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This work focuses on the intensification of BrO3− (200 μg L−1) reduction by TiO2-assisted heterogeneous photocatalysis, using the NETmix mili-photoreactor illuminated by UVA light-emitting diodes (UVA-LEDs). The mili-photoreactor was assembled in two configurations: i) catalyst deposition on the channels and chambers of a back stainless steel slab (SSS) and ii) catalyst deposition on the front borosilicate glass slab (BGS), allowing the study of front-side (FSI) and back-side (BSI) illumination mechanisms, respectively. The BrO3− reduction rate in aqueous solution was assessed as a function of: i) pH; ii) dissolved oxygen (DO); iii) addition of formic acid (CH2O2) as a sacrificial agent (SA); iv) photocatalyst film thickness; v) illumination mechanism; vi) irradiation intensity; vii) temperature; and viii) water matrix. Higher BrO3− reduction rates were observed using the FSI mechanism and lower pH values. Nitrogen injection (to eliminate DO) did not significantly improve the reaction rate and the addition of CH2O2 had a negative effect at pH 6.5. Neither temperature nor irradiance increase showed a considerable improvement on the reduction rate. Moreover, TiO2 film remains stable for at least 13 consecutive reactions without significant catalyst leaching. The chemically pre-treated fresh water (FW) matrix negatively affected the reaction rate when compared with the synthetic water (SW), under the best operational conditions (SSS: pH = 5.5, 287 mg of TiO2, 25 °C, SA absence, [DO] = 232–263 μM). This was associated with the presence of both inorganic and organic matter at much higher concentrations than BrO3−. Notwithstanding, heterogeneous TiO2 photocatalysis, using the NETmix mili-photoreactor, was successfully applied to fresh water, achieving [BrO3−]

The current work focused on the sunlight-driven thermo-photocatalytic reduction of carbon dioxide (CO2), the primary greenhouse gas, by ethane (C2H6), the second most abundant element in shale gas, aiming at the generation of ethanol (EtOH), a renewable fuel. To promote this process, a hybrid catalyst was prepared and properly characterized, comprising of strontium titanate (SrTiO3) co-doped with ruthenium oxide (RuO2) and nickel oxide (NiO). The photocatalytic activity towards EtOH production was assessed in batch-mode and at gas-phase, under the influence of different conditions: (i) dopant loading, (ii) temperature, (iii) optical radiation wavelength, (vi) consecutive uses, and (v) electron scavenger addition. From the results here obtained, it was found that: (i) the functionalization of the SrTiO3 with RuO2 and NiO allows the visible light harvest and narrows the band gap energy (ca. 14–20%), (ii) the selectivity towards EtOH depends on the presence of Ni and irradiation, (iii) the catalyst photoresponse is mainly due to the visible photons, (iv) the photocatalyst loses &gt, 50% efficiency right after the 2nd use, (v) the reaction mechanism is based on the photogenerated electron-hole pair charge separation, and (vi) a maximum yield of 64 μmol EtOH gcat−1 was obtained after 45-min (85 μmol EtOH gcat−1 h−1) of simulated solar irradiation (1000 W m−2) at 200 °C, using 0.4 g L−1 of SrTiO3:RuO2:NiO (0.8 wt.% Ru) with [CO2]:[C2H6] and [Ru]:[Ni] molar ratios of 1:3 and 1:1, respectively. Notwithstanding, despite its exploratory nature, this study offers an alternative route to solar fuels’ synthesis from the underutilized C2H6 and CO2.

The production of biopolymers has been shown to be one of the most viable alternatives for the reduction of the use of conventional plastics. The oat hulls are a by-product with great ability to be incorporated into the production of biopolymers since it is a lignocellulosic compound. The lignin present in its composition can improve the strength of the material, however, it can also hamper its degradation. The aim of this study was to evaluate the degradation levels of composites produced from starch and polylactic acid with absence (T1) and presence of oat hulls (T2) through the Sturm test. In T2 it was a more uniform and smooth biopolymer. In addition, the use of oat hulls favored CO2 production, 8% more than T1. Although the loss of dry mass in T1 was 3% higher, it was possible to observe degradation in T2.

Anaerobic digestion of crude glycerol from biodiesel production is a feasible way for methane production. However, crude glycerol (CG) contains impurities, such as long-chain fatty acids (LCFA) that can inhibit methanogenic microorganisms. Ultrasound promotes the hydrolysis of LCFA and deagglomerates the microorganisms in biological flocs. Furthermore, Aspergillus niger and Escherichia coli produce lipases capable of degrading LCFA. This study aims at improving the methane yield from anaerobic digestion by coupling with ultrasound or E. coli/A. niger biodegradation. The effect of the different treatments was first assessed in a perfectly mixed batch reactor (PMBR), using diluted CG at concentrations of 0.2%, 1.7%, and 3.2% (v/v). Later, the best conditions were replicated in an upflow anaerobic sludge blanket (UASB) reactor to simulate full- scale practical applications. Experiments in the PMBR showed that ultrasound or A. niger biodegradation steps improved methane yield up to 11% for 0.2% CG and 99% for 1.7% CG, respectively. CG biodegradation by E. coli inhibited the subsequent anaerobic digestion for all concentrations tested. Using a UASB digester, ultrasonic treatment of CG led to an average increase of 29% in methane production. The application of ultrasound led to a lower accumulation of propionic acid in the digested material and increased biogas production. On the other hand, an average 77% increase in methane production was achieved using a preliminary CG biodegradation step by A. niger, when operated at a loading rate of 2.9 kg COD m-3 day-1. Under these conditions, an energy gain of 0.48 kWh day-1, with the production of the 0.434 m3 CH4 kg-1 CODremoval and 0.573 m3 CH4 kg-1 VS, and a biogas quality of 73% in methane were obtained. The digested material was analyzed for the detection and quantification of added-value by-products in order to obtain a broad assessment of the CG valorization through anaerobic digestion. In some experiments, propionic and oxalic acid were detected. However, the accumulation of propionic caused the inhibition of the acetogenic and methanogenic microorganisms. info:eu-repo/semantics/publishedVersion

World production and trade of fruits generate losses in the harvest, post-harvest, handling, distribution and consumption phases, corresponding to 6.8% of total production. These residues present high potential as a substrate for the anaerobic digestion process and biogas generation. Thus, the energy valuation of the agro-industrial residues of kiwi production was evaluated by anaerobic digestion, aiming at optimizing the biogas production and its quality. Ten assays were carried out in a batch reactor (500 mL) under mesophilic conditions and varying a number of operational factors: different substrate/inoculum ratios; four distinct values for C: N ratio; inoculum from different digesters; and inoculum collected at different times of the year. The following parameters were used to control and monitor the process: pH, alkalinity, volatile fatty acids (VFA), volatile solids (VS) and chemical oxygen demand (COD). Among the tests performed, the best result obtained for the biogas production corresponded to the use of 2 g of substrate and 98 mL of inoculum of the anaerobic digester of the Wastewater Treatment Plant (WWTP) of Bragança, with addition of 150 mg of bicarbonate leading to a production of 1628 L biogas.kg-1 VS (57% methane). In relation to the biogas quality, the best result was obtained with 20 g of substrate and 380 mL of inoculum from the anaerobic digester sludge of WWTP of Ave (with addition 600 mg of sodium bicarbonate), presenting a value of 85% of CH4, with a production of 464 L biogas.kg-1 VS. This work was financially supported by: Project POCI-01-0145-FE DER-006984 – Associate Laboratory LSRE-LCM funded by FEDER through COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI) – and by national funds through FCT – Fundação para a Ciência e a Tecnologia. info:eu-repo/semantics/publishedVersion