Potassium promoted Ru/meso-macroporous SiO2 catalyst for the preferential oxidation of CO in H2-rich gases

A series of potassium promoted Ru/meso-macroporous SiO₂ catalysts were prepared and used for the preferential oxidation of CO (CO-PROX) in H₂-rich gases. The catalysts were characterized by using techniques of TEM, SEM TPR, XPS, and N₂ adsorption/desorption. The catalytic activity of Ru/meso-macroporous SiO₂ was markedly improved by the introduction of potassium. The catalyst of K-5 wt.% Ru/meso-macroporous SiO₂ with molar ratio of K:Ru = 5:7 exhibited relatively high activity and selectivity for CO-PROX. Nanoparticles of ruthenium species can be highly dispersed on the meso-macroporous SiO₂ support by the simple impregnation method. The addition of potassium weakened the interaction between metallic Ru and the silica support. Lowering the reduction temperature of ruthenium ions could keep ruthenium in the state of metallic Ru, and it was proposed that potassium acted as an electron donating agent. The electron donating effect of potassium improved the low temperature activity for CO oxidation and increased the selectivity of O₂ for CO oxidation, thus K-modified Ru/meso-macroporous SiO₂ catalyst showed obviously a wide temperature window for CO elimination from H₂-rich gases, meanwhile the related mechanism was discussed.     

Precursor-Derived Si-B-C-N Ceramics: Oxidation Kinetics

The oxidation behavior of three precursor-derived ceramics—Si_4.46BC_7.32N_4.40 (AMF2p), Si_2.72BC_4.51N_2.69 (AMF3p), and Si_3.08BC_4.39N_2.28 (T2/1p)—was investigated at 1300° and 1500°C. Scale growth at 1500°C in air can be approximated by a parabolic rate law with rate constants of 0.0599 and 0.0593 μm²/h for AMF3p and T2/1p, respectively. The third material does not oxidize according to a parabolic rate law, but has a similar scale thickness after 100 h. The results show that at least within the experimental times these ceramics develop extremely thin scales, thinner than pure SiC or Si₃N₄.     

Model interpretation of electrochemical impedance spectroscopy and polarization behavior of H2/CO mixture oxidation in polymer electrolyte fuel cells

A mathematical model is proposed based on electrode kinetics analysis for the oxidation of 2% CO+H₂ mixture in polymer electrolyte fuel cells. Successful simulation of the polarization curve and experimental impedance spectra for Pt/C electrode system confirm the validity of the model which shows that the impedance is strongly dependent on electrode potential. With the increase of potential, an inductive behavior will occur. It is believed that the appearance of this inductive pattern can be used as a criterion for the onset of CO oxidation by the coincidence of the potential at which inductive behavior occurs with the ignition potential for CO oxidation. The effects of change of CO oxidation rate constant and CO adsorption equilibrium constant on impedance pattern, as well as on CO surface coverage and Faradaic current are also delineated with the use of the proposed model.     

Ultraviolet-enhanced bioactivity of ZrO2 films prepared by micro-arc oxidation

Macroporous and nano-crystallized monoclinic zirconia (m-ZrO₂) film was prepared by micro-arc oxidation (MAO). The effect of ultraviolet (UV) irradiation on the microstructure, water contact angle and bioactivity of the film were investigated. The MAO-formed ZrO₂ film exhibits high hardness and elastic modulus. UV irradiation of the ZrO₂ film does not alter surface morphology, grain size and phase component, however, can significantly improve hydrophilicity and bioactivity of the film. The enhanced hydrophilicity and bioactivity are thought to result from the abundant basic Zr-OH groups on the UV-irradiated film, which have relative long-term stability.     

Performance of direct carbon fuel cell

A direct carbon fuel cell (DCFC) is a variation of the molten carbonate fuel cell (MCFC) which converts the chemical energy of carbon directly into electrical energy. Thus, the energy conversion efficiency is very high and correspondingly CO₂ emission is very low for given power output. DCFC as a high temperature fuel cell performs better at elevated temperatures (>800 °C) but because of the corrosive nature of the molten carbonates at elevated temperatures the degradation of cell components becomes an issue when DCFC is operated for an extended period of time.We explored the DCFC performance at lower temperatures (at 700 °C and less) using different sources of carbon, different compositions of electrolytes and some additives on the cathode surface to increase catalytic activity. Experiments showed that with petroleum coke as a fuel at low temperatures the ternary eutectic (43.4 mol % Li₂CO₃ - 31.2 mol% Na₂CO₃ - 25.4 mol % K₂CO₃) spiked by 20 wt % Cs₂CO₃ performed better than any binary or ternary eutectics described in the published work by other researchers. Maximum power output achieved at 700 °C was 49 mW/cm² at a current density of 78 mA/cm² when modified cathode was fed with O₂/CO₂ gases.     

Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

BACKGROUND: A highly stable Fe/γ‐Al₂O₃ catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ‐Al₂O₃ with an aqueous solution of Fe(NO₃)₃· 9H₂O. The influence of pH, temperature, catalyst and H₂O₂ doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L^?1 of phenol, a dose of H₂O₂ corresponding to the stoichiometric amount and 1250 mg L^?1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L^?1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by‐product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ‐Al₂O₃ supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long‐term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry     

钼添加对CrN涂层抗氧化性能的影响

研究钼添加对CrN涂层微观结构和抗氧化性能的影响,采用反应磁控溅射法在硅片和高速钢片上制备不同Mo含量的Cr-Mo-N涂层,并在500~800 ℃的高温空气中退火1 h,用X射线衍射（XRD）、拉曼光谱和扫描电子显微镜（SEM）对涂层退火前后的微观形貌进行表征。沉积的CrN和Cr-Mo-N涂层均表现出基于CrN晶格的B1面心立方相（fcc）。Mo离子取代Cr-N晶格中的Cr离子,形成Cr-Mo-N固溶体。在600 ℃时,XRD和拉曼光谱表明,Mo含量较高的Cr-Mo-N涂层中形成MoO₃相,表面较粗糙,含氧量较高。在700 ℃时,CrN涂层由于内应力的作用,其横截面形貌为疏松的柱状晶,并有一定的多孔区,而Cr-Mo-N涂层则为致密的柱状晶结构。低Mo含量（<17at%）的Cr-Mo-N涂层比CrN涂层具有更好的抗氧化性。     

改性TiO2纳米管阵列电极的光电化学性能研究

近年来,掺杂改性的TiO₂纳米管作为光催化材料的研究受到广泛关注。本实验采用阳极氧化法在Ti板表面制备规则有序的TiO₂纳米管,通过在电解液中直接添加含Fe、N元素的化学试剂对其进行掺杂改性。利用扫描电子显微镜、X射线衍射仪和X射线光电子能谱对TiO2纳米管进行表征,确定TiO₂纳米管的最佳制备条件。最后利用瞬态光电流曲线、开路电位曲线、线性伏安扫描曲线对其光电化学性能进行比较。研究发现,1%的Fe元素掺杂材料具有更好的光电响应,光照时开路电位可达0.345 V;9%的N元素掺杂材料具有最好的光电活性,光照时开路电位可达0.3 V。     

钛表面改性Al/NiCu组合涂层反应机理及抗氧化性能

采用等离子结合电弧喷涂的工艺方法在工业纯钛表面制备了Al/Ni Cu组合涂层,在700℃的大气环境下对Al/Ni Cu/Ti试件进行加热处理,使得Al、Ni Cu复合涂层之间发生扩散反应并原位生成具有一定抗高温氧化性能的Ni-Al金属间化合物涂层。对加热改性处理前后涂层的微观组织及Ni-Al金属间化合物的形成机理进行了研究,并对经加热和打磨处理后的Al/Ni Cu/Ti试件及无防护涂层的Ti块进行了800℃/100 h的高温氧化试验。研究结果显示,Ti基体表面Al/Ni Cu涂层经700℃炉中加热改性处理后,Al、Ni Cu涂层间可发生扩散反应并原位生成Ni Al3、Cu Al2、Ni2Al3及含有一定Cu元素的Ni Al金属间化合物,但只有高熔点的Ni Al金属间化合物能够始终稳定地存在,且此金属间化合物对Ti基体起到了较好的高温防护作用。