Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol.
Ontology highlight
ABSTRACT: Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO) nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC) was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region.
Project description:Photocatalytic degradation of organic pollutants has emerged as a promising green technology. In this study, we present a facile approach to enhance photocatalytic performance by fabricating zinc oxide (ZnO) nanorods (NRs)/silver (Ag) seed layer heterojunctions. The heterojunction fabrication process involves the deposition of a Ag seed layer via spin coating, followed by hydrothermal growth of vertically aligned ZnO NRs (∼2 ± 0.20 μm length, ∼200 nm diameter) on the seed layer at 80 ± 2 °C for 80 min. The growth of ZnO NRs on the Ag seed layer formed a metal-semiconductor heterojunction at their contact surfaces, significantly increasing the surface-to-volume ratio. The appearance of a double band regime at 3.06 eV for Ag and 3.37 eV for ZnO NRs confirms the formation of the Ag-ZnO heterojunctions. Photocatalytic efficacy is demonstrated by the degradation efficiency of methylene blue under UV light irradiation, surpassing previous approaches using ZnO-based photocatalysts. This enhanced degradation efficiency is attributed to the synergistic effects between ZnO and Ag, promoting efficient charge separation and reducing photocorrosion. This research provides a promising approach for designing highly efficient photocatalysts aimed at environmental remediation.
Project description:Benzene, toluene, ethylbenzene and xylenes (BTEX) are some of the common environmental pollutants originating mainly from oil and gas industries, which are toxic to human as well as other living organisms in the ecosystem. Here we investigate photocatalytic degradation of BTEX under visible light irradiation using supported zinc oxide (ZnO) nanorods grown on glass substrates using a microwave assisted hydrothermal method. ZnO nanorods were characterized by electron microscopy, X-ray diffraction (XRD), specific surface area, UV/visible absorption and photoluminescence spectroscopy. Visible light photocatalytic degradation products of BTEX are studied for individual components using gas chromatograph/mass spectrometer (GC/MS). ZnO nanorods with significant amount of electronic defect states, due to the fast crystallization of the nanorods under microwave irradiation, exhibited efficient degradation of BTEX under visible light, degrading more than 80% of the individual BTEX components in 180 minutes. Effect of initial concentration of BTEX as individual components is also probed and the photocatalytic activity of the ZnO nanorods in different conditions is explored. Formation of intermediate byproducts such as phenol, benzyl alcohol, benzaldehyde and benzoic acid were confirmed by our HPLC analysis which could be due to the photocatalytic degradation of BTEX. Carbon dioxide was evaluated and showed an increasing pattern over time indicating the mineralization process confirming the conversion of toxic organic compounds into benign products.
Project description:The development of efficient and environmentally friendly photocatalysts is crucial for addressing global energy and environmental challenges. Perylene diimide, an organic supramolecular material, holds great potential for applications in mineralized phenol. In this study, through the integration of different mass ratios of unmodified perylenimide (PDI-NH) into the self-assembly of amino acid-substituted perylenimide (PDI-COOH), a novel supramolecular organic heterojunction (PDICOOH/PDINH) was fabricated. The ensuing investigation focuses on its visible-light mineralized phenol properties. The results show that the optimal performance is observed with a composite mass fraction of 10%, leading to complete mineralization of 5 mg/L phenol within 5 h. The reaction exhibits one-stage kinetics with rate constants 13.80 and 1.30 times higher than those of PDI-NH and PDI-COOH, respectively. SEM and TEM reveal a heterogeneous interface between PDI-NH and PDI-COOH. Photoelectrochemical and Kelvin probe characterization confirm the generation of a built-in electric field at the interface, which is 1.73 times stronger than that of PDI-COOH. The introduction of PDI-NH promotes π-π stacking of PDI-COOH, while the built-in electric field facilitates efficient charge transfer at the interface, thereby enhancing phenol decomposition. The finding demonstrates that supramolecular heterojunctions have great potential as highly effective photocatalysts for environmental remediation applications.
Project description:Different approaches like doping and sensitization have been used to develop photocatalysts that can lead to high reactivity under visible-light illumination, which would allow efficient utilization of solar irradiation and even interior lighting. We demonstrated a conceptually different approach by changing reaction route via introducing the idea of conventional Pd catalysis used in cross-coupling reactions into photocatalysis. The -O-Pd-Cl surface species modified on Ni-doped TiO2 can play a role the same as that in chemical catalysis, resulting in remarkably enhanced photocatalytic activity under visible-light irradiation. For instance, Pd/Ni-TiO2 has much higher activity than N-TiO2 (about 3 ~ 9 times for all of the 4-XP systems) upon irradiation with wavelength of 420 nm. The catalytically active Pd(0) is achieved by reduction of photogenerated electrons from Ni-TiO2. Given high efficient, stable Pd catalysts or other suitable chemical catalysts, this concept may enable realization of the practical applications of photocatalysis.
Project description:The formation of copper oxide and zinc oxide mixture in montmorillonite was conducted by the reaction of an aqueous dispersion of Cu2+/Zn2+ exchanged montmorillonite and an aqueous solution of sodium hydroxide under hydrothermal treatment. The resulting product was characterized by X-ray diffraction, scanning and transmittance electron microscopies, as well as UV-visible and photoluminescence spectroscopies. The diffuse reflectance absorption spectra showed the absorption onsets due to copper oxide (885 nm) and zinc oxide (310 and 580 nm) in the product. The adsorption of methylene blue was fitted well by the Langmuir model with the maximum adsorption capacity of 454 mg⋅g-1. The thermodynamic studies revealed that the process is exothermic and spontaneous. The photocatalytic activity of the hybrid was assessed by the degradation of methylene blue in aqueous solution under visible light irradiation. The most active species in the photocatalytic process was hydroxyl radicals. The regenerated copper oxide/zinc oxide-montmorillonite was reused up to 5 cycles, the photodegradation efficiency dropped only 5% (from 94% to 89%), supporting the good stability of the photocatalyst. The result was in agreement with the advantages of the nanocomposite heterostructure and the unique nature of montmorillonite.
Project description:A facile, solvothermal synthesis of mesoporous cerium oxide nanospheres is reported for the purpose of the photocatalytic degradation of organic dyes and future applications in sustainable energy research. The earth-abundant, relatively affordable, mixed valence cerium oxide sample, which consists of predominantly Ce7O12, has been characterized by powder X-ray diffraction, X-ray photoelectron and UV-vis spectroscopy, and transmission electron microscopy. Together with N2 sorption experiments, the data confirms that the new cerium oxide material is mesoporous and absorbs visible light. The photocatalytic degradation of rhodamin B is investigated with a series of radical scavengers, suggesting that the mechanism of photocatalytic activity under visible-light irradiation involves predominantly hydroxyl radicals as the active species.
Project description:Removing wastewater pollutants using semiconducting-based heterogeneous photocatalysis is an advantageous technique because it provides strong redox power charge carriers under sunlight irradiation. In this study, we synthesized a composite of reduced graphene oxide (rGO) and zinc oxide nanorods (ZnO) called rGO@ZnO. We established the formation of type II heterojunction composites by employing various physicochemical characterization techniques. To evaluate the photocatalytic performance of the synthesized rGO@ZnO composite, we tested it for reducing a common wastewater pollutant, para-nitro phenol (PNP), to para-amino phenol (PAP) under both ultraviolet (UV) and visible light irradiances. The rGOx@ZnO (x = 0.5-7 wt%) samples, comprising various weights of rGO, were investigated as potential photocatalysts for the reduction of PNP to PAP under visible light irradiation. Among the samples, rGO5@ZnO exhibited remarkable photocatalytic activity, achieving a PNP reduction efficiency of approximately 98% within a short duration of four minutes. These results demonstrate an effective strategy and provide fundamental insights into removing high-value-added organic water pollutants.
Project description:In recent decades, antibiotics have been found in aquatic environments, raising severe concerns. In this study, a unique reduced graphene oxide-zinc sulfide-copper sulfide (rGO-ZnS-CuS) nanocomposite (NC) prepared by using a straightforward surfactant-free in situ microwave method was used for antibiotic degradation via photocatalysis. The structural and morphological characteristics of the produced catalysts were characterized using various techniques, confirming the successful development of nanocomposite structures of better quality than that of the pure samples. The photocatalytic degradation of antibiotics containing ofloxacin was also investigated. The results suggest that the rGO-ZCS NC outperformed the other composites in terms of photocatalytic activity toward ofloxacin degradation. Superoxide and hydroxyl radicals were the main active species during the degradation process. According to our results, the catalytic activity of rGO-ZCS NC is much better than that of the other composites.
Project description:Herein we explore the role of localized plasmonic heat generated by resonantly excited gold (Au) NPs on visible light driven photocatalysis process. Au NPs are deposited on the surface of vertically aligned zinc oxide nanorods (ZnO NRs). The localized heat generated by Au NPs under 532 nm continuous laser excitation (SPR excitation) was experimentally probed using Raman spectroscopy by following the phonon modes of ZnO. Under the resonant excitation the temperature at the surface of the Au-ZnO NRs reaches up to about 300 °C, resulting in almost 6 times higher apparent quantum yield (AQY) for photocatalytic degradation of methylene blue (MB) compared to the bare ZnO NRs. Under solar light irradiation the Au-ZnO NRs demonstrated visible light photocatalytic activity twice that of what was achieved with bare ZnO NRs, while significantly reduced the activation energy required for the photocatalytic reactions allowing the reactions to occur at a faster rate.
Project description:A hybrid of ZnO nanorods grown onto three-dimensional (3D) reduced graphene oxide (RGO)@Ni foam (ZnO/RGO@NF) is synthesized by a facile hydrothermal method. The as-prepared hybrid material is physically characterized by SEM, XRD, Raman, and X-ray photoelectron spectroscopy (XPS). When the as-prepared 3D hybrid is investigated as a photocatalyst, it demonstrates significant high photocatalytic activity for the degradation of methylene blue (MB), rhodamine (RhB), and mixed MB/RhB as organic dye pollutants. In addition, the practical application and the durability of the as-prepared catalyst to degradation of malachite green (MG) in seawater are firstly assessed in a continuous flow system. The catalyst shows a high degradation efficiency and stable photocatalytic activity for 5 h continuous operation, which should be a promising catalyst for the degradation of organic dyes in seawater.