不同实验条件下Cu3(BTC)2的制备及表征

以硝酸铜Cu(NO3)2为铜源,1,3,5-苯三甲酸为有机配体,采用溶剂热法合成了金属有机骨架Cu3(BTC)2(即HKUST-1),通过调节水热温度、原料配比、反应助剂等在不同条件下制备了目标化合物.进一步借助X射线衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱仪(FTIR)对所制备样品的表面性质及形貌结构...     

以介孔TiO_2膜为过渡层在玻璃基底上制备Cu_3(BTC)_2连续膜

通过在玻璃基底上预先制备一层介孔TiO_2膜作为过渡层用于制备完整的Cu_3(BTC)_2(BTC:1,3,5-苯三甲酸)连续膜。场发射(FESEM)图像显示由此制得的Cu_3(BTC)_2膜在TiO_2/玻璃基底上是致密且连续,膜厚度为200 nm左右。相比之下,Cu_3(BTC)_2晶粒在空白玻璃基底上较难成核并生长,不能形成连续膜,而在无孔TiO_2/玻璃基底上,Cu_3(BTC)_2晶粒与在介孔TiO_2/玻璃基底上一样能够形成典型的八面体Cu_3(BTC)_2但不能形成连续膜。由于介孔TiO_2膜过渡层的存在,Cu_3(BTC)_2晶粒可以与基底结合紧密,经30 min超声波测试后,在介孔TiO_2/玻璃基底上的Cu_3(BTC)_2膜仍然能保持连续且完整形貌,而在空白玻璃基底上的Cu_3(BTC)_2晶粒完全脱落。推断介孔TiO_2的表面性质有利于Cu_3(BTC)_2晶粒的成核,而介孔TiO_2膜的多孔结构可以促进Cu_3(BTC)_2晶粒形成连续的薄膜:介孔TiO_2膜过渡层在Cu_3(BTC)_2膜与玻璃基底间扮演了类似桥梁的重要角色。     

H6P2Mo9W9O62/Cu3(BTC)2的制备及催化合成缩醛(酮)

采用浸渍法制得H_6P_2Mo_9W_9O_(62)/Cu_3(BTC)_2,利用傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)、热重分析仪(TG)以及扫描电镜(SEM)表征其组成、结构、热稳定性以及形貌。以H_6P_2Mo_9W_9O_(62)/Cu_3(BTC)_2为催化剂,环己酮和乙二醇合成缩酮的反应为探针,探究出较佳反应条件:环己酮用量为0.2 mol,n(环己酮)∶n(乙二醇)=1∶1.3,催化剂用量占反应物总质量的0.3%,反应时间为60 min,带水剂用量为6 mL。在此条件下,环己酮乙二醇缩酮收率可达83.7%。且以上条件下催化合成苯甲醛乙二醇缩醛、丁酮乙二醇缩酮、丁酮1,2-丙二醇缩酮、苯甲醛1,2-丙二醇缩醛和环己酮1,2-丙二醇缩酮的收率分别为70.1%,66.0%,62.1%,66.3%和75.8%。与分子筛MCM-48负载硅钨酸、活性炭负载对甲苯磺酸和铝交联蒙脱土催化剂相比,H_6P_2Mo_9W_9O_(62)/Cu_3(BTC)_2是一种催化性能较好的催化剂。     

H4GeW12O40/Cu3(BTC)2催化Biginelli反应合成3,4-二氢嘧啶-2(1H)-酮衍生物

采用浸渍法以金属有机骨架Cu_3(BTC)_2负载锗钨酸(H_4GeW_(12)O_(40))制备H4Ge W_(12)O_(40)/Cu_3(BTC)_2催化剂,并用该催化剂催化芳醛、尿素和乙酰乙酸乙酯通过"一锅法"Biginelli缩合反应,以无水乙醇为溶剂,合成6种3,4-二氢嘧啶-2(1H)-酮衍生物;通过熔点的测定,IR,1H NMR和MS等对产物3,4-二氢嘧啶-2(1H)-酮衍生物进行表征。结果表明:在芳醛用量为0.04 mol,n(芳醛)∶n(乙酰乙酸乙酯)∶n(尿素)=1∶1.5∶1.5,催化剂的用量占反应物料总质量的4.0%,反应温度为90℃,反应时间为90 min的条件下,目标产物收率可达63.0%~76.3%。     

电泳沉积法γ-Al2O3微孔膜的制备与表征

采用电泳沉积法制备γ－Al2O3微孔膜，考察了干燥及烧成制度对膜形成的影响，并用IR，XRD，SEM，N2吸附－脱附等测试手段对γ－Al2O3微孔膜进行了表征。结果表明：采用电泳沉积法可成功地制备均匀的γ－Al2O3保护膜；实验中采用室温慢速干燥法，制得了完整的凝胶膜，经过焙烧可获得与基片结合良好的γ－Al2O3多孔膜，在焙烧过程中，γ－AlOOH发生如下的晶型转变：γ－AlOOH→345℃γ－Al2O3，并且随着焙烧温度的升高，γ－Al2O3膜的结晶性得到改善。此外，γ－Al2O3膜的断面结构较疏松，膜厚度大面均匀：一次成膜厚度达十几μm，γ－Al2O3微孔膜的孔径尺寸为纳米级。     

MIL-101(Cr)-NH2与硫化铟锌复合材料的制备及其光催化性能

采用水热法制备得到颗粒状MIL-101(Cr)-NH2,随后用油浴法将ZnIn2S4纳米片原位生长均匀分散在MIL-101(Cr)-NH2表面,成功制得ZnIn2S4/MIL-101(Cr)-NH2光催化材料.通过X射线衍射(XRD),扫描电镜(SEM),固体紫外-可见漫反射光谱(UV-Vis DRS)和傅立叶红外光谱...     

金属有机骨架材料Cu_3(BTC)_2的脱硫行为研究

采用吸附法生产低硫及超低硫燃料油备受各国研究者关注。设计制备了具有脱硫功能的金属有机骨架(MOFs)吸附剂,对其吸附、脱附行为进行了考察,对MOFs的脱硫机理进行了讨论。研究表明,制备的Cu3(BTC)2具有MOFs典型结构,吸附容量随吸附时间而增大,适当高温预处理可以提高其吸附能力,吸附容量可达10.7 mg S/g,具备深度脱硫能力,吸附功能与其三维孔道结构及与硫化物的络合作用有关;再生后,吸附剂的吸附容量有所降低,再生率在90%左右。     

共价有机骨架聚合物功能膜制备方法的研究进展

共价有机骨架聚合物（COFs）是由共价键连接,经热力学可逆聚合形成的有序多孔有机晶态材料,具有比表面积大、孔分布规则可调和可拆剪等特性,其二维或三维COFs功能膜在气体分离、化学传感、催化、药物传输等方面具有广阔的发展前景。COFs膜材料的制备决定膜组成、微规整结构和性能,成为COFs膜功能应用的研究基础和技术关键。本文综述了COFs材料提出以来形成的共混法、原位聚合法、层层堆叠法和界面聚合等制备方法的研究现状,结合各方法优缺点,分析并提出COFs膜制备技术的关键方向和技术要点。为COFs功能膜分子设计、优化和功能化应用提供合理的制备方法,促进高性能COFs功能膜实用化制备方法的形成。     

热处理工艺对制备Al2O3超滤膜的影响

本文以无机盐Al(NO) 3和氨水为原料 ,采用sol-gel法制备出稳定透明的勃姆石溶液 ;采用浸渍法工艺将勃姆石溶胶均匀地涂覆在Al2 O3载体上 ,通过对膜热处理工艺制度的研究 ,探讨了热处理工艺对Al2 O3超滤膜性能的影响。     

电化学沉积制备的Cu(In,Ga)Se_2薄膜性能研究

采用电沉积制备出成分富Cu的Cu(In,Ga)Se2薄膜,将薄膜在Se气氛中退火后采用物理气相法(PVD)沉积少量的In、Ga调整薄膜成分。通过不同测试手段分析了薄膜的成分、表面状况、结晶质量以及制备的太阳电池性能参数。结果表明,硒化后的CIGS薄膜成分贫Cu,表面光滑无裂纹,晶粒尺寸增加,结晶度提高,形成单一的黄铜矿结构,制备的电池效率达到6.89%。     

Preparation of (110)-oriented SrTiO3 film on quartz glass by laser chemical vapor deposition

SrTiO₃ (STO) film was prepared on quartz glass by laser chemical vapor deposition at a deposition temperature (T_dep) ranged from 760 to 1104 K. Effect of the T_dep on the orientation, crystallinity, texture, and microstructure of the STO film was investigated. As the T_dep was increased, the preferred orientation of the STO film tended to be (110)-orientated with corresponding texture coefficient (TC) on the (110) reflection enhanced from 2.3 to 6; meanwhile, the full width at half maximum of the ω-scan on the (110) reflection decreased from 0.85° to 0.59°. The (110)-oriented grains were in wedge shape about 60 × 150 nm in size, which tended to be flat at an elevated T_dep of 1104 K.     

气体-溶液-固体法制备铜基Cu（OH）2纳米带阵列

文章报道一种新的Cu（OH）2纳米带阵列合成方法,即气体-溶液-固体法。这种方法主要特点是把铜片置于氨水的液面上,使铜片基板表面有氧气、氨水和铜参与反应,最终在铜片基板上生长出Cu（OH）2纳米带阵列。Cu（OH）2纳米带的尺寸可以通过控制氨水的浓度进行调节,即氨水浓度降低,Cu（OH）2纳米带的尺寸也变小了;而且Cu（OH）2在一定温度下可以脱水转变成为CuO纳米带;最后研究了Cu（OH）2和CuO纳米带阵列的生长机理。     

Optimization of electrochemically synthesized Cu3(BTC)2 by Taguchi method for CO2/N2 separation and data validation through artificial neural network modeling

Cu₃(BTC)₂, a common type of metal organic framework (MOF), was synthesized through electrochemical route for CO₂ capture and its separation from N₂. Taguchi method was employed for optimization of key parameters affecting the synthesis of Cu₃(BTC)₂. The results indicated that the optimum synthesis conditions with the highest CO₂ selectivity can be obtained using 1 g of ligand, applied voltage of 25 V, synthesis time of 2 h, and electrode length of 3 cm. The single gas sorption capacity of the synthetized microstructure Cu₃(BTC)₂ for CO₂ (at 298 K and 1 bar) was a considerable value of 4.40 mmol·g⁻¹. The isosteric heat of adsorption of both gases was calculated by inserting temperature-dependent form of Langmuir isotherm model in the Clausius-Clapeyron equation. The adsorption of CO₂/N₂ binary mixture with a concentration ratio of 15/85 vol-% was also studied experimentally and the result was in a good agreement with the predicted value of IAST method. Moreover, Cu₃(BTC)₂ showed no considerable loss in CO₂ adsorption after six sequential cycles. In addition, artificial neural networks (ANNs) were also applied to predict the separation behavior of CO₂/N₂ mixture by MOFs and the results revealed that ANNs could serve as an appropriate tool to predict the adsorptive selectivity of the binary gas mixture in the absence of experimental data.     

三光气法合成N-硝基-N-(2,4,6-三氯苯基)氨基甲酰氯

用三光气法合成了N 硝基 N (2,4,6 三氯苯基)氨基甲酰氯,并进行了结构表征。结果表明,用三氯甲基碳酸酯代替光气合成该化合物反应安全,条件温和,选择性好,收率高,消除了光气的危险性。     

Chemical instability of Cu3(BTC)2 by reaction with thiols

In contrast to Fe(BTC) (BTC: 1,3,5-benzenetricarboxylate), the crystal structure of Cu₃(BTC)₂, a commercial metal organic framework widely used as solid catalyst, collapses when contacted with thiols under mild reaction conditions forming copper nanoparticles.     

沉淀法制备氧化亚铜颗粒及其在(CH3)2SiCl2单体合成反应中应用

通过调控沉淀法中样品老化时间制备了粒径0.10~0.15, 0.5~1和1~2 mm的球状Cu2O催化剂,研究了其粒径对直接合成(CH3)2SiCl2反应性能的影响. 结果表明,在所制粒径范围内,催化剂粒径对硅粉转化率影响不大,转化率约为12%;目的产物选择性随催化剂粒径增大而逐渐降低,3种粒径的Cu2O催化剂上(CH3)2SiCl2的选择性分别为86.48%, 80.65%和74.31%. 对反应前后触体的表征显示,硅粉表面以催化剂颗粒为中心发生了辐射状刻蚀反应,且随催化剂粒径增大,反应积碳量增加.     

Methanol synthesis by the hydrogenation of CO2 over Zn-deposited Cu(111) and Cu(110) surfaces

The hydrogenation of CO₂ over Zn-deposited Cu(111) and Cu(110) surfaces was performed at 523 K and 18 atm using a high pressure flow reactor combined with XPS apparatus. It was shown that the ZnO _x species formed on Cu(111) during reaction directly promoted the methanol synthesis. However, no such promotional effect of the Zn was observed for methanol formation on Cu(110). Thus, Zn on Cu(111) acts as a promoter, while Zn on Cu(110) acts as a poison. The activation energy and the turnover frequency are in fairly good agreement with those obtained for Cu/ZnO powder catalysts.     

[Cu（en）3]^2＋发生Jahn-Teller畸变吗

就大一学生对[Cu（en）3]^2＋是否发生Jahn-Teller畸变的作答情况,引发的关于规律的总结、知识的连续性、阶段性及教材处理方面的思考。     

Preparation of nano-crystalline strontium-doped lanthanum manganate (LSM) powder and porous film by aerosol flame deposition

To improve the performance of the cathode, many groups have studied the relationship between the cathode microstructure and the electrochemical performance. In this study, a porous La_0.8Sr_0.2MnO_3±δ (LSM) cathode film with primary particles of under 10 nm diameters was prepared by aerosol flame deposition (AFD). The AFD technique was applied to synthesize the spherical particles and dense LSM thin film. The cathode performance was improved, and the polarization resistance was decreased by extending the active triple phase boundary. The electrochemical characteristics were investigated in the temperature range of 600–900 °C and oxygen partial pressure range of 0.1–1.0 atm. For oxygen reduction reaction on the LSM cathode, it was turned out that both oxygen atom diffusion and oxygen ion transfer from the three phase boundary to the yttria-stabilized zirconia electrolyte lattice were the rate-determining steps with comparable contributions. The polarization resistance of the prepared LSM film decreased from 206 to 1.7 Ω cm² with increasing temperature from about 600 to 900 °C and the activation energy was 1.48 eV.