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1.
The reaction between transition metal alkoxides and benzyl alcohol provides a novel soft chemistry route to metal oxide nanoparticles. The method allows the preparation of nanocrystals of two important transition metal oxides, namely V2O3 and Nb2O5. Although the reaction temperatures of 200–220 °C are comparably low, the obtained particles are highly crystalline. According to TEM investigations, the V2O3 crystals exhibit particle sizes between 20 and 50 nm, and the Nb2O5 crystals display platelet-like particle shapes with sizes of 50–80 nm, without any indications of amorphous character.  相似文献   

2.
The hetro-structured oxide thin films from metal fluorocomplex solution have been prepared by the liquid phase deposition (LPD) method. The Pt/Nb2O5 and Au/Nb2O5 composite films can be prepared from a mixed solution of niobium source, H3BO3, Pt(NH3)4Cl2 and HAuCl4 aqueous solutions under the ambient temperature and atmosphere. In the case of Au/SiO2 composite film, (NH4)2SiF6 solution is used as a mother solution. The Pt and Au ionic species are deposited in Nb2O5 and SiO2 matrices. They are reduced to their metallic state after treatment above 200 °C. The size of dispersed particles can be controlled by heat treatment temperature. It is also clear that, gold nanoparticles are also found to interact with SiO2, although the interaction is smaller than that with Nb2O5 showing the size of Au nanoparticles remain smaller in Nb2O5 that in SiO2.  相似文献   

3.
化学工业生产中,用氢气为还原剂,通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物,而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径,但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb2O5(PVP: 聚乙烯吡咯烷酮)催化剂,该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应,系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能,在最优条件下,5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。  相似文献   

4.
Selective hydrogenation is a vital class of reaction. Various unsaturated functional groups in organic compounds, such as aromatic rings, alkynyl (C≡C), carbonyl (C=O), nitro (-NO2), and alkenyl (C=C) groups, are typical targets in selective hydrogenation. Therefore, selectivity is a key indicator of the efficiency of a designed hydrogenation reaction. 5-(Hydroxymethyl)furfural (HMF) is an important platform compound in the context of biomass conversion, and recently, the hydrogenation of HMF to produce fuels and other valuable chemicals has received significant attention. Controlling the selectivity of HMF hydrogenation is paramount because of the different reducible functional groups (C=O, C-OH, and C=C) in HMF. Moreover, the exploration of new routes for hydrogenating HMF to valuable chemicals is becoming attractive. 5-Methylfurfural (MF) is also an important organic compound; thus, the selective hydrogenation of HMF to MF is an essential synthetic route. However, this reaction has challenging thermodynamic and kinetic aspects, making it difficult to realize. Herein, we propose a strategy to design a highly efficient catalytic system for selective hydrogenation by exploiting the synergy between steric hindrance and hydrogen spillover. The design and preparation of the Pt@PVP/Nb2O5 catalyst (PVP = polyvinyl pyrrolidone; Nb2O5 = niobium(V) oxide) were also conducted. Surprisingly, HMF could be converted to MF with 92% selectivity at 100% HMF conversion. The reaction pathway was revealed through the combination of control experiments and density functional theory calculations. Although PVP blocked HMF from accessing the surface of Pt, hydrogen (H2) could be activated on the surface of Pt due to its small molecular size, and the activated H2 could migrate to the surface of Nb2O5 through a phenomenon called H2 spillover. The Lewis acidic surface of Nb2O5 could not adsorb the C=O group but could adsorb and activate the C-OH group of HMF; therefore, when HMF was adsorbed on Nb2O5, the C-OH groups were hydrogenated by the spilled over H2 to form MF. The high selectivity of this reaction was realized because of the unique combination of steric effects, hydrogen spillover, and tuning of the electronic states of the Pt and Nb2O5 surfaces. This new route for producing MF has great potential for practical application owing to its discovered advantages. We believe that this novel strategy can be used to design catalysts for other selective hydrogenation reactions. Furthermore, this study demonstrates a significant breakthrough in selective hydrogenation, which will be of interest to researchers working on the utilization of biomass, organic synthesis, catalysis, and other related fields.   相似文献   

5.
Herein, the nano-sized niobium pentoxide (Nb2O5) with different morphologies and phase structures are synthesized through a very simple thermal treatment method, including the pseudohexagonal Nb2O5 nanosheets and pseudohexagonal Nb2O5 nanoparticles, orthorhombic Nb2O5 nanoparticles. The synthesized pseudohexagonal Nb2O5 nanosheets and orthorhombic Nb2O5 nanoparticles exhibit better cycling and rate performance than the pseudohexagonal Nb2O5 nanoparticles due to the different morphologies and phase structures.  相似文献   

6.
C-doped Nb2O5 with abundant mesopores has been successfully synthesized through a facile solvothermal synthetic strategy followed by calcination treatment. The resulting C-doped Nb2O5 displayed the highest BET surface area(345 m2/g) and large mesopore size(ca. 4.2 nm), capable of offering more accessible active sites as well as faster mass transfer for catalysis. Besides, the doping of C(2.21%, molar fraction) at the O sites in Nb2O5 lattice greatly enhanced visible-light response by lowering the band gap, thereby making the material a photocatalyst under visible-light irradiation. Typically, the C-doped Nb2O5 exhibited a high H2 evolution rate of ca. 39.10 μmol·g-1·h-1 and also degraded RhB dye completely after 30 min of visible light exposure, which turned out to be much better than Degussa P25 and pure Nb2O5 catalysts.  相似文献   

7.
After Nb2O5 was added to Y2O3-stabilized ZrO2, the bulk conductivity decreased distinctly. Positron annihilation lifetime and Doppler broadening spectra were measured to study the effects of Nb2O5 on electrical properties of Y2O3-stabilized ZrO2. The result shows that the additions of Nb2O5 can decrease the V2+O concentration and increase the (YZrV2+OYZr)0 concentration, which is why bulk conductivity decreases. The additions of Nb2O5 were expected to suppress the formation of defect associates, however, only adverse experimental results were found in the present work.  相似文献   

8.
Nb2O5/C nanosheets are successfully prepared through a mixing process and followed by heating treatment.Such Nb2O5/C based electrode exhibits high rate performance and remarkable cycling ability, showing a high and stable specific capacity of ~380 mAh g-1 at the current density of 50 mA g-1(much higher than the theoretical capacity of Nb2O5).Further more,at a current density of 500 mA g-1,the nanocomposites electrode still exhibits a specific capacity of above 150 mAh g-1 after 100 cycles.These results suggest the Nb2O5/C nanocomposite is a high performance anode material for lithium-ion batteries.  相似文献   

9.
CO加H2合成甲醇的工作已应用于工业化生产,其中多采用锌、铬、铜基催化剂。而CO2加H2合成甲醇研究工作尚不很多,其催化剂多数是在CO/H2制甲醇催化剂基础上发展而来。  相似文献   

10.
通过电化学的方法将CO2转化为CO是解决资源和环境问题的经济友好的策略。在本次工作中,利用湿化学方法制备了铌/碳的前驱体,在NH3和Ar氛围下煅烧后分别转化为Nb4N5/C和Nb2O5/C。当氮化温度达到700℃时,制备的Nb4N5/C表现出优异的催化活性,在CO2饱和的0.5 mol·L-1的NaCl溶液中,电解电位为-0.83V(RHE)时,CO的法拉第效率最高,达到57%。实验结果表明,Nb4N5/C的催化活性与Nb4N5中的N掺杂有关。  相似文献   

11.
Gas diffusion electrodes for electrochemical reduction of carbon dioxide were prepared and their electrocatalylic activities were investigated using KOH aqueous solution as an electrolyte. Various metal oxides such as ZnO, ZrO2, TiO2,Al2O3, Nb2O5 were used as the support for Cu catalyst. The current density was amounted to 500 mA/cm2, and reduction products significantly changed depending on the metal oxide supports.  相似文献   

12.
合成了一系列氨基醇杂多酸类离子液体, 并将其用于催化环酮的Baeyer-Villiger氧化反应. 以2-庚基环戊酮为模板底物, H2O2为氧化剂, 探究了此类氨基醇杂多酸类离子液体的催化活性, 筛选出催化活性最高的催化剂为[Pro-ps]H2PW12O40, 最佳反应条件: n(2-庚基环戊酮)∶n(催化剂)∶n(H2O2)=1∶0.03∶4, 反应温度40 ℃, 反应时间8 h, 无溶剂. 在最佳条件下, 2-庚基环戊酮的转化率为98.19%, 产物δ-十二内酯的选择性可达82.84%. 水相中的离子液体[Pro-ps]H2PW12O40经干燥后可以重复使用. 经过5次循环使用后催化活性未见明显下降. [Pro-ps]H2PW12O40还可用于催化其它多种环酮的Baeyer-Villiger氧化反应, 结果表明, 该催化剂具有良好的重复使用性和底物普适性.  相似文献   

13.
锂离子混合电容器由于兼备锂离子电池和超级电容器的优势,即较高的能量密度和功率密度,而成为当前能量存储体系的研究热点。本工作合成了具有三维花状微纳结构的正交相五氧化二铌(T-Nb_2O_5),并将其与活性炭(AC)相匹配,设计出一种新型的T-Nb_2O_5/AC锂离子混合电容器。循环伏安和恒电流充放电的测试结果表明该锂离子混合电容器具有较好的电化学性能,如在碳酸酯类的有机电解液中,工作电压可达到3.0 V;在100 m A·g~(-1)的电流密度下,电容器的比能量和比功率密度可达到53.79 Wh·kg~(-1)和294 W·kg~(-1);在200 m A·g~(-1)的电流密度下,经过1000次充放电循环后,该电容器的比能量保持率为73%。由此可见,本工作开发的T-Nb_2O_5/AC锂离子混合电容器将在高功率的储能设备中有很好地应用前景。  相似文献   

14.
铌酸锂多晶粉体的水热合成及表征   总被引:3,自引:0,他引:3  
铌酸锂(LiNbO3)晶体由于本身具有的优良性能在许多领域中都获得了广泛的应用.以LiOH·H2O和Nb2O5为原料采用水热合成法成功地合成了铌酸锂多晶粉体,并采用FTIR谱、XRD谱和SEM对产物进行了表征.结果表明,采用水热合成法能够得到结晶完整的四方柱形LiNbO3多晶粉体.同时考察了反应温度、晶化时间和Li源对水热合成产物的影响.  相似文献   

15.
Membrane-like H3PMo12O40 or H5PMo10V2O40-imbedded polymer films were prepared by blending these materials using a chloroform-methanol mixture as solvent, and they were tested as catalysts for the ethanol conversion reaction in a continuous flow fixed-bed reactor. It was found that the chloroform-methanol mixture itself gave no influence on the catalytic activity of bulk H3PMo12O40 and H5PMo10V2O40. Polysulfone, polyethersulfone and polyphenylene oxide were used as blending polymers in this study. H3PMo12O40-imbedded polymer films showed a higher catalytic activity than H3PMo12O40 itself due to uniform and fine dispersion of H3PMo12O40 through polymer films, but the extent of activity and selectivity was varied according to a kind of polymer materials. It was revealed that H3PMo12O40 or H5PMo10V2O40-imbedded polyphenylene oxide film showed much higher oxidation catalytic activity than the corresponding bulk heteropoly acids. This may be due to the interaction (or bonding) of proton of heteropoly acid with polyphenylene oxide, judging from the fact that glass transition temperature of polyphenylene oxide was increased after blending with heteropoly acid. The catalytic activity of the heteropoly acid imbedded in the same polymer was greatly affected by the composite of heteropoly acid. The permeabilities of reactants through polymer films also affected the product selectivity.  相似文献   

16.
以十二磷钨杂多酸(Tungstophosphoric acid,H_3PW_(12)O_(40))为基体,分别通过普通浸渍法、溶胶凝胶法和超声浸渍法进行了La3+改性作用,合成了三种固体酸催化剂A-LaPW_(12)O_(40)、B-LaPW_(12)O_(40)/Si O2和C-LaPW_(12)O_(40)。采用X射线荧光光谱(XRF)、孔径比表面积测定、X射线粉末衍射(XRD)、透射电镜(TEM)、红外光谱(FT-IR)、热重(TG)、N2吸附-脱附、NH3程序升温脱附(NH3-TPD)、吡啶吸附红外光谱(Py-FTIR)、X射线光电子能谱(XPS)等方法对合成的催化剂进行了表征,并比较了以上催化剂在用于催化以油酸和甲醇为反应物经酯化反应合成生物柴油时的活性和稳定性。结果表明,B-LaPW_(12)O_(40)/Si O2具有最高催化活性,当甲醇与油酸的物质的量比为8∶1,催化剂用量为反应物总质量的2%,反应温度为65℃,反应1 h后,油酸的转化率即高达93%。循环使用B-LaPW_(12)O_(40)/Si O2催化剂六次后,油酸的转化率仍高达86.4%。B-LaPW_(12)O_(40)/Si O2的高催化活性和稳定性可归因于在溶胶凝胶的转化过程中,作为硅源材料的四乙氧基硅(TEOS)易在酸性条件下发生水解反应形成Si O2网络,进而Si O2网络中的硅醇键与H_3PW_(12)O_(40)中的H+发生配位作用,生成具有强静电吸附力的(≡Si-OH2+)(H2PW12O-40)络合物。随着该络合物的形成,促进了La3+在Si O2表面的吸附而堵塞了H_3PW_(12)O_(40)的孔道结构,抑制了H_3PW_(12)O_(40)颗粒在焙烧过程中进一步聚集长大。Si O2将作为载体并以干凝胶状态存在于B-LaPW_(12)O_(40)/Si O2催化剂中,由于Si O2凝胶的高比表面积而使B-LaPW_(12)O_(40)/Si O2具有了较大的比表面积,从H_3PW_(12)O_(40)的1.4 m2/g增加至31.3 m2/g。并且,通过吡啶吸附红外光谱确定B-LaPW_(12)O_(40)/Si O2为Br9nsted-Lewis酸型固体酸,由于Br9nsted酸位易与酯化反应过程中生成的水发生水合反应而失活,因而Lewis酸位的形成有助于减少催化剂的失活现象发生。Lewis酸位的出现可归因于(≡Si-OH2+)(H2PW12O-40)与吸附在其表面的具有强吸电子作用的La3+发生键合作用后生成了LaPW_(12)O_(40)/Si O2。  相似文献   

17.
本文采用浸渍涂覆法成功制备出多孔Ti负载纳米Co3O4电催化膜电极(Co3O4/Ti),以该膜电极为阳极,辅助电极为阴极,构建电催化膜反应器(electrocatalytic membrane reactor,ECMR)用于可控催化氧化苯甲醇制备苯甲醛和苯甲酸,并考察了 Co3O4/Ti 膜电极结构、电化学性能以及ECMR不同操作参数对苯甲醇转化率、苯甲醛和苯甲酸选择性的影响. 结果表明,负载Co3O4纳米颗粒可以显著提高Ti膜电极的电化学性能和催化活性. 在常温常压下,当反应物苯甲醇浓度为10 mmol·L-1,pH为7.0,停留时间为5.0 min,电流密度为2.5 mA·cm-2,苯甲醇的转化率达到49.8%,苯甲醛选择性为51.5%,苯甲酸选择性为23.6%.  相似文献   

18.
Gas phase synthesis of methyl tert-butyl ether (MTBE) from methanol and isobutylene has been studied with several heteropolyacids at 303–383 K. It was found that a Dawson-type heteropolyacid, H6P2W18O62, was much active than Keggin-type heteropolyacids, HnXW12O40 (X = P, Si, Ge, B, and Co), and other solid acids such as SO2−4/ZrO2, SiO---Al2O3 and H-ZSM-5 at 323 K. Since the acid strength of H6P2W18O62 was weaker than H3PW12O40 and H4SiW12O40, factors other than the acid strength are important for the catalytic activity. Pseudoliquid phase behavior was demonstrated for H6P2W18O62 and H3PW12O40 by the measurements of the absorption of methanol during the reaction and by the unique pressure dependencies of the rate of synthesis. From the absorption data (the amount and rate), it is concluded that the high catalytic activity of H6P2W18O62 is brought about by a high-activity state of the pseudoliquid phase in which controlled amounts of molecule are absorbed and the absorption-desorption is rapid. On the other hand, the pseudoliquid phase of H3PW12O40 is in a low-activity state absorbing excessive amounts of molecule.  相似文献   

19.
负载Pt催化生物柴油加氢脱氧性能研究   总被引:1,自引:0,他引:1  
采用XRD、BET、SEM、NH_3-TPD对Pt/Al_2O_3、Pt/Al_2O_3-ZSM-5、Pt/ZSM-5催化剂进行表征,在不同反应工艺条件下考察三种分子筛的酸性、孔径分布、外部形貌、晶体结构对其加氢脱氧性能的影响。结果表明,Br■nsted酸性位点和中孔体积占比对脂肪酸甲酯的加氢脱氧反应来说至关重要,其中,Br■nsted酸性位点在脱氧反应中的C-O键断裂发挥主要作用,中孔孔径则能提高整个反应的质量传递效率以及避免C_(12-18)长链烷烃发生裂解。三种催化剂的加氢脱氧催化效果大小为:Pt/Al_2O_3-ZSM-5Pt/Al_2O_3Pt/ZSM-5;适宜的反应工艺条件为:t=350℃,p=2 M Pa,H2/oil=1000,WHSV=0.5 h~(-1),在此条件下Pt/Al_2O_3-ZSM-5的脂肪酸甲酯转化率为99.4%,目标产物液体收率为86.8%。  相似文献   

20.
Since H2O2 decomposition can result in selectivity/yield loss in the direct H2O2 synthesis process from H2 and O2 over supported Pd catalysts, it is important to have an enhanced understanding about the factors affecting the H2O2 decomposition reaction. Herein, detailed studies have been undertaken to investigate the influence of different factors, such as (a) nature and concentration of acid in reaction medium, (b) nature and concentration of halide in presence and absence of acid in reaction medium, (c) pretreatment procedures and (d) catalyst modification by incorporation of different halides, on the H2O2 decomposition reaction over a 5% Pd/C catalyst in aqueous medium at 25 °C. This study has shown that the H2O2 decomposition activity is profoundly influenced by all the above factors. The effectiveness of the acids in suppressing the H2O2 decomposition activity decreased in the following order: hydroiodic acid > hydrobromic acid > hydrochloric acid  acetic acid > phosphoric acid > sulfuric acid > perchloric acid. The ability of the acid to decrease the H2O2 decomposition activity was found to very strongly depend on the nature of its associated anion. Halides, such as iodide, bromide and chloride were particularly effective in suppressing the H2O2 decomposition activity. Oxidation pretreatment of the catalyst was found to strongly suppress its H2O2 decomposition activity, while a reduction treatment was found to promote its activity. A gradual decrease in the H2O2 decomposition activity of the catalyst was observed with each successive usage due to in situ sub-surface oxidation of Pd by H2O2. Halide incorporation either via the reaction medium or prior catalyst modification had a similar qualitative effect on the H2O2 decomposition activity.  相似文献   

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