locus, however, where the isothermal compressibilities were much larger than 0.01, the relationship between retention factor and density was complicated. Both retention factors were proportional to the isothermal compressibility, irrespective of methanol mole fraction at each temperature.

Measurements of binary diffusion coefficients, retention factors and partial molar volumes for myristoleic acid and its methyl ester in supercritical carbon dioxide.

The binary diffusion coefficients, D(12), and retention factors for myristoleic acid and its methyl ester at infinite dilution were measured by the chromatographic impulse response technique in supercritical carbon dioxide at temperatures of 313.2, 333.2 and 343.2 K and pressures from 9.2 to 30 MPa for the acid, and from 8.0 to 14 MPa for the ester. Although the D(12) values were represented by the two correlations, the D(12)/T vs. CO(2) viscosity and the Schmidt-number correlations, which are valid for more than 40 compounds that we have measured so far, significant temperature dependences were observed for the ester. Moreover, the D(12) values for the ester at 313.2 K downward deviated from the background values around 400 kg m(-3), where the partial molar volumes, obtained from the correlation between the retention factors measured and CO(2) densities, showed large negative values.

Chromatographic impulse response technique with curve fitting to measure binary diffusion coefficients and retention factors using polymer-coated capillary columns.

The theoretical basis of a Gaussian-like approximate solution was applied to a chromatographic impulse response technique with curve fitting for measuring binary diffusion coefficients and retention factors using a polymer-coated capillary column. The formulae were derived for evaluating both the accuracy of the approximate solution and the sensitivity of the parameters. The validity of the solution also was confirmed experimentally for pulse injection of phenol in acetone into supercritical carbon dioxide flowing at 313.15 K and 11.6-28.6 MPa. Potential sources for experimental errors of the method are discussed.

Impulse response techniques to measure binary diffusion coefficients under supercritical conditions.

This review describes impulse response techniques with a curve-fitting method to measure thermodynamic properties, such as binary diffusion coefficient, retention factor, and partial molar volume, under supercritical conditions. Theoretical background, parameter sensitivity, sources of experimental error, noise elimination technique, and the correction of apparent binary diffusion coefficients due to column coiling are discussed based on recent studies, together with data sources and predictive correlations for binary diffusion coefficients.

Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide.

Flexible graphene-graphene composites of superior thermal and electrical transport properties.

Graphene is known for high thermal and electrical conductivities. In the preparation of neat carbon materials based on graphene, a common approach has been the use of well-exfoliated graphene oxides (GOs) as the precursor, followed by conversion to reduced GOs (rGOs). However, rGOs are more suitable for the targeted high electrical conductivity achievable through percolation but considerably less effective in terms of efficient thermal transport dictated by phonon progression. In this work, neat carbon films were fabricated directly from few-layer graphene sheets, avoiding rGOs completely. These essentially graphene-graphene composites were of a metal-like appearance and mechanically flexible, exhibiting superior thermal and electrical transport properties. The observed thermal and electrical conductivities are higher than 220 W/m · K and 85000 S/m, respectively. Some issues in the further development of these mechanically flexible graphene-graphene nanocomposite materials are discussed and so are the associated opportunities.

Diffusion coefficients of phenylbutazone in supercritical CO2 and in ethanol.

The diffusion coefficients D(12) of phenylbutazone at infinite dilution in supercritical CO(2) were measured by the chromatographic impulse response (CIR) method. The measurements were carried out over the temperature range from 308.2 to 343.2 K at pressures up to 40.0 MPa. In addition, the D(12) data of phenylbutazone at infinite dilution in ethanol were also measured by the Taylor dispersion method at 298.2-333.2K and at atmospheric pressure. The D(12) value of phenylbutazone increased from 4.45×10(-10) m(2) s(-1) at 298.2 K and 0.1 MPa in ethanol to about 1.43×10(-8) m(2) s(-1) at 343.2 K and 14.0 MPa in supercritical CO(2). It was found that all diffusion data of phenylbutazone measured in this study in supercritical CO(2) and in ethanol can be satisfactorily represented by the hydrodynamic equation over a wide range of fluid viscosity from supercritical state to liquid state with average absolute relative deviation of 5.4% for 112 data points.

Applications of the chromatographic impulse response method in supercritical fluid chromatography.

The use of chromatographic impulse response (CIR) method with a coated open tubular capillary column has potential advantages in supercritical fluid chromatography. In this review, applications of the CIR method to measuring the thermodynamic properties such as diffusion coefficients, solubilities and partial molar volumes are presented. This survey gives the theoretical backgrounds for the CIR method with linear adsorption and nonlinear adsorption models. Furthermore, the brief theoretical backgrounds for using retention factors to determine solubilities and partial molar volumes are also provided. In addition, the data sources for the diffusion coefficients with an emphasis on the results published after 2004 and for the partial molar volumes in supercritical carbon dioxide are presented.

Graphene oxides dispersing and hosting graphene sheets for unique nanocomposite materials.

Graphene oxides (GOs), beyond their widely reported use as precursors for single-layer graphene sheets, are in fact excellent materials themselves (polymers in two-dimension, polyelectrolyte-like, aqueous solubility and biocompatibility, etc.). In this reported work we used aqueous GOs to effectively disperse few-layer graphene sheets (GNs) in suspension for facile wet-processing into nanocomposites of GNs embedded in GOs (as the polymeric matrix). The resulting lightweight and plastic-like nanocomposite materials remained mechanically flexible even at high loadings of GNs, and they were found to be highly efficient in thermal transport, with the experimentally determined thermal diffusivity competitive to those typically observed only in well-known thermally conductive metals such as aluminum and copper. As demonstrated, GOs apparently represent a unique class of two-dimensional polymeric materials for potentially "all-carbon" nanocomposites, among others, which may find technological applications independent of those widely proclaimed for graphene sheets.

Graphene oxides for homogeneous dispersion of carbon nanotubes.

Graphene oxides (GOs) in terms of both structure and property are essentially polyelectrolytes in a two-dimensional sheet configuration. As is well-established in the literature, polyelectrolytes are, in general, good dispersion agents for single-walled carbon nanotubes (SWNTs), which are otherwise in bundles because of strong van der Waals interactions. We report here a study in which GOs were used to disperse SWNTs, both as-purified and separated semiconducting SWNTs, for solution-like homogeneous suspensions. As a demonstration for their potentials, the optically transparent dispersions were used in a more accurate determination of the absorptivities for the band-gap transitions in semiconducting SWNTs. Results on exploration of the use of the GO-dispersed SWNTs in the development of unique carbon nanocomposite materials are also presented and discussed.