1,720,971 research outputs found
Crashing flatland: defective and hybrid 2D-materials for (Electro) catalysis
Full text linkThis Ph.D. project is aimed to discover new strategies to develop materials to utilize in the fields of Green Energy and Green Chemistry and it was directed at the application of 2D Materials in particular. This thesis is divided into five main chapters where we presented five exemplary systems in which we focused our attention on different aspects of materials design. Each chapter comprises an introduction and a conclusion section, in which we tried to go into the details of each targeted application and of the specific design strategy employed. However, at the beginning and at the end of the thesis, the reader can find an Introduction and a Conclusion section where we tried to collocate the goals and challenges of this work within a broader context of materials science and catalysis/electrocatalysis.
In our studies in the Green Energy area, we focused on the use of MoS2-based materials in water splitting cathodic half-reaction in order to obtain the best possible performance in hydrogen generation in different conditions. To do that, different strategies were developed to drive the original material to adapt to specific application. In detail, in Chapter Two we investigated the design of three-dimensional MoS2 structures doped with different amount of Ni in order to activate MoS2 for the Hydrogen Evolution Reaction (HER) performed in alkaline environment, which typically hinder this reaction. We carried out an extensive structural characterization in order to establish the role of each type of active sites formed on the material in the HER activity and kinetics. In Chapter Three, we developed an electrodeposition method for preparing amorphous MoS2/Ag2S hybrid using recycled DVD as the support; this revealed as a viable opportunity to turn an abundant waste into an added-value material. After a suitable investigation to understand what kind of material was formed upon electrodeposition, MoS2/Ag2S/DVD was tested for HER in acidic medium. In Chapter Four another kind of hybrid was prepared by designing a one-pot solvothermal synthesis of MoS2(1-x)Se2x nanosheets grown on N-doped reduced Graphene Oxide (N-rGO). The goal was the control of the optoelectronic properties of the final material, since the combination of MoS2(1-x)Se2x and N-rGO allows to form p-n nanojunctions, which induce an enhancement of HER activity upon illumination with visible light. Then we used different techniques to prove what was the best Se:S ratio to optimize both the absolute performances in HER and the enhancement upon light irradiation.
Regarding Green Chemistry area, we used Graphene Acid (GA) as starting material and we exploited its uniform surface functionalization to prepare materials for heterogeneous catalysis for different reactions, comparing them with the benchmark Graphene Oxide (GO), modified with the same protocol. In Chapter Five, we synthesized a heterogeneous catalyst by covalently grafting Ferrocene (Fc) moieties to –COOH surface groups of GA and GO. The resulting Fc-modified graphene derivatives have been tested as heterogeneous catalysts for the C-H insertion of aryl diazonium salts into several arene substrates. The tests revealed a strong influence of the support, which we could attribute the intrinsic properties of GA. In Chapter Six, we have grown Pd nanoparticles on GA to prepare a catalyst for Suzuki-Miyaura cross coupling reaction. We have studied the effect of surface functionalization on the nanoparticles formation process and on the derived capability on the controlling the size distribution. The catalysts were tested in Suzuki cross coupling in green conditions and we could highlight the influence of nanoparticles size on activity. Moreover, we studied the same catalysts also for boronic acid homocoupling reaction, that can provide similar final products, but in a more atom economically way
Shaping bioinspired photo-responsive microstructures by the light-driven modulation of selective interactions
Full text linkA set of thymine-functionalized chromophores such as tetraphenylporphyrin, azobenzene and carbon quantum dots were synthesized and studied in terms of their self-recognition abilities to generate ordered nano-architectures. Additionally, fully adenine-capped, water soluble, gold nanoparticles were synthesized and properly characterized. In particular, we observed a strong self-recognition between thymine–thymine systems, the fully functionalized adenine-capped nanoparticles act as a “breaking” molecular binder thus to allow complementary recognition with the thymine-functionalized chromophores and the consequent molecular reorganization. It was found that adenine–thymine binding, occurring between these complementary self-organized complex systems, allowed the formation of precisely assembled nano-systems that depend powerfully on their morphologies from the nature of the chromophores utilized. These well-organized supramolecular architectures are able to undergo morphologically self-shaping processes under illumination by visible light, through the activation of the plasmon resonance of gold nanoparticles, which are affected selectively and precisely rearranged by the binding modes of the self-assembled microstructures at the nanoscale level. Finally, these studies were extended to selective molecular recognition at the surface, confirming the high binding affinity of these complex systems even at this level
Light-driven topochemical polymerization under organogel conditions of a symmetrical dipeptide-diacetylene system
No full text
Combined high degree of carboxylation and electronic conduction in graphene acid sets new limits for metal free catalysis in alcohol oxidation
No full textGraphene oxide, the most prominent carbocatalyst for several oxidation reactions, has severe limitations due to the overstoichiometric amounts required to achieve practical conversions. Graphene acid, a well-defined graphene derivative selectively and homogeneously covered by carboxylic groups but maintaining the high electronic conductivity of pristine graphene, sets new activity limits in the selective and general oxidation of a large gamut of alcohols, even working at 5 wt% loading for at least 10 reaction cycles without any influence from metal impurities. According to experimental data and first principles calculations, the selective and dense functionalization with carboxyl groups, combined with excellent electron transfer properties, accounts for the unprecedented catalytic activity of this graphene derivative. Moreover, the controlled structure of graphene acid allows shedding light upon the critical steps of the reaction and regulating precisely its selectivity toward different oxidation products
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Full text link“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Full text linkWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Dispelling the Myths Behind First-author Citation Counts
Full text linkWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
- …
