MnO_2@graphene复合材料的制备及其对微生物燃料电池阴极氧还原反应的催化活性EI北大核心CSCD

以高锰酸钾、草酸锰、石墨烯为原料,采用化学共沉淀法制备MnO_2@graphene复合材料,用X射线衍射、红外光谱、拉曼光谱、扫描电镜、比表面测定等对其进行表征。以MnO_2@graphene为MFC阴极氧还原反应催化剂,采用循环伏安法和电化学阻抗法研究MnO_2@graphene催化电极对氧还原反应的催化活性。结果表明:粒度为400 nm左右的MnO_2颗粒通过静电相互作用均匀而牢固地分散在纸片状graphene表面,形成MnO_2@graphene复合材料。循环伏安测试结果表明:当扫描速率为5 m V/s时,虽然MnO_2@graphene催化电极在p H为7.0的磷酸盐缓冲体系(PBS)的氧还原反应起峰电位比Pt/C催化电极负0.048V,但其峰电位(-0.440 V)与Pt/C催化电极的起峰电位(-0.434 V)接近。随着循环次数的增加,MnO_2@graphene催化电极的起峰电位稍有下降,但峰电流密度下降很小,表明MnO_2@graphene催化剂具有更好的氧还原催化活性和更优秀的循环稳定性。电化学阻抗实验发现:MnO_2@graphene催化电极的电荷转移阻抗为12.6?,比同条件下Pt/C催化电极和MnO_2催化电极的低,表明由于graphene增加MnO_2的导电性,降低催化电极电荷转移阻抗,加快电子的转移速率,促进阴极氧还原反应。     

MnO_2@graphene复合材料的制备及其对微生物燃料电池阴极氧还原反应的催化活性

以高锰酸钾、草酸锰、石墨烯为原料,采用化学共沉淀法制备MnO_2@graphene复合材料,用X射线衍射、红外光谱、拉曼光谱、扫描电镜、比表面测定等对其进行表征。以MnO_2@graphene为MFC阴极氧还原反应催化剂,采用循环伏安法和电化学阻抗法研究MnO_2@graphene催化电极对氧还原反应的催化活性。结果表明:粒度为400 nm左右的MnO_2颗粒通过静电相互作用均匀而牢固地分散在纸片状graphene表面,形成MnO_2@graphene复合材料。循环伏安测试结果表明:当扫描速率为5 m V/s时,虽然MnO_2@graphene催化电极在p H为7.0的磷酸盐缓冲体系(PBS)的氧还原反应起峰电位比Pt/C催化电极负0.048V,但其峰电位(-0.440 V)与Pt/C催化电极的起峰电位(-0.434 V)接近。随着循环次数的增加,MnO_2@graphene催化电极的起峰电位稍有下降,但峰电流密度下降很小,表明MnO_2@graphene催化剂具有更好的氧还原催化活性和更优秀的循环稳定性。电化学阻抗实验发现:MnO_2@graphene催化电极的电荷转移阻抗为12.6?,比同条件下Pt/C催化电极和MnO_2催化电极的低,表明由于graphene增加MnO_2的导电性,降低催化电极电荷转移阻抗,加快电子的转移速率,促进阴极氧还原反应。     

纳米Fe_2O_3/KIT-6介孔结构材料的制备及非均相Fenton催化降解亚甲基蓝性能研究

采用等体积浸渍法设计制备纳米Fe_2O_3/KIT-6介孔结构非均相Fenton催化材料,并测试其对亚甲基蓝的降解性能。采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、小角X射线衍射(SAXRD)和氮气吸附脱附等方法表征其粒子尺寸、介孔有序性、比表面积及孔径分布等。结果表明,介孔KIT-6孔道内均匀分布着纳米尺寸的Fe_2O_3粒子,10%铁含量(质量分数)的纳米Fe_2O_3/KIT-6介孔结构材料具有最优的Fenton催化降解性能。这是因为适量的纳米Fe_2O_3负载使催化材料具有较大的比表面积和较多活性位点的同时具有一定的催化介质传质通道,同时减少纯纳米粒子在催化过程中的团聚,从而最终提高催化剂的Fenton催化降解性能。     

纳米SCR催化剂Ce-V/TiO_2的制备与研究

采用溶胶-凝胶法和浸渍法制备选择性催化还原(SCR)脱硝反应复合纳米催化剂Ce-V/TiO_2,在不同的实验条件下制备出一系列的TiO_2凝胶用作催化剂载体.然后通过浸渍法依次负载CeO_2和V_2O_5于多孔TiO_2载体.用氨气作为还原性气体,对选择性催化还原NOx进行实验研究.在不同的TiO_2载体煅烧温度、CeO_2和V_2O_5负载量以及催化还原反应温度等条件下,对催化剂的表面结构和催化性能采用BET、XRD、SEM等手段进行表征分析.结果表明,纳米Ce-V/TiO_2固溶体复合催化剂以及对其制备工艺技术参数的优化可增大催化剂的比表面积和微孔体积,使催化剂的催化活性有很大的提高.此外,相当数量的多孔纳米TiO_2大大增加了光催化活性的有效面积,有利于增大与反应物的接触面积和提高光催化活性.当载体TiO_2 的煅烧温度和催化还原反应温度为500 ℃时,5%Ce-10%V/TiO_2催化剂反应的NO_x转化率可达96.2%.     

热处理对Pt纳米线电催化性能的影响

采用阳极氧化铝(AAO)模板法电化学沉积制备了Pt纳米线催化剂,并进行了热处理。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学测试对热处理前后Pt纳米线催化剂的晶体结构、形貌和电催化性能进行了表征,并与商业碳载铂(Pt/C)做对比。SEM照片表明制备了表面粗糙的Pt纳米线。循环伏安法(CV)和计时电流曲线表明,Pt纳米线较Pt/C催化活性高,退火后Pt纳米线更利于甲醇氧化,且稳定性更好。旋转圆盘电极(RDE)测试研究发现,未经热处理的Pt纳米线催化剂氧还原反应(ORR)极化曲线的半波电势相对Pt/C有正移,有更大的极限扩散电流,利于氧还原反应的发生。     

简单一步法合成Co_9S_8氧还原反应电催化剂（英文）

采用低温回流技术,以Co_4(CO)_(12)和S粉为原料,在1,6-己二醇溶剂中一步合成了钴硫化物催化剂。用X射线衍射仪和扫描电子显微镜对合成的化合物进行了表征。XRD分析表明合成样品为立方结构的Co_9S_8化合物,其SEM图片显示了花椰菜状的表面形貌。Co9S8化合物表现出良好的氧还原催化活性,开路电位为0.75 V(vs.NHE)。在电荷转移控制电位区,电极反应传递系数和塔菲尔斜率分别为0.50和119 mV。同时,将催化剂的催化活性和电化学稳定性与商业铂催化剂进行了比较。     

Fe_2O_3/TiO_2纳米复合材料对304不锈钢的光生阴极保护性能

采用化学浴法在阳极氧化的TiO_2纳米管表面沉积Fe_2O_3,制备Fe_2O_3/TiO_2纳米复合材料。通过扫描电子显微镜(SEM),X射线衍射(XRD),X射线光电子能谱(XPS),紫外-可见漫反射吸收光谱(UV-vis DRS)等手段对材料的形貌、晶相、成分、光响应性等进行表征。通过测试可见光下开/闭光时的开路电位(OCP)、光致激发电流(i-t)、电化学阻抗谱(EIS)等研究复合材料的光电性能。结果表明,Fe_2O_3纳米颗粒的修饰能增加TiO_2纳米管对可见光的利用效率,增强阴极保护性能。0.05 mol/L Fe(NO_3)_3制备的Fe_2O_3/TiO_2纳米复合材料在可见光下,耦联304不锈钢后光生电位达-740mV,比纯TiO_2纳米管低约300 mV,对304不锈钢起到更好的阴极保护效果。     

溶胶凝胶法制备纳米贵金属稀土复合氧化物研究

通过溶胶凝胶法以无机盐为原料制备纳米贵金属稀土复合氧化物,并采用透射电镜(TEM)、低温氮吸附、X射线衍射(XRD)和程序升温H2还原(TPR-H2)对其形貌特征和物化性能进行了研究.复合氧化物为无定形或不规则多晶物质,以不规则球形粒子聚集成团存在,平均粒径约为70 nm.其比表面积和总孔容适中,孔容呈现双峰分布特征.其储氧值和还原起点温度分别为2767 μmol/g和200℃,具有作为汽车尾气净化三元催化剂涂层料的潜在优异起燃和储氧特性.     

Cu-BTC前驱体制备碳基催化剂的结构和脱硝性能（英文）

以Cu-BTC为前驱体,采用水热法制备碳基催化剂,并进行低温脱硝性能研究。通过X射线衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)和能量弥散X射线谱(EDS)等技术对碳基催化剂的结构进行表征。结果表明:碳基催化剂基本保持着Cu-BTC前驱体的八面体形貌,并主要呈现面心立方铜结构。通过碳基催化剂的脱硝性能研究发现:CuO_x/C表现出最佳的催化活性,且其活性随着Ag的掺入得到进一步的提高。当Cu/Ag摩尔比为6:1,活化温度为600°C时,碳基催化剂具有最优的催化活性,其脱硝效率达到100%时温度可降低至235°C。该催化反应过程中,主要是Cu~+起催化作用。     

适于水合肼分解制氢的Ni-Pt/CeO_2催化剂的表面组分调控

采用共还原方法制备了Ni-Pt/Ce O_2催化剂,并在不同气氛(空气、H_2、NH_3和CO)和不同温度下对催化剂进行热处理。结果表明,改变热处理条件可调变催化剂表面Ni/Pt摩尔比,进而调控催化性能,Ni-Pt/Ce O_2催化剂表面的Ni/Pt摩尔比为0.8~1.14时,催化剂具有较高的催化活性。此外,在催化剂表面引入非金属元素N可大幅度提高Ni-Pt/Ce O_2的催化活性,该发现有望为发展高性能水合肼分解制氢催化剂提供新的思路与途径。     

NiSe2化合物对氧还原反应的电催化性能

以NiCl2和Se粉为原料,采用溶剂热法合成了NiSe2化合物。利用SEM、XRD技术对化合物的微观形貌和相结构进行了表征,化合物由立方结构的NiSe2晶粒组成,呈现出类似花椰菜的表面形貌。利用旋转圆盘电极研究了NiSe2化合物对氧还原反应的电催化性能。在0.5 mol/L H2SO4电解液中,NiSe2化合物对氧还原反应呈现明显的电催化活性,开路电位为0.80 V(vs.NHE)。在0.63~0.77 V(vs.NHE)电位范围内,测定的交换电流密度为1.35×10-5 mA/cm2。根据Koutecky-Levich方程计算出每个氧分子还原转移电子数约为3.8。     

Effect of electrolysis voltage on electrochemical reduction of titanium oxide to titanium in molten calcium chloride

The electrochemical reduction of solid TiO2 directly to solid metal is a ptomising alternative to the current Kroll process. The present work is aimed at studying the effect of electrolysis voltage on the rate of electrochemical reduction. The products of electrochemical reduction of TiO2 and Ti2O were examined using the scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The results show that Ti2O was reduced to low valent titanium oxide at 1.5 -1.7 V, which was the result of ionization of oxygen. TiO2 and Ti2O were reduced to titanium metal at 2.1-3.1 V, which was the co-action of ionization of oxygen and calciothermic reduction. The oxygen content decreased rapidly with voltage increasing from 2.1 to 2.6 V, while it changed little from 2.6 to 3.1 V. The optimized cell voltage was 2.6-3.1 V.     

Reduction mechanism of natural ilmenite with graphite

Reduction of Bama ilmenite concentrate containing 49.78% TiO2 and 27.96% total Fe by graphite was studied using thermogravimetric analysis system under argon gas ambient from 850 to 1 400 ℃. The reduction degree of Bama ilmenite is enhanced with increasing temperature and the molar ratio of carbon to oxygen, and the reaction rate varies with temperature and reduction time simultaneously. The phase transformation, chemical composition, microstructure and morphology of reduced samples were investigated by using X-ray diffractometry, scanning electron microscopy, and energy disperse spectroscopy, respectively. The high content of impurities in Bama ilmenite evidently bates the reduction of ilmenite. Forming the enrichment zone of manganese prevents complete reduction of Fe^2＋. The reduction products are mostly reduced iron, rutile, reduced rutiles, Ti3O5 and pseudobrookite solid solution. The reduction kinetics was also discussed. The results show that the reduction temperature is a key factor to control reaction rate.     

Preparation of Pt-based ternary catalyst as cathode material for proton exchange membrane fuel cell by solution route method

In this research, Pt-based ternary catalysts for proton exchange membrane fuel cell (PEMFC) have been successfully prepared by the solution route method. This type of catalyst was claimed to improve the activities of oxygen reduction reaction (ORR). The ternary catalyst was prepared using 10% platinum, 5% cobalt, and 5% chromium by weight support on untreated and treated carbons by reduction with NaBH₄ at room temperature. The FTIR spectra showed a new functional group as carboxyl group on treated carbon using H₂O₂. The XRD patterns for both carbon samples confirmed platinum and carbon phases in the products. The EDS spectra detected platinum, cobalt, chromium, oxygen and carbon atoms in the prepared catalysts. The XAS patterns revealed that the products were mixed Pt-CoO-Cr₂O₃ catalysts. The SEM and TEM images showed more dispersion of catalyst on the treated carbon support surface than on the untreated carbon support. Particles size were 3.97 nm for untreated carbon and 1.93 nm for treated carbon. Finally, the electrochemical property was tested by CV technique. It indicated that Pt-CoO-Cr₂O₃/C catalyst supported on treated carbon exhibited the highest performance among the prepared ternary alloy catalysts.     

Surface Modification of Li1.6(Fe0.2Ni0.2Mn0.6)O2.6 by V2O5- Coating

在采用低温共沉淀-水热-煅烧法合成锂离子电池Fe-Ni-Mn体系正极材料Li1.6(Fe0.2Ni0.2Mn0.6)O2.6的基础上,对合成的材料Li1.6(Fe0.2Ni0.2Mn0.6)O2.6进行V2O5的包覆改性研究,以提高材料Li1.6(Fe0.2Ni0.2Mn0.6)O2.6的首次放电比容量和循环性能。用XRD、SEM、TEM、ICP光谱和恒流充放电测试研究包覆材料的结构和电化学性能。结果表明,V2O5包覆并没有改变材料的晶体结构,只存在于材料的表面,与未包覆的材料相比,V2O5包覆后的材料具有更好的首次放电容量和容量保持率。50周循环后,添加质量分数3%V2O5样品Li1.6(Fe0.2Ni0.2Mn0.6)O2.6的放电比容量可以维持在200.3 mAh/g,大于未添加V2O5样品Li1.6(Fe0.2Ni0.2Mn0.6)O2.6的194.0 mAh/g。CV测试表明,包覆层的存在有效抑制了材料层状结构的转变及电极与电解液的负反应。     

常压低温冷等离子体还原Fe2O3的研究

目的研究常压低温冷等离子体还原过程中气体常量对Fe_2O_3还原过程的影响。方法采用冷压成形后高温烧结的方式制备Fe_2O_3试样块,利用射流型常压冷等离子体还原铁基氧化物,通过X射线衍射仪分析还原前后的物相,用扫描电镜观察还原前后的微观形貌,讨论了还原过程中气氛的作用和影响。结果等离子体的还原能力取决于还原气体的成分与含量,其中氮等离子体在常温常压条件下无法还原Fe_2O_3,氨气+氮气混合气体为工作气体的常压低温冷等离子体能将Fe_2O_3还原成Fe_3O_4和金属Fe,还原能力随着氨气含量的增加而增强,还原速率随着氨气含量的增加而下降。氨气在等离子体中可产生多种还原性物质,如N_2H_4、H和H_2*等,能将Fe_2O_3还原,且过程表现为过渡还原,即Fe_2O_3先被还原成Fe_3O_4,再被还原成金属Fe。结论常压低温冷等离子体中的电子与热效应无法还原Fe_2O_3,添加氨气后的等离子体中产生了一系列的活性物质,才能还原金属Fe表面的氧化物。     

直接气相还原法制备金属铱及其氧还原活性

采用直接气相还原法制备了金属铱催化剂。通过X射线衍射(XRD)分析了金属铱的物相组成,采用循环伏安(CV)和线性电势扫描(LSV)等电化学手段评价了金属铱的电化学性能。XRD分析结果表明在氨气气氛中,氧化铱经400℃还原3h能完全转化为金属铱单质。CV和LSV结果表明金属铱具有良好的氧还原电催化活性,且其氧还原起始电压可以达到0.51V(vs.SCE)。从原子状态角度考虑,金属铱的d带空穴多于金属铂,最终导致金属铱的氧还原电催化活性低于金属铂,但金属铱具有与金属铂相似的氧还原电催化路径。     

Metal dusting of ferritic Fe‐Al‐M‐C (M = Ti,V, Nb,Ta) alloys in CO‐H2‐H2O gas mixtures at 650 °C

Iron aluminides are known for their resistance to high temperature oxidation and sulphidation. Only little information is available about carburisation and metal dusting of Fe‐Al alloys. Metal dusting experiments with Fe‐15Al and Fe‐15Al‐2M‐1C alloys (in at.%) with M = Ti, V, Nb, or Ta were conducted at 650°C in CO‐H₂‐H₂O gas mixtures with the carbon activity a_c = 28. The kinetics of the carbon transfer was measured using thermogravimetric analysis (TGA). It is shown that the mass gain kinetics decreases by adding the alloying elements Nb, Ta, V, or Ti with C. Alloying with titanium and carbon leads to the most significant decreasing effect. The metallographic cross section observation showed a general metal wastage for Fe‐15Al, but local pitting for the Fe‐15Al‐2Nb‐1C and Fe‐15Al‐2Ta‐1C alloys. For the Fe‐15Al‐2V‐1C and Fe‐15Al‐2Ti‐1C alloys no significant attack was observed. Needle‐ or plate‐like Fe₃AlC_x precipitates were detected in the carburised samples. The existence of this ternary carbide with perovskite structure was predicted by thermodynamic calculations using the software Thermo‐Calc. The morphology of graphite on the surface was analysed by scanning electron microscopy (SEM). Mainly fine filaments with iron containing particles were detected. Cementite was detected in the coke layer by X‐ray diffraction analysis (XRD).     

Hydrothermal synthesis of titanium-supported nanoporous palladium–copper electrocatalysts for formic acid oxidation and oxygen reduction reaction

Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction (ORR) in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPd₈₁Cu₁₉/Ti catalyst presents the highest current density of 39.8 mA/cm² at ?0.5 V or 66.4 mA/cm² at ?0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPd₈₁Cu₁₉/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at ?0.3 V is 2.12 mA/cm², which is 3.7 times larger than that on the nanoPd/Ti.     

Fe-Cr-O和Fe-Cr-Ni-O体系中C还原产物(英文)

研究不同条件下C还原Fe-Cr-O体系(FeCr2O4和Fe2O3+Cr2O3)及Fe-Cr-Ni-O体系(Fe2O3+Cr2O3+NiO)的还原行为及产物特性。结果表明:温度与碳氧比对C还原Fe-Cr-O和Fe-Cr-Ni-O体系所得产物的组成有很大的影响,在较高温度和较低碳氧比的条件下,产物中残余碳含量更少且Fe-Cr和Fe-Cr-Ni合金含量更多;样品的还原率在很大程度上取决于还原时间和温度,在不同温度条件下,产物中的残余碳含量均随着碳氧比的增加而升高。此外,对不同时间条件下C还原Fe-Cr-O体系所得产物进行XRD分析,利用SEM和EDS研究C还原Fe-Cr-O和Fe-Cr-Ni-O体系所得最终产物中不同相的微观形貌和元素分布。