纳米Al-MoO3发火性能研究
纳米铝热剂的研究进展

万方数据万方数据万方数据增刊周超等:纳米铝热剂的研究进展·7·微有点高,见表2。
表2Fe:QIAllVitaaA体系的感度图1溶胶一凝胶法制备的纳米F乜03/A1/VitonA铝热剂的微观结构纳米Fez03/Al/VitonA铝热剂的燃烧速度快而且剧烈,伴有大量的光、热和烟,甚至还有自燃的现象,但具体原因还未确定[22讨论和展望制备纳米铝热剂的方法不断在发展,其目标是制备出粒径小、纯度高、分散性好、易于工业化生产的纳米复合粒子。
但从上所述可看出现有的各种制备方法各有优点和不足:(1)固相反应法具有设备和工艺简单等优点。
但是固相反应法通常需要在高温下进行,伴随着反应的进行,反应物和产物的物理化学性质将会变化,而且也不适合工业化生产;(2)抑制反应球磨法具有处理时间短、反应过程易控制、可批量生产等优点,但是也具有易造成无机粒子的晶型破坏、包覆不均匀等缺点,而且一般要求母粒子在微米级,并需要事先制备单一超细粒子;(3)自组装法具有原位自发形成、热力学稳定、制作方便简单等优点,但是此法也存在生产成本高、合成周期长加上有机溶剂毒性大等缺点,不适合工业生产;(4)溶胶一凝胶法是制备纳米铝热剂的优秀方法。
但此法也存在所用有机溶剂有毒性、合成周期长、粉体团聚以及不易制备碱金属纳米氧化物等缺点。
今后的研究中需大力发展溶胶一凝胶法与其他方法结合的一些廉价、高效、环保的新方法;(5)虽然喷雾热分解法制得的纳米铝热剂产品纯度高,分散性好,粒度均匀可控,但生成的纳米粒子中有许多空心粒子且组分分布不均匀,目前也不适合工业化生产。
可以看到,以上所述的各种制备方法没有一种方法真正满足工业化生产的高效、廉价、环保的要求。
且目前的制备研究中仍有许多理论和实践问题有待解决。
这些问题主要是:缺乏合成纳米复合颗粒的过程机理,以及控制颗粒的形状、性能、分布的理论研究;纳米铝热剂在空气中极易吸湿、团聚;制备工艺还不够先进,成本较高。
MoO3微纳米片的简单制备及其光致发光性能

MoO3微纳米片的简单制备及其光致发光性能∗钟明龙【摘要】Single-crystalline lamellarα-MoO3 micro-sheets were synthesized on ITO glass substrates by a simple thermal evaporation method.The micro-sheets with a length and a width of 100 and 1-5μm,were composed of nanosized layers with thickness about 100 nm.The common vapor-solid (VS)mechanism is adopted for the growth of lamellarα-MoO3 micro-sheets,which grow along [001]direction.The room temperature photolumi-nescence (PL)properties of theα-MoO3 micro-sheets were investigated.The emission intensity increased with deposition temperature increases due to the increasing defect density for the micro/nanostructures.%采用简单热氧化蒸发沉积法在 ITO 玻璃基片上制备了大面积Mo O 3微纳米片。
制备出的微纳米片具有良好晶体结构,其长度、宽度和片层厚度分别可达100,1~5μm 和约100 nm;微纳米片沿[001]方向生长,这是因为晶体各方向键合能的不同而具有不同的生长速度,其形成过程遵循气-固生长机制。
光致发光谱显示室温下 Mo O 3微纳米片同时具有紫光发射峰、蓝光发射峰和绿光发光带,发射光强度随氧化沉积温度升高而增大,这是由于温度升高,微纳米片缺陷增加导致的。
液相法制备MoO3纳米结构

液相法制备MoO3纳米结构摘要“纳米”是一个长度单位,1纳米是1米的十亿分之一(1nm=10-9m)相当于头发丝直径的十万分之一。
纳米材料指的是晶粒尺寸为纳米级(10-9m)的超细材料。
纳米材料由于具有与块体材料不同的尺寸效应、体积效应、表面界面效应和宏观量子隧道效应等,使其在电子信息、化工、生物工程、医药、航空航天、国防等高尖端领域有着广泛的应用前景。
纳米材料既是一种新材料又是构成新材料的重要原料。
钼和钼合金材料不仅具有良好的耐高温强度和硬度,而且具有良好的导电、导热、抗腐蚀等性能,此广泛应用于化学化工、冶金机械及航空航天等工业领域。
三氧化钼( MoO3) 不仅是制备钼和钼合金材料的主要原料,而且本身也具有电致变色、光致变色、光催化降解及气敏等特性,因此在合成敏感元件、催化剂、快离子导体及潜在的电池电极等许多功能材料方面具有特殊用途。
制备性能优异的三氧化钼薄膜一直是研究的重点。
近年来,随着科学技术的进步,不断出现许多新型的三氧化钼薄膜制备方法。
目前已有多种制备Mo O3薄膜的方法,如蒸镀法、电化学沉积法、溅射法、溶胶-凝胶法等。
本文主要从沉淀法,水热法,化学气象沉积法,溶胶凝胶法等工艺流程来阐述MoO3的制备。
关键词:纳米,三氧化钼,液相法,纳米薄膜,钼合金材料THE LIQUID PHASE PREPARATION OF NANO MoO3ABSTR ACT"N ano" is a un it o f len gth,1nano meter is o ne hu nd red b illio nt h o f a meter (1nm =10-9 m),and it is eq u ivale nt to o ne o ver o nehu nd red tho usand the d ia meter o f a hair.Nano materia l refers to the grain size fo r the nano meter leve l (10-9m) o f sup er fine mater ia l. Because o f N ano materia ls have d ifferent size effect, sur face effect, vo lu me inter face effect and macro sco p ical q uant u m t un nel e ffect etc, when co mp ared wit h b u lk materia ls,mak in g N ano materia ls have a wid e range o f app licat io ns in electro n ic in fo rmat io n ind ustry, chemica l ind ustry,b io lo g ical en g ineerin g,med icine,aviat io n,fro nt ier defe nse etc. N ano materia l is no t o nly a k ind o f new mater ia l b ut also an imp o rtant raw materia l o f the new materia l.Mo lyb d enu m and mo lyb den u m allo y materia l no t o n ly has go o d resista nce to hig h temp erature and go o d hard ness strengt h,b ut also has goo d electr ic co nd uct iv ity,ther mal co nd uct iv ity,co rro sio n resista nce and o ther p rop erties,they are wid e ly used in chemica lind ustry,meta llurg y mecha n ical ,aero sp ace and o ther ind ustries. Three mo lyb den u m o x id e (MoO3) is no t o n ly the ma in raw mater ial tomak e mo lyb d enu m and mo lyb d enu m allo y mater ial,meanw h ile it a lso has the effect o f electro chro mic,p ho to chro mic,p ho to catalyt ic degrad atio n and characterist ics o f air sensit ive,what’s mo re,it has sp ecial use in man y funct io na l materia ls w ith d ifferentp urpo ses ,such as the synt hesis o f sens it ive co mp o nents,c atalyst,fast io n,and battery electrod es etc.The man ufacture o f t hree mo lyb den u m o x id e film w it h o utstand ing p erfo r mance has b eco me t he fo cus o f recent research.In recent years, w ith the deve lo p ment o f scient ific techno lo g y, d ifferent metho d s o f mak in g three mo lyb d enu m o x id e film app ear.Recent ly, there exists a variet y o f p rep aratio n MoO3film metho d s, such as steamed p latin g metho d, electro chemica l depo sit io n metho d, sp utter in g,so l-gel,etc. Th is artic le exp lains the p rep aratio n o f MoO3 ma in ly fro m the p ro cess o f p recip itat io n,h yd ro therma l sy nthes is, chemica l meteo ro lo g ical d epo sit io n met ho d.K EY WO RDS:nano,MoO3,liq u id p hase,mo lyb d enu m a llo y目录第一章前言 (5)§1.1纳米材料 (5)§1.1.1 纳米材料概念 (5)§1.1.2 纳米材料的结构与性能 (5)§1.2 M O O3的结构和性质 (6)§1.3 M oO3发展现状 (7)§1.3.1 纳米线/纳米棒(na no w ir e/n an or o d) (7)§1.3.2 纳米带(na no be l t/na n or ib b on) (8)§1.3.3 纳米管(na no tu b e) (8)纳米材第二章液相法制备M nO3料 (10)§ 2.1沉淀法 (11)§2.2水热法 (15)§2.2.1 无模板水热结晶法 (16)§2.2模版水热法 (19)§2.2.1 软模板水热法 (19)§2.2.2 软模板与无模板水热的比较: (22)§2.2.3硬模板水热法: (23)§2.3溶胶一凝胶流程 (24)§2.3.2 钼酸溶胶 (27)§2.4化学气相沉积法(C V D法) (28)的结构与性能 (31)第三章Mo O3§3.1 M oO3的相结构 (31)§3.2 M oO3的形貌: (32)§3.3 M o03的性能 (33)§3.3.1.电致变色及其应用 (33)§3.3.2抑烟一阻燃性及其应用 (34)§3.3.3 催化性能及其应用 (35)§3.3.4 气敏性能 (36)第四章结论和展望 (38)第一章前言1.1 纳米材料1.1.1纳米材料概念在20世纪60年代,著名的诺贝尔奖获得者F eyne man【1】曾预言:如果我们对物体微小规模上的排列作某种控制,我们就能使物体得到大量异常的特性,看到材料的性能产生丰富的变化。
MoO_3纳米材料化学合成流程的研究

1 MoO3 的相结构和形貌
1. 1 M oO 3 的相结构 已经知道 ,MoO3 的相结构通常分为 3 种形式 ,
·8·
中 国 钼 业 2010年 2月
中包括线形 、纤维形 、棒形 、晶须形 、薄片形 、薄膜形 、 单壁纳米管 、多壁纳米管 、纳米带 、球形等非碳纳米 材料 。它们的制备方法和工艺参数可以千差万别 , 观察形 貌 的 方 法 有 各 种 电 子 显 微 镜 分 析 ( TEM、 SEM、HRTEM、HRSEM 等 ) 。本文仅举以下 2例 ,足 见其形貌的琳琅满目 。图 3是模板 ( CTAB )水热法 制备的纳米带 ,α - MoO3 TEM 照片 [ 31 ] 。图 4是无模 板水热法制备的 h - MoO3 六棱柱形 SEM 照片 [ 34 ] 。
MoO3 纳米材料具有很多特殊的性能 ,具有广泛 的应用潜力 ,其中包括 ,电子显示 、固体微生物 、气体
收稿日期 : 2009 - 10 - 25 作者简介 :徐志昌 (1935 - ) ,男 ,清华大学教授 ,《中国钼业 》编委 。
传感器 、记录材料 、石油催化剂等 。它也是制备其他 含钼纳米材料理想的前驱体 , 如 , 层状纳米 MoS2 、 MoSe2 、纤维状 Mo 粉以及各种主 - 客化合物 。此 外 ,良好的光致变色和电致变色性能在智能材料中 具有广泛的应用潜力 。纳米级 MoO3 具有优异的可 逆光色性和较高的光学对比度 ,其性能在信息存储 、 图像显示及调节光线等方面具有潜在的应用价值 , 可作为电致变色 、光致变色 、智能伪装等器件的核心 材料 ,在显示设备和军事装备等领域具有广阔的应 用价值 。
火焰法制备Al_MoO_3磁控铮度

赵娜,沈金朋,李瑞,杨光成,黄辉文章编号:1006-9941﹙2013﹚06-0734-04火焰法制备Al /MoO 3纳米片阵列的影响因素赵娜1,沈金朋2,李瑞2,杨光成2,黄辉2(1.西南科技大学,四川绵阳621000;2.中国工程物理研究院化工材料研究所,四川绵阳621900)摘要:亚稳态分子间复合物﹙MIC ﹚阵列由于具有高能量密度、小尺寸条件下能自持反应的优点,在集成化火工品方面具有潜在的应用价值。
采用火焰法在硅基底上原位制备了高度有序的MoO 3纳米片阵列,探讨了基底材料、纳米阵列生长时间、火焰源因素对生成MoO 3形貌的影响,得到了MoO 3纳米片阵列的优化制备工艺条件:以硅片为基底,生长时间为5min 和甲烷为火焰源。
制备的纳米片厚度为100~200nm ,宽度约5μm ,长度达到十几个微米。
分别采用磁控溅射和热蒸发在MoO 3纳米片阵列表面镀铝得到Al /MoO 3MIC 阵列,在铝膜厚度相同的情况下,采用热蒸发镀铝方式优于磁控溅射。
热蒸发铝膜厚度为900nm 时,所获得的Al /MoO 3MIC 阵列具有较高的放热量,达到3276J ·g −1。
关键词:应用化学;含能材料;Al /MoO 3;亚稳态分子间复合物﹙MIC ﹚;火焰法中图分类号:TJ 55;O69文献标识码:ADO I :10.3969/j.issn.1006-9941.2013.06.009收稿日期:2013-04-08;修回日期:2013-05-24基金项目:国家自然科学基金﹙11002128,11272292,11172276﹚作者简介:赵娜﹙1985−﹚,女,硕士研究生,主要从事纳米含能材料研究。
e-mail :zhaona0909@通讯联系人:黄辉﹙1961−﹚,研究员,主要从事含能材料研究。
e-mail :huanghui@1引言亚稳态分子间复合物﹙Metastable Intermolecular Composites ,MIC ﹚是近年来出现的一种具有广阔应用前景的新型含能材料,该复合含能材料不仅具有高的能量密度,而且由于反应物尺寸达到纳米级,使得氧化剂﹙如金属氧化物﹚和还原剂﹙主要是纳米铝粉﹚间的传质距离变短,传质输运界面面积增大,从而达到较快的能量释放率[1],在新型火工品起爆药剂方面有突出的应用前景。
原位限域生长策略制备有序介孔碳负载的超小MoO_(3)纳米颗粒

Vol.42 2021年5月No.51589~1597 CHEMICAL JOURNAL OF CHINESE UNIVERSITIES高等学校化学学报原位限域生长策略制备有序介孔碳负载的超小MoO3纳米颗粒王常耀,王帅,段林林,朱晓航,张兴淼,李伟(复旦大学化学系,上海200433)摘要采用原位限域生长策略制备了一系列有序介孔碳负载的超小MoO3纳米颗粒复合物(OMC-US-MoO3).其中,有序介孔碳被用作基质来原位限域MoO3纳米晶的生长.依此方法制备的MoO3纳米晶具有超小的晶粒尺寸(<5nm),并在介孔碳骨架内具有良好的分散度.制得的OMC-US-MoO3复合物具有可调的比表面积(428~796m2/g)、孔容(0.27~0.62cm3/g)、MoO3质量分数(4%~27%)和孔径(4.6~5.7nm).当MoO3纳米晶的质量分数为7%时,所得样品OMC-US-MoO3-7具有最大的孔径、最小的孔壁厚度和最规整的介观结构.该样品作为催化剂时,表现出优异的环辛烯选择性氧化性能.关键词有序介孔碳;氧化钼纳米晶;纳米材料;限域生长中图分类号O611.4文献标志码AIn situ Confinement Growth Strategy for Ordered Mesoporous CarbonSupport Ultrasmall MoO3NanoparticlesWANG Changyao,WANG Shuai,DUAN Linlin,ZHU Xiaohang,ZHANG Xingmiao,LI Wei*(Department of Chemistry,Fudan University,Shanghai200433,China)Abstract Ultrasmall particle sizes and excellent dispersity of the MoO3active species on support majorly dominate their catalytic performances.Herein,a series of ordered mesoporous carbon support ultrasmall mo⁃lybdena nanoparticles(OMC-US-MoO3)composites was synthesized through an in situ confinement growth strategy.Ordered mesoporous carbon was used as the matrix to in situ confine the growth of MoO3nanocrystals. The obtained MoO3nanocrystals show ultrasmall particle sizes(<5nm)and excellent dispersity on the meso-porous carbon frameworks.The obtained OMC-US-MoO3exhibits tunable specific surface areas(428―796 m2/g),pore volumes(0.27―0.62cm3/g),MoO3contents(4%―27%,mass fraction)and uniform pore sizes (4.6―5.7nm).As a typical example,the obtained sample with7%MoO3(denoted as OMC-US-MoO3-7)shows the largest pore size,smallest thickness of pore wall and most regular mesostructures.When being used as a catalyst,the OMC-US-MoO3-7exhibits an excellent catalytic activity for selective oxidation of cyclooctene with a high stability.Keywords Ordered mesoporous carbon;MoO3nanocrystal;Nanomaterials;Confinement growthdoi:10.7503/cjcu20200303收稿日期:2020-05-28.网络出版日期:2020-09-24.基金项目:国家自然科学基金(批准号:21975050)、国家重点研发计划纳米科技重点专项(批准号:2016YFA0204000, 2018YFE0201701)和中国博士后科学基金(批准号:2019M651342)资助.联系人简介:李伟,男,博士,教授,主要从事介孔材料的合成及应用研究.E-mail:*******************.cn1590Vol.42高等学校化学学报Epoxides,an important industrial chemicals,has been widely used in the fields of food additives,phar⁃maceutical intermediates,etc.[1,2].Catalytic epoxidation of olefin is one of the essential route to produce epo-xides,which oxygenation of carbon-carbon double bond to form cyclic epoxide groups.The kind of catalyst plays a key role on the epoxidation reaction.Among all catalysts,precious metal of gold based one illustrates high activity for olefin epoxidations[3,4].However,gold is limited resource and very expensive,even though it shows high conversion efficiency.Molybdenum oxide(MoO3),as one of the low cost,non-toxic and environ⁃mentally benign transition metal oxides,is widely used as heterogeneous catalysis for Friedel-Crafts alkyla⁃tion[5],hydrogenation reaction[6,7],epoxidation reaction[8,9],hydrogen evolution reaction[10],electrochemical energy storage for lithium-ion batteries[11,12],and gas sensors[13,14],etc..Gratifyingly,MoO3has been reported by several groups which have high activity for epoxidation of olefins in recent years[15,16].It is obvious that the size and morphology of MoO3active species are critical factors that affect their prop⁃erties for application[17~20].However,the synthesis and reaction process often easily causes serious sintering,migration and agglomeration of the MoO3nanoparticles,leading to the degradation of catalytic activity.Sup⁃ports are necessary for the immobilization of active species.Carbon has been widely used as an outstanding matrix to control the size and dispersity of supported metal oxides attributing to its advantages of intrinsical chemical inertness,high thermal stability,non-toxic and wide-sources[21~23].Molybdena supported carbon have been reported and show excellent performance as the catalyst for cyclooctene epoxidation[24,25].Recently,Chen group[26]fabricatedγ-Fe2O3@C@MoO3core-shell structured nanoparticles as a magnetically recyclable catalyst for the epoxidation reaction of olefins.The coated carbon layer play an efficient role for the stabiliza⁃tion of magnetic core.Biradar group[8]also reported a carbon microspheres-supported molybdena nanoparticles catalyst which also show outstanding effect for the epoxidation of olefins.However,above-mentioned catalysts are less porosity.Porous supports,especially,mesoporous carbon have been reported on many catalytic areas because of its large surface area,pore volume and pore size,which can not only improve the load capacity but also enlarge the reaction progress,where the diffusion process may be the rate-limiting step[26~28].Up to now,it is still urgent to fabricate mesoporous carbon supported MoO3catalyst with ultrasmall particle size and excel⁃lent dispersity.Herein,we construct an ordered mesoporous carbon support ultrasmall MoO3nanoparticles(OMC-US-MoO3)composites via an in situ confinement growth strategy.In this strategy,the ordered mesoporous carbon works as a matrix to in situ confine the growth of MoO3nanocrystals.The obtained MoO3nanocrystals show ultrasmall particle size(<5nm)and excellent dispersity on the mesoporous carbon frameworks.The content (mass fraction)of MoO3can be tuned from4%to27%.The obtained OMC-US-MoO3shows tunable specific surface areas(428―796m2/g),pore volumes(0.27―0.62cm3/g)and uniform pore size(4.6―5.7nm).As a typical example,the obtained sample with7%MoO3(denoted as OMC-US-MoO3-7)shows largest pore size,smallest thickness of pore wall and most regular mesostructures.When being used as a catalyst,the OMC-US-MoO3-7exhibits an excellent catalytic activity for selective oxidation of cyclooctene with a high stability.1Experimental1.1Chemicals and MaterialsPluronic F127(EO106PO70EO106,M w=12600)was purchased from Aldrich.All others chemicals were obtained from Aladdin company and used directly.Deionized water was used in all experiments.1.2Synthesis of Ordered Mesoporous Carbon Support Ultrasmall Molybdena NanoparticlesIn detail synthesis procedure,1.0g of Pluronic F127powders was added into10.0g of ethanol solution and stirred to a homogeneous clear solution at40℃.Afterwards,5.0g of20%(mass fraction)preformedNo.5王常耀等:原位限域生长策略制备有序介孔碳负载的超小MoO 3纳米颗粒phenolic resins ethanol solution and 1.0mL of peroxomolybdenum precursor solution were added into the ho⁃mogeneous system (5—200mg/mL ).The preformed phenolic resins was synthesized based on the reported method [27,28].Peroxomolybdenum precursor solution [29]was prepared by dissolving different contents of molyb⁃denum trioxide into 10.0mL of 30%hydrogen peroxide.The mixture solution was poured into dishes after 2h and then the dishes were heat treated at 40and 100℃for 8and 20h ,respectively ,forming the as -made com⁃posites consisting of Pluronic F127,phenolic resins ,and Mo species (denoted as as -made sample ).Then ,the calcination of as -made sample was implemented in a tubular furnace under N 2atmosphere.The temperature program was set from 25℃to 350℃with a ramp of 1℃/min ,maintenance for 3h ,and then to 600℃with 1℃/min ,maintenance for 2h.The obtained sample after pyrolysis was named as ordered mesoporous carbon support ultrasmall molybdena nanoparticles (OMC -US -MoO 3-x ),wherein x represent the actual mass fraction of MoO 3.1.3Activity Test The selective oxidation reaction of cyclooctene was carried out in the round -bottom flask (50mL ).In which ,40.0mmol of cyclooctene ,40.0mmol of 5.5mol/L TBHP in decane ,10mg of OMC -US -MoO 3-7cata⁃lyst (0.0048mmol/L of MoO 3),6.0g of 1,2-dichloroethane as solvent ,and 15.0mmol of chlorobenzene as internal standard.The reaction temperature is 80℃.At different time intervals ,conversion was calculated by sampling.The samples were analyzed on an Agilent 7890A gas chromatograph equipped with a HP -5column and products were confirmed by GC -MS.TOF values (mol of reacted cyclooctene per mol of catalyst and hour )was calculated at about half conversion of the reaction.The catalyst was reused after washing by water and drying.The test condition was kept same to the first time on the cyclic test.2Results and Discussion2.1Synthesis and CharacterizaitonThe developed in situ confinement growth strategy is employed to the preparation of ordered mesoporous carbon support ultrasmall molybdena nanoparticles (OMC -US -MoO 3)composites (Fig.1).In the synthesis sys⁃tem ,Pluronic F127is used as the structure -directing agent (soft -template ),preformed phenolic resins is used as carbon resource ,peroxomolybdenum solution is used as precursor ,and ethanol/H 2O is used as co -solvent ,respectively.The as -made sample and product OMC -US -MoO 3composites can be obtained after heat -treatment at 100and 600℃,respectively.The mass content of MoO 3in the OMC -US -MoO 3composites can be well tuned through adjusting the amount of peroxomolybdenum precursor in the synthesis system.TGA curves (Fig.2)show that the mass fractions of MoO 3species in the OMC -US -MoO 3composites areFig.1Illustration of the construction of OMC ⁃US ⁃MoO 3composites via the in situ confinementgrowth strategy Fig.2TGA curves of the OMC ⁃US ⁃MoO 3composites with different MoO 3contents obtained afterpyrolysis at 600℃,respectivelyMass fraction of MoO 3(%):a .4;b .7;c .10;d .16;e .27.1591Vol.42高等学校化学学报4%,7%,10%,16%and 27%(Table 1),respectively ,when adjusting the amount of molybdenum precursors in the synthesis system.The mass loss below 100℃is caused by the volatilization of adsorbed water in the composites.A slight mass increasement can be detected between 100and 300℃,demonstrating the existence of trace amount of MoO 2and abundant MoO 3in the composites.The mass increasement can be attributed to the oxidation of the trace amount MoO 2.Subsequently ,the huge mass loss above 300℃can be observed attribu -ting to the remove of carbon species in the composites.The mass loss between 100and 600℃is approximate to the mass fraction of MoO 3species in the composites.The SAXS patterns [Fig.3(A )]of OMC -US -MoO 3-4and OMC -US -MoO 3-7composites show two scatteringdiffraction peaks at 0.391and 0.782nm −1,and 0.412and 0.824nm ‒1,respectively ,indexing to the (100)and (200)reflections of a hexagonal mesosturtures with space group P 6mm .With the increasement of MoO 3content ,the q values of the (100)diffraction peaks shift to 0.532,0.617,and 0.678nm −1,for samples OMC -US -MoO 3-10,OMC -US -MoO 3-16,and OMC -US -MoO 3-27,respectively.The corresponding cell parame⁃ters of five composites are calculated to be about 18.5,17.6,13.6,11.7,and 10.7nm with the increased MoO 3content ,respectively.WAXRD patterns [Fig.3(B )]of five composites all show no diffraction peaks of MoO 3phase ,suggesting the ultrasmall particle size of MoO 3nanocrystals in the frameworks.This result demonstrates that the ordered mesoporous carbon frameworks can confine the size of MoO 3nanocrystals to an ultrasmall size even at a high MoO 3content effectively.Nitrogen adsorption -desorption isotherms of five OMC -US -MoO 3composites obtained after calcined at 600℃in N 2all display representative type -Ⅳcurves with H2hysteresis loops [Fig.4(A )],in agreement with the previously reported ordered mesoporous materials [30~32].Sharp capillary condensation steps in the relative pressure (p /p 0)of 0.41―0.70are observed for five composites ,demonstrating the narrow pore size distribu⁃tion.The Brunauer -Emmett -Teller (BET )surface area and pore volume of five composites are calculated and listed on Table 1.The surface area and pore volume decrease with the increased MoO 3content ,which can be attributed to the partial destroy and disappear of pore structures.The average pore sizes of five composites are also calculated and listed on Table 1from their pore size distribution curve [Fig.4(B )]derived from the adsorption branch based on BJH model.The average pore sizes are 4.7,5.7,5.5,5.4,and 4.6nm ,Table 1Structural and textural parameters for OMC -US -MoO 3with different content Sample No.12345MoO 3content (%,mass fraction )47101627S BET /(m 2·g -1)796693652574428V /(cm 3·g -1)0.620.540.490.410.27D /nm 4.75.75.55.4 4.6Fig.3SAXS(A)and WA ⁃XRD(B)patterns of the OMC ⁃US ⁃MoO 3composites with differentMoO 3contents obtained after pyrolysis at 600℃Mass fraction of MoO 3(%):a .4;b .7;c.10;d .16;e .27.1592No.5王常耀等:原位限域生长策略制备有序介孔碳负载的超小MoO 3纳米颗粒respectively.According to the cell parameters results ,the pore walls of five composites are calculated to be 14.1,11.9,8.1,6.3,and 6.1nm ,respectively.SEM images (Fig.5)show that OMC -US -MoO 3-4and OMC -US -MoO 3-7composites own the most regular mesostructures.Notably ,the regular [100]and [110]directions can be clear observed from the SEM images of OMC -US -MoO 3-7composites [Fig.5(B )and (F )].In addition ,the mesopores are opened and no obvious big metal nanoparticles can be observed from the surface.With further increasement of MoO 3content ,the reg⁃ular mesostructures is partial destroyed.TEM images of OMC -US -MoO 3-7composites [Fig.6(A )—(C )]taken along the [100]and [110]directions manifest a well -defined 2D hexagonal mesostructures in agreement with the result of the SAXS pattern [Fig.2(A )].The lattice spacing is measured to be 0.35nm from the HRTEM image [Fig.6(D )],attributing to the (040)crystalline planes of α-MoO 3[33].The average size of MoO 3nano⁃crystals is estimated to be (4.1±1.0)nm from the size statistics diagram.The survey spectrum of the OMC -US -MoO 3-7composites shows the presence of only Mo ,O and C elements [Fig.7(A )].The high -resolution Mo 3d core level XPS spectra [Fig.7(B )]show four peaks at 230.5,232.7,233.6,and 235.9eV ,demon⁃strating the co -existence of Mo 4+and Mo 6+species [34~36].The ratio of Mo 4+/Mo 6+is calculated to be about 13%.Only a few Mo 4+signals can be detected from the spectrum ,in agreement with the TGAresults.Fig.4N 2adsorption⁃desorption isotherms(A)and pore size distributions(B)of the OMC⁃US⁃MoO 3composites with different MoO 3contents obtained after pyrolysis at 600℃Mass fraction of MoO 3(%):a .4;b .7;c.10;d .16;e .27.Fig.5SEM images of OMC⁃US⁃MoO 3composites with different MoO 3contents obtained afterpyrolysis at 600℃Mass fraction of MoO 3(%):(A)4;(B)7;(C)10;(D)16;(E)27.1593Vol.42高等学校化学学报2.2Formation Mechanism Studies Based on the above results ,we propose that the in situ confinement growth strategy show significant impact on the formation of final OMC -US -MoO 3composites.The obtained MoO 3nanocrystals show ultrasmall particle size (<5nm )and excellent dispersity on the mesoporous carbon frameworks.This structure can be retained even the mass fraction of MoO 3is increased to 27%.However ,the regular mesostructures can be partial destroyed with the increased MoO 3mass content.According to the results that no large MoO 3nanocrys⁃tals can be detected from samples obtained after pyrolysis at 600℃,the unregular mesostructures can be attributed to the uncontrollable origin co -assembly process.2.3Selective Oxidation of Cyclooctene The selective oxidation reaction of cyclooctene with high catalytic performance and stability is still highly desired.However ,the stability of active nanoparticles in catalytic reaction is a major challenge ,especially for active nanoparticles with ultra -small size.For our case ,the OMC -US -MoO 3-7composites show most regular mesostructures ,largest pore sizes ,appropriate hole wall size ,MoO 3content and dispersity.So ,the obtained OMC -US -MoO 3-7composites catalyst is selected as the catalyst for cyclooctene epoxidation.The reactions were carried out using 1,2-dichloroethane as solvent in flask with chlorobenzene as internal standard at 80℃.The OMC -US -MoO 3-7composites catalyst shows a high TOF value of 2163h ‒1which is calculated on the basis of the experimental data at 2h.Meanwhile ,a high conversion (100%)of cyclooctene ,and selectivity (>99%)to 1,2-epoxycyclooctane at 8h can also be parison with the reported heterogeneous Mo -based catalyst using similar conditions was shown in Table 2.The present OMC -US -MoO 3-7catalystshowsFig.7Survey XPS spectrum(A)and high⁃resolution XPS spectra of Mo 3d (B)for OMC⁃US⁃MoO 3⁃7composites obtained after pyrolysis at 600℃Fig.6TEM images of OMC⁃US⁃MoO 3⁃7composites obtained after pyrolysis at 600℃Viewed along the hexagonal (A )and columnar (B ,C )directions and HRTEM image (D )of a representative MoO 3nanoparticle.1594No.5王常耀等:原位限域生长策略制备有序介孔碳负载的超小MoO 3纳米颗粒a higher TOF value than MoO 3/C [8],MoO 3/SiO 2[37],Mo -MOFs [9],Mo -MCM -41[38],Mo -SBA -15[38],[Pipera⁃zinCH 2{MoO 2(Salen )}]n [39],and MNP 30-Si -inic -Mo [40]as previous reported.It should be noted that cyclooc⁃tene still gave about 18%conversion [Fig.8(A )]in the absence of catalyst owing to the presence of strong TBHP oxidants ,which is consistent with previous reports [41,42].Further ,two other substrates ,cyclohexene and styrene were also tested under the same conditions to test the versatility of OMC -US -MoO 3-7as an epoxida⁃tion catalyst.Surprisingly ,the conversion of cyclohexene to 1,2-epoxyclohexane can reach 54%in 8h.Inaddition ,the conversion of styrene to styrene oxide can reach 95%in 36h ,respectively (Fig.S1,see the Sup⁃porting Information of this paper ).Beside the efficient conversion of catalyst and high TOF values ,the stability of catalyst is also very impor⁃tant ,especially for heterogeneous catalysis.Here ,the hot filtration test was used to assess the presence of active Mo species in solution.When the reaction lasted for 2h ,we removed the catalyst by hot filtration and let the mother liquid for reacting another 6h.The results showed that there was only a slight increase in con⁃version [Fig.8(A )],which is proof of a heterogeneous catalysis.For the recycling study ,cyclooctene epoxida⁃tion was performed maintaining the same reaction conditions except using the recovered catalyst.It can be clearly found that obvious changes are undetected for catalytic performance after five runs [Fig.8(B )].It indi⁃cates that ultrasmall MoO 3nanoparticles supported on ordered mesoporous carbon is highly stable and can be reused ,demonstrates its potential for industrial applications.The high conversion ,selectively ,and the TOF value for the cyclooctene epoxidation reaction can be attributed to the unique structure of the OMC -US -MoO 3-7composites.The high surface area ,volume ,andTable 2Calculating TOF value for epoxidation of cyclooctene and comparing with other catalysts *Catalyst OMC -US -MoO 3-7MoO 3/C MoO 3/SiO 2Mo -MOFs Mo -MCM -41Mo -SBA -15[PiperazinCH 2{MoO 2(Salen )}]n MNP 30-Si -inic -MoTime/h 2267331224Conv.(%)5280909397999546Epoxide sel.(%)>9910010099959398100TOF/h -1216353[8]72[35]270[9]22[36]40[36]16[37]2[38]*.TOF values(mol of reacted cyclooctene per mol of catalyst and hour)were calculated at abouthalf conversion of the reaction.Fig.8Time course plots of cyclooctene epoxidation(A)and reusability(B)by using OMC⁃US⁃MoO 3⁃7com⁃posites as catalystReaction conditions :40.0mmol of cyclooctene ,40.0mmol of 5.5mol/L TBHP in decane ,10mg of OMC -US -MoO 3-7catalyst (0.0048mmol/L of MoO 3),6.0g of 1,2-dichloroethane as solvent ,and 15.0mmol of chlorobenzene as internalstandard.The reaction temperature is 80℃.15951596Vol.42高等学校化学学报uniform mesopores can not only enrichment the reaction substrate but also in favor to the diffusion of sub⁃strates.The ultrasmall MoO3nanocrystals size and its excellent dispersity in the frameworks can expose more active sites.All these features are beneficial to the rapid conversion of substrate molecular with high selective⁃ly and conversion.3ConclusionsIn summary,an in situ confinement growth strategy was developed to the construction of ordered mesopo⁃rous carbon support ultrasmall molybdena nanoparticles(OMC-US-MoO3)composites.Ordered mesoporous carbon was used as an effective matrix to in situ confine the growth of MoO3nanocrystals.The obtained MoO3 nanocrystals show ultrasmall particle size(<5nm)and excellent dispersity on the mesoporous carbon frame⁃works.In addition,a serious of OMC-US-MoO3composite can be obtained with controllable specific surface areas(428―796m2/g),pore volumes(0.27―0.62cm3/g),MoO3contents(4%―27%,mass fraction)and uniform pore size(4.6―5.7nm).The mesostructures can be retained even the MoO3content as high as27%. 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纳米含能材料国内外研究现状

纳米含能材料国内外研究现状在新型含能材料中,具有高能量释放速率、高能量转化速率和低敏感性的纳米含能材料已成为研究的热点,而介稳态分子间纳米复合含能材料(MIC)由于其高放热性和能量释放率的可调性成为国内外主要研究的对象。
国外研究表明将铝热剂的粒度从微米超细化到纳米级时,它的反应速度会大大的提高,能量释放迅速,最快的可以超过千倍,如纳米Al/MoO3铝热剂,燃速大约为400m/s,反应区温度为3253 K。
因此纳米铝热剂近年来成为国内外研究的热点,其中如何制备性能良好的纳米铝热剂是最为关键。
通常制备MIC的方法分为为机械球磨法、溶胶.凝胶法和物理气相沉积法。
自上世纪90年代开始,就已经见有关纳米级的MIC/HMX 的公开报道,国外对于MIC/HMX的研究比国内要早。
而国内则是最主要集中在Al/CuO等极少数材料,纳米Al/MoO3含能材料在国内则没有见公开的报道,而添加纳米级炸药HMX 的MIC/HMX更是少之又少。
32261Kevin C W[1]等研究者通过采用固相反应的方法,再进一步加入分散剂来改善纳米粒子的团聚问题,制备出了纳米Al/MoO3铝热剂。
方法为:称取一定量的纳米铝粉和纳米三氧化钼粉末,置于反应容器中,然后加入正己烷进行进一步的处理,之后再进行超声分散混合,处理,最后真空干燥,得到复合颗粒。
与微米级这两种成分粒子通过常规物理混合得到的样品相比,纳米铝热剂的燃速更高,可以达到442m/s。
谯志强[2]等研究者基于猛炸药的起爆药替代物的主要原料为超细颗粒猛炸药、纳米铝粉和纳米金属氧化物,采用溶胶-凝胶的方法制备出了纳米级的Fe2O3,采用溶剂-非溶剂的方法制备出超细的RDX 颗粒,最后再采用超声波复合法进一步实现纳米铝热剂对RDX 颗粒表面的包覆。
它是通过一种特殊的复合物微观结构进行设计(如图1所示),在细颗粒炸药表面包裹一层具有很高燃烧速度的添加剂,从而形成一个以细颗粒炸药为核以高速添加剂为壳的核/壳型复合物,壳层添加剂高速燃烧释放的热量可以作为核层细颗粒炸药的点火源。
金属氧化物MoO3(WO3)和V2O5对烟气脱硝催化性能试验

TO 催化 剂表 面酸性 位 数量 ,从 而提 高 了催 化 剂 的活性 . i,
本 文对 自制 的 V O / i ( 钛 型 ) 基 脱 硝 催 化 剂 进 行 活 性 试 验 ,在 此 基 础 上 分 析 Mo , ( TO 锐 O 或 WO )及 V O 对 催 化剂 活性 影响 的贡 献.
N O和 N : O 脱除率 以及 N O生成量 的影响 .结果表 明 ,V O 的加入使得 Mo , WO ) TO 催化剂 的活性 和 : :5 O ( ,/ iz 选择性得到 了改善.Mo WO ) O ( , 的加人 主要是 改善了催化剂表面的活性位数 量 ,从而使得 v 0 / i : 2 TO 基催 化剂表现出更高的活性.
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使用 制备 V O/ i2 2 TO ,Mo ,TO ,WO/ i2 2 5WO/ O / i2 ,TO ,V O - , TO i 和 V O . o TO M O / i 等催化 剂 ,为使 催 化 剂 保 持 一 定 的还 原 性 ,制 备 过 程 添 加 一 定量 的草 酸 .
催化 剂 中 WO 和 Mo 量分 别为 1 %和 6 ( 量 比 ) . O含 0 % 重 在 二元 催化 剂 的制备 中 ,将 纳米 TO i 粉 末 在浸 渍 液 热 溶 液 中连 续 搅拌 3 、随 后 在 烘 箱 中 15C h 0 ̄ 干燥 1h 2 、马弗炉 4 0C 烧 5 ,煅烧 物经 冷却 、粉 碎 、筛分 至特 定 的粒径 备用 . 5  ̄煅 h 三元催 化剂 的制 备采 用分 步法 ,即在 TO i 表 面负载 WO 或 Mo , , O 后再 负 载 V O ,制 备 中取 粒 径 小于 0 1 . mm的 二元催 化剂 作为 负载 基体 ,具体 步 骤 同二元 催化剂 的制备 . 12 催 化剂 活性试 验 .
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