二次烧结气氛对La0.7Sr0.3MnO3氧还原催化活性的影响

采用溶胶-凝胶法结合二次高温烧结技术,制备了锰系钙钛矿催化剂。利用XRD和EDS对催化剂的物相与元素组成进行了分析,并利用电化学分析方法研究了催化剂的氧还原催化性能。XRD与EDS结果表明,N_2气氛二次烧结不改变La_(0.7)Sr_(0.3)MnO_3物相组成,但NH3气氛二次烧结会造成La_(0.7)Sr_(0.3)MnO_3分解。电化学结果表明,N_2气氛二次烧结催化剂的氧还原催化活性高于NH3气氛二次烧结催化剂,其氧还原起始电势与极限电流分别为0.028V(vs.Hg/HgO)和2.181mA·cm~(-2)(2 000r/min)。     

转炉烟尘制备氮化铁磁粉的研究

转炉烟尘通过湿法(硫酸和氨水)冶金提纯净化、高能球磨处理后,在NH3/H2气氛下进行还原氮化,以穆斯堡尔谱学、X光衍射等方法对处理试样进行物相分析.结果表明,Ar气氛下球磨2h后,经550℃/2h还原、550℃/3h氮化(NH3/H2=3/4,降温时NH3/H2=1/6)处理,γ'-Fe4N 的生成量≥91%.     

S/N共掺杂石墨烯的制备及其电催化性能

采用一步水热法制备了S/N共掺杂石墨烯催化剂材料。利用扫描电子显微镜(SEM)、透射电镜(TEM)、拉曼光谱、红外光谱以及X射线衍射仪(XRD)对催化剂物理形貌、组成、物相等进行了分析,并利用电化学分析方法对催化剂的电催化性能进行了研究。通过不同的物理表征证明S和N成功地掺杂入石墨烯晶格,共掺杂石墨烯具有典型的石墨烯形貌。掺杂石墨烯的高电催化活性是源于对石墨烯进行S和N的掺杂后仍然具有高比表面积及石墨烯本身所特有的一些性质。该掺杂石墨烯在0.1 mol/L的KOH溶液中对氧进行催化还原时,无论是起始电位、半波电位、还是极限电流密度,都可与商业生产的贵金属催化剂相媲美,说明S/N共掺杂石墨烯在氧还原催化活性上可被用来替代当前所使用的贵金属催化剂。     

直接甲醇燃料电池阴极催化剂Pt/MnO2(C)的制备与研究

采用液相化学沉积的方法制备了含有不同二氧化锰晶型的Pt/MnO2(C)催化剂.通过XRD对该催化剂的结构进行了初步表征,电化学循环伏安法考察了催化剂在氧饱和的0.5mol/L H2SO4溶液中的电化学性能.结果表明,Pt/MnO2(C)催化剂具有良好的氧还原催化性能,二氧化锰晶体的加入起到了一定的助催化效果.     

TiO2氧空位形成的影响因素

为了研究TiO2氧空位形成的影响因素,用管式电阻炉在空气、Ar及不同温度下对TiO2烧结.采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对烧结TiO2样品的微观形貌、物相组成、元素及价态进行了表征,研究了烧结温度、烧结气氛和Ar+刻蚀对TiO2样品氧空位形成的影响.结果表明:相同气氛下,随着烧结温度的升高,TiO2氧空位浓度逐渐增大;相同温度下,惰性气氛有利于TiO2氧空位的产生;Ar+刻蚀有利于TiO2氧空位的形成.     

热处理对FeN/C催化剂氧还原性能的影响

高活性、低沉本的阴极氧还原催化剂是目前质子交换膜燃料电池的重要研究内容之一。考察了FeN/C作为氧还原催化剂的催化性能,研究氨气气氛下的二次热处理对催化剂氧还原催化活性与稳定性的影响。使用X射线衍射、比表面积和孔径分布测试、透射电子显微镜等方法对催化剂的结构进行表征,使用线性扫描伏安法对催化剂的氧还原活性进行测试。结果表明,经二次热处理后,催化剂表现出更好的氧还原催化活性及稳定性。催化剂在二次热处理后,具有更高的比表面积(931.2 m~2/g)、较高的表面氮含量(1.67%(原子分数))、以及催化剂中存在的Fe_3C,是其催化性能提高的可能原因。     

仿生制备多孔氮化硅陶瓷

以松木炭化后形成的多孔木炭为模板,经Y2O3/SiO2混合溶胶浸渍生物碳模板形成Y2O3/SiO2/C复合体,在高压氮气氛下(0.6MPa),1600°C碳热还原氮化制备出牛物形态多孔氮化硅陶瓷.借助XRD、SEM研究了烧结助剂、烧结温度、反应时间和烧结气氛对烧结产物显微结构和晶相的影响,探讨了多孔Si3N4陶瓷的反应过程和机理.结果表明,多孔si3N4陶瓷是由主晶相β-Si3N4和少量晶间玻璃相YsSi4n4O14组成;多孔Si3N4不仅保留了松木的管胞结构,还在孔道中生长出纤维状形貌的β-Si3N4颗粒;Si3N4的反应烧结过程包括α-Si3N4的形成、晶形转变(α-β相变)和晶粒生长三个阶段.在1450°C烧结的机理是气-固和气-气反应机理,在1600°C通过液相烧结的溶解-沉淀机理形成纤维状的多孔Si3N4陶瓷.     

NH_4F改性MWCNTs负载Pd纳米粒子的电催化性能研究

以无机物NH4F为改性剂,对NaOH处理后的多壁碳纳米管(f1-MWCNTs)进行共价键表面修饰得到f2-MWCNTs,将前驱体溶液在紫外光照射下边还原边负载于f2-MWCNTs表面,制得Pd/f2-MWCNTs催化剂。利用FT-IR、TEM、EDS、XRD和XPS等手段对其进行表征,结果表明f2-MWCNTs表面形成C—F、C—N等化学键和Pd/f2-MWCNTs表面存在Pd-F配位键,通过这些化学键的相互作用改变了Pd的电子结构,从而提高Pd纳米粒子的负载率和分散性。通过电化学测试发现,Pd/f2-MWCNTs催化剂对甲醇具有优异的催化性能,其质量电流密度是JM公司商业Pd/C催化剂的2.87倍。     

TiC_(0.7)N_(0.3)增强ZrO_2基复合材料的微观结构及力学性能

为提高ZrO2基复合材料硬度,采用热压烧结法制备了TiC0.7N0.3/ZrO2复合材料,并研究了TiC0.7N0.3颗粒增强相对复合材料的物相组成、微观结构和力学性能的影响。结果表明:TiC0.7N0.3的添加具有稳定四方相ZrO2(t-ZrO2)的作用,能增加TiC0.7N0.3/ZrO2复合材料中t-ZrO2的含量,提高断裂韧性。随着热压烧结温度的升高和TiC0.7N0.3含量的增加,复合材料的硬度升高。1 400℃下热压烧结时,TiC0.7N0.3发生部分分解,分解的N与被还原的ZrO2反应生成ZrN,提高了复合材料的硬度。1 400℃下热压烧结后的35wt%TiC0.7N0.3/ZrO2复合材料的相对密度达99.9%,维氏硬度达17 GPa。而1 300℃下热压烧结后,复合材料断裂韧性较高,为6.48 MPa·m1/2。研究结果为TiC0.7N0.3/ZrO2复合材料的组织控制及性能改进提供了参考。     

碱金属碳酸盐掺杂的Ce-Zr-O对甲烷转化催化性能的影响

采用共沉淀法制备了Ce-Zr-O载体,通过等体积浸渍法得到碱金属碳酸盐掺杂的M2CO3/Ce-Zr-O(M=Li,Na,K)催化剂。采用自制的小型固定床反应器考察了催化剂的甲烷转化催化活性,并利用XRD和H2-TPR对催化剂进行了表征。研究结果表明,碱金属碳酸盐的添加均不同程度地提高了Ce-Zr-O催化剂的催化活性、抗积碳性能和抗烧结性能,还改善了催化剂表面氧物种和体相氧物种的氧化还原性能。     

恒压电沉积Pt-Fe合金催化剂及在PEMFC阴极的应用

利用循环伏安法探究Pt与Fe共沉积的还原电位, 并在此电位下在多孔碳布表面恒压电沉积制备Pt-Fe合金, 研究其作为质子交换膜燃料电池 (PEMFC)阴极催化剂的电催化活性。通过X射线衍射 (XRD)、扫描电子显微镜(SEM)及场发射扫描电子显微镜 (FESEM)、能量色散谱 (EDS)、循环伏安 (CV)、单电池极化、电化学交流阻抗谱 (EIS)等测试技术对所得催化剂进行物理及电化学性能表征。实验表明, 在0.075 V电位下可还原得到Pt-Fe合金, 其颗粒在碳布表面呈空心球状且分散均匀; 共沉积时间对Pt-Fe合金催化剂成分组成有显著的影响, 随着时间的增加, 合金中Pt与Fe原子比增加, Fe相对含量下降。Fe可与Pt形成稳定的合金催化剂, 显著提高铂对氧还原的催化活性。电沉积30 min制得的合金催化剂具有最佳的催化活性。     

铂钴合金纳米电催化剂的制备及性能研究

研制高活性的电催化剂是实现质子交换膜燃料电池的商业化应用必须解决的关键技术之一。本研究以三乙胺为碱性络合剂、硼氢化钠为还原剂, 采用液相合成法制备PtCo纳米合金电催化剂, 再通过高温热处理实现最佳电化学性能。采用各种表征方法对催化剂的微观结构及电化学性能进行测定, 探究硼氢化钠、三乙胺的添加量及高温热处理对催化剂电化学性能的影响。结果显示, 适量的硼氢化钠可提升催化剂的电化学活性面积, 三乙胺可以改变催化剂的质量活性, 高温热处理能有效提升催化剂的质量活性, 极大提升催化剂的氧还原反应(ORR)能力; 在同一测试体系下, 添加100 mg硼氢化钠及100 μL三乙胺在500 ℃高温热处理条件下制备的PtCo纳米合金电催化剂的质量活性达到133 mA/mg_Pt, 是田中贵金属工业株式会社(TKK)商用PtCo合金催化剂的3倍。     

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.     

Steam reforming of glycerol into hydrogen over nano-size Ni-based hydrotalcite-like catalysts

Steam reforming (SR) of glycerol for the production of hydrogen was investigated over the nano-sized Ni-based catalysts. The Ni-based catalysts were prepared by solid phase crystallization and impregnation methods, and characterized by N2 physisorption, CO chemisorption, XRD, SEM, and TEM techniques. The Ni/gamma-Al2O3 catalyst showed higher conversion and H2 selectivity. However, it was slowly deactivated due to the carbon formation on the surface of catalyst and the sintering. It was found that the Ni based hydrotalcite-like catalyst (spc-Ni/MgAl) showed higher catalytic activity to prevent carbon formation than Ni/gamma-Al2O3 catalyst in the SR of glycerol.     

MnOx/ZrO2纳米催化剂的制备及对CO-SCR-NO性能研究

以氧氯化锆和硝酸锰为主要原料，采用Sol—Gel—VFD技术制备了MnOx／ZrO2超细粉体材料。用XRD，TG—DSC，TEM和BET等技术对试样进行了表征，用微反应器-气相色谱仪在线研究了试样不同配合比例对试样催化还原NO的活性的影响。结果表明：用Sol—Gel—VFD技术可制得粒子尺寸约为20nm、具有高催化活性的负载型MnOx／ZrO2纳米催化剂，锰由低价向高价转变。添加了Ce组分能提高MnOx／ZrO2纳米催化剂催化还原NO的活性。     

Preparation and application of granular ZnO/Al2O3 catalyst for the removal of hazardous trichloroethylene

Trichloroethylene (TCE) is a volatile and nerve-toxic liquid, which is widely used in many industries as an organic solvent. Without proper treatment, it will be volatilized into the atmosphere easily and hazardous to the human health and the environment. This study tries to prepare granular ZnO/Al(2)O(3) catalyst by a modified oil-drop sol-gel process incorporated the incipient wetness impregnation method and estimates its performance on the catalytic decomposition of TCE. The effects of different preparation and operation conditions are also investigated. Experimental results show that the granular ZnO/Al(2)O(3) catalyst has good catalytic performance on TCE decomposition and the conversion of TCE is 98%. ZnO/Al(2)O(3)(N) catalyst has better performance than ZnO/Al(2)O(3)(O) at high temperature. Five percent of active metal concentration and 550 degrees C calcination temperature are the better and economic preparation conditions, and the optimum operation temperature and space velocity are 450 degrees C and 18,000 h(-1), respectively. The conversions of TCE are similar and all higher than 90% as the oxygen concentration in feed gas is higher than 5%. By Fourier transform infrared spectrography (FT-IR) analyses, the major reaction products in the catalytic decomposition of TCE are HCl and CO(2). The Brunauer-Emmett-Teller (BET) surface areas of catalysts are significantly decreased as the calcination temperature is higher than 550 degrees C due to the sintering of catalyst materials, as well as the reaction temperature is higher than 150 degrees C due to the accumulations of reaction residues on the surfaces of catalysts. These results are also demonstrated by the results of scanning electron micrography (SEM) and energy disperse spectrography (EDS).     

Effect of controlling nano-sized copper by silver in copper-based catalyst on catalytic oxidation of toluene

Catalytic oxidation of VOC (toluene) over a copper based catalyst was carried out to assess its properties and performance. The Brunauer Emmett Teller (BET) method, X-ray diffraction (XRD), temperature programmed reduction (TPR), N2O pulse titration and energy dispersive spectroscopy (EDS) were used to characterize a series of 5 wt% Cu/gamma-Al2O3 catalysts modified with silver. The experimental results revealed that the addition of silver to 5 wt% Cu/gamma-Al2O3 catalyst highly enhanced its catalytic activity. With increasing addition amount of silver, the light-off curve for complete oxidation of toluene shifted to lower temperature. In addition, the increase of the addition amount of silver caused the copper particle size of 5 wt% Cu/gamma-Al2O3 catalyst to gradually increase. Subsequently, it demonstrated that the increase in the copper particle size is closely associated with the increase in catalytic activity.     

B4C与NH4Cl生成BN反应的研究

研究了Ｂ４Ｃ,ＮＨ４Ｃl和Ｌi3N在不同条件下的反应,分析了Ｌi3Ｎ及Ｈ２,Ｎ２,ＮＨ３等气体在上述反应中的作用,结果表明,在Ｎ２气氛及１２２３Ｋ温度下,Ｂ４Ｃ与Ｌi3N反应生成hBN,B4C与ＮＨ４Ｃl反应只生成少量hBN,而Ｂ４Ｃ,ＮＨ４Ｃl,Li3N共同反应有大量hBN生成,说明在高温高压下合成cBN的常催化剂Li3N,在常压高温下Ｂ４Ｃ与ＮＨ４Ｃl生成hBN的反应中也起催化作用。     

Plasma Enhanced Chemical Vapor Deposition Nanocrystalline Tungsten Carbide Thin Film and Its Electro-catalytic Activity

Nanocrystalline tungsten carbide thin films were fabricated on graphite substrates by plasma enhanced chemical vapor deposition (PECVD) at H2 and Ar atmosphere, using WF6 and CH4 as precursors. The crystal phase, structure and chemical components of the films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS), respectively. The results show that the film prepared at CH4/WF6 concentration ratio of 20 and at 800℃is composed of spherical particles with a diameter of 20-35 nm. Electrochemical investigations show that the electrochemical real surface area of electrode of the film is large, and the electrode of the film exhibits higher electro-catalytic activity in the reaction of methanol oxidation. The designated constant current of the film catalyst is 123.6 mA/cm2 in the mixture solution of H2SO4 and CH3OH at the concentration of 0.5 and 2.0 mol/L at 70℃, and the designated constant potential is only 0.306 V (vs SCE).