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In this study, glutaraldehyde cross-linked chitosan support, as well as the catalysts obtained after loading Ag metal (Ag/Chitosan), were synthesised and applied for adsorption and reduction of phenol red dye in an aqueous solution. The Ag/chitosan catalysts were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis techniques. The catalytic reduction and adsorption performance of phenol red dye with Ag/chitosan and cross-linked chitosan, respectively, was performed at ambient reaction conditions. The reduction of dye was carried out using sodium borohydride (NaBH4) as the reducing agent, while the progress of adsorption and reduction study was monitored with ultraviolet-visible (UV-vis) spectrophotometry technique. The reduction of the phenol red dye varied with the amount of catalyst, the concentration of NaBH4, Ag metal loading, reaction temperature, phenol red dye concentration and initial pH of the dye solution. The dye solution with a nearly-neutral pH (6.4) allowed efficient adsorption of the dye, while acidic (pH = 4) and alkaline (pH = 8, 11, 13.8) solutions showed incomplete or no adsorption of dye. The reusability of the Ag/chitosan catalyst was applied for the complete reduction of the dye, where no significant loss of catalytic activity was observed. Hence, the applicability of cross-linked chitosan and Ag/catalyst was thus proven for both adsorption and reduction of phenol red dye in an aqueous solution and can be applied for industrial wastewater treatment.

High nitrate levels in groundwater must be reduced as per legal guidelines to ensure that water is suitable for human consumption. Techniques such as ion exchange, reverse osmosis, electrodialysis, and biological denitrification have proven to be successful on an industrial scale. Unfortunately, the catalytic reduction of nitrate to nitrogen with hydrogen has not been commercialized despite 30 years of research. The main problem is that the reduction produces nitrite and ammonium byproducts above the permitted legal levels, making water unsuitable for human consumption. This research postulates that thermodynamics, rather than kinetics, limits achieving the desired selectivity. We use a thermodynamic approach, known as the attainable region, to compare the theoretical analysis to the experimental data. The graphical results show why it is so difficult to avoid the production of byproducts. M.J. Fernandez-Torres acknowledges financial support to the Spanish “Ministerio de Ciencia e Innovación” under project PID2021-124139NB-C21 and thanks the visiting researcher program, at the University of South Africa, for financial support.

Up to now, facile and pollution-free routes for catalyst preparation are in high demand. In this study, a green and cost-effective strategy was successfully developed to construct platinum/graphene aerogel (Pt/GA) nanocomposites by the co-reduction of graphene oxides (GO) and chloroplatinic acid (H2PtCl6·6H2O) with the assists of γ-ray irradiation in the absence of any other reductants. Characterization studies indicated that the energy of γ-ray irradiation and the hole scavenger isopropanol (IPA) played a vital role in forming small Pt nanoparticles with uniform size of ∼3 nm on the surface of graphene aerogel (GA). Furthermore, Pt/GA synthesized with a mass ratio of 2:1 (Pt/GA-2) exhibited a lowest activation energy value and outstanding catalytic properties for the reduction of 4-nitrophenol (4-NP). The excellent catalytic and cycling performance suggest that Pt/GA-2 catalyst has a promising prospect for the reduction of nitroaromatic compounds in wastewater treatment and other industrial applications.

In this work, we have developed novel beads based on carboxymethyl cellulose (CMC) encapsulated copper oxide-titanium oxide (CuO-TiO2) nanocomposite (CMC/CuO-TiO2) via Al+3 cross-linking agent. The developed CMC/CuO-TiO2 beads were applied as a promising catalyst for the catalytic reduction of organic and inorganic contaminants; nitrophenols (NP), methyl orange (MO), eosin yellow (EY) and potassium hexacyanoferrate (K3[Fe(CN)6]) in the presence of reducing agent (NaBH4). CMC/CuO-TiO2 nanocatalyst beads exhibited excellent catalytic activity in the reduction of all selected pollutants (4-NP, 2-NP, 2,6-DNP, MO, EY and K3[Fe(CN)6]). Further, the catalytic activity of beads was optimized toward 4-nitrophenol with varying its concentrations and testing different concentrations of NaBH4. Beads stability, reusability, and loss in catalytic activity were investigated using the recyclability method, in which the CMC/CuO-TiO2 nanocomposite beads were tested several times for the reduction of 4-NP. As a result, the designed CMC/CuO-TiO2 nanocomposite beads are strong, stable, and their catalytic activity has been proven.

Nitrate (NO3–) pollution of water bodies is a serious environmental problem worldwide. One of the major concerns about NO3– contamination is the lack of cost-effective solutions for its removal from potential drinking water resources. Current technologies, such as ion exchange, reverse osmosis and electrodialysis, produce a reject with high NO3– concentration. Catalytic reduction is an emerging technology, capable of transforming NO3– into harmless N2. A critical issue is to achieve almost complete selectivity to this last species so that the final concentrations of NO2– and NH4+ can fit the stringent allowed limits. Numerous studies have been carried out evaluating the activity and N2 selectivity of bimetallic catalysts. Catalyst deactivation by surface fouling, irreversible oxidation of the metal promoter, metal leaching and aggregation of metallic particles remain a major challenge for full-scale implementation of catalytic nitrate reduction. Therefore, it is necessary to develop highly stable catalyst and/or effective solutions for catalyst regeneration. The existing literature on this respect is reviewed hereby., The authors wish to thank for the financial support the Spanish MINECO (PID2019-108445RB-I00) and Comunidad de Madrid (BIOTRES-CM, S2018/EMT-4344). I. Sanchis also thanks Comunidad de Madrid for award of a research grant (PEJD-265 2017-PRE/AMB-4616)

In the present study, a biopolymer nanocomposite hydrogel based on gelatin and tin-doped gadolinium oxide (Sn-Gd2O3@GH) was prepared for the efficient reduction of water pollutants. The method of Sn-Gd2O3@GH preparation consisted of two steps. A Sn-Gd2O3 nanomaterial was synthesized by a hydrothermal method and mixed with a hot aqueous solution (T > 60 °C) of gelatin polymer, followed by cross-linking. Due to the presence of abundant functional groups on the skeleton of gelatin, such as carboxylic acid (–COOH) and hydroxyl (–OH), it was easily cross-linked with formaldehyde. The structure, morphology, and composition of Sn-Gd2O3@GH were further characterized by the FESEM, XRD, EDX, and FTIR techniques. The FESEM images located the distribution of the Sn-Gd2O3 nanomaterial in a GH matrix of 30.06 nm. The XRD patterns confirmed the cubic crystalline structure of Gd2O3 in a nanocomposite hydrogel, while EDS elucidated the elemental composition of pure Sn-Gd2O3 powder and cross-linked the Sn-Gd2O3@GH samples. The synthesized Sn-Gd2O3@GH nanocomposite was used for the removal of different azo dyes and nitrophenols (NPs). It exhibited an efficient catalytic reduction of Congo red (CR) with a reaction rate of 9.15 × 10−1 min−1 with a strong NaBH4-reducing agent. Moreover, the Sn-Gd2O3@GH could be easily recovered by discharging the reduced (colourless) dye, and it could be reused for a fresh cycle.

Nanomaterial-based catalytic conversion of hazardous organic pollutants into benign substances is one of the green methods employed for wastewater treatment. This study demonstrates the fabrication of (rGO-ZnO)/CuO nanocomposites (NCs) via a microwave (MW)-assisted method for (photo)catalytic application. The crystal structure, optical, morphological, and electrochemical characteristics were examined using X-ray diffraction (XRD), spectroscopic, microscopic, and electrochemical techniques. The analysis indicated that rod-like (rGO-ZnO)/CuO NCs having a nanoscale diameter with enhanced light absorption and well-matched band positions between rGO-ZnO and CuO were formed. Furthermore, the catalytic reduction of 4-nitrophenol (4-NP) and photocatalytic degradation of methylene blue (MB) tests showed remarkable results with rate constants of 0.468 min−1 for 4-NP reduction within 8 min and 0.02213 min−1 for MB degradation within 105 min. Thus, the artful decoration of ZnO nanorods (NRs) with CuO into the (rGO-ZnO)/CuO NCs interface is an effective strategy for fabricating highly efficient photocatalysts.

Copper oxide-antimony oxide (Cu2O-Sb2O3) was prepared and entrapped inside Na-alginate hydrogel (Alg@Cu2O-Sb2O3). The developed Alg@Cu2O-Sb2O3 was used as catalytic reactor for the reduction of 4-nitrophenol (4-NP), 2-nitrophenol (2-NP), 2,6-dinitrophenol (2,6-DNP), methyl orange (MO), congo red (CR), acridine orange (AO), methylene blue (MB) and potassium ferricyanide (K3[Fe(CN)6]). Alg@Cu2O-Sb2O3 was found to be selective and more efficient for the reduction of 2-NP among all the pollutants. Therefore, 2-NP was selected for a detailed study to optimize various parameters, e.g., the catalyst amount, reducing agent concentration, 2-NP concentration and recyclability. Alg@Cu2O-Sb2O3 was found to be very stable and easily recyclable for the reduction of 2-NP. The Alg@Cu2O-Sb2O3 nanocatalyst reduced 2-NP in 1.0 min, having a rate constant of 3.8187 min−1.

Pelagic clay is an emerging marine resource with strong hydrophilicity, fine particles and a large specific surface area. In this work, a 1T-MoS2/pelagic clay composite was fabricated by hydrothermal synthesis. In the composite, 1T-MoS2 nanosheets are evenly dispersed on the surface of the clay minerals, significantly reducing the agglomeration of MoS2. Compared with pure 1T-MoS2, the 1T-MoS2 nanosheets generated on the surface of pelagic clay have significantly smaller lateral dimensions and thicknesses. Moreover, the specific surface area is much larger than that of the pure 1T-MoS2 nanosheets fabricated by the same method, indicating that the active sites of the MoS2 sheets are fully exposed. In addition, the composite exhibited excellent hydrophilicity, leading to a high dispersibility in aqueous solutions. In this work, the composite was used as a catalyst in the reduction of 4-nitrophenol (4-NP), and the conversion of 4-NP reached up to 96.7%. This result shows that the 1T-MoS2/pelagic clay composite is a promising catalyst in a variety of reactions.

The molecular functionalization of two-dimensional MoS2 is of practical relevance with a view to, for example, facilitating its liquid-phase processing or enhancing its performance in target applications. While derivatization of metallic 1T-phase MoS2 nanosheets has been relatively well studied, progress involving their thermodynamically stable, 2H-phase counterpart has been more limited due to the lower chemical reactivity of the latter. Here, we report a simple electrolytic strategy to functionalize 2H-phase MoS2 nanosheets with molecular groups derived from organoiodides. Upon cathodic treatment of a pre-expanded MoS2 crystal in an electrolyte containing the organoiodide, water-dispersible nanosheets derivatized with acetic acid or aniline moieties (∼0.10 molecular groups inserted per surface sulfur atom) were obtained. Analysis of the functionalization process indicated it to be enabled by the external supply of electrons from the cathodic potential, although they could also be sourced from a proper reducing agent, as well as by the presence of intrinsic defects in the 2H-phase MoS2 lattice (e.g., sulfur vacancies), where the molecular groups can bind. The acetic acid-functionalized nanosheets were tested as a non-noble metal-based catalyst for nitroarene and organic dye reduction, which is of practical utility in environmental remediation and chemical synthesis, and exhibited a markedly enhanced activity, surpassing that of other (1T- or 2H-phase) MoS2 materials and most non-noble metal catalysts previously reported for this application. The reduction kinetics (reaction order) was seen to correlate with the net electric charge of the nitroarene/dye molecules, which was ascribed to the distinct abilities of the latter to diffuse to the catalyst surface. The functionalized MoS2 catalyst also worked efficiently at realistic (i.e., high) reactant concentrations, as well as with binary and ternary mixtures of the reactants, and could be immobilized on a polymeric scaffold to expedite its manipulation and reuse.

The green chemistry method is the preferred approach for synthesizing metal and metal oxide nanoparticles because of its low toxicity, environmental friendliness, feasibility, and safety to human health compared with other chemical or physical methods. The present work reports the phytogenic synthesis of palladium nanoparticles (PdNPs) using an aqueous extract of Matricaria recutita (Chamomile). The phytochemical-mediated synthesis of PdNPs is an economical and eco-friendly approach without using toxic elements as reducing and capping or stabilizing agents. The UV-visible spectroscopic characterization was initially used to confirm the preparation of PdNPs using an aqueous extract of M. recutita flowers as a bioreductant for the reduction of Pd2+ to Pd0 without using any extra capping and reducing agents. The appearance of surface plasmon resonance (SPR) peak at 286 nm confirmed the formation of M. recutita extract-based PdNPs. Furthermore, the PdNPs were characterized by TEM, SEM, EDX, XRD, XPS, and FTIR to confirm their proper synthesis. The thermogravimetric analysis (TGA) was implemented to interpret the decomposition pattern and thermal stability of as-synthesized PdNPs. The biosynthesized PdNPs were further applied as a nanocatalyst in degradation of an azo dye Congo red (CR) in the presence of NaBH4. The catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) was also investigated in the presence of NaBH4. All the catalytic reactions were performed in water, and no significant loss in catalytic activity was observed after recovery and reusability of the biosynthesized PdNPs.

In the catalytic reduction of various environment pollutants, cobalt-doped tin oxide, i.e., Co-SnO2 intercalated gelatin (GL) hydrogel nanocomposite was prepared via direct mixing of Co-SnO2 doped with GL. Then, it was crosslinked internally using formaldehyde within a viscous solution of gelatin polymer, which led to the formation of GL/Co-SnO2 hydrogel nanocomposite. GL/Co-SnO2 hydrogel nanocomposite was fully characterized by using field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (XRD), and attenuated total reflection–Fourier transform infrared spectroscopy (ATR-FTIR). The FESEM images indicate that the Co-SnO2 composite has a spherical structure on the GL matrix while EDX elucidates the elemental composition of each atom in the crosslinked GL/Co-SnO2 hydrogel nanocomposite. The GL/Co-SnO2 nanocomposite was checked for the reduction of various pollutants, including 2-nitro-phenol (2-NP), 2,6-dinitro-phenol (2,6-DNP), 4-nitro-phenol (4-NP), Congo red (CR), and methyl orange (MO) dyes with a strong sodium borohydride (NaBH4) reducing agent. The GL/Co-SnO2 nanocomposite synergistically reduced the MO in the presence of the reducing agent with greater reduction rate of 1.036 min−1 compared to other dyes. The reduction condition was optimized by changing various parameters, such as the catalyst amount, dye concentration, and the NaBH4 amount. Moreover, the GL/Co-SnO2 nanocomposite catalyst can be easily recovered, is recyclable, and revealed minimal loss of nanomaterials.

In this work, novel urchin-like Fe3O4@polydopamine (PDA)-Ag hollow microspheres have been prepared via a facile synthesis method by in situ reduction and growth of Ag nanoparticles on mussel-inspired PDA layers coated on Fe3O4 hollow cores. The catalytic reduction efficiency and adsorption performance of the as-prepared urchin-like Fe3O4@polydopamine (PDA)-Ag hollow microspheres for model organic dyes (i.e., methylene blue and rhodamine B) under varying pH condition have been systematically investigated, which are demonstrated to be significantly enhanced as compared to that of spherical (relatively smooth) solid Fe3O4@PDA-Ag microspheres. The as-prepared urchin-like Fe3O4@PDA-Ag hollow microspheres show high reusability, easy separability, and fast regeneration ability, with no obvious drop in the catalytic and adsorption efficiency after cyclic reuse. The versatile PDA coatings on the urchin-like microspheres allow further surface functionalization for development of multifunctional catalyst and adsorbent materials. This work provides a very useful and facile methodology for synthesizing and tuning the urchin-like morphology of Fe3O4@PDA-Ag microspheres, with great potential applications in catalysis and wastewater treatment.

Silver based-nanoparticles (Ag NPs) have been recently shown to be promising catalysts for the degradation of toxic organic dyes in wastewater despite the challenges of recycling. In this paper, self-supported Ag NPs were obtained at the surface of AgTi2(PO4)3 NASICON-type phosphates through in situ chemical reduction by sodium borohydride (NaBH4). The adopted approach enables the self-growth of zero-valent Ag NPs on the NASICON matrix, and concomitantly leads to the formation of Ag1−xNaxTi2(PO4)3. The crystalline structure, morphology and phase composition of the Ag nanocomposite has been characterized by several techniques. The catalytic performance of the as-fabricated Ag NPs/Ag1−xNaxTi2(PO4)3 has then been verified in the reduction of methylene blue (MB) and methyl orange (MO) dyes, chosen as target pollutants. Our findings reveal a good catalytic activity with an efficiency and time of reaction of respectively ∼ 96.30% and 320 s in the case of the MB reduction and ∼ 94.60% and 270 s in the case of the MOreduction. Additionally, the initial AgTi2(PO4)3 phase can be regenerated via simple calcination route and recycled up to five times with no appreciable loss of catalytic activity.

In the present research, a rapid, simple and efficient green method is used for the incorporation of silver nanoparticles (AgNPs) into poly(ethylene glycol) methacrylate (PEGMA) to create biocatalysts with excellent properties for pharmaceutical purpose. In the first phase, Caralluma tuberculata capped AgNPs (Ca-AgNPs) were prepared using green synthetic approach and in the second phase Caralluma tuberculata capped AgNPs were hybridized with poly(ethylene glycol) methacrylate to form PEGMA-AgNPs. Both the virgin (naked or uncapped) and polymer-capped materials were characterized spectroscopically and their results were compared. Fourier transform infrared spectroscopy showed no new peak after the capping procedure, showing that only physical interactions takes place during capping. After PEGMA capping, the spectra of the AgNPs red shifted (from 450 nm to 520 nm) and the overall particle size of AgNPs increased. Catalytic activity of the nanoparticles and hybrid system were tested by choosing the catalytic reduction of 4-nitrophenol (4-NP) as a model reaction. Both synthesized NPs and polymer capped NPs exhibits catalytic activity for the reduction of 4-NP to 4-aminophenol. The polymer hybrid exhibits remarkable antiproliferative, antioxidant, cytotoxic, antidiabetic and antileishmanial activities.

An efficient sintering process was proposed based on the autocatalytic denitrification of the sintered ore. The catalytic denitrification of sintered ore, the effect of double-layer ignition sintering process on the emission reduction in nitrogen oxides, and the impact on the quality of sintered ore were studied. The results showed that the catalyzed reduction of NO with sinter ore as a catalyst has a significant effect; when the airspeed reaches 3000 h−1, the temperature is 500 °C, and the conversion rate of NO can reach 99.58%. The sinter yield of double-layer ignition sintering is increased, solid fuel consumption is slightly reduced, falling strength is slightly increased, and drum strength is slightly decreased. Under the conditions of layer height proportion of 320/400 mm (lower/upper) and ignition time interval of 10 min, the yield, drum strength, shatter strength, and solid fuel consumption reached 61.60%, 54.82%, 46.75%, and 69.55%, respectively. NOx concentration under the 16% baseline oxygen content (c(NOx)’) in the flue gas of double-layer ignition sintering is reduced to a certain extent, and the generation time of NOx is greatly shortened. The double-layer ignition sintering process can reduce the emission of nitrogen oxides in the sintering process under the condition of guaranteeing the quality of sinter, which has great economic and environmental benefits.

Porous hypercross-linked polymers based on perbenzylated monosugars (SugPOP-1–3) have been synthesized by Friedel–Crafts reaction using formaldehyde dimethyl acetal as an external cross-linker. Three perbenzylated monosugars with similar chemical structure were used as monomers in order to tune the porosity. These obtained polymers exhibit microporous and mesoporous features. The highest Brunauer–Emmett–Teller specific surface area for the resulting polymers was found to be 1220 m2 g−1, and the related carbon dioxide storage capacity was found to be 14.4 wt % at 1.0 bar and 273 K. As the prepared porous polymer SugPOP-1 is based on hemiacetal glucose, Ag nanoparticles (AgNPs) can be successfully incorporated into the polymer by an in situ chemical reduction of freshly prepared Tollens’ reagent. The obtained AgNPs/SugPOP-1 composite demonstrates good catalytic activity in the reduction of 4-nitrophenol (4-NP) with an activity factor ka = 51.4 s−1 g−1, which is higher than some reported AgNP-containing composite materials.

Two-dimensional 2H-phase MoS2 nanosheets can be used as a non-noble metal-based catalyst for nitroarene and organic dye reduction, thus being of potential utility towards the treatment of industrial wastewater. However, their activity is severely limited by the inertness of their pristine basal surface. We report here a simple approach for the catalytic activation of solvent-dispersed MoS2 nanosheets based on the introduction of sulfur vacancies by hydrazine treatment. MoS2 nanosheets boasting markedly improved catalytic activities in the reduction of 4-nitrophenol, 4-nitroaniline, methyl orange and methylene blue by NaBH4 could be obtained, outperforming many prior non-noble metal-based catalysts developed for such reactions. Notably, the improvement in catalytic activity was not compromised by the use of a proper dispersant to colloidally stabilize the activated nanosheets in the aqueous reaction medium. Substrate-supported catalysts could be prepared by immobilizing the nanosheets on melamine foam, facilitating their handling and reutilization. The chemical processes taking place between the investigated reagents and the MoS2 catalyst were also discussed and rationalized, based on which a mechanism for nitroarene/dye reduction mediated by the sulfur vacancies was proposed., Funding by the Spanish Ministerio de Economía y Competitividad (MINECO) and the European Regional Development Fund (ERDF) through project MAT2015-69844-R, the Spanish Ministerio de Ciencia, Innovación y Universidades (MICINN), Agencia Estatal de Investigación (AEI) and the ERDF through project RTI2018-100832-B-I00, and Plan de Ciencia, Tecnología e Innovación (PCTI) 2013-2017 del Principado de Asturias and the ERDF (project IDI/2018/000233) is gratefully acknowledged. S.G.-D. is grateful to the Spanish MINECO for his pre-doctoral contract (BES/2016 077830). A.A. acknowledges the financial support from Spanish MINECO (MAT2016-78155-C2-1-R) and the Government of the Principality of Asturias (GRUPIN-IDI/2018/170).

Au@Cu2O core-shell nanocomposites (NCs) were synthesized by reducing copper nitrate on Au colloids with hydrazine. The thickness of the Cu2O shells could be varied by adjusting the molar ratios of Au: Cu. The results showed that the thickness of Cu2O shells played a crucial role in the catalytic activity of Au@Cu2O NCs under dark condition. The Au@Cu2O-Ag ternary NCs were further prepared by a simple galvanic replacement reaction method. Moreover, the surface features were revealed by TEM, XRD, XPS, and UV–Vis techniques. Compared with Au@Cu2O NCs, the ternary Au@Cu2O-Ag NCs had an excellent catalytic performance. The degradation of methyl orange (MO) catalyzed by Au@Cu2O-Ag NCs was achieved within 4 min. The mechanism study proved that the synergistic effects of Au@Cu2O-Ag NCs and sodium borohydride facilitated the degradation of MO. Hence, the designed Au@Cu2O-Ag NCs with high catalytic efficiency and good stability are expected to be the ideal environmental nanocatalysts for the degradation of dye pollutants in wastewater.

The green chemistry method is the preferred approach for synthesizing metal and metal oxide nanoparticles because of its low toxicity, environmental friendliness, feasibility, and safety to human health compared with other chemical or physical methods. The present work reports the phytogenic synthesis of palladium nanoparticles (PdNPs) using an aqueous extract of Matricaria recutita (Chamomile). The phytochemical-mediated synthesis of PdNPs is an economical and eco-friendly approach without using toxic elements as reducing and capping or stabilizing agents. The UV-visible spectroscopic characterization was initially used to confirm the preparation of PdNPs using an aqueous extract of M. recutita flowers as a bioreductant for the reduction of Pd2+ to Pd0 without using any extra capping and reducing agents. The appearance of surface plasmon resonance (SPR) peak at 286 nm confirmed the formation of M. recutita extract-based PdNPs. Furthermore, the PdNPs were characterized by TEM, SEM, EDX, XRD, XPS, and FTIR to confirm their proper synthesis. The thermogravimetric analysis (TGA) was implemented to interpret the decomposition pattern and thermal stability of as-synthesized PdNPs. The biosynthesized PdNPs were further applied as a nanocatalyst in degradation of an azo dye Congo red (CR) in the presence of NaBH4. The catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) was also investigated in the presence of NaBH4. All the catalytic reactions were performed in water, and no significant loss in catalytic activity was observed after recovery and reusability of the biosynthesized PdNPs.

The introduction of toxic chemicals into the environment can result in water pollution leading to the degradation of biodiversity as well as human health. This study presents a new approach of using metal oxides (Al2O3 and SiO2) modified with a plasmonic metal (silver, Ag) nanoparticles (NPs)-based nanofluid (NF) formulation for environmental remediation purposes. Firstly, we prepared the Al2O3 and SiO2 NFs of different concentrations (0.2 to 2.0 weight %) by ultrasonic-assisted dispersion of Al2O3 and SiO2 NPs with water as the base fluid. The thermo-physical (viscosity, activation energy, and thermal conductivity), electrical (AC conductivity and dielectric constant) and physical (ultrasonic velocity, density, refractive index) and stability characteristics were comparatively evaluated. The Al2O3 and SiO2 NPs were then catalytically activated by loading silver NPs to obtain Al2O3/SiO2@Ag composite NPs. The catalytic reduction of 4-nitrophenol (4-NP) with Al2O3/SiO2@Ag based NFs was followed. The catalytic efficiency of Al2O3@Ag NF and SiO2@Ag NF, for the 4-NP catalysis, is compared. Based on the catalytic rate constant evaluation, the catalytic reduction efficiency for 4-NP is found to be superior for 2% weight Al2O3@Ag NF (92.9 × 10−3 s−1) as compared to the SiO2@Ag NF (29.3 × 10−3 s−1). Importantly, the enhanced catalytic efficiency of 2% weight Al2O3@Ag NF for 4-NP removal is much higher than other metal NPs based catalysts reported in the literature, signifying the importance of NF formulation-based catalysis.

Chemically exfoliated MoS2 (ce-MoS2) has emerged in recent years as an attractive two-dimensional material for use in relevant technological applications, but fully exploiting its potential and versatility will most probably require the deployment of appropriate chemical modification strategies. Here, we demonstrate that extensive covalent functionalization of ce-MoS2 nanosheets with acetic acid groups (∼0.4 groups grafted per MoS2 unit) based on the organoiodide chemistry brings a number of benefits in terms of their processability and functionality. Specifically, the acetic acid-functionalized nanosheets were furnished with long-term (>6 months) colloidal stability in aqueous medium at relatively high concentrations, exhibited a markedly improved temporal retention of catalytic activity toward the reduction of nitroarenes, and could be more effectively coupled with silver nanoparticles to form hybrid nanostructures. Furthermore, in vitro cell proliferation tests carried out with murine fibroblasts suggested that the chemical derivatization had a positive effect on the biocompatibility of ce-MoS2. A hydrothermal annealing procedure was also implemented to promote the structural conversion of the functionalized nanosheets from the 1T phase that was induced during the chemical exfoliation step to the original 2H phase of the starting bulk material, while retaining at the same time the aqueous colloidal stability afforded by the presence of the acetic acid groups. Overall, by highlighting the benefits of this type of chemical derivatization, the present work should contribute to strengthen the position of ce-MoS2 as a two-dimensional material of significant practical utility., Financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) and the European Regional Development Fund (FEDER) through project MAT2015-69844-R is gratefully acknowledged, as well as partial support of the ERDF/FEDER. Operative Program of the Región de Murcia 2007–2013. We also acknowledge partial funding by Plan de Ciencia, Tecnología e Innovación 2013-2017 del Principado de Asturias and FEDER through grant GRUPIN14-056.

In this study, LaMn1−xFexO3 (x = 0, 0.3, 0.5, 0.7, 1) and La0.8A0.2Fe0.7Mn0.3O3 (A = Sr, Cs, Ba, Ce) perovskite oxides were synthesized by sol–gel method and their activities were evaluated in catalytic reduction of NO by CO. Perovskite catalysts were characterized by XRD, BET, H2-TPR, XPS and SEM. Synthesized perovskites present a high activity for the catalytic reduction of NO by CO, LaMn0.3Fe0.7O3 Show the highest activity among LaMn1−xFexO3 perovskite catalysts (71 % CO conversion and 82 % NO conversion at 350 °C). The effect of partial substitution of Sr, Cs, Ba and Ce in A-site was also examined on the structure and catalytic activity of LaMn0.3Fe0.7O3 perovskite catalyst. La0.8Sr0.2Fe0.7Mn0.3O3 and La0.8Ce0.2Fe0.7Mn0.3O3 present the highest activities among La0.8A0.2Fe0.7Mn0.3O3 perovskites. The introduction of Sr2+ and Ce4+ in A-site of perovskite change the reducibility of B-site cations and Fe4+/Fe3+ and Mn4+/Mn3+ ratios, and increase Oads/Olatt ratio and these factors create structural defects in perovskite which lead to higher catalytic activities. Financial supports from the Iran National Science Foundation (INSF) are gratefully acknowledged.

International audience; The grafting of Au nanoparticles onto reduced graphite oxide sheets (GO) having attached chitosan chains was investigated through the use of glutaraldehyde and dithiooxamide as linkers. First, the functionalization of graphite oxide sheets by dithiooxamide was accomplished followed by the grafting of chitosan onto the activated graphite oxide sheets in the presence of glutaraldehyde. Finally, the corresponding material was doped with gold nanoparticles after a chemical reduction and their electrical properties were studied as a function of temperature. Moreover, it was found that this material exhibits a catalytic activity toward the reduction of nitrophenol.

The ground water (GW) is a real sample of water which contains nitrates (81 mg/L), carbonates and sulphates. 3 This sample was treated by catalytic reduction in a bubble column fixed-bed reactor. The reaction conditions 4 were room temperature and atmospheric pressure, and hydrogen was used as reducing agent. A comparison 5 between the catalytic activity of Pd,In/SiO2 and Pd,In/Al2O3 catalysts was performed, giving the latter the best 6 results regarding the nitrate conversion and the former the selectivity to nitrogen. Synthetic water containing 7 nitrates (SW) and the groundwater (GW) with high salinity (81 mg/L nitrates) and humic acid content were 8 treated in these conditions using HCl and CO2 as acidifiers. When the SW was acidified with CO2 at an H2 flow 9 (2.17 mL/min), more than 50% of conversion was obtained with an ammonia and nitrite concentrations of 0.44 10 and 0.92 ppm respectively. These results reached the level established by the WHO and the USEPA. However, 11 both Pd,In/SiO2 and Pd,In/Al2O3 catalysts showed evidence of some deactivation process. This deactivation was 12 higher in the GW sample, possibly due to the presence of Ca+2 and Mg+2 cations that precipitate on the active 13 sites, and/or the presence of humic acids. The characterization studies indicated that, after the reaction, the 14 composition of the metal phases was modified, specifically on their surface. As the catalyst activity is related to 15 surface ratio Pd/In, a relative increase in the concentration of Pd decreases the activity and causes changes in the 16 selectivity to N2. Some sintering of the metal particles was also observed to contribute to catalyst deactivation. 17 Nevertheless, promising results were obtained since a high water volume could be treated with a relatively low 18 amount of low metal loading catalysts. Fil: Marchesini, Fernanda Albana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Mendow, Gustavo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Picard, N. P.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Miranda Zoppas, Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Aghemo, Vanina Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Gutierrez, Laura Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Querini, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Miro, Eduardo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina

Metal–organic framework (MOF)-based derivatives are attracting increased interest in various research fields. In this study, nano-cellulose MOF-derived carbon-doped CuO/Fe3O4 nanocomposites were successfully synthesized via direct calcination of magnetic Cu-BTC MOF (HKUST-1)/Fe3O4/cellulose microfibril (CMF) composites in air. The morphology, structure, and porous properties of carbon-doped CuO/Fe3O4 nanocomposites were characterized using SEM, TEM, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The results show that the as-prepared nanocomposite catalyst is composed of Fe3O4, CuO, and carbon. Compared to the CuO/Fe3O4 catalyst from HKUST-1/Fe3O4 composite and CuO from HKUST-1, this carbon-doped CuO/Fe3O4 nanocomposite catalyst shows better catalytic efficiency in reduction reactions of 4-nitrophenol (4-NP), methylene blue (MB), and methyl orange (MO) in the presence of NaBH4. The enhanced catalytic performance of carbon-doped CuO/Fe3O4 is attributed to effects of carbon preventing the aggregation of CuO/Fe3O4 and providing high surface-to-volume ratio and chemical stability. Moreover, this nanocomposite catalyst is readily recoverable using an external magnet due to its superparamagnetic behavior. The recyclability/reuse of carbon-doped CuO/Fe3O4 was also investigated.

New catalysts based on Pd(0) nanoparticles (Pd NPs) on a bimodal porous silica of the UVM-7/polydopamine (PDA) support have been synthesized following two preparative strategies based on the sequential or joint incorporation of two components of the composite (Pd and PDA). We analyzed the role played by the PDA as &lsquo, interfacial glue&rsquo, between the silica scaffold and the Pd NPs. The catalysts were tested for the hydrogenation of 4-nitrophenol using (NEt4)BH4 as the hydrogenating agent. In addition to the palladium content, the characterization of the catalysts at the micro and nanoscale has highlighted the importance of different parameters, such as the size and dispersion of the Pd NPs, as well as their accessibility to the substrate (greater or lesser depending on their entrapment level in the PDA) on the catalytic efficiency. Staged sequential synthesis has led to better catalytic results. The most active Pd(0) centers seem to be Pd NPs of less than 1 nm on the PDA surface. The efficiency of the catalysts obtained is superior to that of similar materials without PDA. A comprehensive comparison has been made with other catalysts based on Pd NPs in a wide variety of supports. The TOF values achieved are among the best described in the literature.

Herein, a label-free colorimetric nanosensor for Hg(II) is developed utilizing the hindering effect of Hg(II) on the kinetic aspect of gold nanoparticle (AuNPs) growth on the surface of gold nanostars (AuNSs). H-AuNS probes are synthesized and modified by 2-[4-(2-hydroxyethel) piperazine-1-yl] ethanesulfonic acid (HEPES). After the formulation of the reagents and testing conditions are optimized, HEPES-capped AuNSs (H-AuNSs) demonstrates good selectivity and sensitivity towards Hg(II) determination. A H-AuNS probe, in the presence of HCl/Au(III)/H2O2, is capable of detecting a Hg(II) concentration range of 1.0 nM&ndash, 100 &micro, M, with a detection limit of 0.7 nM, at a signal-to-noise ratio of 3.0, and a visual detection limit of 10 nM with naked eyes. For practicality, the H-AuNS probe is evaluated by measuring Hg(II) in the environmental water matrices (lake water and seawater) by a standard addition and recovery study. The detection limits for environmental samples are found to be higher than the lab samples, but they are still within the maximum allowable Hg concentration in drinking water (10 nM) set by the US Environmental Protection Agency (EPA). To create a unique nanosensor, the competitive interaction between Hg(II) and Pt(IV) toward the H-AuNSs probe is developed into a logic gate, improving the specificity in the detection of Hg(II) ions in water samples.

WOS: 000438662500029, PubMed: 29660458, Polysaccharides are excellent support materials for catalytic systems due to their superior metal binding capacity, high mechanical strength, and green nature. Among the polysaccharides, agar can be considered a good support material for catalytic reactions from the point of its low cost, easy availability, high thermal durability, and biodegradability. In this study, agar-supported palladium catalyst (AG-Pd) was designed for the first time, and then its catalytic performance was tested towards (i) Suzuki-Miyaura coupling reactions and (ii) catalytic reduction of o-nitroaniline to o-phenylenediamine under mild reaction conditions. Additionally, the reproducibility of the designed AG-Pd catalyst was investigated in both catalytic reactions, and the tests showed that the catalyst could be reused many times. AG-Pd catalyst displayed excellent selectivity and efficiency in Suzuki-Miyaura coupling reactions in only 6 min under solvent-free media. In addition, AG-Pd catalyst provided good catalytic reduction by completely reducing o-nitroaniline in 90 s at room temperature. These findings reveal that agar is a good support material, and it can be used for different catalytic systems as a support. (C) 2018 Elsevier B.V. All rights reserved., Aksaray University Scientific Research Projects Coordination [2017-047], The authors would like to thank Aksaray University Scientific Research Projects Coordination for their financial support (Project number: 2017-047).

Raising health and environmental concerns over the nanoparticles synthesized from hazardous chemicals have urged researchers to focus on safer, environmentally friendlier and cheaper alternatives as well as prompted the development of green synthesis. Apart from many advantages, green synthesis is often not selective enough (among other issues) to create shape-specific nanoparticle structures. Herein, we have used a biopolymer conjugate and Pd and Pt precursors to prepare sustainable bimetallic nanoparticles with various morphology types. The nanoparticles were synthesized by a novel green approach using a bio-conjugate of chitosan and polyhydroxybutyrate (Cs-PHB). The bio-conjugate plays the simultaneous roles of a reducing and a capping agent, which was confirmed by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and energy dispersive X-ray spectrometry (EDS) analysis, proving the presence of a Cs-PHB layer on the surface of the prepared nanoparticles. The EDS profile also revealed the elemental structure of these nanoparticles and confirmed the formation of a Pd/Pt alloy. TEM morphological analysis showed the formation of star-like, octahedron or decahedron Pd/Pt nanoparticles, depending on the synthesis conditions. The bimetallic Pd/Pt nanoparticles synthesized with various Pd/Pt molar ratios were successfully applied for the catalytic reduction of 4-nitrophenol to 4-aminophenol by borohydride. The calculated &kappa, c values (ratio of kapp to the concentration of the catalyst) revealed that the decahedron nanoparticles (size of 15 &plusmn, 4 nm), synthesized at the molar ratio of 2:1 (Pd/Pt), temperature of 130 &deg, C, 10 g/L of Cs-PHB conjugate and time of 30 min, exhibited excellent catalytic activity compared to other bimetallic nanoparticles reported in the literature.

*Yılmaz Baran, Nuray ( Aksaray, Yazar ) *Baran, Talat ( Aksaray, Yazar ), Palladium nanoparticles (Pd NPs) were decorated on Schiff base-modified boehmite (Sch-boehmite) particles via a simple method without deploying any additional reducing agents and their structure was confirmed by different characterization methods. The ensuing Pd NPs@Sch-boehmite was evaluated as a retrievable catalyst for multiple cycles in Suzuki cross-coupling reactions with extensive substrate tolerance to produce biaryls in high yields within 6 min, and the reduction of 2-nitroaniline (2-NA) and 4-nitrophenol (4-NP) at room temperature in 3e4 min, respectively. Moreover, Pd NPs@Sch-boehmite catalyst could be conveniently recovered and reused multiple times.

WOS: 000349277700020, A novel highly efficient and recyclable catalyst based on Fe@Ag bimetallic nanoParticles involved parninothiophenol (ATP) functionalized calcium alginate (Fe@Ag-ATP-CA) beads was prepared and characterized by transmission electron microscope (TEM), and x-ray photoelectron spectroscopy (XPS). The catalytic properties of 4-nitrophenol (4-NP) and 2-nitrophenol (2-NP) were performed using Fe@Ag-ATP-CA catalyst synthesized in the presence of sodium borohydride (NaBH4). The effects of various variables such as the catalyst dosage, the concentration of sodium borohydride, and temperature were also investigated. The rates of catalytic reduction of 4-NP and 2-NP compounds have been found as the sequence: 4-NP > 2-NP. The kinetic models and the thermodynamic parameters were studied to show the reduction mechanisms. The Fe@Ag-ATP-CA catalyst has highly efficient recyclability and excellent catalytic activity. (C) 2013 Elsevier B.V. All rights reserved.

WOS: 000412681900013 An effective method for the fabrication of well designed nanocomposite for the catalytic reduction of 2,4,6-trinitrotoluene (TNT) was developed. Here, cubic palladium (Pd) nanoparticles were utilized for enhancing the interface properties, attachment quality, catalytic yield and stability after the catalysis reactions. Ligand controlled facet growth by the Br- anions during thermal decomposition of the palladium-precursor resulted with cubic shaped average similar to 13nm palladium nanocubes (Pd NC). The anisotropic Pd NC were utilized to decorate the surface of the zinc oxide (ZnO) nanolayers deposited by atomic layer deposition (ALD) technique on the electrospun polyacrylonitrile (PAN) nanofibers. Due to the polymeric nature of the electrospun PAN nanofibers, Pd NC decorated nanoweb is highly flexible and has a high surface area. For the sustainable Pd NC decoration on the ZnO surfaces coated on PAN nanofibers, anchor points were formed by the functional thiol groups which can facilitate the Pd NC attachment and stability on the ZnO surface. The -OH and alkyl thiol groups obtained via sol-gel reactions positioned on the ZnO layer providing a better interface between ZnO and Pd NC which cannot be obtained by pristine PAN nanofibers. Additionally, due to the increased surface interaction, geometrical positioning on fibers for a better intermediate complex formation and stability via soft-soft interaction, Pd NC decorated flexible polymeric electrospun nanoweb provided enhanced catalytic reduction of TNT in aqueous medium. Turkish Academy of Sciences-Outstanding Young Scientists Award Program (TUBA-GEBIP); TUBITAK BIDEB Fellowships for 2232-Post Doctoral programme [115C095] Prof. Arslan acknowledges TUBITAK BIDEB Fellowships for 2232-Post Doctoral programme (project no. 115C095) for financial support. T. U acknowledges partial support of The Turkish Academy of Sciences-Outstanding Young Scientists Award Program (TUBA-GEBIP). The authors acknowledge Dr. F. Topuz for the synthesis of Pd NC and thank to M. Guler for TEM investigations.

Fabrication and decoration of flexible Nylon 6,6 polymeric nanofibrous mats for production of multifunctional electrospun material was accomplished via visible light-emitting surface-protected silicon quantum dots (Si QD), ZnO nanoparticles (ZnO NP) and Pd nanocubes (Pd NC). UV-range light was utilized for Si QD production and, after hydrolysis/condensation together with nucleation and growth reactions, amine-modified, fluorescent Si QD were obtained. Additionally, available molecular groups on the Si QD coated onto the polymeric nanofibrous mats provided further attachment of metal oxide and metal NP for various catalytic purposes. Analytical investigations showed that visible-light emission could be maintained on the Nylon 6,6 mats for trinitrotoluene (TNT) sensing. Also, due to consecutive NP decoration, multifunctional, polymeric, flexible nanofibrous mats were obtained. Experiments revealed that fabricated multifunctional mats could reduce molecules such as paranitrophenol effectively or decompose waste dyes such as methylene blue via photocatalytic experiments, and sense the pollutant TNT in aqueous solutions as an all-in-one concept.

In current work the general methods and technologies used for the removal of nitrates from groundwater, waste and drinking water are studied. Each of the denitrification methods has numerous disadvantages, so their individual use is ineffective. Last years a complex use of the investigated methods is being developed. In this work we propose the use of complex wastewater denitrification on the base of ion exchange and catalytic reduction of nitrates in secondary water flow in the presence of developed bimetallic catalyst at atmospheric hydrogen pressure at 288 °K. Theoffered complex process allows decreasing nitrate concentration in waste water from 100 g/kg up to 10 mg/kg.

The structural and functional design of metal nanoparticles has recently allowed remarkable progress in the development of high-performance catalysts. Gold nanoparticles (AuNPs) are among the most innovative catalysts, despite bulk Au metal being regarded as stable and inactive. The hybridization of metal NPs has attracted major interest in the field of advanced nanocatalysts, due to electro-mediated ligand effects. In practical terms, metal NPs need to be supported on a suitable matrix to avoid any undesirable aggregation; many researchers have reported the potential of polymer-supported AuNPs. However, the use of conventional polymer matrices make it difficult to take full advantage of the inherent properties of the metal NPs, since most of active NPs are imbedded inside the polymer support. This results in poor accessibility for the reactants. Herein, we report the topochemical synthesis of Au and palladium (Pd) bimetallic NPs over the surfaces of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibers (TOCNs), and their exceptional catalytic performance. Highly-dispersed AuPdNPs were successfully synthesized in situ on the crystal surfaces of TOCNs with a very high density of carboxylate groups. The AuPdNPs@TOCN nanocomposites exhibit excellent catalytic efficiencies in the aqueous reduction of 4-nitrophenol to 4-aminophenol, depending on the molar ratios of Au and Pd.

A new AuNPs-based thermosensitive nanoreactor (SiO2@PMBA@Au@PNIPAM) was designed and prepared by stabilizing AuNPs in the layer of poly(N,N&rsquo, methylenebisacrylamide) (PMBA) and subsequent wrapping with the temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) layer. The new nanoreactor exhibited high dispersibility and stability in aqueous solution and effectively prevented the aggregation of AuNPs caused by the phase transformation of PNIPAM. The XPS and ATR-FTIR results indicated that AuNPs could be well stabilized by PMBA due to the electron transfer between the N atoms of amide groups in the PMBA and Au atoms of AuNPs. The catalytic activity and thermoresponsive property of the new nanoreactor were invested by the reduction of the environmental pollutant, 4-nitrophenol (4-NP), with NaBH4 as a reductant. It exhibited a higher catalytic activity at 20 &deg, C and 30 &deg, C (below LCST of PNIPAM), but an inhibited catalytic activity at 40 &deg, C (above LCST of PNIPAM). The PNIPAM layer played a switching role in controlling the catalytic rate by altering the reaction temperature. In addition, this nanoreactor showed an easily recyclable property due to the existence of a silica core and also preserved a rather high catalytic efficiency after 16 times of recycling.

In this work, we report the enhanced catalytic reduction of 4-nitrophenol driven by Fe3O4-Au magnetic nanocomposite interface engineering. A facile solvothermal method is employed for Fe3O4 hollow microspheres and Fe3O4-Au magnetic nanocomposite synthesis via a seed deposition process. Complementary structural, chemical composition and valence state studies validate that the as-obtained samples are formed in a pure magnetite phase. A series of characterizations including conventional scanning/transmission electron microscopy (SEM/TEM), Mössbauer spectroscopy, magnetic testing and elemental mapping is conducted to unveil the structural and physical characteristics of the developed Fe3O4-Au magnetic nanocomposites. By adjusting the quantity of Au seeds coating on the polyethyleneimine-dithiocarbamates (PEI-DTC)-modified surfaces of Fe3O4 hollow microspheres, the correlation between the amount of Au seeds and the catalytic ability of Fe3O4-Au magnetic nanocomposites for 4-nitrophenol (4-NP) is investigated systematically. Importantly, bearing remarkable recyclable features, our developed Fe3O4-Au magnetic nanocomposites can be readily separated with a magnet. Such Fe3O4-Au magnetic nanocomposites shine the light on highly efficient catalysts for 4-NP reduction at the mass production level.

Nowadays, synthetic organic dyes and pigments discharged from numerous industries are causing unprecedentedly severe water environmental pollution, and conventional water treatment processes are hindered due to the corresponding sophisticated aromatic structures, hydrophilic nature, and high stability against light, temperature, etc. Herein, we report an efficient fabrication strategy to develop a new type of highly efficient, low-cost, and magnetically recoverable nanocatalyst, i.e., FePt⁻Ag nanocomposites, for the reduction of methyl orange (MO) and rhodamine B (RhB), by a facile seed deposition process. X-ray diffraction results elaborate that the as-synthesized FePt⁻Ag nanocomposites are pure disordered face-centered cubic phase. Transmission electron microscopy studies demonstrate that the amount of Ag seeds deposited onto the surfaces of FePt nanocrystals increases when increasing the additive amount of silver colloids. The linear correlation of the MO and RhB concentration versus reaction time catalyzed by FePt⁻Ag nanocatalysts is in line with pseudo-first-order kinetics. The reduction rate constants of MO and RhB increase with the increase of the amount of Ag seeds. FePt⁻Ag nanocomposites show good separation ability and reusability, and could be repeatedly applied for nearly complete reduction of MO and RhB for at least six successive cycles. Such cost-effective and recyclable nanocatalysts provide a new material family for use in environmental protection applications.

Bimetallic Pt-In and Pd-In catalysts supported on alumina or silica were studied for the reduction of nitrate to N2 in water, using H2 as reducing agent. Characterization results indicate that bimetallic particles with the surface enriched in indium, metallic crystals of Pt or Pd, and oxides of Pt or Pd and In2O3 are the main surface species present in the catalysts. Several catalysts studied in this work could fulfill the requirements usually established as limit values: 50 ppm of-NO3-, 0.1 ppm of NO2- and 0.5 ppm of NH4+. The reaction rate is strongly influenced by either the Pt:In or the Pd:In ratio, the optimum being observed at low contents of In. Of all the catalysts studied in this work, Pd(1 wt.%)In(0.25 wt.%)/Al2O3 is the most active one, but unfortunately, it presents an undesirable high selectivity towards ammonia when nitrate conversion reaches 100%. Pt(1.0%)In(0.25%)/Al2O3 presents a high initial activity but it fastly deactivates during reaction. In general, Pd-In catalysts are more active for nitrate conversion than Pt-In, and alumina is a better support than silica. The composition of the catalysts changes both after reduction and after contacting the liquid reaction media. These changes have been observed by XPS and TEM. In general, the samples used in the reaction have lower dispersion of metallic phases than the fresh-calcined ones. For most of the catalysts used in this work, the Pt:In or Pd:In surface ratio is lower than the bulk ones, this probably being the reason for the low amount of In that is sufficient to have an optimal performance for nitrate conversion. Fil: Marchesini, Fernanda Albana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Irusta, S.. Universidad de Zaragoza; España Fil: Querini, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Miro, Eduardo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina

Herein we report a study involving the homogeneous catalytic reduction ofunsaturated substrates in aqueous solutions or water-organic solvent mixtures. The reduction of olefins has been carried out in the presence of catalytic amounts of [Fe(CN)5NH3] 3- and excess of NH2OH, which under mild reaction conditions can be used to reduce carbon-carbon unsaturations without affecting carbonyl functionalities and aromatic rings. To explore the scope of the catalytic reduction, a wide variety of representative unsaturated substrates have been examined. The steric effects of the substituents on the carbon-carbon multiple bond as well as the regioselectivity and stereoselectivity of the catalyst have been studied. The deuterium kinetic isotope effect on the catalytic reduction of double bonds in olefins has been analyzed, and no significant kinetic isotope effect was found. Among the great advantages of this novel procedure for catalytic reduction are that hydrogen and high pressures are not needed, the catalyst is inexpensive and easily prepared, and water as well as water-organic solvent mixtures can be used as reaction media. Fil: Gaviglio, Carina del Valle. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Doctorovich, Fabio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials and Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsami.5b06974, The liquid-phase exfoliation of graphitic carbon nitride (g-C3N4) to afford colloidal dispersions of two-dimensional flakes constitutes an attractive route to facilitate the processing and implementation of this novel material toward different technological applications, but quantitative knowledge about its dispersibility in solvents is lacking. Here, we investigate the dispersion behavior of exfoliated g-C3N4 in a wide range of solvents and evaluate the obtained results on the basis of solvent surface energy and Hildebrand/Hansen solubility parameters. Estimates of the three Hansen parameters for exfoliated g-C3N4 from the experimentally derived data yielded δD ≈ 17.8 MPa1/2, δP ≈ 10.8 MPa1/2, and δH ≈ 15.4 MPa1/2. The relatively high δH value suggested that, contrary to the case of other two-dimensional materials (e.g., graphene or transition metal dichalcogenides), hydrogen-bonding plays a substantial role in the efficient interaction, and thus dispersibility, of exfoliated g-C3N4 with solvents. Such an outcome was attributed to a high density of primary and/or secondary amines in the material, the presence of which was associated with incomplete condensation of the structure. Furthermore, cell proliferation tests carried out on thin films of exfoliated g-C3N4 using murine fibroblasts suggested that this material is highly biocompatible and noncytotoxic. Finally, the exfoliated g-C3N4 flakes were used as supports in the synthesis of Pd nanoparticles, and the resulting hybrids exhibited an exceptional catalytic activity in the reduction of nitroarenes., M. A.–V., S. V.–R.,J. I. P., J. M. M., A. M.–A., and J. M. D. T. gratefully acknowledge financial support from the Spanish MINECO and the European Regional Development Fund (project MAT2011-26399). The same authors also acknowledge partial funding of this work by Plan de Ciencia, Tecnología e Innovación 2013-2017 del Principado de Asturias and European Regional Development Fund through project GRUPIN14-056. A. P., A. A. L-P. and J. L. C. acknowledge financial support from the European Regional Development Fund within the Operative Programme of Región de Murcia 2007-2013.

This work tried to identify the influence of dosing vaporized urea solution in a selective catalytic reduction (SCR) system. In the SCR method, optimising the urea evaporation and mixing properties can significantly improve the NOx conversion efficiency in the catalyst. It can also exert a positive effect on the uniformity of NH3 concentration distribution across the catalyst face. The concept of an electrically evaporated urea-dosing system was investigated and it was found that urea pre-heating prior to introduction into the exhaust gas is favourable for enhancing NOx removal under steady-state and transient engine operation. In the urea evaporating system the heating chamber was of a cylindrical tube shape and the urea vapour was introduced into the exhaust by means of a Venturi orifice. The concept urea dosing was only a custom-made solution, but proved to be superior to the regular dosing system operating in the liquid phase.

Gold nanoparticles (AuNPs) have attracted widespread attention for their excellent catalytic activity, as well as their unusual physical and chemical properties. The main challenges come from the agglomeration and time-consuming separation of gold nanoparticles, which have greatly baffled the development and application in liquid phase selective reduction. To solve these problems, we propose the preparation of polyvinyl alcohol(PVA)/poly(acrylic acid)(PAA)/Fe3O4 nanocomposites with loaded AuNPs. The obtained PVA/PAA/Fe3O4 composite membrane by electrospinning demonstrated high structural stability, a large specific surface area, and more active sites, which is conducive to promoting good dispersion of AuNPs on membrane surfaces. The subsequently prepared PVA/PAA/Fe3O4@AuNPs nanocomposites exhibited satisfactory nanostructures, robust thermal stability, and a favorable magnetic response for recycling. In addition, the PVA/PAA/Fe3O4@AuNPs nanocomposites showed a remarkable catalytic capacity in the catalytic reduction of p-nitrophenol and 2-nitroaniline solutions. In addition, the regeneration studies toward p-nitrophenol for different consecutive cycles demonstrate that the as-prepared PVA/PAA/Fe3O4@AuNPs nanocomposites have outstanding stability and recycling in catalytic reduction.

In this study, a novel catalyst based on Fe@Au bimetallic nanoparticles involved graphene oxide was prepared and characterized by transmission electron microscope (TEM), and x-ray photoelectron spectroscopy (XPS). The nanomaterial was used in catalytic reductions of 4-nitrophenol and 2-nitrophenol in the presence of sodium borohydride. The experimental parameters such as temperature, the dosage of catalyst and the concentration of sodium borohydride were studied. The rates of catalytic reduction of the nitrophenol compounds have been found as the sequence: 4-nitrophenol>2-nitrophenol. The kinetic and thermodynamic parameters of nitrophenol compounds were determined. Activation energies were found as 2.33kcalmol-1 and 3.16kcalmol-1 for 4-nitrophenol and 2-nitrophenol, respectively. The nanomaterial was separated from the product by using a magnet and recycled after the reduction of nitrophenol compounds. The recyclable of the nanocatalyst is economically significant in industry. © 2013 Elsevier Ltd.

This present paper deals with primary methods for reducing tar in biomass gasification, namely by feeding a natural catalyst into a fluidized bed. This method is verified using an experimental pilot plant.

A malária é a endemia tropical mais devastadora do mundo e esse quadro é agravado pela ausência de tratamento eficaz. Entretanto, a resistência dos plasmódios à artemisinina não apresenta relevância clínica e seu mecanismo de ação está associado ao grupo heme, com formação de radicais livres e rompimento da ponte endoperóxido. O comportamento voltamétrico da artemisinina foi estudado por voltametria cíclica e voltametria de onda quadrada. O fármaco é irreversivelmente reduzido em eletrodos de carbono vítreo e os valores de potencial de pico não sofrem influência da acidez do meio, porém observou-se o maior valor de corrente em pH 6,0. O comportamento voltamétrico da artemisinina foi significativamente alterado na presença do grupo heme, provocando uma antecipação de seu pico de redução em cerca de 600 mV. Por voltametria de onda quadrada observou-se que este novo pico foi sensível à adição crescente de concentração de hemina, atingindo valor de corrente cerca de 10 vezes maior em relação ao pico original da artemisinina, numa relação de concentração de 20 mmol/L para o primeiro e 50 mmol/L do segundo. Além disso, resultados indicaram que esse processo eletrocatalítico ocorreu pela formação de Fe(II)-hemina na superfície do eletrodo, com provável processo de eletro-polimerização da hemina sobre o eletrodo de carbono vítreo. Esse efeito adsortivo foi avaliado a partir da estimativa da concentração superficial (G) de hemina sobre o eletrodo de trabalho em pH 6,0. A modificação do eletrodo de carbono vítreo por hemina mostrou que a interação entre artemisinina e o grupo heme ocorre predominantemente sobre a superfície do eletrodo e não em solução. Portanto, esclarecer o mecanismo de ação da artemisinina é importante para o planejamento e desenvolvimento de novos agentes antimaláricos. Malaria is the tropical disease most devastating of the world and this situation is worsened by the absence of effective treatment. However, the plasmodium resistance to artemisinin does not show clinical relevance. The drug mechanism of action is associated to the heme group, with free radical formation and endoperoxide moiety breakage. The voltammetric behavior of artemisinin was studied by cyclic and square-wave voltametries. This drug was irreversibly reduced on glassy carbon electrode and the peak potential values are pH independent, however the biggest value of current peak was observed at pH 6.0. The voltammetric behavior of artemisinin was significantly changed in the heme group presence, provoking an anticipation of about 600 mV on cathodic peak. By square-wave voltammetry it was observed that this new peak was sensitive to the hemin concentration, reaching a value around 10 times larger regarding the original cathodic peak of artemisinin, being the concentration of 20 mmol/L for the former and 50 mmol/L for the latter. In addition, results indicated that this electro-catalytic process depends on the Fe(II)-hemin formation on the electrode surface, indicating the possible electro-polymerization of hemin on the glassy carbon electrode. This adsorptive effect was evaluated from the superficial concentration (G) estimation of the hemin on the working electrode at pH 6.0. The modification of the glassy carbon electrode using hemin showed that the interaction between artemisinin and the heme group predominantly occurs on the electrode surface and not in solution. Therefore, clarifying artemisinin mechanism of action is important in order to contribute for the design and development of new antimalarial agents.

Steady State Isotopic Transient Kinetic Analysis (SSITKA) coupled with Temperature-Programmed Surface Reaction (TPSR) experiments, using on line Mass Spectroscopy (MS) and in situ DRIFTS have been performed to study essential mechanistic aspects of the selective catalytic reduction of NO by H2 under strongly oxidizing conditions (H2-SCR) at 140°C over a novel 0.1 wt % Pt/MgO-CeO2 catalyst for which patents have been recently obtained. The nitrogen paths of reaction from NO to N2 and N2O gas products were probed by following the 14NO/H 2/O2 → 15NO/H2/O2 switch (SSITKA-MS and SSITKA-DRIFTS) at 1 bar total pressure. It was found that the N-pathways of reaction involve two different in structure active chemisorbed NOx species, one present on the MgO and the other one on the CeO2 support surface. The amount of these active NOx intermediate species formed was found to be 14.4 πmol/g, corresponding to a surface coverage of θ = 3.1 (based on Pt metal surface) in agreement with the SSITKA-DRIFTS results. A large fraction of it (87.5%) was found to participate in the reaction path for N2 formation, in harmony with the high N2 selectivity (82%) exhibited by this catalyst. Inactive adsorbed NOx species were also found to accumulate on both Pt and support (MgO and CeO2). The mechanism of reaction must involve a H-spillover from the Pt metal to the support surface (location of active NO x species). It was proven via the NO/H2/ 16O2 → NO/H2/18O2 (SSITKA-MS) experiment that gaseous O2 does not participate in the reaction path of N2O formation. κ 2007 American Chemical Society. 111 7 3010 3020 Cited By :69

Catalytic conversion of formic acid into methanol was investigated with Cu as a catalyst and Al as a reductant under hydrothermal conditions. It was found that formic acid can be converted into methanol by such means. The highest yield of methanol (30.4%) was attained with a temperature of 300 °C and a reaction time of 9 h. The AlO(OH) formed from Al oxidation may also play a catalytic role in the formation of methanol. This process may provide a promising solution to producing methanol from carbohydrate biomass combined with the process of converting the carbohydrate into formic acid, which is expected to emit no CO2.