The Use of High Surface Area Mesoporous-Activated Carbon from Longan Seed Biomass for Increasing Capacity and Kinetics of Methylene Blue Adsorption from Aqueous Solution.

Microporous- and mesoporous-activated carbons were produced from longan seed biomass through physical activation with CO2 under the same activation conditions of time and temperature. The specially prepared mesoporous carbon showed the maximum porous properties with the specific surface area of 1773 m2/g and mesopore volume of 0.474 cm3/g which accounts for 44.1% of the total pore volume. These activated carbons were utilized as porous adsorbents for the removal of methylene blue (MB) from an aqueous solution and their effectiveness was evaluated for both the adsorption kinetics and capacity. The adsorption kinetic data of MB were analyzed by the pseudo-first-order model, the pseudo-second-order model, and the pore-diffusion model equations. It was found that the adsorption kinetic behavior for all carbons tested was best described by the pseudo-second-order model. The effective pore diffusivity (De) derived from the pore-diffusion model had the values of 4.657 × 10-7-6.014 × 10-7 cm2/s and 4.668 × 10-7-19.920 × 10-7 cm2/s for the microporous- and mesoporous-activated carbons, respectively. Three well-known adsorption models, namely the Langmuir, Freundlich and Redlich-Peterson equations were tested with the experimental MB adsorption isotherms, and the results showed that the Redlich-Peterson model provided the overall best fitting of the isotherm data. In addition, the maximum capacity for MB adsorption of 1000 mg/g was achieved with the mesoporous carbon having the largest surface area and pore volume. The initial pH of MB solution had virtually no effect on the adsorption capacity and removal efficiency of the methylene blue dye. Increasing temperature over the range from 35 to 55 °C increased the adsorption of methylene blue, presumably caused by the increase in the diffusion rate of methylene blue to the adsorption sites that could promote the interaction frequency between the adsorbent surface and the adsorbate molecules. Overall, the high surface area mesoporous carbon was superior to the microporous carbon in view of the adsorption kinetics and capacity, when both carbons were used for the removal of MB from an aqueous solution.

A New Approach for Controlling Mesoporosity in Activated Carbon by the Consecutive Process of Air Oxidation, Thermal Destruction of Surface Functional Groups, and Carbon Activation (the OTA Method).

A new and simple method, based entirely on a physical approach, was proposed to produce activated carbon from longan fruit seed with controlled mesoporosity. This method, referred to as the OTA, consisted of three consecutive steps of (1) air oxidation of initial microporous activated carbon of about 30% char burn-off to introduce oxygen surface functional groups, (2) the thermal destruction of the functional groups by heating the oxidized carbon in a nitrogen atmosphere at a high temperature to increase the surface reactivity due to increased surface defects by bond disruption, and (3) the final reactivation of the resulting carbon in carbon dioxide. The formation of mesopores was achieved through the enlargement of the original micropores after heat treatment via the CO2 gasification, and at the same time new micropores were also produced, resulting in a larger increase in the percentage of mesopore volume and the total specific surface area, in comparison with the production of activated carbon by the conventional two-step activation method using the same activation time and temperature. For the activation temperatures of 850 and 900 °C and the activation time of up to 240 min, it was found that the porous properties of activated carbon increased with the increase in activation time and temperature for both preparation methods. A maximum volume of mesopores of 0.474 cm3/g, which accounts for 44.1% of the total pore volume, and a maximum BET surface area of 1773 m2/g was achieved using three cycles of the OTA method at the activation temperature of 850 °C and 60 min activation time for each preparation cycle. The two-step activation method yielded activated carbon with a maximum mesopore volume of 0.270 cm3/g (33.0% of total pore volume) and surface area of 1499 m2/g when the activation temperature of 900 °C and a comparable activation time of 240 min were employed. Production of activated carbon by the OTA method is superior to the two-step activation method for better and more precise control of mesopore development.

The Analysis of Pore Development and Formation of Surface Functional Groups in Bamboo-Based Activated Carbon during CO2 Activation.

Pore development and the formation of oxygen functional groups were studied for activated carbon prepared from bamboo (Bambusa bambos) using a two-step activation with CO2, as functions of carbonization temperature and activation conditions (time and temperature). Results show that activated carbon produced from bamboo contains mostly micropores in the pore size range of 0.65 to 1.4 nm. All porous properties of activated carbons increased with the increase in the activation temperature over the range from 850 to 950 °C, but decreased in the temperature range of 950 to 1000 °C, due principally to the merging of neighboring pores. The increase in the activation time also increased the porous properties linearly from 60 to 90 min, which then dropped from 90 to 120 min. It was found that the carbonization temperature played an important role in determining the number and distribution of active sites for CO2 gasification during the activation process. Empirical equations were proposed to conveniently predict all important porous properties of the prepared activated carbons in terms of carbonization temperature and activation conditions. Oxygen functional groups formed during the carbonization and activation steps of activated carbon synthesis and their contents were dependent on the preparation conditions employed. Using Boehm's titration technique, only phenolic and carboxylic groups were detected for the acid functional groups in both the chars and activated carbons in varying amounts. Empirical correlations were also developed to estimate the total contents of the acid and basic groups in activated carbons in terms of the carbonization temperature, activation time and temperature.

Improving porous properties of activated carbon from carbon gel by the OTA method.

High-surface-area microporous-mesoporous carbons were produced from carbon gel by applying the three consecutive steps of air oxidation, thermal treatment, and activation (the OTA method) to the gel. The formation of mesopores occurs both inside and outside the nanoparticles which form the carbon gel, while micropores are predominantly created within the nanoparticles. The OTA method offered a greater increase in pore volume and BET surface area of the resulting activated carbon in comparison with conventional CO2 activation either under the same activation conditions or at the same degree of carbon burn-off. Under the best preparation conditions, the maximum values of micropore volume, mesopore volume, and BET surface area achievable using the OTA method were found to be 1.19 cm3 g-1, 1.81 cm3 g-1, and 2920 m2 g-1, respectively at a 72% carbon burn-off. The larger increase in porous properties of activated carbon gel prepared by the OTA method over those based on conventional activation stems from the effects of the oxidation and heat treatment steps of the OTA method that could produce a large number of reaction sites which lead to efficient pore formation during the following CO2 activation process.