[ES] Las comunicaciones ópticas inalámbricas (OWC) constituyen una tecnología muy prometedora para el desarrollo de futuras comunicaciones inalámbricas. De hecho, ha despertado un interés creciente entre los investigadores y varias empresas de todo el mundo trabajan actualmente en el desarrollo de redes inalámbricas de muy alta velocidad. Las comunidades científica e industrial consideran la OWC como una tecnología complementaria en sus diversas formas: comunicaciones ópticas en el espacio libre (FSO), comunicaciones de luz visible (VLC) o fidelidad de la luz (Li-Fi). El espectro óptico ha sido considerado durante muchos años como una gran oportunidad para las comunicaciones inalámbricas, especialmente debido a la saturación del espectro de radiofrecuencia (RF). Esta disertación trata del uso de fuentes de banda ancha en sistemas de transmisión de luz visible (VLC), así como en sistemas de transmisión en el espectro infrarrojo por fibra óptica. En el trabajo de investigación realizado se pueden distinguir tres partes: En la primera parte, se considera el estudio y la simulación de componentes de Diodos Emisores de Luz (LED) con el software WIEN2k centrándose en las propiedades ópticas y eléctricas de los elementos II-VI. La segunda parte trata del diseño, la implementación y las pruebas de diferentes prototipos de comunicación VLC para la transmisión analógica y digital en modo simplex y semidúplex. Hemos demostrado un sistema OWC empleando una fuente de banda ancha (LED) para la transmisión no sólo de datos, sino también para la transmisión inalámbrica de energía. Además, se aborda el problema de la sincronización y la detección del nivel "1" o "0" de un bit en los sistemas de comunicación inalámbrica óptica implementados que surge como consecuencia de la atenuación de la luz a lo largo de la distancia y al problema de la pérdida de línea de visión (NLOS) entre el emisor y el receptor. Para hacer frente a este problema, se ha proporcionado un protocolo de comunicación que garantiza la transmisión fiable de datos digitales con un algoritmo de detección de nivel de bits adaptativo y se ha demostrado su eficacia mediante la transmisión de textos e imágenes. Además, esta tesis aporta una solución para la implementación de transmisores multiplexados en redes con división de longitud de onda (WDM) para formatos de modulación con multiplexación por división de frecuencia ortogonal (OFDM) basados en el uso de fuentes de banda ancha en el espectro infrarrojo para redes de fibra bidireccionales centralizadas. A pesar de las limitaciones impuestas por la dispersión cromática en el uso de este tipo de fuentes ópticas, la inclusión de ciertas estructuras antes de la detección permite la transmisión de señales OFDM en enlaces ópticos. En este trabajo se ha demostrado experimentalmente la reutilización de portadoras, la asignación dinámica de ancho de banda y la transmisión de señales OFDM multibanda mediante el uso de fuentes ópticas de banda ancha en redes WDM. Los principales resultados obtenidos en cada parte de esta tesis doctoral muestran los procedimientos de estudio, la eficacia de las soluciones propuestas y las limitaciones encontradas. / [CA] Les comunicacions òptiques sense fils (OWC) constitueixen una tecnologia molt prometedora per al desenvolupament de futures comunicacions sense fils. De fet, ha despertat un interés creixent entre els investigadors i diverses empreses de tot el món treballen actualment en el desenvolupament de xarxes sense fils de molt alta velocitat. Les comunitats científica i industrial consideren la OWC com una tecnologia complementària en les seues diverses formes: comunicacions òptiques en l'espai lliure (FSO), comunicacions de llum visible (VLC) o fidelitat de la llum (Li-Fi). L'espectre òptic ha sigut considerat durant molts anys com una gran oportunitat per a les comunicacions sense fils, especialment a causa de la saturació de l'espectre de radiofreqüència (RF). Aquesta dissertació tracta de l'ús de fonts de banda ampla en sistemes de transmissió de llum visible (VLC), així com en sistemes de transmissió en l'espectre infraroig per fibra òptica. En el treball de recerca realitzat es poden distingir tres parts: ¿ En la primera part, es considera l'estudi i la simulació de components de Díodes Emissors de Llum (LED) amb el software WIEN2k centrant-se en les propietats òptiques i elèctriques dels elements II-VI. ¿ La segona part tracta del disseny, la implementació i les proves de diferents prototips de comunicació VLC per a la transmissió analògica i digital de manera simplex i semidúplex. Hem demostrat un sistema OWC emprant una font de banda ampla (LED) per a la transmissió no sols de dades, sinó també per a la transmissió sense fil d'energia. A més, s'aborda el problema de la sincronització i la detecció del nivell "1" o "0" d'un bit en els sistemes de comunicació sense fil òptica implementats, que sorgeix a conseqüència de l'atenuació de la llum al llarg de la distància i al problema de la pèrdua de línia de visió (NLOS) entre l'emissor i el receptor. Per a fer front a aquest problema, s'ha proporcionat un protocol de comunicació que garanteix la transmissió fiable de dades digitals amb un algorisme de detecció de nivell de bits adaptatiu i s'ha demostrat la seua eficàcia mitjançant la transmissió de textos i imatges. ¿ A més, aquesta tesi aporta una solució per a la implementació de transmissors multiplexats en xarxes amb divisió de longitud d'ona (WDM) per a formats de modulació amb multiplexació per divisió de freqüència ortogonal (OFDM) basats en l'ús de fonts de banda ampla en l'espectre infraroig per a xarxes de fibra bidireccionals centralitzades. Malgrat les limitacions imposades per la dispersió cromàtica en l'ús d'aquest tipus de fonts òptiques, la inclusió d'unes certes estructures abans de la detecció permet la transmissió de senyals OFDM en enllaços òptics. En aquest treball s'ha demostrat experimentalment la reutilització de portadores, l'assignació dinàmica d'amplada de banda i la transmissió de senyals OFDM multibanda mitjançant l'ús de fonts òptiques de banda ampla en xarxes WDM. Els principals resultats obtinguts en cada part d'aquesta tesi doctoral mostren els procediments d'estudi, l'eficàcia de les solucions proposades i les limitacions trobades. / [EN] Optical wireless communication (OWC) is a very promising technology for future wireless communications developments. It has attracted increasing interest from researchers and several companies around the world are currently working on the development of very high-speed wireless networks. The scientific and industrial communities believe that OWC will be a complementary technology in its various forms: Free Space Optical communications (FSO), Visible Light Communications (VLC), Light Fidelity (Li-Fi). In fact, the optical spectrum has been considered for many years as a great opportunity for wireless communications especially due to the saturation of the radio frequency (RF) spectrum. This dissertation deals with the use of broadband sources in visible light transmission systems (VLC) as well as fiber optic systems. To carry out the research, three parts can be distinguished: In the first part, we consider the study and simulation of Light Emitting Diode (LED) components with the WIEN2k software by focusing on the optical and electrical properties of elements II-VI. The second part deals with the design, implementation and testing of different VLC communication prototypes for analog and digital transmission in simplex and half-duplex mode. We have demonstrated that an OWC system using a broadband source (i.e. an LED) can be used not only for data transmission, but also for wireless power transmission. Moreover, the synchronization problem and the detection of level "1" or "0" of a bit often arise in the optical wireless communication systems. This is a result of the attenuation nature of the light over the distance and the problem of Non Line-Of-Sight (NLOS) between the emitter and the receiver. To deal with this problem, a communication protocol ensuring reliable digital data transmission with an adaptive bit level detection algorithm has been provided and its effectiveness has been demonstrated by the transmission of texts and images. In addition, this thesis provides a solution for the implementation of wavelength division multiplexed - orthogonal frequency division multiplexed (WDM-OFDM) transmitters based on the use of broadband sources in the infrared spectrum for centralized bidirectional fiber networks. Despite the chromatic dispersion that avoids the use of this type of optical sources, the inclusion of certain structures before detection allows the transmission of OFDM signals in optical links. Carrier reuse, dynamic bandwidth allocation and multiband OFDM signals transmission will be experimentally demonstrated by using optical broadband sources in WDM networks. The main results obtained during this thesis work demonstrate the study procedures, for each part, the effectiveness of the proposed solutions as well as the constraints encountered. / Sekkiou, I. (2021). Design of communication systems based on broadband sources for fiber and free space optical links [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/172542 / TESIS

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Lung diseases, cancers, and trauma can result in injury to the connective tissue lining the lung, i.e., the pleura. Pleural injuries lead to pneumothoraxes or pleural effusions, i.e., air or fluid leaking out of the lung respectively, and potential lung collapse - an immediately life threatening condition. While several bioengineered soft tissue sealants exist on the market, there is only one sealant FDA-approved for use in pulmonary surgery. In addition, very limited techniques are presented in the literature for characterizing the burst properties of hydrogel tissue sealants. For my thesis, I proposed to develop a protocol for characterizing the burst properties of hydrogel sealants using a novel burst pressure test chamber. I further proposed a novel combination of oxidation and methacrylation reactions of alginate for tissue sealant applications, with a particular focus on developing a pulmonary sealant. The proposed research objectives are: 1) To develop protocol for testing hydrogel sealants for soft tissue applications; 2) To verify alginate as a potential for tissue sealant applications; and 3) To optimize an alginate hydrogel sealant and perform ex vivo analysis for a pleural sealant application. Alginate materials with varying degrees of oxidation and methacrylation were synthesized and characterized. Oscillatory rheometry was used to characterize material properties such as viscosity, hydrogel gelation kinetics, and complex moduli. Burst pressure measurements properties and failure mechanisms, i.e. delamination or material failure, were collected for a liquid and dry-state application. Preliminary ex vivo mouse lung model testing demonstrated that methacrylated alginate hydrogels are able to withstand physiological pressures associated with breathing, and failure occurs within the hydrogel for adhesive alginate-based tissue sealants.

O efeito da exposição à luz visível e a limitação de oxigênio durante o crescimento micelial foi investigado na tolerância de conídios de dez fungos entomopatogênicos a: (A) radiação UV; (B) estresse osmótico causado pelo cloreto de potássio (KCl) e (C) estresse genotóxico provocado por 4-nitroquinoline-1-óxido (4-NQO). No primeiro experimento, foi avaliado o limiar de fotoativação de Metarhizium robertsii. Foram estudadas quatro intensidades de luz com 1, 3, 4 e 5 lumens, nas quais, foi avaliada a germinação e o aumento de tolerância ao estresse osmótico. No segundo experimento, foi analisada a influência da luz branca no aumento da tolerância à radiação UV, KCl, e 4-NQO em dez espécies de fungos entomopatogênicos. No terceiro experimento, foi avaliado a influência da luz branca, azul, verde e vermelha no aumento de tolerância à radiação UV e estresse osmótico em M. robertsii. No quarto experimento, foi avaliada a influência da limitação de oxigênio no aumento de tolerância à radiação UV, KCl, e 4-NQO em dez espécies de fungos entomopatogênicos. No quinto experimento, foi utilizado o isolado M. robertsii (ARSEF 2575), foi analisado a expressão dos genes provavelmente envolvidos na indução da tolerância ao estresse quando conídios são produzidos sob luz visível e limitação de oxigênio. No primeiro experimento, conídios produzidos sob a luz branca apresentaram maior tolerância ao estresse osmótico em comparação com os conídios produzidos no escuro. Não houve grande diferença de tolerância entre as intensitdades de luz testadas. No segundo experimento, a luz branca induziu o aumento de tolerância aos estresses em B. bassiana (KCl e 4NQO), M. brunneum (KCl e 4NQO), M. robertsii (UV e KCl), T. cylindrosporum (KCl), I. fumosorosea (UV), L. aphanocladii (KCl) e A. aleyrodis (KCl e 4NQO). No terceiro experimento, conídios produzidos sob a luz branca e azul, foram mais tolerantes à radiação UV e ao estresse osmótico, conídios crescidos sob a luz vermelha foram menos tolerantes. No quarto experimento, a hipoxia induziu o aumento de tolerância aos estresses em B. bassiana (UV, KCl e 4NQO), M. brunneum (UV, KCl e 4NQO), M. robertsii (UV, KCl), M. anisopliae (UV e KCl), T. inflatum (KCl) e A. aleyrodis (KCl e 4NQO). A anoxia induziu o aumento de tolerância ao estresse em seis isolados, B. bassiana (UV e 4NQO), M. brunneum (KCl), M. anisopliae (KCl e 4NQO), M. robertsii (UV e KCl), T. inflatum (KCl), A. aleyrodis (4NQO). O estresse nutritivo (MM) induziu o aumento de tolerância aos estresses em B. bassiana (UV, KCl e 4NQO), M. brunneum (UV e KCl), M. robertsii (UV e KCl) e M. anisopliae (UV e KCl), T. cylindrosporum (UV), I. fumosorosea (KCl), T. inflatum (UV) e S. lanosoniveum (KCl). No quinto experimento, os genes superexpressos foram: Mrhsp30 (MM, luz branca, luz azul, vermelha, luz verde, anoxia), Mrhsp101 (luz vermelh, a luz verde e hipoxia), Mr6-4 phr (MM, luz branca, luz azul), Mrsod2 (MM, luz vermelha), Mrtps (luz azul, vermelha, verde e hipóxia), Mrpr1 (luz verde). Neste estudo, a luz branca e limitação de oxigênio foram determinantes no aumento de tolerância aos estresses. / The effect of exposure of visible light and oxygen limitation during mycelial growth was investigated in the tolerance of conidia of ten entomopathogenic fungi to: (A) UV radiation; (B) osmotic stress caused by potassium chloride (KCl) and (C) genotoxic stress caused by 4-nitroquinoline 1-oxide (4NQO). In the first experiment, the photoactivation threshold of Metarhizium robertsii was evaluated. Four light intensities with 1, 3, 4 and 5 lumens were studied, where germination and increased tolerance to osmotic stress were evaluated. In the second experiment, the influence of white light without increasing the tolerance to UV, KCl, and 4-NQO in ten species of entomopathogenic fungi was analyzed. In the third experiment, the influence of white, blue, green and red light on the increase of tolerance to UV radiation and osmotic stress in M. robertsii was evaluated. In the fourth experiment, the influence of oxygen limitation on the increase of tolerance to UV, KCl, and 4-NQO in tem entomopathogenic fungi species were evaluated. In the fifth experiment, the M. robertsii isolate (ARSEF 2575) was used; an expression of the genes involved in the induction of stress tolerance was analyzed when conidia are produced under visible light and oxygen limitation. In the first experiment, conidia produced under white light presented greater tolerance to osmotic aesthetics in comparative eaters. There were no major differences in tolerance between tested light intensities. In the second experiment, white light induced increased stress tolerance in B. bassiana (KCl e 4NQO), M. brunneum (KCl e 4NQO), M. robertsii (UV e KCl), T. cylindrosporum (KCl), I. fumosorosea (UV), L. aphanocladii (KCl) e A. aleyrodis (KCl e 4NQO). In the third experiment, conidia produced under white and blue light were more tolerant to UV radiation and osmotic stress, conidia grown under the red light so tolerant. In the fourth experiment, hypoxia induced increased stress tolerance in B. bassiana (for UV, KCl e 4NQO), M. brunneum (UV, KCl e 4NQO), M. robertsii (UV, KCl), M. anisopliae (UV e KCl), T. inflatum (KCl) e A. aleyrodis (KCl e 4NQO). Anoxia induced higher tolerance in B. bassiana (for UV e 4NQO), M. brunneum (KCl), M. anisopliae (KCl e 4NQO), M. robertsii (UV e KCl), T. inflatum (KCl), A. aleyrodis (4NQO). The nutritive stress (MM) induced increased stress tolerance in B. bassiana (UV, KCl e 4NQO), M. brunneum (UV e KCl), M. robertsii (UV e KCl) e M. anisopliae (UV e KCl), T. cylindrosporum (UV), I. fumosorosea (KCl), T. inflatum (UV) e S. lanosoniveum (KCl). In the fifth experiment, the over-expressed genes were Mrhsp30 (MM, white light, blue light, red, green light, anoxia), Mrhsp101 (red light, green light and hypoxia), Mr6-4 phr (MM, white light, blue light), Mrsod2 (MM, red light), Mrtps (blue, red, green and hypoxia light), Mrpr1 (green light). In this study, white light and oxygen limitation were determinants of increased stress tolerance.

Approximately, two-thirds of earth's surface is covered by water. There is a growing interest from the military and commercial communities in having, an efficient, secure and high bandwidth underwater wireless communication (UWC) system for tactical underwater applications such as oceanography studies and offshore oil exploration. The existing acoustic and radio frequency (RF) technologies are severely limited in bandwidth because of the strong frequency dependent attenuation of sound in seawater and the high conductivity of seawater at radio frequencies, respectively. Recently, underwater wireless optical communication (UWOC) has been proposed as the best alternative or complementary solution to meet this challenge. Taking advantage of the low absorption window of seawater in blue-green (400-550 nm) regime of the electromagnetic spectrum, UWOC is expected to establish secure, efficient and high data rate communication links over short and moderate distances (< 100 m) for versatile applications such as underwater oil pipe inspection, remotely operated vehicle (ROV) and sensor networks. UWOC uses the latest gallium nitrite (GaN) visible light-emitting diode (LED) and laser diode (LD) transmitters. Although some research on LED lased UWOC is being conducted, both the military and academic 5 research communities are favoring the use of laser beams, which potentially could enhance the available bandwidth by up to three orders of magnitude. However, the underwater wireless channel is optically very challenging and difficult to predict. The propagation of laser beams in seawater is significantly affected by the harsh marine environments and suffers from severe attenuation which is a combined effect of absorption and scattering, optical turbulence, and multipath effects at high transmission rates. These limitations distort the intensity and phase structure of the optical beam leading to a decrease in signal-to-noise ratio (SNR) which ultimately degrades the performance of UWOC links by increasing the probability of error. In this dissertation, we seek to experimentally demonstrate the feasibility of short range (≤ 20 m) UWOC systems over various underwater channel water types using different modulation schemes as well as to model and describe the statistical properties of turbulence-induced fading in underwater wireless optical channels using laser beam intensity fluctuations measurements.

O efeito da exposição à luz visível e a limitação de oxigênio durante o crescimento micelial foi investigado na tolerância de conídios de dez fungos entomopatogênicos a: (A) radiação UV; (B) estresse osmótico causado pelo cloreto de potássio (KCl) e (C) estresse genotóxico provocado por 4-nitroquinoline-1-óxido (4-NQO). No primeiro experimento, foi avaliado o limiar de fotoativação de Metarhizium robertsii. Foram estudadas quatro intensidades de luz com 1, 3, 4 e 5 lumens, nas quais, foi avaliada a germinação e o aumento de tolerância ao estresse osmótico. No segundo experimento, foi analisada a influência da luz branca no aumento da tolerância à radiação UV, KCl, e 4-NQO em dez espécies de fungos entomopatogênicos. No terceiro experimento, foi avaliado a influência da luz branca, azul, verde e vermelha no aumento de tolerância à radiação UV e estresse osmótico em M. robertsii. No quarto experimento, foi avaliada a influência da limitação de oxigênio no aumento de tolerância à radiação UV, KCl, e 4-NQO em dez espécies de fungos entomopatogênicos. No quinto experimento, foi utilizado o isolado M. robertsii (ARSEF 2575), foi analisado a expressão dos genes provavelmente envolvidos na indução da tolerância ao estresse quando conídios são produzidos sob luz visível e limitação de oxigênio. No primeiro experimento, conídios produzidos sob a luz branca apresentaram maior tolerância ao estresse osmótico em comparação com os conídios produzidos no escuro. Não houve grande diferença de tolerância entre as intensitdades de luz testadas. No segundo experimento, a luz branca induziu o aumento de tolerância aos estresses em B. bassiana (KCl e 4NQO), M. brunneum (KCl e 4NQO), M. robertsii (UV e KCl), T. cylindrosporum (KCl), I. fumosorosea (UV), L. aphanocladii (KCl) e A. aleyrodis (KCl e 4NQO). No terceiro experimento, conídios produzidos sob a luz branca e azul, foram mais tolerantes à radiação UV e ao estresse osmótico, conídios crescidos sob a luz vermelha foram menos tolerantes. No quarto experimento, a hipoxia induziu o aumento de tolerância aos estresses em B. bassiana (UV, KCl e 4NQO), M. brunneum (UV, KCl e 4NQO), M. robertsii (UV, KCl), M. anisopliae (UV e KCl), T. inflatum (KCl) e A. aleyrodis (KCl e 4NQO). A anoxia induziu o aumento de tolerância ao estresse em seis isolados, B. bassiana (UV e 4NQO), M. brunneum (KCl), M. anisopliae (KCl e 4NQO), M. robertsii (UV e KCl), T. inflatum (KCl), A. aleyrodis (4NQO). O estresse nutritivo (MM) induziu o aumento de tolerância aos estresses em B. bassiana (UV, KCl e 4NQO), M. brunneum (UV e KCl), M. robertsii (UV e KCl) e M. anisopliae (UV e KCl), T. cylindrosporum (UV), I. fumosorosea (KCl), T. inflatum (UV) e S. lanosoniveum (KCl). No quinto experimento, os genes superexpressos foram: Mrhsp30 (MM, luz branca, luz azul, vermelha, luz verde, anoxia), Mrhsp101 (luz vermelh, a luz verde e hipoxia), Mr6-4 phr (MM, luz branca, luz azul), Mrsod2 (MM, luz vermelha), Mrtps (luz azul, vermelha, verde e hipóxia), Mrpr1 (luz verde). Neste estudo, a luz branca e limitação de oxigênio foram determinantes no aumento de tolerância aos estresses. / The effect of exposure of visible light and oxygen limitation during mycelial growth was investigated in the tolerance of conidia of ten entomopathogenic fungi to: (A) UV radiation; (B) osmotic stress caused by potassium chloride (KCl) and (C) genotoxic stress caused by 4-nitroquinoline 1-oxide (4NQO). In the first experiment, the photoactivation threshold of Metarhizium robertsii was evaluated. Four light intensities with 1, 3, 4 and 5 lumens were studied, where germination and increased tolerance to osmotic stress were evaluated. In the second experiment, the influence of white light without increasing the tolerance to UV, KCl, and 4-NQO in ten species of entomopathogenic fungi was analyzed. In the third experiment, the influence of white, blue, green and red light on the increase of tolerance to UV radiation and osmotic stress in M. robertsii was evaluated. In the fourth experiment, the influence of oxygen limitation on the increase of tolerance to UV, KCl, and 4-NQO in tem entomopathogenic fungi species were evaluated. In the fifth experiment, the M. robertsii isolate (ARSEF 2575) was used; an expression of the genes involved in the induction of stress tolerance was analyzed when conidia are produced under visible light and oxygen limitation. In the first experiment, conidia produced under white light presented greater tolerance to osmotic aesthetics in comparative eaters. There were no major differences in tolerance between tested light intensities. In the second experiment, white light induced increased stress tolerance in B. bassiana (KCl e 4NQO), M. brunneum (KCl e 4NQO), M. robertsii (UV e KCl), T. cylindrosporum (KCl), I. fumosorosea (UV), L. aphanocladii (KCl) e A. aleyrodis (KCl e 4NQO). In the third experiment, conidia produced under white and blue light were more tolerant to UV radiation and osmotic stress, conidia grown under the red light so tolerant. In the fourth experiment, hypoxia induced increased stress tolerance in B. bassiana (for UV, KCl e 4NQO), M. brunneum (UV, KCl e 4NQO), M. robertsii (UV, KCl), M. anisopliae (UV e KCl), T. inflatum (KCl) e A. aleyrodis (KCl e 4NQO). Anoxia induced higher tolerance in B. bassiana (for UV e 4NQO), M. brunneum (KCl), M. anisopliae (KCl e 4NQO), M. robertsii (UV e KCl), T. inflatum (KCl), A. aleyrodis (4NQO). The nutritive stress (MM) induced increased stress tolerance in B. bassiana (UV, KCl e 4NQO), M. brunneum (UV e KCl), M. robertsii (UV e KCl) e M. anisopliae (UV e KCl), T. cylindrosporum (UV), I. fumosorosea (KCl), T. inflatum (UV) e S. lanosoniveum (KCl). In the fifth experiment, the over-expressed genes were Mrhsp30 (MM, white light, blue light, red, green light, anoxia), Mrhsp101 (red light, green light and hypoxia), Mr6-4 phr (MM, white light, blue light), Mrsod2 (MM, red light), Mrtps (blue, red, green and hypoxia light), Mrpr1 (green light). In this study, white light and oxygen limitation were determinants of increased stress tolerance.

Titanium dioxide(TiO2) is a stable, effective and well-known photocatalyst for degradation of pollutants. However, its practical applications are limited due to the need for energy higher than 3.2 eV, or a wavelength lower than 390 nm (high frequency waves, ultraviolet and above) hindering its ability to effectively work in the visible light region (about 400 nm to 700 nm). Nitrogen-doped TiO2 (N-TiO2) has garnered some attention as a photocatalyst as it appears to work even in the visible light region. This could allow the utilization of a larger part of the solar spectrum. This thesis presents the results of photocatalytic degradation of methylene blue (MB) carried out under simulated visible light by using TiO2 and N-TiO2(doped in the lab) to evaluate and compare their efficiencies under similar conditions.

As a potential solution to the global energy and environmental pollution, design and synthesis of artificial photocatalysts with high activities have attracted increasing scientific interests worldwide. In recent years, the graphitic carbon nitride (g-C3N4) has shown new possible applications in the photocatalytic field due to its unique properties. However, the photocatalytic efficiency of the pristine g-C3N4 is greatly limited by the high recombination rate of the photo-induced electron-hole pairs. In this thesis, the aim is to design and fabricate efficient g-C3N4 based photocatalysts with enhanced photocatalytic activities under a visible light irradiation. In order to achieve this goal, two strategies have been employed in the present thesis. First, the as-obtained g-C3N4 was used as the host material to construct staggered-aligned composite photocatalysts by selecting semiconductors with suitable band positions. By this method, three kinds of g-C3N4-based composite photocatalysts such as g-C3N4/ZnS nanocage, g-C3N4/m-Ag2Mo2O7 and g-C3N4/MIL-88A were successfully fabricated. Second, the microstructure of the g-C3N4 was modified by the H2O2-treatment at an elevated temperature and ambient pressure. In this study, the g-C3N4 was prepared by a simple pyrolysis of urea. As for all the as-synthesized phtocatalysts, the structures, morphologies and the optical properties were carefully characterized by the following techniques: XRD, SEM, TEM, FT-IR and DRS. Also, the band edge positions of m-Ag2Mo2O7 and MIL-88A were studied by the Mott-Schottky methods. Thereafter, the photocatalytic activities were evaluated by using a solution of rhodamine B (RhB) as a target pollutant for the photodegradation experiments performed under a visible light irradiation. The results showed that all the aforementioned g-C3N4-based photocatalysts exhibited enhanced photocatalytic activities in comparison with the pristine g-C3N4. For the case of the g-C3N4-based composite photocatalysts, the enhancement factor over the pristine g-C3N4 can achieve values ranging from 2.6 to 3.4. As for the H2O2-treated g-C3N4, the degradation rate constant can be 4.6 times higher than that of the pristine g-C3N4. To understand the key factors in new materials design, we also devote a lot of efforts to elucidate the basic mechanisms during the photocatalytic degradation of organic pollutant. Based on the results of the active species trapping (AST) experiments, the main active species in each photocatalytic system were determined. In the g-C3N4/m-Ag2Mo2O7 and the g-C3N4/MIL-88A system, three kinds of active species of ·O2-, h+ and ·OH were found to be involved in the photocatalytic reaction. Among them, the ·O2- and h+ were the main active species. In the g-C3N4/ZnS and H2O2-treated g-C3N4 photocatalytic systems, the main active species was determined as the ·O2-. The reaction pathways of these active species were also demonstrated by comparing the band edge positions with the potentials of the redox couple. In addition, the relationship between the active species and the photocatalytic behaviors of N-de-ethylation and conjugated structure cleavage were studied. Finally, possible mechanisms to explain the enhanced photocatalytic activities were proposed for each photocatalytic system. The results in this thesis clearly confirm that the photocatalytic activity of the g-C3N4 based photocatalyst can efficiently be enhanced by constructions of staggered-aligned composites and by modification of the microstructure of the g-C3N4. The enhanced photocatalytic performance can mainly be ascribed to the efficient separation of the photo-induced electron-hole pairs and the increase of the active sites for the photocatalytic reaction. / <p>QC 20150909</p>

Highly reactive transition metal-oxo intermediates are important active oxidant involved in numerous enzymes such as cytochrome P450 monooxygenases as well as in many useful metal-catalyzed oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes. In this work, a series of metalloporphyrin and metallocorrole complexes have been successfully synthesized and spectroscopically characterized by UV-vis, GCMS and 1H-NMR. The utilization of these complexes as catalysts for selective oxidation of sulfides and photocatalytic aerobic oxidations of activated hydrocarbons were investigated. Ruthenium(II) porphyrin complexes (2) and iron(III) corrole complexes (4) with iodobenzene diacetate [PhI(OAc)2] as a mild and excellent oxygen source efficiently catalyzed sulfides to sulfoxides under mild conditions. Ruthenium porphyrins (2) catalyzed the highly selective oxidation of para-substituted thioanisoles and allylic sulfides with PhI(OAc)2 in the presence of visible light. Over 95% conversion and 100% selectivity were achieved within 12 h. Results from competitive catalytic oxidations and spectra studies of the reaction of complexes (2) with PhI(OAc)2 in the absence of organic sulfide showed that the low-reactivity ruthenium(IV)-oxo intermediates (9) are most likely to be the active oxidant in the sulfoxidation reactions. An outstanding method for the highly selective oxidation of sulfides to sulfoxides was developed by using iron(III) corroles (4) and PhI(OAc)2 as mild oxygen source. Allylic thioanisoles and hydroxy sulfides could be successfully oxidized with good conversions and excellent selectivities within short time period. A significant accelerating effect on the rate of sulfoxidation reactions by small amount of water was noticed and will be understood by more studies. Fluorinated diiron(IV) μ-oxo biscorrole complex (5b) catalyzes alkenes and activated hydrocarbons using atmospheric oxygen and visible light (sunlight) with up to 1200 TONs. The observed photocatalytic oxidation is ascribed to a photodisproportionation mechanism to afford a highly reactive corrole-iron(V)-oxo species that can be directly observed by laser flash photolysis methods. It is noteworthy that the use of visible light (solar light) for activation of atmospheric oxygen without the consumption of a reducing agent in aforementioned photocatalysis is particularly relevant to realizing innovative and economically advantageous processes for conversion of hydrocarbons into oxygenates.

The aim of this study is to test the limits of photocatalytic reduction of CO2 over Pt and light harvesting dye promoted TiO2 films under UV and visible light. Thick and thin TiO2 film catalysts are coated onto 1 cm long glass beads via a common sol-gel procedure and dip coating technique. TiO2 thin films were promoted by Pt and three different light harvesting molecules: RuBpy (Tris (2,2&rsquo / &ndash / bipyridyl) ruthenium (II) chloride hexahydrate) , BrGly (1,7-dibromo-N,N&rsquo / -(t-butoxycarbonyl-methyl)-3,4:9,10-perylene-diimide) and BrAsp (1,7-dibromo-N,N&rsquo / -(S-(1-t-butoxy-carbonyl-2-t-butoxycarbonyl-methyl)-ethyl)- 3,4:9,10-perylenediimide). Their SEM, XRD, UV-Vis spectroscopy and hydrogen chemisorption characterizations are performed. Reaction tests are performed for the catalysts under UV and visible light. The only quantifiable reaction product was methane. With RuBpy containing catalysts hydrogen production was observed under UV light, but not quantified. The results indicated that Pt addition resulted in higher yields in UV experiments. The presence of light harvesting molecules resulted in increase in photocatalytic activity for thin films, whereas it resulted in no change or decrease for the thick films. The latter case may occur due to the UV filtering effect of these dyes. Use of dyes (with visible range absorption bands) as promoters made visible light excitation possible. This resulted in photocatalytic activity under visible light, which was not observed with unpromoted and Pt promoted TiO2 thin film catalysts. Under visible light methane was the only quantified photoreduction product. CO evolution was also observed, but not quantified. The photocatalytic activities of the dye promoted TiO2 were in the order of RuBpy~BrAsp&gt / BrGly. The methane yields of visible light experiments were one order of magnitude lower than the ones under UV light.