Tungsten trioxide (WO₃) possesses a small band gap energy of 2.4-2.8 eV and is responsive to both ultraviolet and visible light irradiation including strong absorption of the solar spectrum and stable physicochemical properties. Thus, controlled growth of one-dimensional (1D) WO₃ nanotubular structures with desired length, diameter, and wall thickness has gained significant interest. In the present study, 1D WO₃ nanotubes were successfully synthesized via electrochemical anodization of tungsten (W) foil in an electrolyte composed of 1 M of sodium sulphate (Na₂SO₄) and ammonium fluoride (NH₄F). The influence of NH₄F content on the formation mechanism of anodic WO₃ nanotubular structure was investigated in detail. An optimization of fluoride ions played a critical role in controlling the chemical dissolution reaction in the interface of W/WO₃. Based on the results obtained, a minimum of 0.7 wt% of NH₄F content was required for completing transformation from W foil to WO₃ nanotubular structure with an average diameter of 85 nm and length of 250 nm within 15 min of anodization time. In this case, high aspect ratio of WO₃ nanotubular structure is preferred because larger active surface area will be provided for better photocatalytic and photoelectrochemical (PEC) reactions.
Well aligned TiO2 nanotubes were successfully synthesized by anodization of Ti foil at 60 V in a fluorinated bath comprised of ethylene glycol with 5 wt% of NH4F and 5 wt% of H2O2. In order to enhance the visible light absorption and photoelectrochemical response of pure TiO2 nanotube arrays, a mixed oxide system (W-TiO2) was investigated. W-TiO2 nanotube arrays were prepared using radio-frequency (RF) sputtering to incorporate the W into the lattice of TiO2 nanotube arrays. The W atoms occupy the substitutional position within the vacancies of TiO2 nanotube arrays. The as-anodized TiO2 is amorphous in nature while the annealed TiO2 is anatase phase. The mixed oxide (W-TiO2) system in suitable TiO2 phase plays important roles in efficient electron transfers due to the reduction in electron-hole recombination. In this article, the effect of the sputtered W into the as-anodized/annealed TiO2 nanotube arrays on the photoelectrochemical response was presented.
Using solar-powered water electrolysis systems for hydrogen generation is a key decision for the development of a sustainable hydrogen economy. A facile approach is presented in the present investigation to improve the solar-powered photoelectrochemical performance of water electrolysis systems by synthesising well-aligned and highly ordered TiO₂ nanotube films without bundling through the electrochemical anodisation technique. Herein, geometrical calculations were conducted for all synthesised TiO₂ nanotubes, and determination of the aspect ratio (AR) and geometric surface area factor (G) was achieved. On the basis of the collected data, well-aligned TiO₂ nanotubes with an AR of approximately 60 and G of approximately 400 m² ·g-1 were successfully formed in an electrolyte mixture of ethylene glycol with 0.3 wt% NH4F and 5 wt% H₂O₂ at 40 V for 60 min. The nanotubes were subsequently annealed at 400 °C to form anatase-phase TiO₂ nanotube films. The resultant well-aligned and highly ordered TiO₂ nanotube films exhibited a photocurrent density of 1.5 mA · cm-2 due to a large number of photo-induced electrons moving along the tube axis and perpendicular to the Ti substrate, which greatly reduces interfacial recombination losses.
Uniformly sized TiO2 nanotubes with high aspect ratios were synthesised on a large substrate (100 mm x 100 mm) via the bubbling system through anodisation of Ti in ethylene glycol containing 5 wt% NH4F and 5 wt% H2O2. The benefits of bubbling system in producing uniformly sized TiO2 nanotubes throughout the Ti foil are illustrated. Moreover, the effects of applied voltage and fluoride content on the resulting nanotubes were also considered. Such uniform sized TiO2 nanotubes are a key to produce hydrogen efficiently using PEC cell. The results show higher photocurrent responses for the high aspect ratio, uniform TiO2 nanotubes because of excellent interfacial electron transfer.
Today, a major issue about water pollution is the residual dyes from different sources (e.g., textile industries, paper and pulp industries, dye and dye intermediates industries, pharmaceutical industries, tannery and craft bleaching industries, etc.), and a wide variety of persistent organic pollutants have been introduced into our natural water resources or wastewater treatment systems. In fact, it is highly toxic and hazardous to the living organism; thus, the removal of these organic contaminants prior to discharge into the environment is essential. Varieties of techniques have been employed to degrade those organic contaminants and advanced heterogeneous photocatalysis involving zinc oxide (ZnO) photocatalyst appears to be one of the most promising technology. In recent years, ZnO photocatalyst have attracted much attention due to their extraordinary characteristics. The high efficiency of ZnO photocatalyst in heterogeneous photocatalysis reaction requires a suitable architecture that minimizes electron loss during excitation state and maximizes photon absorption. In order to further improve the immigration of photo-induced charge carriers during excitation state, considerable effort has to be exerted to further improve the heterogeneous photocatalysis under UV/visible/solar illumination. Lately, interesting and unique features of metal doping or binary oxide photocatalyst system have gained much attention and became favourite research matter among various groups of scientists. It was noted that the properties of this metal doping or binary oxide photocatalyst system primarily depend on the nature of the preparation method and the role of optimum dopants content incorporated into the ZnO photocatalyst. Therefore, this paper presents a critical review of recent achievements in the modification of ZnO photocatalyst for organic contaminants degradation.
A controllable electrochemical synthesis to convert reduced graphene oxide (rGO) from graphite flakes was introduced and investigated in detail. Electrochemical reduction was used to prepare rGO because of its cost effectiveness, environmental friendliness, and ability to produce rGO thin films in industrial scale. This study aimed to determine the optimum applied potential for the electrochemical reduction. An applied voltage of 15 V successfully formed a uniformly coated rGO thin film, which significantly promoted effective electron transfer within dye-sensitized solar cells (DSSCs). Thus, DSSC performance improved. However, rGO thin films formed in voltages below or exceeding 15 V resulted in poor DSSC performance. This behavior was due to poor electron transfer within the rGO thin films caused by poor uniformity. These results revealed that DSSC constructed using 15 V rGO thin film exhibited high efficiency (η = 1.5211%) attributed to its higher surface uniformity than other samples. The addition of natural lemon juice (pH ~ 2.3) to the electrolyte accelerated the deposition and strengthened the adhesion of rGO thin film onto fluorine-doped tin oxide (FTO) glasses.
Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO) was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5) dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO) solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers' method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis), X-ray powder diffraction (XRD), Raman, and Scanning Electron Microscopy (SEM) to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm-1) was observed in the UV spectrum. Further, the appearance of a broad peak (002), centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.
WO₃-decorated TiO₂ nanotube arrays were successfully synthesized using an in situ anodization method in ethylene glycol electrolyte with dissolved H₂O₂ and ammonium fluoride in amounts ranging from 0 to 0.5 wt %. Anodization was carried out at a voltage of 40 V for a duration of 60 min. By using the less stable tungsten as the cathode material instead of the conventionally used platinum electrode, tungsten will form dissolved ions (W(6+)) in the electrolyte which will then move toward the titanium foil and form a coherent deposit on the titanium foil. The fluoride ion content was controlled to determine the optimum chemical dissolution rate of TiO₂ during anodization to produce a uniform nanotubular structure of TiO₂ film. Nanotube arrays were then characterized using FESEM, EDAX, XRD, as well as Raman spectroscopy. Based on the FESEM images obtained, nanotube arrays with an average pore diameter of up to 65 nm and a length of 1.8 µm were produced. The tungsten element in the samples was confirmed by EDAX results which showed varying tungsten content from 0.22 to 2.30 at%. XRD and Raman results showed the anatase phase of TiO₂ after calcination at 400 °C for 4 h in air atmosphere. The mercury removal efficiency of the nanotube arrays was investigated by photoirradiating samples dipped in mercury chloride solution with TUV (Tube ultraviolet) 96W UV-B Germicidal light. The nanotubes with the highest aspect ratio (15.9) and geometric surface area factor (92.0) exhibited the best mercury removal performance due to a larger active surface area, which enables more Hg(2+) to adsorb onto the catalyst surface to undergo reduction to Hg⁰. The incorporation of WO₃ species onto TiO₂ nanotubes also improved the mercury removal performance due to improved charge separation and decreased charge carrier recombination because of the charge transfer from the conduction band of TiO₂ to the conduction band of WO₃.
In pursuit of advancing photocatalysts for superior performance in water treatment and clean energy generation, researchers are increasingly focusing on layered double hydroxides (LDHs) which have garnered significant attention due to their customizable properties, morphologies, distinctive 2D layered structure and flexible options for modifying anions and cations. No review has previously delved specifically into ZnCr and NiCr LDH-based photocatalysts and therefore, this review highlights the recent surge in ZnCr and NiCr-based LDHs as potential photocatalysts for their applications in water purification and renewable energy generation. The structural and fundamental characteristics of layered double hydroxides and especially ZnCr-LDHs and NiCr-LDHs are outlined. Further, the various synthesis techniques for the preparation of ZnCr-LDHs, NiCr-LDHs and their composite and heterostructure materials have been briefly discussed. The applicability of ZnCr-LDH and NiCr-LDH based photocatalysts in tackling significant issues in water treatment and sustainable energy generation is the main emphasis of this review. It focuses on photocatalytic degradation of organic pollutants in wastewater, elucidating the principles and advancements for enhancing the efficiency of these materials. It also explores their role in H2 production through water splitting, conversion of CO2 into valuable fuels and NH3 synthesis from N2, shedding light on their potential for clean energy solutions. The insights presented herein offer valuable guidance for researchers working towards sustainable solutions for environmental remediation and renewable energy generation.
The immobilization of photocatalyst nanoparticles on a solid substrate is an important aspect for improved post-treatment separation and photocatalyst reactor design. In this study, we report the simple preparation of reduced graphene oxide (rGO)-hybridized zinc oxide (ZnO) thin films using a one-step electrochemical deposition, and investigated the effect of rGO-hybridization on the photoinactivation efficiency of ZnO thin films towards Staphylococcus aureus (S. aureus) and Salmonella enterica serovar Typhi (S. Typhi) as target bacterial pathogens. Field-emission scanning electron microscopy (FESEM) revealed the formation of geometric, hexagonal flakes of ZnO on the ITO glass substrate, as well as the incorporation of rGO with ZnO in the rGO/ZnO thin film. Raman spectroscopy indicated the successful incorporation of rGO with ZnO during the electrodeposition process. Photoluminescence (PL) spectroscopy indicates that rGO hybridization with ZnO increases the amount of oxygen vacancies, evidenced by the shift of visible PL peak at 650 to 500nm. The photoinactivation experiments showed that the thin films were able to reduce the bacterial cell density of Staph. aureus and S. Typhi from an initial concentration of approximately 10(8) to 10(3)CFU/mL within 15min. The rGO/ZnO thin film increased the photoinactivation rate for S. aureus (log[N/No]) from -5.1 (ZnO) to -5.9. In contrast, the application of rGO/ZnO thin film towards the photoinactivation of S. Typhi did not improve its photoinactivation rate, compared to the ZnO thin film. We may summarise that (1) rGO/ZnO was effective to accelerate the photoinactivation of S. aureus but showed no difference to improve the photoinactivation of S. Typhi, in comparison to the performance of ZnO thin films, and (2) the photoinactivation in the presence of ZnO and rGO/ZnO was by ROS damage to the extracellular wall.
Gold Nanostars (GNS) have attracted tremendous attention toward themselves owing to their multi-branched structure and unique properties. These state of the art metallic nanoparticles possess intrinsic features like remarkable optical properties and exceptional physiochemical activities. These star-shaped gold nanoparticles can predominantly be utilized in biosensing, photothermal therapy, imaging, surface-enhanced Raman spectroscopy and target drug delivery applications due to their low toxicity and extraordinary optical features. In the current review, recent approaches in the matter of GNS in case of diagnosis, bioimaging and biomedical applications were summarized and reported. In this regard, first an overview about the structure and general properties of GNS were reported and thence detailed information regarding the diagnostic, bioimaging, photothermal therapy, and drug delivery applications of such novel nanomaterials were presented in detail. Summarized information clearly highlighting the superior capability of GNS as potential multi-functional materials for biomedical applications.
Iron-doped titanium dioxide loaded on activated carbon (Fe-TiO2/AC) was successfully synthesized from oil palm empty fruit bunch (OPEFB) using sol-gel method. The properties of the synthesized pure TiO2, Fe-doped TiO2, AC, TiO2/AC and Fe-TiO2/AC were examined by various techniques such as field emission scanning electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and nitrogen adsorption-desorption analyses at 77 K. FE-SEM revealed that Fe-doped TiO2 particles were dispersed homogeneously on the AC surface. FT-IR demonstrated high surface hydroxylation after Fe doping on TiO2 and UV-Vis DRS showed that Fe-TiO2/AC had the lowest band gap energy. Catalytic performance results proved that Fe dopants could restrict the recombination rate of hole and electron pairs, whereas AC support improved the Malachite Green (MG) adsorption sites and active sites of the hybrid catalyst. Photocatalytic degradation of 100 mg/L MG in the presence of 1.0 g/L 15 wt% Fe-TiO2 incorporated with 25 wt% AC, initial solution pH of 4 and 3 mM H2O2 could achieve the highest removal efficiency of 97% after 45 min light irradiation. This work demonstrates a promising approach to synthesis an inexpensive and efficient Fe-TiO2/AC for the photocatalytic degradation of organic dye.
Recent foodborne outbreaks in multiple locations necessitate the continuous development of highly sensitive and specific biosensors that offer rapid detection of foodborne biological hazards. This work focuses on the development of a reduced graphene oxide‑titanium dioxide (rGO-TiO2) nanocomposite based aptasensor to detect Salmonella enterica serovar Typhimurium. A label-free aptamer was immobilized on a rGO-TiO2 nanocomposite matrix through electrostatic interactions. The changes in electrical conductivity on the electrode surface were evaluated using electroanalytical methods. DNA aptamer adsorbed on the rGO-TiO2 surface bound to the bacterial cells at the electrode interface causing a physical barrier inhibiting the electron transfer. This interaction decreased the DPV signal of the electrode proportional to decreasing concentrations of the bacterial cells. The optimized aptasensor exhibited high sensitivity with a wide detection range (108 to 101 cfu mL-1), a low detection limit of 101 cfu mL-1 and good selectivity for Salmonella bacteria. This rGO-TiO2 aptasensor is an excellent biosensing platform that offers a reliable, rapid and sensitive alternative for foodborne pathogen detection.
Since the turn of the 21st century, water pollution has been a major issue, and most of the pollution is generated by dyes. Adsorption is one of the most commonly used dye-removal methods from aqueous solution. Magnetic-particle integration in the water-treatment industry is gaining considerable attention because of its outstanding physical and chemical properties. Magnetic-particle adsorption technology shows promising and effective outcomes for wastewater treatment owing to the presence of magnetic material in the adsorbents that can facilitate separation through the application of an external magnetic field. Meanwhile, the introduction of activated carbon (AC) derived from various materials into a magnetic material can lead to efficient organic-dye removal. Therefore, this combination can provide an economical, efficient, and environmentally friendly water-purification process. Although activated carbon from low-cost and abundant materials has considerable potential in the water-treatment industry, the widespread applications of adsorption technology are limited by adsorbent recovery and separation after treatment. This work specifically and comprehensively describes the use of a combination of a magnetic material and an activated carbon material for dye adsorption in wastewater treatment. The literature survey in this mini-review provides evidence of the potential use of these magnetic adsorbents, as well as their magnetic separation and recovery. Future directions and challenges of magnetic activated carbon in wastewater treatment are also discussed in this paper.
Cellulose constitutes most of a plant's cell wall, and it is the most abundant renewable polymer source on our planet. Given the hierarchical structure of cellulose, nanocellulose has gained considerable attention as a nano-reinforcement for polymer matrices in various industries (medical and healthcare, oil and gas, packaging, paper and board, composites, printed and flexible electronics, textiles, filtration, rheology modifiers, 3D printing, aerogels and coating films). Herein, nanocellulose is considered as a sustainable nanomaterial due to its substantial strength, low density, excellent mechanical performance and biocompatibility. Indeed, nanocellulose exists in several forms, including bacterial cellulose, nanocrystalline cellulose and nanofibrillated cellulose, which results in biodegradable and environmentally friendly bionanocomposites with remarkably improved material properties. This paper reviews the recent advances in production, physicochemical properties, and structural characterization of nanocelluloses. It also summarises recent developments in several multifunctional applications of nanocellulose with an emphasis on bionanocomposite properties. Besides, various challenges associated with commercialisation and economic aspects of nanocellulose for current and future markets are also discussed inclusively.
Recent advances in the field of nanotechnology contributed to the increasing use of nanomaterials in the engineering, health and biological sectors. Graphene oxide (GO) has great potentials as it could be fine-tuned to be adapted into various applications, especially in the electrical, electronic, industrial and clinical fields. One of the important applications of GO is its use as an antibacterial material due to its promising activity against a broad range of bacteria. However, our understanding of the mechanism of action of GO towards bacteria is still lacking and is often less described. Therefore, a comprehensive overview of bactericidal mechanistic actions of GO and the roles of physicochemical factors including size, aggregation, functionalization and adsorption behavior contributing to its antibacterial activities are described in this review. As the use of GO is expected to increase exponentially in the health sector, the cytotoxicity of GO among the cell lines is also discussed. Thus, this review emphasizes the physicochemical characteristics of GO that can be tailored for optimal antibacterial properties that is of importance to the health industry.
A highly mesoporous graphitic carbon nitride g-C3N4 (GCN) has been produced by a template-free method and effectively photodegrade tetracycline (TC) antibiotic under solar light irradiation. The mesoporous GCN (GCN-500) greatly improves the photoactivity (0.0247 min-1) by 2.13 times, as compared to that of bulk GCN (0.0116 min-1). The efficiently strengthened photoactivity is ascribed to the high porosity (117.05 m2/g), and improves the optical absorption under visible light (Eg = 2.65 eV) and good charge carrier separation efficiency. The synthesized mesoporous GCN shows a uniform pore size (~3 nm) distribution. GCN-500 shows large pore volume (0.210 cm3/g) compared to GCN-B (0.083 cm3/g). Besides, the GCN-500 also exhibits good recyclability and photostability for TC photodegradation. In conclusion, GCN-500 is a recyclable photocatalyst for the removal of TC under visible light irradiation.
There are various approaches to enhancing the catalytic properties of TiO₂, including modifying its morphology by altering the surface reactivity and surface area of the catalyst. In this study, the primary aim is to enhance the photocatalytic activity by changing the TiO₂ nanotubes' architecture. The highly ordered infrastructure is favorable for a better charge carrier transfer. It is well known that anodization affects TiO₂ nanotubes' structure by increasing the anodization duration which in turn influence the photocatalytic activity. The characterizations were conducted by FE-SEM (fiend emission scanning electron microscopy), XRD (X-ray diffraction), RAMAN (Raman spectroscopy), EDX (Energy dispersive X-ray spectroscopy), UV-Vis (Ultraviolet visible spectroscopy) and LCMS/MS/MS (liquid chromatography mass spectroscopy). We found that the morphological structure is affected by the anodization duration according to FE-SEM. The photocatalytic degradation shows a photodegradation rate of k = 0.0104 min-1. It is also found that a mineralization of Simazine by our prepared TiO₂ nanotubes leads to the formation of cyanuric acid. We propose three Simazine photodegradation pathways with several intermediates identified.
Graphene oxide (GO) has displayed antibacterial activity that has been investigated in the past, however, information on synergistic activity of GO with conventional antibiotics is still lacking. The objectives of the study were to determine the combinatorial actions of GO and antibiotics against Gram-positive and Gram-negative bacteria and the toxicological effects of GO towards human epidermal keratinocytes (HaCaT). Interactions at molecular level between GO and antibiotics were analyzed using Attenuated Total Reflectance-Fourier-transform infrared spectroscopy (ATR-FTIR). Changes in the antibacterial activity of antibiotics towards bacteria through the addition of GO was investigated. Toxicity of GO towards HaCaT cells were examined as skin cells play a role as the first line of defense of the human body. The ATR-FTIR characterizations of GO and antibiotics showed adsorption of tested antibiotics onto GO. The combinatorial antibacterial activity of GO and antibiotics were found to increase when compared to GO or antibiotic alone. This was attributed to the ability of GO to disrupt bacterial membrane to allow for better adsorption of antibiotics. Cytotoxicity of GO was found to be dose-dependent towards HaCaT cell line, it is found to impose negligible toxic effects against the skin cells at concentration below 100 μg/mL.
Oily wastewater, especially water-oil emulsion has become serious environmental issue and received global attention. Chemical demulsifiers are widely used to treat oil-water emulsion, but the toxicity, non-recyclable and non-environmental friendly characteristic of chemical demulsifiers had limited their practical application in oil-water separation. Therefore, it is imperative to develop an efficient, simple, eco-friendly and recyclable demulsifiers for breaking up the emulsions from the oily wastewater. In this study, a magnetic demulsifier, magnetite-reduced graphene oxide (M-rGO) nanocomposites were proposed as a recyclable demulsifier to break up the surfactant stabilized crude oil-in-water (O/W) emulsion. M-rGO nanocomposites were prepared via in situ chemical synthesis by using only one type Fe salt and GO solid as precursor at room temperature. The prepared composites were fully characterized by various techniques. The effect of demulsifier dosage and pH of emulsion on demulsification efficiency (ED) has been studied in detailed. The demulsification mechanism was also proposed in this study. Results showed that M-rGO nanocomposites were able to demulsify crude O/W emulsion. The ED reaches 99.48% when 0.050 wt.% of M-rGO nanocomposites were added to crude O/W emulsion (pH = 4). Besides, M-rGO nanocomposites can be recycled up to 7 cycles without showing a significant change in terms of ED. Thus, M-rGO nanocomposite is a promising demulsifier for surfactant stabilized crude O/W emulsion.