Turk J Chem

(2016) 40: 402 – 411

c⃝ TUBITAK

doi:10.3906/kim-1507-54

Turkish Journal of Chemistry

http :// journa l s . tub i tak .gov . t r/chem/

Research Article

Photocatalysis of formaldehyde in the aqueous phase over ZnO/diatomite

nanocomposite

Reza DARVISHI CHESHMEH SOLTANI1,∗, Alireza KHATAEE2,Masumeh MASHAYEKHI1, Mahdi SAFARI3

1Department of Environmental Health Engineering, School of Health, Arak University of Medical Sciences,Arak, Iran

2Research Laboratory of Advanced Water and Wastewater Treatment Processes, Department of Applied Chemistry,Faculty of Chemistry, University of Tabriz, Tabriz, Iran

3Department of Environmental Health Engineering, School of Health, Kurdistan University of Medical Sciences,Sanandaj, Iran

Received: 20.07.2015 • Accepted/Published Online: 24.11.2015 • Final Version: 17.05.2016

Abstract: In the present study, ZnO nanostructures were synthesized and immobilized on the surface of diatomite via

a simple sonochemical method for the photocatalytic degradation of formaldehyde in the aqueous phase. The character-

ization of as-prepared ZnO/diatomite nanocomposite was carried out by means of scanning electron microscopy (SEM),

X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). The photocatalysis of formaldehyde was

favored at neutral pH. At a ZnO to diatomite ratio of 0.3, increasing the photocatalyst dosage from 0.2 to 1.5 g/L resulted

in increasing the photocatalytic removal of formaldehyde from 37.51% to 88.05%. At a formaldehyde concentration of

100 mg/L, the complete removal of formaldehyde was attained within the reaction time of 50 min. A mineralization

efficiency of 53% was achieved, thereby confirming a suitable mineralization of formaldehyde within the short reaction

time of 60 min.

Key words: Formaldehyde, immobilization, nanocatalyst, photocatalysis, ZnO nanostructures

1. Introduction

Discharging industrial effluents containing hazardous compounds can pollute receiving waters such as rivers

and lakes. Formaldehyde is one of the most toxic refractory organic compounds and is widely used in chemical

industries and anatomy laboratories. Thus, its discharge into the aqueous environment can cause serious

environmental and sanitary impacts.1−3 The carcinogenic effect of formaldehyde has been demonstrated by

the International Agency for Research on Cancer (IARC). It is also the most toxic organic substance of 45

organic compounds causing environmental problems.2 There are various industries discharging effluents with

formaldehyde concentrations ranging from 100 to 10,000 mg/L, indicating an urgent need for the treatment of

such effluents before discharge into the environment.1 One of the promising alternatives for the degradation of

refractory organic compounds such as formaldehyde is the application of advanced oxidation processes (AOPs).

Among the various AOPs, the application of photocatalytic processes has gained much more attention due to

their high potential to degrade toxic organic compounds.4,5 The photocatalysis of gaseous formaldehyde has

been studied by many researchers,6−9 but little attention has been paid to the photocatalysis of this organic

∗Correspondence: darvishi@arakmu.ac.ir

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pollutant from the aqueous phase. Among various photocatalysts, ZnO, in nanosize, has been considered an

efficient and cost-effective photocatalyst because of its large volume to area ratio, wide band gap (3.37 eV), high

potential to absorb UV light irradiation, and low cost.10,11 Generally, photocatalysts with smaller particle size

possess higher photocatalytic activity. However, it is demonstrated that using suspended nanoparticles leads

to the aggregation and inactivation of nanophotocatalysts in the aqueous phase, causing a significant decrease

in photocatalytic activity. The difficult separation also limits the application of suspended nanophotocatalysts

for the treatment process.12,13 Moreover, discharging nanoparticles into the environment must be limited due

to their toxic effects on the aquatic and terrestrial environments.14 Therefore, suspended ZnO nanoparticles

should be immobilized on a suitable support before application as photocatalyst. Different supports have been

used for the immobilization of nanosized photocatalysts such as glass plates,14,15 ceramic sheets,16 and clay-like

materials.12,17,18 Considering the economical point of view, in the present study, Iranian diatomite was applied

as a promising clay-like support for the immobilization of ZnO nanostructures. Diatomite is a sedimentary rock

of microfossils of aquatic plants, especially single-celled algae, that is mainly composed of SiO2 . It is used in

many industries as insulation material, filter aid, surface cleaning material, abrasive agent, adsorbent, catalyst

support, and silica source in chemical industries. Furthermore, diatomite has high surface area, creating a

suitable structure for the immobilization of nanosized photocatalysts.19−21 To the best of our knowledge, there

is no report on the use of ZnO-coated diatomite for the photocatalysis of formaldehyde in aqueous solutions.

Thus, in the present study, ZnO nanostructures were synthesized and immobilized on the surface of diatomite

through a simple sonochemical method for the photocatalysis of formaldehyde. After the characterization of

as-prepared photocatalyst, the effects of various operational parameters on the photocatalysis of formaldehyde

were evaluated. In the following, reusability and mineralization tests were carried out.

2. Results and discussion

2.1. Structural characteristics

Figure 1a shows the scanning electron microscopy (SEM) image of pure diatomite. As shown, diatomite particles

have nonuniform size distribution. The porous and rough structure of diatomite particles could be beneficial

for the efficient immobilization of ZnO nanostructures. Figure 1b exhibits the morphological structure of

ZnO/diatomite nanocomposite. Figure 1b also shows that the immobilization of ZnO nanostructures on the

diatomite surface is accomplished well. The stability of immobilized catalyst is of great importance. In fact, the

immobilization procedure applied in the present study results in the strong attachment of ZnO to the surface of

each siliceous support such as diatomite. According to our previous studies, the release of Zn into the solution

after the reaction was not significant due to the useful approach applied for the immobilization of ZnO.22,23

XRD analysis was performed to show the crystallite structure of as-prepared ZnO/diatomite nanocom-

posite. Figure 2 displays the XRD pattern of ZnO/diatomite nanocomposite, together with the XRD pattern of

pure diatomite. The XRD pattern of ZnO/diatomite nanocomposite contains peaks of both ZnO and diatomite.

Two peaks located at 2θ of 21.8◦ and 26.7◦ indicated the presence of a crystallite silica structure, which is in

accordance with the major peaks of a pure phase of silica in the JCPDS Card no. 00-001-0647.24 According to

JCPDS Card no. 36-1451, the main peaks of pure ZnO are located at 2θ of 32.0◦ , 34.6◦ , 36.3◦ , 47.6◦ , 56.7◦ ,

62.9◦ , 66.3◦ , and 68.0◦ , corresponding to the (100), (002), (101), (102), (110), (103), (200), and (112) planes of

hexagonal wurtzite ZnO, respectively.25−27 These main peaks were shifted to 33.0◦ , 33.8◦ , 38.0◦ , 44.8◦ , 54.0◦ ,

58.6◦ , 59.8◦ , and 68.9◦ in the XRD pattern of ZnO/diatomite nanocomposite. These shifts are significant to

confirm the formation of a ZnO pillar in the interlayer space of the diatomite. In addition, the peaks with

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high intensity reflect the formation of highly crystallite ZnO nanostructures at a high content incorporated into

the diatomite lattice.17 The Debye–Scherrer formula was utilized to estimate the crystallite size of as-prepared

samples.28 Accordingly, the average crystallite size of ZnO nanostructures in immobilized form was calculated

to be 43 nm.

Figure 1. SEM images of pure diatomite (a) and ZnO-coated diatomite (b).

Functional groups placed on the photocatalyst surface play an important role in photocatalysis because

of the fact that photocatalytic processes take place on the photocatalyst surface. In addition, functional groups

can be involved in the immobilization of ZnO nanostructures on the diatomite surface. FT-IR spectra of pure

ZnO, pure diatomite, and ZnO/diatomite nanocomposite were recorded in the range between 400 and 4000

cm−1 (Figure 3). As shown in Figure 3, a broad peak centered at 3400 cm−1 is associated with the stretching

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6000

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40080012001600200024002800320036004000

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%)

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Pure ZnO

Pure diatomite

ZnO/diatomite

Figure 2. XRD pattern of ZnO/diatomite nanocompos-

ite.

Figure 3. FT-IR spectra of pure ZnO, pure diatomite,

and ZnO/diatomite nanocomposite.

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vibrations of the –OH groups and free silanol group (Si–OH) on the diatomite surface.20,29,30 This peak was

shifted from 3400 to 3520 cm−1 after the immobilization of ZnO nanostructures. In addition, hydroxyl groups

of the catalyst surface react with the photogenerated valence band holes (h+) and subsequently the adsorbed

water on the catalyst surface to generate hydroxyl radicals.14 The peaks located at 1650, 1110, 810, and

480 cm−1 were attributed to the presence of the (H–O–H) bending vibration of water retained in the silica

matrix, asymmetric stretching modes of the Si–O–Si bond, Si–O stretching of the silanol group, and Si–O–Si

bending vibration of the diatomite structure, respectively.31−34 The intensity of these peaks decreased after the

incorporation of ZnO nanostructures into the diatomite lattice. The results of FT-IR analysis confirmed the

important role of functional groups in the immobilization of ZnO nanostructures on the diatomite surface.

2.2. Comparative study

A comparative study was performed before conducting the experiments to specify the role of each process

involved in the photocatalysis of formaldehyde. As depicted in Figure 4, the adsorption of formaldehyde onto

pure ZnO, pure diatomite, and ZnO/diatomite nanocomposite resulted in formaldehyde removal of 15.67%,

27.47%, and 30.21%, respectively. Furthermore, in order to reach the adsorption–desorption equilibrium, the

reactor was placed in the dark for 30 min prior to the experiments. Although ZnO/diatomite nanocomposite

can adsorb some formaldehyde molecules (Figure 4), most of them will desorb. They will be released into the

bulk solution to be more effectively degraded by OH . as well as the photocatalysis of formaldehyde molecules

adsorbed on the photocatalyst surface via hole oxidation.22 Both visible and UV light (photolysis processes)

could not significantly remove formaldehyde from the aqueous solution. The visible light and UV light reduced

the formaldehyde by 9.11% and 33.95%, respectively. However, visible light/ZnO and UV light/ZnO processes

were responsible for formaldehyde removal of 19.22% and 71.87%, respectively. Overall, the photocatalysis

of formaldehyde over UV light-induced photocatalyst was efficient in removing formaldehyde compared with

photolysis alone. A similar result was reported by Mendez et al. in their study on the detoxification of

formaldehyde in aquatic environments.35 The oxidation of water and hydroxyl groups on the photocatalyst

surface produces OH . , resulting in the degradation of formaldehyde to form CO2 and H2O as shown in Eqs.

(1)–(5):

ZnO − diatomite+ hv → e− + h+ (1)

h+ +OH− → OH . (2)

h+ +H2O (ads) → H+ +OH . (3)

CH2O +OH . → HCO−2 + 2H+ (4)

HCO−2 +OH . → H2O + CO2 (5)

The immobilized form of ZnO nanostructures was irradiated with UV light and caused formaldehyde removal of

about 80% at an initial formaldehyde concentration of 500 mg/L within a reaction time of 60 min. In accordance

with our results, Seftel et al. found that TiO2 /LDH clay nanocomposite had photocatalytic activity higher

than that of pure TiO2 , due to the increased adsorption of the target organic pollutant.18 Additionally, it is

demonstrated that the immobilization of photocatalyst on the diatomite surface improves the charge, optical

properties, and mass transfer efficiency during photocatalysis.13,36

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2.3. The effect of ZnO to diatomite ratio

To evaluate the effect of ZnO to diatomite ratio on the photocatalysis of formaldehyde, this ratio was varied

between 0.1 and 1.0. As shown in Figure 5, increasing the ZnO to diatomite ratio from 0.1 to 0.7 resulted in

increasing the removal efficiency of formaldehyde from 67.35% to 90.06%, respectively. However, increasing the

ratio to 1.0 led to a small decrease in removal efficiency (83.56%). In accordance with our results, Saleh et al.37

reported that increasing the photocatalyst to support ratio up to a specified value could cause a significant drop

in the photocatalytic degradation of the target pollutant. The excessive amount of photocatalyst immobilized on

the diatomite results in the accumulation and aggregation of nanostructures. The aggregation of photocatalyst

decreases the interfacial area between the bulk solution and the photocatalyst, which reduces the number of

active sites on the photocatalyst surface. Moreover, the excess amount of photocatalyst can mask some parts of

the photosensitive surface and deactivate the activated molecules caused by the collision with the ground state

of the photocatalyst.13,38 The application of photocatalyst at optimum amount leads to a better distribution of

nanostructures and improved light adsorptive behavior of the photocatalyst, which is helpful for better exciting

the photocatalyst to produce OH . .11,39,40 Overall, it can be deduced that an optimum ZnO to diatomite ratio

is necessary for enhancing formaldehyde removal and avoiding the use of excess photocatalyst.

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Time (min)

Visible light alone

ZnO alone

Visible light/ZnO

Diatomite alone

ZnO/Diatomite

UV light alone

UV light/ZnO

UV light/ZnO/Diatomite

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ZnO/Diatomite: 0.3

ZnO/Diatomite: 0.5

ZnO/Diatomite: 0.7

ZnO/Diatomite: 1.0

Figure 4. Contribution of each process involved in

the photocatalytic degradation of formaldehyde (formalde-

hyde concentration = 500 mg/L, photocatalyst dosage =

1 g/L, ZnO to diatomite ratio = 0.3, and initial pH = 7).

Figure 5. The effect of photocatalyst to support ratio on

the photocatalytic degradation of formaldehyde (formalde-

hyde concentration = 500 mg/L, photocatalyst dosage =

1 g/L, and initial pH = 7).

2.4. The effect of initial pH

Figure 6 displays the effect of initial pH on the photocatalytic degradation of formaldehyde in the pH range

between 3 and 11. As can be observed, both acidic and basic conditions are unfavorable for the photocatalysis

of formaldehyde over ZnO/diatomite nanocomposite. Decreasing the initial pH from neutral value of 7 to

3 and 11 resulted in decreasing the removal efficiency from the optimum value of 80.07% to 23.45% and

50.79%, respectively. At basic pH values, formaldehyde is converted to methoxide (CH3O−) and formate

anions,41 leading to electrostatic repulsion between the produced anions and the negative surface charge of the

photocatalyst (the zero point charge of pure ZnO nanostructures is about 9.0). This can restrain the efficient

photocatalytic reaction on the photocatalyst surface.1

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2.5. The effect of photocatalyst dosage

In order to avoid the application of excess photocatalyst, it is essential to find out the optimum photocatalyst

dosage for efficient photocatalysis. The effect of photocatalyst dosage on the photocatalysis of formaldehyde

was investigated (Figure 7). As illustrated in Figure 7, a high amount of catalyst enhanced the photocatalysis of

formaldehyde over ZnO/diatomite nanocomposite. With increasing photocatalyst dosage from 0.2 to 1.5 g/L, the

photocatalytic removal of formaldehyde increased from 37.51% to 88.05%, respectively. This can be as a result of

enhanced absorption of photons and subsequently increased photogeneration of OH . .42 However, increasing the

photocatalyst dosage beyond 1.0 g/L did not influence the photocatalysis of formaldehyde. A further increase

in the photocatalyst dosage can cause the screening effect. Moreover, the aggregation of nanostructures may

also decrease the photocatalytic activity at high loadings of the photocatalyst.11,42 Therefore, a photocatalyst

dosage of 1 g/L was chosen as the selective value for performing the rest of the experiments.

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pH=3

pH=5

pH=7

pH=9

pH=11

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0.2 g/L

0.5 g/L

0.7 g/L

1.0 g/L

1.3 g/L

1.5 g/L

Figure 6. The effect of initial pH on the photocatalytic

degradation of formaldehyde (formaldehyde concentration

= 500 mg/L, photocatalyst dosage = 1 g/L, and ZnO to

diatomite ratio = 0.3).

Figure 7. The effect of photocatalyst dosage on the pho-

tocatalytic degradation of formaldehyde (formaldehyde

concentration = 500 mg/L, ZnO to diatomite ratio = 0.3,

and initial pH = 7).

2.6. The effect of initial formaldehyde concentration

Obviously, the effect of initial pollutant concentration can be one of the most important parameters in the

treatment of various organic and inorganic pollutants. For this reason, the effect of the initial formaldehyde

concentration was assessed in the range of 100–2000 mg/L, where the other operational parameters were con-

stant. The result of this set of experiments showed that increasing the initial formaldehyde concentration from

100 to 2000 mg/L led to a significant drop in the photocatalysis of formaldehyde (Figure 8). At formaldehyde

concentration of 100 mg/L, the complete removal of formaldehyde was achieved within the reaction time of 50

min, while the removal efficiency of formaldehyde was insignificant (19.82%) at an initial concentration of 2000

mg/L. The higher the initial formaldehyde concentration, the longer the time needed for its photocatalysis.2

Moreover, at high pollutant concentrations, photonic efficiency decreases and the photocatalyst surface becomes

saturated, resulting in photocatalyst deactivation.35

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DARVISHI CHESHMEH SOLTANI et al./Turk J Chem

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100 mg/L

300 mg/L

500 mg/L

700 mg/L

1000 mg/L

1500 mg/L

2000 mg/L

y = 0.0122x + 0.073

R² = 0.961

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(C

/C0)

Rem

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iency

(%

)

Reaction time (min)

Formaldehyde removal (%)

Mineralization (%)

Formaldehyde removal reaction rate

Figure 8. The effect of initial formaldehyde concentration

on its photocatalytic degradation (photocatalyst dosage =

1 g/L, ZnO to diatomite ratio = 0.3, and initial pH = 7).

Figure 9. Mineralization of formaldehyde over UV light-

induced ZnO/diatomite nanocomposite, together with the

regression line of kinetic study (formaldehyde concentra-

tion = 500 mg/L, ZnO to diatomite ratio = 0.3, photocat-

alyst dosage = 1 g/L, and initial pH = 7).

2.7. Mineralization

The success of each advanced oxidation process in the degradation of target organic pollutants depends on

the rate of mineralization. To assess the mineralization of formaldehyde during photocatalysis, COD analysis

was performed and its removal was compared with the removal efficiency of formaldehyde. Figure 9 reveals

a mineralization efficiency of 53.12% within the reaction time of 60 min. The possible reaction between the

photogenerated hydroxyl radical and formaldehyde is depicted by Eq. (6):

CH2O + OH . → 3H+ + 3e− + CO2 (6)

Comparatively, Guimaraes et al. reported a mineralization efficiency of 46% in the case of the application of

the UV/H2O2 process for the degradation of 400 mg formaldehyde/L,2 and Kajitvichyanukul et al. found

that the complete mineralization of formaline can be achieved in the effluent after a reaction time of 240

min.43 In addition, the linearized pseudo-first-order kinetic model was applied in order to evaluate the reaction

rate constant of the photocatalysis of formaldehyde over ZnO/diatomite nanocomposite (Figure 9). As can

be observed in Figure 9, a relatively straight line of –ln(C/C0) versus reaction time was obtained (R2 =

0.961), which indicated the suitability of the applied model for predicting the rate of photocatalytic removal

of formaldehyde. According to the obtained regression line and its slope, the reaction rate constant of the

photocatalysis of formaldehyde was 0.0122 1/min. The reaction rate constant obtained in our previous study

regarding the photocatalysis of formaldehyde over commercial ZnO nanoparticles immobilized onto glass plates

was higher than that of obtained in the present work (0.0265 1/min). It could be due to the lower particle size

of commercial ZnO nanoparticles, creating more reaction sites for the photocatalysis of formaldehyde.

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3. Materials and methods

3.1. Photocatalyst preparation

All chemicals, which were of analytical grade, were purchased from Merck, Germany. In a typical manner, the

ZnO to diatomite mass ratio was set to 0.3. ZnO/diatomite nanocomposite was prepared as follows: 10 mM

ZnCl2 was prepared in 50 mL of deionized water. Afterwards, 1 M NaOH solution was added dropwise to the

above solution under magnetic stirring until the pH reached 10. After the formation of precipitate, 2.724 g of

the diatomite was slowly added to the resulting precipitate under magnetic stirring. The mixture was sonicated

in an ultrasonic bath (Elmasonic E30H, Elma-Hans Schmidbauer GmbH & Co.KG, Germany) at 50 ◦C for 120

min to achieve homogeneity of ZnO nanostructures. The suspension was filtered and washed with deionized

water and ethanol repeatedly to obtain a salt-free sample. Finally, the solid sample phase was dried in an oven

at 80 ◦C for 48 h.22

3.2. Experimental procedure and analysis

To carry out the experiments, a quartz-made batch flow mode cylindrical reactor equipped with four 6-W

low-pressure UVC lamps with peak intensity at 254 nm (Philips, the Netherlands) was used (working volume

of 700 mL). The visible light source was four 6-W visible lamps with peak intensity at 544 nm. Working

solutions of formaldehyde were prepared by the dilution of stock solution (1000 mg/L). A magnetic stirrer

was applied to mix as-prepared photocatalyst and formaldehyde molecules in the bulk solution. The residual

concentration of formaldehyde was measured spectrophotometrically by Nash’s method.44 The mineralization of

formaldehyde during the photocatalysis was determined by means of chemical oxygen demand (COD) according

to the standard methods for the examination of water and wastewater.45 The surface morphology of the samples

was analyzed via a scanning electron microscope (TESCAN, Mira3, Czech Republic). X-ray diffraction (XRD)

patterns of pure ZnO nanostructures, pure diatomite, and ZnO/diatomite nanocomposite were taken via a

PANalytical diffractometer (Model: X’Pert Pro MPD, the Netherlands) at current intensity = 30 mA, voltage

= 40 kV, λ = 1.54056 A, step size = 0.026◦ /s, measurement temperature = 25 ◦C, and scanning angle = 10–

80◦ . Fourier transform infrared (FT-IR) analysis was conducted on KBr pellets to show the role of functional

groups in the immobilization of ZnO nanostructures (Tensor 27, Bruker, Germany) at wavenumbers ranging

from 400 to 4000 cm−1 .

4. Conclusions

ZnO-loaded diatomite irradiated by UV light lamps was applied for the photocatalysis of formaldehyde in

the aqueous phase. As a result, the adsorption and photolysis processes did not remove formaldehyde from

the solution reasonably well. The immobilization of ZnO nanostructures improved the removal efficiency of

formaldehyde. Increasing the photocatalyst dosage and decreasing the initial dye concentrations enhanced

the photocatalysis. Efficient COD removal was attained by applying the reaction time of 1 h for an initial

formaldehyde concentration of 500 mg/L. It could be concluded that ZnO/diatomite nanocomposite can be

efficiently used for the photocatalysis of formaldehyde in the aqueous environment.

Acknowledgment

The authors wish to thank Arak University of Medical Sciences (Iran) for their financial and instrumental

support.

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