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.     

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.     

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.     

巯基活性炭分离富集发射光谱法同时测定金、铂、钯和铊

研究了巯基活性炭在盐酸介质中对金、铂、钯和铊的吸附能力。该法具有吸附速度快、吸附容量大、在一定条件下，普通金属不被吸附的特点，可用于分离富集各类矿物中微量贵金属。吸附后巯基活性炭低温灰化，与缓冲剂混合发射光谱法同时测定金、铂、钯和铊，选择锆作内标线，直接压样于杯形的石墨电极中，该方法简便、快速、准确。对测定条件、干扰因素进行了研究，从而建立测定金、铂、钯和铊的新方法。金、铂、钯和铊的分析线分别为312.3nm，306．5nm，311．4nm和313．1nm，内标线选择为310．7nm的锆，金、铂、钯和铊的线性范围(原子百分数)分别为0～0．20％，0～0．40％，0～0．20％和0～0．40％。金、铂、钯和铊的检测限分别0．01％，0．003％，0．003％和0．001％。用于样品的测定获得满意结果。     

Epoxidation of β-ionone using molecular oxygen over Pt/MCM-41 catalyst under mild conditions

The epoxidation of β-ionone over the Pt/MCM-41 catalyst using molecular oxygen in the liquid phase had been studied. The results indicated that the β-ionone was catalytically oxidized to 5,6-epoxy-β-ionone, 4-oxo-β-ionone, 4-hydroxy-β-ionone and dihydroactinidiolide using molecular oxygen as the sole oxidant. The effects of solvent, content of Pt, reaction temperature and time on the catalytic activity and product selectivity had also been investigated in detail.     

Sintering of Pt/Al2O3 reforming catalysts: EXAFS study of the behavior of metal particles under oxidizing atmosphere

The effect of an oxidative atmosphere (300 °C) is studied on fresh and sintered unchlorinated naphtha reforming catalysts containing 0.6–1% Pt. The TPR profiles show that only one species is formed using our experimental conditions, regardless of the mean crystallite size of the metal particles. The structural information supplied by EXAFS compared with cuboctahedral particle modeling, implies that such species is a surface platinum oxide, the structure of which is close to that of PtO₂, but largely distorted. This is true whether the catalyst is sintered or not.     

Platinum particle size effect on the oxidative dehydrogenation of aqueous ethanol

The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m^–3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m^–3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.     

Electrochemical reduction of nitrate on Pt(S)[n(1 1 1) × (1 1 1)] electrodes in perchloric acid solution

The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO₄ + 10 mM KNO₃. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO₃⁻ species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as H_nt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO₄ in the absence of nitrate.