Neste trabalho foram estudadas soldas TIG (Tungsten Inert Gas) nos aços inoxidáveis 304 e 316, e no aço carbono 1020. As alterações das microestruturas foram investigadas por microscopias óptica (MO) e eletrônica de varredura (MEV), enquanto que a corrosão destas regiões foi estudada por análises de polarização potenciodinâmica. Um sistema miniaturizado de análise corrosão, denominado sensor pontual de corrosão (SPC), foi utilizado com o objetivo de analisar a estreita região dos cordões de solda, estudando assim a influência da corrente de solda na corrosão desta região nos aços inoxidáveis 304 e 316. Os resultados mostraram que a alteração da estrutura cristalina na solda tornou esta região menos susceptível à corrosão que o material base, e o aumento da corrente de solda intensificou ainda mais este efeito, pela formação de estruturas mais compactas. No caso do aço carbono 1020 (mais susceptível à corrosão), o estudo da corrosão de sua solda foi feito utilizando técnicas eletroquímicas globais (potencial de circuito aberto, PCA, e espectroscopia de impedância eletroquímica, EIE) e técnicas de corrosão localizadas (espectroscopia de impedância eletroquímica localizada, EIEL, e técnica do eletrodo vibratório de varredura, TEVV). Para proteção contra a corrosão do aço inoxidável e suas soldas, foi utilizado um revestimento de polianilina (PAni) na forma de base esmeraldina; análises de polarização potenciodinâmica mostraram a eficiência deste revestimento protetor. Para o aço carbono 1020, devido à sua maior facilidade de oxidação, foi sintetizado um revestimento protetor a base de PAni e nanotubos de TiO2 (PAni/n-TiO2). As variáveis estudadas na síntese do polímero foram: temperatura de síntese, meio reacional, grau de dopagem do polímero (condutor ou isolante) e número de camadas. Os polímeros e compósitos foram caracterizados por espectroscopias nas regiões do ultravioleta-visível (UV-vis) e infravermelho (IV), MEV e espectroscopia de energia dispersiva de raios-X (EDX). Os aços recobertos com os filmes foram analisados por MO e MEV, EDX, e por ensaios eletroquímicos de polarização potenciodinâmica, PCA e resistência de polarização, além de ensaio de corrosão acelerada em câmara de névoa salina. As melhores condições encontradas foi para o revestimento de PAni/n-TiO2 desdopado (base esmeraldina) sintetizado a 25°C em meio de H2SO4, e com 3 camadas; o n-TiO2 apresentou um efeito de aumento da aderência do filme ao substrato metálico. / In this work TIG (Tungsten Inert Gas) welds have been studied in the 304 and 316 stainless steels, and in the 1020 carbon steel. The changes in the microstructure were investigated by optical microscope (OM) and scanning electronic microscope (SEM), and the corrosion behavior in these zones were studied by potentiodynamic polarization analysis. A miniaturized corrosion analysis device, named corrosion punctual sensor, has been used to analyze the close weld bead, researching for the influence of the weld current in the corrosion process in this zone of the 304 and 316 stainless steels. The results showed that the change in the crystalline structure of the weld zone became this region less susceptible to corrosion process than their base material, and the increase in the weld current intensified this effect, by the formation of more compact structures. In the case of the 1020 carbon steel (more susceptible to corrosion processes), the corrosion in its weld zone was researched by global (like open potential circuit, OCP, and electrochemical impedance spectroscopy, EIS) and localized (like localized electrochemical impedance spectroscopy, LEIS, and scanning vibrating electrode technique, SVET) electrochemical techniques. For protecting stainless steels and their weld zones against corrosion processes, a polyaniline (PAni) coating in the emeraldine base form was used; potentiodynamic polarization analysis showed the efficiency of this protective coating. For the 1020 carbon steel, due to its mayor oxidation susceptibly, a protective coating of PAni and TiO2 nanotubes (PAni/n-TiO2) was synthesized. The variables researched were: synthesis temperature, reaction medium, degree of doping of the polymer (conductor or insulator) and number of layers. The polymers and composites were characterized by ultraviolet visible (UV-vis) and infrared spectroscopies, SEM and Energy Dispersive X-Ray Spectroscopy (EDX). The coated steels were analyzed by OM, MEV and EDX spectroscopies, and by potentiodynamic polarization, OCP and polarization resistance electrochemical measurements, besides accelerate corrosion tests in a salt spray chamber. The best conditions found for the dedoped PAni/n-TiO2 coatings (emeraldine base) were: temperature of synthesis of 25°C, H2SO4 as reaction medium, and with 3 layers; n-TiO2 has presented an effect of increasing the adherence of the coating with the steel.

Neste trabalho foram estudadas soldas TIG (Tungsten Inert Gas) nos aços inoxidáveis 304 e 316, e no aço carbono 1020. As alterações das microestruturas foram investigadas por microscopias óptica (MO) e eletrônica de varredura (MEV), enquanto que a corrosão destas regiões foi estudada por análises de polarização potenciodinâmica. Um sistema miniaturizado de análise corrosão, denominado sensor pontual de corrosão (SPC), foi utilizado com o objetivo de analisar a estreita região dos cordões de solda, estudando assim a influência da corrente de solda na corrosão desta região nos aços inoxidáveis 304 e 316. Os resultados mostraram que a alteração da estrutura cristalina na solda tornou esta região menos susceptível à corrosão que o material base, e o aumento da corrente de solda intensificou ainda mais este efeito, pela formação de estruturas mais compactas. No caso do aço carbono 1020 (mais susceptível à corrosão), o estudo da corrosão de sua solda foi feito utilizando técnicas eletroquímicas globais (potencial de circuito aberto, PCA, e espectroscopia de impedância eletroquímica, EIE) e técnicas de corrosão localizadas (espectroscopia de impedância eletroquímica localizada, EIEL, e técnica do eletrodo vibratório de varredura, TEVV). Para proteção contra a corrosão do aço inoxidável e suas soldas, foi utilizado um revestimento de polianilina (PAni) na forma de base esmeraldina; análises de polarização potenciodinâmica mostraram a eficiência deste revestimento protetor. Para o aço carbono 1020, devido à sua maior facilidade de oxidação, foi sintetizado um revestimento protetor a base de PAni e nanotubos de TiO2 (PAni/n-TiO2). As variáveis estudadas na síntese do polímero foram: temperatura de síntese, meio reacional, grau de dopagem do polímero (condutor ou isolante) e número de camadas. Os polímeros e compósitos foram caracterizados por espectroscopias nas regiões do ultravioleta-visível (UV-vis) e infravermelho (IV), MEV e espectroscopia de energia dispersiva de raios-X (EDX). Os aços recobertos com os filmes foram analisados por MO e MEV, EDX, e por ensaios eletroquímicos de polarização potenciodinâmica, PCA e resistência de polarização, além de ensaio de corrosão acelerada em câmara de névoa salina. As melhores condições encontradas foi para o revestimento de PAni/n-TiO2 desdopado (base esmeraldina) sintetizado a 25°C em meio de H2SO4, e com 3 camadas; o n-TiO2 apresentou um efeito de aumento da aderência do filme ao substrato metálico. / In this work TIG (Tungsten Inert Gas) welds have been studied in the 304 and 316 stainless steels, and in the 1020 carbon steel. The changes in the microstructure were investigated by optical microscope (OM) and scanning electronic microscope (SEM), and the corrosion behavior in these zones were studied by potentiodynamic polarization analysis. A miniaturized corrosion analysis device, named corrosion punctual sensor, has been used to analyze the close weld bead, researching for the influence of the weld current in the corrosion process in this zone of the 304 and 316 stainless steels. The results showed that the change in the crystalline structure of the weld zone became this region less susceptible to corrosion process than their base material, and the increase in the weld current intensified this effect, by the formation of more compact structures. In the case of the 1020 carbon steel (more susceptible to corrosion processes), the corrosion in its weld zone was researched by global (like open potential circuit, OCP, and electrochemical impedance spectroscopy, EIS) and localized (like localized electrochemical impedance spectroscopy, LEIS, and scanning vibrating electrode technique, SVET) electrochemical techniques. For protecting stainless steels and their weld zones against corrosion processes, a polyaniline (PAni) coating in the emeraldine base form was used; potentiodynamic polarization analysis showed the efficiency of this protective coating. For the 1020 carbon steel, due to its mayor oxidation susceptibly, a protective coating of PAni and TiO2 nanotubes (PAni/n-TiO2) was synthesized. The variables researched were: synthesis temperature, reaction medium, degree of doping of the polymer (conductor or insulator) and number of layers. The polymers and composites were characterized by ultraviolet visible (UV-vis) and infrared spectroscopies, SEM and Energy Dispersive X-Ray Spectroscopy (EDX). The coated steels were analyzed by OM, MEV and EDX spectroscopies, and by potentiodynamic polarization, OCP and polarization resistance electrochemical measurements, besides accelerate corrosion tests in a salt spray chamber. The best conditions found for the dedoped PAni/n-TiO2 coatings (emeraldine base) were: temperature of synthesis of 25°C, H2SO4 as reaction medium, and with 3 layers; n-TiO2 has presented an effect of increasing the adherence of the coating with the steel.

Η φωτοκαταλυτική αναμόρφωση υδατικών διαλυμάτων γλυκερόλης διερευνήθηκε με τη βοήθεια καταλυτών CuOx/TiO2, οι οποίοι παρασκευάστηκαν με την μέθοδο εναπόθεσης-ισορροπίας-διήθησης (EDF), η οποία οδηγεί στο σχηματισμό καταλυτών υψηλής διασποράς χαλκού (II), τα είδη του οποίου αλληλεπιδρούν ισχυρά με την επιφάνεια του TiO2. Βρέθηκε ότι η γλυκερόλη φωτο-αναμορφώνεται αποτελεσματικά σε αυτά τα υλικά αποδίδοντας H2 και CO2 στην αέρια φάση. Η έκλυση υδρογόνου παρουσιάζει μια υστέρηση με το υδρογόνο να εμφανίζεται μόνο μετά από παρατεταμένη έκθεση του αιωρήματος στο φως, ενώ ο ρυθμός παραγωγής CO2 (και σε μικρότερο βαθμό Η2) ταλαντώνεται σε συνάρτηση με το χρόνο ακτινοβόλησης. Τα αποτελέσματα αυτά εξηγούνται αν λάβει κανείς υπόψη την φωτοεπαγόμενη αναστρέψιμη τροποποίηση της οξειδωτικής κατάστασης του χαλκού που λαμβάνει χώρα υπό τις παρούσες συνθήκες αντίδρασης. Επιπλέον, αναπτύχθηκαν φωτοκαταλύτες με υψηλή απόκριση στην ορατή ακτινοβολία πυρώνοντας σκόνη TiO2 (sol-gel) υπό ροή ΝΗ3. Το φάσμα απορρόφησης των λαμβανόμενων υλικών συντονίστηκε με έλεγχο της θερμοκρασίας. Οι φωτοκαταλύτες χρησιμοποιήθηκαν σε μορφή σκόνης για την παραγωγή υδρογόνου μέσω της φωτοκαταλυτικής αναμόρφωσης της γλυκερόλης. Επιπλέον η απόδοση των ενισχυμένων με άζωτο καταλυτών εξετάστηκε και σε φωτοηλεκτροχημικές διεργασίες καθώς χρησιμοποιήθηκαν ως φωτοάνοδοι σε φωτοεπαγόμενες κυψέλες καυσίμου. / The photocatalytic reforming of aqueous solutions of glycerol has been investigated over CuOx/TiO2 catalysts prepared by the equilibrium deposition filtration (EDF) method, which results in the formation of highly dispersed copper (II) species interacting strongly with the TiO2 surface. Glycerol is photo‐reformed efficiently over these materials yielding H2 and CO2 in the gas phase. Hydrogen evolution exhibits a hysteresis and appears only after prolonged exposure to light, whereas the rate of CO2 (and to a lesser extent H2) evolution fluctuates with irradiation time. Results are explained by considering the light‐induced reversible modification of the oxidation state of deposited copper species that takes place under the present reaction conditions. Visible‐light responsive photocatalysts have been synthesized by nitrogen doping of sol‐gel made nanocrystalline titania followed by heating at various temperatures in a NH3 atmosphere. The absorption spectrum of the obtained materials was tuned by controlling temperature. Photocatalysts were employed in powder form to produce hydrogen by photocatalytic reforming. They were also deposited by means of pastes as thin films on transparent electrodes and employed as photoanode in photoactivated fuel cells.

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.

<p>Kao &scaron;to je poznato, RS-2-(4-hlor-o-toliloksi)propionska kiselina (MCPP),&nbsp;(4-hlor-2-metilfenoksi)sirćetna kiselina (MCPA) i 3,6-dihlorpiridin-2-karboksilna kiselina &nbsp;(klopiralid) su herbicidi sa veoma &scaron;irokim spektrom dejstva, a pored toga su rastvorljivi u&nbsp;vodi, te&scaron;ko biorazgradljivi i prema literaturnim podacima su, nažalost, veoma često prisutni&nbsp;herbicidi u pijaćoj vodi. Proces heterogene fotokatalize uz primenu TiO₂i UV zračenja se&nbsp;pokazao kao veoma pogodan način za njihovo uklanjanje iz vode. Međutim, zbog velikog&nbsp;energetskog procepa od 3,2 eV (anataze-oblik), odnosno, 3,0 eV (rutil-oblik), veoma mali&nbsp;udeo bliskih UV zraka iz sunčeve svetlosti (oko 3&minus;4%) biva iskori&scaron;ćen u toku&nbsp;fotokatalitičkog procesa, &scaron;to ukazuje na to da je TiO_2&nbsp;praktično neaktivan u prisustvu&nbsp;sunčeve svetlosti. Na osnovu literaturnih podataka je zapaženo da postoji mogućnost&nbsp;fotorazgradnje pojedinih supstrata u prisustvu TiO_2&nbsp;primenom vidljive svetlosti. Na&nbsp;primeru MCPP je ispitana aktivnost TiO_2&nbsp;Degussa P25 kao fotokatalizatora u prisustvu&nbsp;vidljive svetlosti. Na osnovu refleksionih spektara je utvrđeno da MCPP adsorbovan na&nbsp;TiO_2&nbsp;Degussa P25 apsorbuje vidljivi deo spektra (&lambda; &ge;400 nm). Nastali prelazni kompleks&nbsp;je potvrđen FTIR merenjima. Efikasnost TiO2Degussa P25 primenom vidljive svetlosti je&nbsp;upoređena sa sunčevim i UV zračenjem, kao i direktnom fotolizom u prisustvu pomenutih&nbsp;izvora zračenja. Brzina fotokatalitičke razgradnje MCPP primenom vidljive svetlosti iznosi&nbsp;0,86 &mu;mol dm^&minus;3min^&minus;1, &scaron;to je oko 4 puta brže u poređenju sa direktnom fotolizom. Nadalje&nbsp;je ustanovljena optimalna masena koncentracija katalizatora od oko 8 mg cm^&minus;3, koja je&nbsp;znatno vi&scaron;a u poređenju sa primenom UV zračenja. Razlog je najverovatnije različit&nbsp;mehanizam fotorazgradnje koji se odvija primenom vidljivog i UV zračenja. Naime,&nbsp;prisustvo 2-metil-2-propanola (poznatog hvatača&nbsp;^&bull;OH-radikala) praktično ne utiče na&nbsp;brzinu fotokatalitičke razgradnje MCPP p rimenom vidljive svetlosti, &scaron;to ukazuje da se&nbsp;mehanizam razgradnje MCPP primenom &nbsp;vidljive svetlosti ne odvija posredstvom&nbsp;^&bull;OH-radikala, za razliku od onog uz primenu UV zračenja.</p><p>S obzirom da se katalizator TiO_2&nbsp;Degussa P25 uz primenu vidljive svetlosti nije&nbsp;<br />pokazao kao naročito efikasan kada je u pitanju razgradnja sva tri herbicida i imajući u&nbsp;vidu da se u poslednje vreme iz razloga praktične primene sve vi&scaron;e pribegava procesu dopovanja TiO_2&nbsp;različitim tipovima metala (alkalnih, zemnoalkalnih, prelaznih i dr.) i nemetala (halogenida, halkogenida i dr.), u okviru ove doktorske disertacije je ispitana aktivnost N-TiO₂(sintetisanih mokrim i suvim putem) i TiO_2&nbsp;(rutil) dopovanog sa različitim količinama Fe³⁺-jona (0,13&minus;1,48 at.%) pri razgradnji herbicida MCPP i MCPA primenom vidljive svetlosti. Pored toga je ispitana efikasnost TiO_2&nbsp;(anataze) takođe dopovanog sa različitim količinama Fe³⁺-jona (0,71&minus;1,80 at.%) na primeru MCPP.&nbsp;</p><p>Poredeći N-TiO_2&nbsp;(sintetisan mokrim putem) i N-TiO_2&nbsp;(sintetisani suvim putem), primećeno&nbsp;je da je u drugom slučaju efikasnost katalizatora veća oko 2 puta. Isto tako je zapažena u&nbsp;slučaju MCPP ne&scaron;to veća fotokatalitička aktivnost N-TiO_2&nbsp;(sintetisani suvim putem) u&nbsp;poređenju sa TiO_2&nbsp;(anataze). Kada je u pitanju MCPA aktivnost sva tri katalizatora je&nbsp;veoma slična. Pored toga je zapažena veća efikasnost N-TiO_2&nbsp;(sintetisan mokrim putem) u&nbsp;poređenju sa TiO_2&nbsp;Degussa P25 (oko 1,5 puta) i oko 5 puta u odnosu na direktnu fotolizu,&nbsp;dok su N-TiO_2&nbsp;(sintetisani suvim putem) oko 3 puta efikasniji u poređenju sa TiO_2&nbsp;Degussa P25 i oko 10 puta u &nbsp;poređenju sa direktnom fotolizom. Brzina solarne razgradnje&nbsp;je preko 100 puta manja nego primenom vidljivog i UV zračenja, &scaron;to je posledica različitih&nbsp;intenziteta pomenutih izvora ozračivanja i različitih uslova pri kojima je vr&scaron;ena razgradnja. &nbsp;Ustanovljena je optimalna masena koncentracija N-TiO_2&nbsp;(sintetisan mokrim putem) od&nbsp;4 mg cm^&minus;3.</p><p>Prilikom razgradnje MCPP i MCPA je nađeno da je brzina veća kada se kao&nbsp;katalizator &nbsp;koristi TiO_2&nbsp;(rutil) u poređenju sa Fe-TiO_2&nbsp;i da sa povećanjem količine Fe³⁺-jona fotokatalitička aktivnost uglavnom opada. Kada je kao fotokatalizator kori&scaron;ćen TiO_{2 &nbsp;}<br />(anataze) dopovan različitim količinama Fe³⁺-jona (od 0,71 do 1,80 at.%), razgradnja&nbsp;<br />MCPP je u svim slučajevima znatno sporija u odnosu na TiO_2&nbsp;(anataze).</p><p>S obzirom da su prema literaturnim podacima kinetika i mehanizam fotokatalitičke&nbsp;<br />razgradnje klopiralida nepoznati, ispitana je njegova stabilnost pri različitim&nbsp;eksperimentalnim uslovima. Tokom ispitivanja uticaja pH kako u prisustvu, tako i u&nbsp;odsustvu dnevne svetlosti u intervalu pH od 1,0&minus;9,0, nađeno je da ni u jednom slučaju ne&nbsp;dolazi do razgradnje supstrata u periodu od sedam meseci koliko je proces praćen. Takođe&nbsp;je ispitana kinetika fotokatalitičke razgradnje klopiralida primenom UV i vidljivog&nbsp;zračenja u prisustvu TiO_2&nbsp;Degussa P25, kao i direktna fotoliza primenom oba izvora&nbsp;zračenja. Nađeno je da je brzina fotokatalitičke razgradnje primenom UV zračenja veća&nbsp;oko 5 puta u odnosu na direktnu fotolizu. Za praćenje toka fotokatalitičke razgradnje&nbsp;klopiralida je izabrana pH-vrednost od 3,2. Nadalje je zapaženo da se u ispitivanom opsegu početnih koncentracija supstrata (0,5&ndash;3,0 mmol dm^&minus;3) kinetika fotokatalitičke razgradnje klopiralida može opisati pseudo-prvim redom. Pri ispitivanju uticaja masene koncentracije katalizatora (0,5&ndash;8 mg cm^&minus;3) na brzinu razgradnje klopiralida, ustanovljena je optimalna masena koncentracija primenjenog fotokatalizatora od oko 4 mg cm^&minus;3. Izračunata ukupna &nbsp;prividna energija aktivacije iznosi 7,74 kJ mol^&minus;1. Pored toga, prisustvo kiseonika ubrzava reakciju 2 puta, dok dodatak elektron-akceptora kao &scaron;to su (NH₄)₂S₂O₈, H₂O_2&nbsp;i KBrO_3&nbsp;pokazuje značajan i različit efekat na kinetiku fotokatalitičke razgradnje klopiralida. Pri ispitivanju uticaja etanola, kao hvatača slobodnih radikala, nađeno je da se heterogena fotokataliza odvija uglavnom preko ^&bull;OH-radikala.</p><p>Na osnovu LC&ndash;MS/MS (ESI+) merenja ustanovljeno je prisustvo nekoliko&nbsp;intermedijera: 3,6-dihlor-piridin-2-ol, 3,6-dihlor hidroksipiridin-2-karboksilna kiselina i&nbsp;3,3&#39;,6,6&#39;-tetrahlor-2,4&#39;-bipiridin-2&#39;-karboksilna kiselina. Na osnovu identifikovanih&nbsp;intermedijera, kao i kinetičkih rezultata, predložen je mogućput mehanizma fotokatalitičke&nbsp;razgradnje klopiralida.</p><p>Prilikom ispitivanja uticaja strukture molekula na brzinu razgradnje, konstatovano&nbsp;<br />je da u slučaju klopiralida praktično ne dolazi do fotokatalitičke razgradnje u prisustvu&nbsp;TiO_2&nbsp;(anataze) i N-TiO_2&nbsp;(sintetisani suvim putem) uz primenu vidljive svetlosti, kao i u&nbsp;slučaju TiO_2&nbsp;Degussa P25. Pored toga, primenom TiO_2&nbsp;(rutil) i Fe-TiO_2&nbsp;kao&nbsp;fotokatalizatora, sa povećanjem količine Fe³⁺-jona od 0,13 do 1,27 at.% raste brzina&nbsp;razgradnje klopiralida, ukazujući da strukturne osobine supstrata utiču na brzinu njihove&nbsp;razgradnje.</p> / <p>It is well known that RS-2-(4-chloro-o-tolyloxy)propionic acid (MCPP), (4-chloro-2- methyl-phenoxy)acetic acid (MCPA) and 3,6-dichloropyridine-2-carboxylic &nbsp;acid&nbsp;(clopyralid) are herbicides of wide activity spectrum. They are soluble in water, hardly&nbsp;biodegradable and, unfortunately, often present in drinking water.</p><p>Heterogeneous photocatalysis by application of TiO_2&nbsp;and UV radiation proved to&nbsp;be very suitable for their removal from water. However, due toits large energy gap, i.e.&nbsp;3.2 &nbsp;eV (anatase-form) and 3.0 eV (rutile-form), a very small fraction of sunlight in the near&nbsp;UV range (about 3&ndash;4%) is used during photocatalytic process, which is an indication of&nbsp;TiO_2&nbsp;inactivity in the presence of this light source. Some literature data report on the&nbsp;possibility of photodegradation of certain substrates by visible light in the presence of&nbsp;TiO₂. MCPP served as substrate for testing TiO_2&nbsp;Degussa P25 &nbsp;photocatalytic activity in the&nbsp;presence of visible light. On the basis of reflection spectra it was established that MCPP&nbsp;adsorbed on TiO_2&nbsp;Degussa P25 was absorbing visible spectrum radiation (&lambda; &ge;400 nm).&nbsp;The existence of thus formed &nbsp;charge-transfer complex was confirmed with FTIR analysis.&nbsp;The efficiency of &nbsp;TiO_2&nbsp;Degussa P25 with application of visible light was compared to&nbsp;sunlight and UV radiation, as well to directphotolysis in the presence of these light&nbsp;sources. The rate of MCPP photocatalytic degradation by means of visible light is&nbsp;0.86 &mu;mol dm^{&minus;3&nbsp;}min^&minus;1, which is about 4 times faster than direct photolysis. In addition, the&nbsp;optimal &nbsp;catalyst concentration of about 8 mg cm^&minus;3, much higher than using UV radiation,&nbsp;<br />was established. The reason is, probably, a different mechanism of &nbsp;hotodegradation &nbsp;in the&nbsp;presence of visible and UV irradiation. Namely, the presence of 2-methyl-2-propanol&nbsp;(well-known&nbsp;^&bull;OH radical scavenger) has practicallyno effect on the rate of &nbsp;MCPP&nbsp;photocatalytic degradation using visible light, which points that this degradation&nbsp;mechanism does not involve&nbsp;^&bull;OH radicals, in contrast to that established &nbsp;for UV radiation.</p><p>Since the catalyst TiO_2&nbsp;Degussa P25 with application of visible light was not very&nbsp;<br />efficient in degradation of all three herbicidesand in view that nowadays is very &nbsp;popular&nbsp;doping process of TiO₂ with different types of metals (alkali, alkaline-earth, transition, etc.)&nbsp;and non-metals (halogen, chalcogen, etc.), in the scope of this Ph.D. &nbsp;thesis activities of N-TiO_2&nbsp;(synthesized by wet and dry procedure) and TiO_2&nbsp;(rutile) doped with various amounts&nbsp;of Fe^3+&nbsp;(0.13&ndash;1.48 at.%) in degradation processes of &nbsp;herbicides MCPP and MCPA using&nbsp;visible light were studied. In addition, the efficiency of TiO_2&nbsp;(anatase) doped with various&nbsp;amounts of Fe^3+&nbsp;(0.71&ndash;1.80 at.%) was also tested for MCPP degradation. When comparing&nbsp;N-TiO_2&nbsp;(synthesized by wet procedure) and N-TiO₂ (dry procedure), it was observed that&nbsp;in the latter case the catalyst efficiency was about two times higher. In this case for MCPP&nbsp;was also observed somewhat higher photocatalytic activity of N-TiO₂ (synthesized by dry&nbsp;procedure) in comparison with TiO₂. When activities of all three catalysts towards MCPA&nbsp;are compared, the results are very alike. In addition, higher efficiency of N-TiO_{2 &nbsp;}(wet&nbsp;procedure) comparing to TiO_2&nbsp;Degussa P25 (about 1.5 times) and about 5 times in&nbsp;comparison to direct photolysis were recorded, while N-TiO₂ (dry procedure) was about 3&nbsp;times more efficient than TiO_2&nbsp;Degussa P25 and about 10 times in comparison with direct&nbsp;photolysis. The rate of solar degradation is about 100 times lower than by application of&nbsp;UV and visible radiation, as a consequence of various intensities of the mentioned light&nbsp;sources and different conditions of photodegradation. An optimal concentration of N-TiO₂&nbsp;(wet procedure) of 4 mg cm^&minus;3<br />&nbsp;was established.</p><p>During degradation of MCPP and MCPA it was observed that the rate is higher if&nbsp;TiO₂(rutile) was applied comparing to Fe-TiO_2&nbsp;and with increasing amount of Fe^3+&nbsp;photocatalytic activity mostly decreases. When TiO₂ (anatase) doped with various amounts&nbsp;of Fe^3+&nbsp;(0.71 to 1.80 at.%) was applied for MCPP degradation, the process was much&nbsp;slower than with undoped catalyst.</p><p>Since we have not found relevant literature data on kinetics and mechanism of&nbsp;photocatalytic degradation of clopyralid, its stability in different experimental conditions&nbsp;was tested. In investigating of influences of pH (1.0&ndash;9.0) both in presence and in absence&nbsp;of daylight, in no cases decomposition was observed during seven months experiments.&nbsp;Also, the kinetics of photocatalytic degradation of clopyralid using UV and visible&nbsp;irradiation in the presence of TiO_2&nbsp;Degussa P25 and in direct photolysis by application of&nbsp;both irradiation sources was studied. It was found that the &nbsp;rate of photocatalytic&nbsp;decomposition using UV radiation was 5 times higher comparing to direct photolysis. For&nbsp;clopyralid photocatalytic monitoring a pH value of &nbsp;3.2 was chosen. In addition, in the investigated concentration range (0.5&ndash;3.0 mmol &nbsp;dm^&minus;3) the photocatalytic degradation kinetics of clopyralid in the first stage of the reaction follows approximately a pseudo-first kinetic order. In investigation of influence of catalyst concentration (0.5&ndash;8 mg cm^&minus;3) on the rate of clopyralid degradation the highest reaction rate was observed at 4 mg cm^{&minus;3&nbsp;}of catalyst concentration The apparent activation energy of the reaction being 7.74 kJ mol^&minus;1. The absence of molecular oxygen resulted in a significant decrease (about 2 times) in the rate of clopyralid photodegradation. The effect of the presence of (NH₄)₂S₂O₈, H₂O_2&nbsp;and KBrO₃, acting as electron acceptors along with molecular oxygen affects clopyralid photocatalytic degradation considerably and indifferent ways. By studying the effect of ethanol as a hydroxyl radical scavenger it was shown that the heterogeneous catalysis takes place mainly via ^&bull;OH radicals.</p><p>LC&minus;MS/MS (ESI+) monitoring of the process showed that several pyridine-containing intermediates are formed: 3,6-dichloropyridin-2-ol, 3,6-dichloro&nbsp;hydroxypyridine-2-carboxylic acid and 3,3&#39;,6,6&#39;-tetrachloro-2,4&#39;-bipyridine-2-carboxylic&nbsp;acid. Based on the identified intermediates and overall kinetic results, a probable&nbsp;photocatalytic degradation mechanism was proposed.&nbsp;</p><p>Finally, in the case of clopyralid it was established that practically no degradation&nbsp;<br />occurs in the presence of TiO_2&nbsp;(anatase) and N-TiO₂ (dry procedure) with visible light &nbsp;and&nbsp;also with TiO_2&nbsp;Degussa P25. Besides of that, by using TiO_2&nbsp;(rutile) and Fe-TiO_2&nbsp;as&nbsp;photocatalysts it was noted that increasing the concentration of Fe^3+&nbsp;from 0.13 to 1.27 at.%&nbsp;comes to increasing photodegradation rate of clopyralid. Results indicate that differences&nbsp;in molecular structure of chosen compound, influence obtained photocatalytic activity to a&nbsp;great extent.</p>