氧化铝增强的PdSe2/Si异质结光电探测器

为了降低暗电流,通过原子层沉积(ALD)生长了一层氧化铝(Al₂O₃)隧穿层,制备了PdSe₂/Al₂O₃/Si异质结光电探测器.通过优化Al₂O₃层的厚度,使得该探测器实现了高速和宽光谱响应.研究结果表明,在波长为808 nm的光照射和-2 V偏压下,所制备的光电探测器与未生长Al₂O₃的器件相比,暗电流降低了约3个数量级,器件的光响应度达到了约为0.31 A/W,对应的比探测率约为2.5×10¹² Jones,器件在零偏压下表现出明显的自驱动效应.经过循环测试1 200次后,器件保持良好的光响应.器件响应的上升时间和下降时间分别为7.1和15.6μs.结果表明,在二维层状半导体材料与Si之间引入Al₂O₃隧穿层,可以有效地降低器件的暗电流,有利于高性能的Si基光电探测器的制备.     

Self‐Assembled Pd@CeO2/γ‐Al2O3 Catalysts with Enhanced Activity for Catalytic Methane Combustion

Pd@CeO₂/Al₂O₃ catalysts are of great importance for real applications, such as three‐way catalysis, CO oxidation, and methane combustion. In this article, the Pd@CeO₂ core@shell nanospheres are prepared via the autoredox reaction in aqueous phase. Three kinds of methods are then employed, that is, electrostatic interaction, supramolecular self‐assembly, and physical mixing, to support the as‐prepared Pd@CeO₂ nanospheres on γ‐Al₂O₃. A model reaction of catalytic methane‐combustion is employed here to evaluate the three Pd@CeO₂/γ‐Al₂O₃ samples. As a result, the sample Pd@CeO₂‐S‐850 prepared via supramolecular self‐assembly and calcined at 850 °C exhibits superior catalytic performance to the others, which has a far lower light‐off temperature (T₅₀ of about 364 °C). Moreover, almost no deterioration of Pd@CeO₂‐S‐850 is observed after five sequent catalytic cycles. The analysis of H₂‐TPR curves concludes that there exists hydrogen spillover related to the strong metal–support interaction between Pd species and oxides. The strong metal–support interaction and the specific surface areas might be responsible for the catalytic performance of the Pd@CeO₂ samples toward catalytic methane combustion.     

Synthesis and electrocatalytic activity of Au@Pd core-shell nanothorns for the oxygen reduction reaction

Bimetallic core-shell nanostructures with porous surfaces have drawn considerable attention due to their promising applications in various fields, including catalysis and electronics. In this work, Au@Pd core-shell nanothorns （CSNTs） with rough and porous surfaces were synthesized for the first time through a facile co-chemical reduction method in the presence of polyallylamine hydrochloride （PAH） and ethylene glycol （EG） at room temperature. The size, morphology, and composition of Au@Pd CSNTs were investigated by transmission electron microscopy （TEM）, X-ray diffraction （XRD）, energy dispersive spec- troscopy （EDX）, EDX mapping, and X-ray photoelectron spectroscopy （XPS）. The electrochemical properties of as-synthesized Au@Pd CSNTs were also studied by various electrochemical techniques. Au@Pd CSNTs exhibited remarkably high electrocatalytic activity and durability for the oxygen reduction reaction （ORR） in the alkaline media, owing to the unique porous structure and the synergistic effect between the Au core and Pd shell.     

乙二醇在氧化物增强Pd/C催化剂上的电化学氧化

研究了乙二醇在氧化物CeO2、NiO和Co3O4增强Pd/C催化剂上的碱性溶液中电化学氧化活性,结果显示虽然纯Pd/C催化剂对乙二醇的电化学氧化活性非常低以及抗催化剂毒化作用非常弱,其电化学性能远远比不上Pt/C催化剂。但添加氧化物CeO2、NiO和Co3O4后,Pd/C对乙二醇电化学氧化催化活性和抗毒化能力都得到大幅度提高,甚至超过商业催化剂E-TEKPt/C。三种氧化物增强Pd/C催化剂的电化学活性顺序为Pd-Co3O4(质量比为2︰1,以下同)/C>Pd-NiO(4︰1)/C>Pd-CeO2(1.3︰1)/C。     

Pressure‐Tunable Ambipolar Conduction and Hysteresis in Thin Palladium Diselenide Field Effect Transistors

Few‐layer palladium diselenide (PdSe₂) field effect transistors are studied under external stimuli such as electrical and optical fields, electron irradiation, and gas pressure. The ambipolar conduction and hysteresis are observed in the transfer curves of the as‐exfoliated and unprotected PdSe₂ material. The ambipolar conduction and its hysteretic behavior in the air and pure nitrogen environments are tuned. The prevailing p‐type transport observed at atmospheric pressure is reversibly turned into a dominant n‐type conduction by reducing the pressure, which can simultaneously suppress the hysteresis. The pressure control can be exploited to symmetrize and stabilize the transfer characteristics of the device as required in high‐performance logic circuits. The transistors are affected by trap states with characteristic times in the order of minutes. The channel conductance, dramatically reduced by the electron irradiation during scanning electron microscope imaging, is restored after an annealing of several minutes at room temperature. The work paves the way toward the exploitation of PdSe₂ in electronic devices by providing an experiment‐based and deep understanding of charge transport in PdSe₂ transistors subjected to electrical stress and other external agents.     

非均相金属钯配体催化剂的研究进展

Suzuki-Miyaura反应是一类具有工业化应用前景的C-C键合成反应。反应多数是在均相金属钯配体催化剂催化下完成。均相催化具有催化效率高、产品选择性好等优点,但催化剂回收困难,增加了反应成本,限制了其应用。非均相金属钯配体催化剂是将均相金属钯配体催化剂固载到载体上,使其在不影响反应活性和选择性的同时,实现循环使用,已成为Suzuki-Miyau-ra反应的研究热点。对几年来以有序介孔材料MCM-41和SBA-15、无机载体SiO2和Al2O3、聚苯乙烯和聚乙二醇等合成材料以及天然高分子材料为载体,制备非均相金属钯配体催化剂的方法及其催化性能进行了综述。     

钯钇合金膜分离器级联分离氢同位素理论计算

钯合金膜分离氢同位素具有分离能力强、氚滞留量小以及装置设计简单等优点,是一种很有发展潜力的氢同位素分离方法,但受膜及泵输系统等因素的制约,目前仍处于概念设计阶段。文中针对级联分离建立了考虑返混的近似模型。模型表明:各级的分流比和分离系数相同时,对含氚体积分数0.065%的氢同位素混合气体,在0.2分流比(体积比),分离系数为2.5时,经过3级富集和4级贫化就可以得到含氚体积分数1.5%的产品和含氚体积分数0.000 5%的贫料;相同分离系数下,分流比较大时分离系统的规模较小。     

Palladium‐Based Nanomaterials: A Platform to Produce Reactive Oxygen Species for Catalyzing Oxidation Reactions

Oxidation reactions by molecular oxygen (O₂) over palladium (Pd)‐based nanomaterials are a series of processes crucial to the synthesis of fine chemicals. In the past decades, investigations of related catalytic materials have mainly been focused on the synthesis of Pd‐based nanomaterials from the angle of tailoring their surface structures, compositions and supporting materials, in efforts to improve their activities in organic reactions. From the perspective of rational materials design, it is imperative to address the fundamental issues associated with catalyst performance, one of which should be oxygen activation by Pd‐based nanomaterials. Here, the fundamentals that account for the transformation from O₂ to reactive oxygen species over Pd, with a focus on singlet O₂ and its analogue, are introduced. Methods for detecting and differentiating species are also presented to facilitate future fundamental research. Key factors for tuning the oxygen activation efficiencies of catalytic materials are then outlined, and recent developments in Pd‐catalyzed oxygen‐related organic reactions are summarized in alignment with each key factor. To close, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields.