RESUMO
SO2 emissions not only affect local air quality but can also contribute to other environmental issues. Developing low-cost and robust adsorbents with high uptake and selectivity is needed to reduce SO2 emissions. Here, we show the SO2 adsorption-desorption capacity of carbon microfibers (CMFs) at 298 K. CMFs showed a reversible SO2 uptake capacity (5 mmol g-1), cyclability over ten adsorption cycles with fast kinetics and good selectivity towards SO2/CO2 at low-pressure values. Additionally, CMFs' photoluminescence response to SO2 and CO2 was evaluated.
RESUMO
The present work reports the changes for the mesoporous materials SBA-15 and KIT-6 associated with the structural, textural, and chemical properties when they are subjected to thermo-alkaline treatment. Despite the fact that the silica supports have not a strong affinity for CO2 adsorption, the adsorption enthalpy profiles (ΔHads) reported that the substrates subjected to the thermo-alkaline treatment (S15H and K6H) have a greater energetic affinity towards CO2 capture if compared to the precursory solids (S15 and K6). The ΔHads is - 26.7 kJ mol-1 at 0.15 mmol g-1 by supported S15H and K6H while the ΔHads is - 20. 7 kJ mol-1 and - 18.7 kJ mol-1 by K6 and S15, respectively, at the same CO2 coverage. Furthermore, the CO2 adsorption performances by the hydrolytic condensation between silica supports and the N´- (3-trimethoxysilylpropyl)diethylenetriamine (NAEPTES) or 3-aminopropiltriethoxysilane (APTES) are presented and it can be seen that the best performer for CO2 adsorption is reported for the S15HN since it is able to absorb 0.93 mmol at 0.15 atm at 318 K. Thereby, the outcomes show that the effects of porous curvature and the magnitude of the amine species are parameters to be considered, as well as the thermo-alkaline treatment, in order to improve the subsequent surface reactions on silica supports. The materials were characterized by XRD, TEM, and N2 adsorption at 77 K, NIR, and pyridine thermodesorption using Fourier Transform Infrared Spectroscopy (FTIR-Py), NMR for 29Si and 13C, DSC, and CO2 adsorption.
RESUMO
This work investigates the interplay of carbonization temperature and the chemical composition of carbon microfibers (CMFs), and their impact on the equilibration time and adsorption of three molecules (N2, CO2, and CH4). PAN derived CMFs were synthesized by electrospinning and calcined at three distinct temperatures (600, 700 and 800 °C), which led to samples with different textural and chemical properties assessed by FTIR, TGA/DTA, XRD, Raman, TEM, XPS, and N2 adsorption. We examine why samples calcined at low/moderate temperatures (600 and 700 °C) show an open hysteresis loop in nitrogen adsorption/desorption isotherms at -196.15 °C. The equilibrium time in adsorption measurements is nearly the same for these samples, despite their distinct chemical compositions. Increasing the equilibrium time did not allow for the closure of the hysteresis loop, but by rising the analysis temperature this was achieved. By means of the isosteric enthalpy of adsorption measurements and ab initio calculations, adsorbent/adsorbate interactions for CO2, CH4 and N2 were found to be inversely proportional to the temperature of carbonization of the samples (CMF-600 > CMF-700 > CMF-800). The enhancement of adsorbent/adsorbate interaction at lower carbonization temperatures is directly related to the presence of nitrogen and oxygen functional groups on the surface of CMFs. Nonetheless, a higher concentration of heteroatoms also causes: (i) a reduction in the adsorption capacity of CO2 and CH4 and (ii) open hysteresis loops in N2 adsorption at cryogenic temperatures. Therefore, the calcination of PAN derived microfibers at temperatures above 800 °C is recommended, which results in materials with suitable micropore volume and a low content of surface heteroatoms, leading to high CO2 uptake while keeping acceptable selectivity with regards to CH4 and moderate adsorption enthalpies.