Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

氢传感器用铂电极的制备及性能研究

采用浆料涂覆烧结法制备铂电极,对比了基材处理方式(磁控溅射/喷砂)、铂黑(Ptb)和氧化铂(PtO₂)粒径差异对电极形貌、附着力、方阻及电催化性能的影响。结果表明,基材采用磁控溅射法制备的涂层表面结构优于喷砂法的涂层,使其剥离强度均略高于喷砂处理的样品;针对于粉末粒度,需控制在一定范围内(即Ptb(350nm)和PtO₂(350nm)),其制备的涂层表面易形成蜂窝状或絮状的微连接结构,可显著降低方阻,提高其附着力。对结构和附着力较好的Ptb/Pt电极和PtO₂/Pt电极进行CV曲线分析,PtO₂/Pt电极的电催化性能优于Ptb/Pt电极。     

Thermodynamic properties of stable and metastable phases of Pt metal

Isometric heat capacity cv and isobaric heat capacity cp of Pt with stable and metastable phases were calculated by using pure element systematic theory. These results are in excellent agreement with of SGTE (Scientific Group Thermodata Europe) database and JANAF (Joint Army-Navy-Air Force) experimental values. The calculation results of cv and cp of Pt metal in natural state are in good agreement with those calculated by FP(first-principles) method. It is found that the electron devotion to heat capacity is important to adjust in OA(one-atom) method while calculating heat capacity. The full information about thermodynamic properties of Pt metal with stable and metastable phases, such as entropy(S), enthalpy(H) and Gibbs energy(G) were calculated from 0 K to random temperature. The results are in good agreement with JANAF experimental value. In contrast to SGTE database, the thermodynamic properties from 0 K to 298.15 K are implemented.     

The structure and activity of Pt6 particles in ZSM-5 type zeolites

Density functional theory was applied to investigate the nature of active sites formed by the interaction of a Pt₆ guest particle with the silicalite and H-form of ZSM-5 as the host zeolites. Interaction of metal cluster with silicalite shows a slight stabilization (36 kJ/mol) and formation of a negatively charged Pt entity. When a metal particle is arranged in the channel of H-form substantial stabilization (187 kJ/mol) and generation of an oxidized Pt₆H⁺ species are observed. The formation of an active site includes interaction between a platinum particle and an acid site accompanied by the suppression of zeolite acidity. The suggestion is made that the alkane transformation on supported platinum particles proceeds via metal–cyclobutane and metal–carbene intermediates and does not need the direct involvement of acid sites. The difference in catalytic behavior of the Pt₆/HZSM-5 and Pt₆/ZSM-5 systems is discussed.     

Clustering of platinum atoms into nanoscale particle and network on NaY zeolite

Platinum has been supported on NaY zeolite by ion exchange of Pt(NH₃)₄ ²⁺. Clustering of Pt atoms into a 1 nm cluster, and three-dimensional quantum-size wire (3 nm thick) network (greater than 100 nm) from reduction of the Pt species has been investigated by extended X-ray absorption fine structure transmission electron microscopy and xenon adsorption measurements.     

Enhanced benzene formation on Pt/H-mordenite and Pd/H-mordenite

The distribution of methylcyclopentane (MCP) ring enlargement (RE) products between benzene (Bz) and cyclohexane (CH) provides information on the reaction mechanism. The Bz/CH ratio is in excess of the calculated and experimentally determined equilibrium ratio. This implies that benzene is a primary product; it eliminates the possibility of direct hydride ion transfer to carbenium ions as the prevailing mechanism. The results are consistent with the concept that metal-proton adducts are instrumental in bifunctional catalysis.     

Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

Reaction Coupling of Ethylbenzene Dehydrogenation with Nitrobenzene Hydrogenation

The chemical equilibrium for the coupling of ethylbenzene dehydrogenation with nitrobenzene hydrogenation, to produce styrene and aniline simultaneously, has been calculated on the basis of the Soave–Redlich–Kwong equation of state. The dehydrogenation of ethylbenzene in the presence of nitrobenzene over the catalysts -Al₂O₃, ZSM-5, activated carbon and platinum supported on activated carbon has been carried out at 400 °C. The effects of Pt loading and the pretreatment of the catalysts have been investigated. It has been revealed that the conversion of ethylbenzene can be greatly improved by the reaction coupling due to the elimination of the hydrogen produced in the reaction by the hydrogenation of nitrobenzene. Platinum supported on the activated carbon has been suggested as a suitable catalyst. The best results with ethylbenzene conversion of 33.8% and styrene selectivity of 99.2% were obtained over Pt(0.02 wt%)/AC at 400 °C. Moreover, such process is also energetically favored since the necessary process heat to drive the ethylbenzene dehydrogenation can be provided by the coupling with the exothermic nitrobenzene hydrogenation reaction.     

NOx storage-reduction catalysts based on hydrotalcite: Effect of Cu in promoting resistance to deactivation

Novel NO_x storage-reduction (NO_xSR) catalysts prepared by Pt and/or Cu impregnation of Mg–Al (60:40) hydrotalcite (HT)-type compounds show better performances in NO_x storage than Pt–Ba/Al₂O₃ Toyota-type NO_xSR catalysts at reaction temperatures lower than 250 °C. The presence of Pt or Cu considerably enhances the activity, with the former more active. The nature of the HT source, however, also influences performance. The co-presence of Pt and Cu slightly worsens the low temperature activity, but considerably promotes the resistance to deactivation after severe hydrothermal treatment and in the presence of SO₂. This effect is attributed to both the possibility of formation of a Pt–Cu alloy after reduction, and the modification of the HT induced during the deposition of Cu. The overall Pt–Cu/HT performances are thus superior to those of the Pt–Ba/Al₂O₃ Toyota-type NO_xSR catalysts.     

一体式再生燃料电池双效氧电极催化剂

对一体式可再生燃料电池双效氧电极催化剂进行研究,考察了析氧催化剂和贵金属Pt黑组成的复合催化剂的双效性能以及催化剂配比和焙烧温度对性能的影响,用XRD对催化剂的物相特性进行表征。结果表明：复合催化剂的燃料电池性能按以下顺序递减：Pt黑＞Pt/Ru/Ir＞Pt/Ru＞Pt/IrO2～Pt/Ir＞Pt/RuO2;水电解性能按以下顺序递减：Pt/IrO2＞Pt/RuO2＞Pt/Ir＞Pt黑。分析比较,Pt/IrO2复合催化剂表现出良好的燃料电池/水电解双功能特性以及循环稳定性,具有最佳的URFC能量转换效率。因此,Pt/IrO2复合催化剂是最适宜的双效氧电极催化剂。一定温度范围内的焙烧处理对Pt/IrO2催化剂燃料电池性能影响不大,而对水电解性能具有一定的影响,大电流密度运行,未焙烧处理的Pt/IrO2催化剂表现出更好的水电解性能。