Arthrobacter sp. JS443‐Based Whole Cell Amperometric Biosensor for p‐Nitrophenol

An amperometric microbial biosensor for highly sensitive and selective determination of p‐nitrophenol (PNP) is reported. The biosensor consisted of PNP‐degrader Arthrobacter sp. JS443 immobilized by entrapment in Nafion polymer deposited on the top of the carbon paste electrode transducer. The biosensor was based on the measurement of the oxidation current of the intermediates 4‐nitrocatechol and 1,2,4‐benzenetriol formed by the highly selective oxidation of PNP by Arthrobacter sp. The sensor signal and response time were optimized with applied potential of +0.4 V (vs. Ag/AgCl reference electrode) and 0.03 mg of cells and operating in pH 7.5, 50 mM citrate‐phosphate buffer at room temperature. When operated at optimized conditions, the Arthrobacter sp.‐based biosensor measured as low as 5 nM (0.7 ppb) of PNP. The biosensor demonstrated excellent selectivity with no interference from phenolic compounds such as 2‐nitrophenol, phenol and 3‐chlorophenol but was interfered by 3‐nitrophenol and 3‐methyl‐4‐nitrophenol. It had good precision and intra‐ and inter‐day reproducibility, accuracy and was stable up to 3 days when stored in buffer at 4 °C. When applied for measurement in water from Lake Elsinore, CA, the results obtained were in excellent agreement with the amounts determined spectrophotometrically.     

Green synthesis of reduced graphene oxide/Fe3O4/Ag ternary nanohybrid and its application as magnetically recoverable catalyst in the reduction of 4‐nitrophenol

Materials having both magnetic and catalytic properties have shown great potential for practical applications. Here, a reduced graphene oxide/iron oxide/silver nanohybrid (rGO/Fe₃O₄/Ag NH) ternary material was prepared by green synthesis of Ag on pre‐synthesized rGO/Fe₃O₄. The as‐prepared rGO/Fe₃O₄/Ag NH was characterized using Fourier transform infrared spectroscopy, X‐ray diffractometry, Raman spectroscopy, vibrating sample magnetometry, transmission electron microscopy and energy‐dispersive X‐ray spectroscopy. rGO sheets were covered with Fe₃O₄ (8–16 nm) and Ag (18–40 nm) nanoparticles at high densities. The mass percentages were 13.47% (rGO), 62.52% (Fe₃O₄) and 24.01% (Ag). rGO/Fe₃O₄/Ag NH exhibited superparamagnetic behavior with high saturated magnetization (29 emu g⁻¹ at 12 kOe), and efficiently catalyzed the reduction of 4‐nitrophenol (4‐NP) with a rate constant of 0.37 min⁻¹, comparable to those of Ag‐based nanocatalysts. The half‐life of 4‐NP in the presence of rGO/Fe₃O₄/Ag NH was ca 1.86 min. rGO/Fe₃O₄/Ag NH could be magnetically collected and reused, and retained a high conversion efficiency of 94.4% after the fourth cycle. rGO/Fe₃O₄/Ag NH could potentially be used as a magnetically recoverable catalyst in the reduction of 4‐NP and environmental remediation.     

Ultrasound‐assisted Synthesis of Ag‐ZnS/rGO and its Utilization in Photocatalytic Degradation of Tetracycline Under Visible Light Irradiation

Recent improvements based on heterojunction nanocomposites have opened new possibilities in photocatalysis. In this research, an ultrasound‐assisted coprecipitation method was used to fabricate silver, zinc sulfide and reduced graphene oxide (Ag‐ZnS/rGO) nanocomposite, and characterization results indicated that 3% Ag‐ZnS spherical nanoparticles are successfully embedded in rGO matrix. The potential of the Ag‐ZnS/rGO, as a visible light active photocatalyst, was assessed through optimizing degradation of Tetracycline (TC) by response surface methodology. It was found that the photocatalytic degradation of TC increased with an increase in the amount of nanocomposite and irradiation time, whereas it decreased with increasing the initial TC concentration. Under the optimal conditions (10 mg L^?1 of TC, 1.25 g L^?1 of Ag‐ZnS/rGO, at pH = 7, and irradiation duration 110 min), more than 90% of the TC was degraded. The study of the mechanism of the photocatalytic process disclosed that the synergistic role of surface plasmon resonance (SPR) induced by Ag nanoparticles and p‐type semiconductor feature of rGO leads to ZnS semiconductor stimulation in the visible light region. Eventually, a pseudo‐first order kinetics model was developed based on the proposed mechanism. The obtained results highlight the role of Ag‐ZnS/rGO nanophotocatalyst toward degradation of some antibiotics under visible light.     

A copper diimine‐based honeycomb‐like porous network as an efficient reduction catalyst

Nitrophenols are among the widely used industrial chemicals worldwide; however, their hazardous effects on environment are a major concern nowadays. Therefore, the conversion of environmentally detrimental p‐nitrophenol (PNP) to industrially valuable p‐aminophenol (PAP), a prototype reaction, is an important organic transformation reaction. However, the traditional conversion of PNP to PAP is an expensive and environmentally unfriendly process. Here, we report a honeycomb‐like porous network with zeolite‐like channels formed by the self‐organization of copper, 1,10‐phenanthroline, 4,4′‐bipyridine, and water. This porous network effectively catalyzed the transformation of hazardous PNP to pharmaceutically valued PAP. In the presence of complex, PNP to PAP conversion occurred in a few minutes, which is otherwise a very sluggish process. To assess the kinetics, the catalytic conversion of PNP to PAP was studied at five different temperatures. The linearity of lnC_t/C_o versus temperature plot indicated pseudo‐first‐order kinetics. The copper complex with zeolite like channels may find applications as a reduction catalyst both on laboratory and industrial scales and in green chemistry for the remediation of pollutants.     

Plant‐supported silver nanoparticles: Efficient,economically viable and easily recoverable catalyst for the reduction of organic pollutants

Ginger rhizome powder was used for the synthesis of supported metallic nanoparticle catalysts. A simple and novel adsorption method was used for the synthesis of silver nanoparticles loaded on ginger powder (Ag/GP), copper on ginger powder (Cu/GP) and nickel on ginger powder (Ni/GP). Among these, Ag/GP showed selective reduction of methyl orange and was used for further reactions. The prepared nanomaterials were characterized through X‐ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, fourier transform infrared spectroscopy and energy‐dispersive X‐ray spectroscopy. The prepared Ag/GP catalyst was employed in the catalytic reduction of 4‐nitrophenol (4‐NP), 2‐nitrophenol (2‐NP), rhodamine B, methyl red and congo red. Ag/GP showed excellent catalytic reduction activity, the rate constants being 1.26 × 10^?3 and 2.38 × 10^?3 s^?1 for 2‐NP and 4‐NP, respectively. The turnover frequency reached 1.06 min^?1 for 2‐NP and 1.16 min^?1 for 4‐NP when using the Ag/GP catalyst. The prepared Ag/GP catalyst demonstrated outstanding activity for the degradation of a mixed solution of dyes. Also, stability and reusability of the prepared catalyst were investigated, which showed outstanding reusability up to five times and was stable up to five days.     

Fabrication of carboxymethylated cellulose fibers supporting Ag NPs@MOF‐199s nanocatalysts for catalytic reduction of 4‐nitrophenol

In this work, we prepared high‐performance and recyclable nanocatalysts that consist of small and well‐dispersed silver nanoparticles (Ag NPs) immobilized onto Cu‐ based metal–organic framework (MOF‐199 s) supported by carboxymethylated cellulose fibers (CCFs). The as‐prepared green nanohybrid catalysts, namely Ag NPs@ MOF‐199 s/CCFs, were characterized using SEM, TEM, XRD and FT‐IR techniques. The catalytic performances showed that Ag NPs@ MOF‐199 s/CCFs catalysts exhibited a very high catalytic efficiency towards the reduction of 4‐nitrophenol to 4‐aminophenol. The enhanced catalytic performances are attributed to the improved dispersity, small particles of Ag NPs stabilized by the MOF‐199 s, and the porous catalyst structures. The introduction of cellulose fiber further facilitates the reuse and sustainability of the nanohybrid catalysts, showing a stable and high reusability (more than 91% of catalytic activity) even after five runs.     

Nanosized Functional MOFs Loading Ag/AgBr with Throughout‐Visible‐Light Absorption for High‐Efficiency Photocatalysis

Porous metal‐organic frameworks (MOFs) loading metal nanoparticles to form a composite photocatalyst demonstrated unique advantages. Modification of the electron donating group on the aromatic linkers of MOFs could increase the absorption range of light, thereby increasing the photocatalytic activity. In this study, we prepared a composite photocatalyst using a stable NH₂‐functionalized MOF (UiO‐66‐NH₂) to load semiconductor Ag/AgBr nanoparticles, and the resultant composites have intense optical absorption throughout visible light range. The greatly enhanced optical absorption and the unique hetero‐junction between Ag/AgBr and UiO‐66‐NH₂ render efficient separation and utilization of photogenerated electron‐hole pairs. Therefore, Ag/AgBr@UiO‐66‐NH₂ showed much more excellent photocatalytic activity, compared with unmodified UiO‐66 loading Ag/AgBr (Ag/AgBr@UiO‐66) and reported AgX@MOF catalysts. Moreover, the composite photocatalysts showed excellent stability during cycling experiment.     

Synthesis of V5+‐doped Ag/AgCl photocatalysts with enhanced visible light photocatalytic activity

V⁵⁺‐doped Ag/AgCl photocatalysts were prepared via the ion exchange method. The catalysts were characterized using X‐ray diffractometry, transmission electron microscopy, and energy‐dispersive X‐ray, X‐ray photoelectron, Fourier transform infrared and ultraviolet–visible spectroscopies. The V⁵⁺‐doped Ag/AgCl photocatalysts show much higher photocatalytic activities than Ag/AgCl under visible light irradiation for methyl orange (MO) decomposition. Especially, the 2.0 wt% V⁵⁺‐doped Ag/AgCl photocatalyst shows the highest photocatalytic activity and also high stability after five cycles. The MO degradation rate during each cycle is almost maintained at 97%. Electron spin resonance spectroscopy and radical trapping experiments reveal that holes play an important role in the photocatalytic process.     

Large-scale synthesis of size-controllable Ag nanoparticles by reducing silver halide colloids with different sizes

By reducing the colloidal silver halide, we successfully synthesized a series of micro-nano Ag particles.     

Preparation and photocatalytic activity of carbon dot/Ag/AgCl

CD (carbon dot)/Ag/AgCl compound photocatalysts with different compounding degrees were prepared via a precipitation method, and their physiochemical properties were characterized by X‐ray diffraction, FE‐SEM, UV–vis and the like. Through the degradation experiment of methyl orange (MO), the effects of different compounding amount and methyl orange concentration on photocatalytic degradation were investigated to find the best ratio. It was found the photocatalytic activity of CD/Ag/AgCl was significantly higher than Ag/AgCl, and the best compounding dosage was 6 mg/l carbon dot. The degradation rate of CD/Ag/AgCl was lower when the initial MO concentration was higher. Five repeated experiments were conducted to test the stability of the catalysts, and showed the MO degradation rates were all above 85%, indicating the CD/Ag/AgCl compound photocatalysts all showed high stability and repeatability. The reaction mechanism of CD/Ag/AgCl photocatalyst was studied by electrochemical experiments and ESR experiments. The results show that the doping of CD effectively improves the photocatalytic degradation ability of MO.     

A New p‐Metal‐n Structure AgBr‐Ag‐BiOBr with Superior Visible‐Light‐Responsive Catalytic Performance

A novel visible‐light‐driven AgBr‐Ag‐BiOBr photocatalyst was synthesized by a facile hydrothermal method. Taking advantage of both p‐n heterojunctions and localized surface plasmon resonance, the p‐metal‐n structure exhibited a superior performance concerning degradation of methyl orange under visible‐light irradiation (λ>420 nm). A possible photodegradation mechanism in the presence of AgBr‐Ag‐BiOBr composites was proposed, and the radical species involved in the degradation reaction were investigated. HO₂^?/^?O₂^? played the same important role as ^?OH in the AgBr‐Ag‐BiOBr photocatalytic system, and both the electron and hole were fully used for degradation of organic pollutants. A dual role of metallic Ag in the photocatalysis was proposed, one being surface plasmon resonance and the other being an electron‐hole bridge. Due to the distinctive p‐metal‐n structure, the visible‐light absorption, the separation of photogenerated carriers and the photocatalysis efficiency were greatly enhanced.     

Degradation of carbon tetrachloride using ultrasound‐assisted nanoscaled zero‐valent iron particles@sulfur/nitrogen dual‐doped reduced graphene oxide composite: Kinetics,activation energy,effects of reaction conditions and degradation mechanism

We report a study of the synthesis of nanoscale zero‐valent iron particles stabilized by sulfur/nitrogen dual‐doped reduced graphene oxide (i.e. nZVI@SN‐rGO) and their applications as major reactants for the dechlorination of carbon tetrachloride (CT) by combining sonolysis with consideration of several operation parameters such as pH, temperature, catalyst dosage, as well as in the presence of common inorganic anions. The experimental results showed that the modified technology could remain effective for up to 180 min of reaction time under optimal conditions. Especially, there was no significant reduction in the removal efficiency toward CT even after five cycles, which was indicative of good stability. A study of the effects of common inorganic anions revealed that the presence of Clˉ and HCO₃ˉ exhibited different positive effects in the following order: Clˉ > HCO₃ˉ; NO₃ˉ and SO₄²ˉ showed inhibition effects on CT removal. The structure and properties of nZVI@SN‐rGO were characterized using X‐ray diffraction, scanning electron microscopy, surface area analysis, Raman spectroscopy and X‐ray photoelectron spectroscopy. Additionally, the corresponding activation energy was approximately 31.04 kJ mol^?1, suggesting that the surface chemical reaction rather than diffusion was the rate‐limiting step in the CT decomposition process. More importantly, the possible reaction mechanism and dechlorination pathway of CT using the ultrasound‐assisted nZVI@SN‐rGO system were also investigated.     

The Visible‐Light Photocatalytic Activity and Antibacterial Performance of Ag/AgBr/TiO2 Immobilized on Activated Carbon

Visible‐light‐driven Ag/AgBr/TiO₂/activated carbon (AC) composite was prepared by solgel method coupled with photoreduction method. For comparison, TiO₂, TiO₂/AC, and Ag/AgBr/TiO₂ were also synthesized. Their characteristics were analyzed by XRD, SEM‐EDS, TG‐DSC and UV–vis techniques. Photocatalytic activity and antibacterial performance under visible‐light irradiation were investigated by ICP‐AES, ATR‐FT‐IR and spectrophotometry methods using methylene blue and Escherichia coli as target systems, respectively. The results showed that Ag/AgBr was successfully deposited on anatase TiO₂/AC surface, and exhibited a distinct light absorption in the visible region. Ag/AgBr/TiO₂/AC displayed excellent antibacterial performance both in dark and under visible‐light illumination. The growth of E. coli cell was inhibited in the presence of Ag/AgBr/TiO₂/AC in dark. Moreover, upon visible‐light illumination, a significant damage of cell membrane was noticed. Ag/AgBr/TiO₂/AC was also shown higher photocatalytic efficiency for methylene blue degradation than those of TiO₂, TiO₂/AC, and Ag/AgBr/TiO₂. This is attributed to the synergetic effect between AC and Ag/AgBr/TiO₂, of which AC acts as the role of increasing reaction areas, continuous enriching, and transferring the adsorbed MB molecules to the surface of supported photocatalysts, and the Ag/AgBr/TiO₂ acts as a highly active photocatalyst for degrading MB molecules under visible‐light irradiation.     

Amorphizing of Ag Nanoparticles under Bioinspired One‐step Assembly of Fe3O4‐Ag/rGO Hybrids via Self‐redox Process with Enhanced Activity

Efficient and reusable nanocatalysts fabricated via a facile assembly are highly desirable for the cost‐effective hydrogenation reduction. Inspired by a fishing process with a fishnet, multifunctional nanostructured catalysts are rationally designed to combine interesting features via the self‐redox assembly of Fe₃O₄‐Ag composites on reduced graphene oxide (rGO) (Fe₃O₄‐Ag/rGO). In detail, Fe₃O₄ nanoparticles (NPs) endow the ternary hybrids with superparamagnetism (21.42 emu g^?1), facilitating catalysts to be separated from the reaction system. rGO could provide electron transfer pathways, enhancing catalytic activity. More interestingly, GO and Ag⁺ could behave as oxidants to oxidize Fe²⁺ for the in situ assembly of Fe₃O₄‐Ag/rGO without any addition of reductant/oxidant or organic solvents, and AgNPs endow the ternary hybrids with excellent catalytic behaviour. Meaningfully, the bioinspired process enables the ternary hybrids to possess more abundant micro?/nanopores, larger surface area, and more amorphization. They exhibit exceptional catalytic performance, and could be recycled with excellent activity by means of convenient magnetic separation (at least 7 times). Moreover, the ternary hybrids could degrade methylene blue under UV light due to different valence states of Fe in Fe₃O₄. Therefore, the proposed bioinspired assembly and structure design for hierarchical catalysts would pave a promising way to assemble other catalysts.     

Ag/ZnO Catalysts with Different ZnO Nanostructures for Non‐enzymatic Detection of Urea

Silver coated ZnO nanorods and nanoflakes with different crystallographic orientations were synthesized by a combination of sputter deposition and solution growth process. Catalytic properties of morphology‐dependent Ag/ZnO nanostructures were then investigated for urea sensors without enzyme. Ag/ZnO nanorods on carbon electrodes exhibit a higher catalytic activity and an improved efficiency than Ag/ZnO nanoflakes on carbon electrodes. Ag/ZnO nanorod catalysts with more electrochemically surface area (169 cm² mg^?1) on carbon electrode facilitate urea electrooxidation due to easier electron transfer, which further promotes the urea electrolysis. The Ag/ZnO nanorod catalysts also show a significant reduction in the onset voltage (0.410 V vs. Ag/AgCl) and an increase in the current density (12.0 mA cm^?2 mg^?1) at 0.55 V vs Ag/AgCl. The results on urea electrooxidation show that Ag/ZnO nanostructures can be a potential catalyst for non‐enzymatic biosensors and fuel cells.     

ZnO纳米柱状阵列表面AgX等离子基元修饰及其可见光光催化活性

采用浸渍法制备了表面AgX（X=I,Br）等离子基元修饰的ZnO纳米柱状阵列,研究了浸渍浓度和时间以及紫外光光照预处理对ZnO纳米柱状阵列可见光光催化活性的影响.采用场发射扫描电子显微镜、X射线衍射仪、紫外可见漫反射吸收光谱以及X射线光电子能谱仪等手段对ZnO纳米柱状阵列的形貌、相组成、禁带宽度及其表面特性进行了表征.结果显示,AgBr颗粒分布于ZnO纳米柱状阵列的顶端及顶端侧面,同时AgBr颗粒之间相互接触而形成网状结构.通过紫外光光照预处理,AgBr表面出现细小颗粒,形成Ag/AgBr/ZnO纳米复合结构.可见光光催化降解甲基橙结果表明,在相同工艺条件下所制AgBr/ZnO的可见光光催化活性明显优于AgI/ZnO,且与浸渍浓度及时间有关.由于ZnO纳米柱状阵列的比表面积大,AgBr的可见光响应特性以及Ag/AgBr纳米结构的表面等离子效应,经过紫外光光照预处理形成的Ag/AgBr/ZnO纳米复合结构表现出最好的可见光光催化活性.     

F‐doped Ag/AgBr with enhanced visible‐light photocatalytic activity and mechanism

Novel F‐doped Ag/AgBr photocatalysts containing various amounts of F^? were synthesized by an ion exchange method. The photocatalysts were characterized using X‐ray diffraction (XRD), scanning and transmission electron microscopies, X‐ray photoelectron, ultraviolet–visible absorption and photoluminescence spectroscopies and electron spin resonance (ESR). Powder XRD revealed that F^? was inserted into the crystal lattices of AgBr and partially replaced Br^?, resulting in the contraction of the AgBr lattices. Methyl orange photodegradation experiments showed that the photocatalytic activity of F‐doped Ag/AgBr was significantly dependent on the amount of F^?. Ag/AgBr doped with 0.02 M F^? achieved the highest activity of 91% after 8 min. ESR showed the main active species in methyl orange degradation was ^?OH. The main enhancement mechanism is that F^? inhibits the recombination of electron–hole pairs.     

Synthesis and characterization nanocomposite of polyacrylamide‐rGO‐Ag‐PEDOT/PSS hydrogels by photo polymerization method

We present a novel approach to the fabrication of advanced polymeric nanocomposite hydrogels from polyacrylamide (PAAm) by incorporation of graphene‐silver‐polyethylenedioxythiophene‐polystyrene sulfonate (rGO‐Ag‐PEDOT/PSS) by photopolymerization method. Infrared spectroscopy was employed to characterize the structure of the hydrogels. The internal network structure of nanocomposite hydrogels was investigated by scanning electron microscope. Swelling, deswelling, and mechanical properties of the hydrogels were investigated. The compressive strength of nanocomposite hydrogels reaches maximum of 1.71 MPa when the ratio of rGO‐Ag‐PEDOT/PSS to PAAm was 0.3 wt%, which is 1.57 times higher than that of PAAm hydrogels (1.09 MPa). The electrical conductivity of the PAAm‐rGO‐Ag‐PEDOT/PSS hydrogel was found to be 3.91 × 10^?5 S cm^?1. Copyright © 2015 John Wiley & Sons, Ltd.     

Excellent photocatalytic reduction of nitroarenes to aminoarenes by BiVO4 nanoparticles grafted on reduced graphene oxide (rGO/BiVO4)

A novel heterogeneous composite material based on reduced graphene oxide (rGO) and bismuth vanadate (BiVO₄) was prepared and characterized by various techniques such as powder XRD, HRTEM, EADX, UV–Vis‐DRS, FT‐IR, Raman, BET and XPS analyses. The characterization results reveal that the rGO well decorated by BiVO₄. The electrochemical impedance spectroscopy (EIS) shows the increasing of charge transfer of rGO/BiVO₄ in presence of light irradiation. In this research, the pure BiVO₄ and rGO/BiVO₄ composite have been explored for photocatalytic reduction of nitroarenes. Among the prepared nanocomposites, rGO loaded with 10% BiVO₄ catalyst (noted as rGO/BiVO₄–10%) shows the best performance for the photo‐reduction of various nitroaromatic molecules to their corresponding amine compounds under visible‐light irradiation at room temperature. The catalyst exhibited in particular excellent photocatalytic activity for the conversion of 1,4‐dinitrobenzene to 4‐nitroanilline (100% conversion) in 20 min, 4‐chloronitrobenzene to 4‐chloroaniline and 2‐nitrophenol to 2‐aminophenol (100% conversion) in only 30 min. In addition, the conversion of 4‐bromonitrobenzene, 4‐iodonitrobenzene to their corresponding amine compounds (100% conversion) was achieved in 60 min. The catalyst was recovered for several times and reused without decreasing of its efficiency.     

Sensitive and Selective Electrochemical Analysis of Methyl‐parathion (MPT) and 4‐Nitrophenol (PNP) by a New Type p‐NiTSPc/p‐PPD Coated Carbon Fiber Microelectrode (CFME)

A novel modified carbon fiber microelectrode (CFME) was obtained by combination of tetrasulfonated nickel phtalocyanine (p‐NiTSPc) electroformed film associated to para‐phenylenediamine (p‐PPD) electropolymerized outer‐coating. The modified CFMEs where denoted C/p‐NiTSPc and C/p‐NiTSPc/p‐PPD, respectively. These electrodes are dedicated to the organophosphates compounds (OPs) methyl‐parathion (MPT) and para‐nitrophenol (PNP). Our contribution shows that both OPs can be determined simultaneously on the unmodified and modified C/p‐NiTSPc CFMEs. A clear electrocatalytic activity towards both MPT and PNP redox process was observed, for the first time, in presence of p‐NiTSPc. The obtained sensitivity for the C/p‐NiTSPc CFME was 80 nA L mg^?1 in the concentration range 0.01 to 10 mg/L with a detection limit of 40 μg/L. Also the combination of p‐NiTSPc and p‐PPD electrodeposited films show, for the first time, the possibility to discriminate on the C/p‐NiTSPc/p‐PPD CFME between MPT and PNP. Stability experiments were also conducted for 3 weeks in acetate buffer showing a good reproductibility of the sensitivity to PNP vs. time in presence of MPT with a little loss of sensitivity (5%) after 3 weeks.