喷雾干燥法制备碳载铂钴镍合金催化剂及其甲醇催化氧化性能研究

本文以氯铂酸、氯化镍和硝酸钴为原料，XC-72炭黑为载体，通过雾化干燥法结合煅烧还原制备碳载铂基（PtCo Ni）分散性好的多元合金纳米粒子催化剂。重点研究表面经过改性的炭黑对合金纳米粒子形成和分散的影响规律，研究碳载PtCoNi（原子比为1:1:1）合金纳米粒子的甲醇催化氧化活性、抗CO中毒能力和耐久性，以及不同原子比对催化氧化甲醇活性和抗CO中毒能力的影响规律。研究结果表明，采用表面改性后的炭黑作为载体，制备的碳载铂基（PtCoNi）催化剂为合金纳米粒子，且纳米粒子在炭黑表面分散均匀，粒径分布在1-4nm，平均粒径为2.3nm；与商用的Pt/C催化剂相比，PtCoNi/C（原子比为1:1:1）催化剂具有更高的甲醇催化氧化活性、耐久性和抗CO中毒性；不同原子比铂基多元催化剂在催化氧化甲醇活性上的顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C，抗CO中毒性顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C。     

Pt:Ni原子比对Pt-Ni八面体氧还原活性的影响

Pt-Ni八面体纳米颗粒被认为是具有开发前景的氧还原反应(ORR)催化剂。在之前的报道中Pt-Ni八面体氧还原活性随Pt:Ni原子比的变化往往被表述为火山曲线,并缺乏相关的构效关系研究。本实验通过对不同Pt:Ni原子比的Pt-Ni八面体纳米粒子ORR性能表征,发现了不同于先前报道的ORR面积比活性与Pt:Ni原子比的关系:Pt3Ni>PtNi2>PtNi。同时,在相同的Pt负载量下,ORR质量比活性的大小顺序为Pt3Ni≈PtNi2>PtNi。此反常的相互关系可以利用晶格收缩程度和Pt利用率进行解释:表面晶格收缩程度Pt3Ni>PtNi2>PtNi,这与ORR面积比活性的顺序一致,而质量比活性同时受面积比活性与表面铂利用率的影响。以上结果证实ORR活性可以通过表面张力和铂利用率进行调变。     

Ni掺杂的Pt/C碱性条件下电催化氧还原性能(英文)

采用溶胶法制备了用于阴离子膜直接甲醇燃料电池的Pt-Ni/C阴极电催化剂,用XRD、XPS和TEM对催化剂进行了表征,电位线性扫描伏安法测试电化学活性及抗甲醇性.结果表明,制备的Pt-Ni合金颗粒分布均匀,粒径为3～5 nm;掺杂Ni元素可显著增加Pt的催化活性和抗甲醇性,在相同碱性电解液中,不同原子比例Pt-Ni/C的催化剂以Pt50Ni50/C的活性最高,抗甲醇性相对Pt/C有显著提高,在0.1 mol/L KOH溶液中其最大电流密度达到106 mA/mg,氧电还原起始过电位比Pt/C的小50 mV.     

Pt:Ni原子比对Pt-Ni八面体氧还原活性的影响（英文）

Pt-Ni八面体纳米颗粒被认为是具有开发前景的氧还原反应(ORR)催化剂。在之前的报道中Pt-Ni八面体氧还原活性随Pt:Ni原子比的变化往往被表述为火山曲线,并缺乏相关的构效关系研究。本实验通过对不同Pt:Ni原子比的Pt-Ni八面体纳米粒子ORR性能表征,发现了不同于先前报道的ORR面积比活性与Pt:Ni原子比的关系:Pt_3NiPtNi_2PtNi。同时,在相同的Pt负载量下,ORR质量比活性的大小顺序为Pt_3Ni≈PtNi_2PtNi。此反常的相互关系可以利用晶格收缩程度和Pt利用率进行解释:表面晶格收缩程度Pt_3NiPtNi_2PtNi,这与ORR面积比活性的顺序一致,而质量比活性同时受面积比活性与表面铂利用率的影响。以上结果证实ORR活性可以通过表面张力和铂利用率进行调变。     

Pt/Co双金属纳米溶胶的制备及催化制氢性能

采用化学共还原法制备了聚乙烯吡咯烷酮(PVP)稳定的Pt/Co双金属纳米溶胶,利用UV-Vis、TEM等对所合成的Pt/Co双金属纳米溶胶进行了表征,并系统研究了PVP用量,还原剂用量,双金属比例对该溶胶型纳米双金属催化剂活性的影响。结果表明:所制备的Pt/Co双金属纳米溶胶的平均粒径在2~3 nm之间,大部分双金属纳米溶胶催化剂催化NaBH4制氢的活性都优于单金属Pt和Co纳米溶胶,Pt10Co90双金属纳米溶胶的催化活性最高,其催化NaBH4制取氢气的活性可以达到8800 mol-H2·mol-催化剂-1·h-1,该双金属纳米溶胶催化NaBH4水解反应的活化能为61.8 kJ/mol。所制备的Pt/Co双金属纳米溶胶催化剂具有很好的稳定性,即使在4次催化试验后该催化剂仍然保持着较高的催化活性。     

Pd/Ni双金属纳米溶胶的制备及催化制氢性能的研究

采用化学共还原法制备了聚乙烯吡咯烷酮(PVP)稳定的Pd/Ni双金属纳米溶胶,采用TEM、HR-TEM等对所合成的Pd/Ni双金属纳米溶胶进行了表征,并系统研究了PVP用量、还原剂用量、金属盐离子浓度及金属比例等对该溶胶型双金属纳米催化剂的影响。结果表明:所制备的Pd/Ni双金属纳米溶胶的平均粒径在2 nm左右,双金属纳米溶胶催化剂催化NaBH_4制氢活性优于单金属Pd和Ni纳米溶胶的活性。其中Pd_(10)Ni_(90)双金属纳米溶胶的催化活性最高,其催化NaBH_4制取氢气的活性可以达到8250 mol_(H2)·mol_(Pd)~(-1)·h~(-1),Pd_(20)Ni_(80)双金属纳米溶胶催化剂催化NaBH_4水解反应的活化能为35.7 kJ/mol,反应焓为33.3 kJ/mol,反应熵为-150 J/mol。研究结果还表明,所制备的Pd/Ni双金属纳米溶胶催化剂具有很好的催化稳定性,即使4次催化试验后该催化剂仍然保持着较高的催化活性。密度泛函理论计算结果表明,Ni原子与Pd原子之间发生的电子转移使得Pd原子带负电而Ni原子带正电,荷电的Pd和Ni原子成为催化反应的活性中心。     

金核/铂壳纳米粒子的光化学合成及电催化活性

在含不同摩尔比的Au(Ⅲ)和Pt(Ⅳ)离子的PEG(聚乙二醇)-丙酮溶液中,采用光化学共还原法合成了一组Au@Pt复合纳米粒子,并以炭黑分别对其负载制成Au@Pt/C催化剂。借助于UV-Vis、TEM和HR-TEM的表征,证实复合纳米粒子为球形的核/壳结构;分别以XPS、EDS和电化学方法分析了复合粒子的化学状态、结构特点和Au@Pt/C催化剂的催化性质。结果表明,不同Au:Pt摩尔比的Au@Pt/C催化剂对甲醇氧化反应具有良好的催化活性和稳定性,其中Au:Pt=1:1时形成的Au@Pt/C催化剂电催化活性最高,约为商品Pt/C催化剂的4倍。简要讨论了核/壳结构产生高催化活性的主要原因。     

Pt-Ni合金/多壁碳纳米管作为直接甲醇燃料电池阳极材料

采用浸渍还原法制备了不同比例的Pt-Ni合金多壁碳纳米管(Pt-Ni/MWCNTs)催化剂材料.X射线衍射和透射电镜等分析表明,所合成的催化剂中Pt-Ni合金纳米粒子具有较小的粒径以及较好的分散程度.循环伏安(CV)、计时电流方法(CA)等测试表明,适量Ni的掺杂不但增强催化剂在碱性环境下对甲醇催化氧化的活性,而且还能提高催化剂的稳定性.     

碳载金铂双金属催化剂催化活性研究

采用KBH4做还原剂、PVP做保护剂,化学法一步合成Au-Pt合金纳米粒子,应用UV-Vis、TEM、XRD等手段对其进行了表征.将所合成的合金纳米粒子负载在碳黑上,获得Au-Pt双金属碳载催化剂,应用循环伏安法(CV)检测了催化剂对甲醇的电催化氧化活性.研究表明,Au-Pt/C催化剂的催化活性明显高于Pt/C的,说明...     

Pt掺杂的纳米Ni电催化氧化甲醇性能的研究

采用溶胶凝胶法制备了碳载纳米双金属Ni-Pt(5%,质量分数)/C电催化剂,用TEM、XRD和XPS表征金属粒子的形貌、晶相结构、表面元素及其价态,循环伏安法测试催化剂在碱性溶液中电催化氧化甲醇的活性。结果表明,Ni-Pt金属粒子在碳载体上分布均匀,粒径为3～6nm,少量Pt的掺杂对纳米Ni活性有明显提高,其中,合金型Ni-Pt(5%)/C在1.0mol/LNaOH+1.0mol/LCH3OH溶液中峰电流密度可达85.6mA/mg,是Ni/C峰电流密度的8.7倍,达到Pt/C峰电流密度的15.3%。单位质量铂的电流显著提高。     

新型的治疗阿尔茨海默氏症药物(1-二甲基磷酰基-2,2,2-三氯)-乙基-1-醇烟酸醋对体外神经细胞的作用

目的: 观察本实验室合成的一种治疗阿尔茨海默氏症(AD)的药物(1-二甲基磷酰基-2, 2, 2 -三氯)-乙基^-1-醇烟酸醋(NMF),对体外培养的皮层神经细胞活性的影响以及对海人藻酸(KA)所致的神经损伤的保护作用。方法: 采用体外培养皮层神经元的方法,解剖分离 15 d胚胎小鼠皮层神经细胞, 接种于 96孔板,48 h 后加药并培养 72 h,以 MIT 法 观察 NMF 对小鼠皮层神经细胞活性的影响;同时将接种于 24 孔板的细胞预先给予 NMF,d 3 时加或不加KA处理后,以台盼蓝染色鉴别并计数死、活细胞,可得出细胞的存活率。结果: NMF 明显促进胎鼠皮层神经元活性,其中 NMF1、0. 1、10nmol·L^-1促进神经元活性增殖率分别高达 34.7%、37.4%、36. 7%, NMF 明显促进正常胎鼠皮层神经元存活卒,与对照组比较,10nmol·L^-1 NMF 对皮层神经元的存活率分别提高 39.3%、73.5%。 NMF能显著 对抗 KA 所致的神经元损伤,与 KA 损伤组相比, NMF0.1、10、10nmol·L^-1对损伤皮层神经元的保护率分别为 77.30%、80.10%、84.15%。结论: NMF 明 显促进胎鼠皮层神经元的洁性、提高正常皮层神经元,的存活卒,并能有效地保护KA所致的神经元损伤,提示 NMF 是一种很有潜力的治疗 AD 的药物。     

Rheology Feature of Simple Metal Melt

The rheology feature of Sb, Bi melt and alloys was studied using coaxial cylinder high-temperature viscometer. The results showed that the curve of torsion-rotational speed for Sb melt presents a linear relation in all measured temperature ranges, whereas for the Bi melt, the curve presents obvious non-Newtonian feature within the low temperature range and at relative high shear stress. The rheology feature of Sb80Bi20 and Sb20Bi80 alloy melts was well correlated with that of Sb and Bi, respectively. It is considered that the rheology behavior of Sb melt plays a crucial role in Sb80Bi20 alloy and that of Bi melt plays a crucial role in Sb20Bi80 alloy.     

Microstructures and Mechanical Properties of a Newly Developed Austenitic Heat Resistant Steel

The effect of heat treatment on the microstructures and mechanical properties of a newly developed austenitic heat resistant steel(named as T8 alloy) for ultra-supercritical applications have been studied. Results show that the main phases in the alloy after solution treatment are γ and primary MX. Subsequent aging treatment causes the precipitation of M_(23)C_6 carbides along the grain boundaries and a small number of nanoscale MX inside the grains. In addition, with increasing the aging temperature and time, the morphology of M_(23)C_6 carbides changes from semi-continuous chain to continuous network.Compared with a commercial HR3C alloy, T8 alloy has comparable tensile strength, but higher stress rupture strength. The dominant cracking mechanism of the alloy during tensile test at room temperature is transgranular, while at high temperature, intergranular cracking becomes the main cracking mode, which may be caused by the precipitation of continuous M_(23)C_6 carbides along the grain boundaries. Typical intergranular cracking is the dominant cracking mode of the alloy at all stress rupture tests.     

Three-Dimensional Growth of Coherent Ferrite in Austenite: A Molecular Dynamics Study

Coherent second phase often exhibits anisotropic morphology with specifi c orientations with respect to both the second and the matrix phases. As a key feature of microstructure, the morphology of the coherent particles is essential for understanding the second-phase strengthening eff ect in various industrial alloys. This letter reports anisotropic growth of coherent ferrite from austenite matrix in pure iron based on molecular dynamics simulation. We found that the ferrite grain tends to grow into an elongated plate-like shape, independent of its initial confi guration. The fi nal shape of the ferrite is closely related to the misfi t between the two phases, with the longest direction and the broad facet of the plate being, respectively, consistent with the best matching direction and the best matching plane calculated via the Burgers vector content(BVC) method. The strain energy calculation in the framework of Eshelby's inclusion theory verifi es that the simulated orientation of the coherent ferrite is energetically favorable. It is anticipated that the BVC method will be applicable in analysis of anisotropic growth and morphology of coherent second phase in other phase transformation systems.     

The 15th Global Foundry Sourcing Conference 2014held in Qingdao China

Organized by Suppliers China Co., Ltd and co-organized by the National Technical Committee 54 on Foundry of Standardization Administration of China, the 15th Global Foundry Sourcing Conference 2014 （hereinafter referred to as FSC 2014） was successfully held on Sep. 23rd in Grand Regency Hotel, Qingdao. More than 500 delegates from home and abroad attended this conference, including over 130 purchasers from 20 countries and 380 domestic and foreign suppliers.     

Secondary Recrystallization Behaviors of Grain-Oriented 6.5 wt% Silicon Steel Sheets Produced by Rolling and Nitriding Processes

By rolling and nitriding processes, 0.23- to 0.3-mm-thick grain-oriented 6.5 wt% silicon steel sheets were produced. The core losses of grain-oriented 6.5 wt% silicon steel at frequencies ranging from 400 Hz to 20 k Hz were lower than that of the grain-oriented 3 wt% silicon steel with the same thickness by 16.6–35.8%. The secondary recrystallization behavior was investigated by scanning electron microscopy, energy-dispersive spectroscopy, and electron backscattered diffraction. The results show that the secondary recrystallization in high-silicon steel sheets develops more completely as the nitrogen content increases after nitriding, secondary recrystallized grain sizes become larger, and the sharpness of Goss texture increases. Because more {110}116 grains in the subsurface and the central layer of the sheets have a lot of 20°–45° high-energy boundaries in addition to Goss grains, {110}116 can be the main component through selective growth during secondary recrystallization when the inhibitor quantity is not enough and inhibitor intensity is weaker. The increases in nitrogen content can increase the inhibitor intensity and hinder abnormal growth of a mount of {110}116 grains and therefore enhance the sharpness of Goss texture.     

Laser Cladded TiCN Coatings on the Surface of Titanium

Laser cladded coatings of TiCN were produced on the surface of titanium. To obtain the optimal techniques, several conditions were tested by varying the laser scanning rate. The choice of shielding gas was also studied. The cladded coatings were then evaluated from the surface mechanics point of view based on their microhardness. The microstructure of some interesting samples was investigated by optical micrographs (OM). The results showed that under the condition of fixed pulse frequency and pulse width, the laser scanning rate and the shielding gas are the main factors influencing the components of coatings. TiCN coatings were decompounded and oxidized during the cladding process in the condition of no shielding gas of N2. X-ray diffraction results indicated that the composite coatings composed of TiCN, TiC, Ti2N, and TiO2 were produced using appropriate techniques. The results indicated that the best condition in terms of the surface microhardness is obtained when the scanning rate is 1.5mm / s, the pulse frequency is 15Hz, the pulse width is 3.0ms, and N2 is chosen as the shielding gas. The microhardness of the composite coatings is about 1331kg · mm - 2, which is about 4 times that of the substrate. The optical micrographs indicated that the cladding zone is made up of TiCN, TiO2, and some interdendritic Ti, but the diffusion zone mainly consists of the dendrites phase, and the cladded depth is about 80?滋m, which is more than 2 times that of the laser nitrided sample. There were no microcracks or air bubbles in the cladded sample, which was cladded using the above optimal techniques.     

Effect of Short-Time Aging on the Pitting Corrosion Behavior of a Novel Lean Duplex Stainless Steel 2002

The effect of short-time aging in the temperature range between 400 and 1000 °C on the pitting corrosion behavior and mechanical property of a novel lean duplex stainless steel(LDSS) 2002 was investigated through the potentiostatic critical pitting temperature(CPT) tests and the Charpy impact tests. Both the pitting corrosion resistance and the toughness of aged specimens degraded due to the precipitation of detrimental secondary phases and the most significant reduction of CPT and impact energy emerged at 650 °C concurrently. The CPT of LDSS 2002 specimen aged at 650 °C decreased by 28 °C, and the impact energy dropped from 69 to 29 J/cm~2 compared with the solution-annealed sample. Transmission electron microscopy characterization showed that the main precipitates in LDSS 2002 were Cr_2N and M_(23)C_6 along the ferrite–austenite grain boundaries.     

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正The Transactions of Nonferrous Metals Society of China,founded in 1991 and sponsored by The Nonferrous Metals Society of China,is published monthly now and mainly contains reports of original research which reflect the new progresses in the field of nonferrous metals science and technology,including mineral processing,extraction metallurgy,metallic materials and heat treatments,metal working,physical metallurgy,powder metallurgy,with the emphasis