Characterisation of two distinctly different processes associated with the electrocrystallization of microcrystals of phase I CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane)

Semi-conducting phase I CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which is of considerable interest as a switching device for memory storage materials, can be electrocrystallized from CH3CN via two distinctly different pathways when TCNQ is reduced to TCNQ˙− in the presence of [Cu(MeCN)4]+. The first pathway, identified in earlier studies, occurs at potentials where TCNQ is reduced to TCNQ˙− and involves a nucleation–growth mechanism at preferred sites on the electrode to produce arrays of well separated large branched needle-shaped phase I CuTCNQ crystals. The second pathway, now identified at more negative potentials, generates much smaller needle-shaped phase I CuTCNQ crystals. These electrocrystallize on parts of the surface not occupied in the initial process and give rise to film-like characteristics. This process is attributed to the reduction of Cu+[(TCNQ˙−)(TCNQ)] or a stabilised film of TCNQ via a solid–solid conversion process, which also involves ingress of Cu+via a nucleation–growth mechanism. The CuTCNQ surface area coverage is extensive since it occurs at all areas of the electrode and not just at defect sites that dominate the crystal formation sites for the first pathway. Infrared spectra, X-ray diffraction, surface plasmon resonance, quartz crystal microbalance, scanning electron microscopy and optical image data all confirm that two distinctly different pathways are available to produce the kinetically-favoured and more highly conducting phase I CuTCNQ solid, rather than the phase II material.

Structural characterization and vibrational spectroscopy of the arsenate mineral wendwilsonite

In this paper, we have investigated on the natural wendwilsonite mineral with the formulae Ca2(Mg,Co)(AsO4)2⋅2(H2O). Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the wendwilsonite arsenate mineral. A comparison is made with the roselite mineral group with formula Ca2B(AsO4)2⋅2H2O (where B may be Co, Fe2+, Mg, Mn, Ni, Zn). The Raman spectra of the arsenate related to tetrahedral arsenate clusters with stretching region shows strong differences between that of wendwilsonite and the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. The Raman arsenate (AsO4)3− stretching region shows strong differences between that of wendwilsonite and the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists of multiple to tetrahedral (AsO4)3− clusters with antisymmetric stretching vibrations observed indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 450 cm−1 are assigned to ν4 bending modes. Multiple bands in the 350–300 cm−1 region assigned to ν2 bending modes provide evidence of symmetry reduction of the arsenate anion. Three broad bands for wendwilsonite found at 3332, 3119 and 3001 cm−1 are assigned to OH stretching bands. By using a Libowitzky empirical equation, hydrogen bond distances of 2.65 and 2.75 Å are estimated. Vibrational spectra enable the molecular structure of the wendwilsonite mineral to be determined and whilst similarities exist in the spectral patterns with the roselite mineral group, sufficient differences exist to be able to determine the identification of the minerals.

Vibrational spectroscopy of the silicate mineral plumbotsumite Pb5(OH)10Si4O8 : an assessment of the molecular structure

We have used scanning electron microscopy with energy dispersive X-ray analysis to determine the precise formula of plumbotsumite, a rare lead silicate mineral of formula Pb5(OH)10Si4O8. This study forms the first systematic study of plumbotsumite from the Bigadic deposits, Turkey. Vibrational spectroscopy was used to assess the molecular structure of plumbotsumite as the structure is not known. The mineral is characterized by sharp Raman bands at 1047, 1055 and 1060 cm−1 assigned to SiO stretching vibrational modes and sharp Raman bands at 673, 683 and 697 cm−1 assigned to OSiO bending modes. The observation of multiple bands offers support for a layered structure with variable SiO3 structural units. Little information may be obtained from the infrared spectra because of broad spectral profiles. Intense Raman bands at 3510, 3546 and 3620 cm−1 are ascribed to OH stretching modes. Evidence for the presence of water in the plumbotsumite structure was inferred from the infrared spectra.

A vibrational spectroscopic study of a hydrated hydroxy-phosphate mineral fluellite, Al2(PO4)F2(OH)·7H2O

Raman and infrared spectra of two well-defined fluellite samples, Al2(PO4)F2(OH)�7H2O, from the Krásno near Horní Slavkov (Czech Republic) and Kapunda, South Australia (Australia) were studied and tentatively interpreted. Observed bands were assigned to the stretching and bending vibrations of phosphate tetrahedra, aluminum oxide/hydroxide/fluoride octahedra, water molecules and hydroxyl ions. Approximate O–H���O hydrogen bond lengths were inferred from the Raman and infrared spectra.

A theoretical study of C4B isomers. The interconversion of CCBCC and CCCCB via cyclic C4B

Theory suggests that CCBCC (1) will rearrange to planar cyclo-C4B (19) if the excess energy of 1 is greater than or equal to16.1 kcal mol(-1) [calculations at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-31G(d) level of theory]. Cyclo-C4B lies only 1.1 kcal mol(-1) above CCBCC. The planar nature of symmetrical cyclo-C4B is attributed to multicentered bonding involving boron. If cyclo-C4B (19) has an excess energy of greater than or equal to24.4 kcal mol-1, it may ring open to form CCCCB (3).

Vibrational spectroscopy of the sulphate mineral sturmanite from Kuruman manganese deposits, South Africa

The mineral sturmanite is a hydrated calcium iron aluminium manganese sulphate tetrahydroxoborate hydroxide of formula Ca6(Fe, Al, Mn)2(SO4)2(B(OH)4)(OH)12•26H2O. We have studied the mineral sturmanite using a number of techniques, including SEM with EPMA and vibrational spectroscopy. Chemical analysis shows a homogeneous phase, composed by Ca, Fe, Mn, S, Al and Si. B is not determined in this EPMA technique. An intense Raman band at 990 cm−1 is assigned to the SO42− symmetric stretching mode. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1069 cm−1 which may be attributed to a carbonate symmetric stretching mode, indicating the presence of thaumasite. Infrared spectra display two bands at 1080 and 1107 cm−1 assigned to the SO42− antisymmetric stretching modes. The observation of multiple bands in this ν4 spectral region offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3622 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3479 cm−1 to water stretching bands. Infrared spectroscopy shows a set of broad overlapping bands in the OH stretching region. Vibrational spectroscopy enables an assessment of the molecular structure of sturmanite to be made.

A vibrational spectroscopic study of the silicate mineral pectolite – NaCa2Si3O8(OH)

The mineral pectolite NaCa2Si3O8(OH) is a crystalline sodium calcium silicate which has the potential to be used in plaster boards and in other industrial applications. Raman bands at 974 and 1026 cm−1 are assigned to the SiO stretching vibrations of linked units of Si3O8 units. Raman bands at 974 and 998 cm−1 serve to identify Si3O8 units. The broad Raman band at around 936 cm−1 is attributed to hydroxyl deformation modes. Intense Raman band at 653 cm−1 is assigned to OSiO bending vibration. Intense Raman bands in the 2700–3000 cm−1 spectral range are assigned to OH stretching vibrations of the OH units in pectolite. Infrared spectra are in harmony with the Raman spectra. Raman spectroscopy with complimentary infrared spectroscopy enables the characterisation of the silicate mineral pectolite.

A vibrational spectroscopic study of the silicate mineral harmotome – (Ba,Na,K)1-2(Si,Al)8O16⋅6H2O – A natural zeolite

The mineral harmotome (Ba,Na,K)1-2(Si,Al)8O16⋅6H2O is a crystalline sodium calcium silicate which has the potential to be used in plaster boards and other industrial applications. It is a natural zeolite with catalytic potential. Raman bands at 1020 and 1102 cm−1 are assigned to the SiO stretching vibrations of three dimensional siloxane units. Raman bands at 428, 470 and 491 cm−1 are assigned to OSiO bending modes. The broad Raman bands at around 699, 728, 768 cm−1 are attributed to water librational modes. Intense Raman bands in the 3100 to 3800 cm−1 spectral range are assigned to OH stretching vibrations of water in harmotome. Infrared spectra are in harmony with the Raman spectra. A sharp infrared band at 3731 cm−1 is assigned to the OH stretching vibration of SiOH units. Raman spectroscopy with complimentary infrared spectroscopy enables the characterization of the silicate mineral harmotome.

SEM, EDS and vibrational spectroscopic study of dawsonite NaAl(CO3)(OH)2

In this work we have studied the mineral dawsonite by using a combination of scanning electron microscopy with EDS and vibrational spectroscopy. Single crystals show an acicular habitus forming aggregates with a rosette shape. The chemical analysis shows a phase composed of C, Al, and Na. Two distinct Raman bands at 1091 and 1068 cm−1 are assigned to the CO32− ν1 symmetric stretching mode. Multiple bands are observed in both the Raman and infrared spectra in the antisymmetric stretching and bending regions showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the dawsonite structure. Multiple OH deformation vibrations centred upon 950 cm−1 in both the Raman and infrared spectra show that the OH units in the dawsonite structure are non-equivalent. Raman bands observed at 3250, 3283 and 3295 cm−1 are assigned to OH stretching vibrations. The position of these bands indicates strong hydrogen bonding of the OH units in the dawsonite structure. The formation of the mineral dawsonite has the potential to offer a mechanism for the geosequestration of greenhouse gases.

A vibrational spectroscopic study of the arsenate minerals cobaltkoritnigite and koritnigite

Raman spectra of two well-defined types of cobaltkoritnigite and koritnigite crystals were recorded and interpreted. Significant differences in the Raman spectra of cobaltkoritnigite and koritnigite were observed. Observed Raman bands were attributed to the (AsO3OH)2− stretching and bending vibrations, stretching and bending vibrations of water molecules and hydroxyl ions. Both Raman and infrared spectra of cobaltkoritnigite identify bands which are attributable to phosphate and hydrogen phosphate anions proving some substitution of phosphate for arsenate in the structure of cobaltkoritnigite. The OH⋯O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X-ray single crystal refinement. The presence of (AsO3OH)2− units in the crystal structure of cobaltkoritnigite and koritnigite was proved from the Raman spectra which supports the conclusions of the X-ray structure analysis.

A Raman spectroscopic study of a hydrated molybdate mineral ferrimolybdite, Fe2(MoO4)3·7–8H2O

Raman spectra of two well-defined ferrimolybdite samples, Fe23+(Mo6+O4)3·7–8H2O, from the Krupka deposit (northern Bohemia, Czech Republic) and Hůrky near Rakovník occurrence (central Bohemia, Czech Republic) were studied and tentatively interpreted. Observed bands were assigned to the stretching and bending vibrations of molybdate anions, Fe–O units and water molecules. Number of Raman and infrared bands assigned to (MoO4)2− units and water molecules proved that symmetrically (structurally) nonequivalent (MoO4)2− and H2O are present in the crystal structure of ferrimolybdite. Approximate O–H⋯O hydrogen bond lengths (2.80–2.73 Å) were inferred from the published infrared spectra.

Tailoring surface properties and structure of layered double hydroxides using silanes with different number of functional groups

Four silanes, trimethylchlorosilane (TMCS), dimethyldiethoxylsilane (DMDES), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS), were adopted to graft layered double hydroxides (LDH) via an induced hydrolysis silylation method (IHS). Fourier transform infrared spectra (FTIR) and 29Si MAS nuclear magnetic resonance spectra (29Si MAS NMR) indicated that APTES and TEOS can be grafted onto LDH surfaces via condensation with hydroxyl groups of LDH, while TMCS and DMDES could only be adsorbed on the LDH surface with a small quantity. A combination of X-ray diffraction patterns (XRD) and 29Si MAS NMR spectra showed that silanes were exclusively present in the external surface and had little influence on the long range order of LDH. The surfactant intercalation experiment indicated that the adsorbed and/or grafted silane could not fix the interlamellar spacing of the LDH. However, they will form crosslink between the particles and affect the further surfactant intercalation in the silylated samples. The replacement of water by ethanol in the tactoids and/or aggregations and the polysiloxane oligomers formed during silylation procedure can dramatically increase the value of BET surface area (SBET) and total pore volumes (Vp) of the products.

A vibrational spectroscopic study of the silicate mineral kornerupine

We have studied the mineral kornerupine, a borosilicate mineral, by using a combination of scanning electron microscopy with energy-dispersive analysis and Raman and infrared spectroscopy. Qualitative chemical analysis of kornerupine shows a magnesium–aluminum silicate. Strong Raman bands at 925, 995, and 1051 cm−1 with bands of lesser intensity at 1035 and 1084 cm−1 are assigned to the silicon–oxygen stretching vibrations of the siloxane units. Raman bands at 923 and 947 cm−1 are attributed to the symmetrical stretching vibrations of trigonal boron. Infrared spectra show greater complexity and the infrared bands are more difficult to assign. Two intense Raman bands at 3547 and 3612 cm−1 are assigned to the stretching vibrations of hydroxyl units. The infrared bands are observed at 3544 and 3610 cm−1. Water is also identified in the spectra of kornerupine.

SEM, EDX and vibrational spectroscopic study of the phosphate mineral ushkovite MgFe3+2(PO4)2(OH)2·8H2O: Implications of the molecular structure

The mineral ushkovite has been analyzed using a combination of electron microscopy with EDX and vibrational spectroscopy. Chemical analysis shows the mineral contains P, Mg with very minor Fe. Thus, the formula of the studied ushkovite is Mg32+(PO4)2·8H2O. The Raman spectrum shows an intense band at 953 cm−1 assigned to the ν1 symmetric stretching mode. In the infrared spectra complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong infrared bands around 827 cm−1 are attributed to water librational modes. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 2881, 2998, 3107, 3203, 3284 and 3457 cm−1. The wavenumber band at 3457 cm−1 is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH bending modes where a strong infrared band centered around 1653 cm−1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH bending bands from strongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. Vibrational spectroscopy enhances our knowledge of the molecular structure of ushkovite.