ChemInform Abstract: The Crystal Structures of m,o‐Ce3Pt4Sn6 and Ce1‐xPt6Al13+2x.

Single crystals of Ce₃Pt₄Sn₆ (I) and Ce_1‐xPt₆Al_13+2x (x = 0.207, (II)) are isolated by mechanical fragmentation of specimens grown from self‐fluxes (Sn or Al, resp.) by slow cooling from the melt.     

Electrochemical Determination of Uric Acid Using a Multiwalled Carbon Nanotube Platinum–Nickel Alloy Glassy Carbon Electrode

Platinum–nickel nanoparticles were synthesized by a reduction procedure. The Pt–Ni/C composite was characterized by X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and electrochemical analysis. The measurements show that the Pt–Ni/multiwalled carbon nanotubes provided higher electrocatalytic activity for the oxidation of uric acid than Pt–Ni/carbon black. The sensor prepared from the characterized material provided a long linear dynamic range from 0.1 to 240.4?µM with a detection limit of 0.03?µM and a sensitivity of 41.21?µA?mM^?1?cm^?2. The reported modified electrode also provided excellent selectivity, good stability, and satisfactory reproducibility for the determination of uric acid.     

Nonenzymatic Electrochemical Glucose Sensor Based on Pt Nanoparticles/Mesoporous Carbon Matrix

A nonenzymatic amperometric sensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported onto mesoporous carbons (MCs). The Pt nanoparticles/mesoporous carbons (Pt/MCs) composites modified electrode displayed high electrocatalytic activity towards the oxidation of glucose. At an applied potential of 0.1 V, the Pt/MCs electrode has a linear dependence (R=0.996) in the glucose concentration up to 7.5 mM with a sensitivity of 8.52 mA M^?1 cm^?2. The Pt/MCs electrode has also shown highly resistant toward poisoning by chloride ions and without interference from the oxidation of common interfering species.     

Theoretical studies on the electronic structures and spectroscopic properties of a series of novel N?C?N‐coordinating Pt(II) complexes

The electronic structures and spectroscopic properties of the three tridentate cyclometalated Platinum(II) complexes PtL¹Cl [L¹ = 1,3‐di(2‐pyridyl)‐5‐methyl‐benzene] ( 1 ), PtL²Cl [L² = 1‐(2‐pyridyl)‐3‐(1‐pyrazolyl)‐5‐methyl‐benzene] ( 2 ), and PtL³Cl [L³ = 1,3‐bis(1‐pyrazolyl)‐5‐methyl‐benzene] ( 3 ) were calculated to explore their spectroscopic nature. The geometry structures of 1 – 3 in the ground and excited states were optimized under the density functional theory (DFT) and the single‐excitation configuration interaction (CIS) level, respectively. The absorption and emission spectra in CH₂Cl₂ solution were calculated by the time‐dependent density‐functional theory (TD‐DFT) with the polarized continuum model solvent model. As revealed from the calculations, the LUMO of 1 and 2 are localized on phenyl and pyridyl, but that of 3 has 50.3% π*(pyrazolyl) and 47.8% π*(phenyl). The energy gap of the d‐d state was much greater than that of the CT transitions. With the replacement of pyridyl by pyrazolyl, the electron‐donating ability of N atom decreases, whereas the LUMO energy level increases. The lowest‐energy absorptions and emissions are blue‐shifted in the order 1 > 2 > 3 , which are assigned as the ILCT/MLCT/LLCT and ³ILCT/³MLCT/³LLCT characters, respectively. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Five-membered ring chelate complexes of Ni(II), Pd(II) and Pt(II) derived of di-(2-pyridyl)-N-ethylimine

Cis-diaquobis{di-(2-pyridyl)-N-ethylimine}nickel(II) chloride (2) was obtained from the reaction of di-(2-pyridyl)-N-ethylimine (1) and [NiCl₂dppe] [dppe = cis-1,2-bis(diphenylphosphino)ethylene] in a 2:1 ratio in hot acetonitrile. Cis-dichloro{di-(2-pyridyl)-N-ethylimine}palladium(II) (3) and cis-dichloro{di-(2-pyridyl)-N-ethylimine}platinum(II) (4) complexes were obtained from the reaction of MCl₂ (M = Pd, Pt) and (1) in equimolar ratio in hot acetonitrile. Compounds 1–4 were characterized by IR spectroscopy, elemental analysis, and mass spectrometry; the complexes 3 and 4 were characterized in solution by NMR. In addition, solid state structures of compounds 1–4 were determined using single crystal X-ray diffraction analyses. X-ray diffraction data of the complexes 3 and 4 showed a distorted square planar local geometry at palladium and platinum atoms with the chlorine atoms in a cis-coordination; in 2 a local octahedral geometry at nickel atom was observed. Complexes 3 and 4 are arranged as dimers with a M?M distance of 3.4567(4) Å (M = Pd) and 3.4221(4) Å (M = Pt), respectively; 2 consists of units linked by intermolecular hydrogen bonding.     

碳载Pt-Ni催化剂对直接甲醇燃料电池阴极氧电还原性能的影响

采用间歇式微波法制备了不同Pt、Ni原子比的碳载Pt-Ni催化剂。XRD结果表明,用这种方法制备的催化剂分散得比较好,具有较小的平均粒径,其中Pt-Ni/C(3∶1)催化剂的粒径最小。在旋转圆盘电极上进行氧的还原测试结果表明,当电解质溶液中没有甲醇和有甲醇存在时,Pt-Ni/C(3∶1)催化剂对氧的催化还原活性都很高,说明Pt-Ni/C(3∶1)催化剂对氧的催化还原受甲醇的影响较小。     

Reaction mechanism of methanol decomposition on Pt‐based model catalysts: A theoretical study

The decomposition mechanisms of methanol on five different Pt surfaces, the flat surface of Pt(111), Pt‐defect, Pt‐step, Pt(110)(1 × 1), and Pt(110)(2 × 1), have been studied with the DFT‐GGA method using the repeated slab model. The adsorption energies under the most stable configuration of the possible species and the activation energy barriers of the possible elementary reactions involved are obtained in this work. Through systematic calculations for the reaction mechanism of methanol decomposition on these surfaces, we found that such a reaction shows the same reaction mechanism on these Pt‐based model catalysts, that is, the final products are all H (H_ads) and CO (CO_ads) via O? H bond breaking in methanol and C? H bond scission in methoxy. These results are in general agreement with the previous experimental observations. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010.     

CO和H在Pt/WC(0001)表面的吸附

采用密度泛函理论(DFT)和周期平板模型,研究两种WC(0001)表面的几何结构和表面能,并对Pt原子单层(PtML)在两种WC(0001)表面的高对称性吸附位上的吸附能和分离功进行计算.结果发现,终止于W原子的WC(0001)为最稳定的WC(0001)表面,Pt原子单层以hcp位的方式吸附于W终止的WC(0001)表面是PtML/WC(0001)体系最稳定的几何构型.在此基础上研究了CO分子和H原子分别在PtML/WC(0001)表面和具有相似表面结构的Pt(111)表面的吸附行为.在0.25 ML(monolayer)低覆盖度下,与在Pt(111)表面相比,在PtML/WC(0001)表面上的Pt—C间距明显拉长和CO分子吸附能减少,说明PtML/WC(0001)表面抗CO中毒能力比Pt(111)表面高;态密度分析进一步解释了CO分子与不同表面Pt原子的成键机理.在同一覆盖度下,H原子在PtML/WC(0001)表面的最大吸附能等于甚至略高于在Pt(111)表面的,表明Pt/WC对氢气氧化反应具有良好的催化活性,是一种很有前途的质子交换膜燃料电池(PEMFC)阳极催化剂.     

Correlation between microstructure and property of electroless deposited Pt counter electrodes on plastic substrate for dye-sensitized solar cells

Flexible Pt counter electrodes (CEs) were prepared on indium-doped tin oxide coated polyethylene naphthalate (ITO-PEN) substrate by electroless deposition. The correlation between the microstructure and the property of the Pt CEs was investigated. Results showed that isolated Pt nanoparticles were uniformly distributed on the ITO surface at a short deposition duration, and then grew with the deposition duration, leading to the interconnection of adjacent Pt nanoparticles. The interconnection of Pt nanoparticles was beneficial to the electrical property of the Pt CEs, while it was unfavorable to the electrocatalytic property of the Pt CEs. A microstructure model was proposed to explain the correlation between the microstructure and the property of the Pt CEs. In addition, the Pt CEs showed low charge transfer resistance (1.66-0.58 Ω cm²), which was comparable to that (1.16 Ω cm²) of the conventional sputtered Pt CE. The high electrocatalytic property of the electroless deposited Pt CEs makes the assembled DSCs present comparable energy conversion efficiency of the DSCs using sputtered Pt CE.     

Swiss-Roll燃烧器催化剂结构的实验研究

实验研究了装有Pt覆盖的多孔陶瓷的Swiss-Roll燃烧器的燃烧特性,分别得到了3种不同长度的催化剂基底的熄火极限,并测量3种情况下催化剂壁面及催化剂后部空间的温度。实验结果表明,3种情况中,催化剂基底长4.5mm的燃烧器可燃范围最大,所以此长度较适合此Swiss-Roll燃烧器。从温度数据可以看出来,催化剂后部空间存在反应,且受上游催化剂表面反应强度的影响。