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Lanthanum oxide was successfully synthesized by hydrothermal method by varying the reaction time such as 6, 12, and 24 h. In XRD, study confirms the presence of a hexagonal structure, and the phase remains the same at different times; the main goal is to assess the average crystallite size of prepared La2O3 nanoparticles, which was found in the range of 6 to 8 nm. An interesting observation from the XRD data was the apparent increase in crystalline nature as the synthesis time was extended. The UV-Vis spectroscopic studies show a change in the band gap when the reaction time is changed. The morphology analysis shows that the image revealed that the particles formed were agglomerated and formed a spherical shape, with diameters ranging between 35 and 86 nm. When tested for photocatalytic activity, the La2O3 nanoparticles show a degradation of methylene blue dye when the time varies. Remarkably, the nanoparticles synthesized exhibited a profound ability to degrade the dye, with an efficiency rate hitting as high as 89% under halogen light illumination.
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Corantes , Lantânio , Óxidos , Lantânio/química , Catálise , Óxidos/química , Corantes/química , Corantes/síntese química , Tamanho da Partícula , Nanopartículas/química , Azul de Metileno/química , Fatores de Tempo , Propriedades de SuperfícieRESUMO
Photocatalysis is one of the most effective ways to solve environmental problems by solving pollutants. This article designed and prepared a conjugated system of 2,4,6-triaminopyrimidine-g-C3N4 (TAP-CN) to modify ZnO NWs. We systematically studied the photocatalytic performance of ZnO NWs modified with different ratios of TAP-CN. The results showed that 9 wt% TAP-CN-30/ZnO NWs had the best degradation effect on Rhodamine B dye. The degradation rate was 99.36% in 80 min. The excellent degradation performance was attributed to the TAP-CN conjugated system promoting photo-generated charge transfer. This work provided guidance for designing efficient composite catalysts for application in other renewable energy fields.
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Organic pollutants were one of the main sources of environmental pollutants. The degradation of organic pollutants through photocatalytic technology was one of the effective solutions. By preparing zinc oxide(ZnO) nanowires modified with sodium-doped conjugated 2,4,6-triaminopyrimidin-g-C3N4 (NaTCN) heterojunction (ZnO/NaTCN), the photocatalytic performance of NaTCN modified with different ratios of ZnO was systematically studied. The photocatalytic performance was studied through the degradation performance of methyl blue (MB) dye. The results showed that 22.5 wt% ZnO/NaTCN had the best degradation effect on MB dye. The degradation rate of MB reached 98.54% in 70 min. After three cycles, it shows good cycling stability (degradation rate is 96.99%) for dye degradation. It was found that there are two types of active species: ·OH and h+, of which h+ is the main active species produced by photocatalytic degradation of dyes. The excellent degradation performance was attributed to the fact that ZnO facilitated the extraction and transport of photogenerated carriers. The doping of sodium facilitated charge transfer. The NaTCN conjugated system promoted the extraction and transfer of photogenerated carriers. It provided guidance for designing efficient composite catalysts for use in other renewable energy fields.
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A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL-R) or ethylene glycol-based bridge chains (CL-TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL-TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5-fold compared to that obtained using non-crosslinked F8BT photocatalysts, whereas CL-R-based photocatalysts yield HER rates comparable to those of non-crosslinked counterparts. Photophysical analyses including time-resolved photoluminescence and transient absorption measurements reveal that adding CL-TEG accelerates exciton separation, forming long-lived charge carriers. Additionally, the in-depth study using molecular dynamics simulations elucidates the dual role of CL-TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high-permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.
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In this study, we developed a novel p-n/Z-scheme heterojunction photocatalyst, ZnCo2O4/BiOBr (ZCo/BB), through a straightforward and safe hydrothermal-calcination-solvent thermal method. The composite photocatalyst demonstrated exceptional photocatalytic efficacy, particularly when the mass ratio of ZnCo2O4 was 25% (referred to as 25% ZCo/BB). Structural characterization and electrochemical analysis revealed that 25% ZCo/BB exhibited a larger specific surface area and a faster electron transfer rate. Under visible light exposure for 30 min, methylene blue (MB) degradation reached 92%, and the reaction rate constants were 8.2 and 3.7 times higher than those observed for individual ZnCo2O4 and BiOBr, respectively. Furthermore, the 25% ZCo/BB demonstrated exceptional photocatalytic stability over four cycles, maintaining over 80% MB degradation after each cycle. The outstanding photocatalytic activity was attributed to the p-n/Z-scheme heterojunction construction, which promoted charge separation and inhibited carrier recombination. In addition, ·OH and h+ were the major active species in photocatalysis, and · O 2 - was identified as a secondary active species. This work presents an efficient heterojunction photocatalyst for the degradation of organic wastewater.
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Azul de Metileno , Catálise , Azul de Metileno/química , Bismuto/químicaRESUMO
In response to the escalating global issue of microbial contamination, this study introduces a breakthrough photocatalyst: bismuth ferrite-activated carbon (BFO-AC) for visible light-driven disinfection, specifically targeting the Gram-positive bacterium Staphylococcus aureus (S. aureus). Employing an ultrasonication method, we synthesized various BFO-AC ratios and subjected them to comprehensive characterization. Remarkably, the bismuth ferrite-activated carbon 1:1.5 ratio (BA 1:1.5) nanocomposite exhibited the narrowest band gap of 1.86 eV. Notably, BA (1:1.5) demonstrated an exceptional BET surface area of 862.99 m2/g, a remarkable improvement compared to pristine BFO with only 27.61 m2/g. Further investigation through FE-SEM unveiled the presence of BFO nanoparticles on the activated carbon surface. Crucially, the photocatalytic efficacy of BA (1:1.5) towards S. aureus reached its zenith, achieving complete inactivation in just 60 min. TEM analysis revealed severe damage and rupture of bacterial cells, affirming the potent disinfection capabilities of BA (1:1.5). This exceptional disinfection efficiency underscores the promising potential of BA (1:1.5) for the treatment of contaminated water sources. Importantly, our results underscore the enhanced photocatalytic performance with an increased content of activated carbon, suggesting a promising avenue for more effective microorganism inactivation.
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Compostos Férricos , Nanocompostos , Staphylococcus aureus , Bismuto/farmacologia , Carvão Vegetal/farmacologia , Descontaminação , Luz , CatáliseRESUMO
The exploration of highly efficient sunlight-assisted photocatalyst for photodegradation of organic contaminants or energy conversion is strongly encouraged. In this work, we designed a novel three-dimensional spindle-like Sv-ZIS@NMFe heterojunction made of amino functionalized NH2-MIL-88B(Fe) (NMFe) and ZnIn2S4 nanosheets with abundant sulfur vacancies (Sv-ZIS). The structural properties of NMFe materials, such as a clearly defined system of pores and cavities, were retained by the Sv-ZIS@NMFe composites. Additionally, the incorporation of sulfur vacancies, -NH2 functional groups, and well-matched energy level positions led to various synergistic effects that considerably enhanced internal electron transformation and migration, as well as improved adsorption performance. Consequently, under visible light irradiation, the optimized sample exhibited superior hydrogen production activity and tetracycline hydrochloride photodegradation performance. At last, density functional theory calculations was used to further elucidated the possible photoreactivity mechanism. This study demonstrates that the Sv-ZIS@NMFe heterojunction materials formed by ZnIn2S4 with suitable sulfur vacancies and amino functionalized Fe-MOFs have promising applications in photocatalysis.
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Resorcinol-formaldehyde (RF) resin represents a promising visible-light responding photocatalyst for oxygen reduction reaction (ORR) toward H2 O2 production. However, its photocatalytic ORR activity toward H2 O2 generation is still unsatisfied for practical application. Herein, 3-hydroxythiophenol-formaldehyde (3-HTPF) resin microspheres synthesized through polycondensation reaction between 3-HTP and formaldehyde at room temperature and subsequent hydrothermal treatment exhibit enhanced photocatalytic ORR activity is reported. The experimental results show that the partial substitution of hydroxy group (âOH) by sulfhydryl one (âSH) through using 3-HTP to replace resorcinol could slow the rates of nucleation and growth of the resin particles and lead to strongly π-stacked architecture in 3-HTPF. The introduction of âSH group can also improve adsorption ability of 3-HTPF to O2 molecules and enhance ORR catalytic activity of the photocatalysts. Stronger built-in electric field, better adsorption ability to O2 molecules, and increased surface catalytic activity collectively boost photocatalytic activity of 3-HTPF microspheres. As a result, H2 O2 production rate of 2010 µm h-1 is achieved over 3-HTPF microspheres at 273 K, which is 3.4 times larger than that obtained using RF submicrospheres (591 µm h-1 ). The rational substituent group modulation provides a new strategy for designing polymeric photocatalysts at the molecular level toward high-efficiency artificial photosynthesis.
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This study reports the synthesis of (Cd0.4Ni0.4Mn0.2)Fe2-xRuxO4 nanoparticles (NPs), where x = 0.00, 0.005, 0.01, 0.015, 0.02, and 0.04, via co-precipitation method. The synthesized samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), and photoluminescence (PL) spectroscopy. The results confirmed the purity of the samples with the presence of a very small fraction of the hematite phase. Pseudo-spherical morphology was recognized from TEM images. Then, the prepared samples were further used as effective photocatalysts for the degradation of nitrobenzene under UV irradiation to examine the effect of doping on the photocatalytic activity. Among the synthesized samples, (Cd0.4Ni0.4Mn0.2)Fe1.985Ru0.015O4 NPs exhibited superior photocatalytic activity. This result is in good agreement with photoluminescence (PL) analysis in which (Cd0.4Ni0.4Mn0.2)Fe1.985Ru0.015O4 NPs revealed the slowest recombination rate of the electron-hole pair. To further improve the photocatalytic performance, different weight % of graphene was incorporated with (Cd0.4Ni0.4Mn0.2)Fe1.985Ru0.015O4 NPs. Finally, 81.41% of nitrobenzene was degraded after 180 min in the presence of 5 wt% graphene/(Cd0.4Ni0.4Mn0.2)Fe1.985Ru0.015O4 nanocomposites, and the degradation rate constant was estimated as 8.4 × 10-3 min-1.
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Grafite , Nanopartículas , Cádmio , Raios Ultravioleta , Nanopartículas/química , NitrobenzenosRESUMO
Adsorption and photocatalysis are effective in removing organic pollutants from wastewater. This study is based on the memory effects of MgAl-layered double hydroxides (MgAl-LDHs) after high-temperature calcination. By introducing bismuth vanadate (BiVO4) during the reformation of the layered structure via contact with water, a composite material BiVO4/MgAl-LDHs with enhanced adsorption and visible light catalytic performance was synthesized. The effects of the calcination temperature, ratio, initial methylene blue (MB) concentration, and catalyst dosage on the adsorption and photocatalytic performance were investigated. The BiVO4/MgAl-LDHs showed better photocatalytic performance than the pure BiVO4 and MgAl-LDHs. Under the optimal conditions, the proportion of MB adsorbed in 20 min was 66.1%, and the percentage of MB degraded during 100 min of photolysis was 92.4%. The composite photocatalyst showed good chemical stability and cyclability, and the adsorption-degradation rate was 86% after four cycles. Analyses of the adsorption and photocatalytic mechanisms for the composite material showed that synergistic adsorption and visible light photocatalysis contributed to the excellent catalytic performance of the BiVO4/MgAl-LDHs. A highly adsorbent photocatalytic composite material exhibiting outstanding performance was prepared via a simple, cost-effective, and environmentally friendly method, providing reference information for the removal of organic pollutants from liquids.
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Metal-organic frameworks (MOFs) are peculiar multimodal materials that find photocatalytic applications for the decomposition of lethal molecules present in the wastewater. In this investigation, two new d10-configuration-based MOFs, [Zn2(L)(H2O)(bbi)] (1) and [Cd2(L)(bbi)] (2) (5,5-(1,4-phenylenebis(methyleneoxy)diisophthalic acid (H2L) and 1,1'-(1,4-butanediyl)bis(imidazole) (bbi)), have been synthesized and characterized. The MOF 1 displayed a (4,6)-connected (3.43.52)(32.44.52.66.7) network topology, while 2 had a (3,10)-connected network with a Schläfli symbol of (410.511.622.72)(43)2. These MOFs have been employed as photocatalysts to photodegrade nitrophenolic compounds, especially p-nitrophenol (PNP). The photocatalysis studies reveal that 1 displayed relatively better photocatalytic performance than 2. Further, the photocatalytic efficacy of 1 has been assessed by altering the initial PNP concentration and photocatalyst dosage, which suggest that at 80 ppm PNP concentration and at its 50 mg concentration the MOF 1 can photo-decompose around 90.01% of PNP in 50 min. Further, radical scavenging experiments reveal that holes present over 1 and ·OH radicals collectively catalyze the photodecomposition of PNP. In addition, utilizing density of states (DOS) calculations and Hirshfeld surface analyses, a plausible photocatalysis mechanism for nitrophenol degradation has been postulated.
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In this study, pure CeO2 and oxygen-vacancy-enriched SnO2-CeO2 composite materials were prepared using the sol-gel method, and their microstructures and photocatalytic properties were investigated. The results indicate that SnO2 coupling promotes the separation and transfer of photogenerated electrons and holes and suppresses their recombination. The 50% SnO2-CeO2 composite material exhibited a decreased specific surface area compared to pure CeO2 but significantly increased oxygen vacancy content, demonstrating the highest photogenerated charge separation efficiency and the best photocatalytic performance. After 120 min of illumination, the degradation degree of MB by the 50% SnO2-CeO2 composite material increased from 28.8% for pure CeO2 to 90.8%, and the first-order reaction rate constant increased from 0.002 min-1 to 0.019 min-1.
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Elétrons , Iluminação , OxigênioRESUMO
This study focuses on the development of heterojunction photocatalysts for the efficient utilization of solar energy to address the energy crisis and reduce environmental pollution. Cadmium sulfide (CdS)/graphite-type carbon nitride (g-C3N4) nanocomposites were synthesized using a hydrothermal method, and their photoelectrochemical properties and photocatalytic performance for hydrogen evolution reaction (HER) were characterized. Scanning electron microscope images showed the intimate interface and caviar-like nanoheterojunction of the CdS nanoparticles on g-C3N4 nanospheres, suggesting their potential involvement in the photocatalytic process. Electrochemical and spectroscopic analyses were conducted to confirm the roles of CdS in the nanoheterojunction. The results showed that 10 wt% CdS/g-C3N4 nanospheres exhibited higher photocatalytic activity than pure g-C3N4 under visible light irradiation. A HER rate of 655.5 µmol/g/h was achieved after three photocatalytic cycles, signifying good photocatalytic stability. The synergistic effect of the Z-scheme heterojunction formed by g-C3N4 and CdS was identified as the main factor responsible for the enhanced photocatalytic performance and stability. The interface engineering effect of CdS/g-C3N4 facilitated the separation of photogenerated electrons and holes. This study provides insights into the design and fabrication of efficient HER photocatalysts.
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The photocatalytic technique has drawn far-ranging interests in addressing the current issues; however, its property suffers from the limited visible light response and rapid recombination of carriers. To address these issues, two specific approaches have been proposed to enhance the photocatalytic activity: (1) ultrasound-assisted synthesis has been utilized to prepare photocatalysts, resulting in refined grain size, increased specific surface area, and reduced photogenerated carrier recombination; (2) sonophotocatalysis and piezoelectric enhanced photocatalysis have been developed to accelerate the reaction, which utilizes the synergism between ultrasound and light. On one side, sonophotocatalysis generates cavitation bubbles which induce more reactive radicals for redox reactions. On the other side, ultrasound induces deformation of the piezoelectric material structure, which changes the internal piezoelectric potential and improves the photocatalytic performance. Currently, intensive efforts have been devoted to related research and great progress has been reached with applications in pollutant degradation, new energy production, and other fields. This work starts by elucidating the fundamental concept of ultrasound-assisted photocatalyst synthesis and photocatalysis. Then, the synergistic behavior between ultrasonic and light in ultrasonic-assisted photocatalysis has been thoroughly discussed, including pollutant degradation, water splitting, and bacterial sterilization. Finally, the challenge and outlook are investigated and proposed.
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Visible-light-assisted photocatalysis has been recognized as an effective solution to the degradation of various pollutants including antibiotics, pesticides, herbicides, microplastics, and organic dyes. Herein, an n-n heterojunction TiO2/Fe-MOF photocatalyst is reported, designed via solvothermal synthesis route. TiO2/Fe-MOF photocatalyst was characterized by XPS, BET, EIS, EDS, DRS, PL, FTIR, XRD, TEM, SEM and HRTEM techniques. Inspired by XRD, FTIR, XPS, EDS, TEM, SEM, and HRTEM analyses, the successful synthesis of n-n heterojunction TiO2/Fe-MOF photocatalysts was proved. The migration efficiency of the light-induced electron-hole pairs was confirmed by the PL and EIS tests. TiO2/Fe-MOF exhibited a significant performance for tetracycline hydrochloride (TC) removal under visible light irradiation. TC removal efficiency for TiO2/Fe-MOF (15%) nanocomposite reached 97% within 240 min, ca. 11 times higher than pure TiO2. The photocatalytic enhancement of TiO2/Fe-MOF could be attributed to the broadening the light response range, forming an n-n junction between Fe-MOF and TiO2 components, suppressing charge recombination. Based on recycling experiments, TiO2/Fe-MOF had a good potential to be used in consecutive TC degradation tests.
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Plásticos , Tetraciclina , Catálise , LuzRESUMO
In this study, novel, metal-free, CP-derived CDs/g-C3N4 nanocomposites (CDCNs) were created by introducing citrus peel-derived carbon dots (CP-derived CDs) into graphite carbon nitride (g-C3N4) by a green hydrothermal method. The CDCNs were revealed to have superior photoelectrochemical properties relative to pristine g-C3N4 for the photocatalytic degradation of the food dye sunset yellow (SY) under visible light. For SY decomposition, the recommended catalyst contributed almost 96.3% to the photodegradation rate after 60 min of irradiation, showing satisfactory reusability, structural stability and biocompatibility. Moreover, a mechanism for enhanced photocatalytic SY degradation was proposed according to band analysis, free radical trapping and electron paramagnetic resonance (EPR) results. A possible pathway for SY photodegradation was also predicted from UV-visible (UV-Vis) spectroscopy and high-performance liquid chromatography (HPLC) results. The constructed nonmetallic nanophotocatalysts afford a novel route for the elimination of harmful dyes and for the resource conversion of citrus peels.
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Compostos Azo , Carbono , Fotólise , Luz , Metais , CatáliseRESUMO
Titanium dioxide (TiO2) has garnered significant attention among various photocatalysts, whereas its photocatalytic activity is limited by its wide bandgap and inefficient charge separation, making the exploration of new strategies to improve its photocatalytic performance increasingly important. Here, we report the synthesis of Ag/P25 nanocomposites through a one-step gamma-ray radiation method using AgNO3 and commercial TiO2 (Degussa P25). The resulting products were characterized by powder X-ray diffraction, UV-Vis diffused reflectance spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The effect of free radical scavengers, feed ratios of Ag/P25, and dose rates on the photocatalytic activity of the Ag/P25 nanocomposites were systematically investigated using rhodamine B under Xenon light irradiation. The results showed that the Ag/P25 photocatalyst synthesized with a feed ratio of 2.5 wt% and isopropyl alcohol as the free radical scavenger at a dose rate of 130 Gy/min exhibited outstanding photocatalytic activity, with a reaction rate constant of 0.0674 min-1, much higher than that of P25. Additionally, we found that the particle size of Ag could be effectively controlled by changing the dose rate, and the Ag/P25 nanocomposites doped with smaller size of Ag nanoparticles performed higher photocatalytic activities. The synthesis strategy presented in this study offers new insight into the future development of highly efficient photocatalysts using radiation techniques.
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This study proposed a technique to enhance the photocatalytic properties of TiO2 using graphene oxide (GO) and modified Montmorillonite (M-MMT). TiO2/GO/M-MMT nano-heterostructured composites were prepared via hydrothermal and co-precipitation. The photocatalytic performance was evaluated by investigating the photodegradation rate and absorption behavior of methyl orange (MO) under visible light irradiation. The results showed that TiO2/GO/M-MMT heterojunction exhibited excellent photocatalytic degradation performance, as the degradation rate of MO was observed to be 99.3% within 150 min. The density of adsorbed MO decreased by 62.1% after 210 min of dark adsorption using the TiO2/GO/M-MMT composite, which was significantly higher than that achieved using M-MMT, GO/M-MMT, and TiO2/M-MMT. The nano-heterostructure increased the effective interface between TiO2, GO, and MMT, which increased the charge transfer ability and prolonged the electron-hole separation time. Therefore, the results of this study can be used to design novel photocatalysts to eradicate environmental pollutants.
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Heterojunctions based on conjugated polymers (PHJs) are of promise as photocatalysts. Here, we fabricate the two-dimensional benzodithiophene (BDT) and thieno[2,3-f]benzofuran (TBF) based conjugated polymers/g-C3N4 PHJs creatively using the symmetry-breaking strategy. PD1 and PD3 with the asymmetric backbone TBF have better crystallinity. Moreover, PD3 utilizing fluorinated benzotriazole as the electron acceptor unit possesses more compact π - π stacking and higher charge mobility. The conjugated polymer PD5 with asymmetric side chains in the donor unit BDT guarantees more efficient charge transfer in the corresponding PD5/g-C3N4 PHJ while maintaining comparable light utilization rate. Consequently, PD5/g-C3N4 shows the champion performance with photocatalytic sterilization rates reaching 99.1% and 97.3% for S. aureus and E. coli. Notably, the reaction rate constant for Rhodamine B degradation of PD5/g-C3N4 is 8 times that of g-C3N4, a record high among conjugated polymers/g-C3N4. This study aims to reveal the structure - property correlation of asymmetric conjugated polymers/g-C3N4 for potential photocatalysis applications.
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In order to solve the problem of poor compatibility between modified-ZIF-8 nanoparticles and mask matrix polypropylene (PP) and melt-blown materials, in this work, PP based modified-ZIF-8 antibacterial masterbatch was prepared employing surface modification and torque blending method. IR, SEM, XRD, XPS, DSC results confirm that the antibacterial masterbatch maintains the chemical and crystal structure of modified-ZIF-8 and the thermal stability of PP. Photocatalytic performance indicates that the antibacterial masterbatch basically maintains the photoresponse range of modified-ZIF-8, has narrower band gap and the superior photocatalytic performance than that of modified-ZIF-8. The photocatalytic antibacterial mechanism of ·O2- and h+ as antibacterial active species is revealed according to the energy band structure and free radical capture experiment. The photocatalytic antibacterial activity of the antibacterial masterbatch against Staphylococcus aureus and Escherichia coli under different dosage holds that the relationship between antibacterial rate and antibacterial agent concentration conforms to Beta distribution, demonstrating second-order kinetic behavior. The antibacterial properties reach the maximum when the loading of modified-ZIF-8 is 2% of the total weight of PP and melt-blown materials. S. aureus and E. coli could be completely killed when the simulated sunlight is irradiated for 30 min. These results indicate that PP based modified-ZIF-8 antibacterial masterbatch has potential application in photocatalytic antibacterial masks.