Facile simultaneous synthesis of tetraaniline nanostructures/silver nanoparticles as heterogeneous catalyst for the efficient catalytic reduction of 4-nitrophenol to 4-aminophenol

Nanocomposites of tetraaniline (TAN) nanostructures/silver nanoparticles (Ag NPs) were synthesized by an interfacial polymerization method using N-phenyl-1, 4-phenylenediamine (NPPD), AgNO₃ and ammonium persulphate (APS) as monomer, oxidizing agent in immiscible solvent toluene–water respectively. The structure and morphology of the as-prepared TAN and Ag NPs were investigated by UV-visible spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and thermogravimetry (TG). The results of FTIR spectroscopy confirmed the formation of TAN and Ag NPs and those of XRD showed the presence of the face centred cubic (fcc) phase of Ag NPs. The FESEM and TEM images gave direct evidence that Ag NPs stabilized with the TAN nanostructures. TGA indicated the enhanced thermal stability of the nanocomposites (NCs). The catalytic activity of TAN/Ag NCs was investigated for the model reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of excess sodium borohydride.

Nanocomposites of tetraaniline/silver nanoparticles were synthesised using an interfacial polymerisation method. The catalytic activity was investigated for the model reduction of 4-nitrophenol to 4-aminophenol in the presence of excess sodium borohydride.     

Reduction of 4-nitrophenol using green-fabricated metal nanoparticles

Noble metal (silver (Ag), gold (Au), platinum (Pt), and palladium (Pd)) nanoparticles have gained increasing attention due to their importance in several research fields such as environmental and medical research. This review focuses on the basic perceptions of the green synthesis of metal nanoparticles and their supported-catalyst-based reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The mechanisms for the formation of these nanoparticles and the catalytic reduction of 4-NP are discussed. Furthermore, the parameters that need to be considered in the catalytic efficiency calculations and perspectives for future studies are also discussed.

Noble metal (silver (Ag), gold (Au), platinum (Pt), and palladium (Pd)) nanoparticles have gained increasing attention due to their importance in several research fields such as environmental and medical research.     

Decoration of silver nanoparticles on nitrogen-doped nanoporous carbon derived from zeolitic imidazole framework-8 (ZIF-8) via in situ auto-reduction

We discovered an in situ auto-reduction method to embed silver nanoparticles onto a nanoporous carbon (NC) derived from the zeolitic imidazole framework-8 (ZIF-8), without any requirement of the reducing agents. The detailed analysis demonstrated the formation of Ag NPs by the replacement of the metallic Zn residue in the NC with Ag ions. The synthesized Ag@NC exhibited a superior catalytic activity toward the reduction reaction of 4-nitrophenol into 4-aminophenol.

Unremoved metal residue and no utilization of reducing agent could be applied for synthesizing metal-supported catalyst.     

A novel Au/electroactive poly(amic acid) composite as an effective catalyst for p-nitrophenol reduction

A Au/electroactive poly(amic acid) (Au/EPAA) composite was synthesized and characterized, and its catalytic ability was evaluated. EPAA was synthesized via oxidative coupling polymerization and Au nanoparticles were anchored to the amino and carboxyl groups. The Au/EPAA composite was characterized via X-ray diffraction analysis, X-ray photoelectron spectroscopy, and scanning electron microscopy, which confirmed that the Au nanoparticles were well dispersed on the EPAA surface. p-Nitrophenol was reduced to p-aminophenol within 5 min at room temperature, with a rate constant of 0.84 min⁻¹. Cycling measurements showed that the Au/EPAA composite achieved higher than 92% conversion. The Au/EPAA composite showed excellent performance and stability as a catalyst for the reduction of p-nitrophenol to p-aminophenol.

The Au/EPAA composite demonstrated excellent performance and stability as a catalyst for the reduction of p-nitrophenol to p-aminophenol.     

Ultrathin 2D metal–organic framework nanosheets prepared via sonication exfoliation of membranes from interfacial growth and exhibition of enhanced catalytic activity by their gold nanocomposites

Ultrathin two-dimensional (2D) metal–organic framework (MOF) nanosheets were prepared by a facile sonication exfoliation of MOF membranes from interfacial growth. The stacked form of nanosheets constituting the MOF membranes was significantly different to that of its layered MOF counterparts. This led to decreased interaction between nanosheets, so they could exfoliate readily from the MOF membranes. Moreover, Au nanoparticles were introduced to form nanocomposites. Enhanced catalytic activity and long-term stability of these nanocomposites were observed by a model reaction of the reduction of 4-nitrophenol to 4-aminophenol. This preparation method could be extended to other 2D MOF nanosheets and their nanocomposites.

Cu-MOF nanosheets were prepared by sonication exfoliation and the Au/Cu-MOF nanocomposites exhibited higher catalytic activity than pure Au NPs.     

Biosynthesis of Ag–Pd bimetallic alloy nanoparticles through hydrolysis of cellulose triggered by silver sulfate

We report a simple but efficient biological route based on the hydrolysis of cellulose to synthesize Ag–Pd alloy nanoparticles (NPs) under hydrothermal conditions. X-ray powder diffraction, ultraviolet-visible spectroscopy and scanning transmission electron microscopy-energy dispersive X-ray analyses were used to study and demonstrate the alloy nature. The microscopy results showed that well-defined Ag–Pd alloy NPs of about 59.7 nm in size can be biosynthesized at 200 °C for 10 h. Fourier transform infrared spectroscopy indicated that, triggered by silver sulfate, cellulose was hydrolyzed into saccharides or aldehydes, which served as both reductants and stabilizers, and accounted for the formation of the well-defined Ag–Pd NPs. Moreover, the as-synthesized Ag–Pd nanoalloy showed high activity in the catalytic reduction of 4-nitrophenol by NaBH₄.

We report a simple but efficient biological route based on the hydrolysis of cellulose to synthesize Ag–Pd alloy nanoparticles (NPs) under hydrothermal conditions.     

Facile synthesis of silver nanocatalyst decorated Fe3O4@PDA core–shell nanoparticles with enhanced catalytic properties and selectivity

In this work, we have successfully prepared core–shell nanoparticles (Fe₃O₄@PDA) wrapped with Ag using a simple and green synthesis method. Without an external reducing agent, silver nanoparticles (Ag NPs) with good dispersibility were directly reduced and deposited on a polydopamine (PDA) layer. Fe₃O₄@PDA@Ag showed excellent catalytic activity and recyclability for 4-nitrophenol, and also exhibited good catalytic selectivity for organic dyes (MO and MB). This simple and green synthesis method will provide a platform for other catalytic applications.

In this work, we have successfully prepared core–shell nanoparticles (Fe₃O₄@PDA) wrapped with Ag using a simple and green synthesis method.     

Boron carbide composites with highly aligned graphene nanoplatelets: light-weight and efficient electromagnetic interference shielding materials at high temperatures

B₄C-based ceramic composites containing 0–2 vol% highly aligned graphene nanoplatelets (GNPs) are fabricated. The electromagnetic interference (EMI) shielding properties of the obtained composites are investigated at X-band (8.2–12.4 GHz) frequency range from room-temperature up to 800 °C. All composites exhibit outstanding EMI shielding properties with satisfactory frequency- and thermal-stability. The shielding effectiveness (SE) of GNP/B₄C composites increases monotonically with increasing GNP loading. Superior room-temperature SE close to 40 dB is achieved with only 2 vol% GNPs and high SE around 35 dB still persists at 800 °C. Considering their relatively low density, GNP/B₄C composites possess a high specific shielding effectiveness (SSE) of 16 dB cm³ g⁻¹ which is among the highest values in reported ceramic-based shielding composites. Especially, the GNP/B₄C composite with 2 vol% GNPs exhibits the highest SSE/t (SSE divided by thickness) values at temperatures above 200 °C for all reported shielding composites, indicating that GNP/B₄C composites belong to the most promising high-temperature shielding composites. The excellent shielding properties of GNP/B₄C composites arise mainly from the high electrical conductivity, high dielectric loss and the multiple reflections by the highly aligned and large-sized GNP layers.

The incorporation of a small amount of highly aligned graphene nanoplatelets into boron carbide leads to light-weight and efficient high-temperature electromagnetic interference shielding composites.     

Kinetic investigation for the catalytic reduction of nitrophenol using ionic liquid stabilized gold nanoparticles

We demonstrate the synthesis of gold nanoparticles (AuNP) stabilized by 1-butyl-3-hexadecyl imidazolium bromide (Au@[C₄C₁₆Im]Br) and their use as a catalyst for the reduction of nitrophenol. The AuNPs show excellent stability in presence of [C₄C₁₆Im]Br ionic liquids for the reduction of 4-nitrophenol and 2-nitrophenol using NaBH₄ as a reducing agent. The detailed kinetics for the reduction of 4-nitrophenol and 2-nitrophenol were investigated and the catalytic activity of Au@[C₄C₁₆Im]Br was evaluated. The pseudo first-order rate constant (k_app) values for 4-nitrophenol was observed to be greater than that of 2-nitrophenol and explained on the basis of hydrogen bonding present in 2-nitrophenol. Au@[C₄C₁₆Im]Br showed good separability and reusability and hence, it can be used for the complete reduction of nitrophenols in multiple cycles. The Langmuir–Hinshelwood reaction mechanism is elucidated for reduction of 4-nitrophenol by Au@[C₄C₁₆Im]Br nanocatalyst on the basis of the k_app values. The thermodynamic activation parameters such as activation energy, enthalpy of activation and entropy of activation were determined and explained using the temperature dependent kinetics for the reduction of nitrophenol using Au@[C₄C₁₆Im]Br. The above results reveal that the Au@[C₄C₁₆Im]Br nanocatalyst demonstrates excellent catalytic performance for the reduction of nitrophenol by NaBH₄ at room temperature.

Catalytic reduction of nitrophenol using ionic liquid stabilized AuNPs.     

Surfactant-free synthesis of porous Au by a urea complex

We report a facile surfactant-free synthetic method to obtain porous and hollow Au nanoparticles using only urea and HAuCl₄·4H₂O as precursors at 200 °C. The formation mechanism was investigated through X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. Moreover, the prepared Au nanocrystals present superior catalytic performance for the reduction of 4-nitrophenol in comparison with solid Au nanoparticles. The catalytic efficiency of porous and hollow Au was nearly 6 times higher than that of Au nanoparticles. Furthermore, the porous and hollow Au maintained excellent stability even after 10 catalytic cycles. Therefore, the as-synthesized porous Au nanoparticles will have potential applications in organic catalysis, biosensing, drug delivery, water pollutant removal, and so on.

A gold–urea complex was incinerated to transform into porous hollow gold nanoparticles (PHAuNPs), and the PHAuNPs present high catalytic activity.     

Hot electron prompted highly efficient photocatalysis based on 3D graphene/non-precious metal nanoparticles

High dispersibility and rapid electron transfer are required for a highly efficient catalyst. In this work, such materials have been designed using a scalable hydrothermal method from graphene oxide and a metal–organic framework. A cross-linked three-dimensional graphene (3DGraphene) material loaded with mono-dispersed nitrogen-doped carbon-coated metallic Co (NC@Co) nanoparticles with uniform size of 12.2 nm (3DGraphene/NC@Co) has been obtained and exhibits excellent activity for catalytic reduction of 4-nitrophenol to 4-aminophenol. Such high catalytic activity can be assigned to the highly energetic hot/free electrons arising from 3DGraphene under light illumination and the synergistic effect between 3DGraphene and NC@Co nanoparticles. The catalytic reaction can be finished in 240 s with NaBH₄ as the reducing agent, and the corresponding rate constant (k) is 1.5 × 10⁻² s⁻¹, comparable to that of reported noble metal catalysts. Furthermore, the magnetic 3DGraphene/NC@Co materials are beneficial for the separation from the mixture after reaction and exhibit excellent cycling stability.

Based on the highly energetic hot/free electrons, 3DGraphene loaded nitrogen-doped carbon-coated Co catalysts show remarkably enhanced photocatalytic activities.     

Hybrids based on borate-functionalized cellulose nanofibers and noble-metal nanoparticles as sustainable catalysts for environmental applications

Polymeric supports from renewable resources such as cellulose nanomaterials are having a direct impact on the development of heterogenous sustainable catalysts. Recently, to increase the potentiality of these materials, research has been oriented towards novel functionalization possibilities. In this study, to increase the stability of cellulose nanofiber films as catalytic supports, by limiting the solubility in water, we report the synthesis of new hybrid catalysts (HC) based on silver, gold, and platinum nanoparticles, and the corresponding bimetallic nanoparticles, supported on cellulose nanofibers (CNFs) cross-linked with borate ions. The catalysts were prepared from metal precursors reduced by the CNFs in an aqueous suspension. Metal nanoparticles supported on CNFs with a spherical shape and a mean size of 9 nm were confirmed by TEM, XRD, and SAXS. Functionalized films of HC-CNFs were obtained by adding a borate solution as a cross-linking agent. Solid-state ¹¹B NMR of films with different cross-linking degrees evidenced the presence of four different boron species of which the bis-chelate is responsible for the cross-linking of the CNFs. Also, it may be concluded that the bis-chelate and the mono-chelates modify the microstructure of the film increasing the water uptake and enhancing the catalytic activity in the reduction of 4-nitrophenol.

We report the synthesis of supported noble metal nanoparticles on cellulose nanofibers cross-linked with borate as highly efficient sustainable catalysts.     

The chemical functionalization of graphene nanoplatelets through solvent-free reaction

Graphene nanoplatelets (GNPs) were functionalized through 1,3-dipolar cycloaddition of azomethine ylide using a solvent-free approach and under different reaction conditions. The yield and the functionality of the carboxyl-terminated pyrrolidine ring attached on the surface of GNPs could be affected by varying the reaction temperature as well as the reactant to GNP weight ratio. The functionalized GNPs were characterized extensively using a range of spectroscopic and microscopy techniques.

Carboxyl-terminated pyrrolidine functionalized graphene nanoplatelets through a solvent-free reaction.     

Electrodeposited nickel–graphene nanocomposite coating: effect of graphene nanoplatelet size on its microstructure and hardness

In this study, the effect of graphene nanoplatelet (GNP) size on the microstructure and hardness of the electrodeposited nickel–graphene nanocomposite coatings were investigated. GNPs with different sizes were prepared by using a high energy ball milling technique. The experimental result revealed the high energy ball milling technique could reduce the size, increase the surface area, and improve the dispersion ability of GNPs. The microstructure, hardness, and components of the nanocomposite coatings were greatly affected by GNP sizes. The highest microhardness was measured to be 273 HV for the nanocomposite coatings containing 5 h-milled GNPs, which is increased up to ∼47% compared to pristine Ni coating. The enhancement in the hardness is attributed to the uniform dispersion of the small GNP sizes inside the Ni matrix and the Ni grain size reduction when using milled GNPs.

The effect of graphene nanoplatelet size on the microstructure and hardness of electrodeposited nickel–graphene nanocomposite coatings was investigated.     

Integrated optical and electrochemical detection of Cu2+ ions in water using a sandwich amino acid–gold nanoparticle-based nano-biosensor consisting of a transparent-conductive platform

In this paper, an optical-electrochemical nano-biosensor was introduced for measuring Cu²⁺ ion concentrations in water. A multi-step procedure was used to fabricate the transparent-conductive biosensor platform consisting of an l-cysteine–gold nanoparticle-based sandwich structure. First, colloidal gold nanoparticles (GNPs) were synthesized according to the Turkevich–Frens method with some modifications and then functionalized with l-cysteine molecules (GNP/l-cys). Then, cyclic voltammetry was preformed in buffered solutions containing HAuCl₄·3H₂O for gold nanoparticle electrodeposition on cleaned ITO glasses. The GNP-electrodeposited ITO glasses (ITO/GNPs) were thermally treated in air atmosphere for 1 hour at a temperature of 300 °C. Following the procedure, the gold nanoparticles on ITO/GNPs substrates were functionalized with l-cysteine to prepare ITO/GNPs/l-cys substrates. Finally, the sandwich-type substrates of ITO/GNPs/l-cys⋯Cu²⁺⋯l-cys/GNPs were fabricated by accumulation of Cu²⁺ ions using an open circuit technique performed in copper ion buffer solutions in the presence of previously produced colloidal GNP/l-cys nanoparticles. The effective parameters including GNP/l-cys solution volume, pre-concentration pH and pre-concentration time on the LSPR and SWV responses were investigated and optimized. The fabricated transparent-conductive platforms were successfully assessed as a nano-biosensor for detection of copper ions using two different methods of square wave voltammetry (SWV) and localized surface plasmon resonance (LSPR). As a result, the proposed biosensor showed a high sensitivity, selectivity and a wide detectable concentration range to copper ions. The total linear range and the limit of detection (LOD) of the nano-biosensor were 10–100 000 nM (0.6–6354.6 ppb) and below 5 nM (0.3 ppb), respectively. The results demonstrated the potential of combining two different optical and electrochemical methods for quantitation of the single analyte on the same biosensor platform and obtaining richer data. Also, these results indicated that the developed LSPR-SWV biosensor was superior to many other copper biosensors presented in the literature in terms of linear range and LOD. The developed nano-biosensor was successfully applied in the determination of trace Cu²⁺ concentration in actual tap water samples.

The transparent-conductive platforms of ITO/GNPs/l-cys⋯Cu²⁺⋯l-cys/GNPs were fabricated for quantitation of Cu²⁺ ions in water samples using combined LSPR and SWV methods.     

Pt incorporated mesoporous carbon spheres: controllable structure with enhanced catalytic activity and stability

We report a simple synthesis process to prepare well-dispersed Pt nanoparticles incorporated in mesoporous carbon spheres. By manipulating the relative ratio of Pt precursor and resorcinol-formaldehyde resin (RF), Pt/carbon composites with different morphologies and Pt content were achieved. The as-prepared Pt/C composite materials show higher catalytic activity and reusability for the reduction of 4-nitrophenol (4-NP) than the Pt deposited commercial activated carbon (Pt/AC), which can be ascribed to the high dispersion of Pt nanoparticles in the carbon spheres.

We report a simple synthesis process to prepare well-dispersed Pt nanoparticles incorporated in mesoporous carbon spheres.     

Magnetic polymer bowl for enhanced catalytic activity and recyclability

This work introduces the fabrication of a magnetic polymer bowl for enhanced catalytic activity and recyclability, which involves the synthesis of silica-coated Fe₃O₄ magnetic clusters, seeded dispersion polymerization using the magnetic clusters, and transformation into a bowl-like structure via a phase separation route. The additional treatment with tannic acid (TA) on the bowls allows the in situ formation of silver nanoparticles (AgNPs) on their surfaces. The openness and larger surface area of the bowls, as compared with those of other structured particles, such as spheres and flowers, enable a considerably higher immobilization of AgNPs, thus leading to an excellent catalytic reduction for 4-nitrophenol (4-NP), methylene blue (MB), and rhodamine B. Furthermore, the strong magnetic response originating from the magnetic clusters inside the bowls endows a good magnetic recovery and an excellent reusability for the repeated reduction of the organic dyes without loss of catalytic activity.

The fabrication of a magnetic polymer bowl with a considerably higher immobilization of AgNPs was demonstrated for enhanced catalytic activity and recyclability.     

Synthesis of polyhydroquinolines and propargylamines through one-pot multicomponent reactions using an acidic ionic liquid immobilized onto magnetic Fe3O4 as an efficient heterogeneous catalyst under solvent-free sonication

A nano-sized Fe₃O₄-supported Lewis acid ionic liquid catalyst for the synthesis of polyhydroquinolines and propargylamines under ultrasound irradiation has been developed. LAIL@MNP was synthesized from imidazolium chlorozincate(ii) ionic liquid grafted onto the surface of Fe₃O₄ nanoparticles and evaluated by FT-IR, TGA, SEM, Raman, TEM, ICP-OES, and EDS. The multicomponent synthesis of polyhydroquinolines and propargylamines proceeded smoothly to afford the desired products in high yields. LAIL@MNP can be separated easily from the reaction mixture and reused for several runs without a significant degradation in catalytic activity.

A nano-sized Fe₃O₄-supported Lewis acid ionic liquid catalyst for the synthesis of polyhydroquinolines and propargylamines under ultrasound irradiation has been developed.     

One-step green synthesis of 2D Ag-dendrite-embedded biopolymer hydrogel beads as a catalytic reactor

Silver (Ag) nanocrystals with a dendritic structure have attracted intensive attention because of their unique structural properties, which include abundant sharp corners and edges that provide a large number of active atoms. However, the synthesis of Ag dendrites via a simple and environmentally friendly method under ambient conditions remains a challenge. In this paper, we report a simple water-based green method for the production of biopolymer hydrogel beads embedded with Ag dendrites without using an additional reducing agent, stabilizer, or crosslinking agent. The obtained Ag dendrites exhibit a unique two-dimensional (2D) structure rather than a conventional three-dimensional structure because Ag⁺ ions are reduced on the surface of the solid-phase hydrogel beads and grow into crystals. Reasonable mechanisms explaining the formation of the nanocomposite hydrogel beads and the formation of 2D Ag dendrites in the hydrogel are proposed on the basis of our observations and results. The hydrogel beads embedded the 2D Ag dendrites were used as an environmentally friendly catalytic reactor, and their catalytic performance was evaluated by adopting the reduction of 4-nitrophenol to 4-aminophenol with NaBH₄ as a model reaction.

Alginate hydrogel beads embedded with 2D Ag dendrites were synthesized by simply adding aqueous alginate droplets to an aqueous AgNO₃ solution.     

Green synthesis of Au decorated CoFe2O4 nanoparticles for catalytic reduction of 4-nitrophenol and dimethylphenylsilane oxidation

Gold nanoparticles (Au NPs) have been widely employed in catalysis. Here, we report on the synthesis and catalytic evaluation of a hybrid material composed of Au NPs deposited at the surface of magnetic cobalt ferrite (CoFe₂O₄). Our reported approach enabled the synthesis of well-defined Au/CoFe₂O₄ NPs. The Au NPs were uniformly deposited at the surface of the support, displayed spherical shape, and were monodisperse in size. Their catalytic performance was investigated towards the reduction of 4-nitrophenol and the selective oxidation of dimethylphenylsilane to dimethylphenylsilanol. The material was active towards both transformations. In addition, the LSPR excitation in Au NPs could be employed to enhance the catalytic performance, which was demonstrated in the 4-nitrophenol reduction. Finally, the magnetic support allowed for the easy recovery and reuse of the Au/CoFe₂O₄ NPs. In this case, our data showed that no significant loss of performance took place even after 10 reaction cycles in the oxidation of dimethylphenylsilane to dimethylphenylsilanol. Overall, our results indicate that Au/CoFe₂O₄ are interesting systems for catalytic applications merging high performances, recovery and re-use, and enhancement of activities under solar light illumination.

We present a cleaner chemical synthesis process of a magnetic recoverable Au/CoFe₂O₄ hybrid nanocomposite catalyst that has remarkable activity in catalytic reduction and oxidation, improved by surface plasmon resonance.