Emulsion Liquid Membranes Based on Os-NP/n-Decanol or n-Dodecanol Nanodispersions for p-Nitrophenol Reduction.

Membrane materials with osmium nanoparticles have been recently reported for bulk membranes and supported composite membrane systems. In the present paper, a catalytic material based on osmium dispersed in n-decanol (nD) or n-dodecanol (nDD) is presented, which also works as an emulsion membrane. The hydrogenation of p-nitrophenol (PNP) is carried out in a reaction and separation column in which an emulsion in the acid-receiving phase is dispersed in an osmium nanodispersion in n-alcohols. The variables of the PNP conversion process and p-aminophenol (PAP) transport are as follows: the nature of the membrane alcohol, the flow regime, the pH difference between the source and receiving phases and the number of operating cycles. The conversion results are in all cases better for nD than nDD. The counter-current flow regime is superior to the co-current flow. Increasing the pH difference between the source and receiving phases amplifies the process. The number of operating cycles is limited to five, after which the regeneration of the membrane dispersion is required. The apparent catalytic rate constant (kapp) of the new catalytic material based on the emulsion membrane with the nanodispersion of osmium nanoparticles (0.1 × 10-3 s-1 for n-dodecanol and 0.9 × 10-3 s-1 for n-decanol) is lower by an order of magnitude compared to those based on adsorption on catalysts from the platinum metal group. The advantage of the tested membrane catalytic material is that it extracts p-aminophenol in the acid-receiving phase.

Nickel on Oxidatively Modified Carbon as a Promising Cost-Efficient Catalyst for Reduction of P-Nitrophenol.

The reduction of p-nitrophenol to p-aminophenol has become a benchmark reaction for testing the efficiency of new catalytic systems. In this study, we use oxidatively modified carbon (OMC) as a structural support to develop a new cost-efficient nickel-based catalytic system. The newly developed material comprises single nickel ions, chemically bound to the oxygen functional groups on the OMC surface. The highly oxidized character of OMC ensures the high lateral density of nickel ions on its surface at relatively low nickel content. We demonstrate excellent catalytic properties of the new material by using it as a stationary phase in a prototype of a continuous flow reactor: the reagent fed into the reactor is p-nitrophenol, and the product, exiting the reactor, is the fully converted p-aminophenol. The catalytic properties of the new catalyst are associated with its specific morphology, and with high lateral density of active sites on the surface. The reaction can be considered as an example of single-atom catalysis. The resulting material can be used as an inexpensive but efficient catalyst for industrial wastewater treatment. The study opens the doors for the synthesis of a new series of catalytic systems comprising transition metal atoms on the OMC structural support.

Development of a Simple Reversible-Flow Method for Preparation of Micron-Size Chitosan-Cu(II) Catalyst Particles and Their Testing of Activity.

A simple flow system employing a reversible-flow syringe pump was employed to synthesize uniform micron-size particles of chitosan-Cu(II) (CS-Cu(II)) catalyst. A solution of chitosan and Cu(II) salt was drawn into a holding coil via a 3-way switching valve and then slowly pumped to drip into an alkaline solution to form of hydrogel droplets. The droplets were washed and dried to obtain the catalyst particles. Manual addition into the alkaline solution or employment of flow system with a vibrating rod, through which the end of the flow line is inserted, was investigated for comparison. A sampling method was selected to obtain representative samples of the population of the synthesized particles for size measurement using optical microscopy. The mean sizes of the particles were 880 ± 70 µm, 780 ± 20 µm, and 180 ± 30 µm for the manual and flow methods, without and with the vibrating rod, respectively. Performance of the flow methods, in terms of rate of droplet production and particle size distribution, are discussed. Samples of 180 µm size CS-Cu(II) particles were tested for catalytic reduction of 0.5 mM p-nitrophenol to p-aminophenol by 100-fold excess borohydride. The conversion was 98% after 20 min, whereas without the catalyst there was only 14% conversion.

Carbonized cellulose microspheres loaded with Pd NPs as catalyst in p-nitrophenol reduction and Suzuki-Miyaura coupling reaction.

Catalytic reduction of p-nitrophenol is usually carried out using transition metal nanoparticles such as gold, palladium, silver, and copper, especially palladium nanoparticles (Pd NPs), which are characterized by fast reaction rate, high turnover frequency, good selectivity, and high yield. However, the aggregation and precipitation of the metals lead to the decomposition of the catalyst, which results in a significant reduction of the catalytic activity. Therefore, the preparation of homogeneous stabilized palladium nanoparticles catalysts has been widely studied. Stabilized palladium nanoparticles mainly use synthetic polymers. Cellulose microspheres, as a natural polymer material with low-cost and porous fiber network structure, are excellent carriers for stabilizing metal nanoparticles. Cellulose microspheres impregnated with palladium metal nanoparticles were carbonized to have a larger specific surface area and highly dispersed palladium nanoparticles, which exhibited excellent catalytic activity in the catalytic reduction of p-nitrophenol. In this work, the cellulose carbon-based microspheres palladium (Pd@CCM) catalysts were designed and characterized by SEM, TEM, EDS, XRD, FTIR, XPS, TGA, BET, and so on. Furthermore, the catalytic performance of Pd@CCM catalysts was investigated via p-nitrophenol reduction, which showed high catalytic activity. This catalyst also exhibited excellent catalytic performance in the Suzuki-Miyaura coupling reaction. Linking aromatic monomer and benzene through Suzuki-Miyaura coupling was presented as an effective route to obtaining biaryls, and the synthesis method is low-cost and simple. In addition, Pd@CCM showed desirable recyclability while maintaining its catalytic activity even after five recycles. This work is highly suggestive of the design and application of the heterogeneous catalyst.

Preparation of PdNi bimetallic loaded amino modified porous carbon material catalyst based on chitosan and its applications.

The utilization efficiency of palladium-based catalysts has sharply increased in many catalytic reactions. However, numerous studies have shown that preparing alloys of palladium with other metals has superior catalytic activity than pure palladium. Additionally, hierarchical porous carbon has gradually developed into an excellent carrier for loading bimetallic nanoparticles. In this study, we firstly pyrolyzed chitosan, sodium bicarbonate and nickel nitrate to create highly dispersed porous carbon materials doped with Ni NPs. The carbon materials were then grafted with silane coupling agent (APTMS) to afford them with amino groups on the surface. Taking advantage of the fact that Pd2+ can react with Ni in spontaneous reduction reaction, Pd was deposited on the surface of Ni to produce PdNi bimetallic-loaded carbon catalysts containing amino groups. The resulting catalysts were examined by a series of characterizations and were found to have a hierarchically porous structure and large specific surface area, which increased the number of active sites of the catalysts. In comparison to other Pd catalysts, the PdNi/HPCS-NH2 catalysts displayed remarkable activity for Suzuki coupling reaction and hydro reduction of nitroaromatics, which exhibited a high turnover frequency value (TOF) of 37,857 h-1 and 680.9 h-1, respectively. These were mainly due to the high dispersion of the PdNi NPs and the superior structure of the carriers. Moreover, the catalysts did not experience a significant decline in activity after ten cycles. All in all, this investigation has created a new approach for the fabrication of novel carriers for Pd catalysts, which is in line with the concept of green chemistry and recyclable.

Templating of catalytic gold and silver nanoparticles by waste plastic PET-derived hydrogel playing a dual role of a reductant and a matrix.

The progressive accumulation of discarded plastic in the environment demands further development of waste management of plastic waste and conversion technologies of such waste to value-added materials. Recently, the conversion of plastic waste to functional materials via chemical recycling has attracted considerable attention. In this report, plastic waste (PET) was utilized for the preparation of a hydrogel-based catalyst via a cross-linking reaction of PET-derived oligo(terephthalamide)s followed by the electroless metallization. The polymeric matrix of PET-derived hydrogel plays multiple roles of (i) an adsorption media for noble metal ions such as Au3+ and Ag+, (ii) a reducing agent of Au3+ and Ag+ ions to Au0 and Ag0, and (iii) a matrix for the controlled growth of Au and Ag nanoparticles (AuNPs and AgNPs). The obtained hybrid hydrogels after metallization contained well-dispersed AuNPs and AgNPs of 6.1 ± 3.7 nm or 6.1 ± 1.4 nm size, respectively. The catalytic activities of the hybrid hydrogels with metal nanoparticles were studied in a model system of p-nitrophenol reduction in an aqueous solution. The hybrid materials of both Au@hydrogel and Ag@hydrogel were catalytically active for the reduction of p-nitrophenol, obeying the first-order kinetics. Importantly, the AuNPs or AgNPs in the hydrogel matrix preserved the original catalytic activity after multiple p-nitrophenol reduction reactions, showing a promising reusability of the catalysts. The proposed here approach aims to broaden the scope of conversion routes of plastic waste to value-added materials as well as to develop new types of polymeric matrices for templating and growth of metal nanoparticles for catalytic applications.

PdCu alloy prepared by ultrasonic method catalyzes the degradation of p-nitrophenol.

PdCu alloy nanocatalysts supported on NiFe layered double hydroxide (PdCu-LDHs) were prepared by a green ultrasound-assisted reduction method. The cavitation effect of ultrasound made part of CO32- decompose to CO2, and NO3- and Cl- replace intercalation, which anchor the PdCu between layers. The action of ultrasound dissociated hydroxyl groups (-OH) on surface of LDHs to H· to reduce Cu2+ and Pd2+ to Cu0 and Pd0 and Cu promote the synergy between Pd alloy and LDHs. The electronic effects between Cu and Pd improved the catalytic performance for the reduction reaction of 4-NP and the stability of PdCu-LDHs. The PdCu-LDHs prepared at 400 W, 25 kHz, 1 h, can completely degrade p-nitrophenol (4-NP) within 5 min with n(4-NP)/n(Pd) = 50 and n(4-NP)/n(NaBH4) = 0.15. The TOF value is 988.20 h-1, which is 27.7 times that of Pd/C catalyst (commercial).

Novel PEPPSI-Type NHC Pd(II) Metallosurfactants on the Base of 1H-Imidazole-4,5-dicarboxylic Acid: Synthesis and Catalysis in Water-Organic Media.

Carrying out organic reactions in water has attracted much attention. Catalytic reactions in water with metallosurfactants, which have both a metallocenter and the surface activity necessary for solubilizing hydrophobic reagents, are of great demand. Herein we proposed new approach to the synthesis of NHC PEPPSI metallosurfactants based on the sequential functionalization of imidazole 4,5-dicarboxylic acid with hydrophilic oligoethylene glycol and lipophilic alkyl fragments. Complexes of different lipophilicity were obtained, and their catalytic activity was studied in model reduction and Suzuki-Miyaura reactions. A comparison was made with the commercial PEPPSI-type catalytic systems designed by Organ. It was found that the reduction reaction in an aqueous solution of the metallosurfactant with the tetradecyl lipophilic fragment was three times more active than the commercially available PEPPSI complexes, which was associated with the formation of stable monodisperse aggregates detected by DLS and TEM.

Phyto Synthesis of Manganese-Doped Zinc Nanoparticles Using Carica papaya Leaves: Structural Properties and Its Evaluation for Catalytic, Antibacterial and Antioxidant Activities.

The current study aims to synthesize bimetal oxide nanoparticles (zinc and manganese ions) using the carica papaya leaf extract. The crystallite size of the nanoparticle from X-ray diffraction method was found to be 19.23 nm. The nanosheet morphology was established from Scanning Electron Microscopy. Energy-dispersive X-ray diffraction was used to determine the elemental content of the synthesized material. The atomic percentage of Mn and Zn was found to be 15.13 and 26.63. The weight percentage of Mn and Zn was found to be 7.08 and 10.40. From dynamic light scattering analysis, the hydrodynamic diameter and zeta potential was found to be 135.1 nm and -33.36 eV. The 1,1-diphenyl-2-picryl hydroxyl radical, hydroxyl radical, FRAP, and hydrogen peroxide scavenging tests were used to investigate the antioxidant activity of Mn-Zn NPs. Mn-Zn NPs have substantial antioxidant properties. The photocatalytic activity of the Mn-Zn NPs was assessed by their ability to degrade Erichrome black T (87.67%), methyl red dye (78.54%), and methyl orange dye (69.79%). Additionally, it had significant antimicrobial action S. typhi showed a higher zone of inhibition 14.3 ± 0.64 mm. Mn-Zn nanoparticles were utilized as a catalyst for p-nitrophenol reduction. The bimetal oxide Mn-Zn NPs synthesized using C. papaya leaf extract exhibited promising dye degradation activity in wastewater treatment. Thus, the aforementioned approach will be a novel, low cost and ecofriendly approach.

Metal-organic framework grown in situ on chitosan microspheres as robust host of palladium for heterogeneous catalysis: Suzuki reaction and the p-nitrophenol reduction.

In this study, the metal-organic framework ZIF-8 has been successfully planted on the surface of chitosan microspheres (CS/PDA@ZIF-8) using polydopamine as connecting material for the first time, which avoids the use of expensive, non-renewable, and non-biodegradable polystyrene microspheres commonly used as templates to prepare core-shell structures. Moreover, the metal-organic framework ZIF-8 was prepared specially by three different methods and all characterized by SEM, TEM, and BET, and the ZIF-8 shell prepared at room temperature presents a regular morphology, uniform size, large specific surface area (353.1 m2/g) than the shells prepared by the other methods including. The CS/PDA@ZIF-825@Pd with high catalytic activity and high stability was especially prepared by encapsulating Pd nanoparticles into the pores of CS/PDA@ZIF-825. Notably, the fabricated catalyst performed well in an array of reactions, for example the Kapp value of the p-nitrophenol reduction reaction reached 0.0426 s-1, and the TOF of the Suzuki coupling reaction reached 128 h-1. In addition, the ZIF-67, UiO-66, UiO-66-NH2, HKUST-1, and NH2-MIL-53(Al) were also grown on chitosan microcapsules successively to prepare the core-shell microspheres, which prove the universal applicability of this strategy. And beyond that, the introduction of chitosan microspheres endows the material with biodegradable properties and excellent recycling properties.

Obtaining and Characterizing the Osmium Nanoparticles/n-Decanol Bulk Membrane Used for the p-Nitrophenol Reduction and Separation System.

Liquid membranes based on nanoparticles follow a continuous development, both from obtaining methods and characterization of techniques points of view. Lately, osmium nanoparticles have been deposited either on flat membranes, with the aim of initiating some reaction processes, or on hollow fiber membranes, with the aim of increasing the contact surface with the phases of the membrane system. This paper presents the obtainment and characterization of a liquid membrane based on osmium nanoparticles (Os-NP) dispersed in ndecanol (nDol) for the realization of a membrane system with a large contact surface between the phases, but without using a liquid membrane support. The dispersion of osmium nanoparticles in n-decanol is carried out by the method of reducing osmium tetroxide with 1-undecenoic acid (UDA). The resulting membrane was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy analysis (EDAX), thermoanalysis (TG, DSC), Fourier transform infra-red (FTIR) spectroscopy and dynamic light scattering (DLS). In order to increase the mass transfer surface, a design for the membrane system was realized with the dispersion of the membrane through the receiving phase and the dispersion of the source phase through the membrane (DBLM-dispersion bulk liquid membrane). The process performance was tested for the reduction of p-nitrophenol (pNP) from the source phase, using sodium tetra-borohydride (NaBH4), to p-aminophenol (pAP), which was transported and collected in the receiving phase. The obtained results show that membranes based on the dispersion of osmium nanoparticles in n-decanol can be used with an efficiency of over 90% for the reduction of p-nitrophenol and the separation of p-aminophenol.

Multistage reclamation of Co2+-containing alginate hydrogels as excellent reduction catalyst and subsequent microwave absorber by facile transformation.

The multistage reclamation of materials has made contributions to sustainable development, but further progress is still sought after. In this work, functionalized seaweed-based composites were successfully prepared and utilized in multiple stages. Specifically, Co2+-containing alginate hydrogels (CHB-Co2+) prepared by sol-gel self-assembly and adsorption method using interior/exterior co-functionalized calcium alginate as raw materials were utilized for efficient reduction of p-nitrophenol. After coupling with freeze-drying and carbonization procedures, a high-performance Co/N co-doped carbonaceous microwave absorber was obtained and investigated in detail. By virtue of unique 3D interconnected network, heterogeneous interfaces and doped heteroatom N species, by which endowing the absorber with optimal impedance matching and attenuation ability, as-fabricated NC-Co-700 exhibited prominent microwave absorption performance with -54.2 dB of RLmin at 6.4 GHz and 5.3 GHz of maximum absorption bandwidth (from 12.7 to 18.0 GHz). Additionally, in view of the dielectric loss and magnetic loss caused by the synergy effect among the functional components, the underlying absorption mechanism was proposed. This work provided a novel idea for designing biomass-based functional materials and simultaneously achieved economic benefits through the rational utilization of other products in the preparation process.

Immobilizing of palladium on melamine functionalized magnetic chitosan beads: A versatile catalyst for p-nitrophenol reduction and Suzuki reaction in aqueous medium.

In this study, an environmental-friendly palladium catalyst with high efficiency, magnetic, recoverability, reusability, and excellent stability was prepared and thoroughly characterized by the Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), X-ray diffraction (XRD), Elemental mapping, Thermogravimetric analysis (TGA) and Energy-dispersive X-ray spectroscopy (EDX). Results demonstrates that melamine provides a coordination point on the surface of chitosan microspheres, which provides a platform for the uniform distribution of palladium (II) and combines with palladium (II) firmly to avoid unnecessary leaching of nanoparticles. Besides, Fe3O4/CS-Me@Pd microcapsules exhibited high catalytic performance in reducing p-NP in water at room temperature (150-300 s). This composite was also effective in the Suzuki-Miyaura coupling reaction under mild conditions with high catalytic performance (TON = 3.8 × 104, TOF = 7.6 × 104). Reproducibility experiments also showed that Fe3O4/CS-Me@Pd microcapsules have high recovery efficiency and can work at least six times during these two catalytic reactions. The hot filtration test indicated that the catalyst has heterogeneous nature.

One-pot green synthesis of bimetallic hollow palladium-platinum nanotubes for enhanced catalytic reduction of p-nitrophenol.

Bimetallic alloy nanostructures have garnered much attention due to their unique performances in catalytic processes. However, decline in catalytic activity over the life span has been a protracted limitation, ascribed largely to the aggregation or dissociation of particles and still remains a challenge for manufacturing bimetallic nanostructures of sufficient stability. Herein, a surfactant- and solvent-free greener strategy is presented for the fabrication of bimetallic palladium-platinum (PdPt) nanotubes (NTs), deploying lipid tubules as template and ascorbic acid as a reducing agent; the ensuing NTs comprise crystalline tubal nanostructures of ∼12 µm length, ∼500 nm cross-sectional diameter, and ∼57 nm tube wall thickness. When used for the catalytic reduction of p-nitrophenol (PNP), the PdPt NTs delivered improved kinetic apparent rate constants (kapp) compared to Pt NTs (0.5 min-1vs. 0.2 min-1). Moreover, the NTs demonstrated high stability when used over multiple catalytic cycles thus opening up new potential routes for the fabrication of alloy NTs using lipid tubules as templates.

Glucose and Applied Voltage Accelerated p-Nitrophenol Reduction in Biocathode of Bioelectrochemical Systems.

p-Nitrophenol (PNP) is common in the wastewater from many chemical industries. In this study, we investigated the effect of initial concentrations of PNP and glucose and applied voltage on PNP reduction in biocathode BESs and open-circuit biocathode BESs (OC-BES). The PNP degradation efficiency of a biocathode BES with 0.5 V (Bioc-0.5) reached 99.5 ± 0.8%, which was higher than the degradation efficiency of the BES with 0 V (Bioc-0) (62.4 ± 4.5%) and the OC-BES (59.2 ± 12.5%). The PNP degradation rate constant (kPNP) of Bioc-0.5 was 0.13 ± 0.01 h-1, which was higher than the kPNP of Bioc-0 (0.024 ± 0.002 h-1) and OC-BES (0.013 ± 0.0005 h-1). PNP degradation depended on the initial concentrations of glucose and PNP. A glucose concentration of 0.5 g L-1 was best for PNP degradation. The initial PNP increased from 50 to 130 mg L-1 and the kPNP decreased from 0.093 ± 0.008 to 0.027 ± 0.001 h-1. High-throughput sequencing of 16S rRNA gene amplicons indicated differences in microbial community structure between BESs with different voltages and the OC-BES. The predominant populations were affiliated with Streptococcus (42.7%) and Citrobacter (54.1%) in biocathode biofilms of BESs, and Dysgonomonas were the predominant microorganisms in biocathode biofilms of OC-BESs. The predominant populations were different among the cathode biofilms and the suspensions. These results demonstrated that applied voltage and biocathode biofilms play important roles in PNP degradation.

Immobilization and characterization of Fe(0) catalyst on NaOH-treated coal fly ash for catalytic reduction of p-nitrophenol.

In this study, coal fly ash (CFA), i.e., an industrial waste product created in large quantities by thermoelectric power plants, was treated with sodium hydroxide to afford a novel Fe (0) catalyst supported on alkaline-treated CFA. The NaOH-treated CFA (NCFA) exhibited a morphological change from slick spheres to pointed, leaf-like spheres, which was accompanied by a noticeable increase in specific surface area from 1.2 to 7.5 m2/g. Sequential addition of an Fe(III) precursor and NaBH4 solution to a suspension of NCFA resulted in the formation of Fe (0) particles on the surface of NCFA (Fe/NCFA). The catalytic activity of Fe/NCFA toward the reduction of p-nitrophenol (p-NP) was examined; among the Fe/NCFAs synthesized from different NCFAs (1, 3, and 7 M NaOH), the Fe/3 M NCFA sample displayed the highest activity owing to the highest Fe content on its surface, without leaching any toxic heavy metals. In addition, the effects of NaBH4 concentration, Fe loading, and catalyst dosage on the catalytic reduction of p-NP by Fe/NCFA were comprehensively investigated. Finally, the recyclability and stability of Fe/NCFA were examined, demonstrating the complete reduction of p-NP over four continuous recycling cycles. The present results demonstrate the marked potential of CFA as a component in reactive catalysts for the removal of environmental pollutants from wastewater.

Polymer-coated palladium nanoparticle catalysts for Suzuki coupling reactions.

A set of seven different palladium nanoparticle (PdNP) systems stabilized by small amounts (1.0mg/mL) of structurally related macromolecular capping agents were comparatively tested as catalyst in p-nitrophenol (Nip) reduction and Suzuki cross-coupling reactions. The observed rate constants (kobs) for Nip reduction were in the range of 0.052-3.120×10(-2)s(-1), and the variation reflected the effects of polymer chain conformation, ionic strength and palladium-polymer complex coordination. Macromolecules featuring pendant pyridyl moieties or inverse temperature-dependent solubility were found to be unsuitable capping agents for PdNPs catalysts, despite being active. The catalytic activity in Suzuki cross-coupling reactions followed the same behavior; the most active particles in the Nip reaction also mediated the cross-coupling reaction providing the expected products in quantitative yields under relatively mild conditions after only 4h at 50°C. Experiments involving the successive addition of reactants and catalyst recovery/re-use indicated that the recycling potential was comparable to those of the standards used in this field.