Multiple Interfaces Structure Derived from Metal–Organic Frameworks for Excellent Electromagnetic Wave Absorption

Hierarchical yolk–shell nanostructure (NiO/Ni/GN@Air@NiO/Ni/GN) derived from Ni‐based metal–organic frameworks (Ni‐MOFs) is synthesized by solvothermal reactions. After successive carbonization and oxidation treatments, hierarchical NiO/Ni nanocrystals covered with a graphene shell are obtained with the yolk–shell nanostructure intact. The NiO/Ni/GN@Air@NiO/Ni/GN composites are characterized by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate that the NiO/Ni/GN@Air@NiO/Ni/GN composites exhibit superior electromagnetic wave absorption properties. A minimum reflection loss (RL_min) of ?34.5 dB is obtained at 17.2 GHz with the thin thickness of 1.7 mm. In addition, the best microwave absorption properties are achieved with a 2.0 mm absorber layer (RL_min = ?22.5 dB, bandwidth of 6.0 GHz). The outstanding absorption ability may arise from the unique yolk–shell structure and nanoporous carbon, which can tune the dielectric of the NiO/Ni/GN@Air@NiO/Ni/GN composites to acquire good impedance matching. Moreover, the interspaces can induce interfacial polarization and multiple reflections.     

Morphological,Structural, and Compositional Evolution of Pt–Ni Octahedral Electrocatalysts with Pt‐Rich Edges and Ni‐Rich Core: Toward the Rational Design of Electrocatalysts for the Oxygen Reduction Reaction

The progress in colloidal synthesis of Pt–Ni octahedra has been instrumental in rising the oxygen reduction reaction catalytic activity high above the benchmark of Pt catalysts. This impressive catalytic performance is believed to result from the exposure of the most active catalytic sites after an activation process, chemical or electrochemical, which leads to a Pt surface enrichment. A foremost importance is to understand the structure and the elemental distribution of Pt–Ni octahedral, which leads to an optimal catalytic activity and stability. However, the factors governing the synthesis of the Pt–Ni octahedra are not well understood. In this study, unprecedented surface atomic segregation of Pt atoms in a Ni‐rich Pt–Ni octahedral nanoparticle structure is established by advanced electron microscopy. The Pt atoms are almost exclusively located on the edges of the Pt–Ni octahedra. This structure is formed in a pristine form, i.e., prior to any chemical or electrochemical etching. A new growth mechanism is revealed, which involves the transformation from an octahedron with a Pt‐rich core to a Ni‐rich octahedron with Pt‐rich edges. This observation may pave the way for a deeper understanding of this class of Pt–Ni octahedral nanoparticles as an electrocatalyst.     

Metal–Organic Framework Supported Palladium Nanoparticles: Applications and Mechanisms

Heterogeneous palladium (Pd)‐based catalysts are extensively applied to improve the catalytic performance and/or expand the reaction scope in many catalytic processes, involving the cross‐coupling, hydrogenation, reduction, and oxidation reactions. Among them, metal–organic framework (MOF)‐supported Pd nanoparticles (Pd NPs) are becoming the most popular one for their excellent catalytic performance and reusable property. To motivate the development of this technology, the applications of MOF‐supported Pd NPs (Pd NPs/MOFs) in heterogeneous catalysis are critically summarized herein, including the hydrogenation reduction of nitro‐ and polyunsaturated compounds, synthesis of carbon–carbon (C? C) bonds compounds, chromium (Cr(VI)) reduction, dehalogenation, alcohol oxidation, CO₂ conversion, and CO oxidation. The influences of base, solvents, electron character of substitutes, and type of halogen on the catalytic performance are comprehensively discussed. Finally, the application prospects of Pd NPs/MOFs and existing shortcomings in the catalytic field are proposed.     

Self‐Supporting AuCu@Cu Elongated Pentagonal Bipyramids Toward Neutral Glucose Sensing

Controlling the electronic structure of a catalyst has become an important approach to tune and optimize its antipoisoning ability and catalytic efficiency for a chemical reaction. Using d ‐mannitol as a structure‐directing agent to induce size transformation and twinned defects in copper particles, penta‐twinned Cu elongated pentagonal bipyramids as supports have been synthesized, and HAuCl₄ is reduced in situ to form an AuCu alloy on the surface of Cu, generating a self‐supporting AuCu@Cu core–shell structure for application as a glucose sensor in a neutral medium. The AuCu@Cu elongated pentagonal bipyramids with 0.42 at% Au show activities comparable with the Au and Pt catalyst but are more tolerant toward Cl^? than Au and more tolerant toward H_3–xPO₄^x? than Cu. The mass activity of AuCu@Cu reaches 0.10 A mg^?1 of Au at 0.6 V versus Ag/AgCl (3 m KCl) in a pH 8.0 buffer. The self‐supporting AuCu@Cu elongated pentagonal bipyramids are promising catalysts for glucose sensing in a neutral medium. This work offers an effective way to design antitoxic and durable catalysts with ultralow content of noble metal for glucose sensing.     

Strain glass behaviour of Ni–Co–Mn–Sn ferromagnetic shape memory alloys

We report the direct experimental observations of the glassy behaviour in Ni–Co–Mn–Sn ferromagnetic shape memory alloys by doping sufficient substitutional point defect Co into the Ni sites (9 at%). The results showed that high level of Co doping had caused the complete suppression of the martensitic transformation and introduction of a strain glass transition in Ni–Co–Mn–Sn alloys. The strain glass transition was definitively characterized by the dynamic mechanical anomalies following the Vogel–Fulcher relationship and the signature nonergodicity of the frozen glass using a zero‐field‐cooled/field‐cooled heating measurement of static strain. The findings clarified the cause of vanishing of the martensitic transformation in Ni–Co–Mn–Sn alloy with high Co doping levels and the generality of glassy state in Ni–Mn based ferromagnetic shape memory alloys with high level of foreign elements doping. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

In situ observation of Ni–Mo–S phase formed on NiMo/Al2O3 catalyst sulfided at high pressure by means of Ni and Mo K‐edge EXAFS spectroscopy

To obtain direct evidence of the formation of the Ni–Mo–S phase on NiMo/Al₂O₃ catalysts under high‐pressure hydrodesulfurization conditions, a high‐pressure EXAFS chamber has been constructed and used to investigate the coordination structure of Ni and Mo species on the catalysts sulfided at high pressure. The high‐pressure chamber was designed to have a low dead volume and was equipped with polybenzimidazole X‐ray windows. Ni K‐edge k³χ(k) spectra with high signal‐to‐noise ratio were obtained using this high‐pressure chamber for the NiMo/Al₂O₃ catalyst sulfided at 613 K and 1.1 MPa over a wide k range (39.5–146 nm^?1). The formation of Ni–Mo and Mo–Ni coordination shells was successfully proved by Ni and Mo K‐edge EXAFS measurement using this chamber. Interatomic distances of these coordination shells were almost identical to those calculated from Ni K‐edge EXAFS of NiMo/C catalysts sulfided at atmospheric pressure. These results support the hypothesis that the Ni–Mo–S phase is formed on the Al₂O₃‐supported NiMo catalyst sulfided under high‐pressure hydrodesulfurization conditions.     

Highly Enhanced Emission of Visible Light from Core–Dual‐Shell‐Type Hybridized Nanoparticles

Core–dual‐shell‐type hybridized nanoparticles (NPs) having Au‐core/dye‐doped silica inner shell/Au outer shell are successfully fabricated by developing a biphasic process that is a kind of so‐called “one‐pot” method. The resulting hybridized NPs exhibit evidently about 20‐fold enhancement of fluorescence intensity, increase in fluorescence quantum yield, and decrease in fluorescence lifetime. These effects depend on the metal nanostructure being optimized, compared with the reference hybridized NPs with neither a Au‐core nor a Au outer shell, due to the gap‐mode effect induced by localized surface plasmon resonance in the core–dual‐shell‐type MIM‐like nanostructure. More detailed elucidation concerning the enhancement mechanism will provide the possibility of photonic device application, for example as a high‐performance point light source, nanolaser, or sensor for bioimaging in the visible region in the near future.     

使用金属掺杂SnO2(110)作为表面催化剂的电催化CO2还原反应：通过调控Sn:O原子比例来控制产物

电催化CO₂还原反应可以产生HCOOH和CO,目前该反应是将可再生电力转化为化学能存储在燃料中的最有前景的方法之一. SnO₂作为将CO₂转换为HCOOH和CO的良好催化剂,其反应发生的晶面可以是不同的. 其中(110)面的SnO₂非常稳定,易于合成. 通过改变SnO₂(110)的Sn:O原子比例,得到了两种典型的SnO₂薄膜：完全氧化型(符合化学计量)和部分还原型. 本文研究了不同金属(Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt和Au)掺杂的SnO₂(110),发现在CO₂还原反应中这些材料的催化活性和选择性是不同的. 所有这些变化都可以通过调控(110)表面中Sn:O原子的比例来控制. 结果表明,化学计量型和部分还原型Cu/Ag掺杂的SnO₂(110)对CO₂还原反应具有不同的选择性. 具体而言,化学计量型的Cu/Ag掺杂的SnO₂(110)倾向于产生CO(g),而部分还原型的表面倾向于产生HCOOH(g). 此外,本文还考虑了CO₂还原的竞争析氢反应. 其中Ru、Rh、Pd、Os、Ir和Pt掺杂的SnO₂(110)催化剂对析氢反应具有较高的活性,其他催化剂对CO₂还原反应具有良好的催化作用.     

Surface chemistry and catalytic activity of Ni/Al2O3 irradiated with high-energy electron beam

The radiation effects induced effects by electron beam (EB) treatment on the catalytic activity of Ni/γ-Al₂O₃ were studied for the carbon dioxide reforming of methane with different EB energy and absorbed radiation dose. Transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to determine the change in structure and surface states of Ni/γ-Al₂O₃ catalyst before and after the EB treatment. Higher energy EB treatment is useful for increasing the proportion of the active sites (such as Ni⁰ and NiAl₂O₄-phase) on the surface. The increase of Ni/Al-ratio indicates that the Ni dispersion on the surface increased with the EB-treatment, resulting in an increase of the active sites, which leads to improving the catalytic activity. XPS measurement also showed a decrease of the surface carbon with EB dose. The maximum 20% increase in the conversion of CO₂/CH₄-mixture into CO/H₂ gas was observed for the catalyst treated with 2 MeV energy and 600 kGy dose of EB relative to untreated.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Theoretical and experimental study of methane steam reforming reactions over nickel catalyst

In this work we perform DFT theoretical calculations of methane and steam interactions on Ni(1 1 1) surface. The calculations allow us to improve our understanding of the competition between these reactants by catalytic sites in methane steam reforming (MSR) process. For this purpose we compare theoretical results with kinetic measurements of MSR on a Ni(II)-Al(III) catalyst prepared from lamellar double hydroxides as precursor. This comparison shows that, for low H₂O/CH₄ ratios methane and water intermediate species adsorb on different catalytic sites. While CHO species adsorbs on top of Ni atom, OH one occupies preferentially a tri-coordinate surface site. On the other hand, for high H₂O/CH₄ ratios a competency between these species by Ni sites would establish, diminishing methane conversion. In addition competition between methane and steam for Ni sites would lead to a decrease in CO production. Nevertheless, intermediate species adsorbed on different active sites would produce CO₂, whatever the steam/methane ratio. Thus, it would be optimum steam concentration in hydrocarbon feed and active sites distribution on catalyst surface, which could maximize H₂ production and minimize CO selectivity. The theoretical findings agree with kinetic measurements, which show that maximum methane conversion depends on steam partial pressure in the feed; whereas always, selectivity to CO₂ increases and to CO diminishes.     

Quasi in situ Ni K‐edge EXAFS investigation of the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant

Ni species on the spent NiMo catalyst from ultra‐deep hydrodesulfurization of gas oil in a commercial plant were studied by Ni K‐edge EXAFS and TEM measurement without contact of the catalysts with air. The Ni–Mo coordination shell related to the Ni–Mo–S phase was observed in the spent catalyst by quasi in situ Ni K‐edge EXAFS measurement with a newly constructed high‐pressure chamber. The coordination number of this shell was almost identical to that obtained by in situ Ni K‐edge EXAFS measurement of the fresh catalyst sulfided at 1.1 MPa. On the other hand, large agglomerates of Ni₃S₂ were observed only in the spent catalyst by quasi in situ TEM/EDX measurement. MoS₂‐like slabs were sintered slightly on the spent catalyst, where they were destacked to form monolayer slabs. These results suggest that the Ni–Mo–S phase is preserved on the spent catalyst and Ni₃S₂ agglomerates are formed by sintering of Ni₃S₂ species originally present on the fresh catalyst.     

Generating Metallic Amorphous Core–Shell Nanoparticles by a Solid‐State Amorphization Process

Metallic crystalline/amorphous core–shell nanoparticles consisting of a crystalline Pd core (c‐Pd) surrounded by an amorphous Fe₂₅Sc₇₅ shell (a‐FeSc) are prepared by inert‐gas condensation. A phase transformation of the c‐Pd by a solid‐state diffusion process resulting in an amorphous core (a‐PdSc) surrounded by an amorphous FeSc shell is observed if the core–shell structure is irradiated at ambient temperature with 300 keV electrons. The amorphization process seems to involve the diffusion of irradiation‐induced defects and is presumably driven by the large negative heat of mixing of Pd and Sc, as well as by the excess enthalpy of the interfaces between the c‐Pd regions and the surrounding a‐FeSc. The structural transformation reported here opens a new way to producing metallic amorphous core–shell nanoparticles of different chemical compositions and probably novel properties.     

A versatile sonication-assisted deposition–reduction method for preparing supported metal catalysts for catalytic applications

This work aims to develop a rapid and efficient strategy for preparing supported metal catalysts for catalytic applications. The sonication-assisted reduction–precipitation method was employed to prepare the heterogeneous mono- and bi-metallic catalysts for photocatalytic degradation of methyl orange (MO) and preferential oxidation (PROX) of CO in H₂-rich gas. In general, there are three advantages for the sonication-assisted method as compared with the conventional methods, including high dispersion of metal nanoparticles on the catalyst support, the much higher deposition efficiency (DE) than those of the deposition–precipitation (DP) and co-precipitation (CP) methods, and the very fast preparation, which only lasts 10–20 s for the deposition. In the AuPd/TiO₂ catalysts series, the AuPd(3:1)/TiO₂ catalyst is the most active for MO photocatalytic degradation; while for PROX reaction, Ru/TiO₂, Au–Cu/SBA-15 and Pt/γ-Al₂O₃ catalysts are very active, and the last one showed high stability in the lifetime test. The structural characterization revealed that in the AuPd(3:1)/TiO₂ catalyst, Au–Pd alloy particles were formed and a high percentage of Au atoms was located at the surface. Therefore, this sonication-assisted method is efficient and rapid in the preparation of supported metal catalysts with obvious structural characteristics for various catalytic applications.     

Study of flowerlike CeO2 microspheres used as catalyst supports for CO oxidation reaction

Porous flowerlike CeO₂ microspheres were synthesized via a novel hydrothermal method and were used as supports for the oxidation of CO. After loaded with Au or CuO, it exhibited an excellent low-temperature catalytic activity toward CO oxidation reaction. Especially, for the Au-loaded flowerlike CeO₂ microsphere catalyst, CO gas started its conversion into CO₂ above 80% at room temperature. The possible reasons for the superior catalytic activity of flowerlike CeO₂ microsphere catalysts were discussed.     

电子束引起的残余含氧气体在镍(001)面上的吸附

当一束具有一定能量和强度的电子束轰击超高真空系统中残余的水汽、一氧化碳和二氧化碳时,将导致这些气体分子通过如下反应:H₂O→O_ad+H₂,CO₂→O_ad+CO,CO→O_ad+C_ad分解并共吸于镍表面。碳和氧的原子各自占据镍(001)面部份四重吸附位置,形成结构为p(2×2)或c(2×2)的许多独立的吸附畴,电子束轰击促进畴的成核、长大、连结和有序化。当氧和碳的原子占据了镍(001)面约一半的四重吸附位后,上述吸附反应将与导致氧和碳的脱附反应:C^*+O_ad→CO,O^*+C_ad→CO平衡,氧化镍与碳化镍开始成核。由于残余含氧气体中氧的含量超过碳,氧化镍成核占优势,使碳的吸附被排斥,已吸附的碳被排挤,形成电子束斑内氧高碳低、束斑外碳高氧低的“互补”分布。电子束轰击过程中碳的俄歇峰形的变化反映着碳原子与基底原子的不同结合状态。电子束的解离效应在吸附的初始阶段起重要作用,而其热效应对氧化镍的长大起重要作用。 关键词：     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Dual Template Engaged Synthesis of Hollow Ball‐in‐Tube Asymmetrical Structured Ceria

Hollow materials with different configurations are of interest due to their unique structural features, which induce interesting properties e.g. catalysis. Here, the synthesis of asymmetrical hollow ball‐in‐tube (HBT) structured CeO₂ is reported, which is achieved using a dual template engaged solid–liquid interfacial reaction. In this reaction, the SiO₂ sphere (hard template)‐embedded Ce(OH)CO₃ nanorod (sacrificial template) composite is first treated with NaOH solution, followed by an acid wash to obtain asymmetrical hollow structured CeO₂. Such HBT structured CeO₂ is demonstrated to be a good support for Au nanoparticles toward CO oxidation as compared to simple hollow CeO₂ nanotubes, leading to significantly increase catalytic activity.     

Improved device performance in nonpolar a ‐plane GaN LEDs using a Ni/Al/Ni/Au n‐type ohmic contact

The authors report upon the increased light‐output power (P_out) via a reduction in the forward voltage (V_f) for nonpolar a ‐plane GaN LEDs using Ni/Al/Ni/Au n‐type ohmic contacts. The specific contact resistivity of the Ni/Al/Ni/Au contact is found to be as low as 5.6 × 10^–5 whereas that of a typical Ti/Al/Ni/Au contact is 6.8 × 10^–4 Ω cm², after annealing at 700 °C. The X‐ray photoelectron spectroscopy results show that the upward surface band bending is less pronounced for the Ni/Al contact compared to the Ti/Al contact, leading to a decrease in the effective Schottky barrier height (SBH). The V_f of the nonpolar LEDs decreases by 10% and P_out increases by 15% when the Ni/Al/Ni/Au scheme is used instead of the typical Ti/Al/Ni/Au metal scheme. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CO2 dissociation on Ni(2 1 1)

The direct and H-mediated dissociation of CO₂ on Ni(2 1 1) were investigated at the level of density functional theory. Although formate (HCOO) formation via CO₂ hydrogenation was widely reported for CO₂ adsorption on metal surfaces, it is found that on Ni(2 1 1) HCOO dissociation into CHO and O is much difficult, while direct dissociation of adsorbed CO₂ into CO and O is more favorable. It is also found that the degree of electron transfer from surface to adsorbed CO₂ correlates with the elongation of C-O bond lengths and the reduction of the CO₂ dissociation barrier.