Single Crystal of a Prussian Blue Analog based on Rubidium Manganese Hexacyanoferrate

A dark brown single crystal of rubidium manganese hexacyanoferrate, Rb_0.61Mn[Fe(CN)₆]_0.87·1.7H₂O, was obtained by the slow diffusion method. X‐ray single crystal analysis showed that this compound crystallized in the cubic system of space group with cell constants of a = b = c = 10.5354(4) Å, Z = 4, and R₁ = 0.0449. The CN groups bridge octahedral FeC₆ and MnN_0.87O_0.13. Rb and non‐coordinated water (so‐called zeolitic water) exist in the interstitial sites of the cubic lattice.     

Characterization of gold nanoparticles electrochemically deposited on amine-functioned mesoporous silica films and electrocatalytic oxidation of glucose

This study reports the preparation and characterization of gold nanoparticles deposited on amine-functioned hexagonal mesoporous silica (NH₂–HSM) films and the electrocatalytic oxidation of glucose. Gold nanoparticles are fabricated by electrochemically reducing chloroauric acid on the surface of NH₂–HSM film, using potential step technology. The gold nanoparticles deposited have an average diameter of 80 nm and show high electroactivity. Prussian blue film can form easily on them while cycling the potential between −0.2 and 0.6 V (vs saturated calomel electrode) in single ferricyanide solution. The gold nanoparticles loading NH₂–HSM-film-coated glassy carbon electrode (Au–NH₂–HSM/GCE) shows strong catalysis to the oxidation of glucose, and according to the cathodic oxidation peak at about 0.16 V, the catalytic current is about 2.5 μA mM⁻¹. Under optimized conditions, the peak current of the cathodic oxidation peak is linear to the concentration of glucose in the range of 0.2 to 70 mM. The detection limit is estimated to be 0.1 mM. In addition, some electrochemical parameters about glucose oxidation are estimated.     

Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm · HCl) containing Fe^II or Fe^III and M²⁺ (M=Fe, Co, Cu) in a 11 molar ratio were obtained by the reaction of [Fe(CN)₆] ^n– (n=3,4) with M²⁺ ion-PVAm · HCl mixture in aqueous solution. Under a limited polymer concentration (T_VAm/T_Fe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm · HCl was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (Fe^IIFe^III, Co^IIFe^III, Fe^IICu^II) band for MFe(CN)₆]^(n–2)– bound to PVAm · HCl (M=Fe, Co, Cu) were found to be 10,100–9601 · mol^–1 · cm^–1 at 25 C. The formation constants were found to be in the range of 10⁷ to 10¹⁰ M^–1. The changes of enthalpy (H) and entropy (S) were found to be in the range of –10.4 to –22.5 kJ · mol^–1 and 5.7 to 52.9 J · K^–1 mol^–1 respectively, at 25C.     

A novel Prussian blue‐magnetite composite synthesized by self‐template method and its application in reduction of hydrogen peroxide

A novel Prussian blue (PB)‐Fe₃O₄ composite has been prepared for the first time by self‐template method using PB as the precursor. According to this method, Fe₃O₄ nanoparticles distributed uniformly on the surface of PB cube. The feed ratio of sodium acetate to PB has been proved to be a key factor for magnetic properties and electro‐catalysis properties of the composite. Under the experimental conditions, the saturation magnetization value (Ms) of PB‐Fe₃O₄–2 composite was 22 emug^?1, while the Ms value of other samples reduced. The composites also showed a good peroxidase‐like activity for the oxidation of substrate 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of H₂O₂. The catalytic reduction of hydrogen peroxide capacity was PB‐Fe₃O₄–1> PB‐Fe₃O₄–2> PB‐Fe₃O₄–3> PB‐Fe₃O₄–0, which confirmed the Fe(II) centres in PB surface and Fe₃O₄ nanoparticles had synergistic effect on catalytic reduction of hydrogen peroxide.     

表面吸附碱金属原子的超短碳纳米管体系的结构和非线性光学性质

采用密度泛函理论(DFT)方法系统研究了表面吸附碱金属Li原子的超短碳纳米管([8]cyclophenacene)体系的结构和非线性光学性质.在这些体系中,Li原子均能稳定地吸附在超短碳纳米管表面,其吸附能高达84.0~106.2 kJ/mol.当吸附1~2个Li原子时,Li原子和碳纳米管之间发生了明显的电荷转移过程,使体系的一阶超极化率(β0)值明显改善,β0值从0迅速增加到3.42×103~8.29×103a.u.;当吸附的Li原子数增加到3时,体系内部产生了额外电子,有效地降低了体系最主要跃迁的跃迁能,使体系的一阶超极化率进一步提升(高达2.59×106a.u.).此外,Li原子之间的距离也是影响吸附体系β0值的重要因素.     

碱金属原子吸附PPV及其衍生物体系的结构和非线性光学性质的理论研究

采用密度泛函理论(DFT)方法系统研究了碱金属Li原子吸附亚苯基-1,2-亚乙烯基(Phenylenevinylene)聚合物(PPV)及其衍生物(具有给受体基团修饰的)体系的结构和非线性光学性质.Li原子能稳定地吸附在PPV及其衍生物的表面,吸附能高达62.3~78.2 kJ/mol.当碱金属Li原子吸附在[PPV]n(n=2~4)表面时,锂盐效应导致了Li原子和[PPV]n之间发生了明显的电荷转移过程,使体系的一阶超极化率β0从249~756 a.u.明显增加到1.16×104~1.37×105a.u..当碱金属Li原子吸附在只有给体(—NH2)或只有受体(—CN)基团修饰的PPV衍生物{[NH2-(PPV)n]/[(PPV)n-CN]}时,体系的一阶超极化率值进一步提升,分别高达1.61×105a.u.(n=4)和2.85×105a.u.(n=4).这主要源于锂盐效应和Donor-π-Acceptor之间的协同作用导致跃迁能进一步降低所致.在Li原子吸附的具有给受体基团同时修饰的PPV衍生物(Li@[NH2-(PPV)n-CN])体系中,这种协同作用得到进一步加强,显著改善了体系的一阶超极化率(高达3.56×105a.u.,n=4).