载体对铂基疏水催化剂活性的影响

为了研究载体对铂(Pt)基疏水催化剂活性的影响,分别选取了炭黑、SiC纳米粉、铈锆复合氧化物(Ce0.4Zr0.6O2-γ-Al2O3)等三种物质,在氯铂酸的乙二醇溶液中,用高压微波加热法制备了Pt基催化剂,然后将其与聚四氟乙烯一起负载于泡沫镍上,制成疏水催化剂.用X射线衍射、透射电子显微镜、X光电子能谱、扫描电子显微镜等方法分析了催化剂的结构与组成,并研究了疏水催化剂对氢-氧复合反应及氢-水交换反应的催化活性.结果表明:Pt在载体表面分布均匀,在Pt/C、Pt/SiC、Pt/Ce0.4Zr0.6O2-γ-Al2O3中Pt的平均粒径分别为4.46、1.67和1.77nm;Pt/C、Pt/SiC催化剂中Pt存在Pt(0)、Pt(Ⅱ)和Pt(Ⅳ)三种价态;Pt/C、Pt/SiC在泡沫镍表面的分布均匀,而Pt/Ce0.4Zr0.6O2-γ-Al2O3分布不均匀.Pt/C/FN对氢-氧复合反应和氢-水交换反应的催化活性都较高;Pt/SiC/FN和Pt/Ce0.4Zr0.6O2-γ-Al2O3/FN对氢-氧复合反应的催化活性高,但是对氢-水交换反应的催化活性很低.     

Co修饰的碳载Pt纳米粒子催化剂的制备与表征

质子交换膜燃料电池阴极需要使用高活性的电催化剂来加速氧还原反应(ORR)速率,而提高活性成分贵金属铂(Pt)的功能反应利用率可解决其关键问题.本工作利用过渡金属钴Co(Ⅱ)?有机框架(Co?MOF)为前驱体合成ORR催化剂载体Co/C,并采取浸渍?液相还原法负载Pt纳米粒子制备了合金Pt?Co/C催化剂.通过对样品的孔隙结构、物相结构、微观形貌等表征,证实了载体Co/C具有较大的比表面积和相互连通的分级介孔结构,其独特的形貌、丰富的孔隙结构使负载的Pt纳米颗粒均匀分布、粒径范围窄,平均粒径约为6.8 nm.进一步对催化剂进行电化学性能评价,其电化学活性表面积(ECSA)接近于商用Pt/C催化剂的值,结果表明合金催化剂中活性成分Pt具有较高的利用率,同时还表现出载体独特的孔隙结构优势.     

Fe、Co和Ni掺杂LiBH4放氢性能的第一性原理研究

本工作旨在借助基于密度泛函理论的第一性原理计算来考察过渡金属元素Fe、Co、Ni掺杂LiBH_4的放氢性能。研究表明,Fe、Co、Ni掺杂有效提高了LiBH_4的放氢能力,这与掺杂体系B-H共价作用及Li-B/H离子作用的减弱,尤其是Fe/Co/Ni-B键的形成有关。体系Li7MB8H_32(M=Li、Fe、Co、Ni)的氢解离能与中心金属M的电负性负相关,即金属M的电负性越高,体系的氢解离能越小。与Fe、Co掺杂体系相比,具有较低金属占位能及较小氢解离能的Ni掺杂体系表现出良好的放氢特性。本研究从模拟计算的角度证实,利用高电负性金属(相对Li)与LiBH_4复合是实现LiBH_4"失稳"的一种有效方式。     

石墨烯负载Pt-Co纳米粒子及其在氧化还原反应中的应用

采用微波-乙二醇方法还原氧化石墨烯和Pt(v)、Co(Ⅱ)粒子混合物,再经300℃H2还原,制备了石墨烯负载Pt-Co合金催化剂(Pt-Co/G).利用透射电镜、X-射线能谱、X-射线衍射和光电子能谱对所制催化剂进行表征.Pt-Co合金的粒径为3nm～8 nm,均匀地分散在石墨烯片上.与单金属的Pt/G和商品化的Pt/C催化剂相比,所制合金化的Pt-Co/G催化剂对氧还原反应展现出高的催化活性和可比拟的稳定性,显示了其在燃料电池中的应用潜力.     

ZnO增强MxCo3-xO4电催化析氧性能研究

氢能因热值高、燃烧产物无污染等优良特性,成为目前新型能源研究的焦点,有望成为化石能源的理想替代品。电催化水分解作为最具前景的氢气制备方法,包含两个半反应:析氧反应(OER)和析氢反应(HER)。其中OER目前主要采用贵金属作为催化剂,但其高成本极大地限制了电催化产氢的工业化。基于Co 3O 4的Co基掺杂氧化物具有成本低廉、催化活性高且稳定性强等优良特性。目前对于Co基掺杂氧化物的研究主要集中于探究掺杂不同金属元素(Zn,Ni,Fe等)对其催化活性的影响,极少研究掺杂惰性氧化物对其催化活性的影响。合成了一种CoFeNiZn复合氧化物,且具有优良的电催化活性和稳定性。在1 mol/L KOH的电解液中,10 mA/cm 2的电流密度下,CoFeNiZn复合氧化物过电势(η10)为310 mV,塔菲尔斜率(Tafel slope)为40 mV/dec,相比原始CoFeNi氧化物(η10为400 mV)过电势降低了90 mV。CoFeNiZn催化剂催化性能的提高主要是由于以惰性ZnO作为基质可有效地分散催化活性物质,并充分暴露CoFeNi氧化物的催化活性位点。这一基于催化材料掺杂非活性物质提高催化剂催化活性的发现可以为现有催化剂开发提供新的思路。     

稀土掺杂MPt/C(M=La,Nd)催化剂的研究

为了研究稀土掺杂对PEMFC用Pt/C电催化剂的影响,本文使用浸渍法合成了La、Nd稀土掺杂MPt/C催化剂材料,并采用XRD分析了其晶相结构变化规律.用循环伏安和电性能实验测试了样品的催化活性,探讨了其微观结构与催化性能之间的关系.结果表明稀土掺杂使其氧还原反应的活性晶面得到提高,使Pt粒径减小,从而提高其电化学比表面积和催化活性,显著改善了PEMFC的电池性能.     

Ni、Co、Mn、Cu掺杂对K4 Nb6 O17光催化活性的影响

通过高温固相反应合成了铌酸盐K4Nb6O17及Ni2 、Co3 、Mn4 、Cu2 (5.0%mol)掺杂的K4Nb6O17并采用X射线衍射、紫外可见漫反射光谱、扫描电镜、比表面积分析等对其进行了结构和形貌表征.在甲醇为电子给体、Pt为助催化剂的情况下,研究了K4Nb6O17及Ni2 、Co3 、Mn4 、Cu2 掺杂的K4Nb6O17作为催化剂在约400nm紫外辐射下分解水产氢的光催化活性,并讨论了引起催化剂活性差异的原因.     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

La掺杂Ni-SiO2催化剂催化裂解甲烷制备氢气和碳纤维

采用浸渍法制备了不同La掺杂量的Ni-SiO2催化剂,研究了La掺杂量对Ni-SiO2催化剂的Ni活性金属粒径、还原性能、甲烷催化裂解寿命以及反应后生成碳纤维的影响.结果表明:La、Ni物质的量比由0增长至0.3时,Ni-SiO2催化剂的寿命显著提高,而当La、Ni物质的量比由0.3增长至0.6时,催化剂寿命在一定程度上略有降低;La、Ni物质的量比由0增长至0.6时,还原后催化剂Ni金属的平均粒径从26.43nm不断降低至10.57nm.不同La掺杂量Ni-SiO2催化剂甲烷催化裂解过程中Ni金属平均粒径变化趋势明显不同,n(La)∶n(Ni) =0的Ni-SiO2催化剂随反应进行Ni金属平均粒径不断降低,而n(La)∶n(Ni)=0.3的Ni-SiO2催化剂随反应进行Ni金属平均粒径则不断升高.碳纤维形态受掺La掺杂量影响较大,随La、Ni物质的量比由0增长至0.3,反应过程中生成的碳纤维管径变粗,而随La、Ni物质的量比由0.3增长至0.6,碳纤维变短.     

镍、硫共掺杂纳米TiO2的制备及其可见光催化性能

为提高纳米TiO2的可见光催化活性,采用沉淀-浸渍法制备了一种新型Ni和S共掺杂TiO2纳米复合光催化剂.通过紫外-可见(UV-Vis-)漫反射、X-射线衍射(XRD)、透射电子显微镜(TEM)和X-荧光(EDX)等手段对其结晶形态、晶粒尺寸、元素掺杂量和吸光性能等进行了表征.结果显示,催化剂Ni/S/TiO2为锐钛矿晶相,平均粒径约为6～7nm,比表面积高达260.42m2/g,感光范围可拓展到可见光区,且与纯TiO2,S掺杂TiO2和Ni掺杂TiO2相比,光催化剂Ni/S/TiO2的颗粒粒径更小,比表面积更大,光吸收边红移程度更显著.以活性艳蓝198染料溶液为模拟废水,以氙光灯为光源,对光催化剂Ni/S/TiO2的催化活性进行了评价.结果表明,Ni/S/TiO2具有比纯TiO2、S掺杂TiO2和Ni掺杂TiO2更高的可见光催化活性,氙光灯照射120min,活性艳蓝198降解率可达到98.5%.     

Effect of Co and Ni nanoparticles formation on carbon nanotubes growth via PECVD

The effect of cobalt (Co) and nickel (Ni) nanoparticle catalysts on the growth of carbon nanotubes (CNTs) were studied, where the CNTs were vertically grown by plasma enhanced chemical vapour deposition (PECVD) method. The growth conditions were fixed at a temperature of 700 °C with a pressure of 1000 mTorr for 40 minutes with various thicknesses of sputtered metal catalysts. Only multi-walled carbon nanotubes are present from the growth as large average diameter of outer tube (～10–30 nm) were measured for both of the catalysts used. Experimental results show that high density of CNTs was observed especially towards thicker catalysts layers where larger and thicker nanotubes were formed. The nucleation of the catalyst with various thicknesses was also studied as the absorption of the carbon feedstock is dependent on the initial size of the catalyst island. The average diameter of particle size increases from 4 to 10 nm for Co and Ni catalysts. A linear relationship is shown between the nanoparticle size and the diameter of tubes with catalyst thicknesses for both catalysts. The average growth rate of Co catalyst is about 1.5 times higher than Ni catalyst, which indicates that Co catalyst has a better role in growing CNTs with thinner catalyst layer. It is found that Co yields higher growth rate, bigger diameter of nanotube and thicker wall as compared to Ni catalyst. However, variation in Co and Ni catalysts thicknesses did not influence the quality of CNTs grown, as only minor variation in I_G/I_D ratio from Raman spectra analysis. The study reveals that the catalysts thickness strongly affects not only nanotube diameter and growth rate but also morphology of the nanoparticles formed during the process without influencing the quality of CNTs.     

金属对炭黑转化为洋葱状中空结构纳米碳的影响

研究了炭黑分别在 Fe、Co、Ni 三种金属化合物作用下的催化转化行为, 以期使炭黑质点中不连续的无规则小石墨片层重新组装、构筑成洋葱状中空结构纳米碳. 采用透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)和Raman光谱分析表征了炭黑及其催化炭化产物的微观形貌和结构. 结果表明: 尽管三种金属催化剂均可通过溶碳-析出机制形成过渡态碳包覆纳米金属颗粒, 继而构筑成由准球形同心石墨壳层组合的洋葱状中空结构纳米碳, 但三种金属催化剂显示不同的催化效果, 终碳产物的形态和纯度差异较大, 其中以Fe 的催化效果最好.     

Effects of Annealing on High-Magnetoresistance Tunnel Junctions Using Co75Fe25 Ferromagnetic Electrodes

1. IntroductionSpin tunneling magnetoresistive effect in ferromagnet / insulat or / ferromagnet (FM / I / F M ) j "net ionshas been the subject of intense study since the discovery of large tunneling magnetoresistance (TMR) inFe/Alzos/Fe and CoFe/Alzos/Co junctions at roomtemperature (RT)[',']. TMR ratio of FM/I/FM junctions at the early period 'was achieved only a fewpercent at RT due to the restriction of fabricationtechnology and TMR junction structure and area[3-6].Recently, re…     

Giant Magnetoresistance Effect of [bcc-Fe(M)/Cu](M=Co,Ni) Multilayers

1. IlltroductionGiant magnetoresistance (GMR) effect of metallic multilayers has been widely investigated after thefinding by Baibich et al.11], as a new phenomenon tobreak through the memory density in ultra high density magnetic recording, high sensitivity in magnetichead, and so on. Metallic multilsyers of 3d transition elements could be classified into three groups of[bee/bcc], [fee/fccl and [bee/fcc] from the standpointof combination of crystal structure of constituting elements of metal…     

Influence of Mo or Cu doping in Fe/MgO catalyst for synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of methane

A series of mono-, bi- or tri-metallic Fe–Mo-Cu/MgO catalysts with the same metal loading of 6 wt% were prepared by impregnation method and used as catalysts for synthesis single-walled carbon nanotubes (SWCNTs) via methane decomposition. XRD, H₂-TPR, and nitrogen physisorption techniques were used to characterize the freshly calcined catalysts, while HRTEM, Raman spectroscopy and TGA were employed to investigate the morphology and microstructure of the SWCNTs product. The obtained results indicated that the introduction of Mo or Cu in the Fe/MgO catalyst enhanced the catalytic growth activity. TEM images showed that both bundles and isolated SWCNTs were obtained over Mo containing catalysts, whereas only SWCNTs bundles were grown over the Fe-Cu/MgO catalyst. The obtained SWCNTs having a diameter of around 0.9–2.4 nm. Raman analysis illustrated that all promoted catalysts produced high quality of SWCNTs compared to the unpromoted Fe/MgO catalyst.     

Carbon nanotube formation over laser ablated M and M/Pd (M = Fe,Co, Ni) catalysts: The effect of Pd addition

Monometallic and bimetallic M and M/Pd (M = Fe, Co, Ni) nanoparticles were prepared by pulsed Nd:YAG laser ablation of bulk M and Pd targets in acetone and transferred onto Si wafers to catalyze carbon nanotubes from decomposition of liquid petroleum gas via thermal chemical vapor deposition at 750°C. Transmission electron microscopy and optical extinction study revealed that the prepared M and M/Pd nanoparticles have rather spherical shape and their aspect ratios are nearly one. In comparison to monometallic M catalysts by addition of Pd, the average sizes of produced bimetallic M/Pd catalysts increased. Carbon nanotubes' characterization revealed that by addition of Pd to laser ablated M catalysts the average diameter, the yield, and quality of end product carbon nanotubes were increased. The average diameter of grown carbon nanotubes increases as: Ni < Ni/Pd < Co < Co/Pd < Fe < Fe/Pd and the quality of them increases as: Ni < Co < Fe < Ni/Pd < Fe/Pd < Co/Pd.     

磁性多层膜的X射线光电子能谱研究

用射频 /直流磁控溅射法制备了NiOx/Ni81Fe19和Co/AlOx/Co磁性薄膜。利用X射线光电子能谱研究了NiOx 对Ni81Fe19耦合交换场Hex与NiOx 化学状态的关系以及Co/AlOx/Co磁性薄膜中AlOx 对Co膜的覆盖状况。结果表明 :Hex的大小只与 2价镍有关 ,单质镍和 3价镍对Hex没什么作用 ;在Co/AlOx/Co磁性薄膜中 ,Al层将Co膜完全覆盖所需要的最小厚度为 2 .0nm ,用角分辨XPS测出的Al氧化厚度为 1 15nm     

Carburization of Fe/Ni Catalyst for Efficient Growth of Single‐Walled Carbon Nanotubes

Scale‐up production of single‐walled carbon nanotubes (SWNTs) with high quality and purity is in pursuit, since the subsequent post purification treatment of residual metal or amorphous carbon is complicated and restricts further applications. Here, a compatible method to efficiently synthesize pure SWNTs on various supporters by using the precarburized Fe/Ni catalysts is reported. The preparation of catalysts is achieved by gas phase deposition together with CO gas at proper temperature, and the carburization of metal particles occurring simultaneously contributes to the size limitation of catalysts. By using micro‐quartz sand as a recyclable supporter, high‐quality SWNTs with a yield of 50 mg h^?1 are prepared with 60% metal precursor utilization, 81% carbon source utilization, and only 0.12% (m/m) metal residues. Taking advantage of carburized Fe/Ni catalysts and appropriate supports makes it possible to balance the quantity, purity, and quality among SWNTs growth. Furthermore, this method provides a straightforward pathway to strongly combine SWNTs and diverse composite materials for further potential applications.     

Pseudocapacitive Ni‐Co‐Fe Hydroxides/N‐Doped Carbon Nanoplates‐Based Electrocatalyst for Efficient Oxygen Evolution

The oxygen evolution reaction (OER) catalytic activity of a transition metal oxides/hydroxides based electrocatalyst is related to its pseudocapacitance at potentials lower than the OER standard potential. Thus, a well‐defined pseudocapacitance could be a great supplement to boost OER. Herein, a highly pseudocapacitive Ni‐Fe‐Co hydroxides/N‐doped carbon nanoplates (NiCoFe‐NC)‐based electrocatalyst is synthesized using a facile one‐pot solvothermal approach. The NiCoFe‐NC has a great pseudocapacitive performance with 1849 F g^?1 specific capacitance and 31.5 Wh kg^?1 energy density. This material also exhibits an excellent OER catalytic activity comparable to the benchmark RuO₂ catalysts (an initiating overpotential of 160 mV and delivering 10 mA cm^?2 current density at 250 mV, with a Tafel slope of 31 mV dec^?1). The catalytic performance of the optimized NiCoFe‐NC catalyst could keep 24 h. X‐ray photoelectron spectroscopy, electrochemically active surface area, and other physicochemical and electrochemical analyses reveal that its great OER catalytic activity is ascribed to the Ni‐Co hydroxides with modular 2‐Dimensional layered structure, the synergistic interactions among the Fe(III) species and Ni, Co metal centers, and the improved hydrophily endowed by the incorporation of N‐doped carbon hydrogel. This work might provide a useful and general strategy to design and synthesize high‐performance metal (hydr)oxides OER electrocatalysts.     

Synthesis of nanostructured Pt<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni/C and Pt<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Co/C catalysts and their activity in the reaction of oxygen electroreduction

Nanostructured Pt _x Ni/C and Pt _x Co/C catalysts (1 ≤ x ≤ 3) containing from 27 to 40 wt % of metal with the average size of metal (alloy) particles from 2.6 to 4.7 nm are obtained using the methods of liquid-phase synthesis. Addition of a doping component is found to yield a decrease in the average nanoparticle sizes and an improved activity of materials in oxygen electroreduction reactions. The obtained catalysts are characterized by high specific activity as compared to commercial Pt/C materials. The stability of electrocatalysts to selective dissolution of the doping component is evaluated.