RESUMO
The hydrogenation of CO2 to CH4 has gained considerable interest in terms of sustainable energy and environmental mitigation. In this regard, the present work aims to investigate the adsorptive concentration and CO2 methanation performance over CoFe and NiFe bimetallic catalysts supported on fumed alumina-silica SA96 support at 170-450 °C and under atmospheric pressure. The catalysts were prepared by wet impregnation method, subjected to calcination and further reduced with hydrogen, and their performance in CO2 methanation was investigated in a hydrogen-rich 2%CO2-55%H2-43%He gas mixture. In this study, we describe the crystal and mesoporous structures of the prepared catalysts by in-situ XRD and ex-situ nitrogen adsorption, evaluate the NiFe and CoFe metal surface states before and after catalysis by XPS, visualize the surface morphology by SEM, estimate the catalytic activity by gas chromatography, and investigate the adsorbed surface species, showing the presence of *HCOO/*HCO and *CO intermediates, determine two possible pathways of CH4 formation on the studied catalysts by temperature-programmed desorption mass spectrometry, and correlate the structural and surface properties with high CO2 conversions up to 100% and methanation selectivities up to 72%. The latter is related to changes in the elemental chemical states and surface composition of CoFe and NiFe nanocatalysts induced by treatment under reaction conditions, and the surface reconstruction during catalysis transfers the part of active 3d transition metals into the pores of the SA96 support. Our thorough characterization study with complementary techniques allowed us to conclude that this high activity is related to the formation of catalytically active Ni/Ni3Fe and Co/CoFeOx nanoscale crystallites under H2 reduction and their maintenance under CO2 methanation conditions. The successfully applied combination of CO2 chemisorption and thermodesorption techniques demonstrates the ability to adsorb the CO2 molecules by supported NiFe and CoFe nanocatalysts and the pure alumina-silica SA96 support.
Assuntos
Óxido de Alumínio , Dióxido de Carbono , Cobalto , Metano , Níquel , Dióxido de Silício , Propriedades de Superfície , Óxido de Alumínio/química , Catálise , Dióxido de Carbono/química , Metano/química , Níquel/química , Cobalto/química , Dióxido de Silício/química , Ferro/química , AdsorçãoRESUMO
Nitrogen- and oxygen-containing carbon nanoparticles (O, N-CDs) were prepared by a facile one-step solvothermal method using urea and citric acid precursors. This method is cost-effective and easily scalable, and the resulting O, N-CDs can be used without additional functionalization and sample pretreatment. The structure of O, N-CDs was characterized by TEM, AFM, Raman, UV-vis, and FTIR spectroscopies. The obtained O, N-CDs with a mean diameter of 4.4 nm can be easily dispersed in aqueous solutions. The colloidal aqueous solutions of O, N-CDs show significant photothermal responses under red-IR and radiofrequency (RF) irradiations. The as-prepared O, N-CDs have a bright temperature-dependent photoluminescence (PL). PL/PLE spectral maps were shown to be used for temperature evaluation purposes in the range of 30-50 °C. In such a way, the O, N-CDs could be used for biomedicine-related applications such as hyperthermia with simultaneous temperature estimation with PL imaging.
RESUMO
Using the transmission electron microscopy (TEM)/high-resolution TEM (HRTEM) and selected area electron diffraction (SAED) methods, it was shown that the nanocolloids of ZnO contain hydrolyzed ZnO nanoparticles (NPs). Typically, the nanocrystalline ZnO/Zn(OH)2 core is covered by an amorphous shell of zinc hydroxides, preventing the encapsulated crystal core from dissolving. Similar studies were carried out with TiO2 nanocolloids. It was found that burdening of rats for 30 days with a ZnO aqueous nanocolloid (AN) was accompanied by a narrowing of the amplitude range, a decrease (increase) in the frequency of spontaneous contractions (SCs), and an inhibition of the efficiency indices for smooth muscles (SMs) of the antrum and cecum. Under longer (100 days) burdening of rats with AN of ZnO, there was a tendency toward restoring the above parameters. In terms of the value and the direction of changes in most parameters for SCs of SMs, the effects (30 days) of TiO2 AN differed from those for ZnO AN and were almost the same in the case of their long-term impact. It was found that mostly M2-cholinoreceptor-dependent mechanisms of regulating the intracellular concentration of Ca2+ were sensitive to the effect of ZnO and TiO2 ANs. The molecular docking demonstrated that ZnO and TiO2 NPs did not compete with acetylcholine for the site of binding to M3 and M2 cholinoreceptors but may impact the affinity of orthosteric ligands to M2 cholinoreceptors. The studies showed that burdening rats with ZnO and TiO2 ANs was also accompanied by changes in the activity state of both intracellular enzymes and the ion transport systems for Na+, K+, and Ca2+, related to the processes of bile secretion, via the plasma membrane of hepatocytes.
RESUMO
A simple sensitive method for nonspecific recognition of armagnac, cognac, whiskey, and ethanol/water mixture was developed by using photoluminescence (PL) of carbon nanoparticles (NPs). The carbon NPs were synthesized from the mixture of urea and anhydrous citric acid, followed by few annealing processes to achieve the full effect by solvothermal carbonization. PL features of carbon NPs depend on the alcohol environments in which the NPs are dispersed. PL/PL excitation maps of the alcoholic beverages were mathematically treated, and a final principal component analysis diagram allows visualization of different clusters corresponding to each beverage. The optimal measurement conditions (concentration of NPs in colloidal solution and excitation wavelength) were defined to ensure a reliable recognition level.
RESUMO
The present study is objected to develop an analytical remote optical diagnostics of the functionalized carbons surface. Carbon composites with up to 1 mmol g-1 of irreversibly adsorbed bromine were produced by the room temperature plasma treatment of an activated carbon fabric (ACF) derived from polyacrylonitrile textile. The brominated ACF (BrACF) was studied by elastic optical scattering indicatrix analysis at wavelength 532 nm. The obtained data were interpreted within results of the thermogravimetric analysis, X-ray photoelectron spectroscopy and temperature programmed desorption mass spectrometry. The bromination dramatically reduces the microporosity producing practically non-porous material, while the incorporated into the micropores bromine induces the dielectric and structural impact on surface polarizability and conductivity due to the charging effect. We have found that the elastic optical scattering in proper solid angles in the forward and the backward hemispheres is sensitive to the kind of the bromine bonding, e.g., physical adsorption or chemisorption, and the bromination level, respectively, that can be utilized for the express remote fabrication control of the nanoscale carbons with given interfaces.
RESUMO
In this study, we report soft and solvothermal methods for synthesis of zinc oxide nanoparticles (ZnO NPs). Both methods involve a precursor and are carried out at the middle low-temperature regime. The effect of different solvents on the ZnO NPs properties was studied. The nonlinear optical (NLO) response of the NPs was analyzed by the self-action of picosecond laser pulses at 1064 nm and by second harmonic generation (SHG) of a femtosecond laser pulses pump at 800 nm. The luminescence was studied within UV-visible ranges. It was shown that the NLO response efficiency significantly depends on the solvent. The obtained SHG efficiency of small (~2 nm) ZnO NPs is comparable to the one obtained for large (~150 nm) commercial ZnO NPs. The observed results are important for the application of the ZnO NPs in biolabeling.