339 resultados para visible
Resumo:
A central tenet underlying studies on management fashions is that the diffusion of novel forms, models and techniques is driven by an institutional norm of progress, which is the societal expectation that managers will continuously use 'new and improved' management practices. We add to the literature on management fashions by arguing that, if the display of progressiveness in the manner of managing and organizing is expected of organizations, firms that are visibly progressive would be evaluated more positively by organizational audiences following this institutional prescription. Using article counts of co-occurrences of firms and various fashionable management practices in Wall Street Journal, we hypothesize positive effects of such associations on security analysts' evaluations of these firms. Results support this hypothesis. Our study enriches the management fashion literature by highlighting the consequential relevance of organizational adherence to the norm of progress.
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Finely control of product selectivity is an essential issue in organic chemical production. In the synthesis of functionalized anilines via reduction of the corresponding nitroarenes, the challenge is to selectively reduce only the nitro group in the presence of other reducible functional groups in nitroarene molecules at a high reaction rate. Normally, the nitroarene is reduced stepwise through a series of intermediates that remain as byproducts, increasing the aniline synthesis cost. Here we report that alloying small amounts of copper into gold nanoparticles can alter the reaction pathway of the catalytic reduction under visible-light irradiation at ambient temperature, allowing nitroaromatics to be transformed directly to anilines in a highly selective manner. The reasons for the high efficiency of the photocatalytic reduction under these comparatively benign conditions as well as the light-excited reaction mechanisms are discussed. This photocatalytic process avoids byproducts, exhibits a high reaction rate and excellent substituent tolerance, and can be used for the synthesis of many useful functionalized anilines under environmentally benign conditions. Switching of the reaction pathway simply by tailoring the bimetallic alloy NPs of the photocatalysts is effective for engineering of product chemoselectivity.
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The formation of heterojunctions between two crystals with different band gap structures, acting as a tunnel for the unidirectional transfer of photo-generated charges, is an efficient strategy to enhance photocatalytic performance in semiconductor photocatalysts. The heterojunctions may also promote the photoactivity in the visible-light-response of any surface complex catalysts by influencing the transfer of photo-generated electrons. Herein, Nb2O5 microfibers, with a high surface area of interfaces between an amorphous phase and crystalline phase, were designed and synthesised by the calcination of hydrogen-form niobate while controlling the crystallization The photoactivity of these microfibers towards selective aerobic oxidation reactions was investigated. As predicted, the Nb2O5 microfibres containing heterojunctions exhibited the highest photoactivity. This could be due to the band gap difference between the amorphous phase and the crystalline phase, which shortened the charge mobile distance and improved the efficiency.
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The p-block semiconductors are regarded as a new family of visible-light photocatalysts because of their dispersive and anisotropic band structures as well as high chemical stability. The bismuth oxide halides belong to this family and have band structures and dispersion relations that can be engineered by modulating the stoichiometry of the halogen elements. Herein, we have developed a new visible-light photocatalyst Bi 24 O 31 Cl 10 by band engineering, which shows high dye-sensitized photocatalytic activity. Density functional theory calculations reveal that the p-block elements determine the nature of the dispersive electronic structures and narrow band gap in Bi 24 O 31 Cl 10. Bi 24 O 31 Cl 10 exhibits excellent visible-light photocatalytic activity towards the degradation of Rhodamine B, which is promoted by dye sensitization due to compatible energy levels and high electronic mobility. In addition, Bi 24 O 31 Cl 10 is also a suitable photoanode material for dye-sensitized solar cells and shows power conversion efficiency of 1.5%.
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It is a challenge to increase the visible-light photoresponses of wide-gap metal oxides. In this study, we proposed a new strategy to enhance the visible-light photoresponses of wide-gap semiconductors by deliberately designing a multi-scale nanostructure with controlled architecture. Hollow ZnO microspheres with constituent units in the shape of one-dimensional (1D) nanowire networks, 2D nanosheet stacks, and 3D mesoporous nanoball blocks are synthesized via an approach of two-step assembly, where the oligomers or the constituent nanostructures with specially designed structures are first formed, and then further assembled into complex morphologies. Through deliberate designing of constituent architectures allowing multiple visible-light scattering, reflections, and dispersion inside the multiscale nanostructures, enhanced wide range visible-light photoresponses of the ZnO hollow microspheres were successfully achieved. Compared to the one-step synthesized ZnO hollow microspheres, where no nanostructured constituents were produced, the ZnO hollow microspheres with 2D nanosheet stacks presented a 50 times higher photocurrent in the visible-light range (λ > 420 nm). The nanostructure induced visible-light photoresponse enhancement gives a direction to the development of novel photosensitive materials.
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Reducing carbon dioxide (CO2) to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single palladium/platinum (Pd/Pt) atoms supported on graphitic carbon nitride (g-C3N4), i.e. Pd/g-C3N4 and Pt/g-C3N4, acting as photocatalysts for CO2 reduction were investigated by density function theory (DFT) calcu-lations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, depositing atom catalysts on g-C3N4 significantly enhances the visible light absorption, rendering them ideal for visible light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.
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Visible, near-infrared, IR and Raman spectra of magnesian gaspeite are presented. Nickel ion is the main source of the electronic bands as it is the principal component in the mineral where as the bands in IR and Raman spectra are due to the vibrational processes in the carbonate ion as an entity. The combination of electronic absorption and vibrational spectra (including near-infrared, FTIR and Raman) of magnesian gaspeite are explained in terms of the cation co-ordination and the behaviour of CO32– anion in the Ni–Mg carbonate. The electronic absorption spectrum consists of three broad and intense bands at 8130, 13160 and 22730 cm–1 due to spin-allowed transitions and two weak bands at 20410 and 30300 cm–1 are assigned to spin-forbidden transitions of Ni2+ in an octahedral symmetry. The crystal field parameters evaluated from the observed bands are Dq = 810; B = 800 and C = 3200 cm–1. The two bands in the near-infrared spectrum at 4330 and 5130 cm–1 are overtone and combination of CO32– vibrational modes. For the carbonate group, infrared bands are observed at 1020 cm–1(1 ), 870 cm–1 (2), 1418 cm–1 (3) and 750 cm–1 (4), of which3, the asymmetric stretching mode is most intense. Three well resolved Raman bands at 1571, 1088 and 331 cm–1 are assigned to 3, 1 and MO stretching vibrations.
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The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.
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We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.
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The Raman spectra of both low- and high-defect kaolinites in the hydroxyl stretching and low-wavenumber region were obtained with excitation at three visible wavelengths of 633, 514 and 442 nm and a UV wavelength of 325 nm. The UV-excited spectra were comparable to those excited by the visible wavelengths. The Raman spectra show hydroxyl stretching bands at 3621 cm-1 attributed to the inner hydroxyl, at 3692 and 3684 cm-1 attributed to the longitudinal and transverse optic modes of the inner surface hydroxyls and at 3668 and 3653 cm-1 assigned to the out-of phase vibrations of the inner surface hydroxyls. Two bands were observed in the spectral profile at 3695 cm-1 for the high-defect kaolinite at 3698 and 3691 cm-1 and were assigned to TO/LO splitting. An increase in relative intensity of the transverse optic mode is observed with decrease in laser wavelength. The intensity of the out-of-phase vibrations at 3668 and 3653 cm-1 of the inner surface hydroxyls shows a linear relationship with the longitudinal and transverse optic modes. In the low-wavenumber region excellent correlation was found between the experimentally determined and the calculated band positions.
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Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.
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In this article, we take a close look at the literacy demands of one task from the ‘Marvellous Micro-organisms Stage 3 Life and Living’ Primary Connections unit (Australian Academy of Science, 2005). One lesson from the unit, ‘Exploring Bread’, (pp 4-8) asks students to ‘use bread labels to locate ingredient information and synthesise understanding of bread ingredients’. We draw upon a framework offered by the New London Group (2000), that of linguistic, visual and spatial design, to consider in more detail three bread wrappers and from there the complex literacies that students need to interrelate to undertake the required task. Our findings are that although bread wrappers are an example of an everyday science text, their linguistic, visual and spatial designs and their interrelationship are not trivial. We conclude by reinforcing the need for teachers of science to also consider how the complex design elements of everyday science texts and their interrelated literacies are made visible through instructional practice.
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In this chapter, John Howard’s policy speech to The Sydney Institute, a conservative think tank, on October 11, 2007 as the Australian Prime Minister of the day, is analysed within the frame of discourse analysis to make visible how the speech works in old ways to dress up neoliberal policy as new and reformist. Taking centre stage, Howard pointed to concrete steps undertaken to achieve what he called a “new reconciliation.” This cynical manoeuvre, which put reconciliation back onto the election agenda (after it was earlier derided for its divisive and muddle headed symbolism), constituted a “neoliberal quickstep” (Reiger, 2006) or quickfix of sorts. The speech was also used as a place to reintroduce the Northern Territory Intervention, which at the time was purported to be a response to child abuse and Indigenous community dysfunction.
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Although internet chat is a significant aspect of many internet users’ lives, the manner in which participants in quasi-synchronous chat situations orient to issues of social and moral order remains to be studied in depth. The research presented here is therefore at the forefront of a continually developing area of study. This work contributes new insights into how members construct and make accountable the social and moral orders of an adult-oriented Internet Relay Chat (IRC) channel by addressing three questions: (1) What conversational resources do participants use in addressing matters of social and moral order? (2) How are these conversational resources deployed within IRC interaction? and (3) What interactional work is locally accomplished through use of these resources? A survey of the literature reveals considerable research in the field of computer-mediated communication, exploring both asynchronous and quasi-synchronous discussion forums. The research discussed represents a range of communication interests including group and collaborative interaction, the linguistic construction of social identity, and the linguistic features of online interaction. It is suggested that the present research differs from previous studies in three ways: (1) it focuses on the interaction itself, rather than the ways in which the medium affects the interaction; (2) it offers turn-by-turn analysis of interaction in situ; and (3) it discusses membership categories only insofar as they are shown to be relevant by participants through their talk. Through consideration of the literature, the present study is firmly situated within the broader computer-mediated communication field. Ethnomethodology, conversation analysis and membership categorization analysis were adopted as appropriate methodological approaches to explore the research focus on interaction in situ, and in particular to investigate the ways in which participants negotiate and co-construct social and moral orders in the course of their interaction. IRC logs collected from one chat room were analysed using a two-pass method, based on a modification of the approaches proposed by Pomerantz and Fehr (1997) and ten Have (1999). From this detailed examination of the data corpus three interaction topics are identified by means of which participants clearly orient to issues of social and moral order: challenges to rule violations, ‘trolling’ for cybersex, and experiences regarding the 9/11 attacks. Instances of these interactional topics are subjected to fine-grained analysis, to demonstrate the ways in which participants draw upon various interactional resources in their negotiation and construction of channel social and moral orders. While these analytical topics stand alone in individual focus, together they illustrate different instances in which participants’ talk serves to negotiate social and moral orders or collaboratively construct new orders. Building on the work of Vallis (2001), Chapter 5 illustrates three ways that rule violation is initiated as a channel discussion topic: (1) through a visible violation in open channel, (2) through an official warning or sanction by a channel operator regarding the violation, and (3) through a complaint or announcement of a rule violation by a non-channel operator participant. Once the topic has been initiated, it is shown to become available as a topic for others, including the perceived violator. The fine-grained analysis of challenges to rule violations ultimately demonstrates that channel participants orient to the rules as a resource in developing categorizations of both the rule violation and violator. These categorizations are contextual in that they are locally based and understood within specific contexts and practices. Thus, it is shown that compliance with rules and an orientation to rule violations as inappropriate within the social and moral orders of the channel serves two purposes: (1) to orient the speaker as a group member, and (2) to reinforce the social and moral orders of the group. Chapter 6 explores a particular type of rule violation, solicitations for ‘cybersex’ known in IRC parlance as ‘trolling’. In responding to trolling violations participants are demonstrated to use affiliative and aggressive humour, in particular irony, sarcasm and insults. These conversational resources perform solidarity building within the group, positioning non-Troll respondents as compliant group members. This solidarity work is shown to have three outcomes: (1) consensus building, (2) collaborative construction of group membership, and (3) the continued construction and negotiation of existing social and moral orders. Chapter 7, the final data analysis chapter, offers insight into how participants, in discussing the events of 9/11 on the actual day, collaboratively constructed new social and moral orders, while orienting to issues of appropriate and reasonable emotional responses. This analysis demonstrates how participants go about ‘doing being ordinary’ (Sacks, 1992b) in formulating their ‘first thoughts’ (Jefferson, 2004). Through sharing their initial impressions of the event, participants perform support work within the interaction, in essence working to normalize both the event and their initial misinterpretation of it. Normalising as a support work mechanism is also shown in relation to participants constructing the ‘quiet’ following the event as unusual. Normalising is accomplished by reference to the indexical ‘it’ and location formulations, which participants use both to negotiate who can claim to experience the ‘unnatural quiet’ and to identify the extent of the quiet. Through their talk participants upgrade the quiet from something legitimately experienced by one person in a particular place to something that could be experienced ‘anywhere’, moving the phenomenon from local to global provenance. With its methodological design and detailed analysis and findings, this research contributes to existing knowledge in four ways. First, it shows how rules are used by participants as a resource in negotiating and constructing social and moral orders. Second, it demonstrates that irony, sarcasm and insults are three devices of humour which can be used to perform solidarity work and reinforce existing social and moral orders. Third, it demonstrates how new social and moral orders are collaboratively constructed in relation to extraordinary events, which serve to frame the event and evoke reasonable responses for participants. And last, the detailed analysis and findings further support the use of conversation analysis and membership categorization as valuable methods for approaching quasi-synchronous computer-mediated communication.
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In this chapter, we frame YouTube as an example of “co-creative” culture – whatever YouTube is, it is produced dynamically (that is, as an ongoing process, over time) as a result of many interconnected instances of participation, by many different people. In order to understand these co-creative relationships, it is important not to focus exclusively on how the “ordinary consumer” or “amateur producer,” are participating in YouTube; rather, we argue it is necessary to include the activities of “traditional media” companies and media professionals, and more importantly, the new models of media entrepreneurialism that are grounded in YouTube’s “grassroots” culture. Hence, this chapter focuses the role that “YouTube stars” – highly visible and successful “homegrown” performers and producers – play in modelling and negotiating these co-creative relationships within the context of YouTube’s social network; and the new models of entrepreneurship within participatory culture that they represent.