Pd/CMK-3的合成及其在Suzuki-Miyaura碳-碳偶联反应中的应用

利用介孔二氧化硅（SBA-15）为模板、蔗糖为碳源,制备了有序介孔碳材料CMK-3,然后以CMK-3为载体,利用浸渍还原法得到介孔碳负载Pd纳米粒子的复合催化剂（Pd/CMK-3）,通过XRD、TEM以及氮气吸附-脱附等手段对催化剂的微结构和组分进行分析,结果表明CMK-3为有序介孔结构,孔径约为5nm,Pd/CMK-3保留了介孔结构,且孔道中负载有不同尺寸的Pd粒子。应用于无配体催化的Suzuki-Miyaura相似文献   

固相反应制备Pt/C催化剂

利用固相反应法制得具有较高催化活性的Pt/C催化剂,探讨了制备条件对催化剂性能的影响。结果显示:用水作浸渍介质、n(NaOH)/n(H2PtCl6)=6 4、固相还原剂为聚甲醛时,制得的Pt/C催化剂中Pt粒子的平均粒径为3 8nm。线性扫描伏安结果表明:在30℃、扫速为50mV/s时,制得的Pt/C催化剂在c(CH3OH)=0 5mol/L和c(H2SO4)=0 5mol/L混合溶液中,甲醇氧化的峰电流密度为11 3mA/cm2;而同样条件下,E TEK公司商品化的Pt/C催化剂为9 2mA/cm2。     

不同介质中Ni-La2O3/SiO2-Al2O3催化剂稳定性研究

采用浸渍法制备Ni-La2O3/SiO2-Al2O3催化剂,选用四氢呋喃(THF)、γ-丁内酯(GBL)、1,4-丁二醇(BDO)、水(H2O)等常用溶剂作为介质对催化剂进行溶剂热处理,通过XRD、TG、H2-TPR手段对催化剂进行表征。结果表明,不同介质中催化剂活性组分发生不同程度的晶粒尺寸长大。经GBL处理过的催化剂Ni晶粒尺寸长大最明显,H2O处理次之,而THF的影响最小。     

强磁性Fe_3O_4纳米粒子的制备及其性能表征

采用共沉淀法在无N2气保护下制备了比饱和磁化强度达到75 9emu g的强磁性Fe3O4纳米粒子。在用NaOH溶液沉淀Fe3+和Fe2+混合溶液的过程中,考察了n(Fe2+)∶n(Fe3+)、晶化时间、晶化温度、总铁浓度和NaOH溶液浓度等条件对Fe3O4纳米粒子的粒径分布及磁性的影响。当n(Fe2+)∶n(Fe3+)=5 5∶1 0,晶化时间为2h,晶化温度为50℃时,Fe3O4纳米粒子磁性最佳。所制得的Fe3O4粒子为结晶完整、具有较高纯度和粒径分布均匀的立方体形纳米颗粒;其相变温度随着Fe3O4纳米粒子粒径的减小而降低。Fe3O4纳米粒子的等电点约为pH=7 2。     

四氧化三铁纳米粒子合成及表征

采用化学共沉淀法制备纳米磁性Fe3O4粒子。选用NH3.H2O作为沉淀剂,加入到Fe2+和Fe3+的混合溶液中,制得了纳米磁性Fe3O4粒子。考察了影响产物粒径及性能的一些因素,并对其进行了初步性能表征。     

CMK-3中孔炭分子筛负载磷钨酸催化氧化噻吩

采用浸渍法成功合成了新型氧化噻吩催化剂PW/(2MK-3,通过N2吸附、SEM、TEM等方法的表征,说明负载PW后的CMK-3仍然具有有序介孔结构.以噻吩/正辛烷为拟油体系,利用空气为氧化剂,PW/CMK-3为催化剂,在温和的条件下将油品中的噻吩催化氧化,生成相应的砜类物质.实验结果表明,在常压、50℃、空气流量300ml/min、催化剂和油的质量比为1:100、反应时间300min的条件下,噻吩含量为2 000ppm的初始溶液可降低到1ppm以下.该法常压低温一次性操作、无需氢源和H2O2氧化剂,克服了催化加氢脱硫和H2O2氧化脱硫的缺点,是一种油品深度脱硫新方法.     

纳米四氧化三铁降解亚甲基蓝的研究

在浸没循环撞击流反应器中通过共沉淀法,以氨水为沉淀剂,以FeCl3.6H2O和FeSO4.7H2O为原料制备了磁性纳米Fe3O4粒子。采用XRD、TEM等多种方法对制得的纳米粒子的结构和性能进行了表征,并研究了磁性纳米Fe3O4粒子对亚甲基蓝的降解作用。结果表明,纳米Fe3O4粒子具有相对较小的粒径;当溶液pH值为4.2、H2O2加入量为2 mL.L-1时,用0.9 g.L-1的Fe3O4悬浊液对10 mg.L-1的亚甲基蓝溶液进行降解,5 min内亚甲基蓝的降解率可达96.5%。     

中孔材料CMK-3脱除水中铬离子的研究

以SBA-15为模板,以蔗糖为碳源,合成有序介孔炭材料CMK-3。研究了铬离子浓度、酸度和吸附时间对CMK-3吸附铬离子容量的影响。结果表明,随溶液pH值的减小,对铬离子的吸附量增大,在pH为2时,最大吸附量达到32．43mg／g。此材料对Cr（Ⅵ）的吸附具有吸附速度快、吸附量高的特点。     

固体酸负载Cu~Ⅰ催化剂表征及催化甲醇氧化羰基化

采用稀H2SO4和(NH4)2S2O8溶液浸渍Fe(OH)3,高温焙烧制得SO42-/Fe2O3和S2O82-/Fe2O3固体酸,然后与CuCl混合高温处理制备CuⅠ/SO42-/Fe2O3和CuI/S2O82-/Fe2O3催化剂。该催化剂在CH3OH液相氧化羰基化合成碳酸二甲酯(DMC)反应中表现出良好的催化活性,明显高于传统CuCl催化剂。载体和催化剂的XRD、NH3-TPD和XPS等表征结果表明,制备的SO42-/Fe2O3和S2O28-/Fe2O3固体酸为超强酸,与CuCl混合高温处理中发生了固体离子交换,形成了负载CuⅠ的低氯催化剂。固体酸载体酸量越多,离子交换负载的CuⅠ离子的含量越高,催化活性越好。550℃焙烧制备S2O82-/Fe2O3固体酸有较多的酸量,与CuCl热处理获得的CuⅠ/S2O82-/Fe2O3催化剂具有较好的催化活性,CH3OH转化率达到16.58%,DMC选择性和时空收率分别为97.00%和2.83g.g-1.h-1,且Cu/Cl原子比达到1.69。     

Pd/CMK-3催化加氢制备邻氨基苯酚研究

采用浸渍还原法在CMK-3介孔炭上负载Pd制备Pd/CMK-3催化剂,考察了Pd/CMK-3水相催化加氢邻硝基苯酚钠制备邻氨基苯酚钠的催化性能。结果表明:当Pd负载量为5%,反应温度为338 K,反应压力为1 MPa时,邻硝基苯酚钠的转化率达到100%,邻氨基苯酚钠的选择性高于99.5%,邻氨基苯酚收率为98.0%。采用XRD、BET、SEM和TEM对于催化剂进行了表征,结果表明:CMK-3具有良好的介孔结构以及较高的比表面积,Pd纳米颗粒在CMK-3表面高度分散且具有较好稳定性,因此具有更高的催化加氢活性。     

Synthesis of recyclable catalyst-sorbent Fe/CMK-3 for dry oxidation of phenol

The magnetic mesoporous material Fe/CMK-3 acting as a catalyst-sorbent was synthesized by using ordered mesoporous carbon CMK-3 as the supporter, Fe(NO₃)₃ as the iron source, and glycol as the reducing agent. The samples synthesized were characterized by powder X-ray diffraction (XRD), N₂ adsorption-desorption, scanning electron microscope (SEM) and transmission electron microscopy (TEM). The results show that the prepared Fe/CMK-3 preserved the ordered mesoporous structure of CMK-3, and magnetic species was mainly Fe₃O₄, which was dispersed inside channels of CMK-3 as nanoparticles with the diameter of around 10 nm. The adsorption and catalytic dry oxidation efficiency of the prepared Fe/CMK-3 were determined. The results also show that Fe/CMK-3 had good adsorption performance of phenol in aqueous solution and could be easily separated from water and recycled due to its ferromagnetic nature. Iron oxides supported on CMK-3 were excellent catalysts for dry oxidation of phenol. After 15 adsorption-catalytic oxidation cycles, the phenol adsorption capacity of Fe/CMK-3 only decreased a little, suggesting the good practicality. Combined thermogravimetry and mass spectrum (TG-MS) instrument was used to investigate the catalytic oxidation of phenol on Fe/CMK-3 and the ignition characteristics of the catalyst-sorbent. The supported Fe₃O₄ was found to be not only the magnetic component but also the active catalyst for the oxidation of phenol. The adsorbed phenol could be oxidized into CO₂ and H₂O at 220 °C at which no obvious phenol desorption or CMK-3 ignition occurred.     

Preparation and characterization of heteropolyacid/mesoporous carbon catalyst for the vapor-phase 2-propanol conversion reaction

H₃PMo₁₂O₄₀ catalyst was chemically immobilized on the surface modified CMK-3 (SM-CMK-3) support as a charge compensating component, by taking advantage of the overall negative charge of [PMo₁₂O₄₀]³⁻. The supported H₃PMo₁₂O₄₀/SM-CMK-3 catalyst was characterized to have high surface area (≈1000 m²/g) and relatively large pore volume (0.83 cm³/g). The H₃PMo₁₂O₄₀/SM-CMK-3 catalyst was applied to the vapor-phase 2-propanol conversion reaction. The H₃PMo₁₂O₄₀/SM-CMK-3 catalyst exhibited higher 2-propanol conversion than the unsupported H₃PMo₁₂O₄₀ and the impregnated H₃PMo₁₂O₄₀ on CMK-3. Furthermore, the PMo₁₂/SM-CMK-3 catalyst showed the enhanced oxidation activity (acetone formation) and the suppressed acid catalytic activity (propylene formation) compared to the other two catalysts. It is believed that [PMo₁₂O₄₀]³⁻ species were chemically and finely immobilized on the SM-CMK-3 support as charge matching species, and thus, the PMo₁₂/SM-CMK-3 catalyst showed an excellent oxidation activity.     

Platinum and platinum-ruthenium nanoparticles supported on ordered mesoporous carbon and their electrocatalytic performance for fuel cell reactions

Highly ordered meso-porous carbon, denoted CMK-3 was synthesized by using mesoporous silicates, SBA-15 as the starting templating materials. The ordered mesoporous carbon was loaded with platinum and platinum-ruthenium nanoparticles using alternative synthesis techniques. The metal loaded ordered mesoporous carbon powders were characterized by transmission electron microscopy (HRTEM), energy dispersive X-ray analysis (EDX), X-ray diffraction, and nitrogen adsorption isotherm experiments. Micrometer-scale and centimeter-scale electrodes containing the mesocarbon/nanometal electrocatalysts were tested for some typical fuel cell reactions. While the nanometal/mesocarbon catalysts have well-defined and uniform properties in the nanometer scale, they have mixed electrocatalytic performance. A synthesized Pt/mesocarbon electrocatalyst outperformed a commercial electrocatalyst for oxygen reduction on a gas-diffusion electrode. The Pt-Ru/mesocarbon electrocatalyst synthesized, however, was not as effective for methanol oxidation.     

Characterization and electrocatalytic properties of PtRu/C catalysts prepared by impregnation-reduction method using Nd2O3 as dispersing reagent

A simple impregnation-reduction method introducing Nd₂O₃ as dispersing reagent has been used to synthesize PtRu/C catalysts with uniform Pt-Ru spherical nanoparticles. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis have been used to characterize the composition, particle size and crystallinity of the catalysts. Well-dispersed catalysts with average particle size about 2 nm are achieved. The electrochemically active surface area of the different PtRu/C catalysts is determined by the CO_ad-stripping voltammetry experiment. The electrocatalytic activities of these catalysts towards methanol electrooxidation are investigated by cyclic voltammetry measurements and ac impedance spectroscopy. The in-house prepared PtRu/C catalyst (PtRu/C-03) in 0.5 M H₂SO₄ + 1.0 M CH₃OH at 30 °C display a higher catalytic activity and lower charge-transfer resistance (R_t) than that of the standard PtRu/C catalyst (PtRu/C-C). It is mainly due to enhanced electrochemically active specific surface, higher alloying extent of Ru and the abundant Pt⁰ and Ru oxides on the surface of the PtRu/C catalyst.     

前驱体溶液中Fe2+与Fe3+物质的量比对Au/α-Fe2O3催化剂低温水煤气变换性能的影响

改变前驱体溶液中Fe<'2+>与Fe<'3+>物质的量比制备了系列Au/α-Fe<,2>O<,3>水煤气变换催化剂,并运用XRD、拉曼光谱和H<,2>-TPR对样品进行表征.结果表明,Fe<'2+>与Fe<'3+>物质的量比的变化对Au/α-Fe<,2>O<,3>催化剂低温水煤气变换活性具有显著影响,这是由Fe<'2+...     

Controlling the textural parameters of mesoporous carbon materials

The mesoporous carbon materials prepared by inorganic templating technique using mesoporous silica, SBA-15 as a template and sucrose as a carbon source, have been systematically investigated as a function of sucrose to mesoporous silica composition, with a special focus on controlling the mesoporous structure, surface morphology and the textural parameters such as specific surface area, specific pore volume and pore size distribution. All the materials have been unambiguously characterized by XRD, N₂ adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron microscopy, and Raman spectroscopy. It has been found that the porous structure, morphology and the textural parameters of the mesoporous carbons materials, CMK-3-x where x represent the sucrose to silica weight ratio, can be easily controlled by the simple adjustment of concentration of sucrose molecules. It has also been found that the specific surface area of the mesoporous carbon materials systematically increases with decreasing the sucrose to silica weight ratio. Moreover, the specific pore volume of the materials increases from 0.57 to 1.31 cm³/g with decreasing the sucrose to silica weight ratio from 5 to 1.25 and then decreases to 1.23 cm³/g for CMK-3-0.8. HRTEM and HR-FESEM also show a highly ordered pore structure and better surface morphology for CMK-3-1.25 as compared to other materials prepared in this study. Thus, it can be concluded that the sucrose to silica weight ratio of 1.25 is the best condition to prepare well ordered mesoporous carbon materials with good textural parameters, pore structure and narrow pore size distribution.     

Impact of framework structure of ordered mesoporous carbons on the performance of supported Pt catalysts for oxygen reduction reaction

Ordered mesoporous carbons (OMCs) are investigated as support materials for Pt catalysts for oxygen reduction reaction (ORR). Three types of OMCs (CMK-3, CMK-3G, and CMK-5) are prepared by a nanocasting method using ordered mesoporous silica, SBA-15, as a template. These OMCs with the same hexagonal mesostructure have different carbon frameworks and graphiticity, which can affect their surface area and microporosity. Pt nanoparticles with an average size of 1 nm are uniformly supported on the three OMCs and Ketjenblack® and their electrochemical performance and durability are evaluated. Pt/CMK-3G exhibits the highest electrochemically active surface area, kinetic current density, mass activity, and half-wave potential, whereas Pt/CMK-3 shows the lowest values. Pt/CMK-3G also shows the highest ORR activity after an accelerated durability test, with a minimal shift in half-wave potential. The higher ORR activity of Pt/CMK-3G is attributed to the formation of highly crystalline Pt particles as well as its highly graphitic, crystalline carbon structure, which causes the weak adsorption of surface oxide and a strong interaction between the Pt particles and the support. Moreover, we can establish that the mass activity of the catalysts is nearly inversely proportional to the micropore volume of the carbon supports.     

Desulfurization of fuels by means of a nanoporous carbon adsorbent

Mesoporous carbon, CMK-3, was prepared using hexagonal Al-SBA-15 mesoporous silica, instead of SBA-15, as a template. The synthesized materials were examined via X-ray diffraction and N₂-adsorption. The mesoporous carbon was studied for its adsorption of dibenzothiophene (DBT) from petroleum fuels. The performance of this adsorbent was compared with SBA-15 and Al-SBA-15, through which CMK-3 showed higher sulfur adsorption capabilities due to a larger mesopore volume and a higher specific surface area. The uptake capacity for DBT followed the order CMK-3 > Al-SBA-15 > SBA-15. The results confirmed the importance of the adsorbent pore size and its surface chemistry for the adsorption of DBT from liquid phase.Langmuir and Freundlich isotherm models were used to fit equilibrium data for CMK-3. The equilibrium data were best represented by the Langmuir isotherm. Kinetic studies were carried out and showed the sorption kinetics of dibenzothiophene was best described by a pseudo-second-order kinetic model.     

拟薄水铝石脱水产物γ-Al2O3在较低温度下的再水合过程研究

研究了γ-Al₂O₃经过较低温度的水热处理后的晶型变化情况。XRD、SEM和FT-IR表征结果表明，影响γ-Al₂O₃再水合产物晶型的主要因素是水热温度。100 ℃以下水热处理的产物是湃铝石，100～110 ℃水合产物是湃铝石和薄水铝石的混合物，110 ℃以上水热处理的产物是薄水铝石，且不经过湃铝石的中间阶段。随着水合温度升高，薄水铝石的结晶度增大。在保证充分润湿的前提下，水合产物的结晶度和晶粒度与水铝质量比无关。     

Electrical signal effect on electrochemical activities of metal catalysts electrically deposited on carbon nanotubes

The electrochemical deposition of Pt-Ru nanoparticles on carbon nanotubes (CNTs) supports and their electro-catalytic activities, were investigated. Pt-Ru catalysts of 4-12 nm average size were grown successfully on supports by step-potential plating methods. Electro-plating at 0.06 s step intervals was sufficient to obtain small-size 4.8 nm particles, showing good electrochemical activity. The catalysts’ loading contents were enhanced by increasing the plating time. The sizes and morphological structures of the Pt-Ru/support catalysts were evaluated using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical behaviors of the Pt-Ru/support catalysts for methanol oxidation were investigated according to their characteristic current-voltage curves in a methanol solution. In the result, the electrochemical activity increased with increased plating time, reaching the maximum at 24 min, and then decreased. The improved catalytic activity was correlated to the small particle size and the higher specific surface area of the catalysts.