Publications

Export 49 results:
Sort by: Author Title Type [ Year  (Desc)]
2021
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.

2020
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, 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.

Rijo, B, Lemos F, Fonseca I, Vilelas A.  2020.  Development of a model for an industrial acetylene hydrogenation reactor using plant data – Part I. Chemical Engineering Journal. 379:122390. AbstractWebsite

In this work, a dynamic model of an industrial acetylene hydrogenation reactor with a front-end configuration was developed, based on plant operation data. This type of reactor operates in transient state, not only due to the natural fluctuations in operating conditions but also due to the effects caused by the deactivation of the catalyst. To develop the dynamic model of the acetylene hydrogenation reactor a thorough study of the effect of operating conditions was performed; the influence of variables such as the inlet temperature of the 1st reactor, the flowrate, carbon monoxide concentration, on the activity, selectivity and stability of the catalyst was examined by choosing adequate periods of the operation of the reactor. To understand the reaction mechanism of this system, several published kinetics were tested but only one was finally fitted to the industrial data, to interpret the operation of the acetylene hydrogenation reactor. A set of operation periods was used to develop the model which was then validated by applying the model to a different set of operation periods. As a conclusion, the dynamic model that was developed and validated, using actual plant operation data, was able to adequately describe the outlet temperatures of the three reactors in the system as well as the outlet acetylene concentration of the 3rd reactor.

Castanheiro, JE, Vital J, Fonseca IM, Ramos AM.  2020.  Glycerol conversion into biofuel additives by acetalization with pentanal over heteropolyacids immobilized on zeolites. Catalysis Today. 346:76-80. AbstractWebsite

Dodecamolydbophosphoric acid (HPMo) immobilized on USY zeolite was used as a catalyst for the acetalization of glycerol with pentanal at 70 °C. Catalysts were prepared with different amounts of heteropolyacid, and the most active sample was the HPMo2@Y catalyst (1.1 wt.%). The products of glycerol acetalization with pentanal were (2-butyl-1,3-dioxolan-4-yl)methanol, a five-member ring compound, and 2-butyl-1,3-dioxan-5-ol, a six-member ring compound. Good values of selectivity for the five-member ring compound (80–85%) were obtained with all materials. The reaction conditions were optimized using HPMo2@Y as a catalyst. The optimal conditions were determined to be 70 °C reaction temperature with 0.3 g catalyst and a 1:2.5 M ratio of glycerol to pentanal. The catalytic stability of HPMo2@Y was studied. The acetalization of glycerol with pentanal was performed using the same sample. High catalytic activity for HPMo2@Y was observed.

Ferreira, RC, Dias D, Fonseca I, Bernardo M, Pimenta JLCW, Lapa N, de Barros MASD.  2020.  Multi-component adsorption study by using bone char: modelling and removal mechanisms. Environmental Technology. :1-16.: Taylor & Francis AbstractWebsite
n/a
Bernardo, M, Correa CR, Ringelspacher Y, Becker GC, Lapa N, Fonseca I, Esteves IAAC, Kruse A.  2020.  Porous carbons derived from hydrothermally treated biogas digestate. Waste Management. 105:170-179. AbstractWebsite

Porous carbons from digestate-derived hydrochar were produced, characterized and their performance to reclaim phosphate from water was evaluated as a preliminary approach to demonstrate their practical application. In a first step, the digestate was converted into hydrochars through hydrothermal carbonization by using two different pH conditions: 8.3 (native conditions) and 3.0 (addition of H2SO4). The resulting hydrochars did not present significant differences. Consecutively, the hydrochars were activated with KOH to produce activated carbons with enhanced textural properties. The resulting porous carbons presented marked differences: the AC native presented a lower ash content (20.3 wt%) and a higher surface area (SBET = 1106 m2/g) when compared with the AC-H2SO4 (ash content = 43.7 wt% SBET = 503 m2/g). Phosphorus, as phosphate, is a resource present in significative amount in wastewater, causing serious problems of eutrophication. Therefore, the performance of the porous carbons samples to recover phosphate – P(PO43−) – from water was evaluated through exploitation assays that included kinetic studies. The lumped model presented a good fitting to the kinetic data and the obtained uptake capacities were the same for both carbons, 12 mg P(PO43−)/g carbon. Despite the poorer textural properties of AC-H2SO4, this carbon was richer in Ca, Al, Fe, K, and Mg cations which promoted the formation of mineral complexes with phosphate anions. The results obtained in this work are promising for the future development of P(PO43−) enriched carbons that can be used thereafter as biofertilizers in soil amendment applications.

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.

Agostinho, DAS, Paninho AI, Cordeiro T, Nunes AVM, Fonseca IM, Pereira C, Matias A, Ventura MG.  2020.  Properties of κ-carrageenan aerogels prepared by using different dissolution media and its application as drug delivery systems. Materials Chemistry and Physics. 253:123290. AbstractWebsite

This work reports the synthesis of kappa-carrageenan aerogels using different dissolution and crosslinking media in order to evaluate its effects on the textural properties of the matrixes and further on the drug loading and release performance. The different aerogel samples were produced through the dissolution of the biopolymer in water with addition of potassium salts as crosslinking agents and, in two different ionic liquids (ILs) derived from imidazolium ion, being further dried with supercritical CO2. The samples were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), Nitrogen Adsorption-Desorption Analysis, Thermogravimetry (TGA) and Differential Scanning Calorimetry (DSC). The synthesized samples presented surface areas similar to the carrageenan aerogels being their structure constituted mainly by meso and macropores. The absence of ionic liquid in samples was demonstrated by DSC analysis and was corroborated by the cytotoxicity assays which revealed that cellular viability in Caco-2 cells was preserved. Tetracycline was used as a model drug and loaded in two of the prepared aerogels samples. The release experiments were performed with the composites to test in vitro drug release at physiologic pH. With a higher macroporosity, the kappa-carrageenan aerogel prepared by dissolution into ionic liquid showed a higher loading capacity than the one prepared by dissolution into water and a slightly higher release rate. The matrixes were considered to present a good potential to be used as biocompatible carriers on drug controlled delivery.

2019
Godinho, D, Nogueira M, Bernardo M, Dias D, Lapa N, Fonseca I, Pinto F.  2019.  Recovery of Cr(III) by using chars from the co-gasification of agriculture and forestry wastes, Aug. Environmental Science and Pollution Research. 26:22723–22735., Number 22 AbstractWebsite

The aim of the present work was to assess the efficiency of biochars obtained from the co-gasification of blends of rice huskþinspace}+þinspace}corn cob (biochar 50CC) and rice huskþinspace}+þinspace}eucalyptus stumps (biochar 50ES), as potential renewable low-cost adsorbents for Cr(III) recovery from wastewaters. The two gasification biochars presented a weak porous structure (ABETþinspace}=þinspace}63–144 m2 g−1), but a strong alkaline character, promoted by a high content of mineral matter (59.8{%} w/w of ashes for 50CC biochar and 81.9{%} w/w for 50ES biochar). The biochars were used for Cr(III) recovery from synthetic solutions by varying the initial pH value (3, 4, and 5), liquid/solid (L/S) ratio (100–500 mL g−1), contact time (1–120 h), and initial Cr(III) concentration (10–150 mg L−1). High Cr(III) removal percentages (around 100{%}) were obtained for both biochars, due to Cr precipitation, at low L/S ratios (100 and 200 mL g−1), for the initial pH 5 and initial Cr concentration of 50 mg L−1. Under the experimental conditions in which other removal mechanisms rather than precipitation occurred, a higher removal percentage (49.9{%}) and the highest uptake capacity (6.87 mg g−1) were registered for 50CC biochar. In the equilibrium, 50ES biochar presented a Cr(III) removal percentage of 27{%} with a maximum uptake capacity of 2.58 mg g−1. The better performance on Cr(III) recovery for the biochar 50CC was attributed to its better textural properties, as well as its higher cation exchange capacity.

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.

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).

Castanheiro, JE, Vital J, Fonseca IM, Ramos AM.  2019.  Glycerol conversion into biofuel additives by acetalization with pentanal over heteropolyacids immobilized on zeolites. Catalysis Today. AbstractWebsite

Dodecamolydbophosphoric acid (HPMo) immobilized on USY zeolite was used as a catalyst for the acetalization of glycerol with pentanal at 70 °C. Catalysts were prepared with different amounts of heteropolyacid, and the most active sample was the HPMo2@Y catalyst (1.1 wt.%). The products of glycerol acetalization with pentanal were (2-butyl-1,3-dioxolan-4-yl)methanol, a five-member ring compound, and 2-butyl-1,3-dioxan-5-ol, a six-member ring compound. Good values of selectivity for the five-member ring compound (80–85%) were obtained with all materials. The reaction conditions were optimized using HPMo2@Y as a catalyst. The optimal conditions were determined to be 70 °C reaction temperature with 0.3 g catalyst and a 1:2.5 M ratio of glycerol to pentanal. The catalytic stability of HPMo2@Y was studied. The acetalization of glycerol with pentanal was performed using the same sample. High catalytic activity for HPMo2@Y was observed.

Surra, E, Nogueira MC, Bernardo M, Lapa N, Esteves I, Fonseca I.  2019.  New adsorbents from maize cob wastes and anaerobic digestate for H2S removal from biogas. Waste Management. 94:136-145. AbstractWebsite

Two activated carbons (ACs) were prepared by physical activation of Maize Cob Waste (MCW) with CO2, during 2 and 3 h (MCW(PA)2h and MCW(PA)3h, respectively). Two other ACs were prepared by chemical activation: a) MCW(LD) – MCW was impregnated with anaerobic liquid digestate (LD) and carbonized under N2 atmosphere; and b) CAR-MCW(LD) – previously carbonized MCW was impregnated with LD and carbonized under N2 atmosphere. All ACs were fully characterized for textural and chemical properties, and then used in dynamic H2S removal assays from real biogas samples. Regarding H2S removal, the ACs that were physically activated behaved much better than the impregnated ones: MCW(PA)3h and MCW(PA)2h showed H2S uptake capacities of 15.5 and 0.65 mg g−1, respectively, while MCW(LD) and CAR-MCW(LD) showed values of 0.47 and 0.25 mg g−1, respectively. This may indicate that textural properties (surface area and microporosity) are more important than mineral content in H2S removal. Effectively, both surface area and micropore volume were much higher for the samples of MCW(PA)3h (SBET = 820 m2 g−1 and Vmicro = 0.32 cm3 g−1) and MCW(PA)2h (SBET = 630 m2 g−1 and Vmicro = 0.21 cm3 g−1) than for the ACs that were chemically activated (SBET = 38.0 m2 g−1 and Vmicro = 0.01 cm3 g−1 for MCW(LD); SBET = 8.0 m2 g−1 and Vmicro = 0.01 cm3 g−1 for CAR-MCW(LD)). High oxygen content in MCW(PA)3h favoured the catalytic oxidation reaction of H2S, promoting its removal. The use of MCW as precursor and LD as activating agent of the ACs may contribute for the integrated management of maize wastes and to diversify the applications of anaerobic digestate.

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.

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.

2018
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.
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.
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.

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.

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.