Pub Date : 2018-03-01DOI: 10.1016/j.progsolidstchem.2017.12.001
Zalak Joshi , Davit Dhruv , K.N. Rathod , Hetal Boricha , Keval Gadani , D.D. Pandya , A.D. Joshi , P.S. Solanki , N.A. Shah
Single phasic nanostructured YMnO3 manganites were successfully synthesized by employing acetate precursor based modified sol–gel technique followed by their sintering at different temperatures. Structural studies were carried out by performing X–ray diffraction (XRD) measurement and Rietveld analysis on raw data of XRD. Particle size and shape were studied using transmission electron microscopy (TEM) while size distribution was investigated by performing particle size analyzer. Nanostructured samples were studied for their electrical properties under low applied magnetic field of 1.2T. Frequency and magnetic field dependent dielectric behavior has been understood on the basis of boundaries between the particles and inverse Dzyaloshinskii–Moriya (DM) interaction. Nanostructured YMnO3 manganites exhibit positive magnetodielectric (MD) effect. Universal dielectric response (UDR) model and relaxation mechanism have been employed for dielectric behavior of the samples understudy. Role of particle morphology and magnetic disorder have been discussed for the understanding of impedance and negative magnetoimpedance (MI) of the samples. Frequency and magnetic field dependent variation in conductivity has been explained using boundary and magnetic disorders and free charge carriers in the samples. All nanostructured YMnO3 show positive Magnetoconductivity (MC) throughout the frequency and magnetic field range studied. Variation in voltage dependent hysteretic capacitance and estimated built–in potential have been discussed in the context of the role of defects, vacancies, disorder and free charge carriers in the samples sintered at different temperatures.
{"title":"Low field magnetoelectric studies on sol–gel grown nanostructured YMnO3 manganites","authors":"Zalak Joshi , Davit Dhruv , K.N. Rathod , Hetal Boricha , Keval Gadani , D.D. Pandya , A.D. Joshi , P.S. Solanki , N.A. Shah","doi":"10.1016/j.progsolidstchem.2017.12.001","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.12.001","url":null,"abstract":"<div><p>Single phasic nanostructured YMnO<sub>3</sub><span><span> manganites were successfully synthesized by employing acetate precursor based modified sol–gel technique followed by their sintering at different temperatures. Structural studies were carried out by performing X–ray diffraction (XRD) measurement and Rietveld analysis on raw data of XRD. Particle size and shape were studied using transmission electron microscopy (TEM) while size distribution was investigated by performing particle size analyzer. Nanostructured samples were studied for their electrical properties under low applied magnetic field of 1.2T. Frequency and magnetic field dependent </span>dielectric behavior has been understood on the basis of boundaries between the particles and inverse Dzyaloshinskii–Moriya (DM) interaction. Nanostructured YMnO</span><sub>3</sub><span> manganites exhibit positive magnetodielectric (MD) effect. Universal dielectric response (UDR) model and relaxation mechanism have been employed for dielectric behavior of the samples understudy. Role of particle morphology<span> and magnetic disorder have been discussed for the understanding of impedance and negative magnetoimpedance (MI) of the samples. Frequency and magnetic field dependent variation in conductivity has been explained using boundary and magnetic disorders and free charge carriers in the samples. All nanostructured YMnO</span></span><sub>3</sub> show positive Magnetoconductivity (MC) throughout the frequency and magnetic field range studied. Variation in voltage dependent hysteretic capacitance and estimated built–in potential have been discussed in the context of the role of defects, vacancies, disorder and free charge carriers in the samples sintered at different temperatures.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.12.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2344616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-03-01DOI: 10.1016/j.progsolidstchem.2017.10.002
Anatoliy Sokolov , Bruce Gerhart , Robert J. Wright , Anna M. Zink , George L. Athens , Steve Rozeveld , Arkady L. Krasovskiy , Liam P. Spencer , Robert Froese , Peter Nickias , James C. Stevens
Evolved gas analysis (EGA) mass-spectrometry (MS) is used to characterize the solid state pyrolysis decomposition pathways of air- and moisture-sensitive organometallic compounds. In this study, the single-source GaAs compounds (Et2AsGaEt2)3 (1), (t-Bu2AsGaEt2)2 (2), and [t-Bu(H)AsGaEt2]2 (3) were heated in capillary tubes under inert condition and the volatile products were analyzed by MS. In addition, the relative ratios of evolved gases were characterized using gas chromatography (GC), while the solid state pyrolysis products were analyzed by EDS, 1H NMR and XRD. Pyrolysis of GaAs single-source materials in the solid state reveals chemical information on the stability of the GaAs bond, an observation masked in gas-phase analysis of single-source materials during chemical vapor deposition. Information on GaAs bond stability may be elucidated due to the volatility of the by-products formed during Ga-As precursor pyrolysis. Loss of GaAs bond integrity in materials with alkyl substitution on Ga and As leads to formation of mobile and volatile alkyl diarsine species, as was observed for the pyrolysis of 1. An in-situ method to monitor solid-state pyrolysis by mass spectrometry identified the loss of a tetraalkyl-diarsine as the critical factor that drives formation of sub-stoichiometric GaAs products from single-source precursors. Replacing a single alkyl group on the As atom with a H (precursor 3) leads to the loss of an alkane instead of tetraalkyl-diarsine formation. Solid-state pyrolysis precursor 3 results in the formation of polycrystalline GaAs in up to 58% yield with a 52:48 Ga:As stoichiometry.
{"title":"Mass spectrometry drives stoichiometric GaAs formation from single-source precursors","authors":"Anatoliy Sokolov , Bruce Gerhart , Robert J. Wright , Anna M. Zink , George L. Athens , Steve Rozeveld , Arkady L. Krasovskiy , Liam P. Spencer , Robert Froese , Peter Nickias , James C. Stevens","doi":"10.1016/j.progsolidstchem.2017.10.002","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.10.002","url":null,"abstract":"<div><p><span>Evolved gas analysis (EGA) mass-spectrometry (MS) is used to characterize the solid state pyrolysis decomposition pathways of air- and moisture-sensitive organometallic compounds. In this study, the single-source GaAs compounds (Et</span><sub>2</sub>AsGaEt<sub>2</sub>)<sub>3</sub> (<strong>1)</strong>, (<em>t</em>-Bu<sub>2</sub>AsGaEt<sub>2</sub>)<sub>2</sub> (<strong>2)</strong>, and [<em>t</em>-Bu(H)AsGaEt<sub>2</sub>]<sub>2</sub> (<strong>3)</strong><span> were heated in capillary tubes under inert condition and the volatile products were analyzed by MS. In addition, the relative ratios of evolved gases were characterized using gas chromatography (GC), while the solid state pyrolysis products were analyzed by EDS, </span><sup>1</sup><span>H NMR and XRD. Pyrolysis of GaAs single-source materials in the solid state reveals chemical information on the stability of the Ga</span><img><span>As bond, an observation masked in gas-phase analysis of single-source materials during chemical vapor deposition. Information on Ga</span><img>As bond stability may be elucidated due to the volatility of the by-products formed during Ga-As precursor pyrolysis. Loss of Ga<img>As bond integrity in materials with alkyl substitution on Ga and As leads to formation of mobile and volatile alkyl diarsine species, as was observed for the pyrolysis of <strong>1.</strong> An <em>in-situ</em><span> method to monitor solid-state pyrolysis by mass spectrometry identified the loss of a tetraalkyl-diarsine as the critical factor that drives formation of sub-stoichiometric GaAs products from single-source precursors. Replacing a single alkyl group on the As atom with a H (precursor </span><strong>3</strong>) leads to the loss of an alkane instead of tetraalkyl-diarsine formation. Solid-state pyrolysis precursor <strong>3</strong><span> results in the formation of polycrystalline<span> GaAs in up to 58% yield with a 52:48 Ga:As stoichiometry.</span></span></p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.10.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"3388502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-03-01DOI: 10.1016/j.progsolidstchem.2017.10.001
V.I. Mikla , J.M. Turovci , V.V. Mikla , N. Mehta
Structure and its transformation are examined for amorphous Se-rich AsxSe1-x (0 ≤ x ≤ 0.2) alloys by employment of diffraction and non-diffraction structural probes. It is shown that the molecular structure of amorphous Se (a-Se) on the scale of short-range order is close to that of crystalline phase, while medium-range order differs from the structure of most inorganic glasses and may be placed between three-dimensional network glasses and polymeric ones. Further experiments show the existence of successive phases in laser-induced glass-crystalline transition with pronounced threshold behavior. Below the energy density threshold, Eth, only small changes in the local structure of the system can be detected. Above Eth, the changes were attributed to crystallization transformation. The corresponding Raman spectra reveal transformation of the system from amorphous into the crystalline phase under laser irradiation. In the binary AsxSe1-x glass system, a change of structural regime takes place near the composition x ≈ 0.04. The presence of this topological threshold is established by direct and indirect evidence, such as peculiarities in the composition dependence of the basic parameters for electron diffraction and Raman vibration modes. The peculiarities are caused by the transition from a chain-ring-like structure to preferentially a chain-like structure. Experiments described in this section have shown that Raman technique is a particularly sensitive method to determine the presence of microcrystal's in the glassy matrix. Room-temperature polarized Raman scattering spectra of model glass have been collected. Low-frequency peaks were observed in the spectra. A model is proposed for explanation of their appearance. It is shown clearly that the low-frequency Raman spectra allow determining the conditions at the boundaries, sizes as well as concentration of micro-heterogeneities in non-crystalline materials. It was established earlier that for all amorphous (glassy) materials a low-frequency peak, observed in the corresponding spectral region of Raman scattering and called boson peak, is inherent. This peak is absent in crystals of the same chemical composition and is associated with space correlations on the scale of medium-range order Rc ≈ 10 Å. On the contrary, less known is that a boson peak can give important information about the presence of microcrystalline inclusions and heterogeneities in the low-frequency Raman spectra of glasses irrespective to their chemical composition.
{"title":"Molecular structure of Se-rich amorphous films","authors":"V.I. Mikla , J.M. Turovci , V.V. Mikla , N. Mehta","doi":"10.1016/j.progsolidstchem.2017.10.001","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.10.001","url":null,"abstract":"<div><p><span>Structure and its transformation are examined for amorphous Se-rich As</span><sub>x</sub>Se<sub>1-x</sub><span> (0 ≤ x ≤ 0.2) alloys by employment of diffraction and non-diffraction structural probes. It is shown that the molecular structure of amorphous Se (a-Se) on the scale of short-range order is close to that of crystalline phase, while medium-range order differs from the structure of most inorganic glasses<span> and may be placed between three-dimensional network glasses and polymeric ones. Further experiments show the existence of successive phases in laser-induced glass-crystalline transition with pronounced threshold behavior. Below the energy density threshold, E</span></span><sub>th</sub>, only small changes in the local structure of the system can be detected. Above E<sub>th</sub><span>, the changes were attributed to crystallization transformation. The corresponding Raman spectra reveal transformation of the system from amorphous into the crystalline phase under laser irradiation. In the binary As</span><sub>x</sub>Se<sub>1-x</sub><span><span> glass system, a change of structural regime takes place near the composition x ≈ 0.04. The presence of this topological threshold is established by direct and indirect evidence, such as peculiarities in the composition dependence of the basic parameters for electron diffraction and Raman vibration modes. The peculiarities are caused by the transition from a chain-ring-like structure to preferentially a chain-like structure. Experiments described in this section have shown that Raman technique is a particularly sensitive method to determine the presence of </span>microcrystal's<span> in the glassy matrix. Room-temperature polarized Raman scattering spectra of model glass have been collected. Low-frequency peaks were observed in the spectra. A model is proposed for explanation of their appearance. It is shown clearly that the low-frequency Raman spectra allow determining the conditions at the boundaries, sizes as well as concentration of micro-heterogeneities in non-crystalline materials. It was established earlier that for all amorphous (glassy) materials a low-frequency peak, observed in the corresponding spectral region of Raman scattering and called boson peak, is inherent. This peak is absent in crystals of the same chemical composition and is associated with space correlations on the scale of medium-range order R</span></span><sub>c</sub> ≈ 10 Å. On the contrary, less known is that a boson peak can give important information about the presence of microcrystalline inclusions and heterogeneities in the low-frequency Raman spectra of glasses irrespective to their chemical composition.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.10.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2660434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.1016/j.progsolidstchem.2017.09.001
Konstantin N. Semenov , Elena V. Andrusenko , Nikolai A. Charykov , Elena V. Litasova , Gayane G. Panova , Anastasia V. Penkova , Igor V. Murin , Levon B. Piotrovskiy
Carboxylated fullerenes may have wide applications in science and technology. Therefore, there is particular interest in investigating the physico-chemical and biological properties and the applications of these compounds. This review systematizes the current literature data on the synthesis, physico-chemical properties and application of carboxylated fullerenes as nanomodifiers of polyelectrolytes as well as their use in medicine and agriculture. Presented experimental and theoretical data gives a comprehensive overview of these substances and can be valuable to specialists in the fields of nanotechnology, nanomaterials and bionanomedicine.
{"title":"Carboxylated fullerenes: Physico-chemical properties and potential applications","authors":"Konstantin N. Semenov , Elena V. Andrusenko , Nikolai A. Charykov , Elena V. Litasova , Gayane G. Panova , Anastasia V. Penkova , Igor V. Murin , Levon B. Piotrovskiy","doi":"10.1016/j.progsolidstchem.2017.09.001","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.09.001","url":null,"abstract":"<div><p><span>Carboxylated fullerenes may have wide applications in science and technology. Therefore, there is particular interest in investigating the physico-chemical and biological properties and the applications of these compounds. This review systematizes the current literature data on the synthesis, physico-chemical properties and application of carboxylated fullerenes as nanomodifiers of </span>polyelectrolytes<span> as well as their use in medicine and agriculture. Presented experimental and theoretical data gives a comprehensive overview of these substances and can be valuable to specialists in the fields of nanotechnology, nanomaterials and bionanomedicine.</span></p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.09.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2164474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.1016/j.progsolidstchem.2017.06.002
Samir F. Matar , Guillaume Couegnat , Jean Galy
The paper reports a thorough investigation of little inspected two classes of group VIIA based crystals: interhalogen compounds ClF, ClF3, BrF3 and IF3 on one hand and halogen suboxides F2O, Cl2O and Br2O on the other hand, as well as rare gas fluorides (here exemplarily XeF4), all exhibiting peculiar stereochemistry of electron (non-bonding) lone pairs merging in forms of twins and triplets. Particularly with respect to the well known VSEPR (Valence Shell Electron Pair Repulsion) model we present original approach merging crystal chemistry and density functional theory (DFT) electron localization function (ELF) to provide accurate topologic analyses and precise metrics of electron lone pairs geometries. In this context we rewrite the chemical formulae above by adjoining E designing the lone pair (LP) and M* formulating the LP-bearing element: ClF{E3}, M*2OE2{E3}2 (M* = F, Cl, Br), M*F3E2 (M* = Cl, Br, I) and XeF4E2. Then in ClF{E3} and M*2OE2{E3}2 (M* = F, Cl, Br) family an original stereochemistry is developed with LP concentration in E triplets which generate electronic torus revolving around Cl and M* which in the neighborhood of largely electronegative F, exhibit cationic-like behavior. E around Cl in ClF and then around M* of the series under consideration exhibits an ellipsoidic shape with an equivalent sphere of influence radius (rE) increasing along with the atomic number Z, i.e. rE_F = 0.52 Å, rE_Cl = 0.65 Å and rE_Br = 0.70 Å. From selected sections in ELF data we obtained precise topology and metrics details of these tori. For M*2OE2{E3}2 family the E twins attached to O have also been localized, their size remaining constant with rE_O = 0.68 Å in all studied compounds. The lone pair twins in the series M*F3E2 (M* = Cl, Br, I; M* trivalent oxidation state) as well as in noble gas tetrafluoride XeF4E2 provide remarkable examples: rE evolution versus Z, rE_Cl = 0.77 Å (Z = 17), rE_Br = 0.85 Å (Z = Br) and rE_I = 0.90 Å (Z = 53), follow a linear expansion while in the xenon case with a close ZXe = 54 but with tetravalent oxidation state, Xe exhibits a radius rE_Xe = 0.95 Å, indicating the important influence of the charge magnitude on E volume. The interaction of cations with E centroïd: Ec -defined as the electronic volume attached to the lone pair- of neighboring molecules is plausible in explaining unusually short distances between cations. Even surrounded by E torus the cations obviously exert attractive influence through
{"title":"Stereochemistry and ab initio topology analyses of electron lone pair triplets and twins in interhalogen compounds and halogen suboxides","authors":"Samir F. Matar , Guillaume Couegnat , Jean Galy","doi":"10.1016/j.progsolidstchem.2017.06.002","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.06.002","url":null,"abstract":"<div><p>The paper reports a thorough investigation of little inspected two classes of group VIIA based crystals: interhalogen compounds ClF, ClF<sub>3</sub>, BrF<sub>3</sub> and IF<sub>3</sub> on one hand and halogen suboxides F<sub>2</sub>O, Cl<sub>2</sub>O and Br<sub>2</sub><span>O on the other hand, as well as rare gas fluorides (here exemplarily XeF</span><sub>4</sub><span>), all exhibiting peculiar stereochemistry<span> of electron (non-bonding) lone pairs merging in forms of twins and triplets. Particularly with respect to the well known VSEPR (Valence Shell Electron Pair Repulsion) model we present original approach merging crystal chemistry and density functional theory (DFT) electron localization function (ELF) to provide accurate topologic analyses and precise metrics of electron lone pairs geometries. In this context we rewrite the chemical formulae above by adjoining E designing the lone pair (LP) and M* formulating the LP-bearing element: ClF{E</span></span><sub>3</sub>}, M*<sub>2</sub>OE<sub>2</sub>{E<sub>3</sub>}<sub>2</sub> (M* = F, Cl, Br), M*F<sub>3</sub>E<sub>2</sub> (M* = Cl, Br, I) and XeF<sub>4</sub>E<sub>2</sub>. Then in ClF{E<sub>3</sub>} and M*<sub>2</sub>OE<sub>2</sub>{E<sub>3</sub>}<sub>2</sub> (M* = F, Cl, Br) family an original stereochemistry is developed with LP concentration in E triplets which generate electronic torus revolving around Cl and M* which in the neighborhood of largely electronegative F, exhibit cationic-like behavior. E around Cl in ClF and then around M* of the series under consideration exhibits an ellipsoidic shape with an equivalent sphere of influence radius (r<sub>E</sub>) increasing along with the atomic number Z, i.e. r<sub>E_F</sub> = 0.52 Å, r<sub>E_Cl</sub> = 0.65 Å and r<sub>E_Br</sub><span> = 0.70 Å. From selected sections in ELF data we obtained precise topology and metrics details of these tori. For M*</span><sub>2</sub>OE<sub>2</sub>{E<sub>3</sub>}<sub>2</sub> family the E twins attached to O have also been localized, their size remaining constant with r<sub>E_O</sub> = 0.68 Å in all studied compounds. The lone pair twins in the series M*F<sub>3</sub>E<sub>2</sub><span> (M* = Cl, Br, I; M* trivalent oxidation state) as well as in noble gas tetrafluoride XeF</span><sub>4</sub>E<sub>2</sub> provide remarkable examples: rE evolution versus Z, r<sub>E_Cl</sub> = 0.77 Å (Z = 17), r<sub>E_Br</sub> = 0.85 Å (Z = Br) and r<sub>E_I</sub><span> = 0.90 Å (Z = 53), follow a linear expansion while in the xenon case with a close Z</span><sub>Xe</sub> = 54 but with tetravalent oxidation state, Xe exhibits a radius r<sub>E_Xe</sub><span> = 0.95 Å, indicating the important influence of the charge magnitude on E volume. The interaction of cations with E centroïd: Ec -defined as the electronic volume attached to the lone pair- of neighboring molecules is plausible in explaining unusually short distances between cations. Even surrounded by E torus the cations obviously exert attractive influence through ","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.06.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2660435","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-03-01DOI: 10.1016/j.progsolidstchem.2017.02.001
Chi Him A. Tsang , H.Y.H. Kwok , Zhanjun Cheng , D.Y.C. Leung
Due to their extra-large surface area and porosity, high compression power, hydrophobicity, and strong activity characteristics, there have been increasing interests in applying graphene-based materials for pollutant control and disinfection. The topics covered from photocatalytic reactions in the dye removal and organic conversions in liquid or gas phase, disinfection, oil absorption, and pollutant adsorption. In this manuscript, the characteristics of the photocatalytic reactions for toxins and pollutants like toxic hydrocarbons, carbon dioxides, and dye wastewater, removal of pollutants like oil and heavy metal ions via absorption/adsorption, and disinfection by different graphene-based materials via adsorption inactivation or photocatalytic inactivation will be emphasized. The challenges in pollutant removal research by graphene-based materials, such as the deactivation of graphene-based materials in photocatalytic pollutant removal reactions which was discovered recently and solutions to the corresponding weaknesses were discussed.
{"title":"The applications of graphene-based materials in pollutant control and disinfection","authors":"Chi Him A. Tsang , H.Y.H. Kwok , Zhanjun Cheng , D.Y.C. Leung","doi":"10.1016/j.progsolidstchem.2017.02.001","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.02.001","url":null,"abstract":"<div><p><span>Due to their extra-large surface area and porosity, high compression power, hydrophobicity, and strong activity characteristics, there have been increasing interests in applying graphene-based materials for pollutant control and disinfection. The topics covered from photocatalytic reactions in the dye removal and organic conversions in liquid or gas phase, disinfection, oil absorption, and pollutant adsorption. In this manuscript, the characteristics of the photocatalytic reactions for toxins and pollutants like toxic hydrocarbons, carbon dioxides, and dye wastewater, removal of pollutants like oil and heavy </span>metal ions via absorption/adsorption, and disinfection by different graphene-based materials via adsorption inactivation or photocatalytic inactivation will be emphasized. The challenges in pollutant removal research by graphene-based materials, such as the deactivation of graphene-based materials in photocatalytic pollutant removal reactions which was discovered recently and solutions to the corresponding weaknesses were discussed.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2017-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.02.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2120175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-03-01DOI: 10.1016/j.progsolidstchem.2017.02.002
Elena A. Medina, Jun Li, M.A. Subramanian
Colored hibonite-type oxides with a general formula CaAl12-xMxO19 were prepared by solid state reactions through M-site substitution of aluminum with various di-, tri- and tetravalent cations (M = Fe, Mn, Cr, Cu, Ga, In, Ti, Ge, Sn or any combination thereof), where Fe, Mn, Cr and Cu are chromophore ions. Neutron Rietveld refinements of CaAl9.5Fe2.5O19, CaAl11.5Mn0.5O19 and CaAl10SnMnO19 compounds show that Fe3+ and Mn2+ ions prefer to occupy the tetrahedral site, while Mn3+ has an evident preference for both tetrahedral and octahedral sites and Sn4+ for octahedral site in the hibonite structure. No oxygen vacancies are found by structural analyses. Magnetic measurement confirms divalent Mn for CaAl11Sn0.5Mn0.5O19 and trivalent Mn for CaAl11.5Mn0.5O19. Diffuse reflectance spectra reveal that the d-d transitions occurring in transition metal chromophores are mainly responsible for the observed colors. The colored powders exhibit fairly high reflectance in the near-infrared region (750–2500 nm) which makes them potential candidates for cool pigment applications. Synthesis and characterization methods are briefly reviewed for hibonite type of oxides, especially those containing Fe, Mn, Cr and Cu.
{"title":"Colored oxides with hibonite structure II: Structural and optical properties of CaAl12O19-type pigments with chromophores based on Fe, Mn, Cr and Cu","authors":"Elena A. Medina, Jun Li, M.A. Subramanian","doi":"10.1016/j.progsolidstchem.2017.02.002","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2017.02.002","url":null,"abstract":"<div><p>Colored hibonite-type oxides with a general formula CaAl<sub>12-<em>x</em></sub><em>M</em><sub><em>x</em></sub>O<sub>19</sub><span> were prepared by solid state reactions through M-site substitution of aluminum with various di-, tri- and tetravalent cations (</span><em>M</em><span><span> = Fe, Mn, Cr, Cu, Ga, In, Ti, Ge, Sn or any combination thereof), where Fe, Mn, Cr and Cu are chromophore ions. Neutron </span>Rietveld refinements of CaAl</span><sub>9.5</sub>Fe<sub>2.5</sub>O<sub>19</sub>, CaAl<sub>11.5</sub>Mn<sub>0.5</sub>O<sub>19</sub> and CaAl<sub>10</sub>SnMnO<sub>19</sub> compounds show that Fe<sup>3+</sup> and Mn<sup>2+</sup> ions prefer to occupy the tetrahedral site, while Mn<sup>3+</sup> has an evident preference for both tetrahedral and octahedral sites and Sn<sup>4+</sup><span> for octahedral site in the hibonite structure. No oxygen vacancies are found by structural analyses. Magnetic measurement confirms divalent Mn for CaAl</span><sub>11</sub>Sn<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>19</sub> and trivalent Mn for CaAl<sub>11.5</sub>Mn<sub>0.5</sub>O<sub>19</sub>. Diffuse reflectance spectra reveal that the d-d transitions occurring in transition metal chromophores are mainly responsible for the observed colors. The colored powders exhibit fairly high reflectance in the near-infrared region (750–2500 nm) which makes them potential candidates for cool pigment applications. Synthesis and characterization methods are briefly reviewed for hibonite type of oxides, especially those containing Fe, Mn, Cr and Cu.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2017-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2017.02.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2414527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2016-12-01DOI: 10.1016/j.progsolidstchem.2016.11.001
Jun Li , Elena A. Medina , Judith K. Stalick , Arthur W. Sleight , M.A. Subramanian
The crystal structure of hibonite with an ideal formula CaAl12O19 is hexagonal P63/mmc, isostructural with magnetoplumbite. Natural and synthetic hibonites have been widely studied for their formation, compositions, crystal structures, properties and applications. Recent increasing interest in its coloration has led to the search of inorganic pigments based on the hibonite structure. We present here the syntheses and characterization of hibonite compounds with a general formula of AAl12−xMxO19 (A = Ca, Sr, RE (rare earths) or any combination thereof; and M = Ni or Ni coupled with one of the following: Ti, Sn, Ge, Nb, Ta, Sb). Bright sky-blue to royal-blue colors are induced in these oxides prepared by conventional solid state reactions, as demonstrated in the solid solutions of CaAl12−2xNixTixO19 (x = 0–1) and Ca1−xLaxAl12−xNixO19 (x = 0–1). The values of color coordinates L*a*b* range from 64.5, −5.3, −18.5 to 57, −11.33, −30.38. Structure refinements of neutron powder diffraction data reveal that Ni preferably occupies the tetrahedral site in the hibonite structure, and magnetic susceptibility analysis confirms that this Ni is Ni2+. Optical measurements further verify that the observed blue color is due to d-d transitions of tetrahedral Ni2+. The preference of Ni2+ for the tetrahedral site is unusual because Ni2+ prefers the octahedral site in the spinel NiAl2O4. We attribute this unexpected behavior to the unusually large Al−O distances for the tetrahedral site in the hibonite structure. These blue hibonites exhibit excellent thermal stability, superior acid/base durability and better near-infrared reflectance than that of the commercial cobalt blue pigment. Our results suggest a potential route to the development of inexpensive, enduring and cobalt-free blue pigments. Synthesis and characterization methods are briefly reviewed for hibonite type of oxides, especially those with blue colors.
理想分子式CaAl12O19的铁长石晶体结构为六方P63/mmc,与磁铅石同构。天然和人工合成的hibonite在其形成、组成、晶体结构、性质和应用方面得到了广泛的研究。近年来对其着色的兴趣日益增加,导致了基于hibonite结构的无机颜料的研究。本文介绍了一种分子式为AAl12−xMxO19 (a = Ca, Sr, RE(稀土)或其任意组合)的hibonite化合物的合成和表征;M = Ni或Ni与Ti、Sn、Ge、Nb、Ta、Sb的偶联)。在CaAl12−2xNixTixO19 (x = 0-1)和Ca1−xLaxAl12−xNixO19 (x = 0-1)的固溶体中,通过常规固相反应制备的氧化物可诱导出明亮的天蓝色到宝蓝色。颜色坐标L*a*b*的取值范围为64.5、−5.3、−18.5 ~ 57、−11.33、−30.38。中子粉末衍射数据的结构细化表明,Ni较好地占据了hibonite结构中的四面体位置,磁化率分析证实了该Ni为Ni2+。光学测量进一步证实,观察到的蓝色是由于四面体Ni2+的d-d跃迁。在尖晶石NiAl2O4中,Ni2+倾向于八面体位,因此Ni2+对四面体位的偏好是不寻常的。我们将这种意想不到的行为归因于在hibonite结构中四面体位置的异常大的Al - O距离。与商用钴蓝颜料相比,这些蓝色高脂石具有优异的热稳定性、优异的酸碱耐久性和更好的近红外反射率。我们的研究结果为开发廉价、耐用和无钴的蓝色颜料提供了一条潜在的途径。综述了硅辉石型氧化物,特别是蓝色氧化物的合成和表征方法。
{"title":"Colored oxides with hibonite structure: A potential route to non-cobalt blue pigments","authors":"Jun Li , Elena A. Medina , Judith K. Stalick , Arthur W. Sleight , M.A. Subramanian","doi":"10.1016/j.progsolidstchem.2016.11.001","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2016.11.001","url":null,"abstract":"<div><p>The crystal structure of hibonite with an ideal formula CaAl<sub>12</sub>O<sub>19</sub> is hexagonal <em>P</em>6<sub>3</sub>/<em>mmc</em>, isostructural with magnetoplumbite. Natural and synthetic hibonites have been widely studied for their formation, compositions, crystal structures, properties and applications. Recent increasing interest in its coloration has led to the search of inorganic pigments based on the hibonite structure. We present here the syntheses and characterization of hibonite compounds with a general formula of <em>A</em>Al<sub>12−<em>x</em></sub><em>M</em><sub><em>x</em></sub>O<sub>19</sub> (<em>A</em> = Ca, Sr, RE (rare earths) or any combination thereof; and <em>M</em> = Ni or Ni coupled with one of the following: Ti, Sn, Ge, Nb, Ta, Sb). Bright sky-blue to royal-blue colors are induced in these oxides prepared by conventional solid state reactions, as demonstrated in the solid solutions of CaAl<sub>12−2<em>x</em></sub>Ni<sub><em>x</em></sub>Ti<sub><em>x</em></sub>O<sub>19</sub> (<em>x</em> = 0–1) and Ca<sub>1−<em>x</em></sub>La<sub><em>x</em></sub>Al<sub>12−<em>x</em></sub>Ni<sub><em>x</em></sub>O<sub>19</sub> (<em>x</em><span> = 0–1). The values of color coordinates L*a*b* range from 64.5, −5.3, −18.5 to 57, −11.33, −30.38. Structure refinements of neutron powder diffraction<span> data reveal that Ni preferably occupies the tetrahedral site in the hibonite structure, and magnetic susceptibility analysis confirms that this Ni is Ni</span></span><sup>2+</sup>. Optical measurements further verify that the observed blue color is due to d-d transitions of tetrahedral Ni<sup>2+</sup>. The preference of Ni<sup>2+</sup> for the tetrahedral site is unusual because Ni<sup>2+</sup> prefers the octahedral site in the spinel NiAl<sub>2</sub>O<sub>4</sub>. We attribute this unexpected behavior to the unusually large Al−O distances for the tetrahedral site in the hibonite structure. These blue hibonites exhibit excellent thermal stability, superior acid/base durability and better near-infrared reflectance than that of the commercial cobalt blue pigment. Our results suggest a potential route to the development of inexpensive, enduring and cobalt-free blue pigments. Synthesis and characterization methods are briefly reviewed for hibonite type of oxides, especially those with blue colors.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2016-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2016.11.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2660438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2016-12-01DOI: 10.1016/j.progsolidstchem.2016.11.003
M. Iranmanesh, J. Hulliger
A ceramic combinatorial method to investigate the phase space of e.g. metal oxides by a single sample is reviewed along with its application to cuprate superconductors. The main idea behind this method is to use a large number N of starting materials (micrometer size grains) to generate local reaction centers producing possible compounds at the reaction temperature. Mathematical calculations using also empirical data on the occurrence of compounds in phase systems allow to conclude that in 1 cm3 of a sample, there are enough grains to populate all local reaction centers in order to obtain in principle what the N starting materials can produce. A variety of characterization technics have been applied to such libraries to identify e.g. cuprate superconductors. Finally the success of the concept will depend on analytical tools allowing for a simultaneous analysis of the composition and physical properties. Here, we have applied for the first time scanning SQUID microscopy to reveal local superconductivity in inhomogeneous ceramic samples.
{"title":"Ceramic combinatorial syntheses exploring the chemical diversity of metal oxides","authors":"M. Iranmanesh, J. Hulliger","doi":"10.1016/j.progsolidstchem.2016.11.003","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2016.11.003","url":null,"abstract":"<div><p><span><span>A ceramic combinatorial method to investigate the phase space of e.g. metal oxides by a single sample is reviewed along with its application to </span>cuprate<span> superconductors. The main idea behind this method is to use a large number </span></span><em>N</em> of starting materials (micrometer size grains) to generate local reaction centers producing possible compounds at the reaction temperature. Mathematical calculations using also empirical data on the occurrence of compounds in phase systems allow to conclude that in 1 cm<sup>3</sup> of a sample, there are enough grains to populate all local reaction centers in order to obtain in principle what the <em>N</em><span> starting materials can produce. A variety of characterization technics have been applied to such libraries to identify e.g. cuprate superconductors. Finally the success of the concept will depend on analytical tools allowing for a simultaneous analysis of the composition and physical properties. Here, we have applied for the first time scanning SQUID microscopy to reveal local superconductivity in inhomogeneous ceramic samples.</span></p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2016-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2016.11.003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2660433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chalcogenide glasses (ChG) has emerged as important materials due to their potential applications in infrared optics for communication, imaging, limiting, remote sensing and laser power delivery etc. Examining ChG for their various applications, different properties of these were under immense investigation by various researchers from nearly every part of the world. Study of ChG for optical properties like optical band gap and refractive index are the backbone while considering them for applications. The present review focuses on the optical properties of various binary, ternary and quaternary chalcogenide systems. Subsequently applications and future prospects of ChG have been sketched. The attracting prospective applications have drive us to put the review on optical properties of chalcogenide thin films both comprehensive and expedient to new as well as established researchers in this area.
{"title":"Recent developments on the optical properties of thin films of chalcogenide glasses","authors":"Pankaj Sharma , Neha Sharma , Sunanda Sharda , S.C. Katyal , Vineet Sharma","doi":"10.1016/j.progsolidstchem.2016.11.002","DOIUrl":"https://doi.org/10.1016/j.progsolidstchem.2016.11.002","url":null,"abstract":"<div><p><span>Chalcogenide glasses (ChG) has emerged as important materials due to their potential applications in infrared optics for communication, imaging, limiting, remote sensing and laser power delivery </span><em>etc</em><span>. Examining ChG for their various applications, different properties of these were under immense investigation by various researchers from nearly every part of the world. Study of ChG for optical properties<span> like optical band gap and refractive index<span> are the backbone while considering them for applications. The present review focuses on the optical properties of various binary, ternary and quaternary chalcogenide systems. Subsequently applications and future prospects of ChG have been sketched. The attracting prospective applications have drive us to put the review on optical properties of chalcogenide thin films both comprehensive and expedient to new as well as established researchers in this area.</span></span></span></p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":12.0,"publicationDate":"2016-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2016.11.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2660439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}