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1.
通过水热合成了一种有机-无机杂化化合物[Ni4(3-Hpt)6(H2O)10Mo8O26]·Mo8O26·10H2O(3-Hpt=5-(3-吡啶基)-四唑),IR和X-射线单晶衍射实验测定和结构解析结果表明,该化合物是由双支撑形结构的[Ni4(3-Hpt)6(H2O)10Mo8O26]阳离子,β构型[Mo8O26]簇阴离子及晶格水组成的。在阳离子中,β构型[Mo8O26]簇通过中心对称的2个端基氧与2个双核配阳离子[Ni2(3-Hpt)3(H2O)5]4+的镍原子配位形成双支撑形结构。将所得化合物制成碳糊电极(1-CPE),该电极在酸性水溶液中对亚硝酸根,溴酸根的还原有较好的催化活性。  相似文献   

2.
以生物质废弃物桔子皮为原料, 直接氨化后得到OW-NH2生物吸附剂, OW-NH2对Mo(Ⅵ)的吸附具有很高的选择性, 对其他共存离子Re(Ⅶ)、Pb(Ⅱ)、Fe(Ⅲ)、Zn(Ⅱ)、Mn(Ⅶ)、Ca(Ⅱ)和Cu(Ⅱ)基本不吸附, 尤其是对Mo(Ⅵ)、Re(Ⅶ)的分离具有高选择性。红外光谱分析表明阴离子形式的H3Mo7O243-、H2Mo7O244-、HMo7O245-、Mo8O264-、Mo7O246- 和MoO42-与引入在纤维素上的RNH3+发生离子缔合反应。OW-NH2吸附Mo(Ⅵ)的过程符合Langmiur吸附模型, 最大吸附量为1.71 mol·kg-1。另外, OW-NH2对工业实际料液的动态模拟实验的结果表明Mo(Ⅵ)回收率可达99%以上。  相似文献   

3.
通过高温固相法对醋酸镧(C6H9O6La·xH2O)与高钼酸铵((NH46Mo7O24·4H2O)在一定条件下热解制备非Pt催化剂La2Mo2O7(La2O3-2MoO2)。进一步采用2种方法将La2Mo2O7与多壁碳纳米管(MWCNTs)进行复合,一种是将La2Mo2O7喷涂到MWCNTs表层之上得到La2Mo2O7/MWCNTs,另一种是将两者均匀混合掺杂得到La2Mo2O7@MWCNTs,再将上述2种复合材料应用于染料敏化太阳能电池对电极进行相应研究。通过扫描电子显微镜(SEM)表征了复合催化材料的微观形貌,X射线衍射(XRD)确定了微观结构。采用电流密度-光电压曲线、循环伏安,交流阻抗以及塔菲尔极化分析了材料的光电性能。实验结果表明在电解液I3-/I-中,基于La2Mo2O7/MWCNTs与La2Mo2O7@MWCNTs的对电极,相同的条件下在光电池中获得的光电转换效率分别为6.09%和4.84%,明显高于MWCNTs的3.94%和La2Mo2O7的0.87%。电极性能的提高可归因于La2Mo2O7复合催化剂相对大的比表面积和高导电性。  相似文献   

4.
通过高温固相法对醋酸镧(C6H9O6La·xH2O)与高钼酸铵((NH46Mo7O24·4H2O)在一定条件下热解制备非Pt催化剂La2Mo2O7(La2O3-2MoO2)。进一步采用2种方法将La2Mo2O7与多壁碳纳米管(MWCNTs)进行复合,一种是将La2Mo2O7喷涂到MWCNTs表层之上得到La2Mo2O7/MWCNTs,另一种是将两者均匀混合掺杂得到La2Mo2O7@MWCNTs,再将上述2种复合材料应用于染料敏化太阳能电池对电极进行相应研究。通过扫描电子显微镜(SEM)表征了复合催化材料的微观形貌,X射线衍射(XRD)确定了微观结构。采用电流密度-光电压曲线、循环伏安,交流阻抗以及塔菲尔极化分析了材料的光电性能。实验结果表明在电解液I3-/I-中,基于La2Mo2O7/MWCNTs与La2Mo2O7@MWCNTs的对电极,相同的条件下在光电池中获得的光电转换效率分别为6.09%和4.84%,明显高于MWCNTs的3.94%和La2Mo2O7的0.87%。电极性能的提高可归因于La2Mo2O7复合催化剂相对大的比表面积和高导电性。  相似文献   

5.
刘霞  赵军  冯长根 《化学学报》2006,64(19):1988-1992
合成了(C6H9N2O2S)5HP2Mo18O62•15H2O (SPOM-1)和(C6H9N2O2S)H8P2Mo15V3O62•8H2O (SPOM-2)两种新的含有磺胺的多金属氧酸盐, 通过元素分析、IR光谱对其结构进行了表征. 在人雄激素非依赖性前列腺癌细胞系PC-3M内, 对合成的多金属氧酸盐进行了抗肿瘤活性的研究. 研究发现, SPOM-1, SPOM-2在体外能明显抑制前列腺癌PC-3M细胞, 并呈一定的量效关系, EC50分别为38, 11 g•mL-1; 治疗指数(TI)分别为12.07, 26.82; SPOM-2的抗前列腺癌PC-3M细胞活性大于SPOM-1.  相似文献   

6.
采用分步浸渍法制备负载型Ru-Fe3O4/γ-Al2O3 催化剂, 并利用透射电子显微镜(TEM)、X 射线衍射(XRD)、N2吸附-脱附(BET)、傅里叶变换红外(FTIR)光谱与X射线光电子能谱(XPS)表征催化剂的纳米颗粒粒径分布、晶相组成、表面结构及吸附物种等性质. 将Ru-Fe3O4/γ-Al2O3催化剂用于3,4-二氯硝基苯选择性原位液相加氢反应, 考察了反应条件对催化活性的影响, 并讨论了不同制备条件下催化剂的稳定性能. 结果表明, 在473 K、液压3 MPa、原料质量分数2%, 乙醇/水体积比75:25 的反应条件下, 3,4-二氯硝基苯的转化率为100%, 3,4-二氯苯胺的选择性高达96.4%. Fe3O4含量对催化剂稳定性能有显著影响, 当Ru和Fe 的质量分数分别为2%和6%时, 催化剂可稳定200 h以上. 表面吸附CO与积碳是导致催化剂失活的主要原因, 以Fe3O4作为高效的助剂, 进行水汽转换(WGS)反应与费托合成(FTS)可移除CO, 而采用煅烧法去除表面积碳. 晶相变化与纳米颗粒的聚集可能导致催化剂部分失活, 其原因以及再生方法需进一步考察.  相似文献   

7.
以二苯并18-冠-6,3-氟-4-甲基苯铵盐以及多金属氧酸盐[Mo6O19]2-为原料,使用溶剂挥发法合成了有机无机杂化材料[(3-F-4-MeAnis)(DB[18]crown-6)]2[Mo6O19]·2CH3CN (1)(3-F-4-MeAnis=3-氟-4-甲基苯铵盐;DB[18]crown-6=二苯并18-冠-6);以18-冠-6,2-氟-4-甲基苯铵盐以及多金属氧酸盐[SMo12O40]2-为原料,运用H管扩散法制备了晶体材料[(2-F-4-MeAnis)([18]crown-6)]2[SMo12O40]·2CH3CN (2)(2-F-4-MeAnis=2-氟-4-甲基苯铵盐;[18]crown-6=18-冠-6)。通过红外光谱、元素分析、热重分析和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体12通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。在晶体12中,超分子阳离子和多酸阴离子交错堆积形成包合物结构,沿着a轴方向观察,发现每个多酸阴离子被6个超分子阳离子包围着形成六边形堆积结构。通过晶体结构研究和热重分析表明,二苯并18-冠-6中的苯环在维持晶体1的稳定性方面具有重要的作用。  相似文献   

8.
在水热条件下,制备了2个基于多金属氧酸盐(POM)的Cu和Cu新型杂化配合物材料,即[Cu2(4-NH2-trz)4(Mo8O26)(H2O)4]·5H2O(1)和[Cu4(4-NH2-trz)4Mo8O26](2)(4-NH2-trz=4-氨基-1,2,4-三唑)。通过单晶X射线衍射、傅里叶变换红外光谱和粉末X射线衍射分析确定了它们的结构。在配合物1中,4-氨基-1,2,4-三唑双齿配体连接2个相邻的Cu中心形成双核结构单元,这些双核结构单元进一步通过Mo8O264-连接形成一维(1D)的杂化配位结构。在配合物2中,4-氨基-1,2,4-三唑双齿配体连接相邻Cu中心构筑了独特的[Cu4(4-NH2-trz)4]n一维螺旋链,这些左手和右手的一维螺旋链再通过(β-Mo8O264-连接形成2D杂化骨架。光催化实验研究表明,样品1和样品2对于不同有机染料(亚甲基蓝(MB)、罗丹明B(RhB)和甲基橙(MO))具有很好的光催化降解能力。  相似文献   

9.
在水热条件下,制备了2个基于多金属氧酸盐(POM)的Cu和Cu新型杂化配合物材料,即[Cu2(4-NH2-trz)4(Mo8O26)(H2O)4]·5H2O(1)和[Cu4(4-NH2-trz)4Mo8O26](2)(4-NH2-trz=4-氨基-1,2,4-三唑)。通过单晶X射线衍射、傅里叶变换红外光谱和粉末X射线衍射分析确定了它们的结构。在配合物1中,4-氨基-1,2,4-三唑双齿配体连接2个相邻的Cu中心形成双核结构单元,这些双核结构单元进一步通过Mo8O264-连接形成一维(1D)的杂化配位结构。在配合物2中,4-氨基-1,2,4-三唑双齿配体连接相邻Cu中心构筑了独特的[Cu4(4-NH2-trz)4]n一维螺旋链,这些左手和右手的一维螺旋链再通过(β-Mo8O264-连接形成2D杂化骨架。光催化实验研究表明,样品1和样品2对于不同有机染料(亚甲基蓝(MB)、罗丹明B(RhB)和甲基橙(MO))具有很好的光催化降解能力。  相似文献   

10.
以二苯并18-冠-6,3-氟-4-甲基苯铵盐以及多金属氧酸盐[Mo6O19]2-为原料,使用溶剂挥发法合成了有机无机杂化材料[(3-F-4-MeAnis)(DB[18]crown-6)]2[Mo6O19]·2CH3CN (1)(3-F-4-MeAnis=3-氟-4-甲基苯铵盐;DB[18]crown-6=二苯并18-冠-6);以18-冠-6,2-氟-4-甲基苯铵盐以及多金属氧酸盐[SMo12O40]2-为原料,运用H管扩散法制备了晶体材料[(2-F-4-MeAnis)([18]crown-6)]2[SMo12O40]·2CH3CN (2)(2-F-4-MeAnis=2-氟-4-甲基苯铵盐;[18]crown-6=18-冠-6)。通过红外光谱、元素分析、热重分析和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体12通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。在晶体12中,超分子阳离子和多酸阴离子交错堆积形成包合物结构,沿着a轴方向观察,发现每个多酸阴离子被6个超分子阳离子包围着形成六边形堆积结构。通过晶体结构研究和热重分析表明,二苯并18-冠-6中的苯环在维持晶体1的稳定性方面具有重要的作用。  相似文献   

11.
咪唑类高铼酸盐催化微晶纤维素降解反应研究   总被引:2,自引:0,他引:2  
以咪唑类高铼酸盐为催化剂,以离子液体1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)为溶剂降解微晶纤维素(MCC)。分别考察反应温度、反应时间、反应物浓度、催化剂用量和结构对纤维素降解反应的影响。结果表明,以5%1-(3-磺酸)丙基-3-甲基咪唑高铼酸盐([mim-(CH_2)_3SO_3H]ReO_4)为催化剂,在微波辅助加热条件下,0.1 g纤维素在2.0 g离子液体[Amim]Cl中于160℃降解30 min,还原糖收率(TRS)和葡萄糖收率最高可达89.6%和46.7%。研究还对咪唑类高铼酸催化纤维素降解反应的催化机理进行讨论,认为催化剂芳环阳离子、ReO-4中Re=O与纤维素分子中羟基的相互作用是促进纤维素降解的关键  相似文献   

12.
Acidic carbonaceous solids were synthesized from mass pine alkali lignin via hydrothermal carbonization followed by sulfonation. Hydrothermal carbonization of lignin in the presence of acrylic acid (LAHC-SO3H) provided many more carboxylic groups than that in the absence of acrylic acid, allowing subsequent sulfonation to produce a highly active and stable catalyst for cellulose hydrolysis in the [BMIM]Cl-H2O solvent system. The hydrochar and catalyst were characterized using field emission scanning electron microscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, thermal gravimetric analysis, Fourier transform infrared spectrometer, Brunauer–Emmett–Teller and acid–base titration. Results showed that a high acid content of 5.48 mmol/g, including carboxylic group (2.85 mmol/g), phenolic hydroxyl group (1.05 mmol/g) and sulfonic acid group (1.58 mmol/g), contributed significantly to the highly efficient hydrolysis of cellulose. Further, it was found that addition of trace water in [BMIM]Cl was favorable to cellulose hydrolysis. The highest yield (75.4%) of total reducing sugar (TRS) obtained in [BMIM]Cl-H2O at a mass ratio of 100:1 was more than twice that (36.1%) achieved in [BMIM]Cl without water; the corresponding reaction conditions were 50 mg of microcrystalline cellulose, 30 mg of catalyst, 1.0 g of [BMIM]Cl, 10 mg of H2O, reaction temperature of 130 °C and reaction time of 2 h. Furthermore, the TRS yield with 5 cycles for LAHC-SO3H was higher than 68.1%, and the catalytic activity of catalyst could be fully recovered (74.0% of TRS yield) easily by regeneration.  相似文献   

13.
Transparent thin film polymer electrolytes were prepared by solvent casting technique with the doping of environmental-friendly ionic liquid, 1-allyl-3-methylimidazolium chloride ([Amim] Cl) into the matrix formed by cellulose acetate (CA) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The ionic conducting nature of this system improves significantly from the order of 10?7–10?2 S cm?1 upon increasing doping of [Amim] Cl content till a maximum of 4.68 × 10?2 S cm?1 is attained for the composition CA:LiTFSI:[Amim] Cl (14:6:80 wt%). The improving trend in ionic conductivity results from the bond weakening between the connecting atoms in the crystalline region that induces to the increase in amorphous counterpart fractions in the CA matrix. This observation was proved via the accountancies in the reduction of relative viscosity, root mean square value and increase in void as increase in [Amim] Cl doping. The resultant phase conversion hence permits immense lithium ion (Li+) fluidity along the polymer backbone and assisting the improvement in ionic conductivity. The thin film polymer electrolyte is found to be elastic in the presence of crystalline fraction and radically deforms upon the chains diffusion into the amorphous fraction. The linear curvatures of the Arrhenius plot justify the conductivity improvement as via the increasing frequency of Li+ ions hopping as the temperature increases. The increasing addition of [Amim] Cl diminishes both the heat-resistivity and thermal stability of CA:LiTFSI:[Amim] Cl matrix.  相似文献   

14.
In recent years, great progress has been made in the dissolution of cellulose with ionic liquids (ILs). However, the mechanism of cellulose dissolution, especially the role the IL cation played in the dissolution process, has not been clearly understood. Herein, the mixtures of cellulose with a series of imidazolium‐based chloride ionic liquids and 1‐butyl‐3‐methyl pyridinium chloride ([C4mpy]Cl) were simulated to study the effect that varying the heterocyclic structure and alkyl chain length of the IL cation has on the dissolution of cellulose. It was shown that the dissolution of cellulose in [C4mpy]Cl is better than that in [C4mim]Cl. For imidazolium‐based ILs, the shorter the alkyl chain is, the higher the solubility will be. In addition, an all‐atom force field for 1‐allyl‐3‐methyl imidazolium cation ([Amim]+) was developed, for the first time, to investigate the effect the electron‐withdrawing group within the alkyl chain of the IL cation has on the dissolution of cellulose. It was found that the interaction energy between [Amim]+ and cellulose was greater than that between [C3mim]+ and cellulose, indicating that the presence of electron‐withdrawing group in alkyl chain of the cation enhanced the interaction between the cation and cellulose due to the increase of electronegativity of the cations. These findings are used to assess the cationic effect on the dissolution of cellulose in ILs. They are also expected to be important for rational design of novel ILs for efficient dissolution of cellulose.  相似文献   

15.
Levulinic acid (LA) is an industrially important product that can be catalytically valorized into important value-added chemicals. In this study, hydrothermal conversion of glucose into levulinic acid was attempted using Brønsted acidic ionic liquid catalyst synthesized using 2-phenyl-2-imidazoline, and 2-phenyl-2-imidazoline-based ionic liquid catalyst used in this study was synthesized in the laboratory using different anions (NO3, H2PO4, and Cl) and characterized using 1H NMR, TGA, and FT-IR spectroscopic techniques. The activity trend of the Brønsted acidic ionic liquid catalysts synthesized in the laboratory was found in the following order: [C4SO3HPhim][Cl] > [C4SO3HPhim][NO3] > [C4SO3HPhim][H2PO4]. A maximum 63% yield of the levulinic acid was obtained with 98% glucose conversion at 180 °C and 3 h reaction time using [C4SO3HPhim][Cl] ionic liquid catalyst. The effect of different reaction conditions such as reaction time, temperature, ionic liquid catalyst structures, catalyst amount, and solvents on the LA yield were investigated. Reusability of [C4SO3HPhim][Cl] catalyst up to four cycles was observed. This study demonstrates the potential of the 2-phenyl-2-imidazoline-based ionic liquid for the conversion of glucose into the important platform chemical levulinic acid.  相似文献   

16.
An innovative soft chemical approach was applied, using ionic liquids as an alternative reaction medium for the synthesis of tellurium polycationic cluster compounds at room temperature. [Mo2Te12]I6, Te6[WOCl4]2, and Te4[AlCl4]2 were isolated from the ionic liquid [BMIM]Cl/AlCl3 ([BMIM]+: 1‐n‐butyl‐3‐methylimidazolium) and characterized. Black, cube‐shaped crystals of [Mo2Te12]I6, which is not accessible by conventional chemical transport reaction, were obtained by reaction of the elements at room temperature in [BMIM]Cl/AlCl3. The monoclinic structure (P21/n, a = 1138.92(2) pm, b = 1628.13(2) pm, c = 1611.05(2) pm, β = 105.88(1) °) is homeotypic to the triclinic bromide [Mo2Te12]Br6. In the binulear complex [Mo2Te12]6+, the molybdenum(III) atoms are η4‐coordinated by terminal Te42+ rings and two bridging η2‐Te22– dumbbells. Despite the short Mo···Mo distance of 297.16(5) pm, coupling of the magnetic moments is not observed. The paramagnetic moment of 3.53 μB per molybdenum(III) atom corresponds to an electron count of seventeen. Black crystals of monoclinic Te6[WOCl4]2 are obtained by the oxidation of tellurium with WOCl4 in [BMIM]Cl/AlCl3. Tellurium and tellurium(IV) synproportionate in the ionic liquid at room temperature yielding violet crystals of orthorhombic Te4[AlCl4]2.  相似文献   

17.
刘艳梅  应敏  杨志杰  乐长高 《有机化学》2006,26(9):1286-1290
以[Bmim]Cl/FeCl3(三氯化铁/氯化丁基甲基咪唑)离子液体作为反应介质和催化剂, 考察了离子液体的酸度、反应温度及反应时间对α-生育酚与β-D-五乙酰吡喃型葡萄糖糖基化反应的影响. 结果表明, 离子液体的催化活性与其酸强度密切相关, 离子液体的酸性越强, 其对此糖基化反应催化活性越高. 在FeCl3与[Bmim]Cl物质的量比为2的[Bmim]Cl/FeCl3离子液中, α-生育酚与β-D-五乙酰吡喃型葡萄糖在45 ℃下反应3 h, 可以得到较高的转化率, α-生育酚的转化率最高可达70.2%. 同有机溶剂作为反应介质相比, 反应条件温和, 反应时间短, 室温离子液体具有更好的催化活性, 所得产物与离子液体不溶, 便于分离, 催化体系可循环使用, 且对环境友好.  相似文献   

18.
In this report, 1-butyl-3-methylimidazolium chloride ([C4C1im]Cl) is demonstrated to enhance the kinetics of acid-catalysed hydrolysis of 1,4-β-glucans in binary solvent mixtures. [C4C1im]Cl plays other roles in the reaction beyond acting as a solvent for cellulose, as currently accepted. In fact, the presence of the IL increases the Hammett acidity of the catalyst dissolved in the reaction medium. The kinetic data from cellobiose and cellulose hydrolysis directly correlate with the acid strength found for p-toluenesulfonic acid in the different reaction media studied here. The current report identifies neglected, but yet very important phenomena occurring in cellulose depolymerisation.  相似文献   

19.
Developing efficient and robust hydrogen evolution reaction (HER) catalysts for scalable and sustainable hydrogen production through electrochemical water splitting is strategic and challenging. Herein, heterogeneous Mo8O26-NbNxOy supported on N-doped graphene (defined as Mo8O26-NbNxOy/NG) is synthesized by controllable hydrothermal reaction and nitridation process. The O-exposed Mo8O26 clusters covalently confined on NbNxOy nanodomains provide a distinctive interface configuration and appropriate electronic structure, where fully exposed multiple active sites give excellent HER performance beyond commercial Pt/C catalyst in pH-universal electrolytes. Theoretical studies reveal that the Mo8O26-NbNxOy interface with electronic reconstruction affords near-optimal hydrogen adsorption energy and enhanced initial H2O adsorption. Furthermore, the terminal O atoms in Mo8O26 clusters cooperate with Nb atoms to promote the initial H2O adsorption, and subsequently reduce the H2O dissociation energy, accelerating the entire HER kinetics.  相似文献   

20.
The chemical effects of98Mo(n, )99 Mo reaction on molybdenum(II) chloride [(Mo6Cl8)Cl4] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical application in the enrichment of99Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo6Cl8)Cl4] appears to offer good prospects.  相似文献   

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