金属间化合物的合成及其催化应用

简要叙述了合成金属间化合物的化学还原、沉积沉淀还原、化学气相沉积和热退火等方法。这些合成方法各有优缺点,可根据实际需求选择适宜的方法。总结了金属间化合物对加氢、氧化、重整等反应的催化性能,发现金属间化合物是一类性能优良的催化材料,催化活性与其具有的有序原子排列、电子效应、几何效应、空间效应、协同作用等有关。此外,还展望了此类材料的未来研究方向。     

Synergizing Mo Single Atoms and Mo2C Nanoparticles on CNTs Synchronizes Selectivity and Activity of Electrocatalytic N2 Reduction to Ammonia

Previous research of molybdenum-based electrocatalysts for nitrogen reduction reaction (NRR) has been largely considered on either isolated Mo single atoms (MoSAs) or Mo carbide particles (e.g., Mo₂C) separately, while an integrated synergy (MoSAs-Mo₂C) of the two has never been considered. The theoretical calculations show that the Mo single atoms and Mo₂C nanoparticles exhibit, respectively, different catalytic hydrogen evolution reaction and NRR selectivity. Therefore, a new role-playing synergistic mechanism can be well enabled for the multistep NRR, when the two are combined on the same N-doped carbon nanotubes (NCNTs). This hypothesis is confirmed experimentally, where the MoSAs-Mo₂C assembled on NCNTs (MoSAs-Mo₂C/NCNTs) yields an ammonia formation rate of 16.1 µg h⁻¹ cm_cat⁻² at −0.25 V versus reversible hydrogen electrode, which is about four times that by the Mo₂C alone (Mo₂C/NCNTs) and 4.5 times that by the MoSAs alone (MoSAs/NCNTs). Moreover, the Faradic efficiency of the MoSAs-Mo₂C/NCNTs is raised up to twofold and sevenfold of the Mo₂C/NCNTs and MoSAs/NCNTs, respectively. The MoSAs-Mo₂C/NCNTs also demonstrate outstanding stability by the almost unchanged catalytic performance over 10 h of the chronoamperometric test. The present study provides a promising new prototype of synchronizing the selectivity and activity for the multistep catalytic reactions.     

原子级分散负载催化剂的扫描透射电子显微学研究

球差校正扫描透射电子显微镜（STEM）因其原子级的空间分辨率和元素解析能力,在纳米功能材料的结构和成分分析中得到广泛使用。扫描透射电子显微镜高角环形暗场像技术（STEM-HAADF）凭借独特的原子序数衬度（Z衬度）和电子通道效应,在负载型纳米催化剂的结构研究中有着显著优势。通过STEM-HAADF成像,研究人员不仅可以直接观测到单个贵金属原子在较轻的载体上的实空间分布,还可以实现对载体表面上不同的负载贵金属物种的统计分析,这为近十年兴起的单原子催化剂研究提供了最重要的结构分析支持。相对于STEM-HAADF成像,基于STEM的X射线能谱（EDS）和电子能量损失谱（EELS）的谱学分析技术则能够在纳米尺度乃至原子尺度提供直接的化学成分或化学价态信息。成像和谱学的结合能够更准确地确定负载的金属原子在基底上的空间构型。进一步将原位电镜技术引入扫描透射电子显微镜内,则可以在时间尺度上探究催化剂在接近工作环境下的结构演化,从而更全面地揭示催化剂化学活性的结构起源与失效机制。本文结合近几年的部分代表性研究成果,简要介绍球差校正STEM技术在原子级分散负载催化剂研究中的应用,并对其在该研究领域的进一步发展进行了展望。     

氨气氛中镍催化剂和纳米碳管的制备

用X射线衍射仪、扫描电子显微镜和透射电子显微镜,研究了以瓷舟为载体、硝酸镍为原料、乙炔为碳源,在氨气中制备镍催化剂和纳米碳管时温度的影响,并讨论了氨气的作用.结果表明,以氨气还原硝酸镍获得镍催化剂时,最佳温度范围是700～800℃,此时催化剂的颗粒较细小且均匀,有利于纳米碳管的生长;此外,选用孔径比较细小均匀多孔的载体材料,有助于获得颗粒均匀细小的镍催化剂;在制备纳米碳管时,热分解氨得到的活性氢原子有利于维持催化剂的活性,抑制无定型碳的生成,从而促进纳米碳管生长.实验中纳米碳管的最佳制备温度为700～800℃,管径为10～25nm.     

表面动力学过程的二维成像——光发射电子显微镜系统的研制及应用

光发射电子显微镜是 90年代初发展起来的一种新的表面原位技术 ,它能够在多相催化反应过程中原位、动态观察样品表面局域功函数的变化 ,从而获得反应动力学的信息。本实验利用德国Fritz Harber研究所赠送的部分部件 ,并配之于AES ,LEED ,MS等常规分析手段 ,成功地研制了国内首台光发射电子显微镜系统 ,其主要性能指标达到 90年代初国际水平。本文简单介绍了该系统的研制以及已进行的部分研究工作。     

介孔材料的合成机理与应用

对近年来介孔材料的最新研究进展进行了综述.就介孔材料的主要合成机理,即液晶模板机理、电荷匹配机理、静电作用模型、棒状自组装模型和层状折皱模型等进行了简要介绍,对介孔材料在催化、吸附、纳米复合体系及其他领域的应用情况进行了总结,并对未来的发展趋势进行了展望.     

Shape-Controlled Synthesis of Platinum-Based Nanocrystals and Their Electrocatalytic Applications in Fuel Cells

To achieve environmentally benign energy conversion with the carbon neutrality target via electrochemical reactions, the innovation of electrocatalysts plays a vital role in the enablement of renewable resources. Nowadays, Pt-based nanocrystals(NCs) have been identified as one class of the most promising candidates to efficiently catalyze both the half-reactions in hydrogen-and hydrocarbonbased fuel cells. Here, we thoroughly discuss the key achievement in developing shape-controlled Pt and Pt-b...     

高熵合金中间层对TiNi/TC4电子束焊接头组织及性能影响

目的 解决TiNi/TC4异种金属的焊接问题,扩大此2种金属的结合应用.方法 选用3 mm×40 mm×0.5 mm的FeCoCrNiMn高熵合金薄片作为中间层,采用电子束焊接方法焊接TiNi/TC4.对形成的接头进行宏观分析,采用电子显微镜以及X射线衍射仪对其微观组织进行表征;通过拉伸和硬度测试,分析该接头的力学性能.结果 接头宏观成形存在裂纹缺陷,观察微观组织发现,在焊接接头中只形成了AlTi3相和Ni0.35Al0.30Ti0.35相,没有形成Ti2Ni相.接头的抗拉强度为81.8 MPa,伸长率为4.38％,平均显微硬度为HV661,断口呈脆性断裂特征.结论 将高熵合金作为中间层焊接TiNi/TC4是一种有效的方法,可以成功实现异种金属的焊接,中间层的存在可以有效调控焊缝中的析出相种类.     

Synthesis and Applications of Graphdiyne‐Based Metal‐Free Catalysts

The development of carbon materials offers the hope for obtaining inexpensive and high‐performance alternatives to substitute noble‐metal catalysts for their sustainable application. Graphdiyne, the rising‐star carbon allotrope, is a big family with many members, and first realized the coexistence of sp‐ and sp²‐hybridized carbon atoms in a 2D planar structure. Different from the prevailing carbon materials, its nonuniform distribution in the electronic structure and wide tunability in bandgap show many possibilities and special inspirations to construct new‐concept metal‐free catalysts, and provide many opportunities for achieving a catalytic activity comparable with that of noble‐metal catalysts. Herein, the recent progress in synthetic methodologies, theoretical predictions, and experimental investigations of graphdiyne for metal‐free catalysts is systematically summarized. Some new perspectives of the opportunities and challenges in developing high‐performance graphdiyne‐based metal‐free catalysts are demonstrated.     

Advancement of Ag–Graphene Based Nanocomposites: An Overview of Synthesis and Its Applications

Graphene has been employed as an excellent support for metal nanomaterials because of its unique structural and physicochemical properties. Silver nanoparticles (AgNPs) with exceptional properties have received considerable attention in various fields; however, particle aggregation limits its application. Therefore, the combination of AgNPs and graphene based nanocomposites (Ag–graphene based nanocomposites) has been widely explored to improve their properties and applications. Excitingly, enhanced antimicrobial, catalytic, and surface enhanced Raman scattering properties are obtained after their combination. In order to have a comprehensive knowledge of these nanocomposites, this Review highlights the chemical and biological synthesis of Ag–graphene nanocomposites. In particular, their applications as antimicrobial agents, catalysts, and sensors in biomedicine, agricultural protection, and environmental remediation and detection are covered. Meanwhile, the factors that influence the synthesis and applications are also briefly discussed. Furthermore, several important issues on the challenges and new directions are also provided for further development of these nanocomposites.     

双核水杨醛亚胺镍催化剂的制备及对降冰片烯聚合的催化性能

合成了3种5,5′-亚甲基-双-水杨醛亚胺配体,利用它们和trans-[NiCl(Ph)(PPh3)2]反应得到Cat1、Cat2和Cat3三种双核水杨醛亚胺镍催化剂,并通过红外(FT-IR)和元素分析进行了表征。研究了在甲苯为溶剂,MAO为助催化剂下,催化降冰片烯(NBE)单体聚合的催化性能,考察了聚合条件,如温度、Al/Ni物质的量比对降冰片烯的催化活性、单体转化率、聚合物分子量及分子量分布的影响。当在n(Al)/n(Ni)为1000,聚合温度为80℃的条件下,催化剂的催化活性达到最大值1.16×105g of PNB/(mol of Ni.h)。聚合产物的核磁共振(1H-NMR)和红外光谱分析结果表明,该聚合反应是以单体的乙烯基加成聚合机理进行的。     

氨络合物体系中镍在玻璃碳上的电化学成核机理

采用循环伏安法和计时电流法研究了氨络合物体系中镍在玻璃碳上电结晶的初期行为。结果表明．镍在该基体上的沉积没有经历UPD过程，镍的电沉积经历了晶核形成过程，在所研究的外加电位范围内其电结晶按连续成核和三维生长方式进行，外加电位对晶体生长具有显著的影响。通过分析恒电位暂态曲线，求出镍离子的扩散系数D，以及不同外加电位下的饱和晶核数密度Nsat，探讨了外加电位对成核作用的影响。     

高纯氨包装容器中存在痕量水积累问题的理论探讨

充分干燥的高纯氨包装容器,经反复充装若干次以后,会残留积累愈来愈多的水分。水是高纯氨质量控制的主要指标之一,对于5 N电子级高纯氨,水含量应控制在<5 ppm,对于5.5 N以上纯度的超纯氨,水分更应控制在1 ppm以下。对高纯氨水积累原因进行探讨,并提出解决问题的方法。     

Synthesis of Metal/Bimetal Nanowires and Their Applications as Flexible Transparent Electrodes

As a potential alternative to indium oxide (ITO), metal nanowire transparent conductive electrodes (TCEs) have attracted more and more attention. Here, a facile method that can be applied to the synthesis of a variety of metal/bimetallic nanowires has been proposed. Metal/bimetallic nanowires synthesized through this method show high aspect ratios and great dispersibility, which makes them ideal building blocks for transparent electrodes. The synthesis mechanism is discussed in‐depth to give a theoretical basis of morphology control of metal nanostructures in organic synthesizing systems. TCEs with high flexibility, excellent optical–electrical performance as well as outstanding anti‐thermal and anti‐moisture stability are constructed. To the best of our knowledge, this is the first work on synthesizing multiple metal/bimetallic nanowires through one method.     

Design and Synthesis of Noble Metal-Based Alloy Electrocatalysts and Their Application in Hydrogen Evolution Reaction

Hydrogen energy is regarded as the ultimate energy source for future human society, and the preparation of hydrogen from water electrolysis is recognized as the most ideal way. One of the key factors to achieve large-scale hydrogen production by water splitting is the availability of highly active and stable electrocatalysts. Although non-precious metal electrocatalysts have made great strides in recent years, the best hydrogen evolution reaction (HER) electrocatalysts are still based on noble metals. Therefore, it is particularly important to improve the overall activity of the electrocatalysts while reducing the noble metals load. Alloying strategies can shoulder the burden of optimizing electrocatalysts cost and improving electrocatalysts performance. With this in mind, recent work on the application of noble metal-based alloy electrocatalysts in the field of hydrogen production from water electrolysis is summarized. In this review, first, the mechanism of HER is described; then, the current development of synthesis methods for alloy electrocatalysts is presented; finally, an example analysis of practical application studies on alloy electrocatalysts in hydrogen production is presented. In addition, at the end of this review, the prospects, opportunities, and challenges facing noble metal-based alloy electrocatalysts are tried to discuss.     

石墨烯纳米复合材料合成及其在光催化氧化降解和还原制备氢能中应用的研究进展

石墨烯因独特的二维纳米结构和优良的物理化学性能已经成为近年来纳米材料研究的热点领域之一。作为一类新型的碳基材料,石墨烯纳米复合材料已经广泛地应用于多相光催化的诸多方面。对石墨烯纳米复合材料的制备、光催化还原制氢原理、光催化氧化染料降解原理、光催化活性的主要影响因素、石墨烯纳米复合材料在光催化氧化污染物降解、光催化还原制氢以及CO2还原制甲醇中的应用等领域的最新研究进展进行了较系统的综述,对一些新的光催化反应以及反应机理进行了归纳总结,提出了石墨烯纳米复合材料存在的问题以及未来的发展方向。     

扫描透射电子显微镜(STEM)在新一代高K栅介质材料的应用

扫描透射电子显微镜(STEM)原子序数衬度像(Z-衬度像)具有分辨率高(可直接“观察”到晶体中原子的真实位置)、对化学组成敏感以及图像直观易解释等优点, 成为原子尺度研究材料微结构的强有力工具。本文介绍了STEM Z-衬度像成像原理、方法及技术特点, 并结合具体的高K栅介质材料 (如铪基金属氧化物、稀土金属氧化物和钙钛矿结构外延氧化物薄膜)对STEM在新一代高K栅介质材料研究中的应用进行了评述。 目前球差校正STEM Z-衬度的像空间分辨率已达亚埃级, 该技术在高K柵介质与半导体之间的界面微结构表征方面具有十分重要的应用。对此, 本文亦进行了介绍。     

Synthesis of Carbon‐Nanotube Composites Using Supercritical Fluids and Their Potential Applications

Carbon‐nanotube (CNT) composites have attracted a lot of attention because of their potential applications in many fields. Here, recent advances in the synthesis of CNT composites using supercritical fluids (SCFs) are highlighted. SCFs exhibit unique features for the synthesis of composites because of their unusual properties, such as low viscosity, high diffusivity, near‐zero surface tension, and tunability. Preliminary studies show that SCFs show unusual advantages for the synthesis of CNT composites. The morphologies and structures of the resultant CNT composites can be tuned by changing the solvent properties. The SCF methods not only provide a green route for the synthesis of composites, but also result in nanostructures that have not yet been produced by conventional methods. Moreover, the potential applications of the resultant CNT composites are also discussed.