The Application of Nano-TiO2 Photo Semiconductors in Agriculture
© The Author(s). 2016
Received: 29 August 2016
Accepted: 4 November 2016
Published: 28 November 2016
Nanometer-sized titanium dioxide (TiO2) is an environmentally friendly optical semiconductor material. It has wide application value in many fields due to its excellent structural, optical, and chemical properties. The photocatalytic process of nano-TiO2 converts light energy into electrical or chemical energy under mild conditions. In recent years, the study and application of nano-TiO2 in the agricultural sector has gradually attracted attention. The nano-TiO2 applications of degrading pesticides, plant germination and growth, crop disease control, water purification, pesticide residue detection, etc. are good prospects. This review describes all of these applications and the research status and development, including the underlying principles, features, comprehensive applications, functional modification, and potential future directions, for TiO2 in agriculture.
Introduction and Background
Nano-TiO2 photo semiconductors have many applications in many fields including photocatalysis, agriculture, dye-sensitized solar cells, and biomedical devices . However, in the agricultural field, the use of TiO2 nanomaterials is relatively new and requires further exploration. The nano-TiO2 photo semiconductor continues to attract attention of agricultural researchers because of its favorable physical/chemical properties, low cost, availability, and high stability. Thus, nano-TiO2 photo semiconductors have many application possibilities in agriculture including degradation of pesticides, plant protection, and residue detection. However, one disadvantage of TiO2 nanomaterials is that they are mostly active in the presence of UV light due to their large band gap of approximately 3.2 eV [18, 19]. The UV regime is only a small fraction of the Sun’s energy (<10%) . Therefore, this property limits the application of TiO2 nanomaterials in agriculture, and the highly efficient use of TiO2 nanomaterials is sometimes prevented. Thus, several approaches have been developed to alleviate this problem and to improve the photocatalytic activity of TiO2 nanomaterials for a wide range of applications. One effective method for improving the performance of TiO2 nanomaterials is to increase their optical activity by shifting the response onset from the UV to the visible region by doping the TiO2 nanomaterial with different metals or other elements .
This paper aims to review and summarize the recent applications and research on nano-TiO2 photo semiconductors and their doping complexes in agriculture. The topics include pesticide degradation, plant germination and growth, crop disease control, water purification, and pesticide residue detection.
Application of TiO2 Photo Semiconductors in Agriculture
Pesticides are widely used in agriculture, although their excessive usage may create hazards to both humans and the environment. Repeated use of pesticides results in a frequent occurrence of residues in the environment and in biota. Most pesticide residues require effective treatment and further removal due to their toxicity, high chemical stability, and low biodegradability. Consequently, considerable efforts have been devoted to developing methods that can remove residual pesticides and destroy bio-recalcitrant organic contaminants . Semiconductor photocatalysis is a promising approach to remedy the pesticide residue problem, and it has attracted significant attention [14, 23]. TiO2 is the most investigated photo semiconductor. For the past decade, it has been widely studied as an efficient photocatalyst for pesticides .
A substantial amount of research has been focused on modifying the TiO2 photocatalyst for enhancing pesticide degradation . Ramos-Delgado et al. reported the solar photocatalytic activity of TiO2, which was modified with WO3, for degrading the organophosphorus pesticide . The TiO2 semiconductor, which was loaded with 2% WO3, exhibited better solar photocatalytic behavior for degrading the malathion pesticide compared with bare TiO2. This was attributed to the formation of smaller clusters and a higher surface area, which reduced the electron–hole recombination process and resulted in a better contact area between the catalyst particles and the pesticide. Thus, the photocatalytic reactivity and efficiency were improved . Guan et al. reported a W/TiO2 catalyst that was constructed for the photocatalytic degradation and mineralization of avermectin insecticide microcapsules. The catalyst had the highest photocatalytic activity with a 4.0 mol% W-doped amount due to the presence of electron-trapping centers (W6+) in W-doped TiO2 solid solutions. Guan et al. reported different types of TiO2-based photodegradable nano-imidacloprid insecticides . Photocatalysts, including TiO2, sodium dodecyl sulfate (SDS)/TiO2, Ag/TiO2, and SDS/Ag/TiO2, were constructed for the photocatalytic degradation of the nano-imidacloprid insecticide. The photocatalytic activity of SDS/Ag/TiO2 was the highest among all of the photocatalysts due to its large specific surface area compared with TiO2, which led to the fast adsorption of reactants and enrichment of the insecticide. Moreover, depositing silver in the SDS/Ag/TiO2 photocatalyst significantly promotes the photocatalytic activity.
Plant Germination and Growth
Crop Disease Control
Conventional bactericidal methods that are used to protect plants against pathogens apply chemical pesticides to the irrigation water. However, this method of controlling plant diseases is hazardous both to humans and to the environment. Photochemical disinfection of plant pathogens using TiO2 thin films offers an alternative method for preventing plant pathogens . The TiO2 photocatalyst technique has a potential for agricultural applications because it does not form dangerous compounds . Under light, TiO2 nanomaterials generate superoxide ion radicals and hydroxides. These active oxygen species are effective antimicrobial agents. In recent years, various researchers have studied the effect of nano-TiO2 photo semiconductors in controlling crop diseases. However, UV accounts for only approximately 3% of the solar light spectrum. This limits the TiO2 photocatalytic disinfection application under visible light irradiation . Yao et al. reported that the TiO2 thin film photocatalytic efficiency is improved under visible light by doping with a novel photosensitive dye. Thus, phytopathogenic bacteria in vegetable crops can be effectively inhibited by visible light irradiation. Cui et al. studied the bactericidal effect of nano-TiO2 on cucumbers . The nano-TiO2 formed a successive, adhesive, and transparent film on the surface of the leaves. Further, the nano-TiO2-treated cucumber leaves had powerful bactericidal effects on plant pathogens due to the photocatalytic and photo biological effects of TiO2, which inhibited bacterial and fungal diseases.
In recent years, the growing concern about the problem of water decontamination from organic pollutants during agricultural production has led to research on methods that improve the efficiency and lower the consumption of chemical reagents . Because photocatalysts use solar energy, the photocatalytic decomposition of organic pollutants in water is of particular interest and has received significant attention from scientists [47–50]. TiO2 is the most popular semiconductor that is used in photocatalytic processes [47–50]. TiO2 photo semiconductors that are a large size are stoichiometric and thus exhibit poor photocatalytic activity. However, nano-TiO2 crystallites (typical size <50 nm) have the expected electronic properties for applications in photocatalysis because of their higher activity . In this photocatalysis process, reactive species can be formed on the surface of a nano-TiO2 photocatalyst that is exposed to UV radiation. The complete degradation and mineralization of a large variety of organic contaminants can be achieved in most cases [52, 53].
However, the main problem, which has limited the practical application of nano-TiO2 photocatalysis for water purification, is either a relatively low process rate or a limited efficiency for the use of irradiated energy [1, 54, 55]. A possible approach to solve this problem is the exploitation of low-cost radiation such as solar energy [56, 57]. However, the intensity of ultraviolet radiation in the solar spectrum is very limited. Therefore, the use of metals or metal oxide doping to extend the TiO2 absorption to the visible range is currently a good option for solving the problem. This approach enhances the photocatalytic activity of TiO2 and improves the utilization efficiency of the radiation energy [20, 58]. For instance, it was determined that the addition of fluoride to TiO2 significantly enhances the degradation rate of phenol [22, 59]. The dominant parameters (e.g., dopant nature, dopant concentration, and thermal treatment) affect the material . Vione reported that fluoride addition to TiO2 enhanced the photocatalytic degradation of many organic compounds that were transforming via different pathways . Bessekhouad reported that alkaline-doped TiO2 at low concentrations could be a promising material to degrade organic pollutants. The best results were obtained for 5% Li-doped TiO2 that was prepared using the impregnation technique . Brezová et al. reported that the presence of metals, such as Li+, Zn2+, Cd2+, Pt0, Ce3+, Mn2+, Al3+, and Fe3+, could significantly change the photoactivity of TiO2 that was prepared using the sol–gel technique . In addition, the effect of doping TiO2 with Li and Rb was studied by López et al., and the obtained materials were used to decompose 2,4-dinitroaniline .
Pesticide Residue Detection
Depending on their aqueous solubility, pesticides either remain in the soil or enter surface waters and ground waters. Pesticide degradation residues can remain in vegetables, animals, and water sources and can become more concentrated as they move up the food chain. There is an increasing interest in developing systems to sense, monitor, and remove pesticide residues because they are toxic even at trace levels.
Currently, pesticide detection methods typically use liquid or gas chromatography coupled with mass spectrometric detection (HPLC-MS and GC-MS) due to the sensitivity and reliability of these techniques. However, these approaches require meticulous sample preparation and highly qualified technicians . Nanomaterial-based sensors can be used to detect pesticide residues. These nanosensors are alternatives to traditional methods due to their high sensitivity, low detection limits, high selectivity, fast response, and small size. Because of their simplicity, low cost, and ease of miniaturization, electrochemical and optical biosensors are widely used for detecting pesticides.
During recent decades, nano-TiO2 photo semiconductors, which are efficient sorbents for enriching and detecting pesticides, have attracted significant attention in the photocatalytic and photoelectrochemical area due to their nontoxicity, hydrophilicity, availability, and stability against photocorrosion. Additionally, they have a suitable flat band potential and are easily supported on various substrates [62–65].
TiO2 was used as an efficient and selective sorbent to recognize the phosphorylation moiety based on a strong chelation with phospho-moieties. The affinity of TiO2 towards the phosphoric group is favorable for fast enrichment and detection of free organophosphate pesticides . However, the wide band gap of TiO2 (∼3.2 eV, anatase) allows it to absorb only the ultraviolet light (<387 nm). To extend its photo response to the visible region and to promote the photoelectric conversion efficiency, many modification methods have been applied (e.g., dye sensitization, metal ion/nonmetal atom doping, semiconductor coupling, and noble metal deposition) [19, 66]. Of the abovementioned methods, by considering the high electron mobility of nanocrystals and the possibility of shifting the optical band gap to the visible light region using organic materials, the organic–inorganic heterojunction can produce a robust photoelectrochemical sensor. Zhou reported that graphene-modified TiO2 nanotube arrays exhibit an excellent enrichment efficiency for carbamate pesticides including metolcarb, carbaryl, isoprocarb, and diethofencarb. The detection limits of these carbamate pesticides range from 2.27 to 3.26 μg L−1. The method could be used as a faster and easier alternative procedure for routine analysis of carbamate pesticides . Li et al. developed two photoelectrochemical sensors to detect dichlofenthion and chlorpyrifos pesticides. The sensors were based on a TiO2 photocatalyst coupled with electrochemical detection, which is a derivative of an electrochemical sensor and sensitized TiO2 [68, 69].
Over the past decades, nano-TiO2 has shown its potential for agricultural applications because of its high photocatalytic disinfection and photo biological effects coupled with its low price, nontoxicity, and stable performance. The continuous breakthroughs in the synthesis and modifications of TiO2 nanomaterials have resulted in new properties and new agricultural applications including pesticide degradation, plant germination and growth, crop disease control, water purification, and pesticide residue detection with improved performance. The research demonstrates that nano-TiO2 photo semiconductors are essential for degrading organic pollutants, preventing and controlling plant diseases with an antiviral or antibacterial function, and protecting the environment. These characteristics provide new approaches for solving environmental pollution and pesticide residue problems in agriculture.
This research was supported by the Beijing Municipal Natural Science Foundation (6164045), the Major National Scientific Research Program of China (2014CB932200), the National Key Research and Development Program of China (2016YFD0200500), the Basic Scientific Research Fund of National Nonprofit Institutes (BSRF201503), and the Agricultural Science and Technology Innovation Program.
YW collected and reviewed the data and drafted the manuscript. CS, XZ, and AW modified the first version of the draft and after revision. HC, ZZ, BC, and GL participated in discussions. YW and HC analyzed and interpreted the data. All authors read and approved the final manuscript.
YW is an associate professor. HC, ZZ, and GL are professors. CS, XZ, and BC are assistant professors, and AW is a graduate student in the Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of Agricultural Sciences.
The authors declare that they have no competing interests.
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