不同方法合成的沸石咪唑酯骨架结构材料(ZIF-8)的表征和催化性能

以二甲基咪唑为有机连接体和以Zn(OH)2或Zn(NO3)2·6H2O为Zn源,在甲醇与氨水的混合溶液、甲醇和DMF 3种不同的合成体系中合成了沸石咪唑酯骨架结构材料ZIF-8(分别记为ZIF-8(NH4OH)、ZIF-8(MeOH)和ZIF-8(DMF),并采用XRD、FTIR、N2吸附、SEM、TPD及Knoevenagel缩合反应等手段对所合成材料进行了表征。结果表明,采用这3种不同的合成方法均可成功制备出ZIF-8,所合成的ZIF-8的形貌基本一致,但其晶粒大小和酸碱性能有较大区别,同ZIF-8(NH4OH)和ZIF-8(DMF)相比,ZIF-8(MeOH)晶粒分布集中、平均粒径较小且具有较大的外比表面积和较多的酸碱位。不同方法合成的ZIF-8在苯甲醛和丙二腈的Knoevenagel缩合反应中的催化性能有很大差异,ZIF-8(MeOH)催化活性明显高于ZIF-8(DMF)和ZIF-8(NH4OH),其较高的催化活性,同其较大的外比表面积和酸碱性能密切相关。     

沉淀方法对铜基甲醇合成催化剂前驱体及其性能的影响

 分别采用共沉淀法 (CP)、两步沉淀法 (TP) 和分步沉淀法 (FP) 制备了 Cu/ZnO/Al₂O₃ 甲醇合成催化剂. 结果发现, FP 催化剂上甲醇收率比 CP 催化剂上高 46.3%, 比 TP 催化剂上高 9.3%. 采用 X 射线衍射、微分热重分析、红外光谱、N₂ 吸附-脱附、程序升温还原及 N₂O 滴定等方法表征了催化剂. 结果表明, FP 催化剂前驱体中 (Cu,Zn)₂CO₃(OH)₂ 和 (Zn,Cu)₅(CO₃)₂(OH)₆ 两种高活性物相较多, 而 (Cu,Zn)₆Al₂(OH)₁₆CO₃•4H₂O 物相较少, 焙烧后形成了较多的 CuO-ZnO 固溶体, 同时形成了较多的碳酸盐, 因而催化活性更高.     

ZIF-8基复合材料高效、稳定电催化还原CO2

电催化CO₂还原反应(eCO₂RR)受到催化剂本征活性以及传质的限制，导致材料的催化活性低、反应起始电位高等问题。我们以类沸石锌盐咪唑骨架(ZIF-8)材料为研究对象，探究了不同粒径ZIF-8材料的eCO₂RR性能。优选粒径为50 nm的ZIF-8材料，进一步引入碳纳米管(CNT)作为其导电基底材料，通过原位生长，构建了复合材料ZIF-8-50@CNT的多级孔结构和疏水界面。eCO₂RR实验结果表明，CNT的引入提高了催化剂的导电性，优化后的复合材料有效地降低了反应的起始电位。在-1.1 V (相对可逆氢电极(RHE))电位下，CO部分电流密度为15.6 mA·cm^-2，ZIF-8-50@CNT催化剂的比表面活性提升了3.5倍(相比ZIF-8-50)，塔菲尔斜率降低到136 mV·dec^-1。并且产物CO的选择性和稳定性得到了提高，在宽电势窗口-0.9~-1.2 V (vs RHE)内，CO的法拉第效率(FE)保持在80%以上。在10 h稳定性测试中，催化剂活性保持稳定，整体增强了复合材料eCO₂RR的性能。     

用于高性能超级电容器的金属有机骨架衍生Co(OH)2/C-N@GP纳米复合材料

本文报道一种制备β-Co(OH)₂/氮掺杂碳石墨烯纳米复合材料(Co(OH)₂/C-N@GP)的方法。首先，我们通过在含羧基的聚苯乙烯(PS)乙醇分散体中使Co(NO₃)₂·6H₂O与2-甲基咪唑反应，合成了ZIF-67/聚苯乙烯的复合材料。然后将ZIF-67/聚苯乙烯复合材料高温碳化，同时与硫代乙酰胺和石墨烯反应生成Co(SO₄)₂/C-N@GP。最后，Co(SO₄)₂/C-N@GP在KOH水溶液中浸泡以获得 Co(OH)₂/C-N@GP 纳米复合材料。所制备的 Co(OH)₂/C-N@GP 的扫描电镜图显示尺寸为 10~20 nm 的 Co(OH)₂很好地分散在石墨烯上。电化学分析表明Co(OH)₂/C-N作为超级电容器的电极材料表现出典型的法拉第电荷转移行为，并且当石墨烯存在时，其比电容可显著增强。在2 mol·L^-1 KOH中，Co(OH)₂/C-N@GP在2 A·g^-1下表现出985.4 F·g^-1的高比电容，1 000次循环后的比电容保持率为76.6%。     

MnO2的晶相结构和表面性质对低温NH3-SCR反应的影响

采用水热法合成了两种具有相同形貌但是不同物相结构的MnO₂纳米棒, 分别为隧道状和层状结构, 考察其低温NH₃选择性催化还原NO_x (NH₃-SCR)的性能. 结果表明MnO₂纳米棒的比表面积不是影响活性的主要因素, 催化剂的晶相结构和表面性质对催化活性有很大影响, 隧道状α-MnO₂纳米棒的低温NH₃-SCR活性明显高于层状δ-MnO₂纳米棒. 结构分析和NH₃程序升温脱附(NH₃-TPD)实验表明, α-MnO₂纳米棒的暴露晶面(110)面存在大量的配位不饱和Mn离子, 形成较多的Lewis 酸性位点, 而且α-MnO₂较弱的Mn―O键和隧道结构都有利于NH₃的吸附; 而δ-MnO₂纳米棒的暴露晶面(001)面上的Mn离子已达到配位饱和, 所以其表面Lewis 酸性位点较少. X射线光电子能谱(XPS)和热重(TG)分析表明α-MnO₂纳米棒的表面更有利于NH₃和NO_x的活化. 具有有利于吸附NH₃和活化NH₃和NO_x的表面性质和晶型结构, 是α-MnO₂纳米棒活性高的主要原因.     

两个4-连接配位网络的锌(Ⅱ)配位聚合物的合成、结构和荧光性质

以5-氨基四氮唑(HATz), 异烟酸(HPyc)和ZnSO₄·7H₂O或Zn(NO₃)₂·6H₂O为反应物, 在DMF溶剂热条件下分别得到了2个锌(Ⅱ)配位聚合物{[(CH₃)₂NH₂]·[Zn(ATz)(SO₄)]}_n (1)和{[Zn(ATz)(Pyc)]·0.5DMF}_n (2), 并对它们的组成和结构进行了表征。配合物1是由4-连接(4, 4)网络拓扑的[Zn(ATz)(SO₄)]_n^n-二维阴离子层和[(CH₃)₂NH₂]⁺阳离子间通过氢键作用形成的二维波浪层结构。配合物2则是1个二重穿插的4-连接金刚烷拓扑的三维微孔金属-有机框架结构, 客体DMF分子填充在孔道内。室温下的固体荧光实验表明, 在350 nm的光激发下, 配合物1和2分别在为445 nm和458 nm处出现强烈的荧光发射。     

基于5-(2-羧基苯基)吡啶-3-甲酸配体的镍(Ⅱ)和锌(Ⅱ)配位聚合物的合成、晶体结构、催化及抗磨性质

采用水热方法,选用5-(2-羧基苯基)吡啶-3-甲酸配体(H₂cpna)与1,2-二(4-吡啶基)乙烷(dpea)或1,2-二(4-吡啶基)乙烯(dpey)分别与NiCl₂·6H₂O和ZnCl₂在160℃下反应,合成了2个三维配位聚合物{[Ni(μ₃-cpna)(μ-dpea)_0.5]·H₂O}_n (1)和{[Zn(μ₃-cpna)(μ-dpey)_0.5]·H₂O}_n (2),并对其结构、催化和摩擦性质进行了研究。研究表明,在室温条件下化合物2在Knoevenagel缩合反应中显示出较好的催化活性。同时,2在聚α-烯烃合成润滑剂中显示出有效的抗磨性能。     

ZIF-67/CeO2催化CO2和甲醇直接合成碳酸二甲酯

采用沉淀法将ZIF-67负载到CeO₂上,制备了具有多重活性位点的非均相催化剂ZIF-67/CeO₂,并研究其催化CO₂和甲醇直接反应生成碳酸二甲酯(DMC)的性能。采用 X 射线衍射、N2吸附-脱附、傅里叶变换红外光谱和 X 射线光电子能谱研究了ZIF-67/CeO₂的各种理化性质。结果表明,ZIF-67的引入使ZIF-67/CeO₂催化剂产生更多的氧空位。在考察的ZIF-67/CeO₂系列催化剂中,0.3-ZIF-67/CeO₂(0.3为Co、Ce物质的量之比)在具有高的比表面积的同时还能保持介孔结构,具有丰富的酸碱位点,并且具有较高的CO₂吸附容量,表现出最好的催化性能。在反应温度为140℃、压力为4.5 MPa的条件下反应4 h,DMC收率可达到3.79 mmol_DMC·gcat^-1。     

酸碱双功能MgO/HMCM-22催化剂上Knoevenagel缩合反应

采用浸渍法制备了一系列MgO改性催化剂MgO/HMCM-22, 利用X射线衍射、N₂物理吸附-脱附、扫描电镜、傅里叶变换红外光谱、NH₃及CO₂程序升温脱附等技术对所制催化剂进行了表征. 结果表明, MgO改性后MCM-22分子筛仍保持原有的结构; 随着MgO负载量的增加, 催化剂的碱强度和碱含量显著增加, 而强酸含量明显减少, 弱酸酸位有所增加. 以Knoevenagel缩合为探针反应, 考察了所制催化剂的性能. 在优化的反应条件下, MgO/HMCM-22上苯甲醛转化率高达92.6%. 催化剂 MgO/HMCM-22和MgO/NaMCM-22的催化性能明显优于HMCM-22和MgO. 酸中心和碱中心均对该缩合反应起着重要的促进作用. MgO/HMCM-22对Knoevenagel缩合反应显示出较高的催化活性, 体现出明显的酸碱协同催化作用.     

二维网状配合物[Co(dimb)2(MeOH)2](ClO4)2的合成及晶体结构

设计并合成了一个含咪唑基团的柔性双齿配体:1,3-二(咪唑基-1′-甲基)-5-甲基苯(dimb)(1),并进行了 ¹H NMR和结构表征。通过dimb与高氯酸钴的反应,得到了一个新型的具有二维网状结构的配合物:[Co(dimb)₂(MeOH)₂](ClO₄)₂(2)。X-射线晶体结构测定表明,这两个化合物的晶体学参数分别为:配体(1)属单斜晶系, 空间群     

Experimental and molecular simulation studies of CO2 adsorption on zeolitic imidazolate frameworks: ZIF-8 and amine-modified ZIF-8

ZIF-8 has been rapidly developed as a potential candidate for CO₂ capture due to its low density, high surface area, and robust structure. Considering the electron-donating effect of amino functional groups, amino-modification is expected to be an efficient way to improve CO₂ adsorption of ZIF-8. In this work, grand canonical Monte Carlo (GCMC) simulation was performed to study the CO₂ adsorption isotherm based on ZIF-8, ZIF-8-NH₂, and ZIF-8-(NH₂)₂. ZIF-8 was synthesized and CO₂ adsorption isotherms based on ZIF-8 was measured. The experimental surface area, pore volume, and CO₂ adsorption isotherm were used to validate the force field. Adsorptive capacity of ZIF-8-NH₂, and ZIF-8-(NH₂)₂ were first estimated. The GCMC simulation results indicated that the order of increasing CO₂ capacity of the ZIF-8 in the lower pressure regime is: ZIF-8 < ZIF-8-NH₂ < ZIF-8-(NH₂)₂, and in the high pressure is: ZIF-8 < ZIF-8-(NH₂)₂ < ZIF-8-NH₂. New adsorption sites can be generated with the existence of-NH₂ groups. In addition, for non-modified and amino-modified ZIF-8, it was the first time to use density functional theory (DFT) calculations to investigate their CO₂ adsorption sites and CO₂ binding energies. The present work indicates that appropriate amine-functionalized can directly enhanced CO₂ capacity of ZIF-8.     

Electrochemical detection of cystatin C by oriented antibody immobilization on streptococcal protein G–modified ZIF-8-Cu1−xNix(OH)2@Cu core-shell nanostructured electrode

Herein, we prepared a novel nanostructure involving Cu shell on Zeolitic imidazolate frameworks (ZIF-8) and Cu_1?xNi_x(OH)₂ composite (ZIF-8-Cu_1?xNi_x(OH)₂@Cu) combining sol-gel and co-precipitation method. The morphology, stoichiometry, and structure of the nanocomposite were elucidated by various physicochemical analyses. A poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ITO) was modified with the synthesized ZIF-8-Cu_1?xNi_x(OH)₂@Cu nanoparticles (NPs) to obtain an efficient electrode for further antibody immobilization. The ZIF-8-Cu_1?xNi_x(OH)₂@Cu/PEDOT:PSS/ITO was applied for the detection of cystatin C, a promising biomarker of chronic kidney disease (CKD). The electrode was functionalized by streptococcal protein G (SPG) to bind the Fc region of anti-cystatin C in an oriented manner. The synergistic catalytic activities, high surface coverage, enhanced electroactive sites, and excellent redox properties of the proposed electrode lead to excellent electrochemical sensing. The proposed sensor obtained a much lower detection limit (33 pg/mL) for a linear range of 0.1 ng/mL to 1,000 ng/mL with high selectivity, stability, and reproducibility compared with bare ZIF-8/PEDOT:PSS/ITO-based immunosensor. The clinical feasibility of the sensor was confirmed by measuring the human serum in the presence of different concentrations of cystatin C. This work demonstrates a new and facile approach to fabricating a metal-organic framework (MOF) –based nanoimmunosensor for cystatin C, which has significant importance in diagnosing the renal failure.     

Influence of molar ratios of precursor,catalyst, solvent and water on monolithicity and physical properties of TMOS silica aerogels

In continuation to our earlier work on aerogels, the experimental results on the monolithicity and physical properties of silica aerogels as a function of the molar ratios of tetramethoxysilane (TMOS) precursor, catalyst (NH₄OH), methanol (MeOH) solvent and water, are reported. The molar ratios of NH₄OH/TMOS, MeOH/TMOS and H₂O/TMOS were varied from 7.1 × 10^–6 to 9.6 × 10^–1, 1 to 90 and 1 to 18 respectively. It has been found that larger molar ratios of NH₄OH/TMOS (10^–2), MeOH/TMOS (13 to 60) and H₂O/TMOS (>10) resulted in transparent but cracked aerogels, and very low molar ratios of these combinations gave monolithic but less transparent or opaque aerogels. The best quality silica aerogels, in terms of monolithicity, transparency and low density, have been obtained with TMOS:MeOH:H₂O:NH₄OH in the molar ratio of 1:12:4:3.7 × 10^–3 respectively. The aerogels have been characterized by density, optical transmission, surface area and porosity measurements. The results have been discussed by taking into account the hydrolysis and condensation reactions, and syneresis effects.     

Controlled Synthesis of Fe3O4/ZIF‐8 Nanoparticles for Magnetically Separable Nanocatalysts

Fe₃O₄/ZIF‐8 nanoparticles were synthesized through a room‐temperature reaction between 2‐methylimidazolate and zinc nitrate in the presence of Fe₃O₄ nanocrystals. The particle size, surface charge, and magnetic loading can be conveniently controlled by the dosage of Zn(NO₃)₂ and Fe₃O₄ nanocrystals. The as‐prepared particles show both good thermal stability (stable to 550 °C) and large surface area (1174 m²g^?1). The nanoparticles also have a superparamagnetic response, so that they can strongly respond to an external field during magnetic separation and disperse back into the solution after withdrawal of the magnetic field. For the Knoevenagel reaction, which is catalyzed by alkaline active sites on external surface of catalyst, small Fe₃O₄/ZIF‐8 nanoparticles show a higher catalytic activity. At the same time, the nanocatalysts can be continuously used in multiple catalytic reactions through magnetic separation, activation, and redispersion with little loss of activity.     

CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation using mixed matrix membrane-based polyurethane incorporated with ZIF-8 nanoparticles

This study presents using zeolitic imidazolate framework-8 (ZIF-8) as porous filler dispersed phase and polyurethane (PU) as continuous phase to synthesis mixed matrix membranes (MMMs). ZIF-8 nanoparticles were synthesized using centrifugal method. The synthesized nanoparticles were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). In order to investigate the effect of ZIF-8 loading on the membrane performance in CO₂/CH₄ separation, different membranes were prepared with various amounts of ZIF-8 (0–50 wt%). Membranes properties were characterized by SEM, XRD, TGA, differential scanning calorimetry (DSC), and tensile analysis. SEM images exhibit that the ZIF-8 is dispersed uniformly in cross section of membrane. Thermal stability of membranes increases with addition of the ZIF-8 nanoparticles into the polymer matrix. Both tensile strength and strain at break in the MMMs increase with the ZIF-8 loading. To study the effect of feed pressure on CO₂ and CH₄ transport properties of the membranes, single gas experiments were conducted at 4, 8, and 12 bar feed pressures. Incorporation of ZIF-8 crystals into continuous PU matrix resulted in high-performance gas separation membranes. Increasing feed pressure, significantly, increased separation performances in all the membranes.     

ZIF-8基复合材料高效、稳定电催化还原CO2

电催化CO₂还原反应(eCO₂RR)受到催化剂本征活性以及传质的限制,导致材料的催化活性低、反应起始电位高等问题。我们以类沸石锌盐咪唑骨架(ZIF-8)材料为研究对象,探究了不同粒径ZIF-8材料的eCO₂RR性能。优选粒径为50 nm的ZIF-8材料,进一步引入碳纳米管(CNT)作为其导电基底材料,通过原位生长,构建了复合材料ZIF-8-50@CNT的多级孔结构和疏水界面。eCO₂RR实验结果表明,CNT的引入提高了催化剂的导电性,优化后的复合材料有效地降低了反应的起始电位。在-1.1 V(相对可逆氢电极(RHE))电位下,CO部分电流密度为15.6 mA·cm^-2,ZIF-8-50@CNT催化剂的比表面活性提升了3.5倍(相比ZIF-8-50),塔菲尔斜率降低到136 mV·dec^-1。并且产物CO的选择性和稳定性得到了提高,在宽电势窗口-0.9～-1.2 V(vs RHE)内,CO的法拉第效率(FE)保持在80%以上。在10 h稳定性测试中,催化剂活...     

Synthesis,structure, DNA-binding,and nuclease activity of a 3d–4f mixed metal nitrosyl complex, [Pr(phen)2(MeOH)(H2O)2][Fe(CN)5(NO)] · (Phen)(DMF)(MeOH)(H2O)

A cyano-bridged heterometallic lanthanide-transition metal nitrosyl complex, [Pr(phen)₂(MeOH)(H₂O)₂][Fe(CN)₅(NO)]?·?(Phen)(DMF)(MeOH)(H₂O) (Phen?=?1,10-phenanthroline and DMF?=?dimethylformamide), has been synthesized from reaction of PrCl₃?·?6H₂O with 1,10-phenanthroline in methanol and sodium nitroprusside followed by crystallization from DMF. The crystal structure shows that the complex is a 1-D chain, stabilized by coordination, hydrogen-bonding, and π–π stacking interactions. The complex shows nuclease activity with pUC19 supercoiled DNA in DMF/Tris-HCl buffer in the presence of H₂O₂.     

Investigation of СО<Subscript>2</Subscript> adsorption on amine-functionalized silicas and metal-organic polymers

Adsorption properties of amine-functionalized mesoporous silica NH₂-SBA-15, zeolite-like imidazole framework ZIF-8, and amine-functionalized metal-organic polymer NH₂-MIL-53 have been investigated. Non-modified mesoporous adsorbent SBA-15 has a higher sorption capacity for CO₂ than microporous ZIF-8, although microporous sample is characterized by a larger surface area and the values of total pore volume are close. When amine groups are present on the surface of the adsorbents, the chemical adsorption contributes more then the physical one. The adsorption capacity increases with increasing concentration of the functional groups which, in its turn, correlates with adsorbent surface area. Among the studied samples, the best adsorption properties demonstrate amine-functionalized adsorbents, aminefunctionalized mesoporous silica NH₂-SBA-15, and amine-functionalized metal-organic polymer NH₂-MIL-53.