Título: | MICROFABRICATION OF POLYMERIC AND LIGNOCELLULOSIC REACTORS FOR PHOTOCATALYSIS AND CONTINUOUS FLOW CUAAC REACTION | ||||||||||||
Autor: |
DRUVAL SANTOS DE SA |
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Colaborador(es): |
OMAR GINOBLE PANDOLI - Orientador |
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Catalogação: | 07/JAN/2021 | Língua(s): | PORTUGUESE - BRAZIL |
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Tipo: | TEXT | Subtipo: | THESIS | ||||||||||
Notas: |
[pt] Todos os dados constantes dos documentos são de inteira responsabilidade de seus autores. Os dados utilizados nas descrições dos documentos estão em conformidade com os sistemas da administração da PUC-Rio. [en] All data contained in the documents are the sole responsibility of the authors. The data used in the descriptions of the documents are in conformity with the systems of the administration of PUC-Rio. |
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Referência(s): |
[pt] https://www.maxwell.vrac.puc-rio.br/projetosEspeciais/ETDs/consultas/conteudo.php?strSecao=resultado&nrSeq=51184&idi=1 [en] https://www.maxwell.vrac.puc-rio.br/projetosEspeciais/ETDs/consultas/conteudo.php?strSecao=resultado&nrSeq=51184&idi=2 |
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DOI: | https://doi.org/10.17771/PUCRio.acad.51184 | ||||||||||||
Resumo: | |||||||||||||
The present work had two main objectives. The first refers to the development of polydimethylsiloxane photocatalytic microreactors (PDMS) for the comparative scale-up study between micro- and mesoreactors. The second focused on the development of bamboo lignocellulosic microreactors for copper(I) catalyzed alkine-azide cycloaddition reaction (CuAAC). In this scenario, an experimental scale-up and numbering-up configuration of photocatalytic meso- and microfluidic systems were developed, to compare, respectively, the photodegradation efficiency of TiO2-P25 in rhodamine B (RB) and methylene blue (MB) under UV irradiation. The obtained results suggest that the scale-up reduces the values of D (percent), while numbering-up maintains the photocatalytic efficiency with a significant reaction time reduction. The best photocatalytic microfluidic system was M6-60 (micro)L, which presented total MB degradation (1.2 x 10-5 mol L-1) in only 1h, and total phenol photo-oxidation (1,2 x 10-4 mol L-1) in 4h. Furthermore, M6-60 (micro)LM6 had lower electrical energy consumption (0,012 kWh m-3) and higher quantum yield (2,6 x 10-2) compared to others. The development of solid lignocellulosic supports showed important characteristics for the TEMPO-TAL functionalization processes with Cu(II), Zn(II) ions and CuNPs. The supports were properly characterized by SEM/ EDS and FT-IR. The results for the CuAAC reaction showed yields of 79-82 percent with recyclability of up to 7 times and average copper leaching of 1.30 ppm, and were important for the development of the bamboo microreactor. The microfabrication of the bamboo lignocellulosic microreactor (L(micro)R) was performed from cutting steps, without using expensive techniques and clean room. L(micro)R showed easy prototyping and rapid oxidation with N-oxyl-2,2,6,6-tetramethylpiperidine (TEMPO) and functionalization with copper ions (Cu-L(micro)R) and copper nanoparticles (CuNPs-L(micro)R). Cu-L(micro)R continuous flow CuAAC performance was demonstrated by conducting recyclability and yield studies at different flow rates (0.1 to 0.8 mL-1). Cu-L(micro)R presented 60 percent to 96 percent yields for 5 types of CuAAC reactions, indicating promising application in the area of catalysis in microfluidic devices. All reactions were performed under a MeOH:H2O (2:1) flow regime and copper leaching below 6.0 ppm, producing a series of 5 efficiently 1,4-disubstituted 1,2,3-triazols derivatives in a resource-poor environment. CuNPs-L(micro)R presented limitation for CuAAC because it did not reach the ideal heating conditions required for the reaction to occur.
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