Next Article in Journal
A Bifunctional Electroactive Ti4O7-Based Membrane System for Highly Efficient Ammonia Decontamination
Next Article in Special Issue
Suppression of Hydrophobic Recovery in Photo-Initiated Chemical Vapor Deposition
Previous Article in Journal
Effect of Pressure on Na0.5La0.5Ni0.3Al0.7O2.5 Perovskite Catalyst for Dry Reforming of CH4
Previous Article in Special Issue
Bioinspired ZnO-Based Solar Photocatalysts for the Efficient Decontamination of Persistent Organic Pollutants and Hexavalent Chromium in Wastewater
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Highly Efficient Photo-Degradation of Gaseous Organic Pollutants Catalyzed by Diatomite-Supported Titanium Dioxide

1
College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
2
Analysis and Test Center of Beijing University of Chemical Technology, Beijing University of Chemical Technology, Beijing 100029, China
*
Author to whom correspondence should be addressed.
Catalysts 2020, 10(4), 380; https://doi.org/10.3390/catal10040380
Submission received: 15 February 2020 / Revised: 26 March 2020 / Accepted: 27 March 2020 / Published: 1 April 2020
(This article belongs to the Special Issue Photocatalysis and Environment)

Abstract

:
Volatile organic compounds (VOCs) are the most harmful contaminants that have been identified, most of which are gaseous organic pollutants. In this study, TiO2@diatomite catalysts with various loading amounts of TiO2 were fabricated using a facile solvothermal method with anhydrous ethanol as a solvent for the removal of VOCs. X-ray diffraction analysis revealed that TiO2 has an anatase phase and the introduction of diatomite has no negative effect. The catalysts were characterized using scanning electron microscopy and transmittance electron microscopy techniques. The results indicate that after introducing diatomite, TiO2 nanoparticles are mostly square-like and intact, and are uniformly immobilized in the diatomite. Finally, their photocatalytic performance was investigated using liquid ultraviolet spectrometry and gas chromatography-mass spectrometry. Among the catalysts tested, 0.35TiO2@diatomite (with a mass ratio of TiO2 to diatomite of 0.35) exhibited higher photocatalytic activity than the other samples, i.e., pure TiO2 and diatomite, and could effectively remove acetone and benzene, demonstrating its potential market application and practical significance.

1. Introduction

Volatile organic compounds (VOCs) are dominant components of indoor air pollutants. Mainly originating from decorative materials, such as carpets, paints, wallpapers, or PVC, they are also emitted or generated during human activities such as cooking or smoking tobacco [1,2,3,4]. Their harm to human health can thus not be ignored. The main problems resulting from VOCs have been reported by numerous researchers, such as Dai et al., who reported the characteristics and inhalation health risks of VOCs in newly renovated homes in Shanghai, China, and concluded that the concentrations of some VOCs present a mean cancer risk above the acceptable level [5]. Data on the respiratory effects of indoor air pollution among the elderly have been scarce. Therefore, Bentayeb et al. reported the effects of indoor air pollution on the respiratory health of the elderly, and found certain links between a variety of diseases, including respiratory diseases, and indoor air pollution [6]. In addition, Ye et al. estimated the acute cardiorespiratory effects of ambient volatile organic compounds, and their findings further support a link between incomplete combustion and cardiovascular health, as well as a link between atmospheric oxidation products and respiratory health [7]. The above studies have commonly concluded that VOCs are extremely harmful to human health. In addition, according to a survey conducted by the World Health Organization (WHO), the number of premature deaths caused by indoor pollution globally has reached 4 million per year, and the number of deaths from indoor pollution in China is as high as 111,000, or approximately 304 per day. In addition, a 2002 report published by the WHO clearly listed indoor air pollution as one of the top causes of harm to human health [8].
Therefore, it is extremely important to study technologies regarding the removal of VOCs, and VOC removal has recently been considered by numerous researchers [9,10,11,12,13,14,15,16,17]. The materials used in such studies are variable, and mainly include TiO2, ZnO, SnO2, CdS, WO3, and numerous other metal oxides. Among them, TiO2 has been widely applied owing to its low-cost, non-toxicity, and high photo-catalytic activity. For instance, Šuligoj et al. reported the use of TiO2-SiO2 films from organic-free colloidal TiO2 anatase nanoparticles as a photocatalyst for the removal of VOCs from air indoors [18]. In addition, Weon et al. studied an active {001} facet-exposed TiO2 nanotube photocatalyst filter for the removal of VOCs [19]. Haghighatmamaghani, Haghighat, and Lee studied the performance of various types of commercial TiO2 in the photocatalytic degradation of a mixture of indoor air pollutants, and adopted various alcohols, ketones, aromatics, and alkanes as the target pollutants [20].
Numerous other studies have been conducted on VOC removal using TiO2 [21,22,23,24,25,26,27], and have made significant contributions to the photocatalytic degradation of such compounds. However, most of these studies have reported the use of pure TiO2 for achieving the photo-catalytic degradation of gaseous organic pollutants. The aggregation of pure TiO2 often limits its practical application. In addition, pure nanomaterials have their own defects, and it is therefore difficult to apply them to interior decorative materials. To solve this problem, numerous researchers are looking for a carrier for the loading of TiO2, including porous carbon materials, Metal-OrganicFrameworks, a synthetic molecular sieve, activated carbon, and many other types of artificial materials [28,29,30,31]. Not only can such materials prevent the aggregation of TiO2, they can also improve its photodegradability.
However, the above materials must be manufactured for carrier use, and a certain cost is accrued during their synthesis. Therefore, in terms of energy efficiency, it would be better to apply natural materials, such as diatomite, which is one of the most important natural materials on Earth. With rich reserves, diatomite has abundant advantages, including non-toxicity, a stable and porous structure, strong surface adsorption, and a high heat resistance. The specific metal compounds of the material and their content are shown in Table 1 [32]. The main component is silicon dioxide, the surface of which has abundant hydroxyl and silanol groups, in which the silicon element on the surface can be bonded to TiO2 with synergistic degradation of the gaseous organic pollutants [33,34,35]. In addition, Niu et al. prepared a novel diatomite-supported MnCeOx composite (MnCeOx/diatomite) characterized based on its activation of persulfate for the degradation of organic pollutants [36]. He, Luo, and Yu synthesized microdisk-like g-C3N4/diatomite composites utilized for the removal of methylene blue (MB) from MB/MO or MB/RhB mixed dyes [37]. Numerous other studies in this area have also been conducted [38,39,40,41]. The present study focuses on the removal of organic pollutants, the results of which will provide an exciting reference in the area of pollutant degradation.
Thus far, TiO2 supported by diatomite has not been utilized in the degradation of gaseous organic pollutants. Herein, we report the successful application of well-designed TiO2@diatomite as a photo-catalytic agent for the removal of gaseous organic pollutants. In addition, diatomite was selected as a carrier, and diatomite loaded with different ratios of TiO2 was used as a catalyst for the degradation of VOCs at room temperature under UV-Vis illumination. This catalyst is inexpensive and easy to prepare, and is thus a promising application for use in the field of interior decoration.

2. Results and Discussion

2.1. XRD Analysis

Figure 1 shows the XRD patterns of the as-prepared catalysts. Both TiO2 and XTiO2@diatomite show the coexistence of an anatase phase with no additional peak, implying that no impurity appears in TiO2 when TiO2 is supported on diatomite. As indicated in Figure 1, the intensity of the peak at 25.27° decreases with an increase in the amount of diatomite. The diffraction peaks at 25.27°, 37.82°, 47.94°, 53.79°, 54.96°, 62.65°, 70.22°, and 75.08° correspond to the crystal faces (101), (004), (200), (105), (211), (204), (220), and (215) of anatase TiO2, respectively [42,43,44]. The peaks at 21.8° and 36.5° are attributed to the SiO2 features in diatomite [44]. The reflection peak of diatomite becomes relatively low compared with that of TiO2, and the pure diatomite peak is not too weak, as shown in Figure 2 below. Therefore, the introduction of diatomite cannot affect the crystal structure of the catalyst. This result is consistent with the scanning electron microscopy (SEM) and transmittance electron microscopy (TEM) characterizations.

2.2. SEM and TEM Investigations

SEM, TEM, and high-resolution transmission electron microscopy (HRTEM) images of the catalysts are shown in Figure 3. As can be seen from Figure 3(A1,A2) in the figure, diatomite without the loading of TiO2 nanoparticles looks like a sunflower with a smooth surface and numerous pores. The SEM images of pure TiO2 displayed in Figure 3(B1,B2) indicate that the TiO2 nanoparticles are square-like and approximately 10–15 nm in size, corresponding to the results of the TEM images (Figure 3(E1–E8)). As shown in Figure 3(C1–C6), the TiO2 nanoparticles of 0.35TiO2@diatomite are not only uniformly loaded on the surface of the diatomite, but also adhered to the pores. This indicates that TiO2 can be firmly and evenly loaded on the surface of the diatomite. Figure 3(C1–C6) also show that the size of the TiO2 nanoparticles loaded on the surface of the diatomite is approximately 10–15 nm, which is congruent with the TEM results shown in Figure 3(E1–E8). In addition, the other load catalysts shown in Figure 3(D1–D6) were also analyzed. As indicated in D1 and D2, the load of 0.30TiO2@diatomite is quite small, and the surface of the diatomite is thus not completely filled with TiO2, as opposed to 0.40TiO2@diatomite (Figure 3(D3,D4)), 0.45TiO2@diatomite (Figure 3(D5,D6)), and 0.50TiO2@diatomite (Figure 3(D7,D8)). For the latter, as the load mass increases, the degree of aggregation increases significantly, and the aggregation of 0.50TiO2@diatomite thus becomes the most serious. There is no doubt that aggregation will cause a reduction in the photocatalytic efficiency. However, the 0.35TiO2@diatomite load mass was moderate and evenly distributed across the diatomite surface. Therefore, the catalyst of 0.35TiO2@diatomite may perform better than other catalysts in terms of the photocatalytic efficiency for the following two reasons: First, the proportion of TiO2 is full on the surface of the diatomite. Second, TiO2 is evenly distributed and relatively less clustered. In addition, as shown in Figure 3(E2), the lattice distance of TiO2 is approximately 0.35 nm, corresponding to the (101) plane of anatase TiO2. As clearly shown above, the size of the TiO2 nanoparticles loaded on the diatomite is nearly the same as that of pure TiO2, indicating that the introduction of diatomite has almost no influence on the size and morphology of the TiO2. From the HRTEM images shown in Figure 3(E1–E4), it can be clearly seen that the specific shape of TiO2 is square-like.

2.3. UV-Vis Diffuse Reflectance Spectra

As shown in Figure 4, the UV-vis diffuse reflectance spectra of the catalysts were measured to study the optical properties of the samples [45]. Clearly, for pure TiO2, there is no absorption at above 400 nm. However, the absorption intensity at approximately 400 nm is stronger for XTiO2@diatomite than for pure TiO2 and diatomite, and the absorption (at above 400 nm) of 0.35TiO2@diatomite is the strongest among the XTiO2@diatomites considered. It can also be seen that the catalyst of TiO2@diatomite shows a slight red shift, suggesting that the catalyst of TiO2@diatomite can be excited by the visible light and thus an increase in the photocatalytic activity of the catalyst.
It can be seen from Figure 4 that pure XTiO2@diatomite achieves absorption at 200–400 nm, although, according to previous studies [46], pure SiO2 has no absorption at 200–400 nm. Therefore, the composite formed through a combination of the two with Si-O-Ti, which shows a red shift, may be attributed to the formation of this chemical bond, which reduces the energy and causes a slight red shift.

2.4. BET Analysis

The specific surface area and pore size distribution of the different catalysts were analyzed based on the nitrogen adsorption and desorption. The results are summarized in Table 2. The pure TiO2 nanoparticles have the largest specific surface area of approximately 115.74 m2g−1. However, the specific surface area and pore volume of the pure diatomite are quite small, and thus the diatomite contributes less to the specific surface area of the XTiO2@diatomites. In other words, the specific surface areas of the catalysts were not related to the TiO2 loadings. Therefore, the specific surface area and pore volume of the catalysts contribute little to their catalytic activity. As can be seen from Figure 5, the pure TiO2 exhibits type-IV adsorption curves with hysteresis loops between the H1 and H2 types; the diatomite shows IUPAC type-II isotherms, indicating the presence of micropores in the diatomite [47]; and the TiO2@diatomite composites display type-IV isotherms with an overlap of the H2 and H3 hysteresis loops, which is related to the deposition of TiO2 nanoparticles on the surface of the diatomite.

2.5. Photoluminescence (PL) Spectra

For the photocatalysts, apart from the surface area, the nanoparticle size, and the light absorption range, the electron-hole recombination property is also significant. PL can be used to evaluate the electron-hole recombination property. In other words, fluorescence will occur when electron-hole recombination arises [48]. Therefore, the rate of electron-hole recombination is inversely proportional to the fluorescence intensity, and thus a lower fluorescence intensity represents a lower electron and hole recombination rate and a higher photocatalytic activity [49,50]. As shown in Figure 6, the PL of different catalysts was measured at an excitation wavelength of 300 nm. The strongest peaks of different catalysts all appear within approximately 400 nm; however, their emission intensity varies significantly. For photocatalytic reactions, reducing the electron-hole recombination rate is an important goal. In other words, a low electron-hole recombination rate is favorable for a photocatalytic reaction. Among the catalysts applied, 0.35TiO2@diatomite has the lowest emission intensity, indicating that it has the lowest electron-hole recombination rate and thus possesses a better photocatalytic performance. The reduction of the luminescence intensity may be related to the Ti-O-Si band and ascribed to the increased electron capture centering on the surface of the TiO2 nanoparticles, or an enhancement of the non-radiation-decay channels because of the SiO2 around the TiO2 nanoparticles.
Therefore, it can be concluded that the photocatalytic performance of 0.35TiO2@diatomite may be better than that of the other catalysts. This result is consistent with that obtained from the UV-vis diffuse reflectance spectra, confirming that 0.35TiO2@diatomite is the optimal catalyst.

2.6. Photocatalytic Performance of Different Catalysts

The TiO2 photocatalyst has a wide range of applications, such as air purification and sewage treatment. To evaluate the photocatalytic performance of different catalysts, a 5 W ultraviolet light source was used. Methylene blue (MB) was selected as the target pollutant to determine the optimal catalyst, and the optimal catalyst was then selected as the degradation catalyst for gaseous organic pollutants, such as acetone, benzene, methanol, and ethanol. Compared with pure TiO2, the XTiO2@diatomite composite shows a relatively larger adsorption capacity for MB in spite of its lower specific surface area and pore volume. As shown in Figure 7a, minor differences appeared in different catalysts. With the catalyst of 0.35TiO2@diatomite, the concentration of MB was nearly close to 0 within 90 min under UV light irradiation, and thus the degradation rate was faster than in the other similar photocatalysts. Clearly, 0.35TiO2@diatomite (recorded as the optimal catalyst) showed the highest degradation rate for the photocatalytic degradation of MB. The MB degradation efficiency of pure diatomite is shown in Figure 7a, in which the concentration of MB remains almost unchanged as the irradiation time increases, indicating that the photocatalytic activity of TiO2@diatomite is weak in the absence of TiO2, and that the photocatalytic activity of XTiO2@diatomite is better than that of pure TiO2, suggesting a synergy effect between TiO2 and diatomite (which may benefit from the formation of Si-O-Ti bonds). Because a Si-O-Ti bond can be formed when the surface of diatomite is covered with hydroxyl and silanol, this special structure allows TiO2 to laboriously combine with diatomite, and further enhances its dispersibility, thereby significantly increasing its photocatalytic performance [46]. Among the types of XTiO2@diatomite applied, the photocatalytic activity of 0.35TiO2@diatomite was better than that of the other catalysts. In addition, the photocatalytic activity of TiO2@diatomite is not simply promoted by the increasing load ratio of TiO2 to diatomite. By contrast, excessive loading amounts of TiO2 can in turn reduce the photocatalytic capability. This was confirmed through 0.35TiO2@diatomite, which exhibited the highest performance. This can be explained by the fact that excessive TiO2 causes an agglomeration of TiO2 on the surface of the diatomite, and thus reduces the photocatalytic performance of TiO2@diatomite. This result agrees with the results obtained from the UV-vis diffuse reflectance spectra, PL spectra, and degree of aggregation shown on the SEM images. Therefore, 0.35TiO2@diatomite was selected for the degradation experiment of the following gaseous organic pollutants.
Figure 7b,c show the degradation results of gaseous acetone and gaseous benzene, respectively. The gas concentration was controlled by adding 1 mL of saturated gas at room temperature to each of the six headspace bottles with three capacities (100, 200, and 500 mL), which were labeled as 100 mL(1), 100 mL(2), 200 mL(1), 200 mL(2), 500 mL(1), and 500 mL(2). In this experiment, bottles with the volumes shown in Figure 7c were used to degrade the gases, bottles of the same volume were used in repeated experiments three times, and the data were averaged to verify the accuracy. As can be seen from Figure 7b, under UV-Vis light irradiation, the optimal catalyst showed an excellent photocatalytic performance for gaseous acetone at different concentrations. In the experiment on the degradation of gaseous acetone, the concentration of gaseous acetone reached close to 0 in 90 min under UV-Vis light irradiation. This means that gaseous acetone can be completely decomposed in only 90 min at a fast rate, and slow decomposition can be completely achieved within 120 min. This is because the concentration of acetone is so high that it cannot be completely degraded within 90 min. In other words, after 90 min of irradiation, the degradation rate of 0.35TiO2@diatomite for gaseous acetone reaches up to 100%, which is greater than in most other studies [51]. From Figure 7c, it can be seen that gaseous benzene is degraded within 90 min. However, most of the gaseous benzene with different concentrations cannot be completely degraded. One possible reason for this is that the structure of a benzene molecule is extremely stable and difficult to break. Another possible reason is that the concentration of gaseous benzene is too high to be completely degraded. In this study, only two gaseous organic pollutants were investigated. In the future, we will study the degradation of the catalyst under other gaseous organic pollutants (such as methanol, ethanol, propanol, formaldehyde, and acetaldehyde) and summarize whether the effects on the polar and non-polar organics are identical.

3. Experimental Section

3.1. Chemicals and Materials

Diatomite (Macklin, Shanghai, China), titanium tetrachloride (TiCl4, analytical reagent, Adamas, Beijing, China), absolute ethanol (analytical reagent, Tianjin Damao Chemical Reagents Factory, Tianjin, China), benzene (analytical reagent, Tianjin Damao Chemical Reagents Factory, Tianjin, China), acetone (analytical reagent, Tianjin Damao Chemical Reagents Factory, Tianjin, China), and deionized water were used for the synthesis of TiO2 and diatomite/TiO2. During the process of synthesizing diatomite/TiO2, the only difference from TiO2 is that a certain amount of diatomite is added to the synthetic process for TiO2. All the reagents listed were used as purchased and without further treatment.

3.2. Catalyst Preparation

The TiO2@diatomite was prepared using a facile solvothermal method applying absolute ethanol as a solvent. Pure ethanol (50 mL) was transferred into a three-necked flask (250 mL) placed in an ice bath and stirred for 30 min. Then, 0.5 mL of deionized water (0.5 mL) was added. After 5 min, TiCl4 (2 mL) was added dropwise. The mixture was stirred until it became a transparent light-yellow solution. This solution was transferred to a dry Teflon-lined stainless-steel autoclave (100 mL) containing a certain amount of diatomite, and stirred evenly. The resulting mixture was then kept at 200 °C for 12 h in an oven. After cooling to room temperature, the white precipitates were filtered off, and washed with ethanol and deionized water several times until the pH of the filtrate reached approximately 7. The chlorine was also removed through the washing process. The collected precipitates were dried at 80 °C for 10 h in the oven to afford TiO2@diatomite. Detailed steps regarding the synthesis of TiO2@diatomite are also shown in Figure 8. For convenience, the catalysts are denoted as XTiO2@diatomite, where X represents the mass ratio of TiO2 to diatomite (because diatomite cannot be expressed in moles). The pure TiO2 was prepared according to the above procedure, except with the addition of diatomite steps.

3.3. Characterization

The catalysts were characterized based on X-ray diffraction patterns (XRD, Ultiam IV) recorded using Cu Kα radiation at a scan rate of 5°/min. Their microstructures were observed using field-emission SEM (JEOL-JSM-7800F (Tokyo, Japan) with an energy dispersive spectrometer and S-4700 at an acceleration voltage of 20 KV), TEM (Hitachi-HT7700 (Tokyo, Japan) at an acceleration voltage of 120 KV and JEM-ARM-200F), and HRTEM (JEOL, JEM-ARM200F, Tokyo, Japan). The specific surface area and pore size distribution of the different catalysts were determined using a Brunauer–Emmett–Teller (BET) instrument with nitrogen adsorption at 77 K (Micrometrics ASAP 2020, Georgia, USA). In addition, the ultraviolet-visible spectrophotometer (Shimadzu UV-3600, Tokyo, Japan) was used to analyze the UV-vis diffuse reflectance spectra of the prepared catalysts. Moreover, the electron hole recombination rate was measured using a photoluminescence spectrometer (FL-7000, Hitachi, Tokyo, Japan) to evaluate the photocatalytic activity.

3.4. Evaluation of Photocatalytic Activity

The photocatalytic activities of different catalysts were initially evaluated based on the degradation of MB under UV-light irradiation at ambient temperature [52]. During this process, the catalyst (0.05 g) was dispersed in an MB solution (10 of MB (50 mg/mL, 30 mL)) in a Petri dish. A portion of MB solution was taken every 30 min for measurements using an ultraviolet-visible spectrophotometer. The degradation rate was determined by monitoring the change in concentration of the MB over time using an ultraviolet-visible spectrophotometer (Shimadzu UV-3600). The catalyst with the highest degradation rate was chosen for degradation of the different gaseous organic pollutants, including acetone and benzene. These degradation processes were carried out in sealed headspace bottles with different volumes (100, 200, and 500 mL). The concentration of gas was controlled by adding equal volumes of saturated gas to different volumes of sealed headspace bottles (to the best of our knowledge, at the same temperature, the concentration of saturated gas is constant). The specific experimental details are similar to those of the process of MB degradation described above [52], except that the MB solution was replaced with gaseous phase organic pollutants. The details of the experiment are as follows: A catalyst (0.05 g) was added to each of the headspace bottles, and 1 mL of saturated gaseous phase pollutants at room temperature was transferred to the sealed headspace bottles using a gas chromatography syringe with a capacity of 2.5 mL. In addition, the initial concentrations of gaseous acetone and benzene in the 100, 200, and 500 mL headspace bottles were approximately 2.95 × 10−3, 1.63 × 10−3, and 6.85 × 10−4 mol/L, respectively. A xenon lamp (30 W) was adopted as a light source during the photocatalytic degradation process. The headspace bottle was placed under the light, and the bottle was directly irradiated. The whole process was degraded at room temperature. Throughout the degradation process, no heating and any agitation were used. Simultaneously, gases were taken every 30 min and the corresponding concentrations of organic gaseous pollutants were determined using gas chromatography-mass spectrometry (GC-MS). In addition, the degradation reaction of the organic gaseous pollutants was kept at ambient temperature. Four sealed headspace bottles of each gas were used for gaseous pollutant degradation. All reactions were repeated three times in parallel.

4. Conclusions

In conclusion, we successfully prepared a series of TiO2@diatomite catalysts using a facile solvothermal method applying anhydrous ethanol as a solvent for the removal of VOCs. The XRD patterns showed that TiO2 in the catalyst is in an anatase phase, and the introduction of diatomite has no effect on the crystal structure of TiO2. SEM and TEM images indicated that the size of the TiO2 nanoparticles is approximately 10–15 nm, and the morphologies of most of the TiO2 nanoparticles are square-like. In addition, for the TiO2@diatomite, the TiO2 nanoparticles are uniformly immobilized on the diatomite. Based on photocatalytic activity tests, 0.35TiO2@diatomite (with a TiO2 to diatomite mass ratio of 0.35) displayed higher photocatalytic activity compared with that at other ratios, pure TiO2, and pure diatomite. This result is consistent with the characterization results of the UV-vis diffuse reflectance spectra and PL spectra. The photocatalytic performance and GC-MS test results showed that 0.35TiO2@diatomite can be used to effectively remove acetone and benzene. In addition, both TiO2 and diatomite are low-cost, non-toxic, harmless, and stable. Therefore, a TiO2@diatomite catalyst could potentially be applied in the area of building construction and interior decoration.

Author Contributions

Conceptualization, X.L. & J.Y.; Methodology, X.L.; Software, X.L.; & Q.Y. & B.Y.; Formal Analysis, X.L.; Data curation, X.L. & J.Y.; Writing-Original draft preparation, X.L.; Writing-Review & Editing, X.L. & J.Y.; Visualization, X.L. & J.Y. & Y.H.; Supervision, J.Y.; Funding acquisition, J.Y. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Acknowledgments

The authors express their gratitude to the Analysis and Test Center of Beijing University of Chemical Technology for the received help.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Knudsen, H.N.; Kjaer, U.D.; Nielsen, P.A.; Wolkoff, P. Sensory and chemical characterization of voc emissions from building products: Impact of concentration and air velocity. Atmos. Environ. 1999, 33, 1217–1230. [Google Scholar] [CrossRef] [Green Version]
  2. Salthammer, T. Emission of volatile organic compounds from furniture coatings. Indoor Air 1996, 7, 189–197. [Google Scholar] [CrossRef]
  3. Wolkoff, P. Volatile organic compounds sources, measurements, emissions, and the impact on indoor air quality. Indoor Air 1995, 5, 5–73. [Google Scholar] [CrossRef]
  4. Meininghaus, R.; Gunnarsen, L.; Knudsen, H.N. Diffusion and sorption of volatile organic compounds in building materials−Impact on indoor air quality. Environ. Sci. Technol. 2000, 34, 3101–3108. [Google Scholar] [CrossRef]
  5. Dai, H.; Jing, S.; Wang, H. VOC characteristics and inhalation health risks in newly renovated residences in Shanghai, China. Sci. Total Environ. 2017, 577, 73–83. [Google Scholar] [CrossRef]
  6. Bentayeb, M.; Simoni, M.; Norback, D.; Baldacci, S.; Maio, S.; Viegi, G.; Annesi-Maesano, I. Indoor air pollution and respiratory health in the elderly. J. Environ. Sci. Health A 2013, 48, 1783–1789. [Google Scholar] [CrossRef]
  7. Ye, D.; Klein, M.; Chang, H.H.; Sarnat, J.A.; Mulholland, J.A.; Edgerton, E.S.; Winquist, A.; Tolbert, P.E.; Sarnat, S.E. Estimating acute cardiorespiratory effects of ambient volatile organic compounds. Epidemiology (Camb. Mass.) 2017, 28, 197. [Google Scholar] [CrossRef]
  8. World Health Organization. Burden of Disease from the Joint Effects of Household and Ambient Air Pollution for 2016; Social and Environmental Determinants of Health Department: Geneva, Switzerland, 7 November 2018. [Google Scholar]
  9. Lam, R.C.W.; Leung, M.K.H.; Leung, D.Y.C.; Vrijmoed, L.L.P.; Yam, W.C.; Ng, S.P. Visible-light-assisted photocatalytic degradation of gaseous formaldehyde by parallel-plate reactor coated with Cr ion-implanted TiO2 thin film. Sol. Energy. Mat. Sol. C. 2007, 91, 54–61. [Google Scholar] [CrossRef]
  10. Jeong, J.; Sekiguchi, K.; Sakamoto, K. Photochemical and photocatalytic degradation of gaseous toluene using short-wavelength uv irradiation with TiO2 catalyst: Comparison of three uv sources. Chemosphere 2004, 57, 663–671. [Google Scholar] [CrossRef]
  11. Higashimoto, S.; Tanihata, W.; Nakagawa, Y.; Azuma, M.; Ohue, H.; Sakata, Y. Effective photocatalytic decomposition of voc under visible-light irradiation on n-doped TiO2 modified by vanadium species. Appl. Catal. A Gen. 2008, 340, 98–104. [Google Scholar] [CrossRef]
  12. Azzouz, I.; Habba, Y.G.; Capochichi-Gnambodoe, M.; Marty, F.; Vial, J.; Leprince-Wang, Y.; Bourouina, T. Zinc oxide nano-enabled microfluidic reactor for water purification and its applicability to volatile organic compounds. Microsyst. Nanoeng. 2018, 4, 1–7. [Google Scholar] [CrossRef]
  13. Ghorbani Shahna, F.; Bahrami, A.; Ebrahimi, H. The hybrid effect of non-thermal plasma and activated carbon-zinc oxide nanocomposite on the removal of volatile organic compounds in air. Iran Occup. Health 2017, 14, 24-13. [Google Scholar]
  14. Meng, F.; Zheng, H.; Chang, Y.; Zhao, Y.; Li, M.; Wang, C.; Sun, Y.; Liu, J. One-step synthesis of Au/SnO2/RGO nanocomposites and their VOC sensing properties. IEEE. Trans. Nanotechnol. 2018, 17, 212–219. [Google Scholar] [CrossRef]
  15. Kaur, M.; Kumar, A.G. Synthesis and Characterization of Mesoporous SnO2 Photocatalyst for Degradation of Dye and Volatile Organic Compound. Ph.D. Thesis, 2016. [Google Scholar]
  16. Wang, L.; Xu, X.; Wang, Y.; Wang, X.; Shi, F.-N. Sulfur vacancy-rich CdS loaded on filter paper-derived 3D nitrogen-doped mesoporous carbon carrier for photocatalytic VOC removal. Inorg. Chem. Front. 2018, 5, 1470–1476. [Google Scholar] [CrossRef]
  17. Zhou, H.; Wen, Z.; Liu, J.; Ke, J.; Duan, X.; Wang, S. Z-scheme plasmonic Ag decorated WO3/Bi2WO6 hybrids for enhanced photocatalytic abatement of chlorinated-VOCs under solar light irradiation. Appl. Catal. B Environ. 2019, 242, 76–84. [Google Scholar] [CrossRef]
  18. Šuligoj, A.; Štangar, U.L.; Ristić, A.; Mazaj, M.; Verhovšek, D.; Tušar, N.N. TiO2–SiO2 films from organic-free colloidal TiO2 anatase nanoparticles as photocatalyst for removal of volatile organic compounds from indoor air. Appl. Catal. B Environ. 2016, 184, 119–131. [Google Scholar] [CrossRef]
  19. Weon, S.; Choi, E.; Kim, H.; Kim, J.Y.; Park, H.J.; Kim, S.M.; Kim, W.; Choi, W. Active {001} facet exposed TiO2 nanotubes photocatalyst filter for volatile organic compounds removal: From material development to commercial indoor air cleaner application. Environ. Sci. Technol. 2018, 52, 9330–9340. [Google Scholar] [CrossRef]
  20. Haghighatmamaghani, A.; Haghighat, F.; Lee, C.S. Performance of various commercial TiO2 in photocatalytic degradation of a mixture of indoor air pollutants: Effect of photocatalyst and operating parameters. Sci. Technol. Built. Environ. 2019, 25, 600–614. [Google Scholar] [CrossRef]
  21. Li, F.B.; Li, X.Z.; Ao, C.H.; Lee, S.C.; Hou, M.F. Enhanced photocatalytic degradation of VOCs using Ln3+–TiO2 catalysts for indoor air purification. Chemosphere 2005, 59, 787–800. [Google Scholar] [CrossRef] [Green Version]
  22. Tidahy, H.L.; Siffert, S.; Lamonier, J.F.; Zhilinskaya, E.A.; Aboukais, A.; Yuan, Z.-Y.; Vantomme, A.; Su, B.-L.; Canet, X.; De Weireld, G.; et al. New Pd/hierarchical macro-mesoporous ZrO2, TiO2 and ZrO2-TiO2 catalysts for VOCs total oxidation. Appl. Catal. A Gen. 2006, 310, 61–69. [Google Scholar] [CrossRef]
  23. Pham, T.D.; Lee, B.K. Selective removal of polar VOCs by novel photocatalytic activity of metals co-doped TiO2/PU under visible light. Chem. Eng. J. 2017, 307, 63–73. [Google Scholar] [CrossRef]
  24. Ochiai, T.; Tago, S.; Hayashi, M.; Tawarayama, H.; Hosoya, T.; Fujishima, A. TiO2-impregnated porous silica tube and its application for compact air-and water-purification units. Catalysts 2015, 5, 1498–1506. [Google Scholar] [CrossRef]
  25. Shayegan, Z.; Lee, C.S.; Haghighat, F. TiO2 photocatalyst for removal of volatile organic compounds in gas phase–A review. Chem. Eng. J. 2018, 334, 2408–2439. [Google Scholar] [CrossRef]
  26. Ji, J.; Xu, Y.; Huang, H.; He, M.; Liu, S.; Liu, G.; Xie, R.; Feng, Q.; Shu, Y.; Zhan, Y. Mesoporous TiO2 under VUV irradiation: Enhanced photocatalytic oxidation for VOCs degradation at room temperature. Chem. Eng. J. 2017, 327, 490–499. [Google Scholar] [CrossRef]
  27. Ao, C.H.; Lee, S.C.; Mak, C.L.; Chan, L.Y. Photodegradation of volatile organic compounds (VOCs) and NO for indoor air purification using TiO2: Promotion versus inhibition effect of NO. Appl. Catal. B Environ. 2003, 42, 119–129. [Google Scholar] [CrossRef]
  28. Hwang, J.Y.; Kim, H.M.; Lee, S.K. High-Energy, High-Rate, Lithium–Sulfur Batteries: Synergetic Effect of Hollow TiO2-Webbed Carbon Nanotubes and a Dual Functional Carbon-Paper Interlayer. Adv. Energy. Mater. 2016, 6, 1501480. [Google Scholar] [CrossRef]
  29. Zhu, S.R.; Wu, M.K.; Zhao, W.N.; Yi, F.Y.; Tao, K.; Han, L. Fabrication of heterostructured BiOBr/Bi24O31Br10/TiO2 photocatalyst by pyrolysis of MOF composite for dye degradation. J. Solid State Chem. 2017, 255, 17–26. [Google Scholar] [CrossRef]
  30. Yan, L.; Gu, Y.; Han, L.; Wang, P.; Li, H.; Yan, T.; Kuboon, S.; Shi, L.; Zhang, D. Dual Promotional Effects of TiO2-Decorated Acid-Treated MnO x Octahedral Molecular Sieve Catalysts for Alkali-Resistant Reduction of NOx. ACS. Appl. Mater. Interfaces 2019, 11, 11507–11517. [Google Scholar] [CrossRef]
  31. Li, M.; Lu, B.; Ke, Q.F.; Guo, Y.J.; Guo, Y.P. Synergetic effect between adsorption and photodegradation on nanostructured TiO2/activated carbon fiber felt porous composites for toluene removal. J. Hazard. Mater. 2017, 333, 88–98. [Google Scholar] [CrossRef]
  32. Zuo, R.; Du, G.; Zhang, W.; Liu, L.; Liu, Y.; Mei, L. Photocatalytic degradation of methylene blue using TiO2 impregnated diatomite. Adv. Mater. Sci. Eng. 2014, 2014, 170148. [Google Scholar] [CrossRef] [Green Version]
  33. PENNY Crossley. Clarifying matters-world diatomite reviewed. Ind. Miner. 2000, 390, 119–141. [Google Scholar]
  34. Al-Degs, Y.; Khraisheh, M.A.M.; Tutunji, M.F. Sorption of Lead Ions on Diatomite and Manganese Oxides Modified Diatomite. Water Res. 2001, 35, 3724–3728. [Google Scholar] [CrossRef]
  35. Khraisheh, M.A.M.; Al-degs, Y.S.; Mcminn, W.A.M. Remediation of wastewater containing heavy metals using raw and modified diatomite. Chem. Eng. J. 2004, 99, 177–184. [Google Scholar] [CrossRef]
  36. Niu, L.; Xian, G.; Long, Z.; Zhang, G.; Zhou, N. MnCeOx/diatomite catalyst for persulfate activation to degrade organic pollutants. J. Environ. Sci. 2020, 89, 206–217. [Google Scholar] [CrossRef]
  37. He, H.; Luo, Z.; Yu, C. Diatomite-anchored g-C3N4 nanosheets for selective removal of organic dyes. J. Alloys Compd. 2020, 816, 152652. [Google Scholar] [CrossRef]
  38. Gao, R.; Sun, Q.; Fang, Z.; Li, G.T.; Jia, M.; Hou, X. Preparation of nano-TiO2/diatomite-based porous ceramics and their photocatalytic kinetics for formaldehyde degradation. Int. J. Miner. Metall. Mater. 2018, 25, 73–79. [Google Scholar] [CrossRef]
  39. Wu, Z.; Zhu, Z.; Hao, X.; Zhou, W.; Han, J.; Tang, X.; Yao, S.; Zhang, X. Enhanced oxidation of naphthalene using plasma activation of TiO2/diatomite catalyst. J. Hazard. Mater. 2018, 347, 48–57. [Google Scholar] [CrossRef]
  40. Chen, Y.; Liu, K. Preparation of granulated N-doped TiO2/diatomite composite and its applications of visible light degradation and disinfection. Powder Technol. 2016, 303, 176–191. [Google Scholar] [CrossRef]
  41. Ao, M.; Liu, K.; Tang, X.; Li, Z.; Peng, Q.; Huang, J. BiOCl/TiO2/diatomite composites with enhanced visible-light photocatalytic activity for the degradation of rhodamine B. Beilstein. J. Nanotech. 2019, 10, 1412–1422. [Google Scholar] [CrossRef] [Green Version]
  42. Xu, H.; Reunchan, P.; Ouyang, S.; Tong, H.; Umezawa, N.; Kako, T.; Ye, J. Anatase TiO2 single crystals exposed with high-reactive {111} facets toward efficient H2 evolution. Chem. Mater. 2013, 25, 405–411. [Google Scholar] [CrossRef]
  43. Roy, N.; Park, Y.; Sohn, Y. Green synthesis of anatase TiO2 nanocrystals with diverse shapes and their exposed facets-dependent photoredox activity. ACS Appl. Mater. Interfaces 2014, 6, 16498–16507. [Google Scholar] [CrossRef]
  44. Sun, Z.; Yang, X.; Zhang, G.; Zheng, S.; Frost, R. A novel method for purification of low grade diatomite powders in centrifugal fields. Int. J. Miner. Process. 2013, 125, 18–26. [Google Scholar] [CrossRef] [Green Version]
  45. Liu, E.; Kang, L.; Wu, F.; Sun, T.; Hu, X.; Yang, Y.; Liu, H.; Fan, J. Photocatalytic Reduction of CO2 into Methanol over Ag/TiO2 Nanocomposites Enhanced by Surface Plasmon Resonance. Plasmonics 2014, 9, 61–70. [Google Scholar] [CrossRef]
  46. Wu, L.; Zhou, Y.; Nie, W.; Song, L.; Chen, P. Synthesis of highly monodispersed teardrop-shaped core-shell SiO2/TiO2 nanoparticles and their photocatalytic activities. Appl. Surf. Sci. 2015, 351, 320–326. [Google Scholar] [CrossRef]
  47. Thommes, M.; Kaneko, K.; Neimark, A.V. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 2015, 87, 1051–1069. [Google Scholar] [CrossRef] [Green Version]
  48. Yu, X.; Zhao, Z.; Zhang, J. One-step synthesis of ultrathin nanobelts-assembled urchin-like anatase TiO2 nanostructures for highly efficient photocatalysis. CrystEngComm 2017, 19, 129–136. [Google Scholar] [CrossRef]
  49. Xu, H.Q.; Hu, J.; Wang, D.; Li, Z.; Zhang, Q.; Luo, Y.; Yu, S.H.; Jiang, H.L. Visible-light photoreduction of CO2 in a metal–organic framework: Boosting electron–hole separation via electron trap states. J. Am. Chem. Soc. 2015, 137, 13440–13443. [Google Scholar] [CrossRef]
  50. .Kang, Y.; Yang, Y.; Yin, L.C. Selective breaking of hydrogen bonds of layered carbon nitride for visible light photocatalysis. Adv. Mater. 2016, 28, 6471–6477. [Google Scholar] [CrossRef]
  51. Choi, W.; Ko, J.Y.; Park, H.; Chung, J.S. Investigation on TiO2-coated optical fibers for gas-phase photocatalytic oxidation of acetone. Appl. Catal. B Environ. 2001, 31, 209–220. [Google Scholar] [CrossRef]
  52. Liu, S.; Yu, J.; Jaroniec, M. Tunable photocatalytic selectivity of hollow TiO2 microspheres composed of anatase polyhedra with exposed {001} facets. J. Am. Chem. Soc. 2010, 132, 11914–11916. [Google Scholar] [CrossRef]
Figure 1. XRD patterns of TiO2, diatomite, and XTiO2@diatomite.
Figure 1. XRD patterns of TiO2, diatomite, and XTiO2@diatomite.
Catalysts 10 00380 g001
Figure 2. X-ray diffraction patterns (XRD) patterns of pure diatomite.
Figure 2. X-ray diffraction patterns (XRD) patterns of pure diatomite.
Catalysts 10 00380 g002
Figure 3. Scanning electron microscopy (SEM) images with different magnifications of (A1,A2) diatomite, (B1,B2) TiO2, (C1C6) 0.35TiO2@diatomite, (D1,D2) 0.30TiO2@diatomite, (D3,D4) 0.40TiO2@diatomite, (D5,D6) 0.45TiO2@diatomite, and (D7,D8) 0.50TiO2@diatomite. (E1E4) High-resolution transmission electron microscopy (HRTEM) images of 0.35TiO2@diatomite and (E5E8) transmittance electron microscopy (TEM) images of 0.35TiO2@diatomite.
Figure 3. Scanning electron microscopy (SEM) images with different magnifications of (A1,A2) diatomite, (B1,B2) TiO2, (C1C6) 0.35TiO2@diatomite, (D1,D2) 0.30TiO2@diatomite, (D3,D4) 0.40TiO2@diatomite, (D5,D6) 0.45TiO2@diatomite, and (D7,D8) 0.50TiO2@diatomite. (E1E4) High-resolution transmission electron microscopy (HRTEM) images of 0.35TiO2@diatomite and (E5E8) transmittance electron microscopy (TEM) images of 0.35TiO2@diatomite.
Catalysts 10 00380 g003aCatalysts 10 00380 g003bCatalysts 10 00380 g003cCatalysts 10 00380 g003dCatalysts 10 00380 g003e
Figure 4. UV-visible diffuse reflectance adsorption spectra of the catalysts.
Figure 4. UV-visible diffuse reflectance adsorption spectra of the catalysts.
Catalysts 10 00380 g004
Figure 5. N2 adsorption-desorption isotherms of diatomite, TiO2, and 0.35TiO2@diatomite.
Figure 5. N2 adsorption-desorption isotherms of diatomite, TiO2, and 0.35TiO2@diatomite.
Catalysts 10 00380 g005
Figure 6. Photoluminescence (PL) spectra of TiO2, diatomite, and XTiO2@diatomite.
Figure 6. Photoluminescence (PL) spectra of TiO2, diatomite, and XTiO2@diatomite.
Catalysts 10 00380 g006
Figure 7. (a) Plots of the methylene blue (MB) photodegradation over various catalysts under UV irradiation. (b) Plots of the photodegradation of various concentrations of gaseous acetone over 0.35TiO2@diatomite under UV-Vis light irradiation. (c) Plots of the photodegradation of benzene at various concentrations over 0.35TiO2@diatomite under UV-Vis light irradiation.
Figure 7. (a) Plots of the methylene blue (MB) photodegradation over various catalysts under UV irradiation. (b) Plots of the photodegradation of various concentrations of gaseous acetone over 0.35TiO2@diatomite under UV-Vis light irradiation. (c) Plots of the photodegradation of benzene at various concentrations over 0.35TiO2@diatomite under UV-Vis light irradiation.
Catalysts 10 00380 g007
Figure 8. Synthesis procedure for XTiO2@diatomite catalysts.
Figure 8. Synthesis procedure for XTiO2@diatomite catalysts.
Catalysts 10 00380 g008
Table 1. Chemical analyses of diatomite [32].
Table 1. Chemical analyses of diatomite [32].
Composition%SiO2Al2O3Fe2O3K2OCaOMgONa2OTiO2Other
Diatomite86.823.211.600.560.460.430.250.156.52
Table 2. Surface and structural characterization of the catalysts.
Table 2. Surface and structural characterization of the catalysts.
SampleBET Specific Surface Area (m2/g)Pore Volume (cm3/g)Average Pore Size (nm)
Diatomite0.32020.002-
Pure TiO2115.70.2578.8
0.3TiO2@diatomite20.60.0448.5
0.35TiO2@diatomite19.60.05110.3
0.4TiO2@diatomite22.30.05810.5
0.45TiO2@diatomite21.70.05610.4
0.5TiO2@diatomite21.00.0509.5

Share and Cite

MDPI and ACS Style

Liu, X.; He, Y.; Yang, B.; Yan, Q.; Yang, J. Highly Efficient Photo-Degradation of Gaseous Organic Pollutants Catalyzed by Diatomite-Supported Titanium Dioxide. Catalysts 2020, 10, 380. https://doi.org/10.3390/catal10040380

AMA Style

Liu X, He Y, Yang B, Yan Q, Yang J. Highly Efficient Photo-Degradation of Gaseous Organic Pollutants Catalyzed by Diatomite-Supported Titanium Dioxide. Catalysts. 2020; 10(4):380. https://doi.org/10.3390/catal10040380

Chicago/Turabian Style

Liu, Xuefei, Yugan He, Beibei Yang, Qi Yan, and Junjiao Yang. 2020. "Highly Efficient Photo-Degradation of Gaseous Organic Pollutants Catalyzed by Diatomite-Supported Titanium Dioxide" Catalysts 10, no. 4: 380. https://doi.org/10.3390/catal10040380

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop