基于冰模板法构筑孔道结构的合成策略及研究进展

冰模板法也称为定向冷冻法或冷冻铸造法，具有微观结构可调控性强、原料适用范围广、可制备大尺寸材料等优势，被广泛应用于定向调控陶瓷、聚合物、金属和碳材料等材料的制备领域。探讨冰模板法控制功能纳米材料组装成分级多孔复合材料的影响机制，解析冰模板法与其他材料的加工工艺的相互作用关系，对改善材料性能和开发新材料具有重要意义。该文阐述了冰模板法制备多尺度复杂仿生结构材料的基本原理、合成策略以及孔隙调控作用，并以冰晶成核和生长为重点，总结了冰模板法对孔道结构进行调控的措施。此外，还介绍了冰模板法辅助构造孔几何形状（0D、1D、2D和3D宏观结构），以及组装成块状物体（微球、纤维、薄膜和整体）。最后分析了复合材料的微观结构和宏观形貌的相关性，总结了不同冷冻过程对孔道结构的影响机制，并展望了该领域未来的发展方向。     

多级孔道沸石用于甲醇制丙烯反应研究进展

综述了多级孔道沸石结构、性能及制备方法的最新研究进展。多级孔道沸石因为介孔的引入强化了分子在孔道内的扩散,提高了目标产物的收率和选择性,在催化反应领域具有非常大的应用潜力。针对ZSM-5和SAPO-34两种不同的分子筛体系,介绍了多级孔道沸石制备的后处理法与模板法,指出控制后处理脱硅脱铝的程度以及探寻合适且廉价的模板剂是发展多级孔道材料的关键技术。最后对多级孔道沸石在甲醇制丙烯反应中的应用前景作了展望,得出保证分子筛合理的微孔/介孔比例、分布及催化剂合适的强度,是该材料应用于甲醇制丙烯反应的关键。     

三聚氰胺树脂作为碳基材料前驱体在电化学储能电极材料中的研究进展

电极材料是影响电化学储能系统性能的主要因素，目前，对其性能改善的研究主要集中于结构的优化和杂原子的引入两个方面。以三聚氰胺树脂为前驱体制备的碳基材料凭借其丰富的孔道结构和高含量的氮原子掺杂双重优势，在电化学储能设备的电极材料的应用中表现出高电容性能和出色的循环能力。本文从活化法、模板碳化法、混合聚合物碳化法等孔道控制工艺，探讨了孔道结构对于材料性能的影响。针对当前主流研发的电池和超级电容器，对以三聚氰胺树脂为原料制备的碳基材料展开综述，并分析其研究现状与发展趋势。     

电容吸附去离子技术的理论探讨

从理论上推导了电极的电吸附量，并指出实际的电吸附量与理论不一致的原因。建立了“立体结构的孔道双电层模型”。以此模型讨论了孔道的半径、孔道的长度、孔道的表面积与孔道中孔隙的体积、以及溶液的电阻、固体电吸附材料的电阻等因素与电极性能的关系，还对整个电容吸附去离子装置性能的影响作了分析。     

沸石分子筛孔道和表面化学修饰技术研究进展

沸石分子筛孔道和表面化学修饰是对分子筛进行二次合成的重要手段。本文综述了用离子交换法、化学沉积法和分子反应法等手段对各类沸石分子筛孔道和表面进行化学修饰改性的方法，研究结果表明，孔道和表面化学修饰可以精细调变沸石分子筛的孔道和孔口尺寸，钝化非选择性的表面酸性位，固载活性成分，提高分子筛的反应活性和对目标产物的催化选择性，为设计研制新型功能化的沸石分子筛提供有效的途径。     

多级孔道ZSM-5分子筛的合成及其催化应用

多级孔道ZSM-5分子筛具有微孔沸石分子筛良好的择形催化性能和介孔材料优异的传质扩散性能,在催化领域显示出良好的应用前景。本文综述了近年来多级孔道ZSM-5分子筛的研究进展,重点介绍了多级孔道ZSM-5分子筛的不同合成方法,包括后处理法、硬模板法和软模板法等,同时介绍了不同方法得到的多级孔道ZSM-5分子筛在催化反应中的应用,分析表明多级孔道ZSM-5分子筛以其良好的扩散性能和适宜的酸性提高了反应转化率和目标产物选择性。最后对多级孔道ZSM-5分子筛的发展方向进行了展望,指出研发简单、经济和环保的新合成路线是多级孔道ZSM-5分子筛发展中的重大挑战,深入研究多级孔道分子筛中介孔的形成机理和开发具有多级孔道整体式催化剂以及负载型多级孔道ZSM-5分子筛是今后的研究重点。     

以原位碳化蔗糖为硬模板合成多级孔道SAPO-34分子筛

为强化SAPO-34分子筛内传质过程,增强其酸性位的可接近性,以原位碳化的蔗糖为硬模板,采用双结构导向剂(四乙基氢氧化铵、吗啡啉),通过干凝胶方法合成了多级孔道SAPO-34分子筛。使用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及氮气物理吸附对分子筛结构进行表征,并进行了低密度聚乙烯热解性能考评。结果表明,合成的多级孔道SAPO-34晶体具有纳米尺寸,含有晶内介孔,介孔体积达0.41 cm3/g。四乙基氢氧化铵具有促进成核的作用,使晶体尺寸降低。结晶过程中纳米晶体对碳模板的包裹造成了晶内介孔的形成。该分子筛在低密度聚乙烯热解反应中T50温度显著降低,说明其具有更多可接近的酸性位。     

锂离子电池电极中多级孔道结构设计

在较高充放电速率下,锂电池电极中Li⁺扩散受限严重,致使电池性能显著降低。为了减弱扩散限制,设计电极的孔结构是一种行之有效的方法。本工作以LiCoO₂正极为模型电极,利用建立的二维模型,优化了电极中含低曲折因子孔道的多级孔道结构。这些低曲折因子孔道可作为Li⁺传输的“高速公路”,优化其孔隙率和孔径,可大幅度提升高放电倍率下的能量密度。低曲折因子孔道的最佳孔隙率高度依赖于其孔径,其直径小于10 μm较优。当电极厚度为200 μm且总孔隙率为0.36时,优化后的多级孔电极相比于传统电极,能量密度可提高45.9%~91.4%。此外,当Li⁺的扩散限制较弱时（例如,电极厚度≤50 μm和总孔隙率≥0.48）,优化电极的多级孔结构并不会显著提升电极性能。本工作可为锂电池电极中多级孔道结构的设计提供一定的指导。     

硬模板法合成晶态介孔金属氧化物研究进展

晶态介孔金属氧化物材料因具有窄的孔径分布、大的比表面积、有序的孔道结构以及高度晶化的孔壁而在工业催化、光电等领域有着广泛的应用.在各种制备方法中,硬模板法因制备方法简单、条件温和、产物孔道结晶度高而受到了广泛关注.对硬模板法中介孔硅模板和介孔碳模板进行了介绍;总结了近年来硬模板法合成氧化铬、氧化铁、氧化铈、氧化镁和氧化钴等晶态介孔材料的研究进展;概述了该材料的发展趋势和应用前景.     

非离子模板剂制备有序介孔氧化铝及表征

以硝酸铝为原料,采用非离子型表面活性剂聚乙二醇为模板剂,磷酸氢二铵为辅助剂,通过沉淀方法合成有序介孔氧化铝。探讨了模板剂的选取、反应终点pH值、反应温度、后处理工艺和辅助剂等条件对合成的有序介孔氧化铝结构影响,采用BET、XRD、TEM等测试技术对样品进行了结构表征,研究结果表明合成的有序介孔氧化铝比表面积大且孔分布窄,形成的蠕虫状孔道具有一定的有序性。     

从反应活化能垒角度探讨多晶硅还原机理

三氯氢硅还原反应是改良西门子法生产多晶硅的主要过程,本文对三氯氢硅还原反应进行分子模拟,采用密度泛函理论方法(DFT)研究了三氯氢硅还原成多晶硅的能量变化,对其分子结构进行优化,通过LST/QST方法计算多晶硅还原过程中可能出现的过渡态及能量的变化,得到过渡态TSa、TSb、TSc。结果表明,三氯氢硅还原反应通道Path a所得过渡态的活化能垒较低,过程进行较顺利。     

形貌可控的银纳米颗粒合成及应用

银纳米材料具有独特的物理性质,在光学、生物和催化等领域应用潜力巨大,是近年来材料领域的研究热点。银纳米材料的很多性能与其形貌密切相关,如枝状银纳米颗粒局部表面等离子体共振较强,不同形貌的银纳米颗粒裸露不同的晶面,导致其催化选择性不同。因此,控制合成特定形貌和结构的银纳米颗粒一直是该领域的重要研究方向。本工作综述了近年来银纳米颗粒形貌可控的合成方法,包括溶液还原法、晶种法、生物合成法、光诱导法、反应-扩散调控的动力学法和模板法等,比较了不同方法的优缺点,分析了不同合成方法的机理。重点介绍了基于反应和扩散调控的动力学方法,总结了其优点和普适性。调研了不同形貌银纳米颗粒在抑菌、局部等离子体共振和催化等领域的应用研究,分析了不同形貌银纳米颗粒的工业化应用前景,并对银纳米形貌的可控合成和应用进行了展望。     

Design of biomimetic catalysts by molecular imprinting in synthetic polymers: the role of transition state stabilization

The impressive efficiency and selectivity of biological catalysts has engendered a long-standing effort to understand the details of enzyme action. It is widely accepted that enzymes accelerate reactions through their steric and electronic complementarity to the reactants in the rate-determining transition states. Thus, tight binding to the transition state of a reactant (rather than to the corresponding substrate) lowers the activation energy of the reaction, providing strong catalytic activity. Debates concerning the fundamentals of enzyme catalysis continue, however, and non-natural enzyme mimics offer important additional insight in this area. Molecular structures that mimic enzymes through the design of a predetermined binding site that stabilizes the transition state of a desired reaction are invaluable in this regard. Catalytic antibodies, which can be quite active when raised against stable transition state analogues of the corresponding reaction, represent particularly successful examples. Recently, synthetic chemistry has begun to match nature's ability to produce antibody-like binding sites with high affinities for the transition state. Thus, synthetic, molecularly imprinted polymers have been engineered to provide enzyme-like specificity and activity, and they now represent a powerful tool for creating highly efficient catalysts. In this Account, we review recent efforts to develop enzyme models through the concept of transition state stabilization. In particular, models for carboxypeptidase A were prepared through the molecular imprinting of synthetic polymers. On the basis of successful experiments with phosphonic esters as templates to arrange amidinium groups in the active site, the method was further improved by combining the concept of transition state stabilization with the introduction of special catalytic moieties, such as metal ions in a defined orientation in the active site. In this way, the imprinted polymers were able to provide both an electrostatic stabilization for the transition state through the amidinium group as well as a synergism of transition state recognition and metal ion catalysis. The result was an excellent catalyst for carbonate hydrolysis. These enzyme mimics represent the most active catalysts ever prepared through the molecular imprinting strategy. Their catalytic activity, catalytic efficiency, and catalytic proficiency clearly surpass those of the corresponding catalytic antibodies. The active structures in natural enzymes evolve within soluble proteins, typically by the refining of the folding of one polypeptide chain. To incorporate these characteristics into synthetic polymers, we used the concept of transition state stabilization to develop soluble, nanosized carboxypeptidase A models using a new polymerization method we term the "post-dilution polymerization method". With this methodology, we were able to prepare soluble, highly cross-linked, single-molecule nanoparticles. These particles have controlled molecular weights (39 kDa, for example) and, on average, one catalytically active site per particle. Our strategies have made it possible to obtain efficient new enzyme models and further advance the structural and functional analogy with natural enzymes. Moreover, this bioinspired design based on molecular imprinting in synthetic polymers offers further support for the concept of transition state stabilization in catalysis.     

Shape complementarity, binding-site dynamics, and transition state stabilization: a theoretical study of Diels-Alder catalysis by antibody 1E9

Antibody 1E9 is a protein catalyst for the Diels-Alder reaction between tetrachlorothiophene dioxide and N-ethylmaleimide. Quantum mechanical calculations have been employed to study the 1E9-catalyzed Diels-Alder reaction in the gas phase. The transition states and intermediates were all determined at the B3LYP/6-31G*//HF/6-31G* level. The cycloaddition step is predicted to be rate-determining, and the endo reaction pathway is strongly favored. Binding of the reactants and the transition states to antibody 1E9 was investigated by docking and molecular dynamics simulations. The linear interaction energy (LIE) method was adopted to estimate the free energy barrier of the 1E9-catalyzed Diels-Alder reaction. The catalytic efficiency of antibody 1E9 is achieved by enthalpic stabilization of the transition state, near-perfect shape complementarity of the hydrophobic binding site for the transition state, and a strategically placed hydrogen-bonding interaction.     

高分子固-固相转变储能材料的研究进展

对高分子固-固相转变储能材料的研究进展进行了综述。根据相变储能机理，具有固-固相转变储能功能的聚合物材料被分为2大类即交联型结晶聚合物相变材料和以聚合物为摹体的复合相变材料。详细介绍了各种相变材料的制备方法、性能和应用，并且展望了高分子固-固相转变储能材料的发展前景。     

Preparation and Characterization of Novel Mesoporous Lanthanide–Transition Metal Mixed Oxides

We report a cationic supramolecular templating route to prepare thermally stable mixed oxides of lanthanides–transition metals, and characterization of such materials. The materials have three-dimensional wormhole-like mesoporosity with a partly crystalline lanthanide phase but an X-ray diffraction-invisible transition metal oxide phase that are probably finely dispersed as <3 nm crystallites. The materials had high surface areas with a narrow pore-size distribution in the mesoporous range after calcination up to 973 K. The materials were active for volatile organic compounds (toluene) removal at room temperature, with mesoporous ceria–titania showing the highest activity. These results suggest that these mesoporous mixed oxides are promising for air-purification applications.     

High quality mesoporous materials prepared by supercritical fluid extraction: effect of curing treatment on their structural stability

Mesoporous molecular sieves like SBA-1, SBA-3, MCM-41 and MCM-48 are generally synthesized by using a quaternary ammonium surfactant as a structure-directing agent to form a porous silica framework. The used templating agent is conventionally removed for producing mesopores by calcination at high temperature. In this study, supercritical fluid extraction (SFE) has been employed to remove organic templates from these materials. We found that more than 80% of the templating agent can be successfully removed by using this technique. Among these materials, SBA-3 was observed to experience the collapse of mesoporous structures upon the SFE process. Thus, we have proposed pre-SFE thermal aging as a curing treatment method and found that it has significantly improved the mesoporous structural stability of SBA-3. In the meantime, this curing method has lead to these SFE-processed materials with better ordered mesoporous structures, such as SBA-3 having specific surface area as large as 1670 m²/g.     

基于多孔支撑体的形状稳定复合相变储能材料的研究进展

固-液相变材料（PCMs）是热能储存（TES）技术发展的关键因素,然而一些固有的问题如泄漏和热导率低等严重制约了相变材料的性能。因此,选择合适的方法构建形状稳定的复合相变材料（FSCPCMs）,并有效地提高其热导率是实现相变材料实用化的重要前提。多孔载体封装相变材料为构建具有高储能密度和优异热传输性能的定形复合相变材料提供了一条有效的途径。本文对不同FSCPCMs的制备、结构热学性能、应用等方面进行了综述,详细总结和讨论了孔径和几何形状、表面改性、作用力、组成等因素对FSCPCMs相变行为的影响。重点介绍了具有高热导率、高负载率和高潜热的新型多孔复合相变材料的设计和应用。最后,基于理论、数值和实验方法,展望了FSCPCMs在约束结构中的相变和多尺度传热方面未来的研究方向及其在能源转换方面的商业化应用。     

类沸石咪唑酯骨架材料(ZIFs)的研究进展

类沸石咪唑酯骨架化合物(zeolitic imidazolate frameworks,ZIFs)是一种新型的MOFs材料,ZIFs是将咪唑环上的N原子络合到二价过渡金属离子上而形成的一种具有沸石拓扑结构的多孔晶体材料,通过调变配体或配体间的相互作用就可以形成不同结构的ZIFs。ZIFs的合成方法包括溶剂热法、水热法、液相扩散法、胶体化学法、微波合成法和超声法等,本文综述了ZIFs材料的多种优异性能,介绍了近些年来ZIFs材料在选择性气体吸附/分离、催化反应、光学、磁性材料及其他方面的应用。最后对合成新型的ZIFs材料,并将该ZIFs材料应用在电子设备、能源利用以及环境保护等方面进行了展望。     

Electrochemical synthesis of lamellar structured ZnO films via electrochemical interfacial surfactant templating

Interest in creating tunable, ordered mesoporous materials based on surfactant supramolecular templating has been increasing over the last decade. For the production of film-type mesoporous materials, the most common method currently used is sol-gel based dip-coating method, which utilizes evaporation induced self-assembly (EISA) of surfactants. A more recently developed method, electrochemical interfacial surfactant templating, exploits the interfacial surfactant assembly formed on the working electrode to electrodeposit inorganic mesoporous films. This method offers mechanisms for inorganic wall construction and amphiphilic assemblies that are quite different from those of the sol-gel dip-coating method. As a result, it offers new possibilities to produce mesoporous films that cannot be produced by other means. This paper reviews the recent advances in producing and tuning lamellar structured mesoporous zinc oxide films via electrochemical interfacial surfactant templating. The general principles of this method will be explained in comparison with other methods used for producing mesoporous films. This will be followed by discussions of the key synthesis conditions that govern the repeat unit, quality, and orientation of lamellar structures constructed during electrodeposition. This review will provide a useful foundation to further develop electrochemical interfacial surfactant templating as a versatile method to produce a broader range of mesoporous films.