Green photocatalysts are photocatalysts derived from environmentally friendly sources. [1] [2] They are synthesized from natural, renewable, and biological resources, such as plant extracts, biomass, or microorganisms, minimizing the use of toxic chemicals and reducing the environmental impact associated with conventional photocatalyst production. [3] [4]
A photocatalyst is a material that absorbs light energy to initiate or accelerate a chemical reaction without being consumed in the process. [5] They are semiconducting materials which generate electron-hole pairs upon light irradiation. These photogenerated charge carriers [6] then migrate to the surface of the photocatalyst and interact with adsorbed species, triggering redox reactions. [7] They are promising candidates for a wide range of applications, including the degradation of organic pollutants in wastewater, the reduction of harmful gases, and the production of hydrogen or solar fuels. [8] Many methods exist to produce photocatalysts via both conventional and more green approaches including hydrothermal synthesis or sol-gel, the difference being in the material sources used.
A green source for photocatalyst synthesis refers to a material that is renewable, biodegradable, and has minimal environmental impact during its extraction and processing. [3] [4] This approach aligns with the principles of green chemistry, which aim to reduce or eliminate the use and generation of hazardous substances in chemical processes. [3] [4] Green sources are abundant, readily available, and often considered as waste materials, thus offering a sustainable and cost-effective alternative to conventional photocatalyst precursors. [9]
Plant extracts and agricultural waste products have emerged as promising green sources for photocatalyst production, offering attractive alternatives to conventional precursors due to their abundance, biodegradability, and cost-effectiveness. [10] Extracts from various plant parts, such as leaves, roots, and fruits, contain phyto-chemicals that can act as reducing and stabilizing agents in nanoparticle synthesis, [10] [11] contributing to the formation of desired photocatalyst morphologies. Meanwhile, waste materials from agricultural processes, such as rice husks and sugarcane bagasse, are rich in cellulose and lignin. [12] These components can be used as precursors for carbon-based photocatalyst or as templates for the synthesis of porous nano-materials. [13] [14]
Notes:
Utilizing bio-waste, such as food waste and animal waste, for green photocatalyst synthesis offers a dual benefit of waste management and material production. [27] These waste streams are rich in organic matter, which can be converted into valuable carbon-based photocatalyst through various thermochemical processes. [28] [29]
Bio-waste | NPs synthesized and produced | Size of NPs (nm) | Shape of NPs | Reference |
---|---|---|---|---|
Waste oyster shells | nHAp/ZnO/GO | 9–22 | Spherical | [30] |
Rice husk | TiO2 | 6.2–7.6 | Irregular sharp cylinder-like particles | [31] |
Waste of chicken eggshell | CaO@NiO | 15-20 | Rod-like shape | [32] |
Papaya (Carica papaya L.) peel biowaste | CuO | 85–140 | Agglomerated spherical | [33] |
Dragon fruit (Hylocereus polyrhizus) peel biowaste | ZnO | 56 | Spherical | [34] |
Longan seeds biowaste | ZnO | 10–100 | Irregular and hexagonal | [35] |
Banana pseudo stem | TiO2 | 9.98–24.56 | Polyhedral | [36] |
Agro-waste durva grass | ZrO2 | 15-35 | Spherical | [37] |
Agricultural waste Hibiscus cannabinus | γ-Fe2O3/Si | 48.3 | Spherical | [38] |
Citrus reticulata Blanco (C. reticulata) waste | ZnO | 9 | Hexagonal | [39] |
Rooibos tea waste | Fe2O3–SnO2 | - | Tone-like structures, tiny rod-like structures, and well-dispersed | [40] |
Sugarcane bagasse | Cu2O | 38.02 | Irregular | [41] |
Notes/Explanations:
Seaweed is a highly promising green source for photocatalyst synthesis due to its rapid growth rates and minimal environmental requirements. [42] It does not require freshwater or fertilizers for cultivation, making it a sustainable and environmentally friendly option. [43] [44] Various seaweed species have been explored for their ability to produce nanoparticles and to act as templates for the synthesis of photocatalytic materials. [45] [46] [47]
Species of Macroalgal | Bioactive Substances | Phytochemical Activities | NPs synthesized and produced | Size of NPs (nm) | Shape of NPs | Reference |
---|---|---|---|---|---|---|
Sargassum vulgare | Polyphenols, polysaccharides, phytohormones, carotenoids, vitamins, unsaturated fatty acids and free amino acids. | Reducing and capping agents | Zn | 50-150 | Spherical | [48] |
Sargassum myriocystum | Phenol | Reducing and capping agents | Ag | 20 ± 2.2 | Well dispersed hexagonal | [49] |
Sargassum coreanum | Polysaccharides, polyphenols, lignans | Reducing and stabilizing agent | Ag | 19 | Distorted spherical shape | [50] |
Sargassum spp. | Phenolics compounds | Capping agent | Ag | 2-35 | Spherical | [51] |
Padina tetrastromatica | Favonoids, steroids, saponins, tannins, phenols and proteins | Reducing and stabilizing agent | Au | 11.4 | Nearly spherical | [52] |
Sargassum spp. | Ase terpenoids, flavones, and polysaccharides | Capping and stabilization agent | Fe3O4 | 23.60 ± 0.62 | Agglomerated spherical | [53] |
Sargassum tenerrimum | Polyphenol and proteins | Reducing, capping, and stabilizing agents | Ag | 22.5 | Spherical | [54] |
Sargassum duplicatum | Proteins containing amide and carboxyl groups and carbohydrates | Reducing and stabilizing agent | Ag | 20-50 | Spherical | [55] |
Caulerpa sertularioides | Alkaloids, phenols, flavonoids, tannins, terpenoids, carbohydrates, glycosides, amino acids, and proteins | Reducing and capping agent | Ag | 24-57 | Spherical | [56] |
Galaxaura elongata , Turbinaria ornata , and Enteromorpha flexuosa | Alkaloids, flavonoids, phenolic compounds, proteins, and sugars | Reducing and capping agent | Ag | 20-25 | Spherical | [57] |
Lobophora variegata | Polyphenol, bromophenols, lobophorones, and sulphated polysaccharide | Reduction, capping and stabilizing agent | Ag | 6.5-10 | Oval | [58] |
red marine algae (Bushehr province, Iran) | Amino acids, polysaccharides, carbohydrates | Reducing and coating agent | NiO | 32.64 | Spherical | [59] |
Notes/Explanations:
Reference | Marine Macroalgae | Biogenic Capping Agents | NPs synthesized and produced | Zeta Potential | Stability | PDI | Dispersion | Potential Applications |
---|---|---|---|---|---|---|---|---|
[51] | Sargassum spp. | Polyphenols | Ag | −22.6 mV | High stability | 0.246 | Monodispersity | Pollutant detection in environmental |
[60] | Polycladia crinita | Primary and tertiary amines, polysaccharides, amino acids | Se | − 13.9 mV | High stability | - | Polydispersed | Drug delivery |
[61] | Cystoseira tamariscifolia | Polyphenols and polysaccharides | Au | −24.6 ± 1.5 mV | High stability | - | - | Biomedical |
[62] | Polysiphonia urceolata | Phenols (bromophenols), terpenes, steroids, carbohydrates, and polypeptides | CeO2NPs, NiONPs and CeO2/NiO NCS | - | High stability | - | Polydispersed | Toxic ofloxacin remediation and antibacterial (green surfactant) |
[63] | Padina boergesenii | Phenolic compounds, aromatic amine groups, nitro compounds, and aliphatic amines | Se-ZnO | −16.4 mV | High stability | 0.262 | Polydispersed | Biomedicine (anti-cancer) |
[64] | Ulva lactuca | Polyphenols, flavonoids, terpenoids, polysaccharides, and proteins | Ag | −59.0 mV | High stability | 1.092 | Monodispersed | Azo-dyes Photodegradation and biomedical usage |
[65] | Enteromorpha prolifera | Alcohol, thiol, carbon dioxide, and ketanine, alkene, carboxylic acid and amine and alkene compound | Ag | − 30.8 mV | High stability | 0.277 | Polydispersed | Biomedical field |
[66] | Sargassum wightii | Polyphenols | ZnO | − 49.39 mV | High stability | 0.150 | Polydispersed | Biomedical field |
[67] | Turbinaria ornata | Flavonoid and phenolic | Ag | –63.3 mV | High stability | 0.313 | Monodispersed | Biomedical field |
[68] | Sargassum angustifolium | Polyphenols | Ag | − 27 mV | High stability | 0.15 | Monodispersed | Biomedicine (anti-bactrerial) |
[69] | Gracilaria birdiae | Polysaccharides | Ag | −28.7 ± 0.7 mV - −31.7 ± 0.4 mV | High stability | 0.35 -0.68 | Monodispersed | Biomedicine |
Notes/Explanations:
Material | Green Source(s) | Advantages of Source | Reference |
---|---|---|---|
TiO2 | Plant extracts (e.g., Aloe vera) | Abundant, biocompatible | [70] |
ZnO | Agricultural waste (e.g., rice husks) | Renewable, low cost, high surface area in derived materials | [71] |
CuO | Plant extracts (e.g., Hibiscus sabdariffa L.) | Biocompatible, non-toxic, can act as reducing and capping agents | [72] |
CeO2 | Plant extracts (e.g., Azadirachta indica) | Abundant, eco-friendly | [73] |
Carbon quantum dots | Bio-waste (e.g., food waste) | Waste management, cost-effective, tunable properties | [74] |
Graphene quantum dots | Bio-waste (e.g., Spent tea leaves) | Waste management, cost-effective, tunable properties | [75] |
Hydrothermal synthesis is a green method that utilizes water under high pressure and temperature to facilitate chemical reactions. [76] It often avoids the need for organic solvents and offers control over crystal size and morphology, making it a versatile approach for producing various photocatalyst materials. [76]
Microwave-assisted synthesis employs microwaves to provide rapid and uniform heating, leading to faster reaction rates and potential for significant energy savings compared to conventional heating methods. [77] This technique is increasingly favored in green synthesis due to its reduced energy consumption and potential for shorter reaction times. [77]
The sol-gel method involves the formation of a gel from a solution, followed by its conversion into a solid material through controlled drying and calcination. [78] It is a versatile technique widely used in the production of various photocatalyst materials, offering advantages in terms of controlling material composition and morphology. [78]
The table below provides a comparison of the advantages, potential limitations, and suitability of different green synthesis methods:
Method | Description | Advantages | Potential Limitations | Suitable for... | Reference |
---|---|---|---|---|---|
Hydrothermal Synthesis | Water under high pressure & temperature facilitate chemical reactions | Avoids organic solvents, controls crystal size & morphology | Longer reaction times, specialized equipment needed | Producing various photocatalytic materials | [79] |
Microwave-Assisted Synthesis | Microwaves provide rapid & uniform heating | Faster reaction rates, energy efficient | Limited scalability, potential for uneven heating | Synthesis of nanomaterials with controlled size & morphology | [80] |
Sol-Gel Method | Gel from a solution is converted into a solid material | Versatile in producing various materials, controls composition & morphology | Requires careful control of parameters, can be time-consuming | Metal oxide nanoparticles, thin films, and coatings | [81] |
Green photocatalyst effectively break down organic contaminants in wastewater into less harmful products through a process known as photocatalytic oxidation. [82] Upon light irradiation, the photocatalyst generates reactive oxygen species (ROS), such as hydroxyl radicals (•OH) and superoxide radicals (O2•-), which attack and decompose organic pollutants. [83] Green photocatalyst synthesized from plant extracts or agricultural waste have shown promising results in degrading various dye molecules, including methylene blue, rhodamine B, and methyl orange. [84] Green photocatalyst have demonstrated the ability to remove pharmaceutical contaminants such as carbamazepine, [85] ibuprofen, [86] tetracycline [87] [88] from wastewater. Additionally, green photocatalyst have been successfully employed in the degradation of pesticides such as alachlor. [89]
Plant | Bioactive substances | NPs synthesized and produced | Size of NPs (nm) | Shape of NPs | Applications | Ref |
---|---|---|---|---|---|---|
Froriepia subpinnata | Flavonoids and phenolic | Ag | 18 | Hemispherical and hexagonal | Antimicrobial and adsorption of the Azo dye Acid-Red 58 | [90] |
Rhododendron arboreum | Steroids, terpenoids, alkaloids, saponins, phenols, flavonoids, tannins, glycosides and polyphenolic | ZnO | 29.424 | Spherical | Dye photodegradation | [91] |
Elettaria cardamomum | Phenolic | CoFe2O4 | 20–50 | Spherical | Phenol red dye photodegradation | [92] |
Zingiber officinale | Phenolic | CoFe2O4 | 20–50 | Spherical | Phenol red dye photodegradation | [92] |
Tillandsia recurvata | Tannins, reducing sugars, and carbohydrates | ZnO | 12–61 | Spherical | Methylene blue (MB) photodegradation | [93] |
Ajuga iva | Carbohydrates, phenol groups, acidic fractions | Ag | 100-300 | Polygonal poly–dispersed | Methylene blue (MB) photodegradation | [94] |
Macleaya cordata | Phenolic | CuO | 80 | rectangular and square with irregular rod | Methylene blue (MB) photodegradation and antibacterial | [95] |
Coleus scutellariodes | Phenolic | NiO | 23 | Rod shape | Antibiotic (rufloxacin) photodegradation | [96] |
Eupatorium adenophorum | Sesquiterpenoids, triterpenes, flavonoids, phenolics, coumarins, steroids, polyphenols, and phenylpropanols | Ag | 30–400 | Spherical | Rhodamin B photodegradation | [97] |
Notes/Explanations:
In addition to degrading organic pollutants, green photocatalyst can also contribute to the removal of toxic heavy metals from wastewater. The large surface area and functional groups present on green photocatalyst, particularly those derived from carbon-based sources like bio-waste, can effectively adsorb heavy metal ions from the water. [98] Furthermore, photogenerated electrons [99] from the green photocatalyst can reduce heavy metal ions to their less toxic elemental forms, which can then be more easily removed from the wastewater. [98]
Green photocatalyst exhibit potent antibacterial properties due to their ability to generate ROS upon light irradiation. [100] These ROS, including hydroxyl radicals and superoxide radicals, can damage bacterial cell walls and membranes, leading to cell death. [101]
Several green photocatalyst have shown promising antibacterial activity. ZnO nanoparticles synthesized using plant extracts have demonstrated strong antibacterial activity against a wide range of bacteria, including E. coli and Staphylococcus aureus . [102] TiO2-based photocatalyst, particularly those doped with silver or copper, exhibit enhanced antibacterial properties under visible light irradiation, making them suitable for disinfection applications. [103] Potential applications of these materials include water disinfection and the creation of antibacterial surfaces. Green photocatalyst can be used to disinfect water by killing harmful bacteria, offering a sustainable alternative to conventional disinfection methods. [103] Incorporating them into coatings or surfaces can create self-sterilizing materials, reducing the risk of bacterial contamination in healthcare settings and other environments. [103]
Plant | Bioactive substances | NPs synthesized and produced | Size of NPs (nm) | Shape of NPs | Applications | Ref |
---|---|---|---|---|---|---|
Piper guineense (Uziza) | Phenolics and flavonoids | ZnO | 7.39 | Spherical and well-dispersed | Antibacterial | [104] |
Olea Europaea | Protein, carbonyl, carboxyl, amide, and phenols | Ag/Ag2O | 45 | Spherical | Antimicrobial | [105] |
Froriepia subpinnata | Flavonoids and phenolic | Ag | 18 | Hemispherical and hexagonal | Antimicrobial and adsorption of the Azo dye Acid-Red 58 | [90] |
Vitex negundo | Flavonoids | ZnO | 40-50 | Spherical | Antibacterial and Anticancer | [106] |
Notes/Explanations:
Despite their sustainable origins, a thorough evaluation of the potential toxicity of green photocatalyst is essential to ensure their safe and responsible application in various settings. Even though they are synthesized from environmentally benign materials, their unique properties and nanoscale dimensions can potentially pose risks to human health and the environment. [107] It is crucial to assess the potential for adverse effects before widespread implementation of these materials in water treatment, air purification, or biomedical applications.
Various methods are employed to assess the potential toxicity of green photocatalyst. Eco-toxicity tests expose organisms such as algae, daphnia, or fish to varying concentrations of the photocatalyst to evaluate their effects on growth, reproduction, or mortality. [108] These tests provide valuable insights into the potential impact of green photocatalyst on aquatic ecosystems. Cytotoxicity assays are conducted in laboratory settings using human cell lines to evaluate the potential toxicity of green photocatalysts to human cells. [109] [110] These assays help determine the potential for adverse effects on human health upon exposure to these materials.
Reference | Macroalgal–NPs | Animal/Organism Model | Toxicity Test | Exposure Duration | Concentration/Dose | Toxicity |
---|---|---|---|---|---|---|
[111] | Ericaria amentacea–AgNPs | Artemia salina | Brine shrimp test | 24 h | 17.08 μg/mL | Low |
[112] | Sargassum polycystum–AgNPs | Artemia salina | Brine shrimp test | 24 h and 48 h | 20 to 100 ppm | Low |
[113] | Polycladia myrica–GZ | Amphibalanus amphitrite | Barnacle larvae cytotoxicity | 24 h | 0.031 mg mL−1 | Low |
[114] | Kappaphycus alvarezii–ZnONPs | 3T3 | MTT assay | 24 h and 48 h | 5, 10, 20, 25, 50 and 100 μg/mL | Low |
[114] | Kappaphycus alvarezii–ZnONPs | MCF 7 | MTT assay | 48 h | 75 μg/mL | High |
Notes/Explanations:
Titanium dioxide, also known as titanium(IV) oxide or titania, is the inorganic compound derived from titanium with the chemical formula TiO
2. When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI 77891. It is a white solid that is insoluble in water, although mineral forms can appear black. As a pigment, it has a wide range of applications, including paint, sunscreen, and food coloring. When used as a food coloring, it has E number E171. World production in 2014 exceeded 9 million tonnes. It has been estimated that titanium dioxide is used in two-thirds of all pigments, and pigments based on the oxide have been valued at a price of $13.2 billion.
Methyl violet is a family of organic compounds that are mainly used as dyes. Depending on the number of attached methyl groups, the color of the dye can be altered. Its main use is as a purple dye for textiles and to give deep violet colors in paint and ink. It is also used as a hydration indicator for silica gel. Methyl violet 10B is also known as crystal violet and has medical uses.
Zinc oxide is an inorganic compound with the formula ZnO. It is a white powder which is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement, lubricants, paints, sunscreens, ointments, adhesives, sealants, pigments, foods, batteries, ferrites, fire retardants, semi conductors, and first-aid tapes. Although it occurs naturally as the mineral zincite, most zinc oxide is produced synthetically.
A nanoparticle or ultrafine particle is a particle of matter 1 to 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 100 nm in only two directions. At the lowest range, metal particles smaller than 1 nm are usually called atom clusters instead.
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a photocatalyst, the excited state of which "repeatedly interacts with the reaction partners forming reaction intermediates and regenerates itself after each cycle of such interactions." In many cases, the catalyst is a solid that upon irradiation with UV- or visible light generates electron–hole pairs that generate free radicals. Photocatalysts belong to three main groups; heterogeneous, homogeneous, and plasmonic antenna-reactor catalysts. The use of each catalysts depends on the preferred application and required catalysis reaction.
Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial product and an intermediate in the purification of the element from the ores. The distinctive property of this material is its reversible conversion to a non-stoichiometric oxide.
Silver molybdate (Ag2MoO4), a chemical compound, is a yellow, cubic crystalline substance often used in glass. Its crystals present two types of electronic structure, depending on the pressure conditions to which the crystal is subjected. At room temperature, Ag2MoO4 exhibits a spinel-type cubic structure, known as β-Ag2MoO4, which is more stable in nature. However, when exposed to high hydrostatic pressure, the tetragonal α-Ag2MoO4 forms as a metastable phase.
Platinum nanoparticles are usually in the form of a suspension or colloid of nanoparticles of platinum in a fluid, usually water. A colloid is technically defined as a stable dispersion of particles in a fluid medium.
Photocatalytic water splitting is a process that uses photocatalysis for the dissociation of water (H2O) into hydrogen (H
2) and oxygen (O
2). The inputs are light energy (photons), water, and a catalyst(s). The process is inspired by Photosynthesis, which converts water and carbon dioxide into oxygen and carbohydrates. Water splitting using solar radiation has not been commercialized. Photocatalytic water splitting is done by dispersing photocatalyst particles in water or depositing them on a substrate, unlike Photoelectrochemical cell, which are assembled into a cell with a photoelectrode. Hydrogen fuel production using water and light (photocatalytic water splitting), instead of petroleum, is an important renewable energy strategy.
Silver nanoparticles are nanoparticles of silver of between 1 nm and 100 nm in size. While frequently described as being 'silver' some are composed of a large percentage of silver oxide due to their large ratio of surface to bulk silver atoms. Numerous shapes of nanoparticles can be constructed depending on the application at hand. Commonly used silver nanoparticles are spherical, but diamond, octagonal, and thin sheets are also common.
Calliandra haematocephala, the red powder puff, is a species of flowering plants of the genus Calliandra in the family Fabaceae.
An antimicrobial surface is coated by an antimicrobial agent that inhibits the ability of microorganisms to grow on the surface of a material. Such surfaces are becoming more widely investigated for possible use in various settings including clinics, industry, and even the home. The most common and most important use of antimicrobial coatings has been in the healthcare setting for sterilization of medical devices to prevent hospital-associated infections, which have accounted for almost 100,000 deaths in the United States. In addition to medical devices, linens and clothing can provide a suitable environment for many bacteria, fungi, and viruses to grow when in contact with the human body which allows for the transmission of infectious disease.
Graphitic carbon nitride (g-C3N4) is a family of carbon nitride compounds with a general formula near to C3N4 (albeit typically with non-zero amounts of hydrogen) and two major substructures based on heptazine and poly(triazine imide) units which, depending on reaction conditions, exhibit different degrees of condensation, properties and reactivities.
Photocatalyst activity indicator ink (paii) is a substance used to identify the presence of an underlying heterogeneous photocatalyst and to measure its activity. Such inks render visible the activity of photocatalytic coatings applied to various "self-cleaning" products. The inks contain a dyestuff that reacts to ultraviolet radiation in the presence of the photocatalytic agent in the coating. They are applied to the coated product and show a color change or disappearance when exposed to ultraviolet radiation. The use of a paii based on the dye resazurin forms the basis of an ISO standard test for photocatalytic activity.
In materials and electric battery research, cobalt oxide nanoparticles usually refers to particles of cobalt(II,III) oxide Co
3O
4 of nanometer size, with various shapes and crystal structures.
Photogeochemistry merges photochemistry and geochemistry into the study of light-induced chemical reactions that occur or may occur among natural components of Earth's surface. The first comprehensive review on the subject was published in 2017 by the chemist and soil scientist Timothy A Doane, but the term photogeochemistry appeared a few years earlier as a keyword in studies that described the role of light-induced mineral transformations in shaping the biogeochemistry of Earth; this indeed describes the core of photogeochemical study, although other facets may be admitted into the definition.
A copper nanoparticle is a copper based particle 1 to 100 nm in size. Like many other forms of nanoparticles, a copper nanoparticle can be prepared by natural processes or through chemical synthesis. These nanoparticles are of particular interest due to their historical application as coloring agents and the biomedical as well as the antimicrobial ones.
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Chuanyi Wang is a Chinese American, environmental chemistry scientist, academic, and an author. He is a Distinguished Professor and Academic Dean at the School of Environmental Science and Engineering at the Shaanxi University of Science & Technology. He is recognized for his research in environmental photocatalysis, environmental materials, surface/interface chemistry, nanomaterials, and pollution controlling.
Solar reforming is the sunlight-driven conversion of diverse carbon waste resources into sustainable fuels and value-added chemicals. It encompasses a set of technologies operating under ambient and aqueous conditions, utilizing solar spectrum to generate maximum value. Solar reforming offers an attractive and unifying solution to address the contemporary challenges of climate change and environmental pollution by creating a sustainable circular network of waste upcycling, clean fuel generation and the consequent mitigation of greenhouse emissions.
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