Silver nanoparticles from Tabernaemontana divaricate leaf extract: mechanism of action and bio-application for photo degradation of 4-aminopyridine

Silver nanoparticles (Ag NPs) were synthesised by the reduction of Ag⁺ to Ag⁰ in the presence of enol form of flavonoids present in plant extract of Tabernaemontana divaricate (T. divaricate). Prepared Ag NPs were characterised using UV–Vis, XRD, HR-TEM with EDX and XPS techniques. XPS spectra exhibited peaks at 366 eV and 373 eV, which specified spin orbits for Ag 3d_3/2, and Ag 3d_5/2 that confirmed the formation of Ag NPs. Ag NPs were spherical in shape with an average size of 30 nm as revealed by HR-TEM and FE-SEM techniques. EDX studies verified the high purity of Ag NPs with silver 46.96%, carbon 16.35%, oxygen 16.22%, nitrogen 20.25% and sulphur 0.21%. LC–MS analysis of plant extract confirmed the qualitative presence of alkaloids, tannins, flavonoids, phenols, and carbohydrates. Prepared Ag NPs showed good photocatalytic activity towards degradation of 4-Amniopyridine with 61% degradation efficiency at optimum conditions in 2 h of reaction time under visible light. The ten intermediates were found within the mass number of 0–450. Ag NPs synthesised using bio-extract have also shown good inactivation against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis) bacteria due to the availability of free radicals.

Graphical abstract

     

Fe_3O_4@SiO_2/TiO_2核壳结构纳米颗粒降解TNT溶液

针对TNT炸药废水具有成分复杂、排放量大、有毒等特点,立足于炸药废水在排放前的降解处理,研究开发一种基于核壳结构Fe3O4@SiO2/TiO2纳米颗粒的高效、可控回收、无二次污染且成本低的光催化降解方法。利用高温碳还原法和溶胶凝胶法制备了具有核壳结构的Fe3O4@SiO2/TiO2纳米颗粒。XRD分析表明,内核Fe3O4呈现磁铁矿特征,表面覆盖的纳米TiO2为锐钛矿型。磁滞回线测试结果显示,复合颗粒的饱和磁化强度为46.5 emu/g,N2吸附-解吸分析结果表明,该颗粒具有典型的介孔结构。使用Fe3O4@SiO2/TiO2纳米颗粒在紫外光下对含TNT废水进行降解,降解率达到81.9%,且颗粒的回收率达到88.4%,为实现高效、可控回收、无二次污染光催化-吸附降解TNT奠定了基础。     

碳纳米管/二氧化钛/壳聚糖催化薄膜光催化活性及苯降解机理

通过X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和紫外可见光漫反射谱(UV-vis)对碳纳米管/二氧化钛/壳聚糖复合薄膜的晶体结构和形貌进行表征,以室内空气典型污染物气相苯为模型反应物,研究碳纳米管/二氧化钛/壳聚糖催化薄膜的光催化活性及其对苯的光降解机理。结果表明,制备的碳纳米管/二氧化钛/壳聚糖催化薄膜所具有的良好催化活性归功于碳纳米管、二氧化钛和壳聚糖三者的协调效应;气相苯光降解产生的主要中间产物是乙酸乙酯和十一烷,以及少量的丙烯醛、4-羰基-甲基-苯乙酮、十二烷烃、2,4,-二叔丁基苯酚、二十一烷烃。根据红外光谱分析与GC/MS分析结果,进一步提出了气相苯的降解机理过程。     

High-performance for hydrogen evolution and pollutant degradation of reduced graphene oxide/two-phase g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> heterojunction photocatalysts

We have successfully synthesized the composites of two-phase g-C₃N₄ heterojunction photocatalysts by one-step method. And the reduced graphene oxide/two-phase g-C₃N₄ heterojunction photocatalyst was fabricated via a facile hydrothermal reduction method. The characterization results indicated that the two-phase g-C₃N₄ was integrated closely, and the common phenomenon of agglomeration for g-C₃N₄ was significantly reduced. Moreover, the oxidized graphene was reduced successfully in the composites and the graphene was overlaid on the surface or the interlayers of g-C₃N₄ heterojunction composite uniformly. In addition, we have carried out the photocatalytic activity experiments by H₂ evolution and rhodamine B removal, tetracycline removal under the visible light irradiation. The results revealed that the composite has improved the separation efficiency a lot than the pure photocatalyst. The photocurrent test demonstrated that the recombination of electrons and holes were efficiently inhibited as well as enhanced the photocatalytic activity. The 0.4% rGO loaded samples, 0.4% rGOCN2, own the best performance. Its rate of H₂ evolution was 15 times as high as that of the pure g-C₃N₄.     

Photocatalytic degradation of gaseous toluene over Ag-doping TiO₂ nanotube powder prepared by anodization coupled with impregnation method

In this work, Ag-doping TiO₂ nanotubes were prepared and employed as the photocatalyst for the degradation of toluene. The TiO₂ nanotube powder was produced by the rapid-breakdown potentiostatic anodization of Ti foil in chloride-containing electrolytes, and then doped with Ag through an incipient wetness impregnation method. The samples were characterized by scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, surface photovoltage measurements, X-ray photoelectron spectroscopy and N₂ adsorption. The nanotubular TiO₂ photocatalysts showed an outer diameter of approximately 40 nm, fine mesoporous structure and high specific surface area. The photocatalytic activity of Ag-doping TiO₂ nanotube powder was evaluated through photooxidation of gaseous toluene. The results indicated that the degradation efficiency of toluene could get 98% after 4 h reaction using the Ag-doping TiO₂ nanotubes as the photocatalyst under UV light illumination, which was higher than that of the pure TiO₂ nanotubes, Ag-doping P25 or P25. Benzaldehyde species could be observed during the photocatalytic oxidation monitored by in situ FTIR, and the formed benzaldehyde intermediate during reaction would be partially oxidized into CO₂ and H₂O.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.     

UV–visible light-activated Ag-decorated,monodisperse TiO2 aggregates for treatment of the pharmaceutical oxytetracycline

Noble metal Ag-decorated, monodisperse TiO₂ aggregates were successfully synthesized by an ionic strength-assisted, simple sol–gel method and were used for the photocatalytic degradation of the antibiotic oxytetracycline (OTC) under both UV and visible light (UV–visible light) irradiation. The synthesized samples were characterized by X-ray diffraction analysis (XRD); UV–vis diffuse reflectance spectroscopy; environmental scanning electron microscopy (ESEM); transmission electron microscopy (TEM); high-resolution TEM (HR-TEM); micro-Raman, energy-dispersive X-ray spectroscopy (EDS); and inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that the uniformity of TiO₂ aggregates was finely tuned by the sol–gel method, and Ag was well decorated on the monodisperse TiO₂ aggregates. The absorption of the samples in the visible light region increased with increasing Ag loading that was proportional to the amount of Ag precursor added in the solution over the tested concentration range. The Brunauer, Emmett, and Teller (The BET) surface area slightly decreased with increasing Ag loading on the TiO₂ aggregates. Ag-decorated TiO₂ samples demonstrated enhanced photocatalytic activity for the degradation of OTC under UV–visible light illumination compared to that of pure TiO₂. The sample containing 1.9 wt% Ag showed the highest photocatalytic activity for the degradation of OTC under both UV–visible light and visible light illumination. During the experiments, the detected Ag leaching for the best TiO₂-Ag photocatalyst was much lower than the National Secondary Drinking Water Regulation for Ag limit (0.1 mg L^?1) issued by the US Environmental Protection Agency.     

Facile synthesis of cadmium-doped graphite carbon nitride for photocatalytic degradation of tetracycline under visible light irradiation

In recent years, using semiconductor photocatalysts for antibiotic contaminant degradation under visible light has become a hot topic. Herein, a novel and ingenious cadmium-doped graphite phase carbon nitride (Cd-g-C₃N₄) photocatalyst was successfully constructed via the thermal polymerization method. Experimental and characterization results revealed that cadmium (Cd) was well doped at the g-C₃N₄ surface and exhibited high intercontact with g-C₃N₄. Additionally, the introduction of cadmium significantly improved the photocatalytic activity, and the optimum degradation efficiency of tetracycline (TC) reached 98.1%, which was exceeded 2.0 times that of g-C₃N₄ (43.9%). Meanwhile, the Cd-doped sample presented a higher efficiency of electrical conductivity, light absorption property, and photogenerated electron-hole pair migration compared with g-C₃N₄. Additionally, the quenching experiments and electron spin-resonance tests exhibited that holes (h⁺), hydroxyl radicals (?OH), superoxide radicals (?O₂^?) were the main active species involved in TC degradation. The effects of various conditions on photocatalytic degradation, such as pH, initial TC concentrations, and catalyst dosage, were also researched. Finally, the degradation mechanism was elaborated in detail. This work gives a reasonable point to synthesizing high-efficiency and economic metal-doped photocatalysts.

     

Photocatalytic Degradation of the Herbicide Erioglaucine in the Presence of Nanosized Titanium Dioxide: Comparison and Modeling of Reaction Kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO₂ nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO₂ system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir–Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm^{? 1} and 0.984 ppm min^{? 1}, respectively. In this work, we also compared the reactivity between the commercial TiO₂ Degussa P-25 and a rutile TiO₂. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO₂ for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO₂ process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO₂.     

Cu/La共掺杂TiO2光催化氧化水中的氨氮

采用水解-沉淀法制备了Cu/La共掺杂纳米TiO2催化剂,利用XRD、XPS和BET技术对其进行表征,并考察了在紫外灯下,共掺杂TiO2对氨氮的光催化氧化工艺条件。物相结构和比表面积测试结果表明,共掺杂催化剂具有较好的锐钛矿晶型,孔径分布为4～8 nm,Cu/La共掺杂TiO2La以La3+,Cu是以Cu2+、Cu+的形式掺杂进入TiO2的晶格。光催化实验表明:所得改性光催化剂对氨氮的去除及焦化废水的处理均具有较高的催化活性。     

光催化降解模拟室内挥发性有机污染物研究

用浸渍-提拉法制备玻璃弹簧负载型TiO2薄膜催化剂,在自制的反应器中进行光催化降解由丙酮、甲苯、对二甲苯组成的模拟室内挥发性有机污染物VOCs研究.研究发现:催化剂中掺杂金属离子能影响催化剂的降解效果,降解效果依次为掺铈TiO2＞纯TiO2＞掺银TiO2;气体流量显著影响降解效果,丙酮、甲苯和对二甲苯的最佳降解流量分别为3、5、7 L/min;混合气体中非对称性的极性分子的降解效率高于对称性分子,导致丙酮、对二甲苯组分降解率降低,甲苯降解率增高.     

Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

Photocatalytic behavior of nanosized TiO2 immobilized on layered double hydroxides by delamination/restacking process

Introduction

Efficient immobilization of TiO₂ nanoparticles on the surface of Mg₂Al-LDH nanosheets was performed by delamination/restacking process.

Experimental part

The structural and textural properties of as-prepared nanocomposite were deeply analyzed using different solid-state characterization techniques such as: X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopies, chemical analysis, X-ray photoelecton spectroscopy, N₂ adsorption?Cdesorption, and electronic microscopy.

Results and discussion

The photocatalytic properties of immobilized TiO₂ nanoparticles on Mg₂Al were investigated using the photodegradation of two model pollutants: Orange II and 4-chlorophenol, and compared with pure colloidal TiO₂ solution.

Conclusion

It appears that Orange II photodegradation was systematically faster and more efficient than 4-chlorophenol photodegradation regardless of the medium pH. Moreover under slightly basic conditions, even if the TiO₂ photocatalytic efficiency decreases, photodegradation performed in presence of easily recovered TiO₂/Mg₂Al_1.5 nanocomposite gives rise to comparable or better results than pure TiO₂.     

陶瓷负载Ag、Ce共掺杂TiO_2光催化剂降解甲基橙的研究

以陶瓷为载体,采用溶胶-凝胶法制备了银离子和铈离子共掺杂TiO2的负载型光催化剂——T-AC/陶瓷,研究了pH值、双氧水用量、催化剂用量、紫外灯强度、废水的初始浓度等因素对T-AC/陶瓷光催化剂降解甲基橙染料废水的影响。结果表明,当pH为2、双氧水用量为0.5 mL/100 mL、催化剂用量为3 g/L、紫外灯功率为20 W、废水初始浓度为10mg/L时,甲基橙的降解率可达85.9%,并且甲基橙的光催化降解属于一级动力学方程,T-AC/陶瓷催化剂有较高的活性和稳定性,在废水处理中具有较好的应用前景。     

Removal of anionic azo dye from aqueous solution via an adsorption–photosensitized regeneration process on a TiO2 surface

Textile dye effluents are typically characterized by strong color and recalcitrance, even at very low concentration. The process of enrichment of anionic azo dye on the surface of TiO₂ fibers followed by photosensitization degradation under ambient air conditions was extensively investigated. Adsorption isotherms and zeta potentials were used to describe the “dye/TiO₂ surface” interface, taking into account the effects of pH on the nature and population of the surface groups on the TiO₂ fibers. The extent of the photocatalytic degradation of dye on TiO₂ surface was determined by FTIR. N₂ adsorption isotherms and optical spectra were employed to investigate the effect of photosensitization. The adsorption of dyes on the TiO₂ surface occurs via electrostatic attraction through the formation of single- or multidentate-coordinated surface complexes. Almost complete photobleaching of the absorption band at 534 nm is achieved in ~4 h. Dye-sensitized TiO₂ fiber could absorb part of the visible light spectrum (λ?<?600 nm). Interfacial electron transfer can potentially alter the degradation efficiency. The regenerated TiO₂ fiber could be reused for subsequent decolorization without a decline in adsorption efficiency compared with freshly prepared TiO₂ samples, which may be attributed to preservation of the hierarchical pore structure and restoration of the original surface properties. In summary, we propose an efficient “adsorption–photoregeneration–reuse” process applying TiO₂ fibers for the degradation of dyes in water.     

纳米二氧化钛复合石墨烯催化剂的制备及处理染料废水

以硫酸钛为原料,采用共沉淀法,制备了一系列纳米二氧化钛复合石墨烯催化剂,采用XRD和FTIR对样品进行表征。通过紫外光照射亚甲基蓝溶液光催化降解实验,研究石墨烯的加入量对TiO2光催化性能的影响,结果表明,TiO2-GO-5具有最佳的光催化性能。在pH=6.00、TiO2-GO-5的投加量为0.070 g/50 mL、光照3 h条件下,100 mg/L亚甲基蓝溶液的脱色率达到最大值为90.52%。     

Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

Influence of palladium content dispersed in the TiO2 photocatalyst for degradation of volatile organic compounds in gas emission

Heterogeneous photocatalysis is highlighted to treat volatile organic compound (VOC) emission. Then, this work analysed the influence of palladium (Pd) content loaded in TiO₂ on n-octane and iso-octane photodegradation. For this, TiO₂ was loaded with Pd in different contents: 0.4%, 0.7%, and 1.0%. The samples were characterized, and the photodegradation experiments were conducted by Pd/TiO₂/UV process. The characterization analyses showed that the metal presence did not change the catalyst structure or its surface area; however, it reduced the bandgap energy. The photocatalytic results proved that palladium improved n-octane degradation from 62% (pure TiO₂) to 92.6% (0.4%Pd/TiO₂) and, iso-octane degradation enhanced from 59% (pure TiO₂) to 90.6% (0.7%Pd/TiO₂); all results were obtained in the space time of 39 s. Therefore, 0.4%Pd/TiO₂ and 0.7%Pd/TiO₂ showed better oxidation results to degradation n-octane and iso-octane, respectively. The kinetic model of pseudo-first order showed a good fit for the data of both VOCs. Heterogeneous photocatalysis with Pd/TiO₂ showed to be an adequate technique to reduce VOCs emission.

     

Enhanced photocatalytic activity using GO/TiO<Subscript>2</Subscript> catalyst for the removal of DCA solutions

This work aimed to optimize high-performance photocatalysts based on graphene oxide/titanium dioxide (GO/TiO₂) nanocomposites for the effective degradation of aqueous pollutants. The catalytic activity was tested against the degradation of dichloroacetic acid (DCA), a by-product of disinfection processes that is present in many industrial wastewaters and effluents. GO/TiO₂ photocatalysts were prepared using three different methods, hydrothermal, solvothermal, and mechanical, and varying the GO/TiO₂ ratio in the range of 1 to 10%. Several techniques were applied to characterize the catalysts, and better coupling of GO and TiO₂ was observed in the thermally synthesized composites. Although the results obtained for DCA degradation showed a coupled influence of the composite preparation method and its composition, promising results were obtained with the photocatalysts compared to the limited activity of conventional TiO₂. In the best case, corresponding to the composite synthesized via hydrothermal method with 5% of GO/TiO₂ weight ratio, an enhancement of 2.5 times of the photocatalytic degradation yield of DCA was obtained compared to bare TiO₂, thus opening more efficient ways to promote the application of photocatalytic remediation technologies.     

Titania-supported silver-based bimetallic nanoparticles as photocatalysts

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag–Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO₂-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO₂). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.