Facile synthesis of cubical Co3O4 supported Au nanocomposites with high activity for the reduction of 4-nitrophenol to 4-aminophenol
TL;DR: In this paper, cubic Co3O4 supported Au nanocomposites have been synthesized via a facile impregnation method and they exhibited excellent catalytic activity for the reduction of 4-nitrophenol (TOF = 9.83 min−1).
Abstract: Cubic Co3O4 supported Au nanocomposites have been synthesized via a facile impregnation method. The Au/Co3O4 exhibited excellent catalytic activity for the reduction of 4-nitrophenol (TOF = 9.83 min−1). The unique structure and high catalytic performance make the materials highly promising candidates for diverse applications in the area of catalysis.
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TL;DR: A photochemical green synthesis using thermal exfoliation process is developed to fabricate Au@graphitic carbon nitride (g-C3N4) nanocomposite, highly recyclable and reusable, for the catalytic reduction of nitrophenols by NaBH4.
Abstract: In this study, a photochemical green synthesis using thermal exfoliation process is developed to fabricate Au@graphitic carbon nitride (g-C3N4) nanocomposite, highly recyclable and reusable, for the catalytic reduction of nitrophenols by NaBH4. Au nanoparticles (Au NPs) in the diameter of 5–15 nm are deposited onto the surface of g-C3N4 in 3–6 layers of structure. The synthesized Au@g-C3N4 nanocomposites exhibit excellent catalytic activity and stability in the reduction of nitrophenols including 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4-nitrophenol, and 2,4,6-nitriophenol. The catalytic performance of Au@g-C3N4 is highly dependent on the initial nitrophenol concentration, Au loading, inorganic anions, and pH. The rate constant of 4-nitrophenol reduction over Au@g-C3N4 (2 wt%) is 26.4 times that of pure Au NP in the presence of 7 mM of NaBH4 at pH 5. Moreover, Au@g-C3N4 can be reused for at least 10 consecutive cycles without considerable loss of catalytic activity. The presence of anions (0.1 M) such as H2PO4−, SO42-, HCO3−, and NO3− decreases the rate of 4-nitrophenol reduction by a factor of 1.2–8.8; whereas there is a 1.2-time increase in rate constant upon the addition of Cl− ion. The detection of H radical adducts indicates that Au NPs adsorbs BH4− ions and forms Au-H species. The porous and conductive g-C3N4 provides large surface area for nitroarene adsorption and subsequent electron transfer from the Au-H species to 4-nitrophenol, which results in accelerating the reduction of 4-nitrophenol. Results clearly demonstrate that Au@g-C3N4 is a promising green catalyst of enormous potential for nitroaromatic reduction, which provides a new venue for tailoring Au-based nanomaterials in elucidation of a wide variety of heterogeneous catalytic reactions.
144 citations
TL;DR: In this paper, a simple thermal route for synthesizing 5.1% cobalt doped CuO nanoparticles (NPs) as the optimized composition of the best heterogeneous CuO catalyst for catalytic reduction of toxic 4-nitrophenol to industrially beneficial 4-aminophenol was presented.
Abstract: We present here a simple thermal route for synthesizing 5.1 wt% cobalt doped CuO nanoparticles (NPs) as the optimized composition of the best heterogeneous CuO catalyst for catalytic reduction of toxic 4-nitrophenol to industrially beneficial 4-aminophenol. The reduction is completed in merely 3 min in the presence of 8 mM NaBH4 as reducing agent. The optimized catalyst dose was 2 mg/L for converting 0.12 mM 4-nitrophenol and the corresponding rate constant (k) for reduction reaction was 43.8 × 10−3 s−1 per mg of catalyst. The catalytic reduction reaction was monitored by UV–vis spectroscopy method and by HPLC analysis. The mechanism is discussed in the light of hydride transfer phenomenon facilitated by large surface area and positive surface charge of the cobalt doped CuO nanoparticles. The cobalt doping resulted in: (a) increasing surface area due to decrease in particle size of the CuO NPs to 10 nm, measured by HRTEM; (b) improve stability of the cobalt doped CuO NPs. The cobalt dopant occupied the grain boundaries of CuO to reduce the particle size as derived from positron annihilation lifetime spectroscopy. The X-ray photoelectron spectroscopy analysis of unused catalyst and the spent catalyst revealed occurrence of Co2+ and Co3+ states at the surface. While the X-ray diffraction studies of spent catalyst confirmed the inhibition of reduction of the surface CuO to metallic copper in the presence of NaBH4, attributable to cobalt doping. It was concluded that cobalt doping led to stable and efficient CuO NPs as catalyst for reduction reaction.
74 citations
TL;DR: Au@Fe3O4 yolk-shell nanocatalysts based on the thermal decomposition of iron pentacarbonyl in the presence of 2.5-10-nm Au core nanoparticles were successfully fabricated for the catalytic reduction of nitroarenes as discussed by the authors.
Abstract: Au@Fe3O4 yolk–shell nanocatalysts based on the thermal decomposition of iron pentacarbonyl in the presence of 2.5–10-nm Au core nanoparticles were successfully fabricated for the catalytic reduction of nitroarenes. The particle sizes of the Au@Fe3O4 nanostructures were in the range 8–15 nm, with Fe3O4 shell layer thicknesses of 2.0–2.4 nm. The Fe3O4 layer not only can form a magnetic shell for recovery but also enables the protection of the catalytic activity of the Au core nanoparticles toward the reduction of nitrobenzene derivatives including 2-nitrophenol, 4-nitrophenol, 4-nitrotoluene, and 1-chloro-4-nitrobenzene in the presence of NaBH4. The catalytic performance of Au@Fe3O4 is highly dependent on the particle size of the Au core materials and the substituent groups of the nitroarenes. The reduction rates of nitroarenes with electron-withdrawing groups were found to be 2.3–2.6 times higher than those of nitroarenes with electron-donating groups. In addition, the reduction of nitroarenes by the Au@Fe...
68 citations
TL;DR: The results indicate that Gd(OH)3 nanorods act as a promoter to enhance the catalytic activity by providing a synergistic effect from the strong metal support interaction and the large surface area for high dispersion of small sized Pd nanoparticles enriched with hydroxyl groups on the surface.
Abstract: Heterogeneous catalytic hydrogenation reactions are of great importance to the petrochemical industry and fine chemical synthesis. Herein, we present the first example of gadolinium hydroxide (Gd(OH)3) nanorods as a support for loading ultra-small Pd nanoparticles for hydrogenation reactions. Gd(OH)3 possesses a large number of hydroxyl groups on the surface, which act as an ideal support for good dispersion of Pd nanoparticles. Gd(OH)3 nanorods are prepared by hydrothermal treatment, and Pd/Gd(OH)3 catalyst with a low loading of 0.95 wt% Pd is obtained by photochemical deposition. The catalytic hydrogenation of p-nitrophenol (4-NP) to p-aminophenol (4-AP) and styrene to ethylbenzene is performed as a model reaction. The obtained Pd/Gd(OH)3 catalyst displays excellent activity as compared to other reported heterogeneous catalysts. The rate constant of 4-NP reduction is measured to be 0.047 s−1 and the Pd/Gd(OH)3 nanocatalyst shows no marked loss of activity even after 10 consecutive cycles. Additionally, the hydrogenation of styrene to ethylbenzene over Pd/Gd(OH)3 nanorods exhibits a turnover frequency (TOF) as high as 6159 h−1 with 100% selectivity. Moreover, the catalyst can be recovered by centrifugation and recycled for up to 5 consecutive cycles without obvious loss of activity. Our results indicate that Gd(OH)3 nanorods act as a promoter to enhance the catalytic activity by providing a synergistic effect from the strong metal support interaction and the large surface area for high dispersion of small sized Pd nanoparticles enriched with hydroxyl groups on the surface. The high performance of Pd/Gd(OH)3 in heterogeneous catalysis offers a new, efficient and facile strategy to explore other metal hydroxides or oxides as supports for organic transformations.
65 citations
TL;DR: In this article, a magnetically separable N doped-cobalt carbon composite (CoNC) was synthesized via thermal treatment of Co3O4-melamine mixture in atmospheric condition.
45 citations
References
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TL;DR: In this paper, gold catalysts were prepared by coprecipitation from an aqueous solution of HAuCl4 and the nitrates of various transition metals, including Auα-Fe2O3, AuCo3O4, and AuNiO.
2,917 citations
TL;DR: This Review highlights morphology-dependent properties of nonspherical noble metal nanoparticles with a focus on localized surface plasmon resonance and local field enhancement, as well as their applications in various fields including Raman spectroscopy, fluorescence enhancement, analytics and sensing, photothermal therapy, (bio-)diagnostics, and imaging.
Abstract: Nanoparticles of noble metals belong to the most extensively studied colloidal systems in the field of nanoscience and nanotechnology. Due to continuing progress in the synthesis of nanoparticles with controlled morphologies, the exploration of unique morphology-dependent properties has gained momentum. Anisotropic features in nonspherical nanoparticles make them ideal candidates for enhanced chemical, catalytic, and local field related applications. Nonspherical plasmon resonant nanoparticles offer favorable properties for their use as analytical tools, or as diagnostic and therapeutic agents. This Review highlights morphology-dependent properties of nonspherical noble metal nanoparticles with a focus on localized surface plasmon resonance and local field enhancement, as well as their applications in various fields including Raman spectroscopy, fluorescence enhancement, analytics and sensing, photothermal therapy, (bio-)diagnostics, and imaging.
922 citations
TL;DR: The as-prepared new solid-phase biopolymer-based catalysts are very efficient, stable, easy to prepare, eco-friendly, and cost-effective, and they have the potential for industrial applications.
Abstract: Silver and gold nanoparticles have been grown on calcium alginate gel beads using a green photochemical approach. The gel served as both a reductant and a stabilizer. The nanoparticles were characterized using UV−visible spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), energy dispersive X-ray (EDS), and selected area electron diffraction (SAED) analyses. The particles are spherical, crystalline, and the size ranges for both Ag and Au nanoparticles are <10 nm. It is noticed from the sorption experiment that the loading of gold on calcium alginate beads is much more compared to that of Ag. The effectiveness of the as-prepared dried alginate-stabilized Ag and Au nanoparticles as a solid phase heterogeneous catalyst has been evaluated, for the first time, on the well-known 4-nitrophenol (4-NP) reduction to 4-aminophenol (4-AP) in the presence of excess borohydride. The reduction was very efficient and followed zero-order kinetics for both Ag and Au nanocompos...
886 citations
TL;DR: The fabrication of multifunctional microspheres which possess a core of nonporous silica-protected magnetite particles, transition layer of active gold nanoparticles, and an outer shell of ordered mesoporous silica with perpendicularly aligned pore channels makes the microsphere to be a novel stable and approachable catalyst system for various catalytic industry processes.
Abstract: The precise control of the size, morphology, surface chemistry, and assembly process of each component is important to construction of integrated functional nanocomposites. We report here the fabrication of multifunctional microspheres which possess a core of nonporous silica-protected magnetite particles, transition layer of active gold nanoparticles, and an outer shell of ordered mesoporous silica with perpendicularly aligned pore channels. The well-designed microspheres have high magnetization (18.6 emu/g), large surface area (236 m(2)/g), highly open mesopores (approximately 2.2 nm), and stably confined but accessible Au nanoparticles and, as a result, show high performance in catalytic reduction of 4-nitrophenol (with conversion of 95% in 12 min), styrene epoxidation with high conversion (72%) and selectivity (80%), especially convenient magnetic separability, long life and good reusability. The unique nanostructure makes the microsphere to be a novel stable and approachable catalyst system for various catalytic industry processes.
864 citations
TL;DR: A cylindrical piece of Au/graphene hydrogel, 1.08 cm in diameter and 1.28 cm in height, has been synthesized through the self-assembly of Au and graphene sheets under hydrothermal conditions for the first time as mentioned in this paper.
Abstract: A cylindrical piece of Au/graphene hydrogel, 1.08 cm in diameter and 1.28 cm in height, has been synthesized through the self-assembly of Au/graphene sheets under hydrothermal conditions for the first time. The hydrogel, containing 2.26 wt% Au, 6.94 wt% graphene, and 90.8 wt% water, exhibited excellent catalytic performance towards the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), which is about 90 times larger than previously reported values for spongy Au nanoparticles and 14 times more than the highest value among the polymer supported Au nanoparticle catalysts. The high catalytic activity arises from the synergistic effect of graphene: (1) the high adsorption ability of graphene towards 4-NP, providing a high concentration of 4-NP near to the Au nanoparticles on graphene; and (2) electron transfer from graphene to Au nanoparticles, facilitating the uptake of electrons by 4-NP molecules.
791 citations