Plasma-enhanced atomic layer deposition of Co using Co(MeCp)_2 precursor

Cobalt （Co） thermal or plasma enhanced atomic layer deposition （PE-ALD） was investigated using a novel metal organic precursor, Co（MeCp）2, and NH3 or H2 or their plasma as a reactant. The growth characteristics, electrical and microstructural properties were investigated. Especially, PE-ALD produced Co thin films at low growth temperature down to 100℃. Interestingly, the low temperature growth of Co films showed the formation of columnar structure at substrate temperature below 300℃. The growth characteristics and films properties of PE-ALD Co using bis（η-methylcyclopentadienyl） Co（II） （Co（MeCp）2） was compared with those of PE-ALD Co using other Cp based metal organic precursors, bis-cyclopentadienyl cobalt （II） （CoCp2） and cyclopentadienyl isopropyl acetamidinato-cobalt （Co（CpAMD））.

Design of the Metal Precursors Molecular Structures in Impregnating Solutions for Preparation of Efficient Ni Mo/Al_2O_3 Hydrodesulfurization Catalysts

The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.

Effect of thermal pretreatment of metal precursor on the properties of Cu_2ZnSnS_4 films

Zn/Sn/Cu （CZT） stacks were prepared by RF magnetron sputtering. The stacks were pretreated at different tem- peratures （200℃, 300 ℃, 350 ℃, and 400 ℃） for 0.5 h and then followed by sulfurization at 500℃ for 2 h. Then, the structures, morphologies, and optical properties of the as-obtained Cu2ZnSnS4 （CZTS） films were studied by x-ray diffraction （XRD）, Raman spectroscopy, UV-Vis-NIR, scanning electron microscope （SEM）, and energy-dispersive x-ray spectroscopy （EDX）. The XRD and Raman spectroscopy results indicated that the sample pretreated at 350℃ had no secondary phase and good crystallization. At the same time, SEM confirmed that it had large and dense grains. According to the UV-Vis-NIR spectrum, the sample had an absorption coefficient larger than 10^4 cm-1 in the visible light range and a band gap close to 1.5 eV.

Impact of preparation conditions on hydrogen storage performance of metallic Ti-doped NaAlH_4

Contrary to the popular opinion, it has been found that metallic Ti powder can be directly utilized as dopant precursor to prepare catalytically enhanced NaAlH4 through mechanical milling. As a novel method for preparation of catalytically enhanced NaAlH4, direct metallic Ti-doping possesses practical advantage over the state-of-the-art doping technology: elimination of the inactive by-products and the gas impurities that are highly detrimental to fuel cell operation. A systematic investigation along this new approach was performed under various preparation conditions, including different starting materials, milling atmosphere and milling time. The materials thus prepared under different conditions were found to share some common features, while at the meantime, differ significantly from each other on hydrogen storage performance. A comprehensive understanding of these results provides valuable insight into a series of fundamental questions in catalytically enhanced Ti-NaAlH4 system.

Formation of Ultrafine Metal Particles and Metal Oxide Precursor on Anodized Al by Electrolysis Deposition

Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.

STUDY ON THE INTERACTION BETWEEN POLYVINYLPYRROLIDONE AND PLATINUM METALS DURING THE FORMATION OF THE COLLOIDAL METAL NANOPARTICLES

Several PVP-stabilized colloidal platinum metals nanoparticles have been synthesized and characterized by FTIR and TEM.Comparing with the pure PVP,carbonyl groups of PVP in the mixture of PVP and the metal precursors or in the PVP-stabilized metal nanoparticles have obvious peak shifts in FTIR spectra.The peak shifts reveal the interaction between PVP and the metal species.The interaction between PVP and metal precursors has effect on the formation of the colloidal metal nanoparticles.Strength of the intera...

Preparation of Highly Dispersed Supported Metal Catalysts via Solvated Metal Atom Impregnation ( V) --The Effects of Hydroxyl Group on the Surface Concentrations of SiO2 on the Properties of Supported Fe Clusters

Two kinds of small iron clusters supported on SiO2-200 (dehydroxylated at 200℃ and SiO2-600 (de-hydroxylated at 600℃) were prepared by Solvated Metal Atom Impregnation (SMAI) techniques. The iron atom precursor complex, bis (toluene) iron(0) formed in the metal atom reactor, was impregnated into SiO2 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by THM, Mosbauer and chemisorption measurements, and the resules show that higher concentration of surface hydroxyl groups of SiO2-200 favours the formation of more positively charged support iron cluster Fen/SiO2-200 and the lower concentration of surface hydroxyl groups of SiO2-600 favours the formation of basically neutral supported iron cluster Fe2/SiO2-600. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the precursor complex,bis(toluene) fron(0), to decompose more rapidly, and favours the formation of relatively large iron cluster. As a consequence, these two kinds of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fe/SiO2-200 in F-T reaction is similar to that of the unreduced a-Fe2O2, while Fe2/SiO2 -600 is similar to that of reduced α-Fe2O2.

Self-supporting nanoporous Ni/metallic glass composites with hierarchically porous structure for efficient hydrogen evolution reaction

Searching for free-standing and cost-efficient hydrogen evolution reaction(HER)electrocatalysts with high efficiency and excellent durability remains a great challenge for the hydrogen-based energy industry.Here,we report fabrication of a unique hierarchically porous structure,i.e.,nanoporous Ni(NPN)/metallic glass(MG)composite,through surface dealloying of the specially designed Ni_(40)Zr_(40)Ti_(20)MG wire.This porous composite is composed of micrometer slits staggered with nanometer pores,which not only enlarges effective surface areas for the catalytic reaction,but also facilitates the release of H2 gas.As a result,the NPN/MG hybrid electrode exhibited the prominent HER performance with a low overpotential of 78 m V at 10 m A cm^(-2)and Tafel slope of 42.4 m V dec^(-1),along with outstanding stability in alkaline solutions.Outstanding catalytic properties,combining with their free-standing capability and cost efficiency,make the current composite electrode viable for HER applications.

N-Doped Carbon Nanofibers Encapsulating CoO@Co_(9)S_(8) Nanoparticles:Preparation from S-Rich Co_(32) Coordination Cluster Precursors by Electrospinning and Application for Superior Li-ion Storage

Thiacalixarene-supported Co_(32) nanoclusters encapsulated in polyacrylonitrile nanofibers(Co_(32)@PAN-NFs)by electrospinning have been utilized as precursors to fabricate N-doped CoO@Co_(9)S_(8) carbon nanofibers(CoO@Co_(9)S_(8)@CNFs)for superior Li-ion storage.The S-rich Co_(32) clusters capped by organic sheets afforded the well dispersed cobalt oxide/sulfide nanoparticles embedded in carbon nanofiber composites by direct calcination.The N-doped CoO@Co_(9)S_(8)@CNFs nanocomposites have been utilized as anode materials for lithium ion battery with the reversible capabilities being of 1051.8,967.6,894.7,782.7,669.5 and 525.4 mA·h/g at 0.1,0.2,0.5,1,2 and 3 A/g,respectively.The CoO@Co_(9)S_(8)@CNFs also showed a relatively high stable capacity of 551.7 mA·h/g at the current density of 1 A/g after 200 cycles of rate experiments.The as-obtained N-doped CoO@Co_(9)S_(8)@CNFs nanocomposites exhibited superior reversible capacity,rate performance,Coulomb efficiency(74.5%vs.63.9%)and cyclic stability comparing with the CoO@Co_(9)S_(8)@C derived from simple annealing of Co_(32) templates.

Efficient visible-light-driven water oxidation by single-crystal Ta_(3)N_(5)nanoparticles

Ta3N5 is regarded as a promising photocatalyst for solar water splitting because of its excellent visible light absorption characteristics and simple composition.Conventional Ta3N5 photocatalysts prepared from oxide precursors typically comprise aggregated polycrystalline particles with defects and grain boundaries that reduce the water oxidation activity of the material.In the present work,well-dispersed Ta3N5 nanoparticulate single crystals were synthesized via a mild nitridation process using pure Ta metal nanopowder or Ta nanopowder mixed with NaCl.The resulting high-quality Ta3N5 nanoparticles,after loading with an oxygen evolution cocatalyst,exhibited impressively high photocatalytic performance during O_(2)evolution from a sacrificial AgNO3 solution,with an apparent quantum yield of 9.4%at 420 nm.Our findings suggest a new approach to the facile fabrication of nanostructured single-crystal photocatalysts for efficient solar water splitting,based on the use of metal nanopowders.