Influence of Size and Shape on the Photocatalytic Properties of SnO2 Nanocrystals

Tuning the functional properties of nanocrystals is an important issue in nanoscience. Here, we are able to tune the photocatalytic properties of SnO₂ nanocrystals by controlling their size and shape. A structural analysis was carried out by using X‐ray diffraction (XRD)/Rietveld and transmission electron microscopy (TEM). The results reveal that the number of oxygen‐related defects varies upon changing the size and shape of the nanocrystals, which eventually influences their photocatalytic properties. Time‐resolved spectroscopic studies of the carrier relaxation dynamics of the SnO₂ nanocrystals further confirm that the electron–hole recombination process is controlled by oxygen/defect states, which can be tuned by changing the shape and size of the materials. The degradation of dyes (90 %) in the presence of SnO₂ nanoparticles under UV light is comparable to that (88 %) in the presence of standard TiO₂ Degussa P‐25 (P25) powders. The photocatalytic activity of the nanoparticles is significantly higher than those of nanorods and nanospheres because the effective charge separation in the SnO₂ nanoparticles is controlled by defect states leading to enhanced photocatalytic properties. The size‐ and shape‐dependent photocatalytic properties of SnO₂ nanocrystals make these materials interesting candidates for photocatalytic applications.     

Near‐forward/high‐pressure‐backward Raman study of Zn1 − xBexSe (x ~ 0.5) – evidence for percolation behavior of the long (Zn―Se) bond

The apparently universal 1‐bond → 2‐mode percolation behavior in the Raman spectra of zincblende semiconductor alloys is generally observed for the short bond only, and not for the long one. In this work we perform a combined high‐pressure‐backward/near‐forward Raman study of the leading percolation‐type (Zn,Be)Se alloy (~50 at.% Be), which exhibits a distinct percolation doublet in the spectral range of its short Be―Se bond, in search of a Zn―Se analogue. The high‐pressure‐backward insight is not conclusive per se, but clarifies the perspective behind the near‐forward Raman study. The latter reveals an unique Zn―Se phonon–polariton. Its fair contour modeling depending on the scattering angle is achieved within the linear dielectric approach, based on ellipsometry measurement of the ZnBeSe refractive index. Somewhat surprisingly this reveals that the phonon–polariton in question is a ‘fractional’ one in that it carries only half of the available Zn―Se oscillator strength, as ideally expected in case of a BeSe‐like bimodal Raman behavior of the long Zn―Se bond. Copyright © 2015 John Wiley & Sons, Ltd.     

Superhalogen properties of CumCln clusters: theory and experiment

Using a combination of density functional theory and anion photoelectron spectroscopy experiment, we have studied the structure and electronic properties of CuCl(n)(-) (n = 1-5) and Cu(2)Cl(n)(-) (n = 2-5) clusters. Prominent peaks in the mass spectrum of these clusters occurring at n = 2, 3, and 4 in CuCl(n)(-) and at n = 3, 4, and 5 in Cu(2)Cl(n)(-) are shown to be associated with the large electron affinities of their neutral clusters that far exceed the value of Cl. While CuCl(n) (n ≥ 2) clusters are conventional superhalogens with a metal atom at the core surrounded by halogen atoms, Cu(2)Cl(n) (n ≥ 3) clusters are also superhalogens but with (CuCl)(2) forming the core. The good agreement between our calculated and measured electron affinities and vertical detachment energies confirm not only the calculated geometries of these superhalogens but also our interpretation of their electronic structure and relative stability.     

Potential candidates for hyperhalogens: a comparative study of BO2, AlO2, and VO3 species

Recent work has shown that BO(2) which is a superhalogen with an electron affinity of 4.46 eV, can be used as building block of a new class of molecules/clusters whose electron affinities can exceed that of BO(2). This class of molecules was named hyperhalogens and the concept was illustrated by focusing on Au(BO(2))(2). Here we explore other superhalogens besides BO(2) to see if they too can be used to form hyperhalogens. We have chosen to focus on AlO(2) which is valence isoelectronic with BO(2) as well as VO(3) which involves a transition metal atom. The results obtained using density functional theory show unexpected behavior: Although AlO(2) and VO(3) are both superhalogens such as BO(2), only Na(BO(2))(2) is a hyperhalogen while Na(AlO(2))(2) and Na(VO(3))(2) are not. The origin of this anomalous result is traced to the large binding energy of the dimers of AlO(2) and VO(3).     

Enhanced photocatalytic and adsorptive degradation of organic dyes by mesoporous Cu/Al2O3-MCM-41: intra-particle mesoporosity, electron transfer and OH radical generation under visible light

Mesoporous Cu/Al(2)O(3)-MCM-41 composite was synthesized by two step processes; in situ incorporation of high surface area mesoporous Al(2)O(3) (MA) into the framework of MCM-41 (in situ method) followed by impregnation of Cu(II) by incipient wetness method. The interesting thing is that starch was used for the first time as template for the preparation of high surface area MA. To evaluate the structural and electronic properties, these catalysts were characterized by low angle X-ray diffraction (LXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-vis DRS, FTIR and photoluminescent (PL) spectra. The various cationic dye such as methylene blue (MB), methyl violet (MV), malachite green (MG) and rhodamine 6G (Rd 6G) of high concentration 500 mg L(-1) were degraded and adsorbed very efficiently (100%) using the 5 Cu/Al(2)O(3)-MCM-41 composite within 30 and 60 min, respectively. The high and quick removal of such concerted cationic organic dyes and also mixed dyes (MB+MV+MG+Rd 6G) by means of photocatalysis/adsorption is basically due to the combined effect three characteristics of synthesized mesoporous 5 Cu/Al(2)O(3)-MCM-41 composite. These characteristics are intra-particle mesoporosity, electron transfer and ˙OH radical generation under solar light.     

Thermally controlled cyclic insertion/ejection of dopant ions and reversible zinc blende/wurtzite phase changes in ZnS nanostructures

We report a reversible phase transformation of platelet-shaped ZnS nanostructures between wurtzite (WZ) and zinc blende (ZB) phases by reversible insertion/ejection of dopant Mn(II) ions induced by a thermocyclic process. In a reaction flask loaded with WZ ZnS platelets and Mn molecular precursors, during heating Mn ions are incorporated and change the phase of the host nanostructures to ZB; during cooling Mn ions are spontaneously ejected, returning the host nanoplatelets to the original WZ phase. These reversible changes are monitored for several cycles with PL, EPR, XRD, and HRTEM. Interestingly, the (0001) WZ platelets transform to (110) ZB following a nucleation and growth process triggered by a local increase/depletion of the Mn(2+) concentration in the nanocrystals.     

Interactions of a Mn atom with halogen atoms and stability of its half-filled 3d-shell

Using density functional theory with hybrid exchange-correlation potential, we have calculated the geometrical and electronic structure, relative stability, and electron affinities of MnX(n) compounds (n = 1-6) formed by a Mn atom and halogen atoms X = F, Cl, and Br. Our objective is to examine the extent to which the Mn-X interactions are similar and to elucidate if/how the half-filled 3d-shell of a Mn atom participates in chemical bonding as the number of halogen atoms increases. While the highest oxidation number of the Mn atom in fluorides is considered to be +4, the maximum number of halogen atoms that can be chemically attached in the MnX(n)(-) anions is 6 for X = F, 5 for X = Cl, and 4 for X = Br. The MnCl(n) and MnBr(n) neutrals are superhalogens for n ≥ 3, while the superhalogen behavior of MnF(n) begins with n = 4. These results are explained to be due to the way different halogen atoms interact with the 3d electrons of Mn atom.     

A systematic study of neutral and charged 3d-metal trioxides and tetraoxides

Using density functional theory with generalized gradient approximation, we have performed a systematic study of the structure and properties of neutral and charged trioxides (MO(3)) and tetraoxides (MO(4)) of the 3d-metal atoms. The results of our calculations revealed a number of interesting features when moving along the 3d-metal series. (1) Geometrical configurations of the lowest total energy states of neutral and charged trioxides and tetraoxides are composed of oxo and∕or peroxo groups, except for CuO(3)(-) and ZnO(3)(-) which possess a superoxo group, CuO(4)(+) and ZnO(4)(+) which possess two superoxo groups, and CuO(3)(+), ZnO(3)(+), and ZnO(4)(-) which possess an ozonide group. While peroxo groups are found in the early and late transition metals, all oxygen atoms bind chemically to the metal atom in the middle of the series. (2) Attachment or detachment of an electron to∕from an oxide often leads to a change in the geometry. In some cases, two dissociatively attached oxygen atoms combine and form a peroxo group or a peroxo group transforms into a superoxo group and vice versa. (3) The adiabatic electron affinity of as many as two trioxides (VO(3) and CoO(3)) and four tetraoxides (TiO(4), CrO(4), MnO(4), and FeO(4)) are larger than the electron affinity of halogen atoms. All these oxides are hence superhalogens although only VO(3) and MnO(4) satisfy the general superhalogen formula.     

Order–disorder transition in nanocrystalline Ni3Al prepared by a chemical route

Ni₃Al alloys of nanometer dimensions in the range 10–38 nm could be synthesized by reaction sintering of sol–gel-derived Ni/SiO₂ nanocomposite and commercially available micrometer-sized aluminum powder. The sintering was carried out at a temperature of 923 K and a pressure of 2.4 MPa. By a suitable choice of sintering conditions a disordered phase of Ni₃Al was stabilized. The disordered phase could be converted to an ordered one by an increase of heat treatment temperature.