基于FeWOx/SiO2载氧体的甲烷化学链部分氧化反应

甲烷具有价格低廉且储量丰富的优点,因此将甲烷转化为合成气(一种H2:CO为2的混合物),从而进一步合成有价值的化学品和液体燃料引起了人们的极大关注.化学链甲烷部分氧化(CLPOM)技术能避免甲烷与空气直接接触而引起爆炸的危险,可以降低后续对合成气与氮气分离操作所带来的费用,因此日益受到关注.CLOPM过程主要分为两步:第一步,CH4被载氧体所携带的氧部分氧化,载氧体被还原;第二步,利用氧化剂(例如空气)将被还原的载氧体再氧化恢复.因此,载氧体在CLOPM过程中起到至关重要的作用.载氧体的选择主要存在两个问题:(1)甲烷被活化所产生含碳产物的能力与晶格氧的给氧能力不匹配所带来的严重碳沉积;(2)金属离子间扩散速率不匹配而造成载氧体在氧化还原过程中结构的不可逆变化.基于上述两个问题,本文设计了FeWOx/SiO2载氧体用于CLPOM.与未改性的WO3/SiO2载氧体相比,甲烷的转化率和合成气的收率都有显著提高.FeWOx/SiO2在900℃、1 atm反应条件下表现出62%的甲烷转化率、93%的CO气相选择性、94%的H2选择性和2.4的H2/CO比值,同时在50个循环中表现出优异的催化活性和稳定性.本工作利用CH4脉冲反应研究了FeWOx/SiO2的甲烷表面反应过程;采用CH4-TPR和H2-TPR相结合探究了甲烷活化速率与晶格氧扩散速率之间的关系;通过XPS和XRD对FeWOx/SiO2在氧化还原过程中的结构稳定性进行了探讨.综合上述实验结果,对FeWOx/SiO2应用于CLPOM的反应机理进行了阐述.H2-TPR结果表明,在FeWOx/SiO2中,相较于Fe2O3/SiO2,Fe-O的活性受到抑制,使其更倾向于与甲烷发生部分氧化反应;相较于WO3/SiO2,W-O的活性得到明显提升,因此更多的晶格氧可以参与到部分氧化反应中来氧化积碳,从而使合成气收率大幅度提升.从CH4-TPR结果可以看出,对于FeWOx/SiO2,CO与H2的生成温度最接近,意味着晶格氧的传输速率较快并且能够与甲烷活化产生含碳中间物种的速率相匹配,将其及时氧化生成CO,避免由于积碳造成的催化剂失活.结合XPS和XRD结果可以得出,在甲烷还原过程中,FeWOx经历一步还原形成Fe-W合金,由于其间存在强相互作用,因而抑制了还原过程中催化剂相分离现象的发生.同时,根据铁钨离子在空气条件下扩散速率的公式计算可以得出,其相近的离子氧化速率也保证了在氧化过程中催化剂结构的稳定性.本工作为进一步构建用于甲烷化学链部分氧化制合成气的复合金属氧化物载氧体提供了研究思路.     

Development of Pt-Co catalysts supported on carbon nanotubes using the polyol method—tuning the conditions for optimum properties

Pt alloys with transition metals supported on carbon substrates are used as improved cathode electrocatalysts for fuel cells. Enhanced catalytic activity is attributed to the structure (Pt-Pt bond distance) and/or electronic effect (Pt d-electron vacancy). This work focuses on the development of Pt₃Co/f-MWCNT catalysts (functionalized multiwalled carbon nanotubes [f-MWCNT]) using ethylene glycol as the dispersing and reducing agent. The aim is to in parallel achieve fine dispersion, quantitative deposition and alloy formation. As described herein, the pH value of the reaction suspension has a critical effect on the composition and morphology of the synthesized nanoparticles. High pH values favor the formation of Pt₃Co alloy, nevertheless negatively influencing the dispersion. A discussion is made on the reduction/deposition mechanism and how to control the conditions to result in optimum properties.     

反对数微分简易示波伏安法的研究

在获得微分简易地波伏安图的实验线路中,增加了反对数装置,提出了反对数微分简易示波伏安法。该方法被应用于铝合金中微量铜和分子筛中微量钴的测定,获得了满意结果。     

Antihypertensive drugs as an inhibitors for corrosion of aluminum and aluminum silicon alloys in aqueous solutions

The corrosion behavior of aluminum and three aluminum–silicon alloys in different concentrations of HCl solutions and its inhibition by antihypertensive drugs was studied using potentiostatic polarization measurements. As the acid concentration increases, the rate of corrosion increases. Aluminum is less susceptible to corrosion than any of Al–Si alloys. The inhibition efficiency of the drug compounds increases with their concentration up to a critical value. At higher additive concentrations the inhibition efficiency starts to decrease. The inhibitive action of these compounds is due to their formation of insoluble complex adsorbed on the metal surface. The adsorption follows Langmuir adsorption isotherms. It was found that the drugs compounds provide protection to Al and Al–Si alloys against pitting corrosion by shifting the pitting potential to more positive direction until critical drug concentrations (250 ppm). After this critical concentration the inhibition against to pitting corrosion starts to decrease.     

火花直读光谱法对铝合金中各元素含量测量结果的不确定度评定

分析了火花直读光谱法测定铝合金中Si、Fe、Cu、Mg、Mn、Zn、Cr、Ti元素含量测量结果的不确定度来源,对不确定度分量进行了评定与计算,Si、Fe、Cu、Mg、Mn、Zn、Cr、Ti测量结果的相对扩展不确定度分别为2. 9%、2. 5%、2. 6%、2. 7%、2. 6%、2. 6%、2. 5%、2. 7%(包含因子k均为2).     

One-step synthesis of porous PtNiCu trimetallic nanoalloy with enhanced electrocatalytic performance toward methanol oxidation

Pt-based alloy nanoporous structures have attracted a lot of attention because of their high activity and stability toward alcohol oxidation reactions. Especially, Pt alloying with Earth-abundant metal can lower the cost of catalyst. Here, we introduce a one-pot approach to synthesize bimetallic PtCu and Ni-doped PtCu nanoalloy with porous structure. The as-synthesized Ni-doped Pt₆₀Ni₃Cu₃₇ nanoalloys exhibit excellent electrocatalytic properties toward methanol oxidation in acidic medium. The mass activity of the as-synthesized Pt₆₀Ni₃Cu₃₇ nanoalloys is 3.6 times and 5.3 times that of Pt₅₅Cu₄₅ nanoalloys and commercial Pt black for methanol oxidation in 0.2?M methanol solution. Besides, the stability of the as-synthesized Pt₆₀Ni₃Cu₃₇ nanoalloys was much better than Pt₅₅Cu₄₅ nanoalloys and commercial Pt black. After 3600?s chronoamperometry test, the remaining values of the Pt₆₀Ni₃Cu₃₇ nanoalloys are 3.7 times and 11.0 times that of Pt₅₅Cu₄₅ nanoalloys and commercial Pt black. And it is the first time to report that small amount of Ni dopants can boost the activity and stability of PtNiCu alloys toward methanol oxidation.     

Analysis of aluminum alloys by resonance-enhanced laser-induced breakdown spectroscopy: How the beam profile of the ablation laser and the energy of the dye laser affect analytical performance

In resonance-enhanced laser-induced breakdown spectroscopy, the sample was ablated by a laser pulse and the expanding plume was photoresonantly rekindled by a dye laser pulse. By sampling aluminum alloys for Mg, Pb, Si, and Cu, we showed that for the ablation step, Gaussian beams gave 2 to 3× better signal-to-noise ratio (SNR) than non-uniform beams. For the rekindling step, if no further sample destruction was allowed, dye laser pulses that intercepted the plume transversely gave 6 to 12× higher SNR than the longitudinal case. By combining Gaussian beams and transverse rekindling, the mass limit-of-detection for Mg was about 100 amol while non-resonant analysis was 10× more destructive. Sub-monolayer of oxides grown on laser-cleaned aluminum surfaces was detected by monitoring the AlO emissions of rekindled plumes; without resonant enhancements, they were not detectable no matter how destructive was the analysis. Time resolved studies showed that the Gaussian beam produced less dispersed plumes and that a stronger dye laser beam directed transversely heated up a bigger plume mass without over-heating the plume core. The analyte emissions were sustained while the continuum background remained low.     

Fe48Co52 Alloy Nanowire Arrays： Effects of Magnetic Field Annealing

The effects of magnetic field annealing on the properties of Fe48Co52 alloy nanowire arrays with various interwire distances （Di=30-60 nm） and wire diameters （Dw=22-46 nm） were investigated in detail. It was found that the array＇s best annealing temperature and crys- talline structure did not show any apparent dependence on the treatment of applying a 3 kOe magnetic field along the wire during the annealing process. For arrays with small Dw or with large Di, the treatment of magnetic field annealing also had no obvious influence on their magnetic performances. However, such a magnetic field annealing constrained the shift of the easy magnetization direction and improved the coercivity and the squareness obviously for arrays with large Dw or with small Di. The difference in the intensity of the effective anisotropic field within the arrays was believed to be responsible for this different variation of the array＇s magnetic properties after magnetic field annealing.     

钇,铈对低铪镍基K444返回合金组织与力学性能的影响

研究了Y,Ce对含铪(Hf)镍基铸造高温合金K444返回料(添加50%返回料)合金的力学性能和组织的影响.研究结果表明:适量Y,Ce(Y<0.03%,Ce<0.015%(质量分数))添加到返回料合金后,一方面,Y,Ce具有去除N,O等有害杂质的作用,使O含量由15×10~(-6)降低到8×10~(-6),N含量由35×10~(-6)降低到18×10~(-6),从而使返回料合金得到净化.另一方面,Y,Ce细化了枝晶组织,减少了共晶和大块状碳化物数量,并且强化了晶界.和未加Y,Ce的返回料合金相比.添加Y,Ce使返回料合金室温拉伸强度提高约100 MPa,塑性提高近一倍;使900℃的高温瞬时拉伸性能波动较为平稳,塑性提高近一倍.添加Y,Ce还可以提高返回合金900℃/274 MPa条件下的持久性能,达到新料水平;可以明显延长K444返回合金900℃/274 MPa条件下的蠕变第二阶段,提高蠕变寿命.