纳米Pt/MgO催化剂的表征和催化性能

"用浸渍法制备了Pt/MgO催化剂,采用X射线衍射、X射线光电子能谱、透射电子显微镜和程序升温表面反应等技术对反应前后的催化剂进行了表征．甲烷部分氧化制备合成气的反应被用来考察催化剂的催化活性和稳定性．TEM结果显示活性组分Pt粒子的尺寸小于10 nm,而载体MgO的晶粒大小在50~200 nm．在固定床微反应器上进行．在800 ℃时,Pt/MgO催化剂表现了非常高的POM催化活性和稳定性,甲烷转化率和合成气的选择性在120 h内保持稳定．活性组分Pt以金属状态存在于载体的表面上,其存在状态和分散状态都很     

双金属RuM(M=Co,Ni)合金纳米粒子负载于MIL-110(Al):协同催化氨硼烷水解释氢（英文）

通过调节不同Ru/M(M=Co, Ni)摩尔比,采用浸渍还原法成功地合成了一系列高分散的双金属RuM合金纳米粒子负载于MIL-110(Al)的催化剂,并首次在室温下用于多相催化氨硼烷水解脱氢.结果表明,在不同RuCo和RuNi摩尔比中,Ru_1Co_1@MIL-110和Ru_1Ni_1@MIL-110分别展现出最高的催化活性,且Ru_1Co_1@MIL-110和Ru_1Ni_1@MIL-110催化剂的转换频率分别达到488.1和417.1 mol H_2 min~(-1)(mol Ru)~(-1),活化能分别为31.7和36.0 kJ/mol.优良的催化活性主要归因于双金属Ru和M之间的协同作用、金属纳米粒子的均匀分布以及RuM合金纳米粒子与MIL-110之间的双功能作用.此外,这些催化剂经过5次催化循环后仍表现出良好的稳定性.     

铂颗粒粒径效应:负载铂纳米颗粒的TiO2薄膜性质研究

制备了负载不同大小Pt纳米颗粒的TiO薄膜。利用TEM测定了Pt粒子的大小,XRD,UV—Vis和测量光电流等方法对TiO2复合膜进行了表征,以亚甲基蓝降解反应评价了Pt／TiO2薄膜的光催化活性。结果表明,在负载相同物质的量的Pt情况下,Pt颗粒的大小直接影响TiO2薄膜的性能,显示较强的粒径效应,当负载平均粒径约5nm的Pt粒子后,薄膜具有最高的光电流和光催化活性。     

常温常压下吡咯及其衍生物的镍催化加氢反应考察

为进一步研究常温常压下及其衍生物的镍催化加氢反应,我们对试剂吡咯、吡咯烷和吡咯烷酮做了相应的催化加氢实验。并采用电镜（TEM－HREM）、X射线衍射（XRD）对Ni基催化剂的形貌、结构、加氢活性和超声波对其影响进行了检测,同时不用紫外吸收光谱、气相色谱等对加氢产物进行了分析考察。结果表明超声波能促进镍催化剂活性,使镍微晶（111）晶面间距增大1．5％,并保持高分状态。常温常压下纳米镍基催化剂对吡咯、吡咯烷和吡咯烷酮的加氢反应显示一定的催化活性;吡咯加氢首先生成吡咯烷,进而使环打开生成低碳烃、氨等产物,总反应为零级,符合表面接触反应特征。     

主晶相为莫来石复合纳米晶的制备、结构表征及性能测试

以高岭土为原料,采用水热晶化法,制得了主晶相为莫来石的复合纳米晶。利用XRD、TEM、BET及TG－TDA以在不同条件下制得的纳米晶物相、粒度及热稳定性进行了表征。对复合纳米晶进行了CO、SO2程序升温脱附性能测试。对负载Ni、Mo、Co进行程序升温还原测试。结果表明：在脱附物中检测出CO2与固体硫,证明吸附质在纳米晶表面发生了反应。微米晶与纳米晶负载Ni、Co、Mn后,随着粒度的不同,负载上的氧化物与载体的相互作用力不同,而表现出不同的峰温与峰面积,表面负载上Ni、Co、Mn的氧化物与载体有结构效应,且随晶体表面结构的不同,而表现出不同的H2消耗量。     

氮掺杂碳纳米管负载铂催化剂的简易制备及催化性能

以氮掺杂碳纳米管为载体,在温和条件下采用简单的浸渍法制备得到铂催化剂,铂的粒径分布在4～7 nm,且氮掺杂碳纳米管无需进行预处理. 采用X射线衍射仪、扫描电子显微镜、透射电镜和能量色散X射线仪等对Pt/CN_x催化剂进行了详细的表征. 结果表明,氮掺杂碳纳米管中高含量的氮原子能够有效俘获Pt(IV) 离子,且表面的含氮官能团及亲水性能的提高都有利于铂纳米粒子的分散. Pt/CN_x催化剂在烯丙醇加氢反应中表现出高的催化性能及循环使用性能,这是由于铂纳米粒子的高分散性及铂与载体间强的连接性阻止了Pt的流失及聚积,从而避免生成Pt黑导致失活等.     

Ni基催化剂在邻甲酚原位加氢反应中的催化性能

采用等体积浸渍法制备了一系列负载型Ni基催化剂,利用XRD、H₂-TPR、NH₃-TPD 等技术表征了催化剂的理化特性,考察了载体(CMK-3、SiO₂ZrO₂、MgO、Al₂O₃)、助剂(Cu、Ce、Fe)对Ni基催化剂理化特性的影响,测试了230 oC、0.1 MPa冷压下催化剂对邻甲酚原位加氢反应的性能．结果表明,在负载型镍基催化剂作用下,甲醇水相重整制氢反应可以与邻甲酚的原位加氢反应相耦合;以CMK-3为载体的催化剂活性明显优于其他三种载体,邻甲酚的转化率为45.35%;助剂的添加对催化剂性能影响显著,Fe 的引入使原位加氢体系的转化率降至40.49%,助剂Ce、Cu的加入提高了Ni/CMK-3催化剂的原位加氢反应性能,转化率分别提高至64.6%、66.8%,Cu的添加改变了产物的分布,在产物中出现了新产物甲苯;同时探讨原位加氢反应路径及反应机理．     

聚乙二醇-b-聚(4-乙烯基吡啶)/氢氧化钇杂化纳米管在金纳米粒子负载方面的应用

利用聚乙二醇-b-聚(4-乙烯基吡啶)(PEO-b-P4VP)胶束在氢氧化钇纳米管(YNTs)表面上的吸附,制备出被致密的P4VP内层和伸展的PEO外层包裹的杂化纳米管. 通过小分子交联剂1,4-二溴丁烷交联P4VP层可进一步稳定其结构. 然后将交联的杂化纳米管(CHNTs)作为金纳米粒子(GNPs)催化剂的新型纳米载体. 金纳米粒子被负载在交联杂化纳米管的P4VP层中(GNPs/CHNTs),并应用于催化对硝基苯酚的还原反应. 结果表明,这种新型的纳米载体在水溶液中具有良好的分散性, 对金纳米粒子有很高的负载效率(0.87 mmol/g),负载的金纳米粒子保持了很高的催化活性(12.9 μmol^-1min^-1),且GNPs/CHNTs有较好的可重复使用性.     

负载型二氧化钛光催化材料的制备及其光催化性能研究

以球形氧化铝为载体,采用溶胶-凝胶法和浸渍涂覆过程制备了负载型二氧化钛光催化材料。以扫描电子显微镜(SEM)和X-射线衍射仪(XRD)等手段对所合成的样品形貌及晶型进行了表征。结果表明,氧化铝载体经负载二氧化钛后,在球形氧化铝表面沉积了一层粒径为10~20nm的锐钛型二氧化钛纳米颗粒。通过能量色散X射线光谱(EDX)对氧化铝载体和所合成的样品进行进一步分析,表明样品中明显存在Ti元素。另外,提高氧化铝载体在二氧化钛溶胶中的浸渍次数能够有效提高二氧化钛的负载量。当浸渍次数增加到5次时,Ti元素的含量由3.8Wt.%提高至15.7Wt.%。另外,以亚甲基蓝为目标降解物,详细研究了不同浸渍次数获得的负载型二氧化钛催化材料的催化性能。结果表明:随着浸渍次数的增加,负载型二氧化钛催化材料的表面形貌不仅得到明显改善,而且显著提高了样品的光催化活性。当浸渍次数由1次提高至4次时,亚甲基蓝的降解率由40%上升至83.1%。然而,当二氧化钛负载量达到一定程度时,由于不断浸渍导致下层的二氧化钛受光照机会和光照强度减弱,导致其光催化活性提高缓慢。当浸渍次数提高至5次时,亚甲基蓝降解率仅为85.6%。所制备的负载型二氧化钛光催化材料重复使用5次,其光催化活性保持相对稳定。     

在Ni/HZSM-5催化剂上低温水蒸汽重整生物油制氢

利用浸渍方法制备的Ni/HZSM-5催化剂在生物油低温水蒸汽重整合成中表现了较高的催化活性． 探讨了催化剂的组成、重整温度、水碳比例对重整过程的影响．在电催化重整研究中,发现催化剂上通过的电流可以显著地促进生物油水蒸汽重整．通过对不同负载量的Ni/HZSM-5催化剂和Ni₂₀/Al₂O₃催化剂的催化活性的比较,NiO在催化剂中负载量为20%(Ni₂₀/ZSM)时表现出了最高的催化活性; 即使在450 oC时, 在Ni₂₀/ZSM催化剂上也可以达到碳转化率接近完全, 氢气产率约为90%的效果． 利用XRD、ICP/AES、H₂-TPR、BET等表征手段对Ni/HZSM-5催化剂的形态和结构进行了表征.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.     

Electrochemical characterization of platinum-based anode catalysts for membraneless fuel cells

In the present work, carbon-supported Pt–Sn, Pt–Ru, and Pt–Sn–Ru electrocatalysts with different atomic ratios were prepared by alcohol-reduction method to study the electro-oxidation of ethanol in membraneless fuel cells. The synthesized electrocatalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) analyses. The prepared catalysts had similar particle morphology, and their particle sizes were 2–5 nm. The electrocatalytic activities were characterized by cyclic voltammetry (CV) and chronoamperometry (CA). The electrochemical results obtained at room temperature showed that the addition of Sn and Ru to the pure Pt electrocatalyst significantly improved its performance in ethanol electro-oxidation. The onset potential for ethanol electro-oxidation was 0.2 V vs. Ag/AgCl, in the case of the ternary Pt–Sn–Ru/C catalysts, which was lower than that obtained for the pure Pt catalyst (0.4 V vs. Ag/AgCl). During the experiments performed on single membraneless fuel cells, Pt ? Sn ? Ru/C (70:10:20) performed better among all the catalysts prepared with power density of 36 mW/cm². The better performance of ternary Pt–Sn–Ru/C catalysts may be due to the formation of a ternary alloy and the smaller particle size.     

Hydrogenolysis of methylcyclopentane over the bimetallic Ir-Au/γ-Al2O3 catalysts

The gas-phase hydrogenolysis of methylcyclopentane (MCP) was investigated over the bimetallic Ir-Au/γ-Al₂O₃ catalysts. The bimetallic systems containing the atomic Au/Ir ratios in the range of 0.125-8 and a fixed total metal content of 8 wt.%, were prepared by the sequential impregnation (SI) and co-impregnation (CI) methods. The corresponding monometallic Ir/γ-Al₂O₃ and Au/γ-Al₂O₃ catalysts were also prepared. The materials were characterized by ICP, XRD, N₂ adsorption, TEM, and H₂ chemisorption. Highly dispersed Ir nanoparticles were obtained in all cases, while the size of Au nanoparticles increased (up to 50 nm) upon the increasing Au content in the catalyst. The monometallic gold catalyst did not adsorb H₂. The incorporation of Au increased the amount of irreversible adsorbed H₂ in the Ir-Au/γ-Al₂O₃ catalysts with respect to the monometallic ones. The products obtained in the MCP hydrogenolysis were 2-methylpentane (2-MP), 3-methylpentane (3-MP) and n-hexane (n-H). The initial rate (molecules of MCP reacted s⁻¹ g_Ir⁻¹) increased with the Au content. The deactivation was lower for bimetallic catalysts, particularly for the CI ones. The addition of Au played a significant effect on chemisorption and catalytic properties of Ir.     

Morphological investigation of nanostructured CoMo catalysts

This work reports the morphological investigation of nanostructured sulfided CoMo catalysts by means of high-resolution transmission electron microscopy (HRTEM). The catalysts were supported on Ti-modified hexagonal mesoporous silica (HMS-Ti) and P-modified HMS-Ti (P/HMS-Ti) materials. The oxide precursors were characterized by specific surface area (S_BET), temperature-programmed reduction (TPR), diffuse reflectance infrared Fourier transform spectroscopy in the OH region (DRIFTS-OH) and X-ray photoelectron spectroscopy (XPS) in order to elucidate the influence of the impregnation sequence (successive vs. simultaneous) and the effect of P-incorporation into HMS-Ti material on the morphology of calcined CoMo catalysts. Both TPR and XPS measurements indicate that the catalysts prepared by successive impregnation possess well-dispersed MoO₃ and CoO phases, whereas their counterparts prepared by simultaneous impregnation additionally possess the CoMoO₄ phase. For all sulfided catalysts, the presence of MoS₂ phase with particle size in the range 3.3-4.4 nm was confirmed by HRTEM. Catalytic activity was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) carried out in a flow reactor at 593 K and hydrogen pressure of 5.5 MPa. P-incorporation into the HMS-Ti material led to an overall increase in HDS activity and the hydrogenation ability of the sulfided catalysts. All catalysts proved to be stable during 10 h time-on-stream (TOS) operation. The activity of sulfide catalysts in the target reaction depends linearly on the surface exposure of Co species in the oxide precursors, as determined by XPS, and on the morphology of the sulfide form of catalysts (surface density of MoS₂ particles and their sizes) as determined by HRTEM.     

Ultrasonic-assisted reduction for facile synthesis of ultrafine supported Pd nanocatalysts by hydroxyl groups on the surfaces of layered double hydroxides and their catalytic properties

Layered double hydroxide (LDH)-supported Pd nanocatalysts (Pd/LDH-OH) were prepared by ultrasonic-assisted reduction at 30 °C using an ultrasonic bath at a frequency of 25 kHz and an input power of 400 W for 30 min without the addition of any stabilizing reagent or chemical reductant, using LDH with a layered structure and interparticle mesoporosity as the reductant and carrier. This kind of pore structure allows ultrasound waves to spread inside the pore and make ultrasound directly act on the surface hydroxyl groups of LDH, producing highly reductive free radicals (H). The reductive free radicals rapidly reduced Pd²⁺ to Pd⁰, forming ultrafine Pd nanoparticles (PdNPs) with a particle size distribution of 1.85 nm–3.45 nm and an average particle size of 2.52 nm. The surface hydroxyl groups were converted to exposed oxygen groups after dissociation of hydrogen radicals, which is beneficial for anchoring and dispersing the resultant PdNPs. The resultant PdNPs were uniformly dispersed on the surface of the LDH carrier. The yield of the Suzuki coupling reaction between 4-bromotoluene and phenylboronic acid catalyzed by Pd/LDH-OH at 60 °C was 95.49% for 5 min and the TOF was 190.98 min⁻¹. After repeated for 5 times, the yield was maintained at 84.59%. The prepared Pd/LDH-OH nanocatalyst and the catalytic system are useful for Suzuki-Miyaura coupling reactions of N- and S-heterocyclic substrates. This provides an efficient and green approach for the preparation of supported nanopalladium catalysts.     

Synthesis and characterization of Pt–Sn–Ce/MC ternary catalysts for ethanol oxidation in membraneless fuel cells

The present work represents the mesoporous carbon-supported Pt–Sn and Pt–Sn–Ce catalysts with different mass ratios have been prepared by co-impregnation reduction method. The prepared catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) investigation. The XRD patterns of prepared Pt/MC (100) Pt–Sn/MC (75:25), Pt–Ce/MC (75:25), and Pt–Sn–Ce/MC (75:20:05) catalysts showed that Pt metal was the predominant material in all the samples, with peaks attributed to the face-centered cubic (fcc) crystalline structures. Additionally changes in the lattice parameters observed for Pt suggest the incorporation of Sn into the Pt crystalling structure with the formation of an alloy mixture with the SnO₂ phase. The TEM analysis designates that the prepared catalysts had similar particle morphology, and their particle sizes were 2–5 nm. The electrochemical studies showed that ternary catalyst shows best performance for oxidation of ethanol molecule at normal temperature. The enhanced ethanol oxidation activity for the ternary Pt–Sn–Ce catalyst is mainly attributed to the synergistic effect of bifunctional mechanism with electronic effect. Additionally, chemical nature of ceria affords oxygen-containing molecule to oxidize acetaldehyde to acetic acid. In this present context, 1 M ethanol was used as a fuel, 0.1 M sodium perborate was used as an oxidant, and 0.5 M sulfuric acid was used as an electrolyte. In mesoporous carbon-supported binary Pt–Sn and ternary Pt–Sn–Ce anode catalysts were effectively tested in a single membraneless fuel cell at normal temperature. The presence of Sn and Ce enhances the CO oxidation; they produced an oxygen-containing species to oxidize acetaldehyde to acetic acid.     

Spectroscopic properties of nano-sized cerium-doped lutetium aluminum garnet phosphors via sol-gel combustion process

Nano-sized cerium-doped lutetium aluminum garnet (LuAG:Ce) phosphors were prepared via a sol-gel combustion process from a mixed aqueous solution of metal nitrates, using glycine as a fuel. The prepared LuAG:Ce phosphors were characterized by XRD, EPMA, and TEM, respectively. The spectroscopic properties of the phosphors were investigated. The as-prepared phosphors are agglomerated with a primary particle size of about 30 nm and have a foamy-like morphology. The pure crystalline LuAG:Ce with uniform size of 40 nm was obtained after calcined at 1000 °C for 2 h. The excitation spectrum shows two bands localized at 350 and 450 nm due to transitions from the 4f ground state to the excited 5d band. Both the photoluminescence excited by UV and the radioluminescence excited by X-ray show the same two emission bands, corresponding to transitions from the lowest 5d excited state (²D) to the 4f ground state of Ce³⁺ (²F_5/2,²F_7/2).     

Ultrasound-assisted green synthesis of Ru supported on LDH-CNT composites as an efficient catalyst for N-ethylcarbazole hydrogenation

N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NEC/12H-NEC) is one of the most attractive LOHCs, and it is of great significance to develop catalysts with high activity and reduce the hydrogen storage temperature. Layered double hydroxides-carbon nanotubes composites (LDH-CNT) were synthesized by a simple in-situ assembly method. Due to the introduction of CNT, a strong interaction occurred between LDH and CNT, which effectively improved the electron transfer ability of LDH-CNT. Ru/LDH-CNT catalysts were prepared via ultrasound-assisted reduction method without adding reducing agents and stabilizers. Under the cavitation effect of ultrasound, the hydroxyl groups on the surface of LDH were excited to generate hydrogen radicals (•H) with high reducibility, which successfully reduced Ru³⁺ to Ru NPs. Ru/LDH-3.9CNT-(300-1) catalyst was of 1.63 nm average Ru particle size with CNT amount of 3.9 wt% and the ultrasonic power of 300 W at 1 h, and its electron transfer resistance was less than that of Ru/LDH-(300-1). The synergy of ultrafine Ru NPs and fast electron transfer made it exhibit exceptional catalytic performance in NEC hydrogenation. Even if the reaction temperature was lowered to 80 °C, its hydrogenation performance was better than that of commercial Ru/Al₂O₃ catalyst at 120 °C. The ultrasound-assisted method is efficient, green and environmentally friendly, and the operation process is simple and economical. It is expected to be used in practical industrial production, which provides a reference for the preparation of high-activity and low-temperature hydrogen storage catalysts.     

Synthesis and characterization of nanoparticulate films for intermediate temperature solid oxide fuel cells

Nanocrystalline strontium-doped lanthanum manganite (LSM) with a high specific surface area of 70 m²/g was synthesized via spray pyrolysis. The as prepared powder was characterized by ex-situ X-ray diffraction (XRD), in-situ high temperature X-ray diffraction (HTXRD), ex-situ nitrogen adsorption and high resolution scanning electron microscopy (HRSEM). LSM nanopowders with a mean particle size of 40 nm were dispersed in water-based media using ultrasonication. Nanocomposite LSM-GDC (gadolinium doped ceria) thin films were prepared by single step spin coating of co-stabilized LSM and GDC dispersions. The thickness of these thin films (≤ 1 μm) is more than 10 times lower than conventional cathode layers prepared by screen printing. The interfacial polarization resistances were 68, 118 and 220 mΩ cm² at 850, 800 and 750 °C, respectively. The high performance is attributed to small grain size, high porosity and large specific surface area. This method offers a very cost effective approach for the preparation of electrochemically highly active porous thin films, particularly applicable for micro solid oxide fuel cells.     

Hydrothermal preparation and photoluminescent properties of MgAl2O4: Eu spinel nanocrystals

Nanoplates of the MgAl₂O₄ spinel doped with Eu³⁺ ions were prepared by a microwave assisted hydrothermal method. Structural properties of the precursor calcined at 700 and 1000 ^oC powders were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to the obtained XRD patterns the formation of single-phase spinels after calcination was confirmed. The average spinel particle size was determined to be 11 nm after calcination at 700 °C and it increased up to 14 nm after calcination at 1000 °C. The photoluminescent properties of prepared powders with different Eu³⁺ ion concentrations (0-5% mol) were investigated using excitation and emission spectroscopy at room and low temperatures (77 K).