Review of Systematic Tendencies in (001), (011) and (111) Surfaces Using B3PW as Well as B3LYP Computations of BaTiO3, CaTiO3, PbTiO3, SrTiO3, BaZrO3, CaZrO3, PbZrO3 and SrZrO3 Perovskites.

We performed B3PW and B3LYP computations for BaTiO3 (BTO), CaTiO3 (CTO), PbTiO3 (PTO), SrTiO3 (STO), BaZrO3 (BZO), CaZrO3 (CZO), PbZrO3 (PZO) and SrZrO3 (SZO) perovskite neutral (001) along with polar (011) as well as (111) surfaces. For the neutral AO- as well as BO2-terminated (001) surfaces, in most cases, all upper-layer atoms relax inwards, although the second-layer atoms shift outwards. On the (001) BO2-terminated surface, the second-layer metal atoms, as a rule, exhibit larger atomic relaxations than the second-layer O atoms. For most ABO3 perovskites, the (001) surface rumpling s is bigger for the AO- than BO2-terminated surfaces. In contrast, the surface energies, for both (001) terminations, are practically identical. Conversely, different (011) surface terminations exhibit quite different surface energies for the O-terminated, A-terminated and BO-terminated surfaces. Our computed ABO3 perovskite (111) surface energies are always significantly larger than the neutral (001) as well as polar (011) surface energies. Our computed ABO3 perovskite bulk B-O chemical bond covalency increases near their neutral (001) and especially polar (011) surfaces.

Mechanistic insight into the tautomerization of histidine initiated by water-catalyzed N-H and C-H cleavages.

The N-H and C-H activation is of great significance in organic chemistry and chemical industry fields, especially, in the utilization of petroleum raw materials. High NδH (tautomer of natural histidine) content would increase Alzheimer's disease risk. To inhibit this and improve the activation of N-H and C-H bonds, the isomerization mechanism from NδH to NεH of histidine-containing dipeptide catalyzed by water cluster was explored. The results discovered that water cluster assists this reaction by reducing the activation energies from 68.20 to 9.60 kcal mol-1, and its size not only affects the reaction rate but also determines the reaction pathway in a degree. Moreover, water cluster, taken as a potential green catalyst, is more effective on the reactions involving N-H and C-H bond cleavages than reported common toxic organometallic compounds and has different catalytic mechanisms. This work also provides some theoretical guidance for the modulation of Alzheimer's disease induced by histidine isomerization.

Amine-functionalized ionic liquids for CO2 capture.

In petroleum industry, the release of more and more carbon dioxide (CO2) brings greenhouse effect and even results in climate change, leading CO2 capture to become an urgent issue. To design ideal and effective absorbent, interaction mechanism for CO2 capture was systematically investigated in a series of imidazolium-based ionic liquids (ILs). The potential effects of alkyl side chain, electron-philic halogen (F, Cl, Br) atom(s), electron-denoting groups OH and NH2 (bound on cation or/and anion), and water solvent were disclosed on CO2 capture using CAM-B3LYP functional with SMD-GIL solvation model, and the most potential green effective absorbent was predicted. This work provides an explicit idea and theoretical basis about the design of desired IL for CO2 capture. Graphical abstract In present work, no/halogen/amino/hydroxy-functionalized imidazolium tetrafluoroborate ILs were studied for CO2 absorption at the CAM-B3LYP/6-311++G** level of theory by SMD-GIL solvation model. NH2 is more potent group in absorbing CO2 than halogen and OH, and its number is proportional to the adsorption capacity of IL. A potentially high-capacity CO2 absorbent with four NH2 groups was predicted. In addition, the mixture of water could further enhance such chemical absorption by lowering the activation energy barriers and viscosity of IL.