Doutorado em Química
URI Permanente para esta coleção
Nível: início
Ano de início: 2014
Conceito atual na CAPES: 5
Ato normativo: Homologação da 85ª Reunião do CTC-ES, Parecer CNE/CES nº 163/2005.
Processo nº 23001.000081/2005-56 do Ministério da Educação.
Publicado no DOU 28/07/2005, seção 1, página 11)
Periodicidade de seleção: Anual
Área(s) de concentração: Química
Url do curso: https://quimica.vitoria.ufes.br/pt-br/pos-graduacao/PPGQ/detalhes-do-curso?id=956/a>
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- ItemSolos e cafés: relações entre composição química, clima e qualidade(Universidade Federal do Espírito Santo, 2025-04-04) Frinhani, Roberta Quintino; Oliveira, Emanuele Catarina da Silva; https://orcid.org/0000-0003-0699-6104; http://lattes.cnpq.br/1715851915787164; Castro, Eustáquio Vinícius Ribeiro de; https://orcid.org/0000-0002-7888-8076; http://lattes.cnpq.br/1055263403980509; https://orcid.org/0000-0001-8713-4877; http://lattes.cnpq.br/7313374219256535; Dalmaschio, Cleocir José; https://orcid.org/0000-0002-3773-5786; http://lattes.cnpq.br/5209978120430790; Athayde, Geisamanda Pedrini Brandão; https://orcid.org/0000-0002-4315-0653; http://lattes.cnpq.br/8037324704189596; Rocha, Julia Tristão do Carmo; https://orcid.org/0000-0002-7484-0139; http://lattes.cnpq.br/6899104555589459; Berilli, Sávio da Silva; https://orcid.org/0000-0003-0554-8756; http://lattes.cnpq.br/1703547133505721Coffee quality results from the interaction between the chemical composition of beans and their sensory characteristics, influenced by factors such as climate, soil, and management. Understanding these factors is essential for establishing quality parameters and improving farming practices. This study aimed to chemically characterize soils and specialty coffee beans from Coffea arabica and C. canephora, from different Brazilian regions, using EDXRF, MIR, and NIR techniques with statistical modeling, to evaluate their contribution to beverage quality and the influence of environmental factors on composition. Data were integrated to assess the relationship between composition and beverage quality in C. arabica, while for C. canephora soils, the influence of environmental variables such as climate and geology was investigated. EDXRF identified Fe, Al, Ti, Zr, K, Ca, and Si as the main elements contributing to soil differentiation. In coffee beans, Ca, Mn, and Rb were prominent in green beans, whereas K, Ni, and Rb were more relevant in roasted beans. Tukey's tests revealed significant variations among sampling points, reflecting environmental and anthropogenic influences. In roasted coffees, a relative increase in elemental concentrations was observed due to mass loss during roasting, localized Ni presence possibly related to contamination, and reduction of volatile elements like sulfur. Pearson correlations showed positive associations between Al and Ga, and between Mg and K, and negative associations between Si and Al, Fe, and Ga. Regarding climate, precipitation was negatively correlated with Ga, Ag and Ca, and positively with Cu; temperature correlated negatively with Rb and Ca, while altitude had a positive correlation with Rb. Infrared spectral data allowed discrimination of soils and coffees based on chemical profiles, revealing bands of minerals (kaolinite, gibbsite, quartz), organic matter in the soil, and compounds like phenolics, caffeine, carbohydrates, and lipids in coffee. Roasting resulted in reductions in water, chlorogenic acids, caffeine, and carbohydrates compared to green beans, relative lipid preservation, and increased bands attributed to carbonyl compounds. Integration of chemical and sensory data did not reveal a direct relationship between soil composition and coffee quality. However, in green coffee, sulfur, Mn, Fe, chlorogenic acids, and lipid oxidation products showed negative correlations with beverage quality. In roasted coffee, sulfur, pyruvic and quinic acids, caffeine, pyridine, and fatty acids were also negatively correlated. Conversely, carbonyl compounds in green coffee, as well as aliphatic acids, esters, and lipids in roasted coffee, were positively associated with better sensory attributes. Results demonstrate that chemical characterization through spectroscopic techniques, combined with statistical modeling and data integration, enabled understanding of relationships between composition and beverage quality, especially in Coffea arabica. Furthermore, the influence of environmental factors on C. canephora soils was highlighted, reinforcing the potential of rapid, sustainable spectroscopic methods to support understanding of coffee quality and improve agricultural management.
- ItemCatalisadores heterogêneos suportados em materiais de carbono porosos partindo de rejeitos de uma rocha ornamental carbonática : preparação, caracterização e aplicação para obtenção de biodiesel(Universidade Federal do Espírito Santo, 2025-03-27) Aleixo, Fábio da Costa; Silveira, Leonardo Luiz Lyrio da; http://lattes.cnpq.br/5020611563370937; Freitas, Jair Carlos Checon de ; https://orcid.org/0000-0002-4474-2474; http://lattes.cnpq.br/3074997830683878; https://orcid.org/0000-0001-5554-5575; http://lattes.cnpq.br/5940065747018743; Labat, Gisele Aparecida Amaral ; https://orcid.org/0000-0003-3745-6119; http://lattes.cnpq.br/9764742132401600; Zagôto, Juliano Tessinari ; https://orcid.org/0000-0002-2878-4615; http://lattes.cnpq.br/8321874088120679; Machado, Marta Albuquerque ; https://orcid.org/0000-0001-8335-3351; http://lattes.cnpq.br/5991893415892784; Santos, Reginaldo Bezerra dos ; https://orcid.org/0000-0003-2966-7231; http://lattes.cnpq.br/6265396050660132The processing of carbonate rocks generates substantial amounts of waste, which are frequently mismanaged—either discarded into the environment or irregularly deposited in landfills—posing significant environmental concerns. This study explores the synthesis of heterogeneous catalysts supported on a carbonaceous matrix, using carbonate ornamental stone tailings (OST) as a low-cost source of calcium and magnesium oxides. Various chemicals routes were initially evaluated, with all materials subjected to thermal treatment at 800 °C for 3 hours under an inert atmosphere. Among them, the wet impregnation method involved mixing OST and coconut shell-activated carbon (CSAC) powders with a NaOH solution under constant stirring. In a subsequent step, the synthesis parameters for this method were optimized using a full factorial experimental design. The catalytic performance of the resulting materials was assessed in the transesterification of soybean oil with methanol for biodiesel production. Conversion efficiency was monitored and quantified by proton nuclear magnetic resonance spectroscopy in solution. Among the tested synthesis routes, wet impregnation yielded the highest conversion rates. In the optimization study, a maximum conversion of 85% was achieved using an OST/CSCA mass ratio of 50:20, followed by thermal treatment at 800 °C for 1 hour. Further optimization of the reaction conditions, performed via a central composite design, led to a maximum biodiesel yield of 91% under the following conditions: 5 wt% catalyst loading (relative to oil mass), 3 hours of reaction time, and a temperature of 60 °C. The catalysts demonstrated excellent activity, attributed to the formation of CaO, MgO, Na₂CO₃, and Na₂CO₃·CaCO₃ phases, as confirmed by X-ray diffraction, depending on the thermal treatment parameters. Analysis of the Ca and Mg content in the biodiesel revealed significantly reduced metal leaching when CACO was used as the support, with concentrations remaining below or only slightly above the 5.0 mg/kg threshold established by the European standard EN 14214. These findings confirm the feasibility of employing OST and coconut shells as sustainable feedstocks for the development of efficient, carbon-supported heterogeneous catalysts. The wet impregnation route emerged as the most effective strategy for depositing calcium and magnesium oxides onto the CSCA matrix, offering both economic and environmental advantages due to its reliance on waste-derived materials and minimal generation of secondary residues
- ItemRemoção do corante preto reativo 5 em solução aquosa por adsorção e/ou oxidação eletroquímica(Universidade Federal do Espírito Santo, 2025-02-27) Paquini, Lucas Destefani; Profeti, Demetrius ; https://orcid.org/0000-0003-4565-3331; http://lattes.cnpq.br/5030262115789096; Ribeiro, Josimar ; https://orcid.org/0000-0002-9544-1647; http://lattes.cnpq.br/1265145498501171; https://orcid.org/0000-0003-1285-8031; http://lattes.cnpq.br/3239593331960071; Lima, Fabio Henrique Barros de ; https://orcid.org/0000-0001-5501-2429; http://lattes.cnpq.br/8978509213666235; Costa, Carla Regina ; https://orcid.org/0000-0002-7057-6393; http://lattes.cnpq.br/0088443679133064; Cestarolli, Dane Tadeu ; https://orcid.org/0000-0003-1453-9499; http://lattes.cnpq.br/6247805873454988; Ferreira, Rafael de Queiroz ; https://orcid.org/0000-0002-5190-8508; http://lattes.cnpq.br/5053247764430323The expansion of the textile sector has played a fundamental role in accelerating industrialization on a global scale. However, this industry has caused significant environmental impacts, particularly due to the improper disposal of effluents with high contamination loads, including azo dyes, with reactive black 5 (RB-5) being one of the most concerning. Thus, the search for effective decontamination methods is essential, among which adsorption and electrochemical advanced oxidation processes stand out as promising strategies for the removal of these pollutants. This study investigated adsorption and electrochemical oxidation applied to RB-5 removal in synthetic effluents. In the adsorption process, a C/TiO2 composite was developed and characterized. X-ray diffraction (XRD) analysis indicated that both the composite and the TiO₂ support predominantly exhibited anatase phases. Scanning electron microscopy (SEM) revealed morphological changes in the material after adsorption. The specific surface area of the adsorbent was approximately 54.24 m2 g–1, while Fourier-transform infrared spectroscopy (FTIR) confirmed the presence of various functional groups, some of which were related to the dye structure after adsorption. The point of zero charge (pHPZC) indicated favorable adsorption conditions for pH ≤ 7.47. After fitting to nonlinear equations, the Sips model best described the adsorption equilibrium. On the other hand, the adsorption kinetics followed the Avrami fractional order model, suggesting an adsorption governed by multiple stages. Thermodynamically, adsorption was classified as endothermic, entropy-controlled, and exergonic. The electrochemical oxidation process involved the development and characterization of dimensionally stable anode (DSA) with the Ti/IrO2-SnO2-Ta2O5 configuration. XRD analysis of the electrodes revealed characteristic phases of IrO2, SnO2, Ti, and Ta2O5, while SEM images displayed the typical "cracked mud" morphology. Cyclic voltammetry (H2SO4) evidenced the capacitive behavior of the electrodes, with a roughness factor ranging from 0.3260 to 0.6812. Electrochemical mass spectrometry (EC-MS) confirmed the predominance of electrogenerated molecular chlorine (Cl2) over the oxygen evolution reaction, especially under high Sn/Ta ratios and acidic pH conditions. Ion chromatography (IC) allowed the quantification of Cl⁻ and ClO⁻, while electrochemical impedance spectroscopy (EIS) evidenced that Cl₂/HOCl formation occurs at potentials above 1.25 V vs. Ag/AgCl, with lower charge transfer resistance (Rtc) in compositions containing up to 10% Ta. The chemical and structural stability of the electrodes was confirmed by the nearly constant solution resistance (Rs) and double-layer capacitance (Cdl), which indicated rough and porous surfaces. The RB-5 dye degradation process was efficient, with apparent rate constants ranging from 0.00121 to 0.00571 s–1, being most effective in the Ir/Sn/Ta 30:70:00, 30:65:05, and 30:60:10 electrodes. The chemical oxygen demand (COD) removal varied between 71.72% and 32.47%, and energy consumption was lower (0.482 kWh m–3) for compositions with lower Ta content. The results highlight the feasibility of both techniques (adsorption and electrochemical oxidation) for the treatment of industrial effluents containing dyes
- ItemSíntese e caracterização de complexos de cobalto com potencial para investigação da tautomeria de valência(Universidade Federal do Espírito Santo, 2024-08-06) Pavan, Jamile Rocha; Ribeiro, Marcos Antônio; https://orcid.org/0000-0002-9350-6419; Simões, Tatiana Renata Gomes; Cassaro, Rafael Alves Allão; Franco, Maurício Portiolli; Dalmaschio, Cleocir JoséSystems capable of switching between two or more different electronic states as a result of external stimuli are of great interest for the development of materials with specific properties that can be used in the construction of molecular electronic devices. In this context, bistable compounds that exhibit valence tautomerism (VT) – a reversible intramolecular electron transfer phenomenon – stand out. Among these compounds, cobalt o-dioxolene derivatives have been widely investigated, where electron transfer occurs from the catecholate ligand to the low-spin cobalt(III) ion, forming a high-spin cobalt(II) ion coordinated to a paramagnetic semiquinonate ligand. In light of this, the objective of this research was to synthesize new dinuclear cobalt compounds containing tetradentate nitrogenous ligands, such as N,N’-bis(2-pyridylmethyl)-1,2-diaminoethane (py2en), N,N’-bis(2-pyridylmethyl)-1,3 diaminopropane (1,3-py2pn), and N,N’-bis(2-pyridylmethyl)-1,2-iaminopropane (1,2py2pn) in order to investigate the VT phenomenon. To this end, in addition to the tetradentate nitrogenous ligands, redox-active ligands 2,5-dihydroxy-1,4 benzoquinone (DHBQH2) and 3,3,3',3'-tetramethyl-1,1'-spiro-bis-indane-5,5',6,6' tetrol (spiroH4) were also used. The nitrogenous ligands py2en, 1,3-py2pn, 1,2-py2pn, and the redox-active ligand DHBQH2 were synthesized and characterized by infrared (IR) spectroscopy, mass spectrometry (MS), and proton nuclear magnetic resonance (1H NMR). The synthesis and characterization of two compounds with nitrogenous ligands (1,3-py2pn or py2en) and the DHBQH2 ligand revealed, through IR and X-ray diffraction analyses, the formation of mononuclear cobalt(III) systems, [Co(DHBQ)(1,3-py2pn)]PF6 and [Co(DHBQ)(py2en)]BF4, instead of the proposed dinuclear compound. For the compounds synthesized from the spiroH4 ligand, characterization by IR, UV-vis, electrical conductivity, and X-ray diffraction on single crystal samples indicated the formation of the suggested dinuclear systems. In addition to the intended compounds, two new cobalt compounds were synthesized and characterized: [Co(bpy)(1,3-py2pn)](BF4)3 and [Co(phen)3](NO3)2·2H2O. Finally, the synthesis of new cobalt-o-dioxolene systems in this study offers a significant contribution to future studies of the VT phenomenon, standing out as promising models to investigate VT in both mononuclear and dinuclear compounds.
- ItemAvaliação da qualidade de águas superficiais: uma abordagem local com proposta de mitigação por adsorção em fase sólida(Universidade Federal do Espírito Santo, 2024-12-17) Rocha, Ana Kelly Simões; Costa, Vinicius Câmara; Lima, Maria Tereza Weitzel Dias Carneiro de; https://orcid.org/0000-0002-8731-5093; Rosa, Thalles Ramon; Costa, Eline Nayara Dantas da; Costa, José Arnaldo Santana; Athayde, Geisamanda Pedrini BrandãoThe assessment of surface water quality through continuous monitoring has received increased attention in recent years due to the increasing degradation of aquatic environments. This monitoring is essential to support Contaminated Area Management (CAM) studies, which include important steps such as the preliminary and detailed assessment of aquatic environments. The deltaic region of the Doce River, a floodplain highly vulnerable to contamination, is affected by mining, agricultural and industrial activities, and possibly by the effects of the Fundão dam collapse in 2015. Thus, the city of Degredo, which belongs to the deltaic region, was addressed in a specific case study, which identified high concentrations of Al, Ba, B, Co, Fe, P, Mn, Ni and Zn in the waters of points P1 and P3, above the CONAMA 357/2005 and IRMA legislation, constituting Potentially Toxic Elements (PTEs). A simulated Human Health Risk Assessment (HHRA) at this site ranged from "insignificant" to "low", with water ingestion as the main route of exposure. In addition, analyses showed that contamination levels increased after the dam breach (IPTTh between 0.40 and 23.73), contrary to the expected trend. The adsorption process was used as an alternative for the remediation of water contaminated by EPTs, using the CA-CaCO3 adsorbent, synthesised by dispersing CaCO3 on a porous carbon support derived from biomass. This material contained 12 wt% of nanocrystalline CaCO3 particles. The adsorbent and pure CA showed high efficiency, removing 99.9% of Fe2+, Mn2+, Cd2+, Ni2+, Zn2+ and Pb2+ ions in 20 min under optimised conditions (pH = 6.00 and adsorbent mass = 100 mg). Structural and chemical analyses (XRD, TG, SEM-EDX, mapping and ICP-OES) of CA and CA-CaCO3 helped to understand the structural and chemical characteristics of these materials, while kinetic and isothermal analyses showed that the process occurs by chemisorption. Thus, this work is linked to concepts of risk management, sustainability and circular economy, and provides an efficient and cost-effective alternative for the remediation of water contaminated by EPTs.