3.2.1. Adsorption Isotherms
Figure 5 shows the adsorption isotherms of HCHO on CGC at different temperatures. As shown, the adsorption capacities of HCHO on CGC significantly decrease with increasing temperature, indicating that HCHO adsorption on CGC is an exothermic process. The Langmuir and Freundlich adsorption models were used to fit the equilibrium HCHO adsorption data of CGC to at concentrations that range from 5 to 45 mg/m
3 [
31].
The Langmuir model is usually used to calculate the monolayer adsorption capacity of the adsorbent, which is expressed as,
where
qe (mg/g) is the equilibrium amount of adsorbed HCHO by CGC,
Ce is equilibrium HCHO concentration (mg/m
3) in air,
qm is the maximum adsorption capacity (mg/g), and
KL is the Langmuir constant for monolayer adsorption (m
3/mg).
qm and
KL are calculated from the intercept and slope of linear plot of
Ce/
qe versus
Ce.
The Freundlich model was adopted for evaluating the multilayer adsorption on a heterogeneous adsorbent surface, which can be expressed as
where
Kf and
n are the Freundlich isotherm constant and adsorption intensity, respectively. They can be regressed from the linear plot of ln
qe against ln
Ce, respectively.
To further understand the adsorption mechanism, the D–R isotherm model was also applied for the adsorption process. It can be determined by
Here,
β is a constant that is related to the mean free energy of adsorption (mol
2/kJ
2) and
ε is the Polanyi potential, which can be calculated by
where
R is the gas constant and
T is the absolute temperature. Adsorption capacity
qm (mg/g) and
β can be obtained from the slope of the plot of ln
qe versus
ε2. The mean free energy of adsorption (
E) can be calculated from the
β value with the following equation,
The parameters calculated from the Langmuir and Freundlich models, as well as D–R models, were listed in
Table 2.
Table 2 indicates the correlation coefficients (
R2) of the linear form for Freundlich model is much higher than those of the Langmuir and D–R models within the temperature studied. The adsorption isotherm of HCHO on CGC is best described by the Freundlich isotherm. The results of the D–R model show that the adsorption capacity (
qm) decreases with the increase of temperatures from 20 to 60 °C, and the maximum adsorption capacities by the Langmuir model are 15.48, 9.71, and 6.33 mg/g, respectively. A comparison between CGC with those recently reported adsorbents shows that CGC holds significantly higher HCHO adsorption capacity per unit BET area (
Table 3) [
32,
33,
34,
35].
As listed in
Table 2, the calculated parameter
n in the Freundlich equations are more than 1 for the Freundlich equations at 20 and 40 °C, indicating that CGC can efficiently enhance the adsorption of HCHO at a low temperature. In addition, the results indicate a multi-molecular layer HCHO adsorption on CGC. The D-R isotherm model is also used to analyze the mechanism. It can give some information for the adsorption process being chemical or physical adsorption. The mean free energy of adsorption (
E) can be employed to classify the adsorption.
E in the range of 1–8 kJ/mol follows physical adsorption;
E between 8 to 16 kJ/mol means chemical ion exchange, while
E in the range of 20–40 kJ/mol is indicative of chemisorptions [
36]. As listed in
Table 2, the values of
E are 10.70, 8.51, and 1.99 kJ/mol for 20, 40, and 60 °C, respectively. The results implies that the adsorption of HCHO on CGC is close to a physicochemical adsorption process, but with a weak chemical interaction.
3.2.2. Adsorption Kinetics for HCHO
Figure 6 shows the measured HCHO adsorption as a function of contact time over CGC at 20, 40, and 60 °C. The adsorption is initially rapid and it then became slow with the increase in contact time at various temperatures. It is attributed to the greater amount of external adsorption sites of CGC that are available at the beginning of the adsorption, and the remaining vacant surface sites are difficult to be taken due to the repulsive forces between HCHO molecule and CGC. In addition, it was observed that maximum adsorption capacities took place within first 40, 60, and 105 h at 60, 40, and 20 °C, respectively. These results indicate that the equilibrium time and the HCHO adsorption capacities decrease with increasing temperature.
Kinetic models are helpful to identify the adsorption mechanism of HCHO adsorption and desorption performance of the adsorbent. In this study, pseudo first-order kinetic, pseudo-second-order kinetic, and intra-particle diffusion models were, respectively, checked to fit the kinetic data and explain the corresponding HCHO adsorption mechanism [
37,
38]. The best-fitted model was then selected on the basis of the correlation coefficient (
R2) of the linear regression of the experimental data with the proposed models. The pseudo-first-order kinetic model assumes reversible interactions between the gas and solid surfaces. This model can be expressed as:
where
qe and
qt are the amounts of HCHO that are adsorbed (mg/g) at equilibrium and time
t (
h), respectively, and
k1 is the rate constant for the pseudo-first-order kinetic model (h
−1). The intercept and the slope of linear plots of ln (
qe −
qt) versus
t are used to calculate
qe and
k1.
The pseudo-second-order kinetic model is proposed by assuming that chemical interactions control the adsorption kinetics and it is expressed as,
where
k2 is the rate constant (g/(mg h)) of the pseudo-second-order kinetic model for the adsorption. Furthermore,
qe and
k2 are determined from the slope and the intercept of the linear plot of
t/
qt against
t.
An intra-particle diffusion model is also employed to analyze the kinetic data.
where
KP is the intra-particle diffusion rate constant (mg/g min
1/2) and
C is related to the boundary layer thickness (mg/g), which is calculated from the slope of the linear plots of
qt versus
t1/2.
These kinetic models were used to fit the HCHO adsorption data and they are compared in
Figure 7, which have been used for the determination of gases mass transfer coefficients on various adsorbents [
39,
40]. The corresponding parameters and the correlation coefficients (
R2) for the three models are summarized in
Table 4.
R2, for the pseudo-second-order adsorption model, were higher (
R2 > 0.99) than those of the pseudo-first-order and intra-particle diffusion models for all of the studied temperatures. In addition,
qe (mg/g), as calculated from the pseudo-second-order kinetic model, agrees better with the experimentally obtained
qt values than those calculated with the pseudo-first-order model and intra-particle diffusion model. Therefore, the pseudo-second-order kinetic model reasonably fits the experimental kinetic curves of HCHO adsorption at all studied temperatures, indicating the weak interactions, such as van der Waals force, hydrogen bonding, as well as hydrophobic interaction, play a crucial role in the adsorption processes and the adsorption capacity is proportional to the active sites of CGC.
Thermodynamic parameters, such as the change in Gibbs free energy (Δ
G), enthalpy (Δ
H), and entropy (Δ
S), can be determined using the equations [
41]:
where
K is the Langmuir equilibrium constant;
R and
T are the gas constant and the temperature (K), respectively. Δ
H and Δ
S can be calculated from the slope and intercept of the van’t Hoff plots of ln (
K) versus 1/
T.
Table 5 lists the calculated results. The negative Δ
G values indicate that the HCHO adsorption over CGC at the temperatures studied is feasible and thermodynamically spontaneous. The Δ
G values increase with increasing temperature, demonstrating that the adsorption of HCHO is more favorable at a low temperature, which agrees well with the experimental findings listed above. The negative value of Δ
H shows that the adsorption is an exothermic process. The negative Δ
S indicates the decrease in randomness at the solid/gas interface during adsorption of HCHO on CGC.
The rate constants (
k2) that were obtained from the kinetic model increase with increasing adsorption temperatures, as shown in
Table 4. The dependence between the rate constant and temperature can be described as:
where
k is the adsorption rate constant of (h
−1),
k0 is the pre-exponential factor,
Ea is the apparent activation energy,
R is the gas constant, and
T is the absolute temperature. A good linearity between ln
k and 1/
T with coefficients of determination (
R2) larger than 0.98 was obtained for
k2 values that were obtained in this work. The activation energy for the HCHO adsorption process was lower than that of previous data [
42], indicating the good HCHO adsorption property of CGC.
Breakthrough experiments were performed for β-CD, chitosan, and CGC at various adsorption temperatures and feed flow rates.
Figure 8 presents the effluent HCHO concentration as a function of time (leakage curve) for each adsorbent at 20, 40, and 60 °C, with varying flow rates of the feed gas from 28 to 84 mL/min in the feed gas. To demonstrate the adsorption leakage behavior of HCHO, the following parameters,
tb,
te, and
LMTZ, were used to analyze the breakthrough curves:
where
tb refers to the time corresponding to
Coutlet/
Cinlet = 0.1,
te is the time when
Coutlet/
Cinlet is equal to 0.9, and
LMTZ is the length of mass transfer zone that is calculated according to previous literature [
43]. The corresponding characteristic parameters of the breakthrough curves under different operating conditions are summarized in
Table 6.
As compared in
Figure 8a, β-CD exhibits a low HCHO adsorption capacity (
q) with a short adsorption saturation time (
te) of 1.4 h. Chitosan shows a high HCHO adsorption capacity and a long adsorption saturation time of 37.2 h. Both the HCHO adsorption capacity and the saturation time of CGC are extremely larger than the two reference samples. The HCHO adsorption on CGC is not saturated in 100 h of adsorption. Calculated by Eq. (1), the HCHO adsorption capacities are 0.2 mg/g for β-CD, 6.0 mg/g for chitosan, and 10.9 mg/g for CGC, respectively. The HCHO adsorption performance difference is related to the structure and surface properties among the adsorbents. Firstly, CGC (10.8 m
2/g) has larger surface area than those of β-CD (0.4 m
2/g) and chitosan (1.7 m
2/g), which is beneficial for the adsorption process. In addition, the synergistic effects between β-CD and the functional group of chitosan also played a crucial role for the adsorption of HCHO. Similar results were observed for the adsorption of benzoic acid from wastewater on CGC [
24]. According to the above results, CGC is very favorable for the improvement of the HCHO adsorption capacity of HCHO. As seen in
Table 6,
q and
tb decrease significantly with increasing temperature, indicating that the adsorption of HCHO onto CGC is significantly affected by the temperature, which is attributed to a consequence of the exothermic reaction and weak adsorption interactions. The HCHO adsorption capacity over CGC gradually decreases from 10.9 mg/g to 1.2 mg/g, when the flow rate increases from around 28 mL/min with the influent concentration of 41.5 mg/m
3 to 84 mL/min, with the influent concentration of 37.2 mg/m
3, which is attributed to the decrease of contact time and increase of mass transfer zone
LMTZ.
3.2.3. Desorption and Reusability Study
The reusability of CGC was investigated by measuring the adsorption capacities of HCHO and their desorption properties, as displayed in
Figure 9. The effect of temperature on HCHO desorption from CGC after saturated adsorption is shown in
Figure 9a. HCHO can be completely desorbed from CGC at 60 °C with a desorption time of around 5 h. While the complete release of HCHO from CGC requires about 24 and 36 h at 40 and 20 °C, respectively. The result is consistent with the effect of temperature on HCHO adsorption discussed above. The result also implies that CGC can be easily regenerated at a high temperature. An adsorption-desorption experiment on CGC for four cycles at a flow rate of 28 mL/min and influent HCHO concentration of 41.5 mg/m
3 was explored. As compared in
Figure 9b, only a very slight drop in the adsorption capacity is observed after four cycles. These results suggest the good HCHO adsorption reusability of CGC, being fully satisfactory for practical applications.
In situ DRIFTS was used to study the HCHO adsorption of CGC with respect to the adsorbed specie on the adsorbent surface.
Figure 10 shows the dynamic changes in the DRIFTS spectra of CGC as a function of time in a flow of gas + HCHO at 20 °C. After exposing the adsorbent to HCHO mixture gas, three bands appear at 1670, 1650, and 1020 cm
−1. The peak at 1670 cm
−1 corresponds to stretching vibrations of C=O of aldehyde group and its intensity increases with exposing time, indicating that HCHO molecules are adsorbed onto CGC. The peak at 1650 cm
−1 is the characteristic stretching vibration of C=N, which is from the Schiff base reaction between the aldehyde group of HCHO and the amino group of chitosan. The peak at 1330 cm
−1 due to stretching vibrations of C–N bond is also observed. The bands of –OH/N–H of chitosan and β-CD and aldehyde group of HCHO shift from 3400 to 3450 cm
−1 and 1656 to 1670 cm
−1, respectively, which is related to the hydrogen bond interactions between chitosan/β-CD and HCHO. The results indicate that the adsorption of HCHO over CGC can be significantly involved by the synergistic effects of the Schiff base reaction and hydrogen bond interaction, and the corresponding HCHO adsorption mechanism is proposed, as shown in
Scheme 2.