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.     

Co3O4 Hollow Nanoparticles and Co Organic Complexes Highly Dispersed on N‐Doped Graphene: An Efficient Cathode Catalyst for Li‐O2 Batteries

Rechargeable Li‐O₂ batteries are promising candidates for electric vehicles due to their high energy density. However, the current development of Li‐O₂ batteries demands highly efficient air cathode catalysts for high capacity, good rate capability, and long cycle life. In this work, a hydrothermal‐calcination method is presented to prepare a composite of Co₃O₄ hollow nanoparticles and Co organic complexes highly dispersed on N‐doped graphene (Co–NG), which acts as a bifunctional air cathode catalyst to optimize the electrochemical performances of Li‐O₂ batteries. Co–NG exhibits an outstanding initial discharge capacity up to 19 133 mAh g^?1 at a current density of 200 mA g^?1. In addition, the batteries could sustain 71 cycles at a cutoff capacity of 1000 mAh g^?1 with low overpotentials at the current density of 200 mA g^?1. Co–NG composites are attractive as air cathode catalysts for rechargeable Li‐O₂ batteries.     

NMR imaging study of various stages of a supported catalyst preparation process: getting the qualitative and quantitative information

Supported metal and metal oxide catalysts are widely used to perform various industrial processes such as hydrogenation reactions, the Fischer–Tropsch synthesis, hydrotreatment, etc. The preparation of such catalysts often involves impregnation of a porous support with a solution containing a desired metal salt (the precursor of an active component) followed by drying, calcination, and reduction. The properties of the obtained in such a way supported catalysts depend significantly on the dispersion and distribution of the active component along the catalyst pellet radius. In this paper nuclear magnetic resonance (NMR) imaging was applied to visualize the distribution of the active component (metal) in catalyst pellets in various stages of their preparation (impregnation, drying, calcination). The possibility to get by NMR imaging the quantitative information on the distribution of the active phase in impregnated, dried, and calcined catalysts was also demonstrated on the example of the Co/γ-Al₂O₃ catalyst. The preparation conditions leading to various (uniform, egg-shell, egg-white and egg-yolk) Co distributions in the calcined Co/γ-Al₂O₃ catalysts were determined.     

Co9S8 Nanoparticles Incorporated in Hierarchically Porous 3D Few‐Layer Graphene‐Like Carbon with S,N‐Doping as Superior Electrocatalyst for Oxygen Reduction Reaction

Electrochemical oxygen reduction reaction (ORR), using nonprecious metal catalysts, has attracted great attention due to the importance in renewable energy technologies, such as fuel cells and metal–air batteries. A simple and scalable synthetic route is demonstrated for the preparation of a novel 3D hybrid nanocatalyst consisting of Co₉S₈ nanoparticles which are incorporated in N,S‐doped carbon (N, S–C) with rational structure design. In particular, the hybrid catalyst is prepared by direct pyrolysis and calcination of a gel mixture of Mg,Co nitrate‐thiourea‐glycine under Ar atmosphere, with subsequent HCl washing. The properties of obtained hybrid catalyst are quite dependent on calcination temperature and added glycine amount. Under a molar ratio of Co5‐Mg15‐tu10‐gl45 and a calcination temperature of 900 °C, Co₉S₈ nanoparticles are embedded in a well‐developed carbon matrix which shows a porous 3D few‐layer graphene‐like N, S–C with open and hierarchical micro–meso–macro pore structure. Because of the synergistic effect between Co₉S₈ nanoparticles and well‐developed carbon support, the composite exhibits high ORR activity close to that of commercial Pt/C catalyst. More importantly, the composite displays superior long‐term stability and good tolerance against methanol. The strategy developed here provides a novel and efficient approach to prepare a cost‐effective and highly active ORR electrocatalyst.     

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.     

Analysis of oxygen shell splitting in hydrothermally grown single crystal ThO2(200)

Single crystals of ThO₂ have been synthesized using hydrothermal growth and studied using the X‐ray absorption fine structure (XAFS) technique. The extended X‐ray absorption fine structure (EXAFS) has been extracted from the XAFS and analyzed using a novel, computational Latin hypercube sampling method. The methodology not only confirms the expected space group and crystal structure, it also identifies the origin of a previously reported split O shell. Since EXAFS is a local order analysis technique, the O shell splitting is identified as an O atom occupying an interstitial site. This result is significant for examining O^2– transport in a ThO₂ matrix and corroborating research indicating partial Th 5f occupancy that is similar to hyper‐stoichiometric UO_2+x compounds. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

焙烧温度对SiO2负载的Co3O4纳米粒子表面氧缺陷浓度和CO氧化催化性能的影响

以传统的浸渍法,在不同焙烧温度下制备了用于CO氧化反应的Co₃O₄/SiO₂催化剂．通过激光拉曼光谱(Raman)、X射线光电子能谱(XPS)、X射线衍射(XRD)、程序升温还原(TPR)和X射线吸收精细结构谱(XAFS)表征了该系列催化剂的结构．在所有的催化剂中,XRD和Raman光谱都只检测到了Co₃O₄晶相的存在．与Co₃O₄体相相比,XPS结果表明在200 oC焙烧的(Co₃O₄(200)/SiO₂)催化剂中Co₃O₄表面上存在着过量的Co²⁺．与XPS的结果一致,TPR结果表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄表面上存在氧缺陷, 并且XAFS结果也表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄具有更多的Co²⁺．提高焙烧温度使得过量的Co²⁺进一步氧化为Co³⁺,同时降低了表面氧缺陷浓度,从而得到计量比的Co₃O₄4/SiO₂催化剂．在所有的负载催化剂中Co₃O₄(200)/SiO₂催化剂表现出了最好的CO氧化催化性能,表明过量Co²⁺和表面氧缺陷的存在能够促进Co₃O₄催化CO氧化反应的活性.     

X-ray study of metal oxide based anodes for Li-ion batteries

Cells were made from Co₃O₄ and Co₂SnO₄ and lithium metal and tested to determine reversible lithium capacity. Li is reversibly inserted into Co₃O₄, as was observed by electrochemistry, coupled with changes of cobalt oxidation state as observed by Co K-edge EXAFS. On lithium insertion the Co₃O₄ is reduced to yield only metallic cobalt species, and then on lithium removal an oxide of Co is formed. The EXAFS data further showed that the initial reduction was to Co(II) and then to metallic Co, and that both the metallic and oxide phases were disordered, having low co-ordination numbers and large shell spacings. The electrochemical behaviour of the Co₂SnO₄ cells was closer to that of SnO₂ than Co₃O₄, but did exhibit changes obviously caused by the cobalt. EXAFS on Co₂SnO₄ cells revealed that the Co is reduced to metallic cobalt on the initial discharge, but does not convert back to an oxide on cycling. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

钴改性Fe3O4-MnO2催化转化生物质合成气制备液体燃料

本文制备了用于费托合成反应的钴改性Fe₃O₄-MnO₂双功能催化剂,并探究了钴负载量对Fe-Co协同效应的影响以及Fe₁Co_xMn₁催化剂的费托合成反应性能. 实验发现,在Fe₃O₄-Mn催化剂中加入Co可促进铁氧化物的还原、增加反应过程中铁位点的活性. 此外,Co的加入可增强Fe-Co金属间的电子转移,加强两者的协同作用,提高催化性能. Co负载较高的Fe₁Co_xMn₁催化剂可进一步促进加氢反应能力,使产品分布向短链烃方向转移. 在280 ^°C、2.0 MPa和3000 h^-1的最佳工况条件下,Fe₁Co₁Mn₁催化剂的液体燃料收率最高.     

Application of glancing‐emergent‐angle fluorescence for polarized XAFS studies of single crystals

X‐ray absorption fine‐structure (XAFS) data were obtained for the V K‐edge for a series of anisotropic single crystals of (Cr_xV_1–x)₂O₃. The data and the results were compared for the as‐prepared bulk single crystals (measured in fluorescence in two different orientations) and those ground to powder (measured in transmission). For the bulk single crystals, the glancing‐emergent‐angle (GEA) method was used to minimize fluorescence distortion. The reliability of the GEA technique was tested by comparing the polarization‐weighted single‐crystal XAFS data with the experimental powder data. These data were found to be in excellent agreement throughout the entire energy range. Thus, it was possible to reliably measure individual V–V contributions parallel and perpendicular to the c axis of the single crystals, i.e. those unavailable by powder data XAFS analysis. These experiments demonstrate that GEA is a premiere method for non‐destructive high‐photon‐count in situ studies of local structure in bulk single crystals.     

Effect of the Calcination Atmosphere on the Structural Properties of the Reduced Fe/SiO2 System

Iron supported systems are frequently used as catalysts in the Fischer–Tropsch synthesis being the Fe⁰ the active phase for the reaction. We have studied the influence of the calcination atmosphere (air or nitrogen) on the iron oxide reducibility and the metallic iron particle size obtained in Fe/SiO₂ system. We have impregnated a silicagel with Fe(NO₃)₃·9H₂O aqueous solution and the solid obtained was calcinated in air or N₂ stream. These precursors, with 5% (wt/wt) of Fe, were characterized by Mössbauer Spectroscopy at 298 and 15 K. Amorphous Fe₂O₃ species with 3 nm diameter in the former, and α-Fe₂O₃ crystals of 48 nm diameter were detected in the last one. Both precursors were reduced in H₂ stream. Two catalysts were obtained and characterized by Mössbauer spectroscopy in controlled atmosphere at 298 and 15 K, CO chemisorption and volumetric oxidation. α-Fe⁰, Fe₃O₄ and Fe²⁺ were identified in the catalyst calcined in air. Instead, only α-Fe⁰ was detected in the catalyst calcined in N₂. The iron metallic crystal sizes were estimated as ≈2 nm for the former and ≈29 nm for the last one. The different oxide crystal sizes, obtained from the diverse calcination atmospheres, have led to different structural properties of the reduced solids. It has been possible to reduce totally the existing iron in an Fe/SiO₂ system with iron loading lower than 10% (wt/wt).     

Hierarchically Porous NaCoPO4–Co3O4 Hollow Microspheres for Flexible Asymmetric Solid‐State Supercapacitors

A template‐free hydrothermal method is developed to prepare hierarchical hollow precursors. An inside‐out Ostwald ripening mechanism is proposed to explain the formation of the hollow structure. After the calcination in the air, hierarchically meso/macroporous NaCoPO₄–Co₃O₄ hollow microspheres can easily be obtained. When being evaluated as electrode materials for a supercapacitor, the hierarchically porous NaCoPO₄–Co₃O₄ hollow microspheres electrode shows a specific capacitance of 268 F g^?1 at 0.8 A g^?1 and offers a good cycle life. More importantly, the obtained materials are successfully applied to fabricate flexible solid‐state asymmetric supercapacitors. The device exhibits a specific capacitance of 28.6 mF cm^?2 at 0.1 mA cm^?2, a good cycling stability with only 5.5% loss of capacitance after 5000 cycles, and good mechanical flexibility under different bending angles, which confirms that the hierarchically porous NaCoPO₄–Co₃O₄ hollow microspheres are promising active materials for the flexible supercapacitor.     

Origin of the ferromagnetism in ZnCoO from chemical reaction of Co3O4

We investigated conversion of Co₃O₄ to Co nanoclusters through hydrogen reduction. Quantitative analysis is performed on the conversion of Co₃O₄ to Co metal as a function of hydrogen-injection conditions. Our results reveal that Co₃O₄ must be completely eliminated to avoid formation of the metal phase in ZnCoO. We also propose a new M–T curve based method for detecting nano-sized Co clusters which are below the detection limit of diffraction techniques. It is also found that the Co phase can be transformed back to the Co₃O₄ phase through oxygen annealing and that, as a result, the ferromagnetism can be eliminated. These findings are discussed in the context of the origin of ferromagnetism in ZnCoO.     

Raman investigations of Zn1−xCoxO nanocrystals: role of starting precursors on vibrational properties

The Raman spectra of sol–gel derived Co‐doped ZnO nanoparticles (NPs) in the spectral range 100–1500 cm⁻¹ were investigated. In the sol–gel method, three different series of Co‐doped ZnO particles, i.e. Zn_1−xCo_xO (x = 0.05, 0.10, 0.15, and 0.20), were obtained using three different starting precursors, viz. cobalt chloride hexahydrate, cobalt acetate tetrahydrate, and cobalt nitrate hexahydrate, respectively. It has been observed that cobalt acetate is a better precursor in comparison to cobalt chloride and cobalt nitrate to obtain single‐phase Co‐doped ZnO NPs. As for cobalt acetate‐derived NPs, no hidden secondary phase of Co₃O₄ was observed for the lower (x = 0.05) Co concentration. The Fröhlich interaction associated with the longitudinal modes was found to be destroyed with increasing Co concentration due to structural disorder and defects induced by the dopant. In addition to ZnO and Co₃O₄ vibrational modes, a few additional modes near 550 and 715 cm⁻¹ were also observed in all cases, which could be attributed to the modes due to Co doping in ZnO. Copyright © 2011 John Wiley & Sons, Ltd.     

Interrelation between inhomogeneity and cyclability in O3‐NaFe1/2Co1/2O2

O3‐NaFe_1/2Co_1/2O₂ shows initial capacity of 160 mAh/g and an average operating voltage of 3.1 V (vs. Na) with good cyclability, and is a promising candidate of the cathode materials for sodium‐ion secondary batteries (SIBs). Here, we found that the cyclability of the slowly‐cooled sample is much worse than that of quenched one, even though the former sample keeps the O3‐type structure. The energy dispersive X‐ray spectroscopy (EDX) images suggest that the slow‐cooled sample (Na_x Fe_1–yCo_y O₂) is inhomogeneous in the Fe concentration (1 – y), perhaps triggered by the Na deficiency (1 – x). We ascribed the poor cyclability in the slowly‐cooled sample to the concentration inhomogeneity (Δy). The Δy is further responsible for the fluctuation of the lattice constants (a and c), as revealed by the Williamson–Hall plot. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Carbon‐Encapsulated Tube‐Wire Co3O4/MnO2 Heterostructure Nanofibers as Anode Material for Sodium‐Ion Batteries

This study presents a general approach for the synthesis of carbon‐encapsulated wire‐in‐tube Co₃O₄/MnO₂ heterostructure nanofibers (Co₃O₄/MnO₂@C) via electrospinning followed by calcination. The as‐synthesized Co₃O₄/MnO₂@C is investigated as the sodium‐ion batteries anode material, which not only exhibits a high reversible capacity of 306 mAh g⁻¹ at 100 mA g⁻¹ over 200 cycles, but also shows a cycling stability of 126 mAh g⁻¹ after 1000 cycles at a high current density of 800 mA g⁻¹. The excellent electrochemical performance can be ascribed to the contribution from carbon‐encapsulated outer‐tube Co₃O₄ and inner‐wire MnO₂ heterostructures, which offer a large internal space and good electrical conductivity. The present work can be helpful in providing new insights into heterostructures for sodium‐ion batteries and other applications.     

Sonochemical synthesis and characterization of Co3O4 nanocrystals in the presence of the ionic liquid [EMIM][BF4]

For the first time, a sonochemical process has been used to synthesis cobalt oxide Co₃O₄ nanoflowers and nanorods morphology in the presence of the ionic liquid 1-Ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄] as reaction media and morphology template. Different sonication time periods and different molar ratios of the ionic liquid (IL) were used to investigate their effects on the structural, optical, chemical and magnetic properties of the produced Co₃O₄ nanoparticles. During synthesis process brown powder contains cobalt hydroxide Co(OH)₂ and cobalt oxyhydroxide (Cobalt hydroxide oxide) CoO(OH) was formed, after calcination in air for 4 h at 400 °C a black powder of Co₃O₄ nanoparticles was produced. The produced Co₃O₄ nanoparticles properties were characterized by X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), transmission electron microscopy (TEM), FTIR spectroscopy, UV–vis spectroscopy, and Vibrating Sample Magnetometer (VSM). To explain the formation mechanism of Co₃O₄ NPs some investigations were carried on the brown powder before calcination.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Insight into growth of Au–Pt bimetallic nanoparticles: an in situ XAS study

Au–Pt bimetallic nanoparticles have been synthesized through a one‐pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X‐ray absorption spectroscopy (XAS) and UV–Vis spectroscopy at the energy‐dispersive EXAFS beamline (BL‐08) at Indus‐2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X‐ray near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L₃‐edges. While the XANES spectra of the precursors provide real‐time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core–shell‐type configuration of a bimetallic alloy in a one‐pot synthesis method. The core–shell‐type structure of the nanoparticles has also been confirmed by ex situ energy‐dispersive spectroscopy line‐scan and X‐ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.     

Modulation of the ferromagnetic insulating phase in Pr0.8Ca0.2MnO3 by Co substitution

Ferromagnetic insulator Pr_0.8Ca_0.2Mn_1–yCo_y O₃ (0 ≤ y ≤ 0.7) thin films were epitaxially grown by pulsed laser deposition on substrates of (LaAlO₃)_0.3(SrAl_0.5Ta_0.5O₃)_0.7 (100). To probe the ferromagnetic insulator state, the Co content dependences of the structural, magnetic, and transport properties were studied. Variation of lattice constant by the Co substitution is well reproduced considering that divalent and trivalent Co ions substitute for Mn ions at the perovskite B‐sites. For 0 ≤ y ≤ 0.3, the Curie temperature, saturation magnetization, and magnetoresistance increase with increasing Co content, retaining the insulating properties. Detailed analyses of transport and magnetic properties indicate the contribution of both double exchange and superexchange interactions to the appearance of the ferromagnetic insulating phase. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)