Search

The pore-size distribution (PSD) of an activated carbon (AC) sample, which is obtained by molecular simulation using a specific probe gas, does not always reproduce the adsorptive behaviour of that sample with other gases. Moreover, different gases generate distinct distributions for the same AC. These facts go against the concept of PSD, which must be unique for a given sample, irrespective of the probe gas used. We analyzed adsorption isotherms of WV-1050 AC sample with nitrogen at 77 K, carbon dioxide at 298 K and methane at 303 K, yielding their respective PSDs, based on local isotherms database (kernels) generated through grand canonical Monte Carlo simulation. The PSD obtained for nitrogen and carbon dioxide was used (individually) to reproduce the three experimental isotherms and significant deviations were observed. By applying a volume normalization methodology, the isotherm fitting was significantly enhanced. Furthermore, a more realistic model of AC pores considering etched slit walls was tested to improve PSD similarity. The new model presented tends to unify the PSDs obtained from different probe gases evaluated.

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 (N 2 , CO 2 , and CH 4 ). 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 N 2 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 CO 2 , CH 4 and N 2 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 CO 2 and CH 4 and (ii) open hysteresis loops in N 2 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 CO 2 uptake while keeping acceptable selectivity with regards to CH 4 and moderate adsorption enthalpies.