Synthesis of MCM–41 mesoporous molecular sieves containing heteroatoms and their catalytic activity

采用水热合成法合成了金属原子(Zn, Ni, Fe, Al, Cu, Ce)掺杂的MCM--41介孔分子筛(简称T--MCM--41), 并将其应用于邻苯二甲酸二(2--乙基己)酯(DOP)的合成反应, 研究了不同原子的掺杂对T--MCM--41的结构、比表面积和孔径、酸性及催化性能的影响. 结果表明, 所制备的T--MCM--41仍然具有六方有序排列结构, 比表面积较高(550--900 m2/g)、孔径大(3 nm左右), 杂原子的引入使T--MCM--41产生了酸中心, 从而使其对DOP的合成具有很好的催化活性和选择性. 用T--MCM--41(T=Zn, Fe, Al, Cu)催化DOP的合成反应, 在5 h的反应时间内苯酐的转化率可以达到95.5%以上, DOP的选择性可达到96.5%以上. T--MCM--41催化剂具有很好的稳定性, Al--MCM--41在重复使用5次后仍具有较好的催化活性.     

Preparation of (Ti, Sn)O2 Nano-Composite Photocatalyst by Supercritical Fluid Dry Combination Technology

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%-30.1%) were prepared from TiCI4 and SnCl4·5H2O by using sol-gel, supercritical fluid dry and solid-phase reaction (SCFD) combination technology. Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0-4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nano-composite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (T     

固体超强酸SO42-/TiO2-Al2O3的制备及其催化合成冰片

采用溶胶-凝胶法和浸渍法制备了系列SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂,运用XRD、NH_3-TPD、FT-IR、PyFTIR、XPS、SEM等技术手段,研究了复合催化剂材料的结构与性质,初步探讨了固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的构效关系,得到适宜的催化剂制备条件为:n(TiO_2)/n(Al_2O_3)=1∶2、硫酸浸渍浓度1mol/L、催化剂焙烧温度500℃。考察了物料物质的量比、催化剂用量、反应时间等对催化合成冰片的影响。结果表明,在物料物质的量比为1∶0.4,催化剂用量为α-蒎烯质量的7%,采用程序升温方式(65℃-1h,75℃-4h,90℃-1h)加热的条件下,固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的催化活性最高,α-蒎烯的转化率高达100%,龙脑的收率高达59.74%,SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂在重复使用6次的条件下,α-蒎烯的转化率均不变,龙脑的收率下降2.99%,催化剂的重复使用性良好。     

CO与烯烃共聚反应钯系催化剂的研究进展

钯系催化剂具有较高的催化活性和选择性,一直是CO与烯烃共聚反应制备聚酮研究较多的催化体系。但由于其价格较高,严重制约了CO与烯烃共聚制备聚酮的工业化进程。系统分析了近几年来钯系催化剂的研究进展,包括钯种类、配体类型、钯的负载方式及反应介质的应用等。以期为制备新型、高效的钯催化剂提供思路,推动CO与烯烃共聚反应制备聚酮的工业化发展。     

不同载体Mn-Ce催化剂的制备及其脱硝性能

以TiO_2、SiO_2及Al_2O_3为载体,采用分步共混法制备了三种均质整体式Mn-Ce负载型催化剂,探究了不同载体对催化剂脱硝活性、N2选择性及机械强度的影响。结果表明,以TiO_2和SiO_2为载体的催化剂80℃的脱硝率接近90%,而以Al2O3为载体的催化剂仅达46%。催化剂的表征发现这与Mn-Ce/TiO2和Mn-Ce/SiO2催化剂的比表面积和表面酸量较Mn-Ce/Al2O3更大、更多有关。而三种催化剂的N2选择性在80~200℃之间均接近100%,然而Mn-Ce/SiO2催化剂200℃以上N2选择性比其余两种催化剂差。三种催化剂的机械强度为Mn-Ce/TiO2Mn-Ce/SiO2Mn-Ce/Al2O3,其微观形貌显示这与催化剂体相结构的密实状况有关,各催化剂的活性组分氧化物均以无定形态存在。     

堇青石蜂窝陶瓷载体酸处理对整体式La0.8Sr0.2MnO3催化剂催化甲苯燃烧性能的影响

整体式催化剂是一种常用的催化剂,蜂窝陶瓷载体是其重要组成部分。酸处理可以改进其结构上的不足。使用不同质量分数、种类的酸溶液对堇青石蜂窝陶瓷载体进行了预处理,考察了酸处理对整体式催化剂的基本性质及甲苯催化活性的影响,并采用XRD、BET等表征手段进行分析。结果表明,蜂窝陶瓷载体经质量分数为30%硝酸溶液处理后可达最佳效果,负载率提高48%以上,比表面积扩大20倍以上,由其制得的催化剂催化甲苯燃烧的起燃温度为219℃,降低了19℃,完全转化温度为281℃。表征结果说明酸洗过程未改变载体组成,而是使载体比表面积增加20倍以上,从而提高了整体催化剂的催化活性。     

Nitrate reduction in water: influence of the addition of a second metal on the performances of the Pd/CeO(2) catalyst

An attempt is made to improve the catalytic nitrate reduction on Pd/CeO(2) catalysts by the addition of a second metal. The influence of the second metal such as Sn, In and Ag on the Pd/CeO(2) for nitrate reduction is explored. The second metal is introduced over monometallic Pd/CeO(2) by a redox reaction. Pd/CeO(2) is more active than the bimetallic catalysts under pure hydrogen flow. Whereas in presence of CO(2) the monometallic Pd/CeO(2) is inactive for nitrate reduction, bimetallic catalysts are found to be more active than under pure hydrogen flow and also than the monometallic catalyst with a low selectivity towards ammonium ions, undesired product of the reaction. The Pd-Sn/CeO(2) catalyst is comparatively the most suited for nitrate reduction.     

Aqueous phase reforming of glycerol over the Pd loaded Ni/Al2O3 catalysts

Bifunctional catalysts containing (0.5-1.5 wt%) palladium and 15 wt% of Nickel supported on gamma-Al2O3 were prepared via an impregnation technique and catalysts were characterzed by XRD BET surface area and SEM, respectively. The aqueous phase reforming of glycerol (APR) was conducted over alumina-supported catalysts at different reaction conditions for catalytic activity. Finally, we concluded that the 1.0 wt% Pd 15 wt% Ni/gamma-Al2O3 catalyst evidences higher conversion, hydrogen selectivity, lower alkane selectivity and CO production. This indicate that Pd loaded Ni/gamma-Al2O3 could be a potential catalyst for the APR of glycerol.     

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。     

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。     

甲苯气相氧化制苯甲醛

考察了甲苯气相氧化制苯甲醛反应条件对反应的影响,对负载型和非负载型催化剂的活性作了对比,在此基础上评价了一系列双组分催化剂的活性,然后通过膜反应器不同进料方式的考察探讨了提高苯甲醛选择性和收率的另外一条途径。结果表明,甲苯气相氧化制苯甲醛有一最佳温度,随空气甲苯比增大甲苯转化率和苯甲醛选择性均增加,随空速增大甲苯转化率降低,苯甲醛选择性增加。Ｍｏ－Ｆｅ中引入载体ＳｉＯ２后对催化剂性能没有改进。Ｍｏ     

Simple and effective synthesis of methoxy-dimethylbenzene from electrochemical oxidation of p-xylene in methanol solvent catalyzed by SO(4)(2-)/ZrO(2)-M(x)O(y)

A series of composite solid superacid catalysts SO(4)(2-)/ZrO(2)-M(x)O(y) (M=Ti, Ni, Si) were prepared and investigated by means of Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). All catalysts exhibit good catalytic activity in the electrochemical reaction of p-xylene with methanol assisted with a pair of porous graphite plane electrodes and the selectivity of main products higher than 90% were observed. In particular, SO(4)(2-)/ZrO(2)-SiO(2) catalyst exhibited excellent catalytic activity. According to the experimental results, a possible free radical reaction mechanism confirmed by XPS and ultraviolet-visible (UV-vis) spectra was proposed. It may be concluded that a simple and feasible electrochemical catalytic oxidation reaction at room temperature and standard atmosphere may be possible.     

Nanoparticle-supported catalysts and catalytic reactions – a mini-review

This article reviews recent developments of using nanometer-sized particular matrices for supporting catalysts and catalytic organic reactions. Immobilization of a catalyst onto the surface of an Au or magnetic (e.g. Fe₂O₃) nanoparticle allowed facile separation and recycling of the catalyst out of the reaction mixture. The activity and selectivity of the nanoparticle-supported catalytic species were found to be comparable to those of their parent catalysts in solution or their counterparts immobilized on the solid-phase. In addition, due to the unique surface structure of the nano-host, cooperative catalysis was observed in a dyad of amino acid residues and peptide analogues on the nanoparticle surface. Thereby, immobilization of catalysts on the surface of a nanoparticular matrix will not only facilitate the isolation and recovery of expensive catalysts, but also open a new avenue to regulate their activity and selectivity.     

Ni-Pd纳米涂层整体式催化剂加氢性能研究

采用浸涂法将自制的介孔空心SiO2纳米粉体涂覆到堇青石基体上,然后采用微波法负载活性组分Pd和助剂Ni制备了纳米涂层整体式加氢催化剂,并考察空速、涂层增重、Ni助剂添加量等因素对其乙炔选择性加氢催化性能的影响。结果表明:经过涂覆后的堇青石整体式催化剂加氢性能与未涂覆时相比有了显著提高,且添加适量的助剂Ni有助于催化性能的进一步改进。在反应温度为54℃、压力为0.1 MPa、空速为3 800 h-1的条件下,使用涂层增重质量分数为6%、Ni与Pd物质的量比为4∶1的催化剂,当乙炔接近完全转化时,乙烯选择性能够到达40.9%。     

催化剂选择性催化氧化NH3的新进展

在处理含NH_3的工业废气方面,氨选择性催化氧化法(NH_3-SCO)一直是研究热点。在讨论氨选择性催化氧化法(NH_3-SCO)反应机理的基础上,重点综述了关于选择性催化氧化NH_3的5种催化剂:贵金属催化剂、过渡金属催化剂、分子筛载体催化剂、复合氧化物催化剂及整体催化剂的最新研究进展,并对未来NH_3-SCO的发展进行了展望。     

Pd Single‐Atom Catalysts on Nitrogen‐Doped Graphene for the Highly Selective Photothermal Hydrogenation of Acetylene to Ethylene

The selective hydrogenation of acetylene to ethylene in an ethylene‐rich gas stream is an important process in the chemical industry. Pd‐based catalysts are widely used in this reaction due to their excellent hydrogenation activity, though their selectivity for acetylene hydrogenation and durability need improvement. Herein, the successful synthesis of atomically dispersed Pd single‐atom catalysts on nitrogen‐doped graphene (Pd₁/N‐graphene) by a freeze‐drying‐assisted method is reported. The Pd₁/N‐graphene catalyst exhibits outstanding activity and selectivity for the hydrogenation of C₂H₂ with H₂ in the presence of excess C₂H₄ under photothermal heating (UV and visible‐light irradiation from a Xe lamp), achieving 99% conversion of acetylene and 93.5% selectivity to ethylene at 125 °C. This remarkable catalytic performance is attributed to the high concentration of Pd active sites on the catalyst surface and the weak adsorption energy of ethylene on isolated Pd atoms, which prevents C₂H₄ hydrogenation. Importantly, the Pd₁/N‐graphene catalyst exhibits excellent durability at the optimal reaction temperature of 125 °C, which is explained by the strong local coordination of Pd atoms by nitrogen atoms, which suppresses the Pd aggregation. The results presented here encourage the wider pursuit of solar‐driven photothermal catalyst systems based on single‐atom active sites for selective hydrogenation reactions.     

不同助剂对合成甲醇工业催化剂二氧化碳加氢性能的影响

采用浸渍法制备了以工业铜基催化剂C301为基体,含CeO2、ZrO2、La2O3、MnO2、Pr2O3、SrO、V2O5助剂的一系列催化剂,在微型固定床反应器上考察了其对CO2加氢合成甲醇的催化性能及影响,并采用XRD、BET、H2-TPR和CO2-TPD等手段进行了表征。研究结果表明,除助剂Pr2O3外,CeO2、ZrO2、La2O3、MnO2、SrO、V2O5助剂的加入均促进了C301催化剂的CO2加氢合成甲醇活性,其中ZrO2的加入使CO2转化率提高了近5%,甲醇收率提高了近8%。     

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。     

Precipitated iron Fischer–Tropsch catalyst manufacturing: impact of Hematite

This study found that promoted precipitated iron catalysts, containing large quantities of Hematite, demonstrated adequate activity, selectivity, and attrition resistance operating under commercial Fischer–Tropsch synthesis conditions in a product demonstration slurry bed reactor run over an approximately 170-day period. While small quantities of Hematite (< 10 to about 30 wt %) in the fresh catalyst have been demonstrated to significantly reduce the BET surface area, give rise to catalysts with poor pore structure, and consequently negatively impact the synthesis behavior, it was found that catalytic effective pore volume (> 0.30 cm³/g) and pore size (60–80 Å) can be induced if larger quantities of about 30–40 wt % Hematite are present in the fresh calcined unreduced catalyst. The catalyst demonstrated exceptional attrition resistance.     

High-temperature and short-time hydrothermal fabrication of nanostructured ZSM-5 catalyst with suitable pore geometry and strong intrinsic acidity used in methanol to light olefins conversion

High temperature hydrothermal synthesis method was developed to preparation of nanostructured ZSM-5 molecular sieves at short crystallization time. A series of catalysts were synthesized at various temperatures and crystallization times for achievement of pure ZSM-5 phase with MFI structure. The synthesized catalysts were investigated with XRD, FESEM, EDX, BET-BJH, FTIR and TPD-NH₃ techniques. The results revealed that hydrothermal synthesis conditions generally affected the nucleation rate, particle size, textural properties and acidic nature of ZSM-5 catalysts. It was found that pure ZSM-5 materials with high crystallinity could be obtained at specific crystallization conditions of about 300?°C for 1.5?h and also 350?°C for 0.5?h. Increasing the hydrothermal temperature to 350?°C and decreasing the crystallization time to 0.5?h led to the formation of small particles with high specific surface area of 392?m²/g. Furthermore, ammonia TPD spectra showed that ZSM-5(300-1.5) catalyst contained higher amount of acid sites and less acid strength compared to ZSM-5(350-0.5) catalyst. The catalytic performance of samples was studied for conversion of methanol to light olefins under different reaction conditions. Interestingly, the proper pore geometry along with the strong intrinsic acidity resulted in a tendency for excessive production of light olefins for ZSM-5(350-0.5) catalyst. The selectivity of light olefins over this catalyst was increased about 94% in the long time on stream (2100?min). Also, the possible reaction pathway for ZSM-5 synthesis at high temperatures was discussed in details.