采用简易方法合成直接乙醇固体氧化物燃料电池海胆状Pd催化层

在室温下,通过电位置换反应在固体氧化物燃料电池的Ni-YSZ(钇掺杂氧化锆)阳极表面制备海胆状Pd催化层。该催化层的结构和性能通过SEM、XRD和电化学等表征手段进行表征。结果表明,三维纳米花状Pd催化剂是由在Ni-YSZ阳极表面形成的多条纳米棒有序的组合而成。通过在Ni/YSZ阳极表面引入该催化层,相比与传统Ni-YSZ阳极,燃料电池的最高功率和稳定性都获得了很大的提升。该研究表明,电位置换反应是一种很高效的在传统Ni-YSZ阳极表面制备纳米抗积炭的功能层的方法。     

采用简易方法合成直接乙醇固体氧化物燃料电池海胆状Pd催化层（英文）

在室温下,通过电位置换反应在固体氧化物燃料电池的Ni-YSZ(钇掺杂氧化锆)阳极表面制备海胆状Pd催化层。该催化层的结构和性能通过SEM、XRD和电化学等表征手段进行表征。结果表明,三维纳米花状Pd催化剂是由在Ni-YSZ阳极表面形成的多条纳米棒有序的组合而成。通过在Ni/YSZ阳极表面引入该催化层,相比与传统Ni-YSZ阳极,燃料电池的最高功率和稳定性都获得了很大的提升。该研究表明,电位置换反应是一种很高效的在传统Ni-YSZ阳极表面制备纳米抗积炭的功能层的方法。     

铂基空心纳米框架的合成及其在直接醇燃料电池中的应用（英文）

与其他铂基纳米晶体材料相比,铂基纳米框架催化剂因其独特的结构特征和优异的催化性能引起研究者的广泛关注。开放的空间结构设计和组分可控调制不仅提高了铂的原子利用率,而且能在减少铂消耗的同时改善其电催化活性。本文简要综述了铂基纳米框架电催化剂的最新进展。在介绍不同的铂基纳米框架制备和蚀刻策略之后,也对框架晶体的结构演变及其在醇燃料电池中氧还原反应和醇氧化反应的催化应用进行了总结。此外,基于纳米框架材料的类型、合成方法、结构形态和催化性能,对铂基纳米框架的当前存在的挑战和未来的发展前景进行了总结和展望。基于铂基纳米框架材料的改进机制和规模化制备策略,我们相信纳米框架材料将会在醇燃料电池等技术中发挥更大作用。     

Pd/Ni异结构纳米催化剂的制备及其对甲酸氧化的电催化

通过两步还原法制备了Pd/Ni双金属催化剂.由于金属Pd原子在先行还原的Ni纳米粒子表面的外延生长以及其在Ni表面及Pd表面生长表现出的吉布斯自由能差异,最终导致了异结构Pd/Ni纳米粒子的形成.高分辨电子透射显微镜结果证实了异结构的存在,然而X射线衍射测量表明Pd/Ni纳米粒子具有类似于Pd的面心立方结构.制备的Pd/Ni纳米粒子与同等条件下合成的Pd纳米粒子相比对甲酸氧化呈现了更高的电催化活性,而且电催化稳定性也要明显优于纯Pd纳米粒子,证明Pd/Ni双金属催化剂是可选的直接甲酸燃料电池阳极催化剂.双金属催化剂对甲酸氧化电催化活性和稳定性增强可能是Ni原子的修饰改变了Pd粒子表面配位不饱和原子的电子结构所致.     

聚苯胺-改性木质素磺酸钠复合材料基活性炭负载Pd催化剂对甲酸氧化的催化性能（英文）

将聚苯胺/改性木质素磺酸钠复合材料在不同炭化温度下进行处理得到活性炭材料,利用红外光谱、拉曼光谱、比表面积分析和扫描电镜等手段对其结构和表面性质进行了表征。通过液相还原方法将Pd纳米颗粒负载在所制备的活性炭材料上,获得Pd/C催化剂用于甲酸氧化,并采用X射线衍射、透射电镜和电化学测试等方法对该Pd/C催化剂进行表征。结果表明,以800℃下炭化得到的活性炭材料为载体所制备的Pd-AC800催化剂其催化性能最优;Pd粒径为5.4 nm,电化学活性面积为53.78 m~2/g。由于在该催化剂上甲酸氧化通过直接途径进行,Pd-AC800可用作直接甲酸燃料电池的催化剂。     

钯纳米粒子在电极表面的制备及其对氧的催化还原

纳米微粒的体积效应使其成为表面纳米工程及功能化纳米结构材料制备的理想研究对象 [1～ 3] .纳米粒子具有独特的电子、催化及光学特性[4 ] ,近年来关于纳米粒子的制备及其在材料科学领域中的应用受到研究者的极大关注 .而贵金属纳米粒子由于其在催化领域中的广泛应用而成为最重要的研究对象之一[5,6 ] .电催化氧还原是一直为化学家瞩目的研究领域[7～ 9] .研究主要目的之一是寻找合适的氧电极反应催化剂 ,并使之能够应用于燃料电池中 .其中催化氧电极材料研究得最多的是贵金属 Pt[10 ,11] .贵金属 Pd对氧催化还原的研究工作很少 .我们首次…     

高活性Pd/MgO催化剂的制备及其CO氧化偶联制草酸二甲酯催化反应

利用溶液法结合高温煅烧处理合成MgO载体,通过浸渍法制备Pd/MgO催化剂并对其进行CO氧化偶联制草酸二甲酯催化性能研究。通过X射线粉末衍射、CO2程序升温脱附、比表面仪、热重分析、扫描电镜、透射电镜和微型催化评价装置对合成的样品进行结构和性能表征。结果表明,合成的MgO载体是一种Lewis碱性很强的纳米片结构,Pd纳米颗粒高度分散在MgO载体上,粒径小且分布均一。此MgO纳米片作为载体制备的Pd/MgO催化剂在较低的Pd负载量(0.5%)下表现出优异的CO氧化偶联催化性能,在反应温度130℃时CO单程转化率高达65%,草酸二甲酯选择性96%,稳定性超过100 h,明显越于工业催化剂(Pd/α-Al2O3),具有潜在的工业应用前景。     

聚苯胺-改性木质素磺酸钠复合材料基活性炭负载Pd催化剂对甲酸氧化的催化性能

将聚苯胺/改性木质素磺酸钠复合材料在不同炭化温度下进行处理得到活性炭材料，利用红外光谱、拉曼光谱、比表面积分析和扫描电镜等手段对其结构和表面性质进行了表征。通过液相还原方法将Pd纳米颗粒负载在所制备的活性炭材料上，获得Pd/C催化剂用于甲酸氧化，并采用X射线衍射、透射电镜和电化学测试等方法对该Pd/C催化剂进行表征。结果表明，以800℃下炭化得到的活性炭材料为载体所制备的Pd-AC800催化剂其催化性能最优；Pd粒径为5.4 nm，电化学活性面积为53.78 m²/g。由于在该催化剂上甲酸氧化通过直接途径进行，Pd-AC800可用作直接甲酸燃料电池的催化剂。     

牺牲模板法制备空心结构钯纳米粒子/石墨烯复合体及其甲酸电氧化性能研究

通过Pd Cl42-与Co之间发生简单的置换反应,在表面活性剂PVP的作用下,成功地制备出由3 nm的Pd纳米粒子组成的空心结构Pd纳米球结构,将其命名为Pd-NS。随后,以石墨烯(GN)作为载体,将Pd-NS负载在GN的表面制备了Pd-NS/GN催化剂。在甲酸电氧化催化反应中,Pd-NS/GN催化剂表现出较大的电化学比表面积、良好的电催化性能以及较高的稳定性。     

高指数晶面纳米催化剂的电化学制备及应用

催化剂的性能与其表面结构及组成密切相关,高指数晶面纳米晶的表面含有高密度的台阶原子等活性位点而表现出较高的催化活性. 本文综述了电化学方波电位方法用于Pt、Pd、Rh等贵金属高指数晶面结构纳米晶催化剂的制备、形成机理及其电催化性能的研究. 针对贵金属利用率问题,还着重介绍了具有较高质量活性的小粒径Pt二十四面体的制备. 在此基础上,还介绍了电化学方波电位方法用于低共熔溶剂中制备高指数晶面纳米晶,以及高指数晶面纳米催化剂的表面修饰及应用;最后对高指数晶面纳米催化剂的发展做出了展望.     

Synthesis of nanocrystals with variable high-index Pd facets through the controlled heteroepitaxial growth of trisoctahedral Au templates

The shape-controlled synthesis of noble metal nanocrystals (NCs) bounded by high-index facets is a current research interest because the products have the potential of significantly improving the catalytic performance of NCs in industrially important reactions. This study reports a versatile method for synthesizing polyhedral NCs enclosed by a variety of high-index Pd facets. The method is based on the heteroepitaxial growth of Pd layers on concave trisoctahedral (TOH) gold NC seeds under careful control of the growth kinetics. Polyhedral Au@Pd NCs with three different classes of high-index facets, including concave TOH NCs with {hhl} facets, concave hexoctahedral (HOH) NCs with {hkl} facets, and tetrahexahedral (THH) NCs with {hk0} facets, can be formed in high yield. The Miller indices of NCs are also modifiable, and we have used the THH NCs as a demonstrative example. The catalytic activities of these NCs were evaluated by the structure-sensitive reaction of formic acid electro-oxidation. The results showed that the high-index facets are generally more active than the low-index facets. In summary, a seeded growth process based on concave high-index faceted monometallic TOH NC templates and careful control of the growth kinetics is a simple and effective strategy for the synthesis of noble metal NCs with high-index facets. It also offers tailorability of the surface structure in shape-controlled synthesis.     

Noble‐Metal Nanocrystals with Controlled Facets for Electrocatalysis

Noble‐metal nanocrystals (NCs) show excellent catalytic performance for many important electrocatalysis reactions. The crystallographic properties of the facets by which the NCs are bound, closely associated with the shape of the NCs, have a profound influence on the electrocatalytic function of the NCs. To develop an efficient strategy for the synthesis of NCs with controlled facets as well as compositions, understanding of the growth mechanism of the NCs and their interaction with the chemical species involved in NC synthesis is quite important. Furthermore, understanding the facet‐dependent catalytic properties of noble‐metal NCs and the corresponding mechanisms for various electrocatalysis reactions will allow for the rational design of robust electrocatalysts. In this review, we summarize recently developed synthesis strategies for the preparation of mono‐ and bimetallic noble‐metal NCs by classifying them by the type of facets through which they are enclosed and discuss the electrocatalytic applications of noble‐metal NCs with controlled facets, especially for reactions associated with fuel‐cell applications, such as the oxygen reduction reaction and fuel (methanol, ethanol, and formic acid) oxidation reactions.     

PVP封端剂对Pd纳米晶电催化氧化甲醇和乙醇性能的影响

Direct alcohol fuel cells (DAFCs) have attracted considerable research interest because of their potential application as alternative power sources for automotive systems and portable electronics. Pd-based catalysts represent one of the most popular catalysts for DAFCs due to their excellent electrocatalytic activities in alkaline electrolytes. Thus, it is of great importance to understand the structure-activity relationship of Pd electrocatalysts for alcohol electrocatalysis. Recently, size- and shape- controlled Pd nanocrystals have been successfully synthesized and subsequently used to study the size and shape effects of Pd electrocatalysts on alcohol electrocatalysis, in which the Pd (100) facet exhibited higher electrocatalytic oxidation activity for small alcohol molecules than the Pd (111) and (110) facets. Although it is well known that capping ligands, which are widely used in wet chemistry for the size- and shape-controlled synthesis of metal nanocrystals, likely chemisorb onto the surfaces of the resulting metal nanocrystals and influence their surface structure and surface-mediated properties, such as catalysis, this issue was not considered in previous studies of Pd nanocrystal electrocatalysts for electrocatalytic oxidation of small alcohol molecules. In this study, we prepared polyvinylpyrrolidone (PVP)-capped Pd nanocrystals with different morphologies and sizes and comparatively studied their electrocatalytic activities for methanol and ethanol oxidation in alkaline solutions. The chemisorbed PVP molecules transferred charge to the Pd nanocrystals, and the finer Pd nanocrystals had a higher coverage of chemisorbed PVP, and thus exposed fewer accessible surface sites, experienced more extensive PVP-to-Pd charge transfer, and were more negatively charged. The intrinsic electrocatalytic activity, represented by the electrochemical surface area (ECSA)-normalized electrocatalytic activity, of Pd nanocubes with exposed (100) facets increases with the particle size, indicating that the more negatively-charged Pd surface is less electrocatalytically active. The Pd nanocubes with average sizes between 12 and 19 nm are intrinsically more electrocatalytically active than commercial Pd black electrocatalysts, while the activity of Pd nanocubes with an averages size of 8 nm is less. This suggests that the enhancement effect of the exposed (100) facets surpasses the deteriorative effect of the negatively charged Pd surface for the Pd nanocubes with average sizes between 12 and 19 nm, whereas the deteriorative effect of the negatively charged Pd surface surpasses the enhancement effect of the exposed (100) facets for the Pd nanocubes with average sizes of 8 nm due to the extensive PVP-to-Pd charge transfer. Moreover, the Pd nanocubes with average sizes of 8 nm exhibit similar intrinsic electrocatalytic activity to the Pd nanooctahedra with (111) facets exposed and average sizes of 7 nm, indicating that the electronic structure of Pd electrocatalysts plays a more important role in influencing the electrocatalytic activity than the exposed facet. Since the chemisorbed PVP molecules block the surface sites on Pd nanocrystals that are accessible to the reactants, all Pd nanocrystals exhibit lower mass-normalized electrocatalytic activity than the Pd black electrocatalysts, and the mass-normalized electrocatalytic activity increases with the ECSA. These results clearly demonstrate that the size- and shape-dependent electrocatalytic activity of Pd nanocrystals capped with PVP for methanol and ethanol oxidation should be attributed to both the exposed facets of the Pd nanocrystals and the size-dependent electronic structures of the Pd nanocrystals resulting from the size-dependent PVP coverage and PVP-to-Pd charge transfer. Therefore, capping ligands on capped metal nanocrystals inevitably influence their surface structures and surface-mediated properties, which must be considered for a comprehensive understanding of the structure-activity relationship of capped metal nanocrystals.     

Nanomaterials of high surface energy with exceptional properties in catalysis and energy storage

The properties of nanomaterials for use in catalytic and energy storage applications strongly depends on the nature of their surfaces. Nanocrystals with high surface energy have an open surface structure and possess a high density of low-coordinated step and kink atoms. Possession of such features can lead to exceptional catalytic properties. The current barrier for widespread industrial use is found in the difficulty to synthesise nanocrystals with high-energy surfaces. In this critical review we present a review of the progress made for producing shape-controlled synthesis of nanomaterials of high surface energy using electrochemical and wet chemistry techniques. Important nanomaterials such as nanocrystal catalysts based on Pt, Pd, Au and Fe, metal oxides TiO(2) and SnO(2), as well as lithium Mn-rich metal oxides are covered. Emphasis of current applications in electrocatalysis, photocatalysis, gas sensor and lithium ion batteries are extensively discussed. Finally, a future synopsis about emerging applications is given (139 references).     

多策略可控合成原子精度合金纳米团簇

合金纳米团簇作为一类新兴的多功能纳米材料已被广泛用于催化、光学传感以及生物医学成像等研究领域,而纳米团簇的可控合成和结构特征是调节纳米团簇性质并对其进一步利用的基础。尽管当前有关金属纳米团簇可控合成和结构特征的研究主要集中在单金属纳米团簇中,但有关合金纳米团簇原子精度的可控合成也取得了显著的进展。本文综述了配体保护的合金金属纳米团簇原子精度可控合成策略,包括一步合成法、金属交换、配体交换、化学刻蚀、簇间反应、原位两相配体交换以及最新的表面模体交换反应,并对相关合成策略的优缺点进行了详细的讨论和阐述。     

Lead‐Free Halide Perovskite Nanocrystals: Crystal Structures,Synthesis, Stabilities,and Optical Properties

In recent years, there have been rapid advances in the synthesis of lead halide perovskite nanocrystals (NCs) for use in solar cells, light emitting diodes, lasers, and photodetectors. These compounds have a set of intriguing optical, excitonic, and charge transport properties, including outstanding photoluminescence quantum yield (PLQY) and tunable optical band gap. However, the necessary inclusion of lead, a toxic element, raises a critical concern for future commercial development. To address the toxicity issue, intense recent research effort has been devoted to developing lead‐free halide perovskite (LFHP) NCs. In this Review, we present a comprehensive overview of currently explored LFHP NCs with an emphasis on their crystal structures, synthesis, optical properties, and environmental stabilities (e.g., UV, heat, and moisture resistance). In addition, strategies for enhancing optical properties and stabilities of LFHP NCs as well as the state‐of‐the‐art applications are discussed. With the perspective of their properties and current challenges, we provide an outlook for future directions in this rapidly evolving field to achieve high‐quality LFHP NCs for a broader range of fundamental research and practical applications.     

Electrocatalytic and photocatalytic applications of atomically precise gold-based nanoclusters

With advances in cluster chemistry, atomically precise gold nanoclusters(NCs) with well-defined composition and tunable structure provide an exciting opportunity to uncover the specific roles of the geometrical and electronic structures as well as the capped ligands in overall catalytic performances. The Au NCs possess quantum energy levels and unique optical properties,which have exhibited unexpected photocatalytic and electrocatalytic activities. In this review, we first highlight the electrocatalytic applications of Au NCs, including hydrogen evolution reaction, oxygen reduction reaction, CO_2 reduction and catalytic oxidation reactions, and then present Au NCs-driven photocatalytic applications such as selective organic reactions, decomposition of pollutants and energy conversion reactions. Finally, we conclude this review with a brief perspective on the catalytic field of Au NCs.     

Facile Synthesis of PdCu Echinus‐Like Nanocrystals as Robust Electrocatalysts for Methanol Oxidation Reaction

Exploiting high‐performance and inexpensive electrocatalysts for methanol electro‐oxidation is conductive to promoting the commercial application of direct methanol fuel cells. Here, we present a facile synthesis of echinus‐like PdCu nanocrystals (NCs) via a one‐step and template‐free method. The echinus‐like PdCu NCs possess numerous straight and long branches which can provide abundant catalytic active sites. Owing to the novel nanoarchitecture and electronic effect of the PdCu alloy, the echinus‐like PdCu NCs display high electrocatalytic performance toward methanol oxidation reaction in an alkaline medium. The mass activity of echinus‐like PdCu NCs is 1202.1 mA mg_Pd^?1, which is 3.7 times that of Pd/C catalysts. In addition, the echinus‐like structure, as a kind of three‐dimensional self‐supported nanoarchitecture, endows PdCu NCs with significantly enhanced stability and durability. Hence, the echinus‐like PdCu NCs hold prospect of being employed as electrocatalysts for direct alcohol fuel cells.     

Polyoxometalate‐Mediated One‐Pot Synthesis of Pd Nanocrystals with Controlled Morphologies for Efficient Chemical and Electrochemical Catalysis

Polyoxometalates (POMs), as inorganic ligands, can endow metal nanocrystals (NCs) with unique reactivities on account of their characteristic redox properties. In the present work, we present a facile POM‐mediated one‐pot aqueous synthesis method for the production of single‐crystalline Pd NCs with controlled shapes and sizes. The POMs could function as both reducing and stabilizing agents in the formation of NCs, and thus gave a fine control over the nucleation and growth kinetics of NCs. The prepared POM‐stabilized Pd NCs exhibited excellent catalytic activity and stability for electrocatalytic (formic acid oxidation) and catalytic (Suzuki coupling) reactions compared to Pd NCs prepared without the POMs. This shows that the POMs play a pivotal role in determining the catalytic performance, as well as the growth, of NCs. We envision that the present approach can offer a convenient way to develop efficient NC‐based catalyst systems.     

Ⅰ-Ⅲ-Ⅵ族半导体纳米晶:合成,性质及应用（英文）

半导体纳米晶具有独特的量子限域效应以及新颖的尺寸和形貌依赖特性,已被证实是在低成本高性能光伏器件、光致及电致发光二极管、生物成像、光催化等领域非常具有潜力的新型材料.其中,II-VI族与I-III-VI族半导体纳米晶由于其优异的性能在过去的数十年中引起了广泛的关注.过去数十年对于II-VI族半导体纳米晶的研究已经十分成熟,然而几乎所有的传统II-VI族半导体纳米晶都含有对环境有害的元素,对人体和环境造成不可逆转的伤害,从而限制了II-VI族半导体纳米晶的进一步应用.与二元II-VI族纳米晶相比,大部分三元I-III-VI族纳米晶不含镉和铅等重金属元素,因而具有低毒性的特点,并且其带隙窄、吸光收系数大、斯托克斯位移大、自吸收小以及发光波长在近红外区,所以有望使其成为新一代荧光纳米晶材料.例如,CuInS_2的带隙为1.53 eV,与太阳光谱匹配且其吸光系数较大,在10.5cm.~1左右,从而使其成为制备太阳能电池的一种优秀材料.另一方面,I-III-VI族纳米晶在可见光和近红外范围内呈现与尺寸相关的发光,它们的荧光量子产率在包覆ZnS壳后可超过50%,因而在照明,显示和生物成像领域具广泛应用的潜力.水溶性的I-III-VI族量子点粒径尺寸可以小于10 nm,可以减小纳米颗粒通过肾清除的淘汰率,并且具有高荧光性能和耐光性的特点,因此成为进行生物成像工作的优秀材料.与此同时,I-III-VI族纳米晶在光催化领域也展现了巨大的发展前景.本综述主要关注I-III-VI族纳米晶的合成,性质及应用.首先,我们概述了不同的化学合成方法,并列举讨论了一些经典的工作,根据纳米晶的种类分类统计了主要合成方法、形貌及尺寸.第二部分,我们讨论了它们的光物理和电子特性,解释了纳米晶的"donor-acceptor pair"(DAP)结合机理,概述了I-III-VI族纳米晶的磁光现象.接下来,我们概述了I-III-VI族纳米晶主要的应用领域,着重总结了在太阳能电池领域、半导体发光二极管领域、生物成像领域以及光催化制氢领域的研究进展.最后,我们会讨论半导体纳米晶的应用前景,以及它的机遇和挑战.