Energy Storage by Poly(<Emphasis Type="Italic">o</Emphasis>-anisidine) Matrix During Oxidative Hydrolysis

The chromaticity of poly(o-anisidine) (POAN) doped with different acids (HA), HA-doped POAN, has been studied by the spectrophotometric technique and the results were substantiated by molecular mechanics (MM+) calculations. The observed absorbance decrease (λ around 720 nm, dark green coloration) with increasing concentration of the inorganic oxidizing agent (KMnO₄) can be attributed to the oxidative hydrolysis mechanism. The oxidative hydrolysis constant (K _h) is highly dependent on the strength of the acid used. The HClO₄-doped POAN matrix has the ability to store about 128.878 kJ⋅g⁻¹ chromogenic energy (CE) at the wavelength 720 nm in a condensed lightweight form. MM+ calculations suggest that the potential energy (PE) in kJ⋅mol⁻¹ of the optimum molecular geometric (OMG) structure of the HClO₄-doped POAN matrix is at least two (2.052) times more stable than the OMG of the base form (POAN-EB) of the POAN matrix. Kinetic parameters of the oxidative hydrolysis reaction of the HA-doped POAN matrix were deduced from absorbance variations with time. The results of computer-oriented kinetic analysis indicate that the rate-controlling step for HA-doped POAN oxidative hydrolysis is governed by the Ginstling-Bronshein equation that represents three-dimensional diffusion (D4). Activation parameters for the oxidative hydrolysis of the HClO₄-doped POAN matrix were computed and discussed.     

M@B<Subscript>9</Subscript> and M@B<Subscript>10</Subscript> molecular wheels containing planar nona- and deca-coordinate heavy group 11, 12, and 13 metals (M=Ag,Au, Cd,Hg, In,Tl)

A density functional and ab initio theory investigation on M@B₉ and M@B₁₀ molecular wheels containing planar nona- and deca-coordinate heavy group 11, 12 and 13 metals (M=Ag, Au, Cd, Hg, In, Ti) has been performed. These unusual clusters all prove to be true minima on the potential energy surfaces of the systems and σ+π double aromatic in nature. The first two vertical one-electron detachment energies of M@B₁₀⁻ (M=Ag, Au) anions and first two ionization potentials of M@B₉ (M=Ag, Au) and M@B₁₀ (M=Cd, Hg) neutrals were calculated to aid future experiments. The cluster complexes designed in this work may expend the domain of planar hyper-coordinate elements to include heavy group 11, 12, and 13 metals and serve as interesting candidates to be targeted in experiments. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by the National Natural Science Foundation of China (Grant No. 20873117)     

Analysis of viscosity abnormalities of polyelectrolytes in dilute solutions

It was found that the interface effects in viscous capillary flow influenced the process of viscosity measurement greatly,and the abnormal viscosity behaviors of polyelectrolytes as well as neutral polymers in dilute solution region were ascribed to interface effect.According to this theory,we have reviewed the previous viscosity data of derivatives of poly-2- vinylpyridine reported by Maclay and Fuoss first.Then,the abnormal viscosity behaviors of a series of sodium polystyrene sulfonate samples with various molecular weights in dilute aqueous solutions were studied further.The solute adsorption behaviors and structural information of polymers have been discussed carefully.     

Guanidine-based task-specific ionic liquids as catalysts for aza-Michael addition under solvent-free conditions

An efficient and facile protocol for aza-Michael addition of aliphatic and aromatic amines to electron-deficit alkenes using [TMG][Lac] as catalyst under solvent-free conditions was established.     

Self-supported metal sulphide nanocrystals-assembled nanosheets on carbon paper as efficient counter electrodes for quantum-dot-sensitized solar cells

Developing efficient counter electrodes (CEs) and quantum dots made of earth-abundant and non-toxic elements is essential but still challenging for quantum dot-sensitized solar cells (QDSSCs). Here, we report a facile strategy to prepare self-supported and robust CoS₂ and NiS nanocrystals-assembled nanosheets directly grown on carbon paper (MSx NS@CP) as efficient counter electrodes for QDSSCs. Such CEs integrate the merits of fast electron transfer from interconnected conductive scaffold, efficient mass transfer from hierarchically vertical nanosheet on 3D open substrate, as well as abundant highly active catalytic sites from metal sulphide nanocrystal units. As a result, QDDSCs based on such CoS₂ NS@CP and NiS NS@CP CEs achieve a PCE of 8.88% and 7.53%, respectively. The detailed analyses suggest that CoS₂ NS@CP has the highest catalytic activity and shows the lowest charger transfer resistance, leading to the highest PCE. These findings may inspire the design and exploration of other self-supported efficient CEs by integrating highly active catalysts onto 3D conductive networks for efficient QDSSCs.