化学镀制备Pd催化剂及在甲醛催化燃烧中的应用

为实现采用催化燃烧法对甲醛进行净化处理,采用化学镀法制备Pd-堇青石蜂窝陶瓷整体式催化剂,并对催化剂进行表征和活性评价。结果表明:化学镀法可以实现纳米Pd微晶颗粒在堇青石蜂窝陶瓷载体上均匀负载,焙烧后PdO与载体结合牢固,具有良好的抗振荡性和热稳定性;500℃焙烧的Pd-堇青石蜂窝陶瓷整体式催化剂的催化活性最高,在甲醛质量浓度为0.4~10 mg/m3,空速为1 500~6 000 h-1的条件下,催化剂具有良好的活性。     

1,2 -二氯乙烷在担载铈钛复合氧化物的蜂窝陶瓷催化净化——催化组分颗粒大小的影响

采用溶胶-凝胶法制备担载 TiO2 和 CeTiOx 复合氧化物涂层的堇青石蜂窝陶瓷整体式催化剂,并考察 1,2-二氯乙烷(DCE)在上述催化剂上的催化效果。结果表明:TiO2 和 CeTiOx 复合氧化物涂层材料对DCE 的催化燃烧均具有很好的催化活性, 前者在 400 ℃时,DCE 的转化率为 93.1%,后者已达 98.5%,可见,CeTiOx 可以更有效地催化燃烧处理 DCE。譬如,在 300 ℃时,在 CeTiOx 涂覆的催化剂上 DCE 的转化率为 85.6%。但随着催化剂处理温度的升高,CeTiOx 催化活性组分的颗粒变大,导致 CeTiOx 蜂窝陶瓷催化剂对于 DCE 的催化活性降低。     

新型Pt基整体式催化剂的结构与催化性能

以堇青石蜂窝陶瓷(CHC)为载体,采用化学镀法制备Pt基整体式催化剂Pt-CHC,研究Pt-CHC催化剂在甲醛催化燃烧中的催化性能;对Pt-CHC催化剂在不同的甲醛初始浓度范围、较宽的空速范围与不同的进样相对湿度条件下进行活性测试,并进行扫描电镜和X射线能量色散谱表征。结果表明:Pt-CHC催化剂在Pt负载量较小(质量分数为0.24%)时,甲醛可在100℃时基本转化完全;活性组分Pt在蜂窝陶瓷载体表面选择性富集,Pt颗粒在催化剂中通孔道内部与孔口处均能基本维持均匀分布,颗粒粒径小于100 nm。     

Ce-Ni-Mn-O复合氧化物催化剂催化燃烧苯的性能研究

以堇青石蜂窝陶瓷为载体,以Ce(NO3)2、Ni(NO3)2和Mn(NO3)2为原料,采用柠檬酸浸渍法制备了负载型Ce-Ni-Mn-O复合氧化物催化剂,考察了Ce、Ni与Mn摩尔比、焙烧温度和焙烧时间对催化燃烧苯的性能影响,并采用比表面积分析仪(BET)、X射线衍射仪(XRD)、扫描电镜(SEM)对催化剂进行表征。实验结果表明,在系列催化剂中,n(Ce)/n(Ni)/n(Mn)=1∶0.5∶0.5,经500℃焙烧7h的催化剂表现出最佳的催化燃烧苯的活性,在300℃及体积空速为15000h-1条件下,即可促使浓度为4.8g/m3的苯催化转化率达到91.8%。     

Mo对贵金属Pd/Al-Ti整体式催化剂催化燃烧苯反应性能的影响

采用浸渍法制备了Mo掺杂的Pd/Al-Ti系整体式催化剂,考察了Mo添加量对Pd-Mo/Al-Ti整体式催化剂催化燃烧苯反应性能的影响,并对催化剂的稳定性做了研究。结果表明,Mo的添加明显提高了Pd/Al-Ti催化剂性能,当Mo添加量为5%时,催化活性最高,在225℃时苯转化率可达90%。采用X射线衍射、X射线光电子能谱、H2程序升温还原、NH3程序升温脱附和氮吸附等手段对催化剂进行表征,结果表明,Mo的加入增加了Pd物种在催化剂表面的分散,并调变了催化剂表面酸性、促进了催化剂表面氧浓度的增加,从而提高催化剂性能。研制的0.10%Pd-5%Mo/Al-Ti整体式催化剂在相同的反应条件下与0.25%Pd/Al-Ti整体式催化剂催化活性相当。     

堇青石蜂窝陶瓷上真空抽提法涂覆氧化铝涂层的研究

应用改进的涂覆方法--真空抽提法,在堇青石蜂窝陶瓷基体表面涂覆氧化铝涂层.在研究铝溶胶的稳定性和粒径分布的基础上,通过牢固度测试、比表面测定、XRD和SEM等手段对涂层的涂覆效果进行了分析,结果表明相对普通浸渍法,采用真空抽提法得到的氧化铝涂层的涂覆率更高、涂布更均匀、比表面积更大、牢固度更强.而且由真空抽提法得到的基底材料制备的整体式催化荆,在甲苯催化燃烧反应中表现出更为优越的催化活性,甲笨催化燃烧起燃温度T10为180℃,近似完全转化温度T99为215℃.     

V2O5/CNFs/蜂窝状堇青石催化剂的结构控制及其烟气脱硝性能

采用化学气相沉积法,在涂层Al2O3的蜂窝状堇青石表面生长纳米碳纤维(CNFs),通过负载V2O5催化剂,制成低温蜂窝状脱硝催化剂.采用SEM、TEM、XRD和XPS等分析方法,对所制催化剂的物化性质及其脱硝性能进行了分析.研究结果表明,当CNFs在堇青石表面的生长厚度为0.74μm时,所制CNFs/堇青石载体的压缩强度达34.46 MPa;在150~250℃范围内,V2O5/CNFs/蜂窝状堇青石催化剂表现出较高的低温脱除NO活性,其中当CNFs的生长量为12.5%、V2O5担载量为1%时,在250℃下NO的转化率达95%左右.     

锰基催化剂的制备及其对气相邻二氯苯的催化燃烧性能

二噁英类含氯挥发性有机物（Cl-VOC）是毒性很强的环境污染物,为了筛选用于催化燃烧Cl-VOC的高效、稳定的催化剂,采用共沉淀法制备了（Fe、Co、Cu、V）-Mn催化剂,并负载于堇青石载体上,用邻二氯苯作为模型化合物对其催化性能进行评价,结果发现Cu-Mn/堇青石催化剂对气相邻二氯苯的催化燃烧性能最好。XRD结果显示Cu-Mn/堇青石催化剂煅烧之后有新的尖晶石CuMn2O4晶相出现;SEM结果表明Cu-Mn/堇青石催化剂颗粒分散均匀;反应前后EDS对比结果表明,反应后催化剂表面残留有少量氯,但是,寿命测试表明持续反应20h,邻二氯苯的降解率能稳定在65%,说明Cu-Mn/堇青石催化剂用于催化燃烧含氯有机挥发物具有较好的应用前景。     

堇青石负载的Fe-Ni基催化剂对合成气合成C_2烃的影响

以堇青石为载体,采用浸渍法制备了一系列不同镍负载量的新型Fe-Ni基催化剂,并利用SEM、TEM、XRD、EDX、XPS手段对催化剂的结构和形貌等进行表征。研究发现,当镍的负载量为0.6%(质量分数)时,Fe-Ni基催化剂的分散性达到最好,导致催化合成C2烃效果最明显。此外,研究不同温度、空速、H2∶CO比例对合成C2烃的影响。结果表明,在450℃,H_2∶CO比例为2,反应空速为2 800mL/g cat-h情况下,一氧化碳转化率达到58.5%,C2烃的选择性达到37.7%,其中乙烯的选择性达26.6%,具有优异的催化合成效果。综上所述,0.6%(质量分数)镍负载量的Fe-Ni基催化剂对合成气合成乙烯以及C2烃,具有高催化效果,为工业生产乙烯以及C2烃提供新的参考与依据。     

液相硝基苯加氢Ni-Zr-B非晶态合金催化剂制备及结构表征

将化学还原法制备的Ni-Zr-B非晶态合金催化剂用于硝基苯液相加氢制苯胺的反应,并通过XRD,TEM和H2-TPD技术对催化剂进行表征,研究了Zr含量对Ni-Zr-B催化剂微观结构和其催化加氢性能的影响。结果表明,Ni-B非晶态合金催化剂表现出较高硝基苯转化率和苯胺选择性,Zr助剂的引入减小了催化剂非晶态结构短程有序范围和催化剂粒径,粒径由60nm减小至10nm左右;增多了Ni活性中心数,并减弱了Ni化学吸附氢强度,使得吸附的氢物种更易于在各吸附中心间迁移并参与反应,导致Ni-B非晶态合金催化硝基苯加氢的活性和选择性进一步提高。当Zr含量为8%时,催化剂具有最优的催化加氢性能,硝基苯转化率和苯胺选择性分别高达99.6%和100%。     

Selective hydrogenation of acetylene over egg-shell palladium nano-catalyst

A novel egg-shell Pd/PHSNs nano-catalyst was prepared by a wet impregnation method using self-synthesized porous hollow silica nanoparticles (PHSNs) as support and applied in selective hydrogenation of acetylene to remove acetylene from the ethylene feed. By controlling the preparing conditions and calcining temperature, the active metal particles were loaded evenly on the support with a size about 5 nm. Compared with conventional catalysts prepared with solid silica nanoparticles, solid Al2O3 millispheres and a commercial catalyst, the Pd/PHSNs catalyst showed higher acetylene conversion rates at same reaction temperatures, and the porous hollow nano structure of PHSNs allowed smoother diffusion of ethylene molecules within the catalyst matrix so that ethylene could migrate away from the active sites in time to avoid turning into ethane, which resulted in superior ethylene selectivity at high acetylene conversion rates.     

Stable and recyclable Pd catalyst supported on modified silica hollow microspheres with macroporous shells for enhanced catalytic hydrogenation of NBR

In this work, a stable and recyclable Pd catalyst supported on N-containing silane coupling agent modified silica hollow microspheres with macroporous shells (Pd/N-SHMs) was successfully prepared and used for the selective hydrogenation of nitrile-butadiene rubber (NBR) with enhanced catalytic performance. The results showed that Pd/N-SHMs possessed small-sized and well-dispersed Pd nanoparticles (NPs) and the macroporous shells were beneficial for the diffusion of macromolecular NBR, and thus with such a catalyst, the reaction could occur under mild conditions and high hydrogenation degree (96.6%) with 100% selectivity to C=C was obtained. The prepared catalyst could be easily recycled and reused with a high efficiency. More importantly, because of the strong coordination between Pd and diamine ligands, Pd NPs could be anchored steadily over the support and only 5.0 ppm Pd residues was detected in products. This reaction was considered as pseudo-first order at high H₂ pressures, and the reaction activation energy was calculated to be as low as 18.1 kJ/mol. Our contribution is to provide an efficient and recyclable supported Pd catalyst, which may promote the development of heterogeneous catalytic systems for unsaturated macromolecular hydrogenation.     

Pd-ZrO2/Al2O3催化剂对丙烯选择性催化还原NO的催化活性研究

采用浸渍法制备了具有高比表面积的氧化铝负载的Pd-ZrO2复合物催化剂(Pd-ZrO2/Al2O3),利用BET、XRD、TEM等手段研究了该复合物催化剂的物理特性,并重点研究了该复合物催化剂对以C3H6为还原剂选择性催化还原(SCR)NO的催化反应活性,分别讨论了反应温度、组分、焙烧温度、原料气组分、空速等因素对该催化反应的影响.结果发现,少量的Pd纳米粒子均匀分散于载体氧化铝上,添加适量ZrO2后,所制备的低负载量的Pd(1wt%)-ZrO2(2wt%)/Al2O3复合物催化剂具有较高的NO选择性催化还原反应活性,在240～250℃可使NO的转化率达到50%～70%.其活性提高的机制在于适量ZrO2的添加增强了反应物中NO和C3H6在催化剂表面的吸附,同时与Pd催化剂形成一种协同催化作用.     

Ni对TiC-Ni超音速火焰喷涂层组织和耐磨性的影响

Ni对Ti-Ni-C体系SHS反应中的热力学与动力学均有重要影响,Ni在超音速火焰喷涂合成中的作用尚不明确.利用超音速火焰喷涂合成技术制备了3种不同Ni含量的TiC-Ni金属陶瓷涂层,并对涂层进行了组织和性能研究.结果表明,Ni在喷涂过程中起到了吸收反应热、减缓喷涂合成过程中粉末组分的氧化、并在涂层中黏结相金属的作用.原料中的Ni含量对涂层的组织和性能影响较大,Ni含量低涂层中含有大量氧化物,且组织疏松、滑动磨损性能差;随着Ni含量升高到40%时,涂层的氧化物含量降低,滑动磨损性能增强; Ni含量过高,涂层中Ni片层增多,硬质相间距加大,涂层的耐磨损性能有所降低.     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。     

Galvanic Replacement–Mediated Synthesis of Ni‐Supported Pd Nanoparticles with Strong Metal–Support Interaction for Methanol Electro‐oxidation

Herein, well‐defined Pd nanoparticles (NPs) developed on Ni substrate (Pd NPs/Ni) are synthesized via a facile galvanic replacement reaction (GRR) route performed in ethaline‐based deep eutectic solvent (DES). For comparison, a Pd NPs/Ni composite is also prepared by the GRR method conducted in an aqueous solution. The Pd NPs/Ni obtained from the ethaline‐DES is catalytically more active and durable for the methanol electro‐oxidation reaction (MOR) than those of the counterpart derived from conventional aqueous solution and commercial Pd/C under alkaline media. Detailed kinetic analysis indicates that the unique solvent environment offered by ethaline plays vital roles in adjusting the reactivity of the active species and their mass transport properties to control over the genesis of the Pd NPs/Ni nanocomposite. The resulting Pd NPs/Ni catalyst possesses a homogeneous dispersion of Pd NPs with a strong Pd (metal)–Ni (support) interaction. This structure enhances the charge transfer between the support and the active phases, and optimizes the adsorption energy of OH^? and CO on the surface, leading to superior electrocatalytic performance. This work provides a novel GRR strategy performed in ethaline‐DES to the rational design and construction of advanced metal/support catalysts with strong interaction for improving the activity and durability for MOR.     

堇青石-氧化锆红外辐射复合粉体的制备

为获得具有高红外辐射性能的粉体,以堇青石颗粒为基体,采用液相共沉淀法,用氧化锆前驱体包覆堇青石基体,煅烧后得到堇青石-氧化锆红外辐射复合粉体;对制备的复合粉体进行热分析、物相分析及形貌分析,并测试其红外辐射性能。结果表明,利用非均匀形核可将氧化锆前驱体包覆于堇青石颗粒表面,氧化锆结晶温度在800～900℃之间,900℃煅烧后得到的氧化锆晶粒尺寸约为8 nm;当在一定初始溶液浓度范围内改变反应物的用量时,可以控制氧化锆的包覆量并且避免其自发团聚;通过氧化锆纳米颗粒包覆的工艺可以提高堇青石粉体在3～5μm波段的红外辐射性能,当氧化锆包覆质量分数为21.11%时,复合粉体具有最佳的红外辐射性能。     

Pd Nanosheet‐Covered Hollow Mesoporous Silica Nanoparticles as a Platform for the Chemo‐Photothermal Treatment of Cancer Cells

A versatile system combining chemotherapy with photothermal therapy for cancer cells using Pd nanosheet‐covered hollow mesoporous silica nanoparticles is reported. While the hollow mesoporous silica core can be used to load anticancer drugs (i.e., doxorubicin) for chemotherapy, the Pd nanosheets on the surface of particles can convert NIR light into heat for photothermal therapy. More importantly, the loading of Pd nanosheets on hollow mesoporous silica nanospheres can dramatically increase the amount of cellular internalization of the Pd nanosheets: almost 11 times higher than the unloaded Pd nanosheets. The as‐prepared nanocomposites efficiently deliver both drugs and heat to cancer cells to improve the therapeutic efficiency with minimal side effects. Compared with chemotherapy or photothermal therapy alone, the combination of chemotherapy and phototherapy can significantly improve the therapeutic efficacy, exhibiting a synergistic effect.     

活性炭负载CaCl2催化五氯乙烷脱HCl的研究

筛选出了催化性能较好的活性炭负载氯化钙(CaCl2/AC)催化剂用于五氯乙烷脱HCl制备四氯乙烯。考察了反应温度、空速、CaCl2负载量对CaCl2/AC催化剂催化性能的影响及催化剂的稳定性。实验结果表明最佳反应条件:反应温度为240℃,空速为3.4h-1,CaCl2负载量为0.3mmol/g,在此反应条件下五氯乙烷的转化率可达99%以上,四氯乙烯的收率达95%以上,催化剂催化性能重现性良好。采用X射线衍射(XRD)、氮气吸附-脱附对催化剂进行了表征。结果表明CaCl2在活性炭表面分散良好;随着CaCl2负载量的增加,CaCl2/AC催化剂的BET比表面及孔容逐渐减小。