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Ab initio calculations are used to provide information on H(3)N...XY...HF triads (X, Y=F, Cl, Br) each having a halogen bond and a hydrogen bond. The investigated triads include H(3)N...Br(2)-HF, H(3)N...Cl(2)...HF, H(3)N...BrCl...HF, H(3)N...BrF...HF, and H(3)N...ClF...HF. To understand the properties of the systems better, the corresponding dyads are also investigated. Molecular geometries, binding energies, and infrared spectra of monomers, dyads, and triads are studied at the MP2 level of theory with the 6-311++G(d,p) basis set. Because the primary aim of this study is to examine cooperative effects, particular attention is given to parameters such as cooperative energies, many-body interaction energies, and cooperativity factors. The cooperative energy ranges from -1.45 to -4.64 kcal mol(-1), the three-body interaction energy from -2.17 to -6.71 kcal mol(-1), and the cooperativity factor from 1.27 to 4.35. These results indicate significant cooperativity between the halogen and hydrogen bonds in these complexes. This cooperativity is much greater than that between hydrogen bonds. The effect of a halogen bond on a hydrogen bond is more pronounced than that of a hydrogen bond on a halogen bond.

Titanium dioxide (TiO2) nanoparticles-functionalized N-doped graphene (NGR) composites (NGR/TiO2) were prepared through solvothermal treatment approach using exfoliated NGR and tetrabutyl titanate as the staring materials. The composites were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectra, photoelectrochemical, and electrochemical measurements. Nitrogen doping provides favorable nucleation and anchor sites for TiO2 nanocrystals formation on NGR sheets, helping to form an intimate interfacial contact between NGR and TiO2 nanoparticles. Moreover, NGR has higher electrical conductivity than the reduced graphene oxide (RGO) due to the recovery of the sp(2) graphite network and decrease of defects, resulting in more effective charge transfer and charge separation in the NGR/TiO2 composite. NGR/TiO2 nanocomposite demonstrated a higher photocatalytic activity for hydrogen production as compared to its counterpart, TiO2-functionalized RGO composite (RGO/TiO2). This work provides new insights to design new more efficient graphene-based nanocomposite photocatalysts for solar energy conversion.

An ab initio study of the complexes formed by hypohalous acids (HOX, X = F, Cl and Br) with formaldehyde has been carried out at the MP2/aug-cc-pVTZ computational level. Two minima complexes are found, one with an H...O contact and the other one with an X...O contact. The former is more stable than the latter, and the strength difference between them decreases as the size of the X atom increases. The associated HO and XO bonds undergo a bond lengthening and red shift, whereas a blue shift was observed in the bond of the hypohalous acid not involved in the interaction. The interaction strength and properties in both complexes are analyzed with atoms in molecules (AIM) and natural bond orbital (NBO) theories. The energy decomposition analyses indicate that the contribution from the electrostatic interaction energy is larger in the hydrogen-bonded complexes than that in the halogen-bonded complexes.

The properties and applications of halogen bonds are dependent greatly on their strength. In this paper, we suggested some measures for enhancing the strength of the halogen bond relative to the hydrogen bond in the H(2)CS-HOX (X = F, Cl, and Br) system by means of quantum chemical calculations. It has been shown that with comparison to H(2)CO, the S electron donor in H(2)CS results in a smaller difference in strength for the Cl halogen bond and the corresponding hydrogen bond, and the Br halogen bond is even stronger than the hydrogen bond. The Li atom in LiHCS and methyl group in MeHCS cause an increase in the strength of halogen bonding and hydrogen bonding, but the former makes the halogen bond stronger and the latter makes the hydrogen bond stronger. In solvents, the halogen bond in the Br system is strong enough to compete with the hydrogen bond. The interaction nature and properties in these complexes have been analyzed with the natural bond orbital theory.

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It is found that Cu 2+ is an effective agent for the controlled preparation of shaped gold nanoparticles. As the concentration of Cu 2+ increases from 0 mM to 0.2 mM to 1.6 mM, the shape of the gold nanoparticles changes from rod to cuboid to decahedron. A possible mechanism based on selectively retarding the growth rate of the {111} plane is proposed.