Condensation-enhanced self-assembly as a route to high surface area α-aluminas

High surface area nanosized α-alumina has been obtained by thermally treating a sol-gel-derived mesophase at 1200 C; the mesophase was synthesized by a sol-gel route involving evaporation induced self-assembly (EISA) of a hydrolyzed gel from Al-tri-sec-butoxide in s-BuOH in the presence of a nonionic surfactant (EO20PO70EO20), HCl as catalyst, and water (H2O/Al = 6). The activated material renders moderate surface areas of about 8.4-10 m2 g-1, associated with significant crystallite coarsening. The key aspect to produce smaller crystallites is making the mesophase more resistant to coarsening. This was achieved by enhancing the condensation step by treating the hydrolyzed gel with tetrabutyl ammonium hydroxide (TBAOH) before evaporation. The characteristics of the mesophase indicate condensation of the primary particles with less AlO5 unsaturated sites, at the expense of a lower solid yield due to small crystallites dissolution. The activated TBAOH condensed EISA material is composed of α-alumina aggregated crystallites of about 60-100 nm, and the material possesses surface areas ranging from 16 to 24 m2 g -1 due to the improved resistance to coarsening. At least two aspects are suggested to play a role in this. The worm-hole morphology of the mesophase aggregates yields high particle coordination, which favors densification rather than coarsening. Furthermore, the decrease of the AlO5 defect sites by the TBAOH condensation makes the mesophase less reactive and consequently more resistant to coarsening. © 2013 American Chemical Society.

Microporous organic polymers based on hexaphenylbiadamantane:synthesis, ultra-high stability and gas capture

Hexaphenylbiadamantane-based microporous organic polymers (MOPs) were successfully synthesized by Suzuki coupling under mild conditions. The obtained MOPs show high surface area (891 m2 g−1), ultra-high thermal (less than 40% mass loss at temperatures up to 1000 °C) and chemical (no apparent decomposition in organic solvents for more than 7 days) stability, gas (H2, CO2, CH4) capture capabilities and vapor (benzene, hexane) adsorption. These combined abilities render the synthesized MOPs an attractive candidate as thermo-chemically stable adsorbents for practical use in gas storage and pollutant vapor adsorption.

Mesoporous silicas as versatile supports to tune the palladium-catalyzed selective aerobic oxidation of allylic alcohols

Surfactant templating offers a simple route to synthesize high-surface area silicas with ordered, tunable mesopore architectures. The use of these materials as versatile catalyst supports for palladium nanoparticles has been explored in the aerobic selective oxidation (selox) of allylic alcohols under mild conditions. Families of Pd/mesoporous silicas, synthesized through incipient wetness impregnation of SBA-15, SBA-16, and KIT-6, have been characterized by using nitrogen porosimetry, CO chemisorption, diffuse reflection infrared Fourier transform spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and high-resolution TEM and benchmarked in liquid phase allylic alcohol selox against a Pd/amorphous SiO2 standard. The transition from amorphous to two-dimensional parallel and three-dimensional interpenetrating porous silica networks conferred significant selox rate enhancements associated with higher surface densities of active palladium oxide sites. Dissolved oxygen was essential for insitu stabilization of palladium oxide, and thus maintenance of high activity on-stream, whereas selectivity to the desired aldehyde selox product over competing hydrogenolysis pathways was directed by using palladium metal. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zirconium phosphate supported tungsten oxide solid acid catalysts for the esterification of palmitic acid

A series of zirconium phosphate supported WOx solid acid catalysts with W loadings from 1–25 wt% have been prepared on high surface area zirconium phosphate by a surface grafting method. Catalysts were characterized by N2 adsorption, FTIR, Raman, UV-Vis, 31P MAS NMR, pyridine TPD and X-ray methods. Spectroscopic measurements suggest a Keggin-type structure forms on the surface of zirconium phosphate as a ([triple bond, length as m-dash]ZrOH2+)(ZrPW11O405−) species. All catalysts show high activity in palmitic acid esterification with methanol. These materials can be readily separated from the reaction system for re-use, and are resistant to leaching of the active heteropolyacid, suggesting potential industrial applications in biodiesel synthesis. © The Royal Society of Chemistry 2006.

Synthesis of a novel and stable g-C3N4–Ag3PO4 hybrid nanocomposite photocatalyst and study of the photocatalytic activity under visible light irradiation

A facile and reproducible template free in situ precipitation method has been developed for the synthesis of Ag3PO4 nanoparticles on the surface of a g-C3N4 photocatalyst at room temperature. The g-C3N4–Ag3PO4 organic–inorganic hybrid nanocomposite photocatalysts were characterized by various techniques. TEM results show the in situ growth of finely distributed Ag3PO4 nanoparticles on the surface of the g-C3N4 sheet. The optimum photocatalytic activity of g-C3N4–Ag3PO4 at 25 wt% of g-C3N4 under visible light is almost 5 and 3.5 times higher than pure g-C3N4 and Ag3PO4 respectively. More attractively, the stability of Ag3PO4 was improved due to the in situ deposition of Ag3PO4 nanoparticles on the surface of the g-C3N4 sheet. The improved performance of the g-C3N4–Ag3PO4 hybrid nanocomposite photocatalysts under visible light irradiation was induced by a synergistic effect, including high charge separation efficiency of the photoinduced electron–hole pair, the smaller particle size, relatively high surface area and the energy band structure. Interestingly, the heterostructured g-C3N4–Ag3PO4 nanocomposite significantly reduces the use of the noble metal silver, thereby effectively reducing the cost of the Ag3PO4 based photocatalyst.

A study in the reduction of efficiency of nitrogen oxide removal catalysts for automobiles

Automotive catalysts are the most effective short-term answer to air pollution from automobiles. Since strict control of exhaust emissions is, or will be,covered by legislation in most developed countries in the world, catalytic devices will be increasingly fitted to cars. There is consequently an urgent need for the development of catalysts that will not compete for scarce precious metal resources. A number of problems have already been identified in connection with base metal catalysts but quantitative investigations are lacking. The base metal reduction catalysts developed by Imperial Chemical Industries Limited, catalysts and Chemical Group, in collaboration with the Air Pollution Control Laboratory, B L Cars Limited for automotive emission control, are susceptible to de-activation by three major mechanisms. These are: physical loss of the wash-coat (a high surface area coating which supports the active species), aggregation of the active species and poisoning by fuel and engine oil additives. This thesis is especially concerned with the first two of these and attempts to indicate the relative magnitude .of their effect on the activity of. the catalysts. Aggregation of the active species or sintering, as it is loosely called, was studied by using impregnated granules to overcome effects due to the loss of the wash-coat. Samples were aged in a synthetic exhaust gas, free from poisons, and metal crystallite sizes were measured by scanning-electron microscopy. The increase in particle size was correlated with the loss in catalytic activity. In order to maintain a link with the real conditions of service a number of monolithic catalysts were tested in an engine-dynamometer and several previously tested endurance catalysts were examined. A mechanism is proposed for the break-up and subsequent 10s.5 of the wash-coat and suggestions for improved resistance to loss of the' coating and active species are proposed.

B2B e-marketplaces in the airline industry:process drivers and performance indicators

Competitive pressures are increasing within and between different strategically oriented groups of airlines. This paper focuses on the level of efficiency improvements gained by using e-Marketplaces in the procurement process. Findings from a survey among 88 international airlines reveal that the use of Business-to-Business (B2B) e-Marketplaces does play different roles across the various airline groupings. Airlines that are involved in strategic alliances show higher joint procurement activities than airlines that are not involved in strategic alliances. However, alliances are probably viewed as loose arrangements and thus airlines may be reluctant to share information on procurement prices and processes with another airline that could also be acting as a competitor. The financial involvement in or initiation of e-Marketplaces by airlines is very low. Low cost airlines show high use of e-Marketplaces, but demonstrate little financial involvement in contrast. Overall, the categories of spares and repairs, office supplies, tools and ground support equipment (GSE) show the greatest potential for reducing costs and increasing procurement process efficiencies. The intense competitive pressures facing carriers will make their search for tools to realise even incremental savings and efficiency gains ever more urgent. There is evidence that e-Marketplaces are one tool to improve such performance indicators.

Hydroxyapatite supported antibacterial Ag3PO4 nanoparticles

High surface area hydroxyapatites have been explored as biocompatible supports for antibacterial applications. Porosimetry, XRD, XPS and XAS reveal that Ag-doped mesoporous hydroxyapatite promotes the genesis of potent Ag3PO4 nanoparticles, effective against Staphylococcus aureus and Pseudomonas aeruginosa. © 2010 The Royal Society of Chemistry.

Preparation of a microporous silicon oximide gel from the reaction of tris(dimethylamino)silylamine with formamide and its pyrolytic conversion into a silicon oxynitride based glass

A high-surface-area silicon oximide-based gel [SiOC(H)=NSi]m[Si2N-C(H)=O]n[SiN(H)-C(H)=O]p[SiOC(H)=NH]q[SiNH]r[SiNH2]s[SiNMe2]t was prepared via a formamide-based aminolysis of tris(dimethylamino)silylamine, (Me2N)3SiNH2. The structure of the gel and the mechanism of formation are elucidated. Pyrolysis of the gel at 1000 °C under N2 flow gave an amorphous microporous oxynitride-based glass with a BET surface area of 195 m2 g−1. © The Royal Society of Chemistry 2005.

Synthesis of highly efficient and recyclable visible-light responsive mesoporous g-C3N4 photocatalyst via facile template-free sonochemical route

Herein we demonstrate a facile template-free sonochemical strategy to synthesize mesoporous g-C3N4 with a high surface area and enhanced photocatalytic activity. The TEM and nitrogen adsorption–desorption studies confirm mesoporous structure in g-C3N4 body. The photocatalytic activity of mesoporous g-C3N4 is almost 5.5 times higher than that of bulk g-C3N4 under visible-light irradiation. The high photocatalytic performance of the mesoporous g-C3N4 was attributed to the much higher specific surface area, efficient adsorption ability and the unique interfacial mesoporous structure which can favour the absorption of light and separation of photoinduced electron–hole pairs more effectively. A possible photocatalytic mechanism was discussed by the radicals and holes trapping experiments. Interestingly, the synthesized mesoporous g-C3N4 possesses high reusability. Hence the mesoporous g-C3N4 can be a promising photocatalytic material for practical applications in water splitting as well as environmental remediation.

Marking high-technology market evolution through the foci of market stories:the case of local area networks

Previous research suggests that changing consumer and producer knowledge structures play a role in market evolution and that the sociocognitive processes of product markets are revealed in the sensemaking stories of market actors that are rebroadcasted in commercial publications. In this article, the authors lend further support to the story-based nature of market sensemaking and the use of the sociocognitive approach in explaining the evolution of high-technology markets. They examine the content (i.e., subject matter or topic) and volume (i.e., the number) of market stories and the extent to which content and volume of market stories evolve as a technology emerges. Data were obtained from a content analysis of 10,412 article abstracts, published in key trade journals, pertaining to Local Area Network (LAN) technologies and spanning the period 1981 to 2000. Hypotheses concerning the evolving nature (content and volume) of market stories in technology evolution are tested. The analysis identified four categories of market stories - technical, product availability, product adoption, and product discontinuation. The findings show that the emerging technology passes initially through a 'technical-intensive' phase whereby technology related stories dominate, through a 'supply-push' phase, in which stories presenting products embracing the technology tend to exceed technical stories while there is a rise in the number of product adoption reference stories, to a 'product-focus' phase, with stories predominantly focusing on product availability. Overall story volume declines when a technology matures as the need for sensemaking reduces. When stories about product discontinuation surface, these signal the decline of current technology. New technologies that fail to maintain the 'product-focus' stage also reflect limited market acceptance. The article also discusses the theoretical and managerial implications of the study's findings. © 2002 Elsevier Science Inc. All rights reserved.

Environmentally stable high-power soliton fiber lasers that use chirped fiber Bragg gratings

Environmentally stable high-power erbium fiber soliton lasers are constructed by Kerr or carrier-type mode locking. We obtain high-energy pulses by using relatively short fiber lengths and providing large amounts of negative dispersion with chirped fiber Bragg gratings. The pulse energies and widths generated with both types of soliton laser are found to scale with the square root of the cavity dispersion. Kerr mode locking requires pulses with an approximately three times higher nonlinear phase shift in the cavity than carrier mode locking, which leads to the generation of slightly shorter pulses with as much as seven times higher pulse energies at the mode-locking threshold.

Packet switching in wide area broadband private networks

B-ISDN is a universal network which supports diverse mixes of service, applications and traffic. ATM has been accepted world-wide as the transport technique for future use in B-ISDN. ATM, being a simple packet oriented transfer technique, provides a flexible means for supporting a continuum of transport rates and is efficient due to possible statistical sharing of network resources by multiple users. In order to fully exploit the potential statistical gain, while at the same time provide diverse service and traffic mixes, an efficient traffic control must be designed. Traffic controls which include congestion and flow control are a fundamental necessity to the success and viability of future B-ISDN. Congestion and flow control is difficult in the broadband environment due to the high speed link, the wide area distance, diverse service requirements and diverse traffic characteristics. Most congestion and flow control approaches in conventional packet switched networks are reactive in nature and are not applicable in the B-ISDN environment. In this research, traffic control procedures mainly based on preventive measures for a private ATM-based network are proposed and their performance evaluated. The various traffic controls include CAC, traffic flow enforcement, priority control and an explicit feedback mechanism. These functions operate at call level and cell level. They are carried out distributively by the end terminals, the network access points and the internal elements of the network. During the connection set-up phase, the CAC decides the acceptance or denial of a connection request and allocates bandwidth to the new connection according to three schemes; peak bit rate, statistical rate and average bit rate. The statistical multiplexing rate is based on a `bufferless fluid flow model' which is simple and robust. The allocation of an average bit rate to data traffic at the expense of delay obviously improves the network bandwidth utilisation.