Performance For Reduction Of 4-nitrophenol Research Articles

Transition metal modified Al2O3 mesoporous nanospheres for catalysis of organic reactions

The performance of metal oxide-based catalysts are usually determined by their characteristics such as material composition, morphology, and surface/interface properties. Therefore, rational design of metal oxide-based catalysts with special surface/interface characteristics and porous microstructure still needs further research. In this work, a facile two-step solvothermal-annealing method is developed for the synthesis of transition metal (TM) modified Al2O3 (TM-Al2O3, TM = Cu, Fe, Ni, Co) nanospheres. The influences of different ratios of solvents (e.g., water and glycerol) on the morphology and particle size of the nanocatalysts are explored. Benefitting from the nano-spherical morphology and unique mesoporous structure, the representative catalyst (i.e., Cu-Al2O3) exhibits favorable catalytic performance in 4-nitrophenol reduction and benzyl alcohol oxidization reactions. The turnover frequency of Cu-Al2O3 is high up to 35.9 min−1 for the reduction of 4-nitrophenol, which is higher than that of its counterparts (i.e., Fe-Al2O3, Ni-Al2O3, and Ni-Al2O3) and many recently reported Al2O3-based catalysts. Moreover, the pH of the reaction system is regulated to enhance the catalytic efficiency in selective oxidization of benzyl alcohol by an additive addition strategy. These results suggest that the nano-spherical and mesoporous morphology is indeed effective for the activity enhancement of TM-Al2O3 catalysts. The same catalyst designing concept and performance regulation strategy may be extended to other TM-modified metal oxide systems, making it possible to tune the catalytic behavior for various chemical reactions.

A Highly Active and Reusable Multicomponent high Entropy Metal Oxide Catalyst for Nitroarenes Hydrogenation

It is well known that multicomponent catalysts can improve catalytic performance, however their rational design and precise control of catalytic activities by varying the composition of the elements is challenging. Herein, we present a facile and scalable synthetic strategy for production of senary and septenary metal oxide nanoparticles with a chemical composition of MSbOx and MSb2Ox (M: Fe, Ni, Co, Cu, and Zn). All samples were formed in a tetragonal crystal structure with space group 136 and crystallographic symmetry P42/mnm while the details of their constituent unit cells are different, belonging to rutile or trirutile structures. These nanocomposites have an oxygen vacancy-rich construction with uniform elemental distributions that produce various surface functionalities. They showed instantaneous hydrogenation catalytic performance for reduction of 4-nitrophenol to 4-aminophenol at room temperature. Among our samples, the senary catalyst with MSbOx chemical composition showed better durability and reusability owning to its morphological and microstructural properties. It showed 100% conversion of 4-nitrophenol to 4-aminophenol within 4 min at the 18th run without any by-products.

Fabrication of graphene nanoplatelets/MgAl-layered double hydroxide nanocomposites as efficient support for gold nanoparticles and their catalytic performance in 4-nitrophenol reduction

The catalytic reduction of 4-nitrophenol is of considerable importance to a multitude of applications and industries. The present work introduces a new catalyst (AuNP/GNP/MgAl-LDH) containing gold nanoparticles (AuNP) supported on graphene nanoplatelets (GNP) intercalated in Mg Al layered double hydroxides (MgAl-LDH) for the reduction of 4-nitrophenol to 4-aminophenol using NaBH4 as a reducing agent. The catalyst was characterised by FTIR, XRD, STEM, TEM, and BET specific surface area. The XRD analysis showed the presence of crystalline phases of gold on the supports, while TEM demonstrated that MgAl-LDH provided uniform binding sites for AuNPs and prevented agglomeration. Similar reaction rate constant was determined for the disappearance of 4-nitrophenol and for the appearance of 4-aminophenol. The reaction rate constant was the highest for AuNP/GNP/MgAl-LDH, followed by AuNP/MgAl-LDH and AuNP/GNP. AuNP/GNP/MgAl-LDH was found stable after five repeated cycles.

Acoustic levitation synthesis and subsequent physicochemical properties of bimetallic composite nanoparticles

Bimetallic noble-metal nanoparticles were synthesized in a containerless state via acoustic levitation. We chose oleylamine as stabilizer and borane-t-butylamine complex as reducing agent to prepare the Au–Ag nanoparticles in organic phase. The synthesis process, particle size distribution, morphology, optical property, chemical composition, and catalytic performance of prepared bimetallic nanoparticles were characterized and analyzed. The Au–Ag nanoparticles synthesized in acoustic levitation exhibited a smaller size, narrower distribution range, and improved catalytic performance in 4-nitrophenol reduction compared with the normal container condition. In acoustic levitation, the catalytic activity of equiatomic Au–Ag nanoparticles was significantly enhanced due to synergistic effects.

TEMPO-oxidized cellulose for in situ synthesis of Pt nanoparticles. Study of catalytic and antimicrobial properties

In this work, platinum nanoparticles (PtNPs) were synthesized by a modified polyol process using TEMPO-oxidized nanocellulose (TOCN) as a stabilizing and co-reducing agent. Different ratios of TOCN nanocellulose to Pt4+ ions were studied to establish the optimum stabilizing effect of PtNPs. The effect of different pH of aqueous TOCN suspensions on the morphology of PtNPs was also examined. It was proved that PtNPs can be obtained solely in the presence of TOCN without the use of an additional reducing agent or ethylene glycol. The morphology and structural properties of the nanocellulose‑platinum nanoparticles composites were assessed using spectroscopic, microscopic and diffraction techniques, The catalytic performance in 4-nitrophenol reduction was evaluated. Significant differences in reaction rate constants k were found depending on the pH of the TOCN suspension applied during Pt4+ reduction. The crucial effect of reaction conditions on PtNPs performance was confirmed in tests of antibacterial efficacy against E. coli.

Floating synthesis with enhanced catalytic performance via acoustic levitation processing

Acoustic levitation supplies a containerless state to eliminate natural convection and heterogeneous crystal nucleation and thus provides a highly uniform and ultra clean condition in the confined levitating area. Herein, we attempt to make full use of these advantages to fabricate well dispersed metal nanoparticles. The gold nanoparticles, synthesized in an acoustically levitated droplet, exhibited a smaller size and improved catalytic performance in 4-nitrophenol reduction were synthesized in an acoustically levitated droplet. The sound field was simulated to understand the impact of acoustic levitation on gold nanoparticle growth with the aid of crystal growth theory. Chemical reducing reactions in the acoustic levitated space trend to occur in a better dispersed state because the sound field supplies continuous vibration energy. The bubble movement and the cavitation effect accelerate the nucleation, decrease the size, and the internal flow inside levitated droplet probably inhibit the particle fusion in the growth stage. These factors lead to a reduction in particle size compared with the normal wet chemical synthetic condition. The resultant higher surface area and more numerous active catalytic sites contribute to the improvement of the catalytic performance.

Formation of SiO2@C-Ni magnetic nanotubes with excellent performance in 4-nitrophenol reduction.

A facile and rational strategy for immobilizing nickel nanoparticles (Ni NPs) on silica nanotubes (SiO2@C-Ni) was developed via the Stöber method, nickel ion mediated dopamine polymerization and carbonization treatment, coupled with removal of the template of one-dimensional (1D) MnO2 nanowires (NWs). The as-prepared SiO2@C-Ni nanotubes show vast interior space with a large specific surface area and an open channel, which offer a spacious transport channel for molecular diffusion and electron transfer. Consequently, SiO2@C-Ni nanotubes exhibited outstanding catalytic efficiency and excellent stability for 4-nitrophenol (4-NP) reduction. Their superior catalytic activity could be ascribed to the high coverage of Ni NPs and the tubular structure of the obtained SiO2@C-Ni, by which the silica nanotubes enhanced the accessibility of the active sites and increased the mass transfer. This facile and controllable strategy may introduce a new avenue for designing metal NP-supported composites with high dispersion for diverse applications.

A new 2D layered aluminophosphate |Hada|6[Al6(PO4)8](H2O)11 supported highly uniform Ag nanoparticles for 4-nitrophenol reduction

This work presents a new 2D aluminophosphate (ZHKU-1) with inorganic sheets containing a 4,6,12-net in AAAA-stacked sequence. Moreover, small Ag clusters supported on ZHKU-1 exhibit excellent catalytic performance in 4-nitrophenol reduction.

In situ preparation of highly dispersed Pd supported on exfoliated layered double hydroxides via nitrogen plasma for 4-nitrophenol reduction.

In this work, a simple and environmental-friendly nitrogen glow discharge plasma reduction method has been developed for synthesizing palladium nanoparticles (PdNPs) supported on exfoliated Mg-Al-layered double hydroxide (Pd/LDH) catalysts. The as-prepared catalysts were characterized by means of characterizations methods, which contain X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometry (XPS), and Fourier transform infrared (FT-IR). Highly dispersed ultrafine PdNPs were supported on exfoliated, defect-induced LDHs uniformly without agglomeration. The effects of treatment time of nitrogen plasma and Pd loading amount on structure, morphology, and catalytic performance of Pd/LDHs were investigated. The comparisons of structure and morphology between LDHs and Pd/LDHs were also discussed. The average particle size of as-synthesized PdNPs with face-centered cubic structure is 2.01 nm, which ranges from 1.18 to 3.01 nm. Nitrogen plasma cannot only reduce Pd2+, but also exfoliate LDHs, introduce defects, and even destroy the structure of LDHs. The Pd/LDH catalyst with 1 wt% Pd loading under nitrogen plasma treatment for 60 min showed the best catalytic performance in 4-nitrophenol reduction. The turnover frequency (TOF) of as-prepared catalyst is 20-fold higher than that of commercial Pd/C catalyst.

Assembly of RGO composite aerogels embedded with ultrasmall Au nanoparticles as an active and recyclable catalyst for reduction of 4-nitrophenol

Metallic Au nanoparticles (NPs) are active catalysts in many chemical reactions. However, small-size Au NPs are difficult to obtain since they tend to agglomerate due to their high surface energies. Herein, we reported a facile and green hydrothermal process, using graphene oxide (GO) as the RGO precursor, HAuCl4 as Au precursor and L-cysteine (L-cys) as both cross-linker and reducing agent, to fabricate an Au/RGO composite aerogel. During the hydrothermal process, the reduction of GO/HAuCl4, the oxidation of L-cys to produce disulfide linkage, and the self-assembly of RGO aerogel occurs simultaneously, leading to the resultant RGO aerogels uniformly and intimately embedded with disulfide protected ultrasmall Au NPs with an average size of 1.3 nm. The as-obtained Au/RGO composite aerogel exhibited superior catalytic performance for reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), with a total transformation of 4-NP achieved in 4 min. The much higher activity over Au/RGO aerogel as compared with unsupported thiol-capped Au NPs can be attributed to the synergistic effect of metallic Au and RGO. Moreover, Au/RGO composite aerogel also showed high stability and can be easily separated from the reaction systems for recycling. No obvious decrease of catalytic reduction activity was observed over the Au/RGO aerogel after five cycles. Considering the high price of metallic Au, the embedding of Au NPs in three-dimensional RGO aerogels to facilitate its recycling is extremely appealing for its practical applications.

Bi-Metal Phosphide NiCoP: An Enhanced Catalyst for the Reduction of 4-Nitrophenol.

Porous phosphide NixCoyP composite nanomaterials are successfully synthesized at different Ni/Co ratios (=0, 0.5, 1, and 2) to reduce 4-nitrophenol. The X-ray diffraction and X-ray photoelectron spectroscopy results demonstrate that the products are CoP, NiCoP/CoP, NiCoP, and NiCoP/Ni2P when the Ni/Co ratio is 0, 0.5, 1, and 2, respectively. The products exhibit different catalytic performance for reduction of 4-nitrophenol at room temperature. Among them, the pure NiCoP delivers a better catalytic efficiency with and , due to the synergy between Ni and Co atoms. The sequence of catalytic efficiency of different samples is CoP < NiCoP/CoP < NiCoP/Ni2P < NiCoP.

Nanoengineering of amino - functionalized mesoporous silica nanospheres as nanoreactors

Selective functionalization of mesoporous silica nanospheres (MSNs) is crucial for nanoengineering of MSNs. Herein, we have combined “surface-protected etching strategy” and “cationic surfactant assisted etching strategy” to prepare functionalized MSNs with externally attached amino groups. The externally attached NH2 groups endow the catalysts with excellent catalytic performance for nitroaldol reaction between nitromethane and benzaldehyde. In addition, those NH2-MSNs can also be used to support gold nanoparticles, which display very good catalytic performance for reduction of 4-nitrophenol. It can be envisioned that the synthesis protocol developed in this work could also be extended to nanoengineered MSNs, which provides opportunities for nanoreactors design.

Novel Prussian-blue-analogue microcuboid assemblies and their derived catalytic performance for effective reduction of 4-nitrophenol

Novel Co–Fe PBA microcuboids (MCBs) were solvothermally synthesized in the presence of PVP for the first time, and the cuboid-derived catalyst, CoFe/NC-MCBs, showed excellent catalytic performance for the reduction of 4-nitrophenol.

Size controlled green synthesis of gold nanoparticles using Coffea arabica seed extract and their catalytic performance in 4-nitrophenol reduction.

Well crystalline gold nanoparticles (AuNPs) of different sizes were fabricated using sundried Coffea arabica seed (CAS) extract at room temperature by controlling the pH of the green extract. The size, shape and crystallinity of the nanoparticles have been studied using electron microscopy and X-ray diffraction. The presence of phenolic groups (revealed through FT-IR studies) from the CAS extract are responsible both for the reduction of Au ions and stabilization of the formed AuNPs. The efficiency of the CAS extract mediated green synthesis technique for the production of AuNPs has been compared to the conventional chemical Turkevich technique, which not only uses a toxic reductant such as NaBH4, but also operates around the boiling point of water. It has been observed that the CAS extract mediated synthesis process produces relatively bigger AuNPs at similar pH values of the reaction mixture in comparison to the AuNPs produced in the Turkevich process. Although the AuNPs synthesized using CAS extract are relatively larger and polydisperse in nature, their catalytic efficiencies for the degradation of an aromatic nitro compound (4-nitrophenol) are found to be comparable to the chemically fabricated AuNPs. Probable mechanisms associated with the formation of AuNPs and their size control in the CAS extract mediated green synthesis process have been discussed.

Imparting Catalytic Activity to a Covalent Organic Framework Material by Nanoparticle Encapsulation.

Integrating covalent organic frameworks (COFs) with other functional materials is a useful route to enhancing their performances and extending their applications. We report herein a simple encapsulation method for incorporating catalytically active Au nanoparticles with different sizes, shapes, and contents in a two-dimensional (2D) COF material constructed by condensing 1,3,5-tris(4-aminophenyl)benzene (TAPB) with 2,5-dimethoxyterephthaldehyde (DMTP). The encapsulation is assisted by the surface functionalization of Au nanoparticles with polyvinylpyrrolidone (PVP) and follows a mechanism based on the adsorption of nanoparticles onto surfaces of the initially formed polymeric precursor of COF. The incorporation of nanoparticles does not alter obviously the crystallinity, thermal stability, and pore structures of the framework matrices. The obtained COF composites with embedded but accessible Au nanoparticles possess large surface areas and highly open mesopores and display recyclable catalytic performance for reduction of 4-nitrophenol, which cannot be catalyzed by the pure COF material, with activities relevant to contents and geometric structures of the incorporated nanoparticles.

Surfactant-assisted selective etching strategy for generation of rattle-like mesoporous silica nanoparticles

Nowadays, rattle-like or so-called yolk-shell nanostructures have set off a new wave of research in view of their prominent features including large surface area, tunable void and flexible functional core, etc. Herein, rattle-like mesoporous silica nanoparticles (RMSNs) with a pure silica core, a hollow cavity and a mesoporous shell have been successfully fabricated via a surfactant-assisted selective etching strategy. The synthetic approach involves the preparation of solid silica spheres with three-layer different structural silica containing the inner core of pure silica, middle layer of hybrid silica and outer shell of surfactant/SiO2 composite, followed by a hydrothermal treatment in hot water. The resulting products show a distinct rattle-like structure and spherical morphology. The average diameter, the shell thickness, and the solid core size of RMSNs are about 290, 35 and 90nm, respectively. During the etching process, the surfactant with different length of alkyl chain (CnTAB, e.g. cetyltrimethylammonium bromide) in outer shell plays a decisive role for the formation of rattle-like structure. Benefiting from the residual amino groups in RMSNs, Au@RMSNs composites can be further constructed by in-situ generating Au nanoparticles into their hollow cavity, demonstrating an excellent catalytic performance for reduction of 4-nitrophenol. Additionally, RMSNs also show a strong ability for adsorption of rhodamine B.

Fabrication of Ag/halloysite nanotubes/Fe3O4nanocatalyst and their catalytic performance in 4-nitrophenol reduction

AbstractAg/halloysite nanotubes/Fe3O4 (Ag/HNTs/Fe3O4) nanocatalyst was synthesized in our work. The structure of the as-prepared composite catalyst was that Fe3O4 nanoparticles with the size of 5.0–8.0 nm were loaded in the internal hollow lumen of HNTs and Ag nanoparticles with a mean diameter of 20 nm were randomly deposited on the external surface of HNTs/Fe3O4. The resultant Ag/HNTs/Fe3O4 exhibited satisfied catalytic activity (with conversion of 100% in 38 min) to the reduction of 4-nitrophenol (4-NP) with sodium borohydride. The catalytic activity was markedly enhanced when the catalysts concentration was increased (the rate constant was gradually increased from 0.40 to 20.18 × 10−3 s−1). Also, the advantage of the obtained magnetic composite catalyst in terms of their fast separation and simple reuse was identified through five successive catalytic and separation process cycles. It could be concluded that Ag/HNTs/Fe3O4 showed satisfied catalytic activity, recoverability, and reusability, which show...

Graphene oxide reduced and modified by environmentally friendly glycylglycine and its excellent catalytic performance

An environmentally friendly new approach to prepare reduced graphene oxide (RGO) was developed by using glycylglycine (gly-gly) as both a reducing and stabilizing agent. Graphene oxide (GO) was transformed to RGO with the appropriate pH, temperature and reducing agent/GO ratio. The RGO was characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermo-gravimetric analysis, x-ray diffraction, x-ray photoelectron spectroscopy (XPS), and transmission electron microscopy. The RGO aqueous suspension showed extraordinary stability in the absence of any external stabilizing reagents. The XPS analysis showed that this excellent stability is due to modifications of the RGO nanosheets by the gly-gly molecules. The modified RGO complex with copper shows good catalytic performance for reduction of 4-nitrophenol to 4-aminophenol.

Controllable synthesis of Ni/SiO₂ hollow spheres and their excellent catalytic performance in 4-nitrophenol reduction.

The high cost of noble metal nanoparticles used for catalytic reduction of 4-nitrophenol (4-NP) leads to an extensive study of Ni nanoparticles (NPs) for their low cost and magnetic properties. However, the conventional routes for preparing the ferromagnetic Ni NPs usually lead to large particle size and aggregation. In this study, we propose a simple two-step method for the synthesis of hierarchical Ni NP supported silica magnetic hollow microspheres (Ni/SiO2 MHMs). Tiny Ni NPs are well dispersed on the supports with high loading amounts (15 wt%). The size of Ni NPs can be tuned from 10 nm to 21 nm with the size of Ni/SiO2 MHMs increasing from 230 nm to 800 nm. The as-prepared samples exhibit excellent catalytic activity in the reduction of 4-NP. Furthermore, the experimental results prove that the size of Ni NPs plays an important role in the catalytic activity. The catalytic activity of small sized Ni NPs is higher than that of large sized and many other supported Ni NP catalysts as reported. In particular, the magnetic properties of Ni/SiO2 MHMs make them easy to recycle for reuse.

Uniform Ni/SiO2@Au magnetic hollow microspheres: rational design and excellent catalytic performance in 4-nitrophenol reduction.

A unique and rational design was presented to fabricate Ni/SiO2@Au magnetic hollow microspheres (MHMs) with interesting structures and well-dispersed metal nanoparticles. Hierarchical nickel silicate hollow microspheres were synthesized using silica colloidal spheres as a chemical template. Then, Ni/SiO2 MHMs with well-dispersed Ni nanoparticles were prepared via an in situ reduction approach. Ni/SiO2@Au MHMs were finally obtained by immobilizing uniform Au nanoparticles onto Ni/SiO2 support through a low-temperature chemical reduction process. It was found that Ni/SiO2@Au MHMs inherit the shape and uniformity of the original silica scaffold, and Ni NPs and Au NPs, which were less than 5 nm in size, were well dispersed on the mesoporous silica shell with narrow size distribution. Both Ni/SiO2 and Ni/SiO2@Au MHMs showed excellent catalytic activity in the 4-nitrophenol reduction reaction. Importantly, introduction of a small amount of Au NPs onto Ni/SiO2 MHMs markedly improved the catalytic activity. In particular, Ni/SiO2@Au MHMs showed high conversion even after re-use for several cycles with magnetic separation. The unique structure, high catalytic performance, and ease of separation make Ni/SiO2@Au MHMs highly promising candidates for diverse applications.