Sol–gel synthesis of porous inorganic materials using “core–shell” latex particles as templates

Here we report on the sol–gel synthesis of porous inorganic materials based on manganese, molybdenum, and tungsten compounds using the “core–shell” siloxane-acrylate latex as a template. The chemical composition and structural characteristics of the materials obtained have been investigated. It was shown that temperature conditions and gaseous media composition during the template destruction controlled the composition and structure of porous materials. To obtain porous inorganic materials for catalytic applications, the “core–shell” latex template was preliminarily functionalized by gold and palladium nanoparticles obtained by thermal reduction of noble metal ions-precursors in a polycarboxylic “shell”. Upon the template removal, noble metals nanoparticles of a size of dozens of nanometers were homogeneously distributed in the material porous structure. The evaluation of the catalytic activity of macroporous manganese, tungsten, and molybdenum oxides under the conditions of liquid phase catalytic oxidation of organic dyes has been performed. The prospects of employing macroporous oxide systems with immobilized nanoparticles of noble metals in the processes of hydrothermal oxidation of radionuclide organic complexes in radioactive waste decontamination have been demonstrated.     

从Mn_3O_4前驱体到MnO_2纳米结构的形貌和结构变化(英文)

锰氧化物是一类重要的且具有广泛应用背景的材料,控制合成不同形貌和组成的锰氧化物纳米结构将有助于拓宽其应用领域.本文报道了以Mn3O4为前驱体,通过水热法控制合成MnO2纳米结构的方法.用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等手段对产物进行表征.在硫酸体系中,当反应温度为80和180℃时,所得产物分别为γ-MnO2海胆结构和β-MnO2单晶纳米棒.此外,MnOOH纳米线可以在稀酸溶液中合成.考察了反应温度、溶液酸度、反应时间对产物结构的影响,并提出了基于γ-MnO2为中间产物的反应机理.实验结果表明,水热体系促进了产物的各向异性生长并最终形成不同形貌和结构的锰氧化物.     

基于同步辐射光源研究水热合成纳米氧化物的生长机理

纳米氧化物的可控制备是提高其应用性能的前提条件。水热反应目前被广泛用于制备纳米氧化物材料,然而由于水热反应是在密闭环境中进行,很难研究前驱体的溶解过程,溶解后在溶液中的配位情况、晶体成核、生长过程以及形成的中间相,因此,难以实现材料的目标制备。同步辐射具有高强度、高亮度、高准直、宽频谱等诸多优点,通过设计和构建特殊的反应装置,可以应用同步辐射光源原位研究纳米氧化物在水热条件下的生长过程。本文结合本课题组及国际的研究工作介绍了原位反应装置的设计原则,以及基于同步辐射光源的原位X射线衍射(XRD)、X射线吸收精细结构谱(XAFS)和小角X射线散射(SAXS)研究纳米氧化物水热生长机理的最新进展,并展望了其发展趋势。     

The properties of gold catalysts precursors adsorbed on the MCM-41 materials modified with Mn and Fe oxides

Silica mesoporous materials modified with manganese and iron were obtained by the hydrothermal method. Gold was introduced to pure and modified silica materials by the direct hydrothermal and impregnation methods. Nitrogen adsorption/desorption studies evidenced formation of the materials with large total surface area and mesoporous structure. Unmodified silica materials showed regular pore arrangement. The uniform porous structure was distorted in the iron or manganese containing samples. XRD, UV-Vis/DRS spectroscopy and temperature programmed reduction studies revealed changes of the nature of transition metal oxide and gold species on the different preparation stages. The oxide species after drying were strongly dispersed and partially incorporated to the silica framework. High temperature treatment led to the formation of extraframework Mn and Fe oxide species. Complex processes of gold deposition were observed during hydrothermal synthesis and impregnation of modified silica materials. The increase of the size of gold species was observed during calcination. The presence of transition metal oxides decreased sintering of gold crystallites.     

A review on multi-component green synthesis of N-containing heterocycles using mixed oxides as heterogeneous catalysts

The use of mixed oxides is a well-appreciated approach in the fields of material science and synthesis, due to remarkable tunable surface properties such as acidic and basic characteristics, oxidation/reduction capabilities, and high agility of lattice oxygen, which makes them ideal choices as heterogeneous catalysts. The activity of the mixed oxides broadly relies on the nature of support and active material used and on the preparation method, calcination temperatures. Wide range of techniques for preparation of mixed oxide materials are adoptable, viz. sol-gel, co-precipitation, wet impregnation, microwave irradiation and hydrothermal methods. Use of mixed oxides as solid catalysts have gained popularity in many valued organic transformations, via alkylation, oxidation, condensation, dehydration, dehydrogenation, cycloaddition and isomerization. Application of mixed oxides in the area of green organic synthesis is a valuable strategy, which contributed significantly to the design of many novel heterocyclic scaffolds. The chemistry of N-heterocycle scaffolds, which generally possess five and six membered rings, is an interesting area for both synthetic and medicinal chemistry research constituting over 60% organics used in various arenas. The position and number of nitrogen atoms in the rings, distinguish them as pyrroles, pyrazoles, imidazoles, triazoles, pyridines and pyramidines classes. In this review, we focus on the scope, importance and versatile applications of mixed metal oxides and their synergetic effects as heterogeneous catalysts in the synthesis of variety of N-heterocyclic derivatives. The scientific aspects of the mixed oxides as catalytic active materials to design efficient synthetic protocols for the organic transformations is also discussed.     

用于超级电容器的锰钴氧化物/碳纤维材料

The development of high-performance supercapacitor electrode materials is imperative to alleviate the ongoing energy crisis. Numerous transition metals (oxides) have been studied as electrode materials for supercapacitors owing to their low cost, environmental-friendliness, and excellent electrochemical performance. Among the developed binary transition metal oxides, manganese cobalt oxides typically show high theoretical capacitance and stable electrochemical performance, and are widely used in the electrode materials of supercapacitors. However, the poor conductivity and active material utilization of manganese cobalt oxide-based electrode materials limit their potential capacitance application. Cotton is mainly composed of organic carbon-containing materials, which can be transformed to carbon fibers after calcination. The resultant carbonaceous material exhibits a large specific surface area and good conductivity. Such advantages could potentially suppress the negative effects caused by the poor conductivity and small specific surface area of manganese cobalt oxides, thereby improving the electrochemical performance. Herein, we firstly deposited manganese cobalt oxides on cotton by a simple hydrothermal method, yielding a composite of manganese cobalt oxides and carbon fibers via subsequent calcination, to improve the electrochemical performance of the electrode material. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), and electrochemical characterizations were used to investigate the physical, chemical, and electrochemical properties of the prepared samples. The fabricated manganese cobalt oxides in the composite were uniformly dispersed on the carbon fiber surface, which increased the contact between the interface of the electrode material and electrolyte, and enhanced electrode material utilization. The electrode material was confirmed to have well contacted with the electrolyte during a contact angle test. Hence, a pseudo-capacitance reaction completely occurred on the manganese cobalt oxide material. Moreover, the addition of carbon fibers reduced the resistance of the material, resulting in excellent capacitive performance. The capacitance of the prepared composite was 854 F∙g^-1 at a current density of 2 A∙g^-1. The capacitance was maintained at 72.3% after 2000 cycles at a current density of 2 A∙g^-1. These results indicate that the manganese cobalt oxide and carbon fiber composite is a promising electrode material for high-performance supercapacitors. The findings presented herein provide a strategy for coupling with carbon materials to enhance the performance of supercapacitor electrode materials based on manganese cobalt oxides. Thus, novel insights into the design of high-performance supercapacitors for energy management are provided.     

Cu-SSZ-13/堇青石整体式催化剂的原位合成及其NH3选择性催化还原NO性能

采用水热合成技术, 在堇青石蜂窝陶瓷载体上原位合成了SSZ-13分子筛, 并借助X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)等手段对其进行表征. 在此基础上, 研究了合成时间对催化剂结构和机械性能的影响. 另外, 使用固定床反应器测试了离子交换度为50%的Cu-SSZ-13/堇青石催化剂和Cu-SSZ-13催化剂水热老化前后的氨气选择性催化还原(NH₃-SCR) NO性能. 结果表明, 通过原位合成法制备的Cu-SSZ-13/堇青石催化剂在200-500 ℃ 的窗口温度内能达到80%以上的转化率, 并在300 ℃ 时达到96.4%的转化率. 在850 ℃水热老化12 h后, Cu-SSZ-13催化剂完全丧失了催化性能, 而Cu-SSZ-13/堇青石催化剂在300 ℃时仍然保持91%的转化率. 使用XRD和固体27Al 核磁共振(²⁷Al NMR)的方法, 研究了水热老化前后两种催化剂结构的变化, 结果表明, 当水热老化12 h 后, Cu-SSZ-13 基本丧失了SSZ-13 结构特征峰, 而Cu-SSZ-13/堇青石仍然保持了一定的SSZ-13 骨架结构. 证明了通过原位合成法制备的Cu-SSZ-13/堇青石催化剂具有较好的抗水热老化性能.     

Direct synthesis of well-ordered and unusually reactive MnSBA-15 mesoporous molecular sieves with high manganese content

The mesoporous MnSBA-15 materials with different n(Si)/n(Mn) ratios of 4, 8, 20, and 50 have been synthesized, for the first time, using manganese nitrate tetrahydrate and Pluronic 123 triblock polymer [(EO)20(PO)70(EO)20] by simply adjusting the molar ratio of water to hydrochloric acid (n(H2O)/n(HCl)) under direct hydrothermal conditions. For the effect of structural and textural properties with incorporation of manganese, the MnSBA-15 has been synthesized with different synthesis temperatures at the fixed molar ratios of n(Si)/n(Mn) = 4 and n(H2O)/n(HCl) = 295 in the synthesis gel. The hydrothermal and thermal stabilities of MnSBA-15 have also been investigated. The calcined MnSBA-15 materials prepared have been characterized by ICP-AES, XRD, N2 adsorption, ESR, FE-SEM, and TEM. The ICP-AES studies show a higher amount of manganese incorporation on the silica pore walls, as MnSBA-15 with a n(Si)/n(Mn) ratio up to 2.2 can be successfully prepared at a fixed n(H2O)/n(HCl) molar ratio of 295 by adjusting the ratios of n(Si)/n(Mn) in the synthesis gel. The structural and textural properties of calcined MnSBA-15 prepared can be found by the results of XRD and N2 adsorption. The investigation of ESR results clearly describe the effect of structure and Mn species coordination on the SBA-15 silica pore walls while the uniform pore diameter and rope-like hexagonal mesoporous structure of MnSBA-15 can be identified by TEM and FE-SEM images. With increasing synthesis temperature, an increase the unit cell parameter, pore size, and pore volume and a decrease the specific surface area and pore wall thickness of MnSBA-15 can be obviously noted by the results of XRD and N2 adsorption. The hexagonal MnSBA-15 materials prepared could be tested as catalysts in epoxidation of trans-stilbene to produce trans-stilbene oxide under various optimal conditions while their catalytic properties could also be compared to the results of MnMCM-41 and ZrMnMCM-41.     

锂离子电池锂锰氧化物高压嵌锂材料的结构和电化学性能研究

利 用 Ｘ Ｒ Ｄ、 Ｉ Ｃ Ｐ、 Ｔ Ｇ Ａ 、 Ｄ Ｔ Ａ 及 恒 流 充 放 电 等 方 法 研 究 分 析 了 一 种 特 殊 天 然 结 构 Ｍｎ Ｏ２（ Ｎ Ｍ Ｄ） 材料的结 构、组成 以及电 化学嵌锂 特性． Ｘ Ｒ Ｄ 分析 表明,该样 品材料 是由钠水 锰矿以及水羟 锰矿复 合结构组 成的 Ｍｎ Ｏ２ 纳米 纤 维． 充放 电 循环 结果 显 示,其 前 期循 环容 量 可高 达 １５０ｍ Ａｈ／ ｇ 左 右,但性 能尚不够 稳定． 本文采 用一种 水热法高 压嵌锂处 理,可将 Ｎ Ｍ Ｄ 样品 转变为 具有３ ×３ 大隧道结 构的钡 镁锰矿（ Ｔｏｄｏｒｏｋｉｔｅ） 型锂 锰氧 化 物,既 增 强了 Ｌｉ ＋ 嵌 入 隧道 或 层间 结 构 的循环稳定 性． 并 显著提 高锂锰氧 化物电 极材料性 能的 稳定 性,以 充放 电电 流密 度 为０ ．８ ｍ Ａ／ｃ ｍ ２ ,经过１８０ 次 循环后 其比容量 仍具有 １１０ ｍ Ａｈ／ ｇ ． 该类 大隧道结 构锂锰 氧化物可 作为一 种３ Ｖ 的锂离子电极 材料．     

Unveiling the Local Structure of Palladium Loaded into Imine-Linked Layered Covalent Organic Frameworks for Cross-Coupling Catalysis

Layered covalent organic frameworks (2D-COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen-enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine-linked 2D-COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine-linked 2D-COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross-coupling reactions.     

In situ spectroscopic investigation of heterogeneous catalysts and reaction media at high pressure

In situ characterization of catalysts by means of complementary spectroscopic techniques can be regarded as the first step towards rational catalyst design. Spurred by the growing interest of catalytic reactions in supercritical fluids and by several industrial reactions traditionally performed at high pressure (>10 bar), new demands and challenges are put to in situ spectroscopic characterization of heterogeneous catalytic reactions. In this article, we discuss the development and the use of spectroscopic and related techniques suitable for elucidating such high-pressure reactions. Selected examples from phase behaviour studies with a view cell, investigations with transmission and attenuated total reflection (ATR) infrared spectroscopy as well as X-ray absorption spectroscopy (EXAFS, XANES), are presented to show the strategies, opportunities and limitations of such high pressure in situ studies. Different facets appear to be important to gain insight into catalytic reactions in supercritical fluids: the identification of the phase behaviour of the reaction mixture, the behaviour of the fluid inside the porous catalyst, the processes occurring at the solid-fluid interface, the possible dissolution of active species and, similar as in gas-solid reactions, the establishment of structure-activity relationships.     

Design and applications of a home-built in situ FT-Raman spectroscopic cell

In the field of heterogeneous catalysis, in situ spectroscopy is one of the topics with growing interest. The characterization of a catalyst under working conditions is essential to identify the catalytic active site and to study the relation between the surface structure of a catalyst and its catalytic performance. For the first time, the design of an in situ spectroscopic cell for FT-Raman is presented and its performance is demonstrated by monitoring the thermal conversion of as synthesized mesoporous titanium and by characterizing the molecular surface structure of the vanadium oxides grafted on MCM-48 after exposure to a probe molecule. The results in both cases indicate that the in situ FT-Raman cell is a promising technique for characterizing the molecular surface structure of catalyst materials.     

Unveiling the Local Structure of Palladium Loaded into Imine‐Linked Layered Covalent Organic Frameworks for Cross‐Coupling Catalysis

Layered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen‐enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine‐linked 2D‐COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine‐linked 2D‐COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross‐coupling reactions.     

过渡金属氧化物掺杂对铜锰氧化物催化CO氧化性能的影响

以乙酸铜和乙酸锰为铜锰前驱体,以NH₄HCO₃为沉淀剂,相应金属硝酸盐为掺杂剂,采用共沉淀法制备了不同过渡金属氧化物掺杂的铜锰氧化物催化剂.?采用N₂物理吸附、X射线衍射,氢气-程序升温还原和原位红外漫反射光谱等方法对催化剂进行了表征,考察了系列催化剂上CO反应性能.?结果表明,掺杂过渡金属氧化物可以调变催化剂对CO的吸附能力,进而影响催化剂性能.     

锰氧化物负载碳氮三维网络结构复合材料的制备及锂电性能

通过硝酸锰和乙醇的水热反应在三聚氰胺泡棉（MF）上生成三氧化二锰颗粒,氮气下高温处理后形成锰氧化物负载碳氮三维网络结构的复合物。碳氮网络结构提高了充放电过程中材料结构的稳定性及导电性,且烧结过程中产生的孔道结构有利于锂离子传输,使得该复合材料作为负极在锂离子电池中表现出优异的充放电性能和循环稳定性。材料的比容量和循环稳定性大大提高,经500℃处理后的MnO/CNnws-500材料在160次循环后仍然保留590 mAh·g^-1的比容量,达到氧化亚锰理论容量755 mAh·g^-1的78%。     

锰氧化物/碳氮三维网络结构复合材料的制备及锂电性能

通过硝酸锰和乙醇的水热反应在三聚氰胺泡棉(MF)上生成三氧化二锰颗粒,氮气下高温处理后形成锰氧化物负载碳氮三维网络结构的复合物。碳氮网络结构提高了充放电过程中材料结构的稳定性及导电性,且烧结过程中产生的孔道结构有利于锂离子传输,使得该复合材料作为负极在锂离子电池中表现出优异的充放电性能和循环稳定性。材料的比容量和循环稳定性大大提高,经500℃处理后的MnO/CNnws-500材料在160次循环后仍然保留590 m Ah·g~(-1)的比容量,达到氧化亚锰理论容量755 m Ah·g~(-1)的78%。     

费-托合成Co/ZrO2-Al2O3催化剂反应性能的研究

以ZrOCl2·6H2O和AlCl3为原料,采用共沉淀方法制得一系列不同ZrO2质量分数的ZrO2-Al2O3混合氧化物载体;并以该混合氧化物为载体,采用初湿浸渍法制得钴质量分数为12％的Co/ZrO2-Al2O3催化剂。XRD、NH3-TPD、TPR和原位IR等表征结果表明,随着混合载体中ZrO2质量分数的增加,载体比表面积先增加后减少,混合载体的平均孔径则小于单一氧化物ZrO2和Al2O3的平均孔径。ZrO2和Al2O3载体混合后会导致氧化物的比表面积和酸性增大并且有新的物相生成。当混合氧化物用作载体时,能够抑制载体表面金属钴的分散,改变催化剂的还原行为,降低催化剂对CO物种的吸附能力。CO加氢反应表明,与单一金属氧化物相比,钴负载ZrO2-Al2O3混合氧化物催化剂的加氢活性和重质烃选择性有所降低。     

Time-resolved in situ studies of the formation of cubic mesoporous silica formed with triblock copolymers

The mechanism of formation of two different cubic mesoporous silica materials formed with Pluronic triblock copolymers is investigated with in situ time-resolved small-angle synchrotron X-ray scattering, in situ time-resolved 1H nuclear magnetic resonance, and time-resolved transmission electron microscopy. The materials studied are the micellar cubic (Imm) SBA-16 formed with Pluronic F108 and the bicontinuous cubic (Iad) silica material formed with Pluronic P103 and NaI. The formation mechanisms of the two cubic structures are shown to be dissimilar. For the Imm material, in the early stages of the synthesis, flocs of unordered micelles are observed, but areas where the micelles have started to order are also present. With time, there is an increase in order; however, there is a coexistence of unordered micelles and ordered material all through this study. The bicontinuous cubic silica is formed via a different path. The system is phase-separated already before the addition of the silica source, which implies that a concentrated phase is present, acting as the structure director of the Iad structure. The results are compared with earlier reports on the formation of the hexagonal SBA-15 material.     

Mixed Oxides FeVOx for Selective Oxidation of Octanol to Octanal under Solvent‐free Condition

The two‐component mixed oxides FeVO_x with various molar ratio of Fe to V were prepared and their phase composition, structure and morphology were determined by XRD and SEM. This prepared material was employed for liquid‐phase oxidation of octanol using H₂O₂ as oxidant. The mixed oxide FeVO_x with 2.5 : 1 of Fe to V molar ratio was found to be an effective catalyst with high selectivity to octanal under solvent‐free condition. The relationship between the catalytic performance and phase compositions of the mixed oxides was investigated by the test of its activity and XRD characterization. The catalytic action of the active sites including redox and acidic sites formed by interaction between VO_x and FeO_x on the surface of the catalyst was discussed. The catalyst was easily recovered and reused.     

从Mn3O4前驱体到MnO2纳米结构的形貌和结构变化

锰氧化物是一类重要的且具有广泛应用背景的材料, 控制合成不同形貌和组成的锰氧化物纳米结构将有助于拓宽其应用领域. 本文报道了以Mn3O4为前驱体, 通过水热法控制合成MnO2纳米结构的方法. 用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等手段对产物进行表征. 在硫酸体系中,当反应温度为80 和180 ℃时, 所得产物分别为γ-MnO2海胆结构和β-MnO2单晶纳米棒. 此外, MnOOH纳米线可以在稀酸溶液中合成. 考察了反应温度、溶液酸度、反应时间对产物结构的影响, 并提出了基于γ-MnO2为中间产物的反应机理. 实验结果表明, 水热体系促进了产物的各向异性生长并最终形成不同形貌和结构的锰氧化物.