3D tuned porous carbon monolith as catalysts in the wet peroxide oxidation of paracetamol

In recent years, many pharmaceuticals have been identified at trace levels worldwide in the aquatic environment [1]. Municipal wastewater treatment plants (WWTPs) are considered the main sources of these pollutants as they are not generally prepared to deal with such complex substances and thus, they are usually ineffective in their removal [1]. Despite the low concentration of drugs contained in those effluents, the presence of pharmaceuticals, even in trace concentrations, affects the quality of water and constitutes a risk of toxicity for the ecosystems and living organisms [1-2]. Consequently, new regulation for micropollutants discharge and monitoring has been issued in Europe (Directive 2013/39/EU). Paracetamol (PCM) deserves particular attention, since it has recently been discovered as a potential pollutant of waters, largely accumulated in the aquatic environment [3]. This work deals with the treatment of PCM, used as a model pharmaceutical contaminant of emerging concern, by catalytic wet peroxide oxidation using carbon-based monoliths (Fig. 1a) as catalysts. Monoliths were prepared by stereolithographic 3D printing of a photoresin, which was later converted into porous carbon by oxidation in air (300 °C, 6 h) and subsequent pyrolysis in N2 (900 °C, 15 min) as described elsewhere [4]. The materials revealed catalytic activity in the CWPO of PCM allowing to reach PCM conversions up to 30% with a residence time of 3.5 min (Fig. 1b).This work is a result of the Project “AIProcMat@N2020 - Advanced Industrial Processes and Materials for a Sustainable Northern Region of Portugal 2020”, with the reference NORTE-01-0145-FEDER-000006, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (ERDF); the Associate Laboratory LSRE-LCM - UID/EQU/50020/2019 - funded by national funds through FCT/MCTES (PIDDAC); and CIMO (UID/AGR/00690/2019) through FEDER under Program PT2020. The authors also acknowledge the joint financial support from Fundação para a Ciência e a Tecnologia (FCT) in Portugal and the Deutscher Akademischer Austauschdienst (DAAD) in Germany.info:eu-repo/semantics/publishedVersio

Carbon‐methanol based adsorption heat pumps : identifying accessible parameter space with carbide‐derived carbon model materials

In adsorption heat pumps, the properties of the porous adsorbent and the refrigerant determine the performance. Major parameters for this working pair are the total uptake of the adsorptive, its kinetics, and the heat transfer characteristics. In the technical application despite powdered adsorbents, thin consolidated layers of the adsorbent can be attractive and obtained by a binder‐based approach but likely result in competing material properties. Thus, for a process optimization, the accessible parameter space and interdependencies have to be known and were deduced in this work for model porous carbons (carbide‐derived carbons derived from TiC and ZrC) and methanol as well as the addition of different amounts of boron nitride, silver, and graphite as heat‐conductive agents and the use of two binders.German Research Council (DFG)Projekt DEA

3D-printed activated carbon for post-combustion CO2 capture

The applicability of 3D-printed activated carbons for their use to CO2 capture in post-combustion streams and the influence of activation conditions on CO2 uptake and CO2 to N2 selectivity were studied. For two monoliths with the same open cellular foam geometry but low and high burnoff during activation, a series of fixed-bed breakthrough adsorption experiments under typical post-combustion conditions, in a wide range of temperature (313 and 373 K), and partial pressure of CO2 up to 120 kPa were carried out. It is shown that the higher burnoff during activation of the 3D printed carbon enhances the adsorption capacity of CO2 and N2 due to the increased specific surface area with sorption uptakes that can reach 3.17 mol/kg at 313 K and 120 kPa. Nevertheless, the lower burnoff time on monolith 1 leads to higher selectivity of CO2 over N2, up to 18 against 10 on monolith 2, considering a binary interaction to a mixture of CO2/N2 (15/85 vol%) at 313 K. The single and multicomponent adsorption equilibrium is conveniently described through the dual-site Langmuir isotherm model, while the breakthrough curves simulated using a dynamic fixed-bed adsorption linear driving force model. Working capacities for the 3D printed carbon with lower burnoff time lead to the best results, varying of 0.15–1.1 mol/kg for the regeneration temperature 300–390 K. Finally, consecutive adsorption-desorption experiments show excellent stability and regenerability for both 3D printed activated carbon monoliths and the whole study underpins the high potential of these materials for CO2 capture in post-combustion streams.Generally, the authors are thankful to Dr. M. Rückriem and Dr. A. Schreiber from Microtrac Retsch GmbH for the kind support with nitrogen physisorption and mercury porosimetry measurements. The authors acknowledge the joint financial support from Fundação para a Ciência e a Tecnologia (FCT), in Portugal, and the Deutscher Akademischer Austauschdienst (DAAD), in Germany. Foundation for Science and Technology (FCT, Portugal) and ERDF under Programme PT2020 to CIMO (UIDB/00690/2020) and POCI-01-0145-FEDER006984-Associate Laboratory LSRE-LCM. Foundation for Science and Technology (FCT, Portugal) under Programme PTDC 2020 * 3599-PPCDTI * Engenharia dos Processos Químicos * project PTDC/EQU-EPQ/0467/2020. Foundation for Science and Technology (FCT, Portugal), through the individual research grants SFRH/BD/148525/2019 for Adriano Henrique and DFA/BD/7925/2020 for Lucas F. A. S. Zafanelli.info:eu-repo/semantics/publishedVersio

Activated Carbon in the Third Dimension—3D Printing of a Tuned Porous Carbon

A method for obtaining hierarchically structured porous carbons, employing 3D printing to control the structure down to the lower μm scale, is presented. To successfully 3D print a polymer precursor and transfer it to a highly stable and structurally conformal carbon material, stereolithography 3D printing and photoinduced copolymerization of pentaerythritol tetraacrylate and divinylbenzene are employed. Mechanically stable structures result and a resolution of ≈15 μm is demonstrated. This approach can be combined with liquid porogen templating to control the amount and size (up to ≈100 nm) of transport pores in the final carbonaceous material. Additional CO2 activation enables high surface area materials (up to 2200 m2 g-1) that show the 3D printing controlled μm structure and nm sized transport pores. This unique flexibility holds promise for the identification of optimal carbonaceous structures for energy application, catalysis, and adsorption

Temperature-Programmed Oxidation: ZrC-CDC

Mass loss curves from temperature-programmed oxidation of ZrC-CDCs produced at temperatures between 1000 and 1500 °

X-Ray Powder Diffraction: SiC-CDC

X-ray powder diffraction patterns of SiC-CDCs produced at temperatures between 1000 and 1600 °

X-Ray Powder Diffraction: NbC-CDC

X-ray powder diffraction patterns of NbC-CDCs produced at temperatures between 1000 and 1500 °

Raman Spectroscopy: TaC-CDC

Raman spectra of TaC-CDCs produced at temperatures between 1000 and 1400 °

X-Ray Powder Diffraction: ZrC-CDC

X-ray powder diffraction patterns of ZrC-CDCs produced at temperatures between 1000 and 1500 °

Raman Spectroscopy: ZrC-CDC

Raman spectra of ZrC-CDCs produced at temperatures between 1000 and 1500 °