A non-isothiocyanate route to synthesize trisubstituted thioureas of arylamines using in situ generated dithiocarbamates

A novel, user-friendly, and convenient method for the synthesis of trisubstituted thioureas of arylamines is presented, for the first time, using in situ generated dithiocarbamates of secondary amines. This strategy provides an excellent opportunity to access thioureas containing primary aryl amines. A non-isothiocyanate route to obtain thioureas is the advantage of this strategy, which may provide a useful route to synthesize a variety of biologically active derivatives of thioureas.

In-situ Stabilization of Tin Nanoparticles in Porous Carbon Matrix derived from Metal Organic Framework: High Capacity and High Rate Capability Anodes for Lithium-ion Batteries

It is a formidable challenge to arrange tin nanoparticles in a porous matrix for the achievement of high specific capacity and current rate capability anode for lithium-ion batteries. This article discusses a simple and novel synthesis of arranging tin nanoparticles with carbon in a porous configuration for application as anode in lithium-ion batteries. Direct carbonization of synthesized three-dimensional Sn-based MOF: K2Sn2(1,4-bdc)(3)](H2O) (1) (bdc = benzenedicarboxylate) resulted in stabilization of tin nanoparticles in a porous carbon matrix (abbreviated as Sn@C). Sn@C exhibited remarkably high electrochemical lithium stability (tested over 100 charge and discharge cycles) and high specific capacities over a wide range of operating currents (0.2-5 Ag-1). The novel synthesis strategy to obtain Sn@C from a single precursor as discussed herein provides an optimal combination of particle size and dispersion for buffering severe volume changes due to Li-Sn alloying reaction and provides fast pathways for lithium and electron transport.

Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation

Here, we report the clean and facile synthesis of Pt and Pd nanoparticles decorated on reduced graphene oxide (rGO) by the simultaneous reduction of graphene oxide (GO) and the metal ions in Mg/acid medium. As-generated Pt and Pd nanoparticles serve as a heterogeneous catalyst for the further reduction of the rGO by the hydrogen spill-over process. The C/O ratio is much higher as compared to the rGO obtained by the reduction of GO by only Mg/acid. Overall, the process is rapid, facile and green that does not require any toxic chemical agent or any rigorous chemical reactions. We perform the catalytic reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP) at room temperature by Pd@rGO and Pt@rGO. The reduction is complete within 35 s for Pd@rGO and 60 s for Pt@rGO when 50 mu g of hybrid catalyst is used for 0.5 ml of 1 mM of 4-NP. In case of ethanol oxidation, the current density for Pd@rGO is comparable to commercial Pt/C but is doubled for Pt@rGO. Overall, both structures show highly stable catalytic activity compared to commercial Pt/C. (C) 2014 Elsevier B.V. All rights reserved.

Report of the 2004 Workshop on In Situ Iron Enrichment Experiments in the Eastern and Western Subarctic Pacific

Foreword 1. BACKGROUND AND OBJECTIVES (pdf, 0.1 Mb) 2. 2004 WORKSHOP SUMMARY (pdf, < 0.1 Mb) 2.1. What have we learned from the enrichment experiments? 2.2 What are the outstanding questions? 2.3 Recommendations for SEEDS-II 3. EXTENDED ABSTRACTS OF THE 2004 WORKSHOP 3.1 Synthesis of the Iron Enrichment Experiments: SEEDS and SERIES (pdf, 0.5 Mb) Iron fertilization experiment in the western subarctic Pacific (SEEDS) by Atsushi Tsuda The response of N and Si to iron enrichment in the Northeast Pacific Ocean: Results from SERIES by David Timothy, C.S. Wong, Yukihiro Nojiri, Frank A. Whitney, W. Keith Johnson and Janet Barwell-Clarke 3.2 Biological and Physiological Responses (pdf, 0.2 Mb) Zooplankton responses during SEEDS by Hiroaki Saito Phytoplankton community response to iron and temperature gradient in the NW and NE subarctic Pacific Ocean by Isao Kudo, Yoshifumi Noiri, Jun Nishioka, Hiroshi Kiyosawa and Atsushi Tsuda SERIES: Copepod grazing on diatoms by Frank A. Whitney, Moira Galbraith, Janet Barwell-Clarke and Akash Sastri The Southern Ocean Iron Enrichment Experiment: The nitrogen uptake response by William P. Cochlan and Raphael M. Kudela 3.3 Biogeochemical Responses (pdf, 0.5 Mb) What have we learned regarding iron biogeochemistry from iron enrichment experiments? by Jun Nishioka, Shigenobu Takeda and W. Keith Johnson Iron dynamics and temporal changes of iron speciation in SERIES by W. Keith Johnson, C.S. Wong, Nes Sutherland and Jun Nishioka Dissolved organic matter dynamics during SEEDS and SERIES experiments by Takeshi Yoshimura and Hiroshi Ogawa Formation of transparent exopolymer particles during the in-situ iron enrichment experiment in the western subarctic Pacific (SEEDS) by Shigenobu Takeda, Neelam Ramaiah, Ken Furuya and Takeshi Yoshimura Atmospheric measurement by Mitsuo Uematsu 3.4 Prediction from Models (pdf, 0.3 Mb) Modelling iron limitation in the North Pacific by Kenneth L. Denman and M. Angelica Peña A proposed model of the SERIES iron fertilization patch by Debby Ianson, Christoph Voelker and Kenneth L. Denman 4. LIST OF PARTICIPANTS FOR THE 2004 WORKSHOP (pdf, < 0.1 Mb) APPENDIX 1 Report of the 2000 Planning Workshop on Designing the Iron Fertilization Experiment in the Subarctic Pacific (pdf, 1 Mb) APPENDIX 2 Terms of Reference for the Advisory Panel on Iron fertilization experiment in the subarctic Pacific Ocean (pdf, < 0.1 Mb) APPENDIX 3 Historical List of Advisory Panel Members on Iron fertilization experiment in the subarctic Pacific Ocean (pdf, < 0.1 Mb) APPENDIX 4 IFEP-AP Annual Reports (pdf, 0.1 Mb) APPENDIX 5 PICES Press Articles (pdf, 0.6 Mb) (194 page document)

Síntese e avaliação de hidrogéis à base de alginato e nanopartículas magnéticas preparadas in situ para remoção de Mn(II) e Ni(II) de efluente industrial

Esta Dissertação teve como objetivo,a síntese de hidrogéis à base de alginato e nanopartículas magnéticas (maghemita) preparadas in situ. Os hidrogéis foram preparados em diferentes concentrações de alginato de sódio (2 e 3% m/v), FeSO4 (0,3 e 0,5 mol L-1) e CaCl2 (0,1 e 0,3 mol L-1). As propriedades físico-químicas dos hidrogéis foram analisadas e, posteriormente, foram avaliados quanto à capacidade de remoção de íons Ni2+ e Mn2+ de soluções aquosas. Para caracterização das amostras foram utilizadas diversas técnicas de análises, tais como, análise granulométrica, microscopia óptica (OM), microscopia eletrônica de varredura (SEM), microscopia eletrônica de transmissão (TEM), magnetometria de amostra vibrante (VSM), espectroscopia na região do infravermelho por transformada de Fourier (FTIR), difratometria de raios-X (XRD), espectroscopia Mössbauer, e análise termogravimétrica (TGA). Foram preparados hidrogéis com morfologia predominantemente esférica e dimensões micrométricas (500 a 850 m), com átomos de Fe e Ca dispersos uniformemente em sua estrutura. Os hidrogéis apresentaram boa resistência térmica e comportamento superparamagnético. As amostras foram intumescidas em água deionizada durante um intervalo de tempo a fim de avaliar o grau de intumescimento (Q) para determinar a amostra com a melhor resposta para posterior aplicação em solução aquosa contendo íons metálicos (Ni2+ e Mn2+). Os resultados revelaram que a amostra cuja concentração de 3% m/v de alginato de sódio, 0,3 mol L-1 de FeSO4 e 0,3 mol L-1 de CaCl2 obteve maior Q (50%). Em consequência deste resultado, optou-se por utilizar estaamostra, na remoção de metais pesados presentes em soluções aquosas e em efluentes industriais. Vários parâmetros,tais como: tempo de contato,pH, concentração inicial do íon e massa de hidrogel foram estudados.Os resultados, para efluente sintético, revelaram que o tempo de equilíbrio foi de 60 minutos; a capacidade de remoção dos metais melhora com o aumento de pH (3 a 9), sendo máxima em pH 7;quanto menor a concentração inicial da solução iônica (50 a 500 mg L-1), maior a capacidade de remoção, 52% de Ni2+ e 49% de Mn2+ (concentração inicial de 50 mg L-1). No efluente industrial, a remoção foi de 61% de Ni2+ e 57% de Mn2+(300 mg de hidrogel). Os resultados encontrados revelaram que os hidrogéis magnéticos produzidos à base de alginato têm potencial uso no tratamento de efluentes industriais contaminados com metais pesados

In situ FT-IR spectroscopic studies of CO adsorption on fresh Mo2C/Al2O3 catalyst

The surface sites of supported molybdenum carbide catalyst derived from different synthesis stages have been studied by in situ FT-IR spectroscopy using CO as the probe molecule. Adsorbed CO on the reduced passivated Mo2C/Al2O3 catalyst gives a main band at 2180 cm(-1), which can be assigned to linearly adsorbed CO on Mo4+ sites. The IR results show that the surface of reduced passivated sample is dominated by molybdenum oxycarbide. However, a characteristic IR band at 2054 cm-1 was observed for the adsorbed CO on MoO3/Al2O3 carburized with CH4/H-2 mixture at 1033 K (fresh Mo2C/Al2O3), which can be assigned to linearly adsorbed CO on Modelta+ (0 < delta < 2) sites Of Mo2C/Al2O3, Unlike adsorbed CO on reduced passivated Mo2C/Al2O3 catalyst, the IR spectra of adsorbed CO on fresh Mo2C/Al2O3 shows similarity to that on some of the group VIII metals (such as Pt and Pd), suggesting that fresh carbide resembles noble metals. To study the stability Of Mo2C catalyst during H-2 treatment and find proper conditions to remove the deposited carbon species, H-2 treatment of fresh Mo2C/Al2O3 catalyst at different temperatures was conducted. Partial amounts of carbon atoms in Mo2C along with some surface-deposited carbon species can be removed by the H, treatment even at 450 K. Both the surface-deposited carbon species and carbon atoms in carbide can be extensively removed at temperatures above 873 K.

In Situ Preparation and Luminescent Properties of CeF3 and CeF3:Tb3+ Nanoparticles and Transparent CeF3:Tb3+/PMMA Nanocomposites in the Visible Spectral Range

CeF3 and CeF3:Tb3+ nanoparticles were prepared by reverse microemulsion with a functional monomer, methyl methacrylate (MMA), as the oil phase, and CeF3:Tb3+/poly (methyl methacrylate) (PMMA) nanocomposites were obtained via polymerization of the MMA monomer. The nanoparticles and nanocomposites have been well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), low- and high-resolution transmission electron microscope (TEM), selected-area electron diffraction (SAED), thermogravimetric analysis (TGA), UV/vis transmission spectra, photoluminescence excitation, and emission spectra and luminescence decays. The well-crystallized CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 15 nm. They show the characteristic emission of Ce3+ 5d-4f (313 nm, D-2-F-2(5/2); 323 nm, D-2-F-2(7/2)) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 541 nm as the strongest one) transitions, respectively.

In situ preparation and luminescent properties of LaPO4:Ce3+, Tb3+ nanoparticles and transparent LaPO4:Ce3+, Tb3+/PMMA nanocomposite

LaPO4:Ce3+, Tb3+ nanoparticles were prepared by the reverse microemulsion with functional monomer, methyl methacrylate (MMA) as oil phase, and LaPO4:Ce3+, Tb3+/poly(methyl methacrylate) (PMMA) nanocomposite was obtained via polymerization of MMA monomer. The nanoparticles and nanocomposite have been well characterized by XRD, SEM, TEM, UV/vis spectrum, photoluminescence excitation and emission spectra and luminescence decays. The obtained solid nanocomposite LaPO4:Ce3+, Tb3+/PMMA is highly transparent and exhibits strong green photoluminescence upon UV excitation, due to the integration of luminescent LaPO4:Ce3+, Tb3+ nanoparticles. The luminescent lifetime of Tb3+ is determined to be 1.25 ms in the nanocomposite. (C) 2009 Elsevier Inc. All rights reserved.

In-situ fabrication of hybrid polyoxometalate nanoparticles composite films

inorganic-organic hybrid nanoparticles multilayer films were fabricated by extending the method of nucleation and growth of particles in polymer assemblies. The polyelectrolyte matrix was constructed by layer-by-layer self-assembly method. Synthesis of polyoxometalate nanoparticles was achieved by alternately dipping the precursor polyelectrolyte matrix into AgNO3 and H4SiW12O40 aqueous solutions. Repeating the above synthesis process, Ag4SiW12O40 nanoparticles with controllable diameters of 20 to 77 nm were synthesized in the multilayer films in-situ. UV-vis absorption spectra indicate that the nanoparticles grew gradually in the synthesis process. Transmission electron microscopy was used to observe the size and morphology of the nanoparticles.

In situ ethylene homopolymerization and copolymerization catalyzed by zirconocene catalysts entrapped inside functionalized montmorillonite

Ethylene homopolymerizations and copolymerizations were catalyzed by zirconocene catalysts entrapped inside functionalized. montmorillonites that had been rendered organophilic via the ion exchange of the interlamellar cations of layered montmorillonite with hydrochlorides Of L-amino acids (AAH(+)Cl(-)) or their methyl esters (MeAAH(+)Cl(-)), with or without the further addition of hexadecyltrimethylammonium bromide (C16H33N+Me3Br-; R4N+Br-). In contrast to the homogeneous CP2ZrCl2/methylaluminoxane catalyst for ethylene homopolymerizations and copolymerizations with 1-octene, the intercalated Cp2ZrCl2 activated by methylaluminoxane for ethylene homopolymerizations and copolymerizations with 1-octene proved to be more effective in the synthesis of polyethylenes with controlled molecular weights, chemical compositions and structures, and properties, including the bulk density. The effects of the properties of the organic guests on the preparation and catalytic performance of the intercalated zirconocene catalysts were studied.

Synthesis and luminescence properties of ternary europium complexes in titania matrix in the presence of dimethylformamide by a sol-gel process

In-situ synthesis of ternary europium complex with thenoyltrifluoacetone (TTA) and 1,10-phenanthroline (phen) in titania matrix in the presence of dimethylformamide (DMF) by a sol-gel process was described, which was confirmed by the luminescence excitation spectra and infrared spectra. The titania gel that contains europium complex exhibits Eu3+ characteristic emission bands and presents a longer fluorescence lifetime than the pure complexes dissolved in ethanol solution. The concentration effect on the luminescence intensity was also investigated.

In situ preparation of Ir/ZSM-5/cordierite honeycombs and their application for NOx abatement

ZSM-5 zeolites were synthesized in situ onto cordierite honeycombs by vapor phase transport (VPT) for the first time. The as-synthesized ZSM-5/cordierite honeycombs were impregnated with IrCl3 and tested for NOx reduction with a simulated exhaust gas as the reducing agent. Under the conditions of excess oxygen, the Ir/ZSM-S/cordierite monolith catalyst exhibited NO reduction of 73% at a temperature of 573 K and a space velocity of 20,000 h(-1).

Method for the in situ preparation of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications

A method for the hydrothermal synthesis of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications has been developed. Before the hydrothermal synthesis, the surface of the substrate was modified by an etching procedure that increases the roughness at the nanoscale level without completely eliminating the surface lay structure. Then, thin films of Al2O3 (170 nm) and TiO2 (50 nm) were successively deposited by atomic layer deposition (ALD) on the substrate. The internal Al2O3 film protects the Mo substrate from oxidation up to 550 degrees C in an oxidative environment. The high wettability of the external TiO2 film after UV irradiation increases zeolite nucleation on its surface. The role of the metal precursor (TiCl4 vs TiI4), deposition temperature (300 vs 500 degrees C), and film thickness (50 vs 100 nm) was investigated to obtain titania films with the slowest decay in the superhydrophilic behavior after UV irradiation. Zeolite Beta coatings with a Si/Al ratio of 23 were grown at 140 degrees C for 48 It. After ion exchange with a 10(-4) M cobalt acetate solution, the activity of the coatings was determined in the ammoxidation of ethylene to acetonitrile in a microstructured reactor. A maximum reaction rate of 220 mu mol C2H3N g(-1) s(-1) was obtained at 500 degrees C, with 42% carbon selectivity to acetonitrile. (C) 2007 Elsevier Inc. All rights reserved.

In-situ Monitoring of Solid Oxide Electrolysis Cells

High temperature co-electrolysis of steam and carbon dioxide using a solid oxide cell (SOC) has been shown to be an efficient route to produce syngas (CO + H-2), which can then be converted to synthetic fuel. Optimization of co-electrolysis requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the SOC during operation. Thermal imaging, Raman spectroscopy and Diffuse Reflectance Infrared Fourier Transform Spectroscopy are being developed to probe in-situ both the reactions occurring during operation and any associated changes within the structure of the electrodes and electrolyte. Here we discuss the challenges in designing experimental apparatus suitable for high temperature operation with optical spectroscopic access to the areas of the SOC that are of interest. In particular, issues with sealing, temperature gradients, signal strength and cell configuration are discussed and final designs are presented. Preliminary results obtained during co-electrolysis operation are also presented.