Revealing the Combined Effect of Active Sites and Intra-Particle Diffusion on Adsorption Mechanism of Methylene Blue on Activated Red-Pulp Pomelo Peel Biochar.

Phosphoric acid-activated biochar has been proven to be a promising adsorbent for pollutant removal in an aqueous solution. It is urgent to understand how surface adsorption and intra-particle diffusion synergistically contribute to the adsorption kinetic process of dyes. In this work, we prepared a series of PPC adsorbents (PPCs) from red-pulp pomelo peel under different pyrolysis temperatures (150-350 °C), which have a broad specific surface area range from 3.065 m2/g to 1274.577 m2/g. The active sites on the surface of PPCs have shown specific change laws of decreasing hydroxyl groups and increasing phosphate ester groups occurring as the pyrolysis temperature rises. Both reaction models (PFO and PSO models) and diffusion models (intra-particle diffusion models) have been applied to simulate the adsorption experimental data to verify the hypothesis deduced from the Elovich model. PPC-300 exhibits the highest adsorption capacity of MB (423 mg/g) under given conditions. Due to its large quantities of active sites on the external and internal surfaces (1274.577 m2/g), a fast adsorption equilibrium can be achieved within 60 min (with an initial MB concentration of 100 ppm). PPC-300 and PPC-350 also exhibit an intra-particle-diffusion-controlled adsorption kinetic process with a low initial MB concentration (100 ppm) or at the very beginning and final stage of adsorption with a high initial MB concentration (300 ppm) at 40 °C, considering that the diffusion is likely hindered by adsorbate molecules through internal pore channels at the middle stage of adsorption in these cases.

Insights into the pH-Dependent Adsorption Behavior of Ionic Dyes on Phosphoric Acid-Activated Biochar.

Activated biochar is a promising porous carbonaceous adsorbent material for organic pollutant removal, but it remains challenging to obtain high porosity and aromaticity through a simple and low-cost synthetic method. The common adsorption mechanisms of organic dyes on activated biochar should be further investigated in order to guide the synthesis of high-efficiency adsorbent materials. Here, we proposed a high-yield (up to 40 wt %) synthetic method of phosphoric acid-activated biochar from pomelo peel (PPC) with a high specific area of 877.3 m2/g through a facile thermal treatment at a relatively low temperature (250 °C). The specific activation mechanism of H3PO4 in the preparation of the adsorbent was investigated by a range of experiments and characterizations. The kinetic and isotherm experiments are also conducted to evaluate its dye adsorption behavior. According to the adsorption experiment results, PPC exhibits high saturated adsorption capacities for methyl orange (MO, 239.1 mg/g), rhodamine B (RhB, 2821.8 mg/g), methylene blue (MB, 580.5 mg/g), and crystal violate (CV, 396.6 mg/g) according to the Langmuir model. The maximum initial concentration of each dye solution for acquiring 90% removal efficiency is estimated to be 234.55 ppm (MO), 2943.8 ppm (RhB), 633.8 ppm (MB), and 423.6 ppm (CV) at 298 K with an adsorbent dosage of 1 g/L. The characterization results also indicate PPC has a complex synergetic mechanism for ionic dye adsorption behavior. This provides perspectives regarding PPC as a promising biochar adsorbent from biomass waste, which is probably useful for high-efficiency dye removal in water treatment.