Search

Activated carbon (AC) is a common material of choice in catalysis, as it is a suitable support material for many catalytic reactions. In this work, the effect of cobalt nanoparticles on activated carbon derived from a biomass waste, peach stone, is reported. The presence of cobalt during heat treatments at 900 °C under reductive (H2) and inert (He) atmospheres resulted in the appearance of an intense 2D band in the Raman spectra, indicating a high degree of graphitization. Temperature-programmed reduction and desorption experiments were conducted to evaluate the activation reactions. Quenched solid density functional theory (QSDFT) analysis using N2 adsorption data revealed that cobalt increased pore development in the samples, regardless of the atmosphere (reductive or inert) used.

Microporous activated carbons with remarkably high CO2 uptake have been synthesized using polyurethane (PU) commercial foams as precursors. The PU samples were pyrolyzed at different temperatures in N2 atmosphere and chemically activated with KOH. Adsorption isotherms at 0 °C and 25 °C and immersion calorimetry were applied to provide a deeper knowledge about the most relevant factors implied in CO2 capture process explaining, hence, the values of adsorption obtained. CO2 adsorption uptakes reached values of 7.4 mmol/g at 0 °C, 5.0 mmol/g at 25 °C and 2.7 mmol/g at 50 °C. The remarkably high values of CO2 uptake are closely related with the BET specific surface area of the carbon foams but also with the high volume of narrow micropores all the samples present a high volume of micropores (between 0.59 and 0.71 cm3/g) as also confirmed by immersion calorimetry.

Activated carbon-based molecular sieves were synthetized, characterized and their kinetics of adsorption were evaluated to be used in separation processes of CO2/CH4 mixtures. Polyurethane (PU) foams were used as carbon precursors and the PU-derived carbons were physical activated with CO2. All the samples present a preferential adsorption of CO2 over methane in kinetic adsorption experiments. Samples activated at 800 ºC during 6 h exhibited the highest selectivity due to the absence of methane adsorption at lower resident times, which makes those samples very interesting for industrial processes of natural gas purification. Kinetic studies were performed to explain the kinetic profiles obtained, confirming that in the samples with smallest pore size, intraparticle diffusion was the limiting step, evidencing that certain oxygen groups favour CO2 adsorption, whereas adsorption was the limiting step in the samples with wider pores.

Here, we report the preparation of microporous-activated carbons from a Brazilian natural lignocellulosic agricultural waste, cupuassu shell, by pyrolysis at 500 ºC and KOH activation under different experimental conditions and their subsequent application as adsorbent for CO2 capture. The effect of the KOH:precursor ratio (wt/wt%) and the activation temperature on the porous texture of activated carbons have been studied. The values of specific surface area ranged from 1132 to 2486 m2/g, and the overall micropore volume ranged from 0.73 to 1.02 cm3/g. Carbons activated with 2:1 ratio of KOH and activation temperature of 700 ºC presented a CO2 adsorption at 1 bar of 7.8 and 4.4 mmol/g at 0 °C and 25 ºC, respectively. The isosteric heat of adsorption, Qst, was calculated for all samples by applying the Clausius–Clapeyron approach to CO2 adsorption isotherms at both temperatures. The values of CO2 adsorption capacities are among the highest reported in the literature, especially for activated carbons produced from biomass.

Activated carbons from different precursors have been synthetized using KOH and mixtures of KOH and KCl as activating agents. The results revealed an increase of surface area and yield of activation related with KCl addition in all the samples. Thermodynamic and mass spectrometry studies reveal that KCl do not act as an activating agent, but promotes the solubilisation of secondary products of the reactions such as carbonates, enhancing the contact of KOH and carbon particles, therefore increasing the efficiency of the activation. Based on mass spectroscopy results, combined with thermodynamic calculations, we proposed four reactions as the most likely responsible for the pore development during activation.

The hydrogenation of nitroarenes to produce the corresponding amines using dihydrogen as reducing agent has an important industrial role, since it allows to obtain important added-value products. This reaction needs the help of a catalyst to proceed. Many catalysts have been already tested and studied. Most of them are based on noble metals supported on metal oxides. These catalysts perform well, but they are expensive and thus, alternative systems are needed. In this context, cobalt-based catalysts have emerged as adequate alternatives, despite cobalt nanoparticles per se are not very active for this reaction. A way to improve the catalytic activity of cobalt nanoparticles is by supporting them on a support with functional groups that are able to change their intrinsic properties and to enhance their catalytic properties. In this sense, N-containing carbons are promising candidates to be used as support, since nitrogen functionalities may modify the catalytic properties of cobalt. In this work, cobalt nanoparticles supported on N-doped activated carbons have been prepared and studied as catalysts for the hydrogenation of 1-chloro-4-nitrobencene to the corresponding chloro-aniline. It is demonstrated that the catalytic activity is enhanced by the presence of nitrogen species in the support. When the temperature of the catalyst activation treatment (reduction under flowing hydrogen) is increased, the catalytic activity increases drastically in the presence of nitrogen functionalities on the support. The catalysts have been characterised by transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction, X-ray photoelectron spectroscopi (XPS) and N2 adsorption at 77 K. It has been found that the enhanced catalytic activity was due to two different factors, namely the interaction of the cobalt particles with the nitrogen functional groups (forming Co4N), and the development of mesopores in the support during the activation process that

En este trabajo se han estudiado diferentes métodos de activación de espumas de poliuretano para generar carbón activo. Así como la aplicabilidad de dichos carbones en procesos de adsorción de CO2, separación de mezclas de gases CO2/CH4, así como su desempeño en procesos biomédicos como adsorción de mercurio, yodometano y ensayos de biocompatibilidad.

Although traditionally high-surface area carbon materials have been considered as rigid structures with a disordered three dimensional (3D) network of graphite microdomains associated with a limited electrical conductivity (highly depending on the porous structure and surface chemistry), here we show for the first time that this is not the case for activated carbon materials prepared using harsh activation conditions (e.g., KOH activation). In these specific samples a clear structural re-orientation can be observed upon adsorption of different organic molecules, the structural changes giving rise to important changes in the electrical resistivity of the material. Whereas short chain hydrocarbons and their derivatives give rise to an increased resistivity, the contrary occurs for longer-chain hydrocarbons and/or alcohols. The high sensitivity of these high-surface area carbon materials towards these organic molecules opens the gate towards their application for sensing devices.