^{1}

^{*}

^{1}

^{2}

^{2}

The adsorption properties of layered double hydroxide (Mg/Al-CO
_{3}) for the removal of Congo Red (CR) dye from aqueous solution were studied. The layered double hydroxide was synthesized by co-precipitation method and characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopic (FTIR) and Energy-Dispersive X-ray Spectroscopic (EDX). The effects of various experimental parameters such as contact time, dye concentrations and temperature variation were investigated. The results show that the amount of Congo Red adsorbed increases with increase in temperature but decreases with increase in initial dye concentration and contact time. The data were also fitted to several kinetic models: zero-order kinetic model, first-order kinetic model, second-order kinetic model, pseudo-second-order kinetic model and third-order kinetic model respectively. The adsorption process was best defined by zero-order-kinetic model (
*R*
^{2} = 1). Langmuir, Freundich, Temkin and Dubinin-kaganer-Radushkevich (DPK) adsorption isotherm models were applied to analyze adsorption data with Temkin isotherm being the most applicable to the adsorption process. Thermodynamic parameters e.g.
*△G*
^{o},
*△*
*S*
^{o},
*△*
*H*
^{o} and
*△*
*H*
_{x} of the adsorption process were found to be endothermic, spontaneous and feasible.

The wastewater disposed by textile industries is causing major hazards to the environment and drinking water due to presence of a large number of contaminants like acids, bases, toxic organic, inorganic, dissolved solids and colour [

Layered double hydroxides also known as hydrotalcite-like compounds or anionic clays, have received much attention in the past decades due to their wide spread applicability. LDHs have positively charged layers of metal hydroxides and the anions and water molecules are located between the layers. The positive charges that are produce from the isomorphous substitution of divalent cations and trivalent cations, are counter balanced by

anions located between the layers [

where M^{2+} and M^{3+} are divalent and trivalent metal cations, respectively; A is the anions, and x is ratio M^{3+}/(M^{2+} + M^{3+}) [

Carbonate form of Mg-Al LDH was synthesized by co-precipitation method. A 50 ml aqueous solution containing 0.3 M Mg(NO_{3})_{2}×6H_{2}O and 0.1 M Al(NO_{3})_{3}×9H_{2}O with Mg/Al ratios 4:1, was added drop wise into a 50 ml mixed solution of NaOH (2 M) + Na_{2}CO_{3} (1 M) with vigorous stirring and maintaining a pH of greater than 10 at room temperature. After complete addition which last between 2 hours 30 minutes to 3 hours, the slurry formed was aged at 60˚C for 18 hours. The products were centrifuged at 5000 rpm for 5 minutes, with distilled water 3 - 4 times and dried by freeze drying.

X-ray diffraction (XRD) pattern of the sample was characterized by using a Shimadzu XRD-6000 diffractometer, with Ni-filtered Cu-Kα radiation (λ = 1.54 Å) at 40 kV and 200 mA. Solid samples were mounted on alumina sample holder and basal spacing (d-spacing) was determined via powder technique. Samples scan were carried out at 10˚ - 60˚, 2θ/min at 0.003˚ steps.

FTIR spectrum was obtained using a Perkin Elmer 1725X spectrometer where samples will be were finely ground and mixed with KBr and pressed into a disc. Spectrums of samples were scanned at 2 cm^{−1} resolution between 400 and 4000 cm^{−1}.

FESEM/EDX was obtained using Carl Zeiss SMT supra 40 VPFESEM Germany and inca penta FET ×3 EDX, Oxford. It was operated at extra high tension (HT) at 5.0 kV and magnification at 20000×. FESEM uses electron to produce images (morphology) of samples and was attached with EDX for qualitative elemental analysis.

Congo Red (

(100 mg/L) by dissolving a required amount of dye powder in deionized water. The stock solution was diluted with deionized water to obtain the desired concentrations of 20, 30 and 40 mg/L. The supernatants were analyzed using a UV-vis spectrophotometer (Shimadzu, Kyoto, Japan) at wavelength of 497 nm.

The quantity of Congo Red removed by the layerd double hydroxide in aqueous solution and the percentage were calculated using Equations (1) and (2) below:

where C_{init} and C_{eql} are, respectively, the initial and equilibrium concentrations of dye in solution (mmol/l) and m is the layered double hydroxide dosage (g/l).

The data for the uptake of Congo Red at different temperatures has been processed in accordance with the linearised form of the Freundlich and Langmuir isotherm equations.

The Langmuir model linearization (a plot of 1/q_{eql} vs 1/C_{eql}) was expected to give a straight line with intercept of 1/q_{max}:

The essential characteristics of the Langmuir isotherm were expressed in terms of a dimensionless separation factor or equilibrium parameter S_{f}.

With C_{o} as initial concentration of Congo Red in solution, the magnitude of the parameter S_{f} provides a measure of the type of adsorption isotherm. If S_{f} > 1.0, the isotherm is unfavourable; S_{f} = 1.0 (linear); 0< S_{f} < 1.0 (favourable) and S_{f} = 0 (irreversible).

For the Freundlich isotherm the In-In version was used:

The DKR isotherm is reported to be more general than the Langmuir and Freundlich isotherms. It helps to determine the apparent energy of adsorption. The characteristic porosity of adsorbent toward the adsorbate and does not assume a homogenous surface or constant sorption potential [

The Dubinin-Kaganer-Radushkevich (DKR) model has the linear form

where X_{m} is the maximum sorption capacity, β is the activity coefficient related to mean sorption energy, and ε is the Polanyi potential, which is equal to

where R is the gas constant (kJ/kmol). The slope of the plot of Inq_{e} versus ε^{2} gives β (mol^{2}/J^{2}) and the intercept yields the sorption capacity, X_{m} (mg/g). The values of β and X_{m}, as a function of temperature are listed in ^{2}. It can be observed that the values of β increase as temperature increases while the values of X_{m} decrease with increasing temperature.

The values of the adsorption energy, E, was obtained from the relationship [

The Temkins isotherm model was also applied to the experimental data, unlike the Langmuir and Freundlich isotherm models, this isotherm takes into account the interactions between adsorbents and dye to be adsorbed and is based on the adsorption that the free energy of adsorption is simply a function of surface coverage [

where B = [RT/b_{T}] in (J/mol) corresponding to the heat of adsorption, R is the ideal gas constant, T (K) is the absolute temperature, b_{T} is the Temkins isotherm constant and A (L/g) is the equilibrium binding constant corresponding to the maximum binding energy.

The experimental data were further subjected to certain kinetic parameters.

Zero-order kinetic model,

First-Order Kinetic model,

Second-Order Kinetic model,

Third-order kinetic model

Pseudo-second order model

where q_{o} (mg/g) and q_{t} (mg/g) are the adsorbed amounts of CR at equilibrium and time t(min); K_{o}, K_{1}, K_{2} and K_{3} are the adsorption rate constants for the kinetic models.

The thermodynamic parameters such as change in free energy DG^{o}, enthalpy change DH^{o} and entropy change DS^{o} were determined by using the following equations:

where K_{d} equals the ratio of C_{solid} and C_{liquid}. C_{solid} is the equilibrium concentration of adsorbate on the adsorbent (mg/L), C_{liquid} is the equilibrium concentration of adsorbate in solution (mg/L), T is temperature (K) and R is the ideal gas constant (8.314 J×mol^{-}^{1}×K^{-}^{1}).

Isotherm model | Isotherm parameter | Results |
---|---|---|

Freundlich | 1/n | 1.0875 |

K_{F}, mg/L | 2.2403 | |

R^{2} | 0.9936 | |

Langmuir | R_{L} | 0.802 |

R^{2} | 0.9925 | |

Dubinin-Kaganer-Radushkevich | E, kJ/mol | 0.698 |

b_{D}, mol^{2}/kJ^{2} | 1.0263 | |

q_{D}, mg/g | 0.9543 | |

R^{2} | 0.996 | |

Temkin | A | 1.372 |

b | 1.36 ´ 10^{3} | |

B | 1.6637 | |

R^{2} | 1 |

The differential isosteric heat of adsorption (DH_{x}) at constant surface coverage was calculated using the Clausius-Clapeyron equation:

Integration gives the following equation [

where K is a constant. The differential isosteric heat of adsorption was calculated from the slope of the plot of ln(C_{eql}) vs 1/T and was used for an indication of the adsorbent surface heterogeneity.

The linear form of the modified Arrhenius expression was applied to the experimental data to evaluate the activation energy (E_{a}) and sticking probability S^{*} as shown in Equation (19).

where q is the degree of surface coverage, T is absolute solution temperature and R is gas constant (8.314 J/mol^{-}^{1}×K^{-}^{1}.

1) SEM

2) XRD

The typical XRD pattern (

3) FT-IR

The pre and post adsorption FT-IR spectra as shown in ^{−1} could be attributed to the stretching vibration of hydroxyl

group. The low intensity band at 1632 cm^{−1} is assigned to bending vibration of strongly adsorbed water (solvation water for compensating anion vibration). The band at 1363 cm^{−1} is assigned to carbonate vibration^{−1}, the band between 1100 cm^{−1} - 1200 cm^{−1} is due to phosphate stressing and the out-of-plane wagging at 650 cm^{−1} - 900 cm^{−1} are characteristic of 1˚ amines. The change in the FTIR spectra confirms the formation of complex between the functional groups present in the adsorbent and Congo Red [

Removal efficiency of Congo Red by adsorbents is illustrated in

To investigate an interaction of adsorbate molecules and adsorbent surface, four well-known models, the Langmuir, Freundlich, Dubinin-Kaganer-Radushkevic and Temkin isotherms, were selected to explicate LDH interaction in this study.

The Langmuir plot in ^{2} = 0.9925 and therefore, confirm monolayer coverage. The favourability or otherwise of a Langmuir type isotherm is determined by a dimensionless constant separation factor (R_{L}), given by Equation (4). The calculated value of R_{L} from

K_{f} is a constant describing the adsorption capacity (mg/L) and n is an empirical parameter related to the adsorption intensity, the plot of lnq_{e} against lnC_{e} is shown in _{F} and n respectively.

The values of k_{F} and n determine the steepness and curvature of the isotherm. The Freundlich equation frequently gives n adequate description of adsorption data over a restricted range of concentration, even though it is not based on any theoretical background. Apart from a homogeneous surface, the Freundlich equation is also suitable for a highly heterogeneous surface and an adsorption isotherm lacking a plateau, indicating a multi- layer adsorption [_{F} and n shows easy separation of Congo Red dye from wastewater and high adsorption capacity.

The fraction of the layered double hydroxide surface covered by the Congo Red is given as 0.47 (

The plots of Inq_{e} against e^{2} as shown in ^{2}, q_{D}, B_{D} and apparent energy E are calculated from the intercepts slopes of the plots respectively are shown on _{D} was determined to 0.9543 mg/g, the mean energy, E = 0.698 kJ/mol indicating a physiosorption process and the R^{2} = 0.996.

Temkin adsorption isotherm model is usually chosen to evaluate the adsorption potentials of an adsorbent for the adsorbate from an experimental data. This model gives the mechanism and adsorption capacity of an adsorbate in a sorption process. From the Temkin plot shown in

A = 1.372 L/g, B = 1.6637 J/mol which is an indication of the heat of sorption, indicating a physical adsorption process and the R^{2} = 1.

As shown in

The values of the enthalpy change (∆H^{o}) and entropy change ∆S^{o} were calculated from Equation (10) to be 3.67 kJ/mol and 12.5 J/mol・K respectively, as shown in ^{o} suggests that sorption proceeded favourably at a higher temperature and the sorption mechanism was endothermic. A positive value of ΔS^{o} (12.5 J/mol・K) reflects the affinity of the adsorbent towards the adsorbate species. In addition, positive value of ΔS^{o} suggests increased randomness at the solid/solution interface with some structural changes in the adsorbate and the adsorbent. The adsorbed solvent molecules, which are displaced by the adsorbate species, gain more translational entropy than is lost by the adsorbate ions/molecules, thus allowing for the prevalence of randomness in the system. The positive ΔS^{o} value also corresponds to an increase in the degree of freedom of the adsorbed species.

Isosteric heat of adsorption DH_{x} is one of the basic requirements for the characterization and optimization of an adsorption process and is a critical design variable in estimating the performance of an adsorptive separation process. It also gives some indication about the surface energetic heterogeneity. Knowledge of the heats of sorption is very important for equipment and process design. A plot of InC_{e} against 1/T in _{x}. The value of DH_{x} derived from Equation (11) was 40.03 kJ/mol which indicates that adsorption mechanism was physical adsorption and in an heterogeneous surface.

The activation energy E_{a} and the sticking probability S^{*} were calculated from Equation (12). The values shown in _{a} and S^{*} are −10.13 kJ/mol and 0.47 respectively, extrapolated from the plot in

The adsorption kinetic study is important in predicting the mechanisms (chemical reaction or mass-transport process) that control the rate of the pollutant removal and retention time of adsorbed species at the solid-liquid interface [

The effect of contact time of the phases on removal of Congo Red by the Layered double hydroxide from solutions of initial concentration equal to 400 mg CR/L at three different times (10, 20 and 30 minutes) is presented in

The result shows that adsorption was highest at 10 minutes, thereafter, a gradual decrease occurred (10 = 56.6%, 20 = 55% and 30 = 53%).

The experimental data were fitted into different kinetic models as shown in Figures 15-18 including zero- order-kinetic model, second-order-kinetic model, pseudo-second-order-kinetic model and third-order-kinetic model to ascertain the suitability of the models [

Layered double hydroxide (Mg/Al-CO_{3}) was successfully synthesized and characterized for the adsorption of

T, K | DG^{o}, kJ/mol | DH^{o}, kJ/mol | DS^{o}, J/mol×K | E_{a}, kJ/mol | DH_{x}, kJ/mol |
---|---|---|---|---|---|

313 | −0.208 | 3.67 | 12.5 | −10.13 | 40.03 |

333 | −0.550 | ||||

353 | −0.707 |

Congo Red dye in aqueous solution. The experimental data were best defined by Temkin isotherm (R^{2} = 1) and zero-order kinetic model (R^{2} = 1). The values of DH^{o} and DS^{o} indicated that the adsorption process was endothermic and process was dependent on increase in temperature, thereby increasing the randomness of the solid/ liquid phase of the reaction system.

NimibofaAyawei,Seimokumo SamuelAngaye,DonbebeWankasi,Ezekiel DixonDikio, (2015) Synthesis, Characterization and Application of Mg/Al Layered Double Hydroxide for the Degradation of Congo Red in Aqueous Solution. Open Journal of Physical Chemistry,05,56-70. doi: 10.4236/ojpc.2015.53007