In recent years, biochar has emerged as a remarkable biosourced material for addressing global environmental, agricultural, biomedical, and energy challenges. However, the performances of biochar rest in part on finely tuning its surface chemical properties, intended to obtain specific functionalities. In this review, we tackle the surface treatment of biochar with silane and other coupling agents such as diazonium salts, titanates, ionic/non-ionic surfactants, as well as nitrogen-containing (macro)molecules. We summarize the recent progress achieved mostly in the last five years and correlate the nature and extent of functionalization to eye-catchy end applications of the surface-engineered biochar.
This paper deals with the adsorption of heavy metal ions on the surface of carbonaceous materials obtained via the chemical activation of biomass. Waste plum stones, pine sawdust and horsetail herb were used as the precursors of carbonaceous adsorbents. The effect of the precursor type and preparation procedure on the physicochemical properties of activated biocarbons and their sorption abilities towards Pb(II) and Cu(II) ions have been checked. The obtained micro-mesoporous activated biocarbons were characterized by determination of elemental composition and ash content, the number of surface functional groups and pH of water extracts as well as textural study based on low temperature nitrogen adsorption/desorption and scanning electron microscopy. Additionally, the electrokinetic studies including solid surface charge density and zeta potential determination were performed. Moreover, the adsorption data modelling (equilibrium and kinetics), XPS results analysis and comparison of parameters characterizing electrical double layer formed at the solid-liquid interface enabled the specification of the mechanism of heavy metals binding with the activated biocarbons surface. The maximum adsorption capacity towards copper and lead ions (177.5 and 178.1 mg/g, respectively) was found for plum stone-based activated biocarbon. For all carbonaceous materials, better fit to the experimental data was achieved with a Langmuir isotherm than a Freundlich one. In turn, a better fit of the kinetics data was obtained using the pseudo-second order model.
Nettle and the sage herbs were used to obtain carbonaceous adsorbents. For the biochar preparation the precursors were dried and subjected to conventional pyrolysis. Activated carbons were obtained during precursor impregnation with phosphoric(V) acid and multistep pyrolysis. The textural parameters and acidic-basic properties of the obtained adsorbents were studied. The activated carbons prepared from the above herbs were characterized by the largely developed specific surface area. The obtained carbonaceous adsorbents were used for polymer removal from aqueous solution. Poly(acrylic acid) (PAA) and polyethylenimine (PEI) were chosen, due to their frequent presence in wastewater resulting from their extensive usage in many industrial fields. The influence of polymers on the electrokinetic properties of activated carbon were considered. PAA adsorption caused a decrease in the zeta potential and the surface charge density, whereas PEI increased these values. The activated carbons and biochars were used as polymer adsorbents from their single and binary solutions. Both polymers showed the greatest adsorption at pH 3. Poly (acrylic acid) had no significant effect on the polyethylenimine adsorbed amount, whereas PEI presence decreased the amount of PAA adsorption. Both polymers could be successfully desorbed from the activated carbons and biochar surfaces. The presented studies are innovatory and greatly required for the development of new environment protection procedures.
The main aim of this study was the determination of temperature influence on adsorption mechanisms of anionic poly(acrylic acid) (PAA) and cationic polyethylenimine (PEI) on the surface of activated carbons (AC) obtained via chemical activation of nettle (NE) and sage (SA) herbs. All measurements were performed at pH 3 at three temperature values, i.e., 15, 25 and 35 °C. The adsorption/desorption of these polymers from single and mixed solution of adsorbates was also investigated. The viscosity studies were additionally performed to obtain hydrodynamic radius values characterizing polymeric macromolecules conformation in the solution. These data are very important for the explanation of changes of linear dimensions of polymer chains with the rise of temperature caused by the modification of polymer–solvent interactions. Moreover, the XPS studies for the systems showing the highest adsorbed amounts in the specific temperature conditions were carried out. These were the systems containing PEI, PAA and NE–AC activated carbon at 25 °C. In such a case, the maximum adsorption capacity towards PAA macromolecules from a single solution of adsorbate reaches the value of 198.12 mg/g. Additionally, the thermodynamic parameters including the free energies of adsorption, as well as changes in free enthalpy and entropy were calculated.
Biochars and activated carbons obtained from the nettle and the sage herbs were used for Cd(II), As(V), poly(acrylic acid) and polyethylenimine simultaneous adsorption from the multicomponent aqueous solutions. Electrokinetic studies proved that both activated carbons show acidic character of the surface. The point of zero charge of the sample obtained from the nettle herb occurs at pH 3.1, whereas that of the adsorbent obtained from the sage herb at pH 4.0. Cd(II) adsorption causes the decrease in the surface charge density and the zeta potential of both activated carbons, whereas As(V) addition results in the increase of solid surface charge density and its impact on the zeta potential value depends on adsorbent type. In case of the simultaneous presence of metals and polymers, the adsorbed macromolecules have greater influence on the surface charge density and the zeta potential values than the metal ions. Cd(II) and As(V) are well adsorbed on the examined activated carbons irrespective of the solution pH (changing in the range 3–9). Maximum adsorption were 218.27 mg/g for Cd(II) and 205.53 mg/g for As(V). The polymers presence causes a decrease (80–90 %) of both metal ions adsorbed amounts, whereas the poly(acrylic acid) and polyethylenimine adsorption mechanism in the presence of cadmium and arsenic ions depends on the adsorbent type and polymer-metal interactions.