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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] The 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.

Trend of Scopus-indexed publications on green photocatalysts, including bio-waste, macroalgae, and plant-based materials, from 2000 to 2024
VOSviewer analysis (© 2024 Centre for Science and Technology Studies, Leiden University) of 5,375 Scopus documents (1999-2026) retrieved using the search query "TITLE-ABS-KEY(green AND photocatalyst) AND PUBYEAR > 1999 AND PUBYEAR < 2026" reveals key trends in green photocatalyst research, including a focus on environmentally friendly synthesis methods and applications in environmental remediation and energy production

Green precursor materials for photocatalysts

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Green sources

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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]

Different synthesis approaches available for the preparation of metal nanoparticles for various application including as Green Photocatalyst

Plant-based precursors

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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,[11][12] 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.[13] These components can be used as precursors for carbon-based photocatalyst or as templates for the synthesis of porous nano-materials.[14][15]

Phenolic compounds role in the M. oleifera NPs synthesis
Plant-Based Nanoparticle/Nanocatalysts: Synthesis, Size, and Shape
Plant Common/Popular Name NPs synthesized and produced Size of NPs (nm) Shape of NPs Reference
Citrus limetta Sweet Lime/Mosambi CdO 54 Quasi-spherical [16]
Dillenia indica Elephant Apple CuO 15 Spherical [17]
Mikania micrantha Mile-a-minute Weed/American Rope CuO 15 Spherical [18]
Jackfruit Jackfruit La2O3 30 Needle-shaped [19]
Sansevieria trifasciata Snake Plant/Mother-in-Law's Tongue ZnFe2O4 5–20 Spherical [20]
Commelina benghalensis Benghal Dayflower/Tropical Spiderwort Ag–ZnO–CSs 20-100 Spherical [21]
Commelina benghalensis Benghal Dayflower/Tropical Spiderwort Au–ZnO–CSs 50-400 Spherical [22]
Senna siamea Siamese Cassia/Kassod Tree ZnO 37.39 Spherical [23]
Acacia nilotica Gum Arabic Tree Ag 5.72 ± 0.16 Spherical [24]
Epipremnum aureum Pothos/Devil's Ivy/Money Plant ZnO 29 Spherical [25]
Chinese Mahogany Chinese Mahogany LO 22.56 Long rod-like particles [26]
Citrullus colocynthis Colocynth/Bitter Apple Cu 17 ± 4.2 Spherical [27]
Aegle marmelos Bael/Bengal Quince FeO 18.78 Spherical [28]
Couroupita guianensis Cannonball Tree CaO 25.2 Clusters with irregular forms [29]

Notes:

  • NPs: Nanoparticles
  • CSS: Core-Shell Structure
  • The table summarizes various plant-based nanoparticles and nanocatalysts, including their synthesis methods, particle sizes, shapes, and corresponding references.
High-resolution transmission electron microscopy (HRTEM) images of ZnO nanoparticles synthesized by chemical and green methods using beetroot, cedar, and pomegranate extracts at different resolutions
SEM images of ZnO nanoparticles synthesized by chemical and green methods using beetroot, cedar, and pomegranate extracts at different resolutions

Bio-waste precursors

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Utilizing bio-waste, such as food waste and animal waste, for green photocatalyst synthesis offers a dual benefit of waste management and material production.[30] These waste streams are rich in organic matter, which can be converted into valuable carbon-based photocatalyst through various thermochemical processes.[31][32]

Bio-Waste/Agro-Waste Derived Nanomaterials: A Summary of Synthesis, Size, and Shape
Bio-waste NPs synthesized and produced Size of NPs (nm) Shape of NPs Reference
Waste oyster shells nHAp/ZnO/GO 9–22 Spherical [33]
Rice husk TiO2 6.2–7.6 Irregular sharp cylinder-like particles [34]
Waste of chicken eggshell CaO@NiO 15-20 Rod-like shape [35]
Papaya (Carica papaya L.) peel biowaste CuO 85–140 Agglomerated spherical [36]
Dragon fruit (Hylocereus polyrhizus) peel biowaste ZnO 56 Spherical [37]
Longan seeds biowaste ZnO 10–100 Irregular and hexagonal [38]
Banana pseudo stem TiO2 9.98–24.56 Polyhedral [39]
Agro-waste durva grass ZrO2 15-35 Spherical [40]
Agricultural waste Hibiscus cannabinus γ-Fe2O3/Si 48.3 Spherical [41]
Citrus reticulata Blanco (C. reticulata) waste ZnO 9 Hexagonal [42]
Rooibos tea waste Fe2O3–SnO2 - Tone-like structures, tiny rod-like structures, and well-dispersed [43]
Sugarcane bagasse Cu2O 38.02 Irregular [44]

Notes/Explanations:

  • NPs: Nanoparticles
  • nHAp/ZnO/GO: Nano-hydroxyapatite/Zinc Oxide/Graphene Oxide composite
  • CaO@NiO: Calcium Oxide coated with Nickel Oxide
  • y-Fe2O3/Si: Gamma-Iron(III) Oxide supported on Silicon
  • Fe2O3-SnO2: Iron Oxide-Tin Oxide composite
Green synthesis of ZnO nanoparticles using extracts from three marine macroalgae: (A) Ulva lactuca, (B) Ulva intestinalis, and (C) Sargassum muticum

Marine macroalgae/seaweed precursors

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Seaweed is a highly promising green source for photocatalyst synthesis due to its rapid growth rates and minimal environmental requirements.[45] It does not require freshwater or fertilizers for cultivation, making it a sustainable and environmentally friendly option.[46][47] Various seaweed species have been explored for their ability to produce nanoparticles and to act as templates for the synthesis of photocatalytic materials.[48][49][50]

Bio-Fabrication of Nanoparticles Using Marine Macroalgae Extracts
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 [51]
Sargassum myriocystum Phenol Reducing and capping agents Ag 20 ± 2.2 Well dispersed hexagonal [52]
Sargassum coreanum Polysaccharides, polyphenols, lignans Reducing and stabilizing agent Ag 19 Distorted spherical shape [53]
Sargassum spp. Phenolics compounds Capping agent Ag 2-35 Spherical [54]
Padina tetrastromatica Favonoids, steroids, saponins, tannins, phenols and proteins Reducing and stabilizing agent Au 11.4 Nearly spherical [55]
Sargassum spp. Ase terpenoids, flavones, and polysaccharides Capping and stabilization agent Fe3O4 23.60 ± 0.62 Agglomerated spherical [56]
Sargassum tenerrimum Polyphenol and proteins Reducing, capping, and stabilizing agents Ag 22.5 Spherical [57]
Sargassum duplicatum Proteins containing amide and carboxyl groups and carbohydrates Reducing and stabilizing agent Ag 20-50 Spherical [58]
Caulerpa sertularioides Alkaloids, phenols, flavonoids, tannins, terpenoids, carbohydrates, glycosides, amino acids, and proteins Reducing and capping agent Ag 24-57 Spherical [59]
Galaxaura elongata, Turbinaria ornata, and Enteromorpha flexuosa Alkaloids, flavonoids, phenolic compounds, proteins, and sugars Reducing and capping agent Ag 20-25 Spherical [60]
Lobophora variegata Polyphenol, bromophenols, lobophorones, and sulphated polysaccharide Reduction, capping and stabilizing agent Ag 6.5-10 Oval [61]
red marine algae (Bushehr province, Iran) Amino acids, polysaccharides, carbohydrates Reducing and coating agent NiO 32.64 Spherical [62]

Notes/Explanations:

Dispersion and stability of green sources

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Marine Macroalgae as Green Stabilizing Agents for Nanoparticle Synthesis: Dispersion and Stability
Reference Marine Macroalgae Biogenic Capping Agents NPs synthesized and produced Zeta Potential Stability PDI Dispersion Potential Applications
[63] Sargassum spp. Polyphenols Ag −22.6 mV High stability 0.246 Monodispersity Pollutant detection in environmental
[64] Polycladia crinita Primary and tertiary amines, polysaccharides, amino acids Se − 13.9 mV High stability - Polydispersed Drug delivery
[65] Cystoseira tamariscifolia Polyphenols and polysaccharides Au −24.6 ± 1.5 mV High stability - - Biomedical
[66] 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)
[67] 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)
[68] Ulva lactuca Polyphenols, flavonoids, terpenoids, polysaccharides, and proteins Ag −59.0 mV High stability 1.092 Monodispersed Azo-dyes Photodegradation and biomedical usage
[69] 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
[70] Sargassum wightii Polyphenols ZnO − 49.39 mV High stability 0.150 Polydispersed Biomedical field
[71] Turbinaria ornata Flavonoid and phenolic Ag –63.3 mV High stability 0.313 Monodispersed Biomedical field
[72] Sargassum angustifolium Polyphenols Ag − 27 mV High stability 0.15 Monodispersed Biomedicine (anti-bactrerial)
[73] Gracilaria birdiae Polysaccharides Ag −28.7 ± 0.7 mV - −31.7 ± 0.4 mV High stability 0.35 -0.68 Monodispersed Biomedicine

Notes/Explanations:

Common green precursor materials for photocatalysts

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Green Synthesis of Nano-materials Using Plant and Bio-Waste Extracts
Material Green Source(s) Advantages of Source Reference
TiO2 Plant extracts (e.g., Aloe vera) Abundant, biocompatible [74]
ZnO Agricultural waste (e.g., rice husks) Renewable, low cost, high surface area in derived materials [75]
CuO Plant extracts (e.g., Hibiscus sabdariffa L.) Biocompatible, non-toxic, can act as reducing and capping agents [76]
CeO2 Plant extracts (e.g., Azadirachta indica) Abundant, eco-friendly [77]
Carbon quantum dots Bio-waste (e.g., food waste) Waste management, cost-effective, tunable properties [78]
Graphene quantum dots Bio-waste (e.g., Spent tea leaves) Waste management, cost-effective, tunable properties [79]

Photocatalyst synthesis methods

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Schematic representation of the preparation of Lemon Peel, LP-ZnO NPs by hydrothermal method

Hydrothermal synthesis

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Main article: Hydrothermal synthesis

Hydrothermal synthesis is a green method that utilizes water under high pressure and temperature to facilitate chemical reactions.[80] 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.[80]

Microwave-assisted synthesis

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Main article: Microwave chemistry

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.[81] This technique is increasingly favored in green synthesis due to its reduced energy consumption and potential for shorter reaction times.[81]

Sol-gel method

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Main article: Sol-gel

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.[82] It is a versatile technique widely used in the production of various photocatalyst materials, offering advantages in terms of controlling material composition and morphology.[82]

The schematic representation of the sol-gel synthesis of ZnO NPs using different types of chitosan sources and their application in antibacterial and photocatalytic degradation of MB dye

Comparing photocatalyst synthesis methods

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The table below provides a comparison of the advantages, potential limitations, and suitability of different green synthesis methods:

Comparison of Common Green Nanomaterials 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 [83]
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 [84]
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 [85]

Applications of photocatalysts

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Wastewater treatment

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Photocatalytic degradation mechanism of Safranin O dye pollutant using Centaurea behen leaf-AgNP composites under sunlight irradiation

Degradation of organic pollutants

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Green photocatalyst effectively break down organic contaminants in wastewater into less harmful products through a process known as photocatalytic oxidation.[86] 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.[87] 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.[88] Green photocatalyst have demonstrated the ability to remove pharmaceutical contaminants such as carbamazepine,[89] ibuprofen,[90] tetracycline[91][92] from wastewater. Additionally, green photocatalyst have been successfully employed in the degradation of pesticides such as alachlor.[93]

Green synthesis of magnetic nanocomposites using Eucalyptus globulus leaf extract and sugarcane bagasse biochar for the photocatalytic degradation of ciprofloxacin and amoxicillin
Plant-Based Synthesis of Nanoparticles for Environmental Remediation (Organic Compounds Degradation)
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 [94]
Rhododendron arboreum Steroids, terpenoids, alkaloids, saponins, phenols, flavonoids, tannins, glycosides and polyphenolic ZnO 29.424 Spherical Dye photodegradation [95]
Elettaria cardamomum Phenolic CoFe2O4 20–50 Spherical Phenol red dye photodegradation [96]
Zingiber officinale Phenolic CoFe2O4 20–50 Spherical Phenol red dye photodegradation [97]
Tillandsia recurvata Tannins, reducing sugars, and carbohydrates ZnO 12–61 Spherical Methylene blue (MB) photodegradation [98]
Ajuga iva Carbohydrates, phenol groups, acidic fractions Ag 100-300 Polygonal poly–dispersed Methylene blue (MB) photodegradation [99]
Macleaya cordata Phenolic CuO 80 rectangular and square with irregular rod Methylene blue (MB) photodegradation and antibacterial [100]
Coleus scutellariodes Phenolic NiO 23 Rod shape Antibiotic (rufloxacin) photodegradation [101]
Eupatorium adenophorum Sesquiterpenoids, triterpenes, flavonoids, phenolics, coumarins, steroids, polyphenols, and phenylpropanols Ag 30–400 Spherical Rhodamin B photodegradation [102]

Notes/Explanations:

  • NPs: Nanoparticles
  • CoFe2O4: Cobalt Ferrite
Magnetic separation of green synthesized of magnetic nanocomposites using Eucalyptus globulus leaf extract and sugarcane bagasse biochar for the photocatalytic degradation of antibiotics, ciprofloxacin and amoxicillin

Removal of heavy metals

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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.[103] Furthermore, photogenerated electrons[104] 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.[103]

Antibacterial mechanism of Cb-AgNPs: disruption of cell membrane, generation of reactive oxygen species (ROS), and damage to cellular components

Antibacterial activity

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Mechanisms of action

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Green photocatalyst exhibit potent antibacterial properties due to their ability to generate ROS upon light irradiation.[105] These ROS, including hydroxyl radicals and superoxide radicals, can damage bacterial cell walls and membranes, leading to cell death.[106]

Antibacterial activity of Ligustrum vulgare berry extracts derived silver nanoparticles (LV-AgNPs) against P. aeruginosa and E. coli at various concentrations

Examples and applications

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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.[107] TiO2-based photocatalyst, particularly those doped with silver or copper, exhibit enhanced antibacterial properties under visible light irradiation, making them suitable for disinfection applications.[108] 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.[108] Incorporating them into coatings or surfaces can create self-sterilizing materials, reducing the risk of bacterial contamination in healthcare settings and other environments.[108]

Plant-Based Synthesis of Nanoparticles for Biomedical Applications (Antimicrobial)
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 [109]
Olea Europaea Protein, carbonyl, carboxyl, amide, and phenols Ag/Ag2O 45 Spherical Antimicrobial [110]
Froriepia subpinnata Flavonoids and phenolic Ag 18 Hemispherical and hexagonal Antimicrobial and adsorption of the Azo dye Acid-Red 58 [94]
Vitex negundo Flavonoids ZnO 40-50 Spherical Antibacterial and Anticancer [111]

Notes/Explanations:

Toxicity assessments

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Importance of toxicity evaluation

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Cytotoxic effect of shilajit-derived ZnO nanoparticles on HeLa cancer cells compared to cisplatin and normal Vero cells

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.[112] It is crucial to assess the potential for adverse effects before widespread implementation of these materials in water treatment, air purification, or biomedical applications.

Methods for toxicity assessment

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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.[113] 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.[114][115] These assays help determine the potential for adverse effects on human health upon exposure to these materials.

Toxicity Assessment of Marine Macroalgae-Derived Nanoparticles
Reference Macroalgal–NPs Animal/Organism Model Toxicity Test Exposure Duration Concentration/Dose Toxicity
[116] Ericaria amentacea–AgNPs Artemia salina Brine shrimp test 24 h 17.08 μg/mL Low
[117] Sargassum polycystum–AgNPs Artemia salina Brine shrimp test 24 h and 48 h 20 to 100 ppm Low
[118] Polycladia myrica–GZ Amphibalanus amphitrite Barnacle larvae cytotoxicity 24 h 0.031mg mL−1 Low
[119] Kappaphycus alvarezii–ZnONPs 3T3 MTT assay 24 h and 48 h 5, 10, 20, 25, 50 and 100 μg/mL Low
[120] Kappaphycus alvarezii–ZnONPs MCF 7 MTT assay 48 h 75 μg/mL High

Notes/Explanations:

See also

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References

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