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1.
The construction of a heterogeneous nanocatalyst with outstanding catalytic performance via an environmentally benign and cost-effective synthetic category has long been one of the challenges in nanotechnology. Herein, we synthesized highly efficient and low-cost mesoporous morphology-dependent CuO/CeO2-Rods and CuO/CeO2-Cubes catalysts by employing a green and multifunctional polyphenolic compound (tannic acid) as the stabilizer and chelating agent for 4-nitrophenol (4-NP) reduction reaction. The CuO/CeO2-Rods exhibited excellent performance, of which the activity was 3.2 times higher than that of CuO/CeO2-Cubes. This can be connected with the higher density of oxygen vacancy on CeO2-Rods (110) than CeO2-Cubes (100), the oxygen vacancy favors anchoring CuO species on the CeO2 support, which promotes the strong interaction between finely dispersed CuO and CeO2-Rods at the interfacial positions and facilitates the electron transfer from BH4 to 4-NP. The synergistic catalytic mechanism illustrated that 4-NP molecules preferentially adsorbed on the CeO2, while H2 from BH4 dissociated over CuO to form highly active H* species, contributing to achieving efficient hydrogenation of 4-NP. This study is expected to shed light on designing and synthesizing cost-effective and high-performance nanocatalysts through a greener synthetic method for the areas of catalysis, nanomaterial science and engineering, and chemical synthesis.  相似文献   

2.
The present work deals with phytogenic synthesis of Ag NPs in the natural polymer alginate as support material using Aglaia elaeagnoidea leaf extract as a reducing, capping, and stabilizing agent. Ag nanoparticles embedded in alginate were characterized using UV–Vis absorption spectroscopy, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscopy techniques and selected area electron diffraction techniques. The formation of AgNPs embedded in the polymer was in spherical shape with an average size of 12 nm range has been noticed. The prepared embedded nanoparticles in polymer were evaluated as a solid heterogeneous catalyst for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and methylene blue to leuco methylene blue in the liquid phase using sodium borohydride (NaBH4) as reducing agent. The silver nanoparticles embedded polymer exhibited extraordinary catalytic efficacy in reduction of 4-NP to 4-AP and the rate constant is 0.5054 min?1 at ambient conditions. The catalyst was recycled and reused up to 10 cycles without significant loss of catalytic activity. The preparation of Ag–CA composite was facile, stable, efficient, eco-friendly, easy to recycle, non-toxic, and cost effective for commercial application.  相似文献   

3.
A simple, green method is described for the synthesis of Gold (Au) and Silver (Ag) nanoparticles (NPs) from the stem extract of Breynia rhamnoides. Unlike other biological methods for NP synthesis, the uniqueness of our method lies in its fast synthesis rates (~7 min for AuNPs) and the ability to tune the nanoparticle size (and subsequently their catalytic activity) via the extract concentration used in the experiment. The phenolic glycosides and reducing sugars present in the extract are largely responsible for the rapid reduction rates of Au(3+) ions to AuNPs. Efficient reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of AuNPs (or AgNPs) and NaBH(4) was observed and was found to depend upon the nanoparticle size or the stem extract concentration used for synthesis.  相似文献   

4.
The excellent photocatalytic hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with NaBH4 in the aqueous medium is still a big challenge. Herein, we report a facile one-pot evaporation-induced self-assembly (EISA) method to synthesize a series of CuO/TiO2 nanocomposites. The as-synthesized CuO/TiO2 photocatalysts exhibit remarkable catalytic activity under direct sunlight in selective hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) due to the synergistic interaction of guest copper nanoparticles with host titanium dioxide (TiO2) species. Especially, 5 wt% CuO/TiO2 nanocomposite revealed superior reaction rate constant (k) value (0.306 min−1) when compared to 3 wt% CuO/TiO2 (0.192 min−1) and 7 wt% CuO/TiO2 (0.240 min−1). Moreover, several characterization techniques (XRD, TEM, N2 adsorption–desorption isotherm, DRS, and XPS) were executed to deeply investigate the effect of copper content on the bulk and interfacial properties of the catalysts. The characterization results proved that the superior photocatalytic hydrogenation over 5 wt% CuO/TiO2 catalyst can be ascribed to moderate CuO loading as well as even dispersion of CuO species on the surface of active TiO2 host, which can largely improve the light absorption ability within visible light region. Besides, the 5 wt% CuO/TiO2 catalyst exhibits remarkable recyclability and durability, retaining its superior activity (above 95%) up to several repeating cycles, proving its practical applicability for hydrogenation reactions at domestic and industrial levels.  相似文献   

5.
Various metal nanoparticles such as, Cu, Co, Ni, and Fe were prepared inside poly(1-vinyl imidazole) p(VI) hydrogel by the absorption of the corresponding metal ions from aqueous solutions and the reduction with suitable reducing agents such as NaBH(4) and/or NaOH. TGA and ICP-AES were used to determine the metal particle content of p(VI)-M (M: Cu, Co, and Ni) composites. The prepared hydrogel-metal nanoparticle composites were proven to be resourceful as reaction container for the catalysis of various organic reactions. It was illustrated that p(VI)-M hydrogel-metal composites can be successfully used in the hydrolysis of NaBH(4) for the generation hydrogen form NaBH(4) and NH(3)BH(3). Additionally, p(VI)-M composites were also illustrated in the catalysis of different organic reactions; e.g., these hydrogel-M are very effective in the reduction nitro aromatic compounds such 2-nitrophenol (2-NP) and 4-nitrophenol (4-NP) to their corresponding amine forms in the presence of aqueous NaBH(4). Various parameters in the catalysis of hydrogen production and 4-NP reduction were determined.  相似文献   

6.
ABSTRACT

Copper sulphide nanoparticles (CuS NPs) were in situ synthesised via irradiation process, using Poly (vinyl alcohol) (PVA) as host polymeric matrices. The as-prepared CuS/PVA nanocomposite films were characterised by X-ray diffraction (XRD) spectroscopy, ultraviolet-visible (UV-VIS) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Both UV-VIS spectra and X-ray diffraction patterns confirmed the formation of CuS nanoparticles. The FTIR spectrum indicates the coordination between CuS nanoparticles and the OH groups of the PVA chains. The TEM image showed that the obtained CuS nanoparticles have spherical shape, monodispersed and uniform particle size distribution. The CuS/PVA nanocomposite film was successfully applied in the reduction of p-nitrophenol into p-aminophenol as a catalyst using NaBH4 as reducing agent. The catalytic test indicates that CuS/PVA nanocomposite film has high activity for the conversion of P-NP into P-AP and effectively recycled and reused for several times.  相似文献   

7.
CoS@MorphcdtH NPs and CoS@4-MPipzcdtH NPs were synthesized by precipitation method involving three mechanisms: inclusion, occlusion, and adsorption. The synthesized NPs were characterized with the help of UV-Vis spectroscopy, FESEM-EDAX, powder x-ray diffraction, TEM, ESIMS, TG/DSC analysis. The morphology of the CoS@MorphcdtH NPs and CoS@4-MPipzcdtH NPs were hexagonal and rectangular, and the particles were in the range 7–12 nm. UV–visible spectral measurements showed surface plasmon resonance at 320 nm–340 nm with band gap of 3.65 eV–3.86 eV. The catalytically active CoSNPs called were investigated for the reduction of 4-nitrophenol (4-NP) via hydrogenation using sodium borohydride (NaBH4) as a reducing agent. Both the CoS NPs successfully reduced 4-NP to 4- aminophenol (4-AP) in a short time, catalytic performances are almost unchanged for the first five cycles. Herein, we report the preparation and characterizations of efficient active CoS NPs consisting carbodithioic acid framework as a support/capping material, along with catalytic property.  相似文献   

8.
《中国化学快报》2023,34(8):108122
By considering the exceptional properties of supramolecular, noble metals (NM) and magnetic nanoparticles (NPs), we successfully synthesized a novel magnetic, metals and supramolecular composite. Briefly, the Fe3O4@SiO2 core-shell spheres were first modified with gold (Au) and palladium (Pd) NPs and then with mono-6-thio-β-cyclodextrin (SH-β-CD). The synthesized Fe3O4@SiO2-Au-Pd@SH-β-CD nanocomposite shows a good magnetic response (42.3 emu/g). The nanocomposite showed good performance for the reductive degradation of rhodamine B (RhB) and 4-nitrophenol (4-NP). The calculated rate constant (k) values for the reduction of 4-NP and RhB were 0.062± 0.02 s−1 and 0.027± 0.01 s−1, respectively. The high catalytical performance was supposed to be due to the host-guest interaction of β-CD and also due to the NM synergic effect. The nanocomposite structural and chemical morphology was investigated by various spectroscopic techniques. Furthermore, the catalyst was recycled six times and it maintains morphology, chemical nature, and high magnetic behavior, as demonstrated by FTIR and TEM analysis of the recycled catalyst. These results demonstrate a very efficient, cost-effective, and recyclable catalyst in the field of catalysis technology development.  相似文献   

9.
Compared to conventional preparation methods for supported heterogeneous catalysts, the use of colloidal nanoparticles (NPs) allows for a precise control over size, size distribution, and distribution/location of the NPs on the support. However, common colloidal syntheses have restrictions that limit their applicability for industrial catalyst preparation. We present a simple, surfactant‐free, and scalable preparation method for colloidal NPs to overcome these restrictions. We demonstrate how precious‐metal NPs are prepared in alkaline methanol, how the particle size can be tuned, and how supported catalysts are obtained. The potential of these colloids in the preparation of improved catalysts is demonstrated by two examples from heterogeneous catalysis and electrocatalysis.  相似文献   

10.
Here,Ag_2S nanoparticles on reduced graphene oxide(Ag_2S NPs/RGO) nanocomposites with relatively good distribution are synthesized for the first time by conversing Ag NPs/RGO to Ag_2S NPs/RGO via a facile hydrothermal sulfurization method.As an noval catalyst for the reduction of 4-nitrophenol(4-NP),it only takes 5 min for Ag_2S NPs/RGO to reduce 98% of 4-NP,and the rate constant of the composites is almost 13 times higher than that of Ag NPs/RGO composites.The high catalytic activity of Ag_2S NPs/RGO can be attributed to the following three reasons:(1) Like metal complex catalysts,the Ag_2S NPs is also rich with metal center Ag(δ~+),with pendant base S(δ) close to it,and thus the Ag and basic S function as the electron-acceptor and proton-acceptor centers,respectively,which facilitates the catalyst reaction;(2)RGO features the high adsorption ability toward 4-NP which provides a high concentration of 4-NP near the Ag_2S NPs;and(3) electron transfer from RGO to Ag_2S NPs,facilitating the uptake of electrons by 4-NP molecules.  相似文献   

11.
Using a micro-calorimetrical DSC we have compared the acid-catalyzed inversion of sucrose in homogeneous and heterogeneous systems. Acetic acid was chosen as catalyst for homogeneous system, and several carboxylic cationites were used as heterogeneous catalysts. The kinetic apparent parameters (A, E, k ap) for all the systems were calculated from DSC data with Friedmann’s method and catalytic constant, k323cat, was further inferred. We found that the specific catalyst efficiency, q cat, in heterogeneous system is over 5000 times higher than in case of homogeneous ones. The activity of heterogeneous carboxylic systems is still about 30 times larger than those of a strong mineral acid in homogeneous catalysis. The results indicate the high efficiency of heterogeneous systems for soft acid catalysis of the sucrose hydrolysis.  相似文献   

12.
《中国化学快报》2023,34(6):107959
Metal-based catalysis, including homogeneous and heterogeneous catalysis, plays a significant role in the modern chemical industry. Heterogeneous catalysis is widely used due to the high efficiency, easy catalyst separation and recycling. However, the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst. To tackle this, the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging. As a recently emerging class of catalytic material, single-atom catalysts (SACs) are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field. In this review, a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented. In addition, recent advances in SACs and their practical applications in organic reactions such as oxidation, reduction, addition, coupling reaction, and other organic reactions are thoroughly reviewed. To understand structure-property relationships of single-atom catalysis in organic reactions, active sites or coordination structure, metal atom-utilization efficiency (e.g., turnover frequency, TOF calculated based on active metal) and catalytic performance (e.g., conversion and selectivity) of SACs are comprehensively summarized. Furthermore, the application limitations, development trends, future challenges and perspective of SAC for organic reaction are discussed.  相似文献   

13.
In this research, we strived to utilize waste fish scale (labeo rohita) for synthesizing CuO nano-particles (CuO NPs), which gained much attention due to its distinctive properties and versatile applications. Upon the heat treatment, the collagen content of the fish scale got transformed into gelatin which in turn converted the precursor material into CuO NPs. The X-Ray diffraction (XRD) analysis confirmed the formation of CuO NPs and revealed the structure to be of monoclinic lattice. The structural parameters i.e. crystallite size, lattice parameters, microstrain, dislocation density was evaluated for the synthesized CuO NPs using the XRD data. Scherrer’s Method (SM), Scherrer Equation Average Method (SEAM), Linear Straight Line Method (LSLM), Straight Line Passing the Origin Method (SLPOM), Monshi Scherrer Method (MSM), Williamson-Hall Method (WHM), Size-Strain Plot Method (SSPM), Halder-Wagner Method (HWM) was exploited for the estimation of crystallite size. According to the calculations, the crystallite size was found to be 87 nm, 41 nm, 1980 nm, 62 nm, 66 nm, 28 nm, 13 nm, 13 nm respectively and the dislocation density was found to be 1.32 × 10-4, 5.95 × 10-4, 0.002 × 10-4, 2.60 × 10-4, 2.29 × 10-4, 12.75 × 10-4, 59.17 × 10-4 and 59.17 × 10-4 respectively. UV–Vis absorption analysis also confirmed the formation of CuO NPs based on the absorption peak at 262 nm (λmax) and Tauc Plot method was used to calculate the optical band gap which was 3.84 eV. Functional group, especially the Cu-O bonding was confirmed by the Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) data. Field Emission Scanning Electron Microscopy (FESEM) showed three different shapes of CuO NPs which was also confirmed by Transmission Electron Microscopy (TEM). Particle size was determined based on FESEM and TEM image using imageJ software and also by the Dynamic Light Scattering (DLS) technique. Thermal analysis showed a four stage weight loss in case of Thermogravimetric (TGA) analysis and three conversion steps was observed in Differential Scanning Calorimetric (DSC) analysis. Such synthesis pathway is evidently green and facile for synthesizing CuO NPs with potentiality of various applications and also utilization of waste fish scale is a perquisite.  相似文献   

14.
在可见光照射下,以乙二醇(EG)作为还原剂和稳定剂,在多壁碳纳米管(MWCNTs)上一步合成了铂纳米颗粒,成功制备Pt/MWCNTs复合材料,并通过p-硝基苯酚(p-NP)的催化还原反应研究了Pt/MWCNTs的催化性能。用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)对所制备材料的形貌和晶体结构进行了表征。实验结果显示,可见光照射促进了EG水溶液中[PtCl4]2-前驱体的水解。通过金属界面的电子效应,铂前驱体被还原成了均匀分散的平均直径2.1 nm的超小颗粒Pt(Pt ultra-small particles,Pt UPs)。所制备的Pt/MWCNTs能有效地催化p-NP还原为p-氨基苯酚(p-AP),表现出较高的催化性能,其表观速率常数为0.25 min-1。Pt/MWCNTs多次使用后没有显著的活性损失,显示出了良好的稳定性。上述实验结果证明,除了传统的紫外光照射等手段以外,可见光照射也同样是制备铂金属催化剂非常有效的方法。而且,催化剂的形貌控制也完全可以通过简单而非复杂的实验条件加以实现。  相似文献   

15.
In this study, graphene oxide was modified during consecutive functionalization steps with 1,4-diphenylamine, cyanuric chloride, and ethylenediamine. Then, star-shaped CuO nanoparticles were synthesized on modified graphene oxide using the seed-mediated growth method in which nucleation, growth stages, and reduction of graphene oxide to graphene occurred simultaneously. After ensuring successful synthesis of CuO nanoparticles and to facilitate recycling, a magnetization process was utilized by adding iron oxide nanoparticles. This nanocomposite was characterized by transmission electron microscopy, X-ray powder diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. The prepared heterogeneous catalyst was investigated for the reduction of organic dyes in the presence of NaBH4 as a reducing reagent. The kinetic data obtained for the reduction of methyl orange (MO), methylene blue (MB), 4-nitrophenol (4-NP), and rhodamine 6G (Rh6G) were fitted to first-order rate equations, and the calculated rate constants for the reduction of MO, MB, 4-NP and Rh6G were as follows: −0.091, −0.071, −0.045, and 0.040, respectively. As star-shaped CuO nanoparticles showed a higher antibacterial effect compared to spherical-shaped CuO nanoparticles, the antibacterial activity of star-shaped CuO nanoparticles immobilized on magnetic functionalized graphene was evaluated against Gram-positive and Gram-negative bacteria through an agar well diffusion assay and demonstrated more antibacterial activity against gram-positive bacteria.  相似文献   

16.
Polymeric Schiff base ligands were synthesized using 2-hydroxybenzaldehyde (L2), 4-hydroxy-3-methoxybenzaldehyde (L4), and 5-aminoisophthalic acid. The nanostructured complexes were then synthesized using Ni2+, Cu2+, and Mn3+. The ligands and complexes thus synthesized were characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis (TGA), and field-emission scanning electron microscopy. The thermal stability of the complexes was confirmed using TGA. The synthesized complexes were used as catalysts in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol in an aqueous phase in the presence of sodium borohydride. In this work, the catalytic reactivity of nanostructured complexes was compared using the rate constant (k) of the reaction. The reaction time for the reduction of 4-NP was 5–14 min for different complexes. The catalytic system based on Ni2+/2-hydroxybenzaldehyde was the most active and displayed reusability in the reduction of 4-NP.  相似文献   

17.
In the developing nanotechnology world, numerous attempts have been made to prepare the nobel metallic nanoparticles (NPs), which can improve their applicability in diverse fields. In the present work, the biosynthesis of silver (Ag) NPs has been successfully achieved through the medicinal plant extract (PE) of G. resinifera and effectively used for the catalytic and antibacterial applications. The size dependant tuneable surface plasmon resonance (SPR) properties attained through altering precursor concentrations. The X-ray and selected area diffraction pattern for Ag NPs revealed the high crystalline nature of pure Ag NPs with dominant (111) phase. The high-resolution TEM images show the non-spherical shape of NPs shifting from spherical, hexagonal to triangular, with wide particle size distribution ranging from 13 to 44 nm. Accordingly, the dual-band SPR spectrum is situated in the UV–Vis spectra validating the non-spherical shape of Ag NPs. The functional group present on the Ag NPs surface was analysed by FT-IR confirms the capping and reducing ability of methanolic PE G. resinifera. Further, the mechanism of antimicrobial activity studied using electron microscope showed the morphological changes with destructed cell walls of E. coli NCIM 2931 and S. aureus NCIM 5021 cells, when they treated with Ag NPs. The Ag NPs were more effective against S. aureus and E. coli with MIC 128 μg/ml as compared to P. aeruginosa NCIM 5029 with MIC 256 μg/ml. Apart from this, the reduction of toxic organic pollutant 4-NP to 4-AP within 20 min reveals the excellent catalytic activity of Ag NPs with rate constant k = 15.69 s?1.  相似文献   

18.
《中国化学快报》2022,33(11):4786-4791
Bromate formation has been found in the SO4??-based oxidation processes, but previous studies primarily focused on the bromate formation in the homogeneous SO4??-based oxidation processes. The kinetics and mechanisms of bromate formation are poorly understood in the heterogeneous SO4??-based oxidation processes, although which have been widely studied in the eliminations of micropollutants. In this work, we found that the presence of CuO, a common heterogeneous catalyst of peroxymonosulfate (PMS), appreciably enhanced the bromate formation from the oxidation of bromide by PMS. The conversion ratio of bromide to bromate achieved over 85% within 10 min in this process. CuO was demonstrated to play a multiple role in the bromate formation: (1) catalyzed PMS to generate SO4??, which then oxidizes bromide to bromate; (2) catalyzed the formed free bromine to disproportionate to bromate; (3) catalyzed the formed free bromine to decomposed back into bromide. In the CuO-PMS-Br system, bromate formation increases with increasing CuO dosages, initial CuO and bromide concentrations, but decreases with increasing bicarbonate concentrations. The presence of NOM (natural organic matter) resulted in a lower formed bromate accompanied with organic bromine formation. Notably, CuO catalyzes PMS to transform more than 70% of initial bromide to bromate even after recycled used for six times. The formation of bromate in the PMS catalysis by CuO system was also confirmed in real water.  相似文献   

19.
Six derivatives ( 1 , 2 , 3 , 4 , 5 , 6 ) of 2‐phenyl‐1H‐imidazole were tested as catalysts of Henry reaction. Three new ( 4 , 5 , 6 ) 2‐phenyl‐1H‐imidazole derivatives, differently substituted (thio)ureas, were synthesized and determined by 1H NMR and IR spectroscopy and elemental analysis. Two types of catalysis, homogeneous and heterogeneous, were examined and compared. Clay minerals Ca‐MMT and Cu‐MMT were used as solid supports for heterogeneous catalysis. The best results were obtained using compound 2 under conditions of heterogeneous method D from the point of view of yield and reaction time. J. Heterocyclic Chem., (2011)  相似文献   

20.
The design and construction of a bimodal catalyst with magnificent performance and high stability is a debatable one for total water splitting and nitro compound reduction. Herein, we report the synthesis of a covalent organic polymer network based on 1,4-phenylenediamine based covalent organic polymer (PD-COP) and its decoration with Au nanoparticles (Au NPs) as well as their confirmation using various analytical and surface techniques. The electrocatalytic activity toward total water-splitting reaction (OER and HER) in KOH solution (1.0 M) was investigated. In addition, the reduction of aromatic nitro compounds (4-nitrophenol (4-NP) and 2-nitroaniline (2-NA)) was carried out in the presence of NaBH4. Among the different electrocatalysts (PD-COP, Au@PD-COP-I, Au@PD-COP-II, Au@PD-COP-III and Au@PD-COP-IV) studied in this work, the Au@PD-COP-II demands a low overpotential of 288 mV and 184 mV to attain a 50-mA/cm2 geometrical current density with a lowest Tafel slope value of 56 and 85 mV/dec for OER and HER respectively. From the OER and HER phenomenal activity, a two-electrode system was constructed, and it needs a cell voltage of 1.615 V to conquer a current density of 10 mA/cm2 with outstanding stability for 34 h. The high electroactivity of Au@PD-COP-II may be allied with the presence of innumerable redox-active sites and high electrochemical active surface area (ECSA) towards effective water electrolysis. Further, the catalytic activity performed towards the reduction of 4-NP to 4-aminophenol (4-AP) and 2-NA to o-PDA (o-phenylenediamine), Au@PD-COP-II showed good catalytic activity with a reduction time of 20 and 14 min respectively.  相似文献   

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