Carbon formation at high temperatures (550–1400 ◦c): Kinetics, alternative mechanisms and growth modes

UIDB/50006/2020This Note aims at clarifying the alternative mechanisms of carbon formation from gases at temperatures above 550 ◦C. Both the growth of carbon nanotubes (CNTs) by a hybrid route, and of graphene layers deposition by a pyrolytic route are analyzed: The transition had no influence in apparent kinetics, but the carbon structure was totally different. The transition temperature from hybrid to pyrolytic growth varies with the gas pressure: Higher temperature transition was possible using lower active gas pressures. The rate-determining step concept is essential to understanding the behavior. In catalytic and hybrid carbon formation, the slower step controls and determines kinetics. In the pyrolytic region, the faster step dominates, and carbon bulk diffusion is blocked: Layers of graphene cover the external catalyst surface. It is easier to optimize CNTs growth (rate, shape, properties) knowing the details of the alternative mechanisms operating.publishersversionpublishe

Kinetics of carbon nanotubes and graphene growth on iron and steel: Evidencing the mechanisms of carbon formation

This work was supported by national funds through FCT-Fundacao para a Ciencia e a Tecnologia, I.P., under the Scientific Employment Stimulus-Institutional Call Partially supported by the Associate Laboratory for Green Chemistry-LAQV, financed by national funds from FCT/MCTES (UIDB/50006/2020).Carbon formation on steel has recently become an active research area with several important applications, using either carbon nanotubes (CNTs) or graphene structures. The production of vertically aligned CNT (VACNT) forests with combined metals has been explored with important results. Detailed kinetics is the best approach to understand a mechanism. The growth behavior seems complex but can be simplified through the knowledge of the three more common alternative reaction mechanisms/routes. The time required to optimize the production and properties might be reduced. The mechanistic proposal reported in 1971 was better explained recently. The volcano shape Arrhenius plot reported is observed only when Fe, Co, and Ni are used as reaction catalysts. Other metals are catalytically active at higher temperatures, following a different route, which does not require surface catalysis decomposition of the reactive gas. C2H2 and low olefins react well, but CH4 is not reactive via this surface catalysis route. Optimizing production of CNTs, research work is usually based on previous experience, but solid-state science-based studies are available.publishersversionpublishe

The Ca2+-ATPase inhibition potential of gold (I, III) compounds

The therapeutic applications of gold are well-known for many centuries. The most used gold compounds contain Au(I). Herein, we report, for the first time, the ability of four Au(I) and Au(III) complexes, namely dichloro (2-pyridinecarboxylate) Au(III) (abbreviated as1), chlorotrimethylphosphine Au(I) (2), 1,3-bis(2,6-diisopropylphenyl) imidazole-2-ylidene Au(I) chloride (3), and chlorotriphenylphosphine Au(I) (4), to affect the sarcoplasmic reticulum (SR) Ca2+-ATPase activity. The tested gold compounds strongly inhibit the Ca2+-ATPase activity with different effects, being Au(I) compounds2and4the strongest, with half maximal inhibitory concentration (IC50) values of 0.8 and 0.9 mu M, respectively. For Au(III) compound1and Au(I) compound3, higher IC(50)values are found (4.5 mu M and 16.3 mu M, respectively). The type of enzymatic inhibition is also different, with gold compounds1and2showing a non-competitive inhibition regarding the native substrate MgATP, whereas for Au compounds3and4, a mixed type of inhibition is observed. Our data reveal, for the first time, Au(I) compounds with powerful inhibitory capacity towards SR Ca(2+)ATPase function. These results also show, unprecedently, that Au (III) and Au(I) compounds can act as P-type ATPase inhibitors, unveiling a potential application of these complexes.FCT: UIDB/04326/2020/ UIDB/50006/2020info:eu-repo/semantics/publishedVersio

Assessing the photocatalytic degradation of fluoroquinolone norfloxacin by Mn:ZnS quantum dots: Kinetic study, degradation pathway and influencing factors

SR/WOS-A/CS-82/2018 UIDB/50006/2020Norfloxacin (NOFX), a broadly used fluoroquinolone antibiotic, has been a subject of great concern in the past few years due to its undesirable effect on human beings and aquatic ecosystems. In this study, novel Mn doped ZnS (Mn:ZnS) quantum dots (QDs) were prepared through a facile chemical precipitation method and used as photocatalysts for NOFX degradation. Prior to photodegradation experiments, morphological and optical parameters of the QDs were examined through transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, fluorescence spectroscopy, Brunauer–Emmett–Teller analysis, and differential thermal and thermogravimetric analyses. Mn:ZnS QDs exhibited excellent properties of photodegradation, not only under UV irradiation but also in sunlight, which induced NOFX to photodegrade. The utmost photodegradation efficiency was obtained under optimal conditions (25 mL of NOFX, 15 mg/L, pH 10, 60 min UV irradiation, 60 mgs QDs), adopting first order kinetics. In addition, hydroxyl radicals produced by the conduction band electrons were found to be the primary reason dominating the transformation of NOFX in basic conditions, while holes, oxygen atoms, as well as the doped metal (Mn) enhanced the degradation. The QDs showed excellent reusability and stability in four repeated cycles. Finally, four different pathways were predicted, derived from the identified intermediates, with piperazinyl ring transformation being the primary one. It is expected that the synthesized Mn:ZnS QDs could be utilized as efficient photocatalytic materials for energy conversion and ecological remediation.publishersversionpublishe

Green chemistry and environmental processes

Funding Information: Acknowledgments: Portuguese FCT—Fundação para a Ciência e a Tecnologia, I.P., under the Scientific Employment Stimulus—Institutional Call (CEECINST/00102/2018) and Associate Laboratory for Green Chemistry—LAQV, financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020) and the Spanish Project ref. RTI 2018-099224-B100 funded by ERDF/Ministry of Science, Innovation and Universities. S.M.-T. also acknowledges the Ramón y Cajal contract (RYC-2019-026634-I/AEI/10.13039/501100011033) from MINECO.publishersversionpublishe

Calcium alginate beads with entrapped iron oxide magnetic nanoparticles functionalized with methionine—a versatile adsorbent for arsenic removal

no. 3114/8/Fin./Sch.// 2018 UIDP/50006/2020A novel beads adsorbent, consisting of calcium alginate entrapped on magnetic nanoparti-cles functionalized with methionine (MFMNABs), was developed for effective elimination of arsenic from water. The material was characterized by FT-IR (Fourier Transform Infrared Spectroscopy), SEM (Scanning Electron Microscopic), XRD (X-ray Diffraction) and TEM (Transmission Electron Microscopy). The arsenic removal capacity of the material was studied by altering variables such as pH of the solution, contact time, adsorbent dose and adsorbate concentration. The maximal removal of As(III) was 99.56% under optimal conditions with an equilibrium time of 110 min and pH 7.0–7.5. The adsorption followed a second order kinetics and data best fitted the Langmuir isotherm with a correlation coefficient of R2 = 0.9890 and adsorption capacity (qm ) of 6.6533 mg/g. The thermodynamic study showed entropy change (∆S) and enthalpy change (∆H) to be 34.32 J mol−1 K and 5.25 kJ mol−1, respectively. This study proved that it was feasible to treat an As(III) solution with MFMNABs. The synthesized adsorbent was cost-effective, environmentally friendly and versatile, compared to other adsorbents. The adsorption study was carried by low cost spectrophotometric method using N-bromosuccinimide and rhodamine-B developed in our laboratory.publishersversionpublishe

Shape effects of ceria nanoparticles on the water-gas shift performance of cuox /ceo2 catalysts

T1EDK-00094 UIDB/EQU/50020/2020 UIDB/00511/2020 CEECINST/00102/2018 UIDB/50006/2020 UIDP/50006/2020 DL 57/2017The copper–ceria (CuOx /CeO2 ) system has been extensively investigated in several catalytic processes, given its distinctive properties and considerable low cost compared to noble metal-based catalysts. The fine-tuning of key parameters, e.g., the particle size and shape of individual counterparts, can significantly affect the physicochemical properties and subsequently the catalytic performance of the binary oxide. To this end, the present work focuses on the morphology effects of ceria nanoparticles, i.e., nanopolyhedra (P), nanocubes (C), and nanorods (R), on the water–gas shift (WGS) performance of CuOx /CeO2 catalysts. Various characterization techniques were employed to unveil the effect of shape on the structural, redox and surface properties. According to the acquired results, the support morphology affects to a different extent the reducibility and mobility of oxygen species, following the trend: R > P > C. This consequently influences copper–ceria interactions and the stabilization of partially reduced copper species (Cu+ ) through the Cu2+ /Cu+ and Ce4+ /Ce3+ redox cycles. Regarding the WGS performance, bare ceria supports exhibit no activity, while the addition of copper to the different ceria nanostructures alters significantly this behaviour. The CuOx /CeO2 sample of rod-like morphology demonstrates the best catalytic activity and stability, approaching the thermodynamic equilibrium conversion at 350◦ C. The greater abundance in loosely bound oxygen species, oxygen vacancies and highly dispersed Cu+ species can be mainly accounted for its superior catalytic performance.publishersversionpublishe

Commercial Gold Complexes Supported on Functionalised Carbon Materials as Efficient Catalysts for the Direct Oxidation of Ethane to Acetic Acid

UIDB/00100/2020 UIDP/00100/2020 LA/P/0056/2020 IST-ID/119/2018 SFRH/BD/146426/2019 CEEC-INST/00102/2018 UIDB/50006/2020 UIDP/50006/2020 Base-UIDB/50020/2020 Programmatic-UIDP/50020/2020The single-pot efficient oxidation of ethane to acetic acid catalysed by Au(I) or Au(III) compounds, chlorotriphenylphosphinegold(I) (1), chlorotrimethylphosphinegold(I) (2), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidenegold(I) chloride (3), dichloro(2-pyridinecarboxylato)gold(III) (4), homogenous and supported on different carbon materials: activated carbon (AC), multi-walled carbon nanotubes (CNT) and carbon xerogel (CX), oxidised with nitric acid followed by treatment with NaOH (-ox-Na), is reported. The reactions were performed in water/acetonitrile. The materials were selective for the production of acetic acid, with no trace of by-products being detected. The best homogenous catalysts were complexes 2 and 3 which showed the highest ethane conversion and an acetic acid yield of ca. 21%, followed by 4 and 1. The heterogenised materials showed much better activity than the homogenous counterparts, with acetic acid yields up to 41.4% for 4@CNT-ox-Na, and remarkable selectivity (with acetic acid being the only product detected). The heterogenised catalysts with the best results were reused up to five cycles, with no significant loss of activity, and maintaining high selectivity for acetic acid. 4@CNT-ox-Na showed not only the best catalytic activity but also the best stability during the recycling runs.publishersversionpublishe

Facile one-pot synthesis of Pt nanoparticles/SBA-15: an active and stable material for catalytic applications

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Pt/SBA-15 with an enhanced surface area but unchanged pore diameter (compared to pure SBA-15) and a Pt average particle size of ∼9 nm shows a high and stable activity for both gas-phase CO oxidation and liquid-phase cyclooctadiene hydrogenation. No intrinsic change in the structure of the catalyst occurs after several reaction cycles, suggesting that the Pt/SBA-15 presented here is an active and stable catalyst.DFG, EXC 314, Unifying Concepts in Catalysi