Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

电子行业用高纯钯的制备研究

高纯钯在电子行业等领域应用广泛，需求迫切。以氯化钯为原料，提出采用氯化铵沉淀-氨水配合联合工艺净化钯溶液，水合肼还原纯净钯溶液制备高纯钯。结果表明，固体氯化钯溶解后，在合适的条件下，该钯溶液经过氧化-氯化铵沉淀、氨水配合有效去除杂质元素，获得纯净二氯四氨合钯溶液，再经水合肼还原后，获得纯度99.999%高纯钯，其碳、氧、氮等杂质元素总含量小于355×10^-6。     

Revised Model of Strain in Ceria–Zirconia-Encapsulated Precious-Metal Particles

A previously proposed model of strain in ceria–zirconia-encapsulated precious-metal particles is revised to reflect several new observations: encapsulation of unstrained Pt particles, quantitative relation between partial reduction and the change in ceria–zirconia cell parameters, temperature/time dependence of strain relaxation/imposition in encapsulated Pd and Rh particles, and strained PdO. According to the revised model, the main cause of strain is partial oxidation of the precious metal (rather than the change in oxygen content of ceria–zirconia, as originally suggested).     

磷酸盐激光玻璃中铂颗粒密度与氧化还原平衡关系的研究

用吸收光谱法研究了Ｒ２Ｏ—ＢａＯ—Ｐ２Ｏ５系统磷酸盐激光玻璃中铂颗粒密度与铭的氧化还原平衡的关系。结果表明，玻璃中铂颗粒密度随平衡向右移动而减小；玻璃中平衡随熔炼气氛中氧分压增大、熔炼温度升高而向右移动，当足够大时，铂颗粒不能形成。     

硫酸铵-氯化亚锡-孔雀绿体系浮选分离铂

研究了在盐酸介质中硫酸铵存在下氯化亚锡—孔雀绿—水体系浮选分离铂的方法。在最佳实验条件下，铂的浮选率可达100．0％，并与常见贱金属完全分离。     

Platinum promoted zirconia-sulfate catalysts: one-pot preparation,physical properties and catalytic activity

A new innovative methodology for the single-stage preparation of ZrO₂-SO₄ and Pt/ZrO₂-SO₄ catalysts is reported, based on the sol-gel technique. Catalysts are characterized by analysis, XRPD, BET and IR methods and are tested in the isomerization of butane.     

Oxidation of methane over platinum in a solid proton-conducting electrolyte cell

Studies of the complete oxidation of methane on a Pt electrode-catalyst in the cell with a solid proton-conducting electrolyte (CH₄ + O₂, Pt ¦ SrCe_0.92Dy_0.08O₃ ¦ Pt, H₂O + N₂) were carried out. The non-Faradaic effect of electrochemical hydrogen pumping on the rate of methane oxidation has been demonstrated. The induced change in the reaction rate at anodic polarization of a Pt electrode-catalyst was over two orders of magnitude higher than the rate of hydrogen pumping from the reaction zone through the electrolyte.     

The applicability of the ITS-90 method to platinum resistance thermometers of different purity

The static characteristics of platinum resistance thermometers with different platinum purities were measured. It is shown that in the 0–420°C range the ITS-90 method gives an error of less than 0.01°C, while in the 0–230°C range the error is less than 0.006°C. __________ Translated from Izmeritel’naya Tekhnika, No. 12, pp. 33–36, December, 2006.     

Changes in seebeck coefficient of Pt and Pt 10% Rh after use to 1700°C in High-purity polycrystalline alumina

A technique is presented that enables the effects of temperature on the Seebeck coefficient to be assessed for individual wires. The technique, involving a high-resolution thermoelectric scanning rig and a nonuniform conditioning furnace of known temperature profile, was applied to 0.5-mm-diameter wires of Pt and Pt 10% Rh. Changes were observed in Seebeck coefficient when these wires were used in high-purity twin-bore insulation for up to 200 h at temperatures over the range 500 to 1700°C. Contamination from the insulation was found to be transmitted by a vaporization process, having an activation energy of 3 eV. This caused changes of up to 0.14 V · °C^–1 in Pt and 0.01 V · °C^–1 in Pt 10% Rh. Rhodium transfer to the pure Pt wire changed its Seebeck coefficient by up to 5 V · °C^–1. The consequences of both processes for thermocouple pyrometry are presented.