钯纳米晶体在电催化甲酸氧化反应中的形貌效应

本文基于课题组前期工作,选用适当的金属前驱物、还原剂、稳定剂和保护剂,通过调控氧化刻蚀和反应动力学等,成功合成了形貌和尺寸均不相同的Pd纳米晶.经过认真的纳米粒子清洗和电极修饰组装,考察了它们在电催化甲酸氧化反应中的形貌与性能的关系.研究结果表明,Pd纳米晶样品的最大电流密度以纳米八面体（nanooctahedra）、纳米线（nanowires）、纳米立方体（nanocubes）、纳米瓜子（nanotapers）、凹面纳米立方体（concave nanocubes）的顺序递增,催化甲酸氧化反应的起始氧化电位均小于0.2V.研究结果印证了Pd纳米晶催化甲酸氧化反应的催化性能在尺寸效应上主要受活性表面积的影响,扣除表面积效应后的催化性能与其尺寸没有明确关系.该系列Pd纳米晶的催化性能主要取决于其表面结构,得出Pd纳米晶催化甲酸氧化反应遵循{111}晶面〈{100}晶面〈高指数晶面的性能活性顺序.综合最大电流密度和最小操作电位因素发现,Pd凹面纳米立方体和Pd纳米瓜子具有相对较好的商用价值.     

氧化铈形貌对Pd纳米粒子分散的影响

氧化铈由于在氧化和还原气氛下具有快速Ce4+/Ce3+氧化还原循环作用,使其具有优异的储放氧能力,不仅可以分散和稳定金属粒子,还可在界面处与金属物种发生化学键合,并形成活性位点,因此已被广泛应用于多个催化反应体系,且表现出显著的形貌效应.通过对氧化铈形貌进行调控,使其暴露特定(111)、(110)和(100)晶面,已成为调节金属-氧化铈相互作用强度及金属物种电子、几何结构,提高催化性能的有效策略,但对其机制及活性位结构还没有清晰的认识.我们以氧化铈纳米粒子和纳米立方体为载体,其中氧化铈立方体平均尺寸为23 nm,主要暴露6个{100}晶面,边缘和截角暴露少量{110}及{111}晶面;球形氧化铈纳米粒子平均尺寸为11 nm,主要暴露{111}晶面;并进一步将2.0 wt％Pd物种分散在氧化铈立方体和球形纳米粒子上,通过扫描透射电子显微镜(STEM)和X射线光电子能谱(XPS)等研究了钯物种在氧化铈球形粒子和立方体上的原子结构和化学环境,进而分析了纳米结构氧化铈形貌对钯物种分散的影响.在球形氧化铈纳米粒子上主要形成了平均尺寸为2.0 nm的非晶态Pd纳米粒子以及极小的Pd物种,这主要是因为球形氧化铈纳米粒子上丰富的表面氧空位可通过Pd-CeO2强相互作用和Pd物种紧密键合.氧化铈立方体上的晶态Pd粒子尺寸为2.9 nm,金属与载体之间具有明显的界面,且Pd原子嵌入到氧化铈晶格中.同时,CO化学吸附测试也证明了氧化铈球形粒子上的钯分散度(70％)高于氧化铈立方体(52％).对于甲烷燃烧反应,主要涉及发生在金属粒子表面的PdO/Pd氧化还原循环,即Pd被O2氧化,PdO被CH4还原,富氧条件下决速步骤是PdO对CH4中C?H的活化,因此氧化铈立方体表面大尺寸的晶态Pd粒子被氧化后更容易被CH4还原,有利于PdO/Pd氧化还原循环,从而具有更高的活性和稳定性;然而在CO氧化反应中Pd/CeO2却呈现了相反的形貌效应,这是由于该反应遵循Mars-van Krevelen机理:CO吸附在金属Pd上,化学吸附的CO移动到钯-氧化铈界面,被氧化铈晶格氧氧化成CO2,产生的氧空位被表面氧补充,最后表面氧空位被气相氧补充;由于氧化铈球形粒子上的较小尺寸Pd具有更大的钯-氧化铈界面周长和更强的氧物种移动性,更易完成界面处的氧化还原循环,因此具有更高的CO氧化活性.     

Co_3O_4纳米立方体的可控合成及其CO氧化反应性能

在乙醇和三乙胺的混合溶液中,采用溶剂热法制备了尺寸为10 nm的Co3O4立方体.考察了钴盐前驱体和溶解氧对Co3O4纳米立方体结构的影响规律,通过对合成过程中不同阶段产物的结构分析和表征,提出了Co3O4纳米立方体的形成机制是溶解再结晶的过程.将所制备的Co3O4纳米立方体在200°C焙烧处理后,尺寸和形貌均可保持稳定,但400°C焙烧后,变为球形纳米粒子.这种主要暴露{100}晶面的Co3O4纳米立方体催化CO氧化反应的活性低于纳米粒子({111}晶面),验证了四氧化三钴纳米材料在CO氧化反应中的晶面效应.     

从头开始理解形貌依赖的CuOx-CeO2相互作用

CuOx/CeO2催化剂在CO氧化反应中表现出高催化活性和显著结构敏感性.文献报道中CuOx/CeO2催化剂体系的合成条件差异较大,从而导致观察到的CuOx-CeO2相互作用存在较大争议.因此,系统研究并阐明CuOx/CeO2催化剂中CuOx-CeO2相互作用对于理解复杂的CuOx-CeO2界面催化作用具有重要的研究意义.近期发现,氧化物纳米晶的形貌可作为一种新的结构参数,在不改变氧化物催化剂组成的条件下实现其结构和性能的调控.本文以不同形貌CeO2纳米晶为载体,包括优先暴露{110}+{100}晶面的CeO2纳米棒、优先暴露{100}晶面的CeO2纳米立方体和优先暴露{111}晶面的CeO2纳米多面体,采用等体积浸渍方法合成了Cu担载量为0.025%~5%的CuOx/CeO2纳米晶催化剂,结合谱学和电镜表征方法,以及CO吸附原位红外光谱,系统研究了CuOx物种在不同形貌CeO2纳米晶上的结构演化及其催化CO氧化的构-效关系.结构表征结果表明, CuOx物种结构不仅依赖于Cu的担载量,也依赖于载体CeO2的形貌.随着Cu担载量的增加, CuOx物种优先沉积在CeO2的表面缺陷位,然后聚集和长大;同时伴随着CuOx物种从孤立Cu离子到与载体强/弱相互作用的CuOx团簇,高分散Cu O颗粒和大尺寸Cu O颗粒.孤立Cu^+离子和与载体弱相互作用CuOx团簇主要形成于CeO2纳米立方体的表面,这可能与CeO2纳米立方体暴露的氧终止CeO2{100}晶面相关.CO吸附原位红外结果表明, CuOx团簇与不同CeO2表面相互作用的强度顺序为:CeO2纳米棒暴露的{110}面>CeO2纳米多面体暴露的{111}面>CeO2纳米立方体暴露的{100}面.CeO2纳米立方体与Cu2+离子间相互作用弱于与Cu^+之间的,因此CeO2纳米立方体负载的CuOx物种在CO还原过程中容易停留在稳定的Cu^+中间物种;而CeO2纳米棒与Cu2+离子之间的相互作用强于与Cu^+之间的相互作用,因此CeO2纳米棒负载的CuOx物种在CO还原过程中容易形成金属铜.因此CO吸附原位红外光谱观察到CeO2纳米立方体负载CuOx催化剂中吸附在Cu^+的CO物种远远多于CeO2纳米棒负载CuOx催化剂.CO氧化反应结果表明, CuOx/CeO2催化剂表现出同时依赖于CuOx物种结构和CeO2形貌的结构敏感性.CuOx/CeO2催化剂活性表现出与CuOx/CeO2催化剂的CO还原性能的正相关性,说明中CuOx/CeO2催化CO氧化反应遵循Mv K反应机理.这些结果系统地关联了CeO2形貌, CuOx-CeO2相互作用, CuOx物种结构和CeO2还原性能, CuOx/CeO2催化CO氧化反应活性.     

从头开始理解形貌依赖的CuOx-CeO_2相互作用（英文）

CuO_x/CeO_2催化剂在CO氧化反应中表现出高催化活性和显著结构敏感性.文献报道中CuO_x/CeO_2催化剂体系的合成条件差异较大,从而导致观察到的CuO_x-CeO_2相互作用存在较大争议.因此,系统研究并阐明CuO_x/CeO_2催化剂中CuO_x-CeO_2相互作用对于理解复杂的CuO_x-CeO_2界面催化作用具有重要的研究意义.近期发现,氧化物纳米晶的形貌可作为一种新的结构参数,在不改变氧化物催化剂组成的条件下实现其结构和性能的调控.本文以不同形貌CeO_2纳米晶为载体,包括优先暴露{110}+{100}晶面的CeO_2纳米棒、优先暴露{100}晶面的CeO_2纳米立方体和优先暴露{111}晶面的CeO_2纳米多面体,采用等体积浸渍方法合成了Cu担载量为0.025%～5%的CuO_x/CeO_2纳米晶催化剂,结合谱学和电镜表征方法,以及CO吸附原位红外光谱,系统研究了CuO_x物种在不同形貌CeO_2纳米晶上的结构演化及其催化CO氧化的构-效关系.结构表征结果表明, CuO_x物种结构不仅依赖于Cu的担载量,也依赖于载体CeO_2的形貌.随着Cu担载量的增加, CuO_x物种优先沉积在CeO_2的表面缺陷位,然后聚集和长大;同时伴随着CuO_x物种从孤立Cu离子到与载体强/弱相互作用的CuO_x团簇,高分散Cu O颗粒和大尺寸Cu O颗粒.孤立Cu+离子和与载体弱相互作用CuO_x团簇主要形成于CeO_2纳米立方体的表面,这可能与CeO_2纳米立方体暴露的氧终止CeO_2{100}晶面相关.CO吸附原位红外结果表明, CuO_x团簇与不同CeO_2表面相互作用的强度顺序为:CeO_2纳米棒暴露的{110}面CeO_2纳米多面体暴露的{111}面CeO_2纳米立方体暴露的{100}面.CeO_2纳米立方体与Cu2+离子间相互作用弱于与Cu+之间的,因此CeO_2纳米立方体负载的CuO_x物种在CO还原过程中容易停留在稳定的Cu+中间物种;而CeO_2纳米棒与Cu2+离子之间的相互作用强于与Cu+之间的相互作用,因此CeO_2纳米棒负载的CuO_x物种在CO还原过程中容易形成金属铜.因此CO吸附原位红外光谱观察到CeO_2纳米立方体负载CuO_x催化剂中吸附在Cu+的CO物种远远多于CeO_2纳米棒负载CuO_x催化剂.CO氧化反应结果表明, CuO_x/CeO_2催化剂表现出同时依赖于CuO_x物种结构和CeO_2形貌的结构敏感性.CuO_x/CeO_2催化剂活性表现出与CuO_x/CeO_2催化剂的CO还原性能的正相关性,说明中CuO_x/CeO_2催化CO氧化反应遵循Mv K反应机理.这些结果系统地关联了CeO_2形貌, CuO_x-CeO_2相互作用, CuO_x物种结构和CeO_2还原性能, CuO_x/CeO_2催化CO氧化反应活性.     

不同形貌的 CeO2 催化 1,4-丁二醇选择性脱水合成 3-丁烯-1-醇

 以 Ce(NO3)3•6H2O 为铈源, 采用不同沉淀剂制备了 CeO2 催化剂. 运用 N2 吸附-脱附、X 射线衍射、高分辨透射电镜和 H2程序升温还原等技术对催化剂进行了表征, 并评价了其对 1,4-丁二醇选择性脱水合成 3-丁烯-1-醇反应的催化性能. 结果表明, 以不同沉淀剂制得的 CeO2 样品形貌不同, 其中以 Na2CO3 为沉淀剂制备的 CeO2 呈边缘清晰的长方体形貌, 晶粒尺寸较大, 结晶较完整, 优先暴露的 (111) 晶面较多, 在 1,4-丁二醇选择性脱水反应中表现出较高的催化活性和选择性, 3-丁烯-1-醇收率可达 59.7%.     

铜-氧化铈界面:几何及电子结构

纳米催化材料的性能主要由粒子尺寸、形貌和界面决定,即活性位点的电子及几何结构.尺寸、形貌可控的纳米催化材料的合成及其反应性能的研究,即催化剂的构效关系,一直是催化领域的研究热点.氧化物负载的金属催化剂广泛应用于多相催化反应过程.基于氧化铈优异的氧化还原性能, Cu/CeO2催化剂在CO氧化、N2O消除、水气变换、甲醇合成等反应中表现出优异性能.其中,通过铜物种与氧化铈表面化学键合形成的金属-载体界面通常被认为是催化活性中心.铜物种和氧化铈的相互作用主要体现在氧化铈固定铜物种,而铜物种促进氧化铈的氧化还原能力,涉及Cu^2+/Cu^+/Cu^0和Ce^3+/Ce^4+之间电子的传输和转移.Cu/CeO2催化剂活性位的原子结构与金属-载体相互作用程度密切相关.氧化铈形貌和铜负载量是决定界面电子和几何结构的重要因素.常见的纳米氧化铈形貌包括纳米粒子(多面体)、纳米棒和纳米立方体,可分别选择性暴露(111)、(110)和(100)晶面;这些晶面上原子配位环境和化学性能决定了铜-氧化铈的键合方式和界面结构.与暴露{100}晶面的纳米立方体相比,主要暴露{100}/{110}镜面的氧化铈纳米棒、暴露{111}/{100}晶面的纳米粒子与铜物种具有更强的金属-载体相互作用程度,也更有利于铜物种的分散.铜的负载量也显著影响铜物种在特定氧化铈表面的分散度和化学状态;随着铜负载量的增加,可在氧化铈表面形成层状铜、铜团簇和铜纳米粒子.通常情况下,低负载量有利于单层、双层铜物种的形成,高负载量时则出现多层铜和铜纳米粒子.催化活性位通常是由铜原子与氧化铈上的氧空穴相互作用产生,与氧化铈表面氧空穴的数量和密度密切相关,即氧化铈形貌.本文总结了Cu/CeO2催化剂的研究进展,讨论了氧化铈形貌和铜负载量对铜物种分散度和化学状态的影响规律,总结了铜氧化铈界面结构的多维度表征结果,比较了Cu/CeO2催化剂在CO氧化、水气变换及甲醇合成中的活性位结构和反应机制.     

铜-氧化铈界面:几何及电子结构（英文）

纳米催化材料的性能主要由粒子尺寸、形貌和界面决定,即活性位点的电子及几何结构.尺寸、形貌可控的纳米催化材料的合成及其反应性能的研究,即催化剂的构效关系,一直是催化领域的研究热点.氧化物负载的金属催化剂广泛应用于多相催化反应过程.基于氧化铈优异的氧化还原性能, Cu/CeO_2催化剂在CO氧化、N_2O消除、水气变换、甲醇合成等反应中表现出优异性能.其中,通过铜物种与氧化铈表面化学键合形成的金属-载体界面通常被认为是催化活性中心.铜物种和氧化铈的相互作用主要体现在氧化铈固定铜物种,而铜物种促进氧化铈的氧化还原能力,涉及Cu~(2+)/Cu~+/Cu~0和Ce~(3+)/Ce~(4+)之间电子的传输和转移.Cu/CeO_2催化剂活性位的原子结构与金属-载体相互作用程度密切相关.氧化铈形貌和铜负载量是决定界面电子和几何结构的重要因素.常见的纳米氧化铈形貌包括纳米粒子(多面体)、纳米棒和纳米立方体,可分别选择性暴露(111)、(110)和(100)晶面;这些晶面上原子配位环境和化学性能决定了铜-氧化铈的键合方式和界面结构.与暴露{100}晶面的纳米立方体相比,主要暴露{100}/{110}镜面的氧化铈纳米棒、暴露{111}/{100}晶面的纳米粒子与铜物种具有更强的金属-载体相互作用程度,也更有利于铜物种的分散.铜的负载量也显著影响铜物种在特定氧化铈表面的分散度和化学状态;随着铜负载量的增加,可在氧化铈表面形成层状铜、铜团簇和铜纳米粒子.通常情况下,低负载量有利于单层、双层铜物种的形成,高负载量时则出现多层铜和铜纳米粒子.催化活性位通常是由铜原子与氧化铈上的氧空穴相互作用产生,与氧化铈表面氧空穴的数量和密度密切相关,即氧化铈形貌.本文总结了Cu/CeO_2催化剂的研究进展,讨论了氧化铈形貌和铜负载量对铜物种分散度和化学状态的影响规律,总结了铜氧化铈界面结构的多维度表征结果,比较了Cu/CeO_2催化剂在CO氧化、水气变换及甲醇合成中的活性位结构和反应机制.     

原子层沉积构筑Pd/TiO2限域催化剂及其在1,4-丁炔二醇加氢的应用

利用ALD制备了TiO₂限域的Pd催化剂, 研究了限域空间内Pd纳米颗粒与TiO₂的界面作用对1,4-丁炔二醇(BYD)加氢性能的影响. 相比于管外负载型催化剂, 限域催化剂在催化1,4-丁炔二醇选择性加氢反应中体现出非常高的催化活性和1,4-丁烯二醇的选择性. HR-TEM、 EDX-Mapping、 XRD、 XPS和H₂-TPR表征说明, 限域体系中Pd-TiO₂的界面相互作用强于传统TiO₂表面负载型Pd催化剂, 这种强界面作用不仅能够提高BYD的加氢活性, 也可抑制半加氢产物1,4-丁烯二醇的异构化和深度加氢, 提高1,4-丁烯二醇的选择性, 而且限域结构也可阻止管内壁Pd纳米颗粒的脱落, 提高催化剂的稳定性.     

CO氧化反应中的二氧化铈晶面效应

二氧化铈(CeO2)因其具有较强的储放氧能力,被用作氧化还原反应的催化材料.自2005年,研究者制备出形貌可控的CeO2纳米棒、纳米立方块和纳米多面体,在CeO2形貌控制及构效关系研究方面取得长足发展.各种结构表征手段包括原位拉曼(in situ Raman)、原位傅里叶变换红外光谱(in situ DRIFTS)、核磁共振(NMR)和电镜等被用来研究不同形貌CeO2的表面结构和在催化反应中的活性差异.一般的活性规律为CeO2纳米棒({110}/{100})>纳米立方块({100})>纳米多面体({111}/{100}).近年来,负载型CeO2催化剂因其能稳定分散金属,通过金属-载体相互作用调控界面电子结构并表现出优异的催化活性而引起广泛关注,其中晶面效应在负载型CeO2催化体系中显得较为复杂.铜铈催化剂被认为是非常经济有效的CO氧化催化剂,然而由于制备和测试条件差异导致的CeO2晶面对铜铈催化剂催化CO氧化活性的影响规律并不统一.我们之前的研究工作发现纳米棒CeO2-{110}晶面上的Cu-[Ox]-Ce结构不利于形成Cu((40)),而纳米颗粒CeO2-{111}晶面上的CuOx团簇很容易形成Cu((40)),从而对CO催化氧化极为有利,这与纯载体CeO2的规律并不一致.与此同时,对于铜负载的CeO2纳米棒(NR)及纳米立方体(NC)所体现的性质及活性差异缺少系统深入的研究.在上述工作基础上,我们采用沉积沉淀法在CeO2 NR及CeO2 NC上负载1%wt的铜分别得到1Cu CeNR和1Cu CeNC,并对所合成催化剂的结构和吸附性能进行了表征.高分辨透射电镜(HRTEM)照片显示,CeO2纳米棒主要暴露{110}晶面,而CeO2纳米立方体以{100}晶面为主.催化测试结果表明,1Cu CeNC在130℃时CO已完全转化为CO2,而相同温度下1Cu Ce NR只有50%转化.进一步通过氢气程序升温还原(H2-TPR)和一氧化碳程序升温脱附(CO-TPD)分析发现, 1Cu Ce NC催化剂具有较强的还原性且表面氧物种含量高.此外, X射线光电子能谱(XPS)和in situ DRIFTS研究表明, 1Cu Ce NC促进Cu((40))位点生成,导致活性Cu((40))-CO物种增多,这些优异的化学性质导致其具有较高的催化CO氧化活性.     

The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions

The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O₂ with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions.     

Selective Semihydrogenation of Alkynes on Shape‐Controlled Palladium Nanocrystals

A systematic study on the selective semihydrogenation of alkynes to alkenes on shape‐controlled palladium (Pd) nanocrystals was performed. Pd nanocrystals with a cubic shape and thus exposed {100} facets were synthesized in an aqueous solution through the reduction of Na₂PdCl₄ with L ‐ascorbic acid in the presence of bromide ions. The Pd nanocubes were tested as catalysts for the semihydrogenation of various alkynes such as 5‐decyne, 2‐butyne‐1,4‐diol, and phenylacetylene. For all substrates, the Pd nanocubes exhibited higher alkene selectivity (>90 %) than a commercial Pd/C catalyst (75–90 %), which was attributed to a large adsorption energy of the carbon–carbon triple bond on the {100} facets of the Pd nanocubes. Our approach based on the shape control of Pd nanocrystals offers a simple and effective route to the development of a highly selective catalyst for alkyne semihydrogenation.     

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.     

Pd cluster nanowires as highly efficient catalysts for selective hydrogenation reactions

Palladium is a key catalyst invaluable to many industrial processes and fine-chemical synthesis. Although recent progress has allowed the synthesis of Pd nanoparticles with various shapes by using different techniques, the facile synthesis of Pd nanocrystals and turning them into a highly active, selective, and stable catalyst systems still remain challenging. Herein, we report the highly selective one-pot synthesis of monodisperse Pd cluster nanowires in aqueous solution; these consist of interconnected nanoparticles and may serve as highly active catalysts because of the enrichment of high index facets on the surface, including {443}, {331}, and {221} steps. For the first time, carbon nanotube and γ-Al(2)O(3) immobilized Pd cluster nanowires showed highly enhanced catalytic performance in the liquid-phase selective hydrogenation of cinnamaldehyde and gas-phase hydrogenation of 1,3butadiene relative to immobilized Pd icosahedra and nanocubes, as well as commercial Pd catalysts.     

Synthesis of Pd-Pt bimetallic nanocrystals with a concave structure through a bromide-induced galvanic replacement reaction

This article describes a systematic study of the galvanic replacement reaction between PtCl(6)(2-) ions and Pd nanocrystals with different shapes, including cubes, cuboctahedrons, and octahedrons. It was found that Br(-) ions played an important role in initiating, facilitating, and directing the replacement reaction. The presence of Br(-) ions led to the selective initiation of galvanic replacement from the {100} facets of Pd nanocrystals, likely due to the preferential adsorption of Br(-) ions on this crystallographic plane. The site-selective galvanic replacement resulted in the formation of Pd-Pt bimetallic nanocrystals with a concave structure owing to simultaneous dissolution of Pd atoms from the {100} facets and deposition of the resultant Pt atoms on the {111} facets. The Pd-Pt concave nanocubes with different weight percentages of Pt at 3.4, 10.4, 19.9, and 34.4 were also evaluated as electrocatalysts for the oxygen reduction reaction (ORR). Significantly, the sample with a 3.4 wt.% of Pt exhibited the largest specific electrochemical surface area and was found to be four times as active as the commercial Pt/C catalyst for the ORR in terms of equivalent Pt mass.     

Nanocrystals composed of alternating shells of Pd and Pt can be obtained by sequentially adding different precursors

This paper describes a layer-by-layer epitaxial approach to the synthesis of multishelled nanocrystals composed of alternating shells of Pd and Pt by starting with seeds made of Pd or Pt nanocrystals. The synthesis was conducted by sequentially adding PtCl(4)(2-) and PdCl(4)(2-) salt precursors into a system containing either Pd or Pt seeds (in the shape of cuboctahedrons, octahedrons, plates, or cubes) together with a weak reducing agent such as citric acid (CA). The slow reduction kinetics associated with CA played an important role in the epitaxial growth of one metal on the other, resulting in the formation of Pd-Pt multishelled nanocrystals. Owing to the capping effect of CA for {111} facets of Pd and Pt, the multishelled nanocrystals tended to be enclosed by {111} facets in the form of octahedrons or thin plates, depending on the shapes of the Pd or Pt seeds: octahedrons for cuboctahedral, cubic, or octahedral seeds, and plates for platelike seeds.     

Design of Pd{111}-TiO_2 interface for enhanced catalytic efficiency towards formic acid decomposition

Supports are commonly implemented in the industrial application of heterogeneous catalysts to improve the stability and recyclability of catalysts.The supported catalysts often show the enhanced activity and selectivity in various catalytic reactions.However,the specific contributions of electronic and steric effects to a catalytic system often remain elusive due to the lack of well-defined model systems.In this work,two types of uniform Pd nanocrystals covered by{111}facets in tetrahedral and octahedral shapes,respectively,are synthesized with identical chemical environment and loaded on Ti O_2supports to form hybrid structures(Pd{111}-Ti O_2)towards the application of formic acid decomposition.Our observation suggests that the polarization effect at the interface of Pd-Ti O_2enhances its activity in formic acid decomposition.Moreover,the Pd tetrahedrons-Ti O_2hybrid structure whose Pd{111}-Ti O_2interface possesses a larger angle shows higher catalytic activity,owing to the reduced steric effect as compared to Pd octahedrons-Ti O_2.This study reveals the nature of interface effects in formic acid decomposition,and provides a guidance for the related catalyst design.     

Catalytic hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol at atmospheric pressure in the liquid phase

Selective hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol on suspended palladium and Raney nickel catalysts at atmospheric pressure was studied. The optimal parameters of this reaction were determined. Samples containing 90% 2-butene-1,4-diol were prepared.     

Quantitative analysis of the role played by poly(vinylpyrrolidone) in seed-mediated growth of Ag nanocrystals

This article presents a quantitative analysis of the role played by poly(vinylpyrrolidone) (PVP) in seed-mediated growth of Ag nanocrystals. Starting from Ag nanocubes encased by {100} facets as the seeds, the resultant nanocrystals could take different shapes depending on the concentration of PVP in the solution. If the concentration was above a critical value, the seeds simply grew into larger cubes still enclosed by {100} facets. When the concentration fell below a critical value, the seeds would evolve into cuboctahedrons enclosed by a mix of {100} and {111} facets and eventually octahedrons completely covered by {111} facets. We derived the coverage density of PVP on Ag(100) surface by combining the results from two measurements: (i) cubic seeds were followed to grow at a fixed initial concentration of PVP to find out when {111} facets started to appear on the surface, and (ii) cubic seeds were allowed to grow at reduced initial concentrations of PVP to see at which concentration {111} facets started to appear from the very beginning. We could calculate the coverage density of PVP from the differences in PVP concentration and the total surface area of Ag nanocubes between these two samples. The coverage density was found to be 140 and 30 repeating units per nm(2) for PVP of 55,000 and 10,000 g/mol in molecular weight, respectively, for cubic seeds of 40 nm in edge length. These values dropped slightly to 100 and 20 repeating units per nm(2), respectively, when 100 nm Ag cubes were used as the seeds.     

Design of Pd{111}-TiO<Subscript>2</Subscript> interface for enhanced catalytic efficiency towards formic acid decomposition

Supports are commonly implemented in the industrial application of heterogeneous catalysts to improve the stability and recyclability of catalysts. The supported catalysts often show the enhanced activity and selectivity in various catalytic reactions. However, the specific contributions of electronic and steric effects to a catalytic system often remain elusive due to the lack of well-defined model systems. In this work, two types of uniform Pd nanocrystals covered by {111} facets in tetrahedral and octahedral shapes, respectively, are synthesized with identical chemical environment and loaded on TiO₂ supports to form hybrid structures (Pd{111}-TiO₂) towards the application of formic acid decomposition. Our observation suggests that the polarization effect at the interface of Pd-TiO₂ enhances its activity in formic acid decomposition. Moreover, the Pd tetrahedrons-TiO₂ hybrid structure whose Pd{111}-TiO₂ interface possesses a larger angle shows higher catalytic activity, owing to the reduced steric effect as compared to Pd octahedrons-TiO₂. This study reveals the nature of interface effects in formic acid decomposition, and provides a guidance for the related catalyst design.