渣油悬浮床加氢水溶性催化剂预硫化研究 Ⅱ 钼酸盐硫化产物的XPS分析

通过XPS分析法对钼酸盐的硫化行为进行了考察,分别考察了四价钼物种质量分数和硫钼元素的质量分数比，发现硫化产物的表面化学组成中四价钼质量分数和硫钼元素质量分数比不成正比，证实了该产物表面钼的硫化物不完全以MoS2形式存在。未经过临氢加热的硫化产物表面的四价钼物种的质量分数显著低于经过临氢加热的样品的质量分数，说明临氢加热在钼酸盐的硫化过程中起了重要作用。氯化铵是钼酸盐硫化过程中有效的助硫化剂，当它的用量增大时，硫化产物表面四价钼的质量分数也增大。以蒽为探针，使用化学探针法测定了硫化产物在渣油加氢过程中的催化活性，发现随着氯化铵用量的增加，产物的催化活性也相应提高，印证了XPS测定结果。     

钼镍负载催化剂表面组份及其活性的研究

利用X光光电子能谱(XPS)，激光拉曼光谱(LRS)和程序升温还原(TRP)等技术，研究了高载钼量的负载钼镍催化剂的表面组份形式．结果表明，催化剂在氧化态、还原态、硫化态时表面的主要组份分别以类似NiMoO_4结构的NiMo_xO_y多种价态钼酸盐及金属镍，氧硫钼镍及硫化钼形式存在．三种化学态的加氢脱硫活性顺序为硫化态，还原态>>氧化态．还原态表面检测到金属镍，据此提出了金属镍所产生的氢溢流效应是还原态活性明显增加的一个原因．文中由硫化态、还原态表面组份与反应活性之间的关联结果支持了Kwart提出的多点催化反应机理．     

甲烷化反应过程中硫化的钼催化剂的拉曼光谱研究

本文研究了以γ-Al_2O_3、ZrO_2、CeO_2及La_2O_3为载体的硫化态钼催化剂在甲烷化反应过程中的激光拉曼光谱,发现在反应初期,催化剂表面氧硫钼结构变化较大,其活性下降也较快.在反应温度下,催化剂表面上的-S-键松动,部分硫原子升华,并发生一系列氧硫交换,形成体相MoS_2.甲烷化催化剂活性达到稳定后,则催化剂表面上的主要变化是MoS_2.晶粒不断长大.由于载体效应的影响.各个催化剂上表面结构的不同,与其达到活性稳定的时间有着直接的联系.另外,在反应过程中,催化剂表面上均无积碳形成.提出了硫化态钼催化剂在甲烷化反应过程中的表面结构变化模型.     

脉冲激光溅射下固液界面生长的碳纳米管及其机理初探

以脉冲激光束直接溅射浸在水中的单质碳样品，发现在固液界而也能产生碳纳米管．实验还发现碳纳米管的形成与样品的结构有密切的关联：石墨的层状结构越完整，碳纳米管的形成越容易，而且石墨层而相对于激光束的取向也会显著地影响碳纳米管的生成．通过对实验结果的分析，探讨了激光液相溅射产生碳纳米管的机理，认为激光溅射产生的碳蒸气被水束缚在固液的界而内，而完整的晶而使碳蒸气在界而内的分布具有准二维的性质，为碳纳米管的生长提供了较为理想的环境．     

溶胶—凝胶法制备K—Co—Mo催化剂的结构及其合成低碳醇性能研究——钾含 …

采用溶胶－凝胶法制备钴钼氧化物催化剂,并将其浸渍不同量的Ｋ２ＣＯ３后进行硫化。使用Ｘ－射线衍射（ＸＲＤ）和激光拉曼光谱（ＬＲＳ）对氧化态及硫化态样品的结构进行表征,同时测试硫化态样品合成低碳混合醇的活性。结果表征的结果表明,不含钾的氧化态样品,以ＣｏＭｏＯ４形式存在;含钾样品中,助剂钾与钴钼复合氧化物之间存在较强的相互作用,有多种Ｋ－Ｍｏ－Ｏ物种生成,且使硫化态物种趋于稳定。活性测试结果表明,所制     

耐硫变换催化剂中活性组分钴、钼的相互作用

采用常压微反评价、程序升温还原（TPR）和硫化（TPS）技术及原位红外（IR）技术，对不同活性组分的CoO/MgO-Al2O3-TiO2、MoO3/MgO-Al2O3-TiO2和CoO-MoO3/MgO-Al2O3-TiO2的变换活性及性能进行了表征测试，结果表明：单独的硫化钴或硫化钼都具有耐硫变换活性，单独硫化钴作为活性组分的催化剂活性优于单独硫化钼作为活性组分的催化剂，并且二者之间具有明显的协同效应。     

镍钼锍合金中钼的物相分析

本文研究了镍钼锍合金中硫化钼、氧化钼及金属钼在溴水-过氧化氢、乙腈-溴水、三氯化铁及碳酸钠溶液中的溶解情况,并对三氯化铁法浸取金属钼作了重点试验。制定了先用15％碳酸钠溶液浸取氧化钼,再用含8％三氯化铁的1mol/L盐酸浸取金属钼,最后用过氧化钠熔融残渣测定硫化钼的分析流程。由试样分析结果和电子探针图象分析结果,验证了本法的准确性及对镍钼锍类试样中钼的物相分析的完全适应性。     

KSM—01硫化钼催化剂甲烷化活性的衰减及其组成结构的变化

自制硫代钼酸铵经热分解所得的硫化钼催化剂有较好的甲烷化活性,但衰减亦较快。本文对反应前后的催化剂及试剂MoS_2进行了IR、LRS、TEM、XPS、XFA、ESR等分析测试,证明了使用后的催化剂中,辉钼矿的晶粒长大,晶型变好,未发现碳的沉积。实验还发现了催化剂中高价钼及硫链的存在,而在反应后均减少或消失,硫钼比降低。本文对上述变化与催化剂活性衰减之间的关系作了分析,认为辉钼矿晶粒的长大以及样品中硫钼原子比的降低,是催化剂活性衰减的两个重要原因。并由此推测硫化钼催化剂上的甲烷化反应是通过双活性中心而进行的。     

离子交换分离钨钼及微波诱导树脂再生的研究

本文研究了不同型号的树脂和硫化条件对离子交换分离钨钼的影响。探讨了用D201树脂交换除钼及其树脂再生的机理。实验结果表明：碱性钨酸铵（AT）溶液经硫化转型后,可用阴离子交换柱除去其微量钼;该除钼树脂经微波场辐照诱导-减性食盐水协同再生处理,可基本恢复其除相交换容量。     

渣油悬浮床加氢水溶性催化剂预硫化研究Ⅰ硫化条件对硫化催化剂物种及分散度的影响

通过对在不同阶段中和不同条件下所获得的硫化产物的XRD和TEM分析发现,镍盐在临氢加热前的硫化产物是结晶程度较低的NiS2,临氢加热后变为结晶程度较高的NiS和Ni7S6,它们的分散状态没有明显地改变;钼酸盐在临氢加热前的硫化产物为部分硫代钼酸盐,临氢加热后变为微晶态MoS2,其分散状态明显提高,临氢加热是两种催化剂前体的硫化过程中的重要阶段。助硫化剂NH4Cl的加入对镍盐的硫化产物的各种物理和化学存在状态都没有产生显著的影响,它是钼酸盐硫化过程中不可缺少的助剂,当NH4Cl加入量增大时,XRD分析未发现其本体化学组成有变化,其结晶程度有所降低,晶粒度由6.6 nm降至3.6 nm。分散介质的种类对催化剂的分散效果产生了显著的影响。以钼酸盐为例,密度和黏度更大的克拉玛依常压渣油更有利于硫化产物的分散,与采用润滑油基础油为分散介质时相比,其晶粒度由3.0 nm降低至2.0 nm,且外观形态由粒径较小（50 nm~100 nm）的较致密的颗粒变为粒径较大（100 nm~500 nm）的呈现蓬松球壳结构的絮状团块。     

Graphite-incorporated MoS2 nanotubes: a new coaxial binary system

Graphite-filled MoS2 nanotubes were synthesized by pyrolizing propylene inside MoS2 nanotubes prepared by a template-assisted technique. The large coaxial nanotubes were constituted of graphite sheets inserted between the MoS2 layers, forming the outer part, and coaxial multiwall carbon nanotubes intercalated with MoS2 inside. High-resolution electron microscopy (HREM) and electron energy loss spectroscopy techniques along with molecular dynamics simulation and quantum mechanical calculations were used to characterize the samples. The one-dimensional structures exhibit diverse morphologies such as long straight and twisted nanotubes with several structural irregularities. The interplanar spacing between the MoS2 layers was found to increase from 6.3 to 7.4 A due to intercalation with carbon. Simulated HREM images revealed the presence of mechanical strains in the carbon-intercalated MoS2 layers as the reason for obtaining these twisted nanostructures. The mechanism of formation of carbon-intercalated MoS2 tubular structures and their stability and electronic properties are discussed. Our results open up the possibility of using MoS2 nanotubes as templates for the synthesis of new one-dimensional binary-phase systems.     

Strain-dependent electronic and magnetic properties of MoS(2) monolayer, bilayer, nanoribbons and nanotubes

We investigate the strain-dependent electronic and magnetic properties of two-dimensional (2D) monolayer and bilayer MoS(2), as well as 1D MoS(2) nanoribbons and nanotubes using first-principles calculations. For 2D monolayer MoS(2) subjected to isotropic or uniaxial tensile strain, the direct band gap of MoS(2) changes to an indirect gap that decreases monotonically with increasing strain; while under the compressive strain, the original direct band gap is enlarged first, followed by gap reduction when the strain is beyond -2%. The effect of isotropic strain is even stronger than that of uniaxial strain. For bilayer MoS(2) subjected to isotropic tensile strain, its indirect gap reduces monotonically to zero at strain about 6%; while under the isotropic compressive strain, its indirect gap increases first and then reduces and turns into direct gap when the strain is beyond -4%. For strained 1D metallic zigzag MoS(2) nanoribbons, the net magnetic moment increases slightly with axial strain from about -5% to 5%, but drops to zero when the compressive strain is beyond -5% or increases with a power law beyond 5%. For 1D armchair MoS(2) nanotubes, tensile or compressive axial strain reduces or enlarges the band gap linearly, and the gap can be fully closed for nanotubes with relatively small diameter or under large tensile strain. For zigzag MoS(2) nanotubes, the strain effect becomes nonlinear and the tensile strain can reduce the band gap, whereas compressive strain can initially enlarge the band gap and then decrease it. The strain induced change in projected orbitals energy of Mo and the coupling between the Mo atom d orbital and the S atom p orbital are analyzed to explain the strong strain effect on the band gap and magnetic properties.     

Low-temperature catalytic preparation of multi-wall MoS_2 nanotubes

Since the first report on inorganic fullerene-like WS2 polyhedra and nanotubes by Tenne et al.[1] in 1992, this kind of nanostructural materials have become extensive research topics owing to their unique electronic structures. WS2 and MoS2 nanomaterials have shown potential applications in the fields of scanning probe microscopy[2], solid-state lubrication[3], heterogeneous catalysis[4], and electrochemical hydrogen storage[5]. Up to now, a great deal of progress has been achieved in the st…     

Formation of MoS2 inorganic fullerenes (IFs) by the reaction of MoO3 nanobelts and S

The reaction of MoO3 and S at temperatures higher than 300 degrees C in an argon atmosphere provides a convenient and effective method for the synthesis of MoS2 nanocrystalline substances. MoS2 nanotubes and fullerene-like nanoparticles have been obtained by the reaction at 850 degrees C under well-controlled conditions. The influences of reaction temperature and duration were carefully investigated in this paper. All of the nanostructures were characterized by Xray powder diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). A stepwise reaction model and rolling mechanism were proposed based on the experimental results.     

Synthesis of open-ended MoS2 nanotubes and the application as the catalyst of methanation

We report the synthesis of open-ended MoS2 nanotubes and their application as the catalyst for methanation of carbon monoxide with hydrogen. Because the catalysis of the methanation reaction occurs at relatively low temperatures, such nanotubes may provide new solutions toward harnessing the environmental load caused by CO emission.     

Atmospheric pressure chemical vapor deposition: an alternative route to large-scale MoS2 and WS2 inorganic fullerene-like nanostructures and nanoflowers

Large-scale MoS2 and WS2 inorganic fullerene-like (IF) nanostructures (onionlike nanoparticles, nanotubes) and elegant three-dimensional nanoflowers (NF) have been selectively prepared through an atmospheric pressure chemical vapor deposition (APCVD) process with the reaction of chlorides and sulfur. The morphologies were controlled by adjusting the deposition position, the deposition temperature, and the flux of the carrier gas. All of the nanostructures have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). A reaction mechanism is proposed based on the experimental results. The surface area of MoS2 IF nanoparticles and the field-emission effect of as-prepared WS2 nanoflowers is reported.     

Inorganic nanotubes and fullerene-like materials

Following the discovery of fullerenes and carbon nanotubes, it was shown that nanoparticles of inorganic layered compounds, like MoS2, are unstable in the planar form and they form closed cage structures with polyhedral or nanotubular shapes. Various issues on the structure, synthesis, and properties of such inorganic fullerene-like structures are reviewed, together with some possible applications.     

复合半导体MoS_2/Cu_2O的制备及其光催化性能研究

采用两步法制备了MoS_2/Cu_2O催化剂,对其催化降解甲基橙(MO)性能进行了研究.首先,通过液相剥离和梯度离心获得少数层MoS_2纳米片,然后采用水热还原法在MoS_2纳米片上合成Cu_2O纳米颗粒,形成MoS_2/Cu_2O复合半导体,并分别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)、UV-Vis紫外可见漫反射光谱(DRS)等手段对催化剂的结构进行表征.在可见光下,MoS_2/Cu_2O复合半导体降解MO的效率明显高于纯MoS_2和Cu_2O.为了获得最佳光催化活性,探究了MoS_2质量分数(5%、10%、20%、30%、40%、50%)对MoS_2/Cu_2O复合半导体光催化降解MO的影响.最后,经过5次循环实验,MoS_2/Cu_2O降解率下降为82.5%,循环稳定性有待进一步提高.     

表面活性剂辅助水热制备形貌结构可控的MoS2及其蒽加氢性能

随着原油资源重质化和劣质化的加剧以及对清洁燃料油品需求的不断增加,将重质油加工成清洁燃料成为现代炼厂面临的挑战.悬浮床加氢是重质油转化为清洁液体燃料的先进技术,其核心难题是高效加氢催化剂的开发.MoS2在石油化工领域油品加氢提质研究中表现出非常好的催化加氢性能.MoS2晶体结构中有两种面:沿S-Mo-S层间的剥离面,又称基面,化学性质稳定;沿Mo-S的断裂面,又称棱面,具有大量的不饱和键,化学性质不稳定,可做催化活性中心.由于MoS2结构和形貌对其物理化学性能有重要影响,所以通过合理设计和调控MoS2的结构和形貌可增加暴露的催化活性位,进而改善其催化性能.本文以七钼酸铵和硫代乙酰胺为原料,水合肼做还原剂,采用不同表面活性剂(包括PEG,PVP,P123,SDS,AOT和CTAB)辅助的水热合成法制备了结构及形貌可控的MoS2,并提出不同表面活性剂条件下MoS2催化剂的生长机理,进一步研究了重油模型化合物稠环芳烃蒽的催化加氢性能.结果表明,在不同表面活性剂辅助的条件下分别制得了由MoS2纳米片组装而成的球形、块状和花状的MoS2产物;通过改变表面活性剂种类可调变MoS2纳米片的长度、堆积层数、层间距以及最终产物的形貌.在PEG或PVP辅助下得到了球形MoS2产物,其中MoS2纳米片长<15 nm,堆积层数<6.在PEG辅助下制备的球形MoS2粒径约为250 nm,尺寸均一且分散性好.在PVP辅助下MoS2粒径在200–450 nm,粒径分布范围宽且有明显团聚.在P123或SDS辅助下得到了团聚较明显的块状微米级MoS2产物.在P123辅助下得到的MoS2纳米片长<15 nm,层数<6.在SDS辅助下制备的MoS2纳米片长>20 nm,堆积层数>8.在AOT或CTAB辅助下得到团聚比较严重的花状微米级MoS2产物,其中MoS2纳米片长>20 nm,堆积层数>8.另外,水热反应过程中,高温高压的环境促进了反应体系中游离的NH4+插入到MoS2层状结构中,导致MoS2纳米片层间距增大.基于此,本文提出了不同表面活性剂辅助的水热过程中不同结构和形貌MoS2产物的形成机理.对不同结构和形貌的MoS2样品进行了悬浮床蒽加氢催化性能评价.结果表明,PEG辅助制备的MoS2催化剂具有最高催化加氢活性.该MoS2催化剂中纳米片层短,堆积层数少,暴露了更多的加氢活性位.单分散的球形MoS2颗粒粒径小,分散性好,有利于加氢活性位的充分暴露,进而表现出较好的催化性能.本文所采用的表面活性剂辅助的水热法为可控合成不同结构和形貌的过渡金属硫化物提供了有效指导和借鉴.     

Advances in the synthesis of inorganic nanotubes and fullerene-like nanoparticles

In analogy to graphite, nanoparticles of inorganic compounds with lamellar two-dimensional structure, such as MoS(2), are not stable against folding, and can adopt nanotubular and fullerene-like structures, nicknamed inorganic fullerenes or IF. Various applications for such nanomaterials were proposed. For instance, IF-WS(2) nanoparticles were shown to have beneficial effects as solid lubricants and as part of tribological surfaces. Further applications of IF for high-tensile-strength fibers, hydrogen storage, rechargeable batteries, catalysis, and in nanotechnology are being contemplated. This Minireview highlights some of the latest developments in the synthesis of inorganic nanotubes and fullerene-like structures. Some structural aspects and properties of IF, which are distinct from the bulk materials, are briefly discussed.