石墨烯纳米筛负载钴铁双金属层状氢氧化物的制备及其在重金属离子电化学传感中的应用

本文采用自组装-碳热造孔-刻蚀的方法将钴铁双金属层状氢氧化物(Co_(3)FeLDH)与石墨烯纳米筛(HG)复合,进而制备了基于Co_(3)FeLDH/HG复合材料的电化学传感器,用于同时检测水中Pb^(2+)、Cd^(2+)和Zn^(2+)。由于HG的高比表面积、多孔性和良好的导电性,以及Co_(3)FeLDH阵列结构对重金属离子的强亲和性,所制备传感器表现出良好的分析性能。实验结果显示,Pb^(2+)与Cd^(2+)的峰电流与浓度在1~1500μg·L^(-1)、Zn^(2+)峰电流与浓度在5~1800μg·L^(-1)范围线性关系良好,方法对Pb^(2+)、Cd^(2+)和Zn^(2+)的检测限分别达2.41 nmol·L^(-1)、4.45 nmol·L^(-1)和15.38 nmol·L^(-1),大大低于世界卫生组织(WHO)允许的生活水中3μg·L^(-1)(27 nmol·L^(-1))、10μg·L^(-1)(48 nmol·L^(-1))和1 mg·L^(-1)(33 mmol·L^(-1))的阈值。所制备的电化学传感器具有良好的稳定性和重现性,在环境分析检测方面具有良好的应用前景。

用于筛膜反应器的γ-MnO_2纳米粉的合成

醋酸锰与柠檬酸发生沉淀反应生成锰配合物,经热分解和酸处理手段最终制备出γ-MnO2纳米材料,用X射线衍射、差热/热重分析、透射电镜及原子力显微镜等手段对合成的样品进行了表征.同时考察了反应条件对反应速度、最终产品粒度的影响.结果表明,通过对反应条件的控制可以在一定程度上控制产品的粒度,得到了均粒度和超细粒度的γ-MnO2纳米材料.对于异丙醇和环己烷等氧化脱氢反应,γ-MnO2纳米筛膜反应器与传统的固定床反应器相比反应物的转化率提高了20%.

石墨烯纳米筛:基础和应用研究

石墨烯纳米筛材料是当前科技前沿中一种新型二维多孔材料,其平面多孔结构有利于电解质离子的纵向传输,缩短了离子传输路径,有效避免了传统石墨烯材料普遍存在的问题,如π–π堆叠造成活性面积低、纵向传输性能差、离子传输路径长和电解液不易浸润等,在能量存储与转换领域中表现出比传统石墨烯基材料更为优异的性能.本文综述了近几年来各种结构可定制、结构/组分复杂性高、形态可控制、电化学性能增强的石墨烯纳米筛材料的合理设计和合成的研究进展,着重讨论了石墨烯纳米筛的结构设计对能源存储与转换方面的性能影响,期望为高性能能源存储与转换方面进一步的创新工作提供参考.

纳米氧化锰离子筛提取卤水溶液中锂的实验研究

锂是重要的战略资源,而自然界中的锂资源主要储存于如海水、盐湖水和地热水等的卤水中。离子筛吸附剂法是目前最有前途的从含锂液态资源中提取锂的方法。本文通过利用水热合成法,以Mn(NO_3)_2·4H_2O、Na_2S_2O_8和LiNO_3为反应原料,分三个步骤制备了宽约40~80 nm、长约400~800 nm的纳米棒状尖晶石型MnO_2离子筛。通过吸附实验得到离子筛对配制的稀锂溶液中锂离子最大吸附量达到20 mg/g。同时,通过吸附实验测定并计算了溶液中各碱金属和碱土金属离子的平衡分配系数K_d的次序为Na^+<K^+<<Mg^(2+)<Li^+,说明离子筛对锂离子具有较高的选择性,溶液中的其他碱金属离子并没有对Li^+吸附造成干扰。

Preparation of Zn-modified nano-ZSM-5 zeolite and its catalytic performance in aromatization of 1-hexene

The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity（WHSV） of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.

Hydrothermal synthesis of nanosized ZSM-22 and their use in the catalytic conversion of methanol

ZSM‐22 zeolite with different crystal lengths was prepared using a modified hydrothermal method. Rotation speed, Si/Al molar ratio and co‐solvent have important effects on the crystal size of ZSM‐22. The nanosized zeolite samples were characterized by X‐ray diffraction, X‐ray fluorescence, nitrogen adsorption, scanning electron microscopy, temperature‐programmed desorption of am‐monia and solid state nuclear magnetic resonance. The catalytic performance of nanosized ZSM‐22 was tested using the conversion of methanol. Compared to conventional ZSM‐22, the nanosized ZSM‐22 zeolite exhibited superior selectivity to ethylene and aromatics and lower selectivity to propylene. Stability against deactivation was clearly shown by the nanosized ZSM‐22 zeolite. A higher external surface area and smaller particle size make this nanosized ZSM‐22 zeolite attractive for catalytic applications.

Nanosized and hierarchical zeolites: A short review

Zeolites are crystalline aluminosilicates with three‐dimensional microporous structures. They have been used as ion‐exchangers, catalysts, and adsorbents in various fields such as oil refining, petro‐chemistry, agriculture, and water and wastewater treatment. Their wide use is because of their many beneficial properties, such as framework and compositional flexibilities, physical and hydro‐thermal stabilities, non‐toxicity, high surface areas, exchangeable cations, and good cost‐benefit ratios. Although many zeolite applications depend on their microporous structures, this can cause diffusional constraints for bulky reactant and product molecules. There have been many efforts to overcome the intrinsic limitations of conventional zeolites by preparing nanosized and hierarchi‐cally structured zeolites. As a result of these efforts, several strategies have been established and the use of new zeolitic materials in various catalytic and adsorptive reactions has been investigated. Longer lifetimes, high catalytic performances, and postponed coking and catalyst deactivation can be achieved using hierarchical and nanosized zeolites. The aim of this review is to provide an over‐view of the enhanced properties of hierarchical and nanosized zeolites, and recent development methods for their synthesis. The advantages and disadvantages of each route are discussed, and the catalytic applications of nanozeolites and zeolites with secondary porosity, and a comparison with conventional zeolites, are briefly presented.

Direct Synthesis of Dimethyl Carbonate from CO_2 and CH_3OH Using 0.4nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst

The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH 3-TPD (temperature programmed desorption) and CO 2-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The catalysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h 1 , the selectivity and yield of DMC were higher than 86.0 % and 5.0 %, respectively.

Correlation between H-ZSM-5 crystal size and catalytic performance in the methanol-to-aromatics reaction

The porosity of H‐ZSM‐5zeolite is known to facilitate the diffusion of molecules in the methanol‐to‐aromatics(MTA)reaction.The activity and selectivity of the H‐ZSM‐5catalyst in the MTAreaction has been studied as a function of crystal size.ZSM‐5zeolites with different crystal sizeswere successfully synthesized by conventional hydrothermal methods.Tailoring ZSM‐5particle sizewas easily controlled by changes to the sol‐gel composition,and in particular,the deionized waterto tetrapropylammonium hydroxide ratio,and crystallization time.The structure of the H‐ZSM‐5zeolites were characterized by X‐ray diffraction and the morphology of the zeolite particles wasdetermined by scanning electron microscopy.N2adsorption‐desorption measurements establishedchanges to the textural properties,and compositional properties were characterized by X‐ray fluorescencespectroscopy.Acidity measurements of the catalysts were measured by pyridine‐adsorbedFourier transform infrared spectroscopy and the temperature‐programmed desorption of ammonia.After subjecting the catalysts to the MTA reaction,the total amount of coke formed on the spentdeactivated catalysts was determined by thermal gravimetric analysis.The results show that theSiO2/Al2O3molar ratios and acidic properties of the H‐ZSM‐5samples are similar,however,thenano‐sized hierarchical ZSM‐5zeolite with an additional level of auxiliary pores possesses a higher

Preparation of a novel supported electrode comprising a nickel(Ⅱ)hydroxide-modified carbon paste electrode(Ni(OH)_2-X/CPE)for the electrocatalytic oxidation of formaldehyde

We prepared a novel nickel（II）hydroxide-modified carbon paste electrode（Ni（OH）2-X/CPE）for the electrocatalytic oxidation of formaldehyde.The electrode was prepared by a simple method without the use of linking chemicals.The prepared Ni（OH）2-X/CPE material was characterized by scanning electron microscopy and energy dispersive X-ray spectrometry.The electrochemical performance of the proposed electrode was investigated using cyclic voltammetry,electrochemical impedance spectroscopy,and chronoamperometry.The results indicate that Ni（OH）2-X/CPE exhibits good electrocatalytic activity with regards to formaldehyde oxidation owing to its nanoporous structure and the large surface area of zeolite X.The values of the electron transfer coefficient and the catalytic rate constant were 0.7 and 6.1 × 104 cm3/（mol·s）,respectively.Therefore,the proposed electrode,which showed remarkable electroactivity with regards to formaldehyde oxidation with long-term stability and good reproducibility,could be useful in fuel cells.

A novel method for enhancing the stability of ZSM-5 zeolites used for catalytic cracking of LPG: Catalyst modification by dealumination and subsequent silicon loading

Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.

Encapsulation of a nickel Salen complex in nanozeolite LTA as a carbon paste electrode modifier for electrocatalytic oxidation of hydrazine

A nickel salen complex was encapsulated in the supercages of nanozeolite NaA,LTA(linde type A)structure,using the flexible ligand method.The electrochemical behavior and electrocatalytic activity of a carbon paste electrode(CPE)modified with Ni(II)‐Salen‐A(Ni(II)‐SalenA/CPE)for hydrazine oxidation in0.1mol/L NaOH solution were investigated by cyclic voltammetry,chronoamperometry,and chronocoulometry.First,organic‐template‐free synthesis of nanozeolite LTA was performed and the obtained material was characterized by various techniques.The average particle size of the LTA crystals was estimated to be56.1and72nm by X‐ray diffraction and particle size analysis,respectively.The electron transfer coefficient was found to be0.64and the catalytic rate constant for oxidation of hydrazine at the redox sites of Ni(II)‐SalenA/CPE was found to be1.03×105cm3/(mol·s).Investigation of the electrocatalytic mechanism suggested that oxidation of hydrazine occurred through reaction with Ni3+(Salen)O(OH)and also direct electrooxidation.The anodic peak currents revealed a linear dependence on the square root of the scan rate,indicating a diffusion‐controlled process,and the diffusion coefficient of hydrazine was found to be1.18×10?7cm2/s.The results indicated that Ni(II)‐SalenA/CPE displays good electrocatalytic activity toward hydrazine oxidation owing to the porous structure of nanozeolite LTA and the Ni(II)‐Salen complex.Finally,the general reaction mechanism for the electrooxidation of hydrazine on Ni(II)‐SalenA/CPE in alkaline solution involves the transfer of four electrons,in which the first electron transfer reaction acts as the rate‐limiting step followed by a three‐electron process to generate environmentally friendly nitrogen and water as final products.

Synthesis of magnetic core–shell structure Fe_3O_4@MCM-41 nanoparticle by vesicles in aqueous solutions

In this study, magnetic core–shell structure Fe3O4@MCM-41 nanoparticles were synthesized with vesicles as soft templates. In the preparation, Fe Cl2 and tetraethy orthosilicate(TEOS) were selected as Fe processor and Si precursor, respectively. Stable vesicles first formed in 0.03 mol·L-11:2 mixture of anionic surfactant sodium dodecyl sulfate and cationic surfactant cetyltrimethyl ammonium bromide. Then, TEOS was added in the vesicle aqueous solution, leading to a highly dispersed solution. After high-temperature calcination, Fe3O4@MCM-41 nanoparticles were obtained. Their structure and morphology were characterized by Saturn Digisizer, transmission electron microscope and vibrating sample magneto-meter. The results indicate that the vesicles are spherical and their size could be tuned between 20 and 50 nm. The average grain diameter of synthesize magnetic core–shell Fe3O4@MCM-41 particles is 100–150 nm and most of them are in elliptical shape. The dispersion of magnetic particles is very good and magnetization values are up to 33.44 emu·g-1, which are superior to that of other Fe3O4 materials reported.

Molecular sieving through a graphene nanopore： non-equilibrium molecular dynamics simulation

Two-dimensional graphene nanopores have shown great promise as ultra-permeable molecular sieves based on their size-sieving effects. We design a nitrogen/hydrogen modified graphene nanopore and conduct a transient non-equilibrium molecular dynamics simulation on its molecular sieving effects. The distinct time-varying molecular crossing numbers show that this special nanopore can efficiently sieve CO_2 and H_2S molecules from CH_4 molecules with high selectivity. By analyzing the molecular structure and pore functionalization-related molecular orientation and permeable zone in the nanopore, density distribution in the molecular adsorption layer on the graphene surface, as well as other features, the molecular sieving mechanisms of graphene nanopores are revealed. Finally, several implications on the design of highly-efficient graphene nanopores, especially for determining the porosity and chemical functionalization, as gas separation membranes are summarized based on the identified phenomena and mechanisms.

Nano CuO/ZSM-5 zeolite as a green and efficient catalyst for dehydration of 1,4-butanediol to tetrahydrofuran

Nano CuO/ZSM-5 zeolite was prepared and used as a catalyst for dehydration of 1,4-butanediol(BDO) to tetrahydrofuran(THF) in liquid-phase. It was found that the 4.6 wt% CuO/ZSM-5 displayed good catalytic performance, and nearly 100%of BDO conversion and more than 99% of THF selectivity could be achieved by a rotary evaporator reactor at 170 °C under the atmospheric pressure. With such mild reaction conditions, 2400 g BDO could be converted to THF over 1 g catalyst under semi-continuous operation. Characterizations with X-ray diffraction(XRD), temperature-programmed reduction(TPR),NH3-temperature programmed desorption(TPD), X-ray photoelectron spectroscopy(XPS), transmission electron microscope(TEM) and Brunauer-Emmett-Teller(BET) over fresh and used 4.6 wt% CuO/ZSM-5 were conducted. Based on the results of the characterization and catalytic performance of 4.6 wt% CuO/ZSM-5, it can be conjectured that the formed 1–3 nm CuO nanoparticles, suitable acidity of the catalyst due to the synergic interaction of CuO and ZSM-5 support promoted the dehydration of BDO to THF.

Synthesis of ultra-small mordenite zeolite nanoparticles

The mordenite（MOR） nanoparticles（MNPs）with ultra-small crystallites（~30 nm） were synthesized by using tetraethylammonium bromide（TEAB） as structure directing agent at low temperature（403K）. The formation of MNPs was considered to be due to high concentration of TEAB and occurrence of limiting Ostwald ripening at low temperature. The MNPs exhibited not only higher catalytic activity at low temperature for selective catalytic reduction of NOx but also higher catalytic activity and longer lifetime for disproportionation of toluene than conventional MOR（cMOR） bulk crystals.