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Book Chapter
Lyubchik, S, Lygina E, Lyubchyk A, Lyubchik S, Loureiro JM, Fonseca IM, Ribeiro AB, Pinto MM, Figueiredo AMSá.  2016.  The Kinetic Parameters Evaluation for the Adsorption Processes at ``Liquid–Solid'' Interface. Electrokinetics Across Disciplines and Continents: New Strategies for Sustainable Development. (Ribeiro, Alexandra B., Mateus, Eduardo P., Couto, Nazaré, Eds.).:81–109., Cham: Springer International Publishing Abstract

The kinetic parameters of the adsorption process at ``liquid–solid'' interface have been evaluated through the sets of time-based experiments of the Cr(III) adsorption under varying temperature, initial metal concentration, and carbon loading for two sets of the commercially available activated carbons and their post-oxidized forms with different texture and surface functionality.

Journal Article
Godino-Ojer, M, Matos I, Bernardo M, Carvalho R, G.P. Soares OS, Durán-Valle C, Fonseca IM, Mayoral PE.  2020.  Acidic porous carbons involved in the green and selective synthesis of benzodiazepines. Catalysis Today. 357:64-73. AbstractWebsite

Eco-sustainable and recyclable porous carbons are reported as metal-free catalysts for the synthesis of benzodiazepines for the first time. The porous carbons were able to efficiently catalyse the synthesis of benzodiazepine 1 from o-phenylendiamine 2 and acetone 3 under mild conditions. Both acidic functions and the porosity of the catalysts were determinant features. High conversion values were obtained when using HNO3 oxidized carbons. The highest selectivity to benzodiazepine 1 was obtained in the presence of the most microporous catalyst N-N, which is indicative of the great influence of porous properties. Stronger acid sites and high microporosity of the carbon treated with H2SO4 yield benzodiazepine 1 with total selectivity.

Dias, D, Bernardo M, Lapa N, Pinto F, Matos I, Fonseca I.  2018.  Activated carbons from the Co-pyrolysis of rice wastes for Cr(III) removal. Chemical Engineering Transactions. 65:601-606.
Dias, D, Bernardo M, Matos I, Fonseca I, Pinto F, Lapa N.  2020.  Activation of co-pyrolysis chars from rice wastes to improve the removal of Cr3+ from simulated and real industrial wastewaters. Journal of Cleaner Production. 267:121993. AbstractWebsite

Chromium is one of the most important raw materials for the European Union. Adsorption has become an important process for the recovery of metals from wastewaters, which has led to a demand for low-cost and eco-friendly adsorbents. The objective of this work was to use new and renewable carbon-based adsorbents from rice wastes in the removal/recovery of Cr(III) from synthetic and real wastewaters. Rice wastes were submitted to co-pyrolysis and the resulting char was optimized through physical and/or chemical activations/treatments. A commercial activated carbon was used for comparison purposes. All adsorbents were characterized (including an ecotoxicity test for the char precursor) and submitted to Cr(III) removal assays from a synthetic solution, in which two solid/liquid ratios (S/L) were tested (5 and 10 g/L). The CO2 activated carbon at a S/L = 5 g/L was the biomass-derived adsorbent that performed better, obtaining a maximum Cr(III) uptake capacity of 9.23 mg/g comparable to the one obtained by the commercial adsorbent at the same S/L (9.80 mg/g). The good results on this biomass-derived carbon were due to the effective volatile matter removal during the activation (from 22.7 to 4.25% w/w), which increased both surface area (from <5.0 to 325 m2/g) and ash content (from 30.0 to 40.4% w/w), allowing an increase in Cr(III) removal due to ion exchange mechanism and porosity development. The best adsorbent, under optimized conditions, was also applied to a chromium rich industrial wastewater. The results obtained in this real case application demonstrated a competition effect due to the presence of other ions.

Rodrigues, ARF, Maia MRG, Cabrita ARJ, Oliveira HM, Bernardo M, Lapa N, Fonseca I, Trindade H, Pereira JL, Fonseca AJM.  2020.  Assessment of potato peel and agro-forestry biochars supplementation on in vitro ruminal fermentation. PeerJ. 8:e9488. AbstractWebsite

Background The awareness of environmental and socio-economic impacts caused by greenhouse gas emissions from the livestock sector leverages the adoption of strategies to counteract it. Feed supplements can play an important role in the reduction of the main greenhouse gas produced by ruminants—methane (CH\textsubscript{4}). In this context, this study aims to assess the effect of two biochar sources and inclusion levels on rumen fermentation parameters \textit{in vitro}. Methods Two sources of biochar (agro-forestry residues, AFB, and potato peel, PPB) were added at two levels (5 and 10%, dry matter (DM) basis) to two basal substrates (haylage and corn silage) and incubated 24-h with rumen inocula to assess the effects on CH\textsubscript{4} production and main rumen fermentation parameters \textit{in vitro}. Results AFB and PPB were obtained at different carbonization conditions resulting in different apparent surface areas, ash content, pH at the point of zero charge (pHpzc), and elemental analysis. Relative to control (0% biochar), biochar supplementation kept unaffected total gas production and yield (mL and mL/g DM, \textit{p} = 0.140 and \textit{p} = 0.240, respectively) and fermentation pH (\textit{p} = 0.666), increased CH\textsubscript{4}production and yield (mL and mL/g DM, respectively, \textit{p} = 0.001) and ammonia-N (NH\textsubscript{3}-N, \textit{p} = 0.040), and decreased total volatile fatty acids (VFA) production (\textit{p} < 0.001) and H\textsubscript{2} generated and consumed (\textit{p} ≤ 0.001). Biochar sources and inclusion levels had no negative effect on most of the fermentation parameters and efficiency. Acetic:propionic acid ratio (\textit{p} = 0.048) and H\textsubscript{2} consumed (\textit{p} = 0.019) were lower with AFB inclusion when compared to PPB. Biochar inclusion at 10% reduced H\textsubscript{2} consumed (\textit{p} < 0.001) and tended to reduce total gas production (\textit{p} = 0.055). Total VFA production (\textit{p} = 0.019), acetic acid proportion (\textit{p} = 0.011) and H\textsubscript{2} generated (\textit{p} = 0.048) were the lowest with AFB supplemented at 10%, no differences being observed among the other treatments. The basal substrate affected most fermentation parameters independently of biochar source and level used. Discussion Biochar supplementation increased NH\textsubscript{3}-N content, \textit{iso}-butyric, \textit{iso}-valeric and valeric acid proportions, and decreased VFA production suggesting a reduced energy supply for microbial growth, higher proteolysis and deamination of substrate N, and a decrease of NH\textsubscript{3}-N incorporation into microbial protein. No interaction was found between substrate and biochar source or level on any of the parameters measured. Although AFB and PPB had different textural and compositional characteristics, their effects on the rumen fermentation parameters were similar, the only observed effects being due to AFB included at 10%. Biochar supplementation promoted CH\textsubscript{4} production regardless of the source and inclusion level, suggesting that there may be other effects beyond biomass and temperature of production of biochar, highlighting the need to consider other characteristics to better identify the mechanism by which biochar may influence CH\textsubscript{4} production.

Cordeiro, T, Paninho AB, Bernardo M, Matos I, Pereira CV, Serra AT, Matias A, Ventura MG.  2020.  Biocompatible locust bean gum as mesoporous carriers for naproxen delivery. Materials Chemistry and Physics. 239:121973. AbstractWebsite

The work reports the impregnation of naproxen into locust bean gum mesoporous matrixes with different textural properties. The matrixes were prepared through the dissolution of the biopolymer in water and in two ionic liquids (ILs): [bmim][Cl] and [C2OHmim][Cl] and dried with scCO2. The poor water-soluble pharmaceutical drug naproxen was loaded into the matrixes and the composites were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy and by differential scanning calorimetry; the results were compared with neat ILs and drug. The naproxen release from the matrixes was attempted at pH 7.4. Sustained release of naproxen in the different composites occurs, and consequently the naproxen release has lower rates compared with neat crystalline naproxen dissolution. Nevertheless, it was possible to observe small differences on release profiles for the studied composites. The higher release rate was observed for the composite where [bmim][Cl] was used as solvent, for which the calorimetric analysis revealed full amorphization of the incorporated drug. Cytotoxicity assays reveal that cellular viability in Caco-2 cells is preserved. This fact allied with the biocompatibility of locust bean gum allow for the composites potential application as naproxen controlled/sustained delivery systems with higher drug bioavailability achieved through naproxen amorphization.

Batista, MKS, Mestre AS, Matos I, Fonseca IM, Carvalho AP.  2016.  Biodiesel production waste as promising biomass precursor of reusable activated carbons for caffeine removal. RSC Adv.. 6:45419-45427.: The Royal Society of Chemistry AbstractWebsite

Biodiesel production generates low particle size rapeseed waste (recovered from warehouse air filtration systems) that was herein explored as promising biomass precursor of chemically activated carbons. The influence of several experimental parameters on the porosity development was investigated. No benefit was observed when solution impregnation was made nor a significant dependence of the biomass : K2CO3 ratio was observed and{,} as expected{,} high porosity development was obtained only for treatments at 700 [degree]C. Microporous materials with apparent surface area around 1000 m2 g-1 were obtained comparing favorably with literature data regarding activated carbons from rapeseed processing by-products. A selected lab-made sample and two commercial carbons were tested as adsorbents of caffeine from aqueous solution. Although commercial materials present a quicker adsorption rate{,} regarding adsorption capacity the lab-made sample reaches the same value attained by a benchmark material. The regeneration tests made over the rapeseed derived carbon through heat treatments at 600 [degree]C for 1 hour under N2 flow proved that at least two exhaustion-regeneration cycles can be made since the material retains a caffeine adsorption capacity similar to that of the fresh carbon. Therefore{,} a waste management problem of biodiesel industry - rapeseed residue - can be transformed in a valuable material with promising properties for environmental remediation processes.

Surra, E, Bernardo M, Lapa N, Esteves IAAC, Fonseca I, Mota JPB.  2019.  Biomethane production through anaerobic co-digestion with Maize Cob Waste based on a biorefinery concept: A review. Journal of Environmental Management. 249:109351. AbstractWebsite

Maize Cob Waste (MCW) is available worldwide in high amounts, as maize is the most produced cereal in the world. MCW is generally left in the crop fields, but due to its low biodegradability it has a negligible impact in soil fertility. Moreover, MCW can be used as substrate to balance the C/N ratio during the Anaerobic co-Digestion (AcoD) with other biodegradable substrates, and is an excellent precursor for the production of Activated Carbons (ACs). In this context, a biorefinery is theoretically discussed in the present review, based on the idea that MCW, after proper pre-treatment is valorised as precursor of ACs and as co-substrate in AcoD for biomethane generation. This paper provides an overview on different scientific and technological aspects that can be involved in the development of the proposed biorefinery; the major topics considered in this work are the following ones: (i) the most suitable pre-treatments of MCW prior to AcoD; (ii) AcoD process with regard to the critical parameters resulting from MCW pre-treatments; (iii) production of ACs using MCW as precursor, with the aim to use these ACs in biogas conditioning (H2S removal) and upgrading (biomethane production), and (iv) an overview on biogas upgrading technologies.

Nogueira, M, Matos I, Bernardo M, Pinto F, Lapa N, Surra E, Fonseca I.  2019.  Char from Spent Tire Rubber: A Potential Adsorbent of Remazol Yellow Dye. C—Journal of Carbon Research. 5, Number 4 AbstractWebsite

A char produced from spent tire rubber showed very promising results as an adsorbent of Remazol Yellow (RY) from aqueous solutions. Spent tire rubber was submitted to a pyrolysis process optimized for char production. The obtained char was submitted to chemical, physical, and textural characterizations and, subsequently, applied as a low-cost adsorbent for dye (RY) removal in batch adsorption assays. The obtained char was characterized by relatively high ash content (12.9% wt), high fixed-carbon content (69.7% wt), a surface area of 69 m2/g, and total pore volume of 0.14 cm3/g. Remazol Yellow kinetic assays and modelling of the experimental data using the pseudo-first and pseudo-second order kinetic models demonstrated a better adjustment to the pseudo-first order model with a calculated uptake capacity of 14.2 mg RY/g char. From the equilibrium assays, the adsorption isotherm was fitted to both Langmuir and Freundlich models; it was found a better fit for the Langmuir model to the experimental data, indicating a monolayer adsorption process with a monolayer uptake capacity of 11.9 mg RY/g char. Under the experimental conditions of the adsorption assays, the char presented positive charges at its surface, able to attract the deprotonated sulfonate groups (SO3−) of RY; therefore, electrostatic attraction was considered the most plausible mechanism for dye removal.

Dias, D, Lapa N, Bernardo M, Ribeiro W, Matos I, Fonseca I, Pinto F.  2018.  Cr(III) removal from synthetic and industrial wastewaters by using co-gasification chars of rice waste streams. Bioresource Technology. 266:139-150. AbstractWebsite

Blends of rice waste streams were submitted to co-gasification assays. The resulting chars (G1C and G2C) were characterized and used in Cr(III) removal assays from a synthetic solution. A Commercial Activated Carbon (CAC) was used for comparison purposes. The chars were non-porous materials mainly composed by ashes (68.3–92.6% w/w). The influences of adsorbent loading (solid/liquid ratio – S/L) and initial pH in Cr(III) removal were tested. G2C at a S/L of 5 mg L−1 and an initial pH of 4.50 presented an uptake capacity significantly higher than CAC (7.29 and 2.59 mg g−1, respectively). G2C was used in Cr(III) removal assays from an industrial wastewater with Cr(III) concentrations of 50, 100 and 200 mg L−1. Cr(III) removal by precipitation (uptake capacity ranging from 11.1 to 14.9 mg g−1) was more effective in G2C, while adsorption (uptake capacity of 16.1 mg g−1) was the main removal mechanism in CAC.

Surra, E, Bernardo M, Lapa N, Esteves IAAC, Fonseca I, Mota JP.  2018.  Enhanced Biogas Production through Anaerobic co-Digestion of OFMSW with Maize Cob Waste Pre-Treated with Hydrogen Peroxide. Chemical Engineering Transactions. 65:121-126.
Godino-Ojer, M, Milla-Diez L, Matos I, Durán-Valle CJ, Bernardo M, Fonseca IM, Pérez Mayoral E.  2018.  Enhanced Catalytic Properties of Carbon supported Zirconia and Sulfated Zirconia for the Green Synthesis of Benzodiazepines. ChemCatChem. 10:5215-5223., Number 22 AbstractWebsite

Abstract This work reports for the first time a new series of promising porous catalytic carbon materials, functionalized with Lewis and Brønsted acid sites useful in the green synthesis of 2,3-dihydro-1H-1,5-benzodiazepine – nitrogen heterocyclic compounds. Benzodiazepines and derivatives are fine chemicals exhibiting interesting therapeutic properties. Carbon materials have been barely investigated in the synthesis of this type of compounds. Two commercial carbon materials were selected exhibiting different textural properties: i) Norit RX3 (N) as microporous sample and ii) mesoporous xerogel (X), both used as supports of ZrO2 (Zr) and ZrO2/SO42− (SZr). The supported SZr led to higher conversion values and selectivities to the target benzodiazepine. Both chemical and textural properties influenced significantly the catalytic performance. Particularly relevant are the results concerning the non-sulfated samples, NZr and XZr, that were able to catalyze the reaction leading to the target benzodiazepine with high selectivity (up to 80 %; 2 h). These results indicated an important role of the carbon own surface functional groups, avoiding the use of H2SO4. Even very low amounts of SZr supported on carbon reveal high activity and selectivity. Therefore, the carbon materials herein reported can be considered an efficient and sustainable alternative bifunctional catalysts for the benzodiazepine synthesis.

Mestre, AS, Nabiço A, Figueiredo PL, Pinto ML, Santos SMCS, Fonseca IM.  2016.  Enhanced clofibric acid removal by activated carbons: Water hardness as a key parameter. Chemical Engineering Journal. 286:538-548. AbstractWebsite

Clofibric acid is the metabolite and active principle of blood lipid regulators, it represents the class of acidic pharmaceuticals, and is one of the most persistent drug residues detected in the aquatic environment worldwide. This interdisciplinary work evaluates the effect of solution pH and water hardness in clofibric acid adsorption onto commercial activated carbons. Kinetic and equilibrium assays revealed that the highest clofibric acid removal efficiencies (>70%) were attained at pH 3, and that at pH 8 water hardness degree plays a fundamental role in the adsorption process. In hard water at pH 8 the removal efficiency values increased by 22 or 46% points depending on the carbon sample. Adsorbents’ textural properties also affect the adsorption process since for the microporous sample (CP) the increase of water hardness has a great influence in kinetic and equilibrium data, while for the micro+mesoporous carbon (VP) the variation of the water hardness promoted less significant changes. At pH 3 the increase of water hardness leads to changes in the adsorption mechanism of clofibric acid onto CP carbon signaled by a transition from an S-type to an L-type curve. At pH 8 the change from deionized water to hard water doubles the maximum adsorption capacity of sample CP (101.7mgg−1 vs 211.9mgg−1, respectively). The adsorption enhancement, with water hardness under alkaline conditions, was reasoned in terms of calcium complexation with clofibrate anion exposed by molecular modeling and conductivity studies. Ca2+ complexation by other acidic organic compounds may also occur, and should be considered, since it can play a fundamental role in improved design of water treatment processes employing activated carbons.

Silva, CAC, Figueiredo FCA, Rodrigues R, Sairre MI, Gonçalves M, Matos I, Fonseca IM, Mandelli D, Carvalho WA.  2016.  Enhancing the biodiesel manufacturing process by use of glycerin to produce hyacinth fragrance, Jun. Clean Technologies and Environmental Policy. 18:1551–1563., Number 5 AbstractWebsite

Oxidized and sulfonated-activated carbons (AC) were tested in the catalytic conversion of glycerol by acetalization reactions. The solids were treated with concentrated nitric acid and/or fuming sulfuric acid (AC, AC-N, AC-S, and AC-NS). The presence of sulfur and an increase in the acidity of the solids demonstrate the suitability of the oxidation as well as the sulfonation process, especially in the sample treated with concentrated nitric acid and fuming sulfuric acid (AC-NS). The best catalyst for the reaction of glycerol acetalization with phenylacetaldehyde was AC-NS, with a phenylacetaldehyde conversion of 95 {%} after 90 min at 383 K and selectivity of 88 and 12 {%}, respectively, to dioxolane and dioxane. These products can be used as hyacinth fragrance flavoring compounds. Furthermore, a contribution of homogeneous catalysis in these systems was not identified. Thus, we identified a possibility of glycerol conversion, a biodiesel by-product, into value-added products by suitable catalysts produced from activated carbons.

Fernandes, MJ, Moreira MM, Paíga P, Dias D, Bernardo M, Carvalho M, Lapa N, Fonseca I, Morais S, Figueiredo S, Delerue-Matos C.  2019.  Evaluation of the adsorption potential of biochars prepared from forest and agri-food wastes for the removal of fluoxetine. Bioresource Technology. 292:121973. AbstractWebsite

Twelve biochars from forest and agri-food wastes (pruning of Quercus ilex, Eucalyptus grandis, Pinus pinaster, Quercus suber, Malus pumila, Prunus spinosa, Cydonia oblonga, Eriobotrya japonica, Juglans regia, Actinidia deliciosa, Citrus sinensis and Vitis vinifera) were investigated as potential low-cost and renewable adsorbents for removal of a commonly used pharmaceutical, fluoxetine. Preliminary adsorption experiments allowed to select the most promising adsorbents, Quercus ilex, Cydonia oblonga, Eucalyptus, Juglans regia and Vitis vinifera pruning material. They were characterized by proximate, elemental and mineral analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, determination of specific surface area and pH at the point of zero charge. Batch and equilibrium studies were performed, and the influence of pH was evaluated. The equilibrium was reached in less than 15 min in all systems. The maximum adsorption capacity obtained was 6.41 mg/g for the Eucalyptus biochar, which also demonstrated a good behavior in continuous mode (packed column).

Bernardo, M, Rodrigues S, Lapa N, Matos I, Lemos F, Batista MKS, Carvalho AP, Fonseca I.  2016.  High efficacy on diclofenac removal by activated carbon produced from potato peel waste, Aug. International Journal of Environmental Science and Technology. 13:1989–2000., Number 8 AbstractWebsite

In the present study, a novel porous carbon obtained by K2CO3 activation of potato peel waste under optimized conditions was applied for the first time as liquid-phase adsorbent of sodium diclofenac in parallel with a commercial activated carbon. The biomass-activated carbon presented an apparent surface area of 866 m2 g−1 and well-developed microporous structure with a large amount of ultramicropores. The obtained carbon presented leaching and ecotoxicological properties compatible with its safe application to aqueous medium. Kinetic data of laboratory-made and commercial sample were best fitted by the pseudo-second-order model. The commercial carbon presented higher uptake of diclofenac, but the biomass carbon presented the higher adsorption rate which was associated with its higher hydrophilic nature which favoured external mass transfer. Both adsorbents presented adsorption isotherms that were best fitted by Langmuir model. The biomass carbon and the commercial carbon presented adsorption monolayer capacities of 69 and 146 mg g−1, and Langmuir constants of 0.38 and 1.02 L mg−1, respectively. The better performance of the commercial sample was related to its slightly higher micropore volume, but the most remarkable effect was the competition of water molecules in the biomass carbon.

Risso, R, Ferraz P, Meireles S, Fonseca I, Vital J.  2018.  Highly active Cao catalysts from waste shells of egg, oyster and clam for biodiesel production. Applied Catalysis A: General. 567:56-64. AbstractWebsite

Calcium oxide (CaO) catalysts derived from waste shells of egg, oyster and clam were prepared and used in the methanolysis of soybean oil. Eggshells were subjected to ultrasound irradiation and mollusc shells were subjected to calcination-hydration-calcination cycles to increase the surface area of CaO and improve its catalytic activity. The catalysts were characterized by XRD, TPD-CO2, TG-DSC, DLS and N2 adsorption, while the catalytic activity for the methanolysis of soybean oil was evaluated. Five hours of sonication reduced the CaO particle size by 34%, which resulted in a 56% increase in the activity. Two cycles of hydration-dehydration applied to the material obtained by calcination of oyster shells provided CaO with 27 m2 g−1. The transesterification rate was 2.5 times higher than that obtained with the untreated sample. After treatments, highly active CaO was obtained which indicates its enormous potential for biodiesel production. A kinetic model assuming the adsorption of methoxide anions on the surface of CaO particles was proposed.

Inocêncio, S, Cordeiro T, Matos I, Florence Danède, Sotomayor JC, Fonseca IM, Correia NT, Corvo MC, Dionísio M.  2021.  Ibuprofen incorporated into unmodified and modified mesoporous silica: From matrix synthesis to drug release. Microporous and Mesoporous Materials. 310:110541. AbstractWebsite

Aiming to rationalize the release profile of an incorporated pharmaceutical drug in terms of its mobility, driven by guest-host interactions, the poorly water-soluble ibuprofen drug was loaded in a mesoporous inorganic silica matrix with unmodified (MCM-41) and modified surface (MCM-41sil) by post-synthesis silylation, both having pore sizes   3 nm. The single calorimetric detection of a broad glass transition step for both ibuprofen composites indicates full drug amorphization, confirmed by the only appearance of an amorphous halo in the powder XRD patterns. Moreover, a gradient profile is disclosed by the heat flux derivative plot in the glass transition, in coherence with the thermogravimetric profile that shows a multi-step decomposition trace for confined ibuprofen in these matrixes. While identical guest dynamics, as probed by dielectric relaxation spectroscopy, were found in both dehydrated composites, a significant molecular population with faster relaxation exists in the hydrated state for the drug inside the unmodified matrix. This was rationalized as the concurrence of true confinement effects, which manifest under nanometer dimensions, and greater water affinity of the unmodified matrix, forcing the drug molecules to be placed mostly in the pore core. Finite size effects are also felt in both dehydrated composites, however guest-host interactions give origin to a dominant population with slowed down mobility that governs the overall guest dynamics. In spite of an inferior number of active sites for drug adsorption in the silylated matrix, a faster ibuprofen delivery in phosphate buffer (pH = 6.8) was observed when the drug is released from unmodified MCM-41 in the hydrated state. Therefore, our results suggest that a relevant role is played by water molecules, which impair a strong guest adsorption in the host surface more efficiently than the limited surface modification, influence the higher ratio of a faster population in the pore core and facilitate the diffusion of the aqueous releasing media inside pores.

Surra, E, Bernardo M, Lapa N, Esteves I, Fonseca I, Mota JP.  2018.  Maize cob waste pre-treatments to enhance biogas production through co-anaerobic digestion with OFMSW. Waste Management. 72:193-205. AbstractWebsite

In the present work, the enhancement of biogas and methane yields through anaerobic co-digestion of the pre-hydrolised Organic Fraction of Municipal Solid Wastes (hOFMSW) and Maize Cob Wastes (MCW) in a lab-scale thermophilic anaerobic reactor was tested. In order to increase its biodegradability, MCW were submitted to an initial pre-treatment screening phase as follows: (i) microwave (MW) irradiation catalysed by NaOH, (ii) MW catalysed by glycerol in water and alkaline water solutions, (iii) MW catalysed by H2O2 with pH of 9.8 and (iv) chemical pre-treatment at room temperature catalysed by H2O2 with 4 h reaction time. The pre-treatments cataysed by H2O2 were performed with 2% MCW (wMCW/v alkaline water) at ratios of 0.125, 0.25, 0.5 and 1.0 (wH2O2/wMCW). The pre-treatment that presented the most favourable balance between sugars, lignin, cellulose and hemicellulose solubilisations, as well as low production of phenolic compound and furfural (inhibitors), was the chemical pre-treatment catalysed by H2O2, at room temperature, with a ratio of 0.5 wH2O2/wMCW (Pre1). This Pre1 was then optimised testing reaction times of 1, 2 and 3 days at a different pH (11.5) and MCW percentage (10% w/v). The optimised pre-treatment that presented the best results, considering the same criteria defined above, was the one carried out during 3 days, at pH 9.8 and 10% MCW w/v (Pre2). The anaerobic reactor was initially fed with the hOFMSW obtained from the hydrolysis tank of an industrial AD plant. The hOFMSW was than co-digested with MCW submitted to the pre-treatment Pre1. In another assay, hOFMSW was co-digested with MCW submitted pre-treatment Pre 2. The co-digestion of hOFMSW + Pre1 increased the biogas yield by 38.9% and methane yield by 29.7%, when compared to the results obtained with hOFMSW alone. The co-digestion of hOFMSW + Pre2 increased biogas yield by 46.0% and CH4 yield by 36.3%. In both cases, the methane content obtained in the biogas streams was above 66% v/v. These results show that pre-treatment with H2O2, at room temperature, is a promising low cost way to valorize MCW through co-digestion with hOFMSW.

Pérez-Mayoral, E, Matos I, Bernardo M, Fonseca IM.  2019.  New and Advanced Porous Carbon Materials in Fine Chemical Synthesis. Emerging Precursors of Porous Carbons. Catalysts. 9, Number 2 AbstractWebsite

The efficiency of porous carbons in fine chemical synthesis, among other application fields, has been demonstrated since both the porous structure and chemical surface provide the appropriated chemical environment favoring a great variety of relevant chemical transformations. In recent years, metal organic frameworks (MOFs) and covalent organic frameworks (COFs) have emerged as interesting opportunities in the preparation of porous carbons with improved physico-chemical properties. Direct calcination of MOFs or COFs, in the presence or not of others carbon or heteroatom sources, could be considered an easy and practical approach for the synthesis of highly dispersed heteroatom-doped porous carbons but also new porous carbons in which single atoms of metallic species are present, showing a great development of the porosity; both characteristics of supreme importance for catalytic applications. The goal of this review is to provide an overview of the traditional methodologies for the synthesis of new porous carbon structures together with emerging ones that use MOFs or COFs as carbon precursors. As mentioned below, the catalytic application in fine chemical synthesis of these kinds of materials is at present barely explored, but probably will expand in the near future.

Figueira, J, Loureiro J, Marques J, Bianchi C, Duarte P, Ruoho M, Tittonen I, Ferreira I.  2017.  Optimization of Cuprous Oxides Thin Films to be used as Thermoelectric Touch Detectors. ACS Applied Materials & Interfaces. 9:6520-6529., Number 7 AbstractWebsite

The electronic and optical properties of p-type copper oxides (CO) strongly depend on the production technique as it influences the obtained phases: cuprous oxide (Cu2O) or cupric oxide (CuO), the most common ones. Cu films deposited by thermal evaporation have been annealed in air atmosphere, with temperature between 225 and 375 °C and time between 1 and 4 h. The resultant CO films have been studied to understand the influence of processing parameters in the thermoelectric, electrical, optical, morphological, and structural properties. Films with a Cu2O single phase are formed when annealing at 225 °C, while CuO single phase films can be obtained at 375 °C. In between, both phases are obtained in proportions that depend on the film thickness and annealing time. The positive sign of the Seebeck coefficient (S), measured at room temperature (RT), confirms the p-type behavior of both oxides, showing values up to 1.2 mV·°C–1 and conductivity up to 2.9 (Ω·m)−1. A simple detector using Cu2O have been fabricated and tested with fast finger touch events.

Afonso, D, Ribeiro AFG, Araújo P, Vital J, Madeira LM.  2018.  Phenol in Mixed Acid Benzene Nitration Systems. Industrial & Engineering Chemistry Research. 57:15942-15953., Number 46 AbstractWebsite
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Matos, I, Bernardo M, Fonseca I.  2017.  Porous carbon: A versatile material for catalysis. Catalysis Today. 285:194-203. AbstractWebsite

Heterogeneous catalysis is an exciting field in constant development. New and improved catalysts that can both be effective and economical are always on demand. Activated carbons may well play an important role in this field, as they are a cheaper alternative while more environmentally benign. In this paper, a brief overview of the effort developed in the application of activated carbon as heterogeneous catalysts in various reactions is presented. Functionalised activated carbon has been used as catalyst for fine chemical reactions. Gas-phase reactions for NO, N2O and CO2 conversions were thoroughly studied using activated carbon as catalyst support. In situ characterization techniques proved to be valuable tools to understand carbon gasification mechanism.

Godino-Ojer, M, Blazquez-García R, Matos I, Bernardo M, Fonseca IM, Mayoral PE.  2019.  Porous carbons-derived from vegetal biomass in the synthesis of quinoxalines. Mechanistic insights. Catalysis Today. AbstractWebsite

We report herein for the first-time acid biomass-derived carbons from vegetal biomass, with high developed porosity, prepared through integrating method comprising pyrolysis and surface phosphonation, able to efficiently catalyze the synthesis of quinoxalines from 1,2-diamines and α-hydroxi ketones, under aerobic conditions. The obtained results indicate that the reaction is mainly driven by a combination of acid function strength and textural properties in terms of conversion and selectivity. Furthermore, our experimental and theoretical observations suggest that the preferred reaction pathway for this transformation, in the presence of the investigated acid carbon catalysts, involves cascade reactions including imination reaction between reactants, successive imine-enamine and keto-enol tautomerisms, heterocyclization followed by dehydration, and aromatization. While the acid sites seem to be a relevant role in each reaction step, the system formed by activated carbon and molecular oxygen could be behind the last oxidative reaction to give the corresponding nitrogen heterocycles.

Godino-Ojer, M, Blazquez-García R, Matos I, Bernardo M, Fonseca IM, Pérez Mayoral E.  2020.  Porous carbons-derived from vegetal biomass in the synthesis of quinoxalines. Mechanistic insights. Catalysis Today. 354:90-99. AbstractWebsite

We report herein for the first-time acid biomass-derived carbons from vegetal biomass, with high developed porosity, prepared through integrating method comprising pyrolysis and surface phosphonation, able to efficiently catalyze the synthesis of quinoxalines from 1,2-diamines and α-hydroxi ketones, under aerobic conditions. The obtained results indicate that the reaction is mainly driven by a combination of acid function strength and textural properties in terms of conversion and selectivity. Furthermore, our experimental and theoretical observations suggest that the preferred reaction pathway for this transformation, in the presence of the investigated acid carbon catalysts, involves cascade reactions including imination reaction between reactants, successive imine-enamine and keto-enol tautomerisms, heterocyclization followed by dehydration, and aromatization. While the acid sites seem to be a relevant role in each reaction step, the system formed by activated carbon and molecular oxygen could be behind the last oxidative reaction to give the corresponding nitrogen heterocycles.