Size-selected Pd nanoparticles were synthesized by the reverse-micelle encapsulation method and deposited on a ZrO2 support for the catalytic NO reduction by H2. All of our samples were found to be highly selective, but a significant size effect was not seen for Pd nanoparticles of between 1.2 nm and 5.5 nm. Ultra-small Pd clusters of less than 1 nm were found to be much less active, and are assumed to be affected by an encapsulation effect of the support. Catalyst activity was comparable to that of literature, and is applicable to H2-SCR research.

Made available in DSpace on 2016-06-02T19:56:55Z (GMT). No. of bitstreams: 1 6143.pdf: 2289936 bytes, checksum: dcf4b81e424bb217ab83315f71624407 (MD5) Previous issue date: 2014-03-31 / Universidade Federal de Sao Carlos / NO, NO2 and N2O nitrogen oxides, named NOx, strongly contribute to the air pollution and to minimize their emissions are used catalytic processes. The catalytic reduction of NO with CO has the advantage to simultaneously abate both pollutants. For that reaction are used noble metal based catalysts, but due to their scarcity and high cost, many research have been established to their substitution by transition metal oxides, which have high potential to catalyze that reaction. Those new catalysts beside to be active to the NO reduction with CO, they must be highly selective to N2 formation, stable at high temperatures and especially resistant to the presence of the interfering compounds (O2, SO2 and H2O). In this work were prepared Fe2O3, CuO or Fe2O3-CuO catalysts supported on y-Al2O3, ZrO2 or ZrO2/y-Al2O3. The supports were prepared via synthesis sol-gel using metallics alkoxides as precursors and the active phases introduced by impregnation of Fe(III) or Cu(II) nitrates. The obtained solids were characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption measurements, hydrogen temperature programmed reduction (H2-TPR) and their activity evaluated by the reduction of NO with CO between 100 to 600°C in the presence or absence of SO2, O2 and H2O. The synthesis via sol-gel resulted in y-Al2O3 and ZrO2/y-Al2O3 supports with high specific surface area that allowed adequately distribute the CuO and Fe2O3 oxides, which did not present X ray diffraction peaks. The catalysts were considerably active in the reduction of NO with CO, with the bimetallic ones being slightly more selective to N2 formation. In the presence of SO2, the Fe2O3/y- Al2O3 and Fe2O3/ZrO2/y-Al2O3 catalysts showed more catalytic stability. The presence of O2 led to a significantly NO conversion loss due to the direct CO oxidation by O2. In the presence of H2O or of all the interfering compounds, the NO conversion loss was more pronounced, except the CuO/ZrO2, that was more resistant in the presence of H2O. / Os óxidos de nitrogênio NO, N2O e NO2, denominados de NOx, são fortes causadores da poluição atmosférica e, para minimizar suas emissões utilizam-se processos catalíticos. A redução de NO com CO tem a vantagem de abater simultaneamente ambos poluentes. Nessa reação, são utilizados catalisadores à base de metais nobres, mas, a sua escassez e alto custo têm direcionado pesquisas para a sua substituição por óxidos de metais de transição, os que mostram potencial para essa reação. Além de ativos, esses catalisadores devem ser seletivos à produção de N2, estáveis em altas temperaturas e sobre tudo estáveis na presença dos interferentes O2, H2O e SO2. Neste trabalho foram preparados catalisadores de Fe2O3, CuO ou Fe2O3-CuO suportados em y-Al2O3, ZrO2 ou ZrO2/y-Al2O3. Os suportes foram preparados via sol-gel, utilizando alcóxidos metálicos como precursores e, a introdução das fases ativas, efetuada via impregnação utilizando nitratos de Fe(III) ou Cu(II). Os suportes e catalisadores foram caracterizados por difração de raios X (DRX), fisissorsão de nitrogênio, redução com hidrogênio à temperatura programada (RTP-H2) e a sua atividade avaliada através da redução de NO a N2 com CO, entre 100 e 600°C, na ausência ou presença de interferentes. A síntese sol-gel resultou em suportes y- Al2O3 e ZrO2/y-Al2O3 de alta área superficial, permitindo uma adequada distribuição de CuO e Fe2O3, os que não apresentaram picos de DRX. Os catalisadores foram bastante ativos na redução de NO a N2, com os bimetálicos sendo ligeiramente mais seletivos à formação de N2. Na presença de SO2 os catalisadores Fe2O3/y-Al2O3 e Fe2O3/ZrO2/y-Al2O3 foram mais estáveis. A presença de O2 provocou significativa queda na conversão de NO, favorecendo a oxidação direta do CO. Na presença de H2O ou de todos os interferentes simultaneamente, a queda da conversão de NO a N2 sobre todos os catalisadores analisados foi total, com exceção ao catalisador de CuO/ZrO2, que foi mais resistente na presença de vapor de água.

Made available in DSpace on 2014-07-29T15:12:44Z (GMT). No. of bitstreams: 1 Dissertacao Gustavo Amorim Santos.pdf: 699656 bytes, checksum: 971524b5001f034de32cefb99d226301 (MD5) Previous issue date: 2010-08-31 / In this work, a methodology for the synthesis of silica-cobalt oxide-based composites was developed by modifying the well known Stöber sol-gel method. The main novelty of the procedure was the use of colloidal suspensions of cobalt oxide or cobalt hydroxide nanoparticles (Co3O4,Co(OH)2), which were previously prepared from the precipitation of Co2+ ions in alkaline medium. The silica-cobalt composites having cobalt contents (w/w) around 8.4 to 11% were characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermogravimetric and differential thermal analysis (TG/DTA), temperature programmed reduction (TPR) and adsorption /desorption of nitrogen. The characteristics of the composites which were prepared by employing the colloidal suspensions were compared to those exhibited by other composites which were obtained from cobalt nitrate solution. The influence of cerium nitrate and citric acid was also evaluated. The methodology employed in the synthesis of nanoparticles and composites were reproducible and the prepared materials showed surface areas (300 to 567 cm3/g) and pore diameters (3.8 to 8.1 nm) values which were considered appropriate to use them as catalysts. The calcined composites which were prepared using colloidal suspensions of Co3O4 nanoparticles showed TPR curves with maximum picks at relatively low temperatures, in the range of 275 to 520 oC, suggesting the existence of weak silica-cobalt interactions. The average diameter of Co3O4 crystallites varied from 22 to 30 nm. However, the use of citric acid as a pore-forming agent in the sol-gel synthesis led to composites with enhanced silica-cobalt interactions as a result of the dissolution of the cobalt oxide particles and formation of cobalt silicate. The incorporation of cerium nitrate in the sol-gel mixture did not modify the textural properties of the composites but the reduction of cobalt oxide to metallic cobalt was retarded. The composite which was obtained from the cobalt hydroxide, β-Co(OH)2, colloidal suspension showed weak silica-cobalt interactions as well as intermediate ones, the average diameter of Co3O4 crystallites being 12 nm. Differently from the composites obtained from colloidal suspensions, those which were synthesized using a cobalt nitrate aqueous solution presented mainly cobalt silicate and a low quantity of Co3O4 particles of 11 and 17 nm. The TPR curves of these composites indicated very strong silica-cobalt interactions, as expected. The composites were evaluated as catalysts in the reduction reaction of NO to N2 with the oxidation of CO to CO2. The composites which were prepared from Co3O4 colloidal suspensions without the use of citric acid as pore-forming agent showed maximum conversions as high as 90% for both NO to N2 and CO to CO2, at temperatures above 600°C. On the other hand, the composite prepared using critic acid showed much lower conversions (60 %) at the same temperature. / Neste trabalho foi desenvolvida uma metodologia de síntese de compósitos de óxido de cobalto e sílica a partir de adaptações no método sol-gel do tipo Stöber. A principal novidade do procedimento consistiu na utilização de suspensões coloidais de nanopartículas de óxido ou hidróxido de cobalto (Co3O4, Co(OH)2), as quais foram previamente preparadas por precipitação de íons Co2+ em meio alcalino. Os compósitos de sílica-cobalto contendo teores de cobalto entre 8,4 e 11% (m/m) foram caracterizados por espectroscopia de absorção atômica (AA), difratometria de raios-X (DRX), espectroscopia na região do infravermelho médio com transformada de Fourier (FTIR), análise termogravimétria e térmica diferencial (TG/DTA), redução a temperatura programada (TPR) e adsorção/dessorção de nitrogênio. As características dos compósitos preparados empregando-se suspensões de nanopartículas foram comparadas com as de outros compósitos obtidos a partir de solução de nitrato de cobalto, sendo também avaliada a influência da adição de nitrato de cério e de ácido cítrico. A metodologia desenvolvida mostrou-se reprodutível e os materiais obtidos apresentaram valores adequados de área superficial (300 a 567 cm3/g) e diâmetro de poros (3,8 a 8,1 nm) para serem utilizados como catalisadores. Os compósitos preparados utilizando-se suspensões coloidais de nanopartículas de Co3O4 apresentaram, após calcinação, curvas de redução termoprogramada cujos picos máximos ocorreram em temperaturas relativamente baixas, na faixa de 275 a 520 oC, sugerindo a existência de interações fracas entre a sílica e o cobalto. O diâmetro médio dos cristalitos de Co3O4 nesses compósitos variou entre 22 e 30 nm. No entanto, a utilização de ácido cítrico como agente formador de porosidade na síntese desses compósitos provocou o aumento da interação sílica-cobalto, como resultado da dissolução das partículas de óxido de cobalto e formação de silicato de cobalto. A utilização de nitrato de cério nas sínteses não alterou as propriedades texturais dos compósitos, mas, como esperado, dificultou a redução do óxido de cobalto para cobalto metálico. O compósito obtido a partir de suspensão coloidal de hidróxido de cobalto, -Co(OH)2, por sua vez, apresentou tanto interações sílica-cobalto fracas como intermediárias, sendo de 12 nm o diâmetro médio dos cristalitos de Co3O4, após calcinação do material. Diferentemente dos compósitos preparados a partir das suspensões coloidais do óxido de cobalto, os compósitos que foram sintetizados utilizando-se solução de nitrato de cobalto mostraram, após calcinação, a presença silicato de cobalto e pequena quantidade de partículas de Co3O4 de diâmetros entre 11 e 17 nm. As curvas de TPR desses compósitos indicaram, como esperado, interações sílica-cobalto fortes. Os compósitos foram avaliados na reação de redução do NO em N2 com oxidação do CO a CO2. Para os compósitos em que foram utilizadas nanopartículas de Co3O4 previamente preparadas, na ausência de ácido cítrico, houve conversões máximas de até 90% do NO em N2 e do CO em CO2.. Isso ocorreu em temperaturas superiores a 600 °C. Por outro lado, a utilização do ácido cítrico concomitantemente à incorporação das nanopartículas de Co3O4, conduziu a taxas de conversões inferiores a 60%, em temperaturas superiores a 600 °C.

The reaction mechanism for the selective catalytic reduction (SCR) of nitric oxide by ammonia on (010) V2O5 surface represented by a V2O9H8 cluster was simulated by density functional theory (DFT) calculations. The computations indicated that SCR reaction consisted of three main parts. In the first part ammonia activation on Br&oslash / nsted acidic V-OH site as NH4+ species by a nonactivated process takes place. The second part includes the interaction of NO with pre-adsorbed NH4 + species to eventually form nitrosamide (NH2NO). The rate limiting step for this part as well as for the total SCR reaction is identified as NH3NHO formation reaction. The last part consists of the decomposition of NH2NO on the cluster which takes advantage of a hydrogen transfer mechanism between the active V=O and V-OH groups. Water and ammonia adsorption and dissociation are investigated on (101) and (001) anatase surfaces both represented by totally fixed and partially relaxed Ti2O9H10 clusters. Adsorption of H2O and NH3 by H-bonding on previously H2O and NH3 dissociated systems are also considered. By use of a (001) relaxed Ti2O9H10 cluster, the role of anatase support on SCR reaction is investigated. Since NH2NO formation on Ti2O9H10 cluster requires lower activation barriers than on V2O5 surface, it is proposed that the role of titanium dioxide on SCR reaction could be forming NH2NO. The role of vanadium oxide is crucial in terms of dissociating this product into H2O and N2. Finally, NH3 adsorption is studied on a V2TiO14H14 cluster which represents a model for vanadia/titania surface.

Made available in DSpace on 2016-06-02T19:55:24Z (GMT). No. of bitstreams: 1 2075.pdf: 4577723 bytes, checksum: 80abdc876165c000f61328875ff2a061 (MD5) Previous issue date: 2008-10-20 / Financiadora de Estudos e Projetos / Mixed oxides with perovskite structure have high potential as catalysts in gas depollution processes and particularly in the abatement of nitrogen oxides (NOx). Such solids could be considered as a promising alternative for the replacement of noble metals based catalysts, whose use is predominant. Great flexibility of composition, easy synthesis, low cost and high thermal stability justify the special interest in these materials. However, the low specific surface areas (<10 m2/g) of these solids, when prepared by conventional methods, limit your use in catalytic processes. Some efforts have been made in order to overcome that disadvantage. Nevertheless, the preparation of high surface area ternary or multinary oxides is not easy once their synthesis is associated with solid state reactions carried out at high temperatures. Considering the discussed context, perovskites were obtained in this work by means of a conventional method or via sequencial nanocasting. In the first case, perovskites with LaFe1-xCoxO3 (x = 0, 0.2, 0.3, 0.4, 0.5 and 1) nominal compositions were prepared using the citrate method and nitrate salts as inorganic precursors. In the second case, LaFeO3 and LaFe0.6Co0.4O3 perovskites were obtained by nanocasting using Fluka 05120 activated carbon, Black Pearls 2000 black carbon (Cabot Corporation), and porous carbons nanocasted in Aerosil 200 pyrogenic silica and sílica-SBA-15 mesoporous molecular sieve. X-ray diffraction (XRD), N2 sorption measurements, X-ray fluorescence (XRF), hydrogen temperature programmed reduction (H2-TPR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transformed infrared spectroscopy (FTIR) and thermogravimetry (TG) were used to characterize the studied solids. The catalytic activity of the prepared perovskites was evaluated in the reduction of NO to N2 with CO and in the oxidation of the latter compound to CO2. According to the obtained results, it was evident that in comparison with the conventional route, the nanocasting technique using carbons as hard template was efficient to obtain the pure perovskite phase with specific surface areas substantially higher (25 a 49 m2/g). The prepared perovskites were highly active and selective in the reduction of NO to N2 with CO, as well as in the oxidation of the latter compound to CO2. The most active samples were those whose B sites contain up to about 30 % Co. However, the activity of these catalysts decreases strongly with the presence of O2 or water steam. The La-Fe nanocasted binary perovskites showed, in the studied reactions, remarkable higher catalytic activity than the perovskite with the same composition prepared using the conventional method. The higher activity of these materials was related with the increase of their specific surface area. The nanocasted ternary perovskites with LaFe0.6Co0.4O3 composition, despite of the significant increase in their specific surface area, did not show a considerable increase in their activity. This result is in agreement with the behaviour of La-Fe-Co ternary perovskites, in which Co occupies a proportion of B sites greater than 30 %. / Óxidos mistos com estrutura perovskita apresentam alto potencial como catalisadores em processos de despoluição de gases e particularmente no abatimento de óxidos de nitrogênio (NOx). Tais sólidos são uma alternativa promissora para substituição de catalisadores à base de metais nobres, cujo uso é predominante. Vantagens como grande flexibilidade de composição, fácil síntese, baixo custo e elevada estabilidade térmica justificam o especial interesse por esses materiais. Contudo, as baixas áreas superficiais específicas desses sólidos (< 10 m2/g), quando sintetizados por métodos convencionais, limitam o seu uso em processos catalíticos. Algumas tentativas têm sido feitas no sentido de contornar essa desvantagem. No entanto, a obtenção de óxidos ternários ou multinários de alta área superficial específica é especialmente difícil, uma vez que sua síntese está associada a reações no estado sólido realizadas em temperaturas elevadas. Considerando o contexto discutido, neste trabalho foram obtidas perovskitas através de método convencional ou via nanomoldagem seqüencial. No primeiro caso, perovskitas com composição nominal LaFe1-xCoxO3 (x = 0; 0,2; 0,3; 0,4; 0,5 e 1) foram preparadas utilizando o método do citrato e sais de nitratos como precursores inorgânicos. No segundo caso, perovskitas LaFeO3 e LaFe0,6Co0,4O3 foram obtidas por nanomoldagem utilizando carbono ativado Fluka 05120, negro de fumo Black Pearls 2000 (Cabot Corporation), e carbonos porosos nanomoldados em sílica pirogênica Aerosil 200 e peneira molecular mesoporosa sílica-SBA-15. Difração de raios X (DRX), medidas de adsorção/dessorção de N2, fluorescência de raios X (FRX), redução com hidrogênio a temperatura programada (RTP-H2), microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (MET), espectroscopia no infravermelho por transformada de Fourier (IV) e termogravimetria (TG) foram utilizadas para caracterizar os sólidos estudados. A atividade catalítica das perovskitas preparadas foi avaliada na redução de NO a N2 com CO e na oxidação desse último composto a CO2. De acordo com os resultados obtidos, ficou evidente que em comparação com a rota convencional, a técnica de nanomoldagem utilizando moldes de carbono foi eficiente na obtenção da fase perovskita pura com área superficial específica substancialmente maior (25 a 49 m2/g). As perovskitas preparadas foram altamente ativas e seletivas na redução de NO a N2 com CO, bem como na oxidação desse último composto a CO2, sendo mais ativas aquelas cujos sítios B contêm até cerca de 30 % de Co. A presença de O2 ou vapor de água, entretanto, reduz fortemente a atividade desses catalisadores. As perovskitas binárias La-Fe nanomoldadas apresentaram, nas reações estudadas, atividade catalítica consideravelmente superior a da perovskita com a mesma composição preparada pelo método convencional. A maior atividade desses materiais foi relacionada com o aumento da sua área superficial específica. As perovskitas nanomoldadas ternárias com composição LaFe0,6Co0,4O3, apesar do significativo aumento na sua área superficial específica, não apresentaram um aumento considerável na atividade, fato esse condizente com o comportamento de perovskitas ternárias La-Fe-Co, nas quais o Co ocupa uma proporção de sítios B superior a 30 %.

No description available.

In recent times, as regulations and legislations for exhaust treatment have become more stringent, a major concern in the arena of environmental catalysis is to find new efficient and economical exhaust treatment catalysts. Chapter 1 is a review of the current status of various NOx abatement techniques and understanding the role of “auto-exhaust catalysts” involved therein. Chapter 2 presents the studies on synthesis of ionically substituted precious metal ions like Pd2+, Pt2+ and Rh3+ in CeO2 matrix and their comparative three-way catalytic performances for NO reduction by CO, as well as CO and hydrocarbon oxidation. Ce0.98Pd0.02O2- showed better catalytic activity than ionically dispersed Pt or Rh in CeO2. The study in Chapter 3 aims at synthesizing 1 atom% Pd2+ ion in TiO2 in the form of Ti0.99Pd0.01O2- with oxide ion vacancy. A bi-functional reaction mechanism for CO oxidation by O2 and NO reduction by CO was proposed. For NO reduction in presence of CO, the model based on competitive adsorption of NO and CO on Pd2+, NO chemisorption and dissociation on oxide ion vacancy fits the experimental data. The rate parameters obtained from the model indicates that the reactions are much faster over this catalyst compared to other catalysts reported in the literature. In Chapter 4 we present catalytic reduction of NO by H2 over precious metal substituted TiO2 (Ti0.99M0.01O2-, where M = Ru, Rh, Pd, Pt) catalysts. The rate of NO reduction by H2 depends on the reducibility of the catalysts. Chapter 5 presents the studies on reduction of NO by NH3 in presence of excess oxygen. 10 atom % of first row transition metal ions (Ti0.9M0.1O2-, where M = Cr, Mn, Fe, Co and Cu) were substituted in anatase TiO2 and TPD study showed that the Lewis and Bronsted acid sites are adsorption sites for NH3, whereas NO is found to dissociatively chemisorbed in oxide ion vacancies. The mechanism of the low temperature catalytic activity of the SCR and the selectivity of the products were studied to understand the mechanism by studying the by-reactions like ammonia oxidation by oxygen. A new catalyst Ti0.9Mn0.05Fe0.05O2- has shown low temperature activity with a broad SCR window from 200 to 400 °C and more selectivity than commercial vanadium-oxides catalysts. We attempted NO dissociation by a photochemical route with remarkable success. In Chapter 6 we report room temperature photocatalytic activity of Ti0.99Pd0.01O2- for NO reduction and CO oxidation by creating redox adsorption sites and utilizing oxide ion vacancy in the catalyst. The reduction of NO is carried out both in the presence and in the absence of CO. Despite competitive adsorption of NO and CO on the Pd2+ sites, the rate of reduction of NO is two orders of magnitude higher than unsubstituted TiO2. High rates of photo-oxidation of CO with O2 over Ti0.99Pd0.01O2- were observed at room temperature. In Chapter 7 the results are summarized and critical issues are addressed. Novel idea in this thesis was to see if both noble metal ions and base metal ions substituted in TiO2 and CeO2 reducible supports can act as better active sites than the corresponding metal atoms in their zero valent state.

Στην παρούσα μελέτη διερευνάται η αρχή του φαινομένου της ηλεκτροχημικής ενίσχυσης με την τεχνική της ηλεκτρονικής μικροσκοπίας σήραγγος (STM) και με την τεχνική Kelvin probe. Συγκεκριμένα, με το STM εξετάστηκε το σύστημα Pt(111)/YSZ υπό συνθήκες περιβάλλοντος προκειμένου να διερευνηθούν σε ατομική κλίμακα οι μεταβολές που υφίσταται η επιφάνεια του μονοκρυστάλλου της Pt μετά από ηλεκτροχημική παροχή ιόντων οξυγόνου στην επιφάνειά της. Βρέθηκε ότι το ηλεκτροχημικά παρεχόμενο οξυγόνο από το στερεό ηλεκτρολύτη στην επιφάνεια της Pt(111) δημιουργεί τη δομή Pt(111)-(12x12)-O. Με την τεχνική Kelvin probe μελετήθηκε το έργο εξόδου ηλεκτροδίων σε υδατικά διαλύματα και εν συνεχεία διερευνήθηκε η αρχή του απόλυτου δυναμικού των ηλεκτροδίων στην υγρή ηλεκτροχημεία. Τα αποτελέσματα επιβεβαιώνουν για πρώτη φορά την ισχύ της εξίσωσης: eUWR= ΦW – ΦR στην υγρή ηλεκτροχημεία και τονίζουν ότι το έργο εξόδου των αναδυόμενων ηλεκτροδίων, διαιρούμενο από το μοναδιαίο φορτίο του ηλεκτρονίου e, μπορεί να οριστεί ως το απόλυτο δυναμικό. Μελετήθηκε επίσης η αναγωγή των οξειδίων του αζώτου από C3H6 και από CO παρουσία οξυγόνου σε διεσπαρμένους καταλύτες ροδίου (Rh) και πλατίνας (Pt). Βρέθηκε ότι η αντίδραση αναγωγής του ΝΟ εξαρτάται από το είδος του φορέα και του μετάλλου. Τα αποτελέσματα συγκρινόμενα με αντίστοιχα πειράματα ηλεκτροχημικής ενίσχυσης, ΗΕ, έδειξαν τη βασική ομοιότητα του μηχανισμού της ΗΕ και των αλληλεπιδράσεων μετάλλου-φορέα, που συνίστανται στην διάχυση (backspillover) ιόντων Ο2- από το φορέα στο μέταλλο και την επακόλουθη αλλαγή της ισχύος των χημειοροφητικών δεσμών των αντιδρώντων. Επίσης μελετήθηκε η συμπεριφορά ζεόλιθου Cu-ZSM-5 στην αναγωγή του ΝΟ από προπυλένιο όπου βρέθηκε ότι ο συγκεκριμένος καταλύτης είναι ιδιαίτερα εκλεκτικός σε Ν2 υπό έντονα οξειδωτικές συνθήκες. / Scanning tunneling microscopy (STM) was used to investigate the surface of Pt single crystal catalyst surfaces interfaced with O2- conducting catalyst supports under conditions simulating electrochemical promotion and metal-support interactions. In both cases STM has clearly shown the reversible migration on the catalyst surface of promoting O2- species which are entirely distinct from normally chemisorbed oxygen originating from the gas phase. These observations provide useful information for the mechanism of electrochemical promotion and metal-support interactions, reveal the existence and fast migration of O2-, a most effective anionic promoter, on metal surfaces and underline its role in inducing the phenomena of electrochemical promotion and of metal-support interactions. In the second part of my thesis a two Kelvin probe setup is used for the first time in aqueous electrochemistry, to measure in situ and simultaneously the work functions, ΦW, ΦC and ΦR, of emersed working, counter and reference electrodes, respectively. The results confirm, for the first time, the validity of equation eUWR= ΦW – ΦR in aqueous electrochemistry and underline that the work function of emersed electrodes, divided by the unit charge e, can be used as the absolute potential. Additionally, in the last part of this thesis, it was studied NOx reduction by C3H6 and CO in the presence of oxygen on Rh and Pt dispersed catalysts. It was found that NO reduction depends on the support, but also on the type of the impregnating metal. The obtained results showed the similarity of electrochemical promotion and of metal-support interactions, when compared with corresponding NEMCA experiments. Finally, an ion-exchanged zeolite, Cu-ZSM-5, was used for NO reduction by propylene. It was found that the used zeolite was highly selective to dinitrogen production in high excess of oxygen.

Η ηλεκτροχημική ενίσχυση της κατάλυσης (EPOC ή αλλιώς μη-φαρανταϊκή τροποποίηση της καταλυτικής ενεργότητας, φαινόμενο NEMCA) είναι ένα φαινόμενο όπου εφαρμογή μικρών ρευμάτων ή δυναμικών (±2V) σε ένα καταλύτη που είναι υποστηριγμένος σε ένα ηλεκτρολύτη, ιοντικό ή μικτό ιοντικό-ηλεκτρονικό αγωγό, μπορεί να επιφέρει τροποποιήσεις στην καταλυτική ενεργότητα αλλά και εκλεκτικότητα, με τρόπο ελεγχόμενο, αντιστρεπτό και έως ένα βαθμό προβλέψιμο. Η ηλεκτροχημική ενίσχυση έχει βρεθεί, με χρήση διαφόρων τεχνικών, ότι πηγάζει από την ηλεκτροχημικά ελεγχόμενη παροχή ενισχυτικών ιοντικών ειδών από το φορέα-ηλεκτρολύτη στα καταλυτικά σωματίδια. Στο πρώτο κεφάλαιο της παρούσας διατριβής γίνεται μια εκτεταμένη αναφορά στους στερεούς ηλεκτρολύτες, στις ιδιότητες τους και τους τομείς στους οποίους χρησιμοποιούνται με ιδιαίτερη σημασία στη σταθεροποιημένη με οξείδιο του υττρίου ζιρκονία (YSZ), που αποτελεί ένα πολύ συχνά χρησιμοποιούμενο αγωγό ιόντων οξυγόνου. Επίσης, εισάγονται οι έννοιες της μετανάστευσης (spillover) και της αντίστροφης μετανάστευσης (backspillover), οι οποίες χρησιμοποιούνται στην ερμηνεία και την κατανόηση του φαινομένου της ηλεκτροχημικής ενίσχυσης και των αλληλεπιδράσεων μετάλλου-φορέα (MSI). Στο δεύτερο κεφάλαιο γίνεται εισαγωγή στις γενικές αρχές του φαινομένου της ηλεκτροχημικής ενίσχυσης όπου παρουσιάζονται μερικά παραδείγματα εφαρμογής του και γίνεται ανασκόπηση όλων των εργασιών που έχουν εμφανιστεί στη βιβλιογραφία και αφορούν στο συγκεκριμένο φαινόμενο. Συζητείται, επίσης, η μελέτη του φαινομένου με χρήση διαφόρων πειραματικών τεχνικών, όπως ηλεκτροκινητικών πειραμάτων δυναμικής απόκρισης, μετρήσεων έργου εξόδου, κυκλικής βολταμμετρίας, XPS, TPD και STM, καθώς και θεωρητικών μελετών, με σκοπό την κατανόηση της αρχής του φαινομένου σε ατομικό επίπεδο καθώς και την επίλυση σημαντικών προβλημάτων που αφορούν στην ετερογενή κατάλυση. Με βάση τα αποτελέσματα από τις ανωτέρω μελέτες, παρουσιάζεται το μαθηματικό μοντέλο που έχει αναπτυχθεί και εξηγεί τα παρατηρούμενα φαινόμενα σε μοριακό επίπεδο καθώς και οι πρόσφατα εδραιωμένοι κανόνες που το διέπουν. Στο τρίτο κεφάλαιο παρουσιάζεται η αξιοποίηση του φαινομένου της ηλεκτροχημικής ενίσχυσης στην αντιμετώπιση ενός εκ των δυσκολότερων και προκλητικότερων προβλημάτων της ετερογενούς κατάλυσης που είναι η αναγωγή του μονοξειδίου του αζώτου (ΝΟ) από αιθυλένιο παρουσία υψηλής περίσσειας (10%) οξυγόνου. Στην μελέτη χρησιμοποιήθηκε ένας πρόσφατα ανεπτυγμένος και βελτιωμένος για την παρούσα διατριβή, μονολιθικός ηλεκτροχημικά ενισχυόμενος αντιδραστήρας (monolithic electrochemically promoted reactor, MEPR) εξοπλισμένος με 22 ηλεκτροχημικά καταλυτικά στοιχεία του τύπου Rh/YSZ/Pt με μικρό πάχος ηλεκτροδίων (~40 nm). Βρέθηκε, δε, ότι η βέλτιστη λειτουργία επιτυγχάνεται σε χαμηλές θερμοκρασίες (220-240οC) με σημαντική ηλεκτροχημική ενίσχυση ακόμα και κάτω από τις ανωτέρω ισχυρά οξειδωτικές συνθήκες (λόγος αέρα-καυσίμου=16.7, περίσσεια οξυγόνου=9.43). Σε αυτό το στενό θερμοκρασιακό εύρος η εκλεκτικότητα προς Ν2 που επετεύχθη από τα Rh/YSZ/Pt ηλεκτροκαταλυτικά στοιχεία, είναι περίπου 100% ενώ η παραγωγή των ανεπιθύμητων CO, ΝΟ2, Ν2Ο ήταν σχεδόν μη-ανιχνεύσιμη. Στο τέταρτο κεφάλαιο μελετάται η χρήση λεπτών καταλυτικών ηλεκτροδίων Pt σκελετικής δομής (Pt-skeletal/YSZ/Au) στην έκταση του φαινομένου της ηλεκτροχημικής ενίσχυσης, χρησιμοποιώντας την πρότυπη αντίδραση οξείδωσης αιθυλενίου, στον μονολιθικό ηλεκτροχημικά ενισχυόμενο αντιδραστήρα. Βρέθηκε ότι και τέτοιου τύπου ηλεκτρόδια – καταλυτικά υμένια είναι ιδιαίτερα καταλυτικά ενεργά και είναι δυνατό να ενισχυθούν ηλεκτροχημικά σε μεγάλο βαθμό. Επίσης, ο αντιδραστήρας λειτούργησε επιτυχώς και παρατηρήθηκε ηλεκτροχημική ενίσχυση, υπό υψηλές ογκομετρικές παροχές (25 l/min), με ταχύτητες χώρου αντιδραστήρα που είναι κοντά σε αυτές που λειτουργούν οι βιομηχανικοί αντιδραστήρες (12000 h-1). Στο πέμπτο κεφάλαιο παρουσιάζεται η ηλεκτροχημική ενίσχυση της αντίδρασης υδρογόνωσης του CO2 με στόχο την παραγωγή μεθανίου χρησιμοποιώντας ηλεκτροχημικά στοιχεία του τύπου Rh/YSZ/Pt. Βρέθηκε ότι η αντίδραση μπορεί να ενισχυθεί σε μεγάλο βαθμό και επιπλέον να τροποποιηθεί και η εκλεκτικότητά της σε CΗ4 που είναι και το επιθυμητό προϊόν. Στο έκτο κεφάλαιο παρουσιάζεται η μελέτη της αντίδραση οξείδωσης του SO2 προς SO3, μιας πολύ σημαντικής αντίδρασης από βιομηχανική (παραγωγή H2SO4) αλλά περιβαλλοντική άποψη, με χρήση του φαινομένου της ηλεκτροχημικής ενίσχυσης, σε λεπτά (~40 nm) ηλεκτροχημικά στοιχεία του τύπου Pt/YSZ/Au. Βρέθηκε πως ηλεκτροχημική ενίσχυση μπορεί να επιτευχθεί ακόμα και σε πολύ υψηλές ογκομετρικές παροχές (30 l/min), όπου αντιστοιχούν σε ταχύτητες χώρου αντιδραστήρα (14000 h-1) πολύ κοντά σε αυτές που λειτουργούν οι βιομηχανικοί αντιδραστήρες και να επιτευχθούν σχετικά υψηλές μετατροπές SO2. / Electrochemical Promotion of Catalysis (EPOC or Non-Faradaic Electrochemical Modification of Catalytic Activity, NEMCA effect) is a phenomenon where the application of small currents or potentials (±2V) alters the activity and selectivity of catalysts supported on ionic or mixed ionic-electronic conductors and modifies the catalytic activity and selectivity, in a controllable, reversible and to some extend predictable manner. As shown by numerous surface science techniques, including STM, electrochemical promotion is due to electrochemically controlled migration (backspillover) of promoting or poisoning ionic species (Oδ- in the case of YSZ) between the ionic or mixed ionic-electronic conductor and the gas exposed catalytic surface. The utilization of electrochemical promotion of catalysis, in order to tackle one of the most difficult and challenging problems of heterogeneous catalysis, which is the NO reduction under high excess oxygen (10%), has been performed. This gas mixture is a typical mixture in a lean-burn engine (or Diesel engine) exhaust. In this study, a recently developed and improved monolithic electrochemically promoted reactor (MEPR) has been used, equipped with 22 thin (~40 nm catalyst-electrode thickness) electrochemical catalytic elements Rh/YSZ/Pt type. It was found that there is an optimum operation temperature of the reactor, in the range from 220oC to 240oC, where the maximum electropromotion effect occurs, even under these extremely oxidizing conditions (air/fuel ratio = 16.7 and oxygen excess = 9.43%). In this narrow temperature window the selectivity to N2 was almost 100% since the production of the undesired N2O and NO2 was almost undetectable. Also, the use of thin catalytic Pt electrodes with skeletal structure (Ptskeletal/ YSZ/Au) was examined in the MEPR for the model reaction of C2H4 oxidation. It was found that such skeletal structure electrodes are catalytically active and can be electropromoted even under high gas flow rates (25 l/min) or high space velocity (HSV~12000 h-1), close to those that the industrial reactors operate. The electrochemical promotion of the CO2 hydrogenation reaction was also examined, towards methane production using Rh/YSZ/Pt type electrochemical catalytic elements. It was found that the reaction rates can be enhanced and similarly the selectivity to CH4 which found to increase upon polarization. Finally, the effect of electrochemical promotion was examined in the study of the SO2 oxidation to SO3 reaction, which is a very important reaction by industrial (H2SO4 production) and environmental point of interest. The monolithic reactor was equipped with 5 or 22 thin (~40 nm) Pt/YSZ/Au type electrocatalytic elements. It was found that electrochemical promotion can be obtained by positive polarization even under high hourly space velocities (14000 h-1), close to those that the industrial reactors operate, with relatively high SO2 conversions.

Η Ηλεκτροχημική Ενίσχυση της Κατάλυσης (ή φαινόμενο NEMCA) είναι ένα φαινόμενο όπου εφαρμογή μικρών ρευμάτων ή δυναμικών (±2 V) μπορεί να τροποποιήσει την ενεργότητα καταλυτών υποστηριγμένων σε ιοντικούς ή μικτούς ιοντικούς-ηλεκτρονικούς αγωγούς, να επηρεάσει την εκλεκτικότητα σε επιθυμητή κατεύθυνση και να μεταβάλλει τις ηλεκτρονικές και συνεπώς τις καταλυτικές ιδιότητες με τρόπο ελεγχόμενο, αντιστρεπτό και σε κάποιο βαθμό προβλέψιμο. Στην παρούσα διατριβή μελετήθηκε η επίδραση του πάχους του καταλυτικού υμενίου στο μέγεθος της ηλεκτροχημικής ενίσχυσης, χρησιμοποιώντας την αντίδραση της οξείδωσης του C2H4 σε πορώδη υμένια Pt πάχους μεταξύ 0.2 και 1.4 μm, εναποτεθειμένα με τη μέθοδο επάλειψης οργανομεταλλικής πάστας, σε στερεό ηλεκτρολύτη YSZ, έναν αγωγό ιόντων Ο2-. Βρέθηκε πως η αύξηση του πάχους των υμενίων που χρησιμοποιούνται στις μελέτες ηλεκτροχημικής ενίσχυσης, προκαλεί μείωση στο λόγο προσαύξησης του ρυθμού, ρ, συμπεριφορά που βρίσκεται σε καλή συμφωνία με τις αναλυτικές προβλέψεις του μαθηματικού μοντέλου που περιγράφει την επιφανειακή διάχυση-αντίδραση των προωθητικών ειδών. Με βάση τις επιτυχείς μελέτες ηλεκτροχημικής ενίσχυσης που έχουν πραγματοποιηθεί σε λεπτά (40 nm), εναποτεθειμένα με τη μέθοδο της ιοντοβολής (sputtering) καταλυτικά υμένια, έγινε επέκταση της μελέτης της επίδρασης του πάχους σε τόσο λεπτά υμένια. Συγκεκριμένα, εξετάσθηκε η καταλυτική και η ηλεκτροχημικά ενισχυμένη συμπεριφορά πολύ λεπτών (30-90 nm) καταλυτικών υμενίων εναποτεθειμένων με τη μέθοδο του sputtering, τη μέθοδο Pulsed Laser Deposition και την τεχνική εναπόθεσης με ατμό (vapor deposition). Τιμές του λόγου προσαύξησης του ρυθμού, ρ, έως και 440 και τιμές φαρανταϊκής απόδοσης, Λ, έως και 1000 παρατηρήθηκαν για τα υμένια που εναποτέθηκαν με τη μέθοδο του sputtering. Η διασπορά μετάλλου στα υμένια αυτά είναι έως και 20%, συγκρίσιμη δηλαδή με αυτή των εμπορικών υποστηριγμένων καταλυτών. Τέλος, παρουσιάζεται η λειτουργία ενός πρόσφατα ανεπτυγμένου μονολιθικού ηλεκτροχημικά ενισχυόμενου αντιδραστήρα (MEPR), χρησιμοποιώντας την περιβαλλοντικού ενδιαφέροντος αντίδραση της αναγωγής του ΝΟ από αιθυλένιο παρουσία Ο2. Χρησιμοποιώντας καταλυτικά στοιχεία τύπου Pt-Rh(1:1)/YSZ/Au, παρουσία 10% Ο2 και σε ογκομετρικές παροχές έως και 1000 cc/min, ο αντιδραστήρας λειτούργησε επιδεικνύοντας τιμές φαρανταϊκής απόδοσης που ξεπερνούν τη μονάδα και επιτυγχάνοντας 50% και 44% προσαύξηση στους ρυθμούς μετατροπής του καυσίμου και του ΝΟ αντίστοιχα. Αυτή η μελέτη είναι η πρώτη που επιδεικνύει ηλεκτροχημική ενίσχυση της αντίδρασης αναγωγής του NO σε τόσο υψηλές τιμές μερικής πίεσης οξυγόνου (10% O2), που είναι αντιπροσωπευτικές για εξατμίσεις μηχανών πτωχού καυσίμου και μηχανών Diesel. Ο MEPR αποδεσμεύει το φαινόμενο NEMCA από την έως σήμερα χρήση του στην καθαρά εργαστηριακή κλίμακα και δείχνει πολλά υποσχόμενος για την πρακτική εφαρμογή του φαινομένου. / The effect of Electrochemical Promotion of Catalysis (EPOC or NEMCA effect) is a phenomenon where application of small currents or potentials (±2 V) alters the activity and selectivity of catalysts supported on ionic or mixed ionic-electronic conductors and modifies the electronic and thus catalytic properties in a controllable, reversible and to some extent predictable manner. The effect of catalyst film thickness on the magnitude of electrochemical promotion (ρ and Λ values) has not been studied experimentally so far but a mathematical model has been developed, accounting for surface diffusion and reaction of the promoting species, which predicts a strong variation of ρ and Λ with catalyst film thickness L. In the present thesis is examined for the first time experimentally the effect of catalyst film thickness on the magnitude of the EPOC, using porous Pt catalyst-electrodes prepared from Engelhard Pt paste with thicknesses in the range 0.2 to 1.4 μm. It was found that increasing the thickness of porous catalyst films used in electrochemical promotion studies causes a decrease in the rate enhancement ratio, ρ, due to the gradual axial decrease from the three-phase-boundaries to the top of the film of the surface concentration of the promoting backspillover O2- species which diffuse and react on the porous catalyst surface. Increasing film thickness causes a moderate increase in the Faradaic efficiency, Λ, which can be predicted by the parameter 2Fro/I0. The ρ and Λ behaviour is in good agreement with the analytical model prediction and provides additional support for the O2- promoter reaction-diffusion model and for the sacrificial promoter mechanism of electrochemical promotion. Most electrochemical promotion studies have been carried out so far with thick (0.1 μm to 5 μm) porous metal catalyst films with a roughness factor of the order of 500 and small (typically less than 0.1%) metal dispersion, deposited on solid electrolytes using a variety of deposition techniques. Very recently, electropromotion studies have been extended to thin (40 nm) sputter coated porous metal catalysts with metal dispersion of the order of 10 to 30%. The effect of thickness with such thin (30 to 90 nm) sputtered Pt catalyst-electrodes on the magnitude of electrochemical promotion is discussed, as well as the effect of the catalyst deposition method (Sputtering, Pulsed Laser Deposition and Vapor Deposition) using the model reaction of ethylene oxidation. Rate enhancement ratio, ρ, values up to 440 and Λ values up to 1000 where obtained for the sputtered films, in agreement with the sacrificial promoter and diffusion-reaction models of EPOC which predict increase in ρ value with thinner films. An environmental interest reaction, the reduction of NO by ethylene in the presence of excess oxygen, was investigated in a recently developed MEPR. In this novel dismantlable monolithic-type electrochemically promoted catalytic reactor, thin (~40 nm) porous catalyst films are sputter-deposited on thin (0.25 mm) parallel solid electrolyte plates supported in the grooves of a ceramic monolithic holder and serve as electropromoted catalyst elements. Using Pt-Rh(1:1)/YSZ/Au-type catalyst elements, the 8-plate reactor operated with apparent Faradaic efficiency exceeding unity achieving significant and reversible enhancement in the rates of C2H4 and NO consumption in presence of up to 10% O2 in the feed at gas flow rates up to 1000 cc/min. The Pt-Rh co-sputtered films exhibited very good performance in terms of stability and selectivity for N2 formation, i.e. practically 100% under all reaction conditions. The reactor, which is a hybrid between a monolithic catalytic reactor and a flat-plate solid oxide fuel cell, permits easy practical utilization of the electrochemical promotion of catalysis.