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1.
Molecules ; 29(18)2024 Sep 13.
Article in English | MEDLINE | ID: mdl-39339349

ABSTRACT

Phenylhydroxylamine and its derivates (PHAs) are important chemical intermediates. Phenylhydroxylamines are mainly produced via the catalytic reduction of aromatic nitro compounds. However, this catalytic reduction method prefers to generate thermodynamically stable aromatic amine. Thus, designing suitable catalytic systems, especially catalysts to selectively convert aromatic nitro compounds to PHAs, has received increasing attention but remains challenging. In this review, we initially provide a brief overview of the various strategies employed for the synthesis of PHAs, focusing on reducing aromatic nitro compounds. Subsequently, an in-depth analysis is presented on the catalytic reduction process, encompassing discussions on catalysts, reductants, hydrogen sources, and a comprehensive assessment of the merits and drawbacks of various catalytic systems. Furthermore, a concise overview is provided regarding the progress made in comprehending the mechanisms involved in this process of catalytic reduction of aromatic nitro compounds. Finally, the main challenges and prospects in PHAs' production via catalytic reduction are outlined.

2.
Molecules ; 29(18)2024 Sep 23.
Article in English | MEDLINE | ID: mdl-39339501

ABSTRACT

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) has been implemented in response to the regulation of NOx emissions from stationary and mobile sources above 300 °C. However, the development of NH3-SCR catalysts active at low temperatures below 200 °C is still needed to improve the energy efficiency and to cope with various fuels. In this review article, recent reports on low-temperature NH3-SCR catalysts are systematically summarized. The redox property as well as the surface acidity are two main factors that affect the catalytic activity. The strong redox property is beneficial for the low-temperature NH3-SCR activity but is responsible for N2O formation. The multiple electron transfer system is more plausible for controlling redox properties. H2O and SOx, which are often found with NOx in flue gas, have a detrimental effect on NH3-SCR activity, especially at low temperatures. The competitive adsorption of H2O can be minimized by enhancing the hydrophobic property of the catalyst. Various strategies to improve the resistance to SOx poisoning are also discussed.

3.
Environ Sci Technol ; 58(37): 16357-16367, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39219475

ABSTRACT

Regulating vanadia-based oxides has been widely utilized for fabricating effective difunctional catalysts for the simultaneous elimination of NOx and chlorobenzene (CB). However, the notorious accumulation of polychlorinated species and excessively strong NH3 adsorption on the catalysts lead to the deterioration of multipollutant control (MPC) activity. Herein, protonated sulfate (-HSO4) supported on vanadium-titanium catalysts via a preoccupied anchoring strategy are designed to prevent polychlorinated species and alleviate NH3 adsorption for the multipollutant control. The obtained catalysts with -HSO4 modification achieve an excellent NOx and CB conversion with turnover frequency values of ∼ 3.63 and 17.7 times higher than those of the pristine, respectively. The protonated sulfate promotes the formation of polymeric vanadyl with a higher chemical state and d-band center of V. The modulated catalysts not only substantially alleviate the competitive adsorption of multipollutant via the "V 3d-O 2p-S 3p" network, but also distinctly strengthen the Brønsted acid sites. Besides, the introduced proton donor of the -HSO4 connecting polymeric structure could markedly reduce the reaction barrier of breaking the C-Cl bond. This work paves an advanced way for low-loading vanadium SCR catalysts to achieve highly efficient NOx and CB oxidation at a low temperature.


Subject(s)
Vanadium , Catalysis , Vanadium/chemistry , Adsorption
4.
Chemistry ; : e202401803, 2024 Aug 07.
Article in English | MEDLINE | ID: mdl-39109481

ABSTRACT

Selective catalytic reduction of nitrogen oxides with NH3 at low temperatures remains a crucial goal for industrial applications. However, effective catalysts operating at 70-90 °C are rarely reported, limiting SCR scenarios to high-temperature conditions. Herein, we report a unique MnO2 nanofilament catalyst grown on activated semi-coke synthesized via a one-step in situ hydrothermal approach, which exhibits a stable and marked 100 % conversion rate of NO to N2 with 100 % selectivity at 90 °C, superior to the other prepared structures (nanowires, nanorods, and nanotubes). Temperature-programmed desorption shows a large number of acid sites on MnO2(NFs)/ASC, benefiting the formation of NH4 + ions. Meanwhile, diffuse reflectance infrared Fourier transform spectroscopy reveals the activation of NO with O2 to form bidentate nitrate/bridging nitrate NO2 intermediates via bidentate nitrate species, triggering the Fast SCR with NH3 at low temperatures. Such an effective, easy-to-prepare, and low-cost catalyst paves a new pathway for low-temperature SCR for a wide range of application scenarios.

5.
J Colloid Interface Sci ; 677(Pt B): 161-170, 2024 Aug 10.
Article in English | MEDLINE | ID: mdl-39142157

ABSTRACT

Two-dimensional nanosheets, with their distinct characteristics, are widely used in various applications such as water splitting, supercapacitors, catalysis etc. In this research, we produced Cu-BDC MOF nanosheets by using Cu2O nanotubes for metal ions and H2BDC as the organic linker. We combined these Cu-BDC MOF nanosheets with reduced graphene oxide (rGO) to form a nanocomposite. The collaboration between Cu-BDC MOF and rGO boosts both the catalytic reduction of 4-nitrophenol and the electrochemical capabilities. The conversion of 4-nitrophenol to 4-aminophenol is achieved using sodium borohydride as both a reducing agent and a catalyst. The study explores the impact of different concentrations of 4-nitrophenol and sodium borohydride on catalytic efficiency. The increase in sodium borohydride concentration enhances catalytic efficiency by providing more BH4- ions and electrons for the reduction process. The catalytic reduction process adheres to the Langmuir-Hinshelwood mechanism with apparent pseudo-first-order kinetics. Specifically, Cu-BDC MOF and rGO/Cu-BDC MOF exhibit specific capacities of 468.4 mA h/g and 656.4 mA h/g at a current density of 2 A/g, respectively, while also enhancing the operating voltage window. Therefore, electrodes based on rGO/Cu-BDC MOF nanosheets present a novel approach for environmental remediation and energy storage applications across various fields.

6.
Molecules ; 29(16)2024 Aug 17.
Article in English | MEDLINE | ID: mdl-39202974

ABSTRACT

In this work, silver nanoparticles (AgNPs) were synthesized from cashew nutshell liquid (CNSL) by varying the concentration of silver ions and the pH of the CNSL extract. The synthesized AgNPs were further characterized to study their surface, structural, and morphological properties and tested for the removal of methylene blue (MB) dye. The results of this study showed that depending on the conditions, particles of various sizes, ranging from 1 to 60 nm, and different degrees of stabilization and agglomeration were produced. The concentration of silver ions equal to 3 mM and the pH of the extract of ~4.5 (AgNP3) resulted in the most efficient synthesis, where particles appeared to be highly stabilized and homogeneously distributed on the surface, exhibiting a small average particle size and a narrow particle size distribution (6.7 ± 6.5 nm). Such particles further showed the highest percent removal of MB, where up to 80% removal was recorded within the first 20 min. Higher concentrations of silver ions and higher pH of the extract resulted in substantial particle agglomeration and particles being over-capped by the CNSL biomolecules, respectively, which further negatively affected the ability of particles to remove MB. Finally, the fact that visible light showed no significant effect on the removal of MB, with the average removal rates found to be about the same as in the dark, suggests the strong catalytic nature of AgNPs, which facilitates the electron transfer reactions leading to MB reduction.

7.
Molecules ; 29(16)2024 Aug 20.
Article in English | MEDLINE | ID: mdl-39203008

ABSTRACT

Graphene oxide-silver poly(vinylidene fluoride) membranes (PVDF@GO-Ag) were successfully synthesized by the electrospinning method, which exhibited a high catalytic activity using the hydrogenation of 4-nitrophenol (4-NP) as a model reaction in a batch reaction study. The hybrid membranes doped with 1 wt% GO and 2 wt% Ag (PVDF-1-2) exhibited the most desired performance for the catalytic reduction of 4-NP. Importantly, PVDF-1-2 exhibited excellent cycling stability in 10 catalytic cycle tests and was highly amenable to separation. This property effectively addresses the significant challenges associated with the practical application of nanocatalysts. Furthermore, density-functional theory (DFT) calculations have demonstrated that the GO-Ag nanocomposites exhibit the strongest adsorption capacity for 4-NP- when a specific ratio of GO and Ag is achieved, accompanied by the loading of Ag nanoclusters onto GO. Additionally, the study demonstrated that an increase in temperature significantly accelerated the reaction rate, in line with the van't Hoff rule. This study provides an effective and environmentally friendly solution for the treatment of 4-NP in wastewater.

8.
Polymers (Basel) ; 16(15)2024 Jul 24.
Article in English | MEDLINE | ID: mdl-39125131

ABSTRACT

Efficient catalytic reduction of 4-nitrophenol (4-NP) is one focus of industry and practical engineering, because 4-NP is one of the most important sources of pollution of the ecological environment and human health. Here, coassembled hybrid composites of pillar[5]arene (P5A) and gold nanoparticles (Au NPs) were successfully developed by a one-step synthetic method as a type of water-insoluble catalyst for the reduction of 4-NP. The geometric and topological structures, as well as physiochemical properties of Au NPs/P5A composite catalyst, were fully characterized and analyzed through various tests such as transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR), indicating that Au NPs were well dispersed on the surface of the two-dimensional film of assembled P5A. The influence factors of the catalytic reduction of 4-NP were further investigated and discussed, confirming that the content of Au NPs and the concentration of 4-NP were very significant during the catalysis. The catalytic reaction was carried out at the catalyst concentration of 100 mg·L-1 and an initial 4-NP concentration of 90 mg·L-1 under 30 °C. The calculated reaction rate constant was 0.3959 min-1 and the reduction rate of 4-NP was more than 95% in 20 min. In addition, the as-prepared catalyst can maintain a high catalytic efficiency after five cycles. Thus, the easily recyclable composite catalyst with poor aqueous solution can exhibit prospective application to the treatment of 4-NP in water.

9.
Environ Sci Technol ; 2024 Aug 13.
Article in English | MEDLINE | ID: mdl-39138907

ABSTRACT

Hitherto, sulfur poisoning and hydrothermal aging have still been the challenges faced in practical applications of the Cu-SSZ-13 catalyst for the selective catalytic reduction (SCR) of NOx from diesel engine exhaust. Here, we elaborately design and conduct an in-depth investigation of the synthetic effects of hydrothermal aging and SO2 poisoning on pristine Cu-SSZ-13 and Cu-SSZ-13@Ce0.75Zr0.25O2 core@shell structure catalysts (Cu@CZ). It has been discovered that Cu@CZ susceptible to 750 °C with 5 vol % H2O followed by 200 ppm SO2 with 5 vol % H2O (Cu@CZ-A-S) could still maintain nearly 100% NOx conversion across the significantly wider temperature region of 200-425 °C, which is remarkably broader than that of the Cu-SSZ-13-A-S (300-400 °C) counterpart. The experimental results show that the hydrothermal aging process results in the migration of highly active Cu species within the cage of Cu-SSZ-13 to the CZ surface, forming CuO/CZ with abundant interfaces, which significantly enhances the adsorption and subsequent activation of NO, leading to the generation of reactive N2O3 and HONO intermediates. Moreover, density functional theory (DFT) calculations reveal that the H of the HONO* species can function as Brønsted acid sites, effectively adsorbing NH3 to generate the active NH4NO2* intermediate, which readily decomposes into N2 and H2O. Furthermore, this pathway is the rate-determining step with an energy barrier of 0.93 eV, notably lower than that of the "standard SCR" pathway (1.42 eV). Therefore, the formation of the new CuO/CZ interface profoundly boosts the low-temperature NH3-SCR activity and improves the coresistance of the Cu@CZ catalyst to sulfur poisoning and hydrothermal aging.

10.
Chem Asian J ; 19(19): e202400658, 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-39037572

ABSTRACT

Cisplatin (CDDP) is an FDA-approved chemotherapeutic drug used for treating various solid tumors. Despite of its effectiveness towards chemotherapy, it faces several challenges, such as multi-drug resistance (MDR) and significant damage to the normal tissues. To address these challenges, various nanoformulations were developed to improve the delivery and safety of CDDP. One of the limitation in these CDDP loaded nanoformulations is that the effective CDDP loading concentrations are very poor. Therefore, this leaves a grand challenge to develop an effective strategy to carry higher concentrations of CDDP molecules, and also simultaneously exhibit very unique properties. Herein, we have developed an one-pot synthesis of Cisplatin encapsulated Plasmonic blackbody (CiP), which offers a double play for near infrared (NIR) light activatable chemo-photothermal therapy in destructing cancer cells as well as mediate catalytic reduction of 4-nitrophenol (4-NP). The CiP nanoformulation exhibits superior light absorbing capabilities in the NIR region with an appreciable photothermal conversion efficiency of 41 %. Further, NIR light activatable combinatorial therapeutic approach of CiP was demonstrated against ovarian cancer cells and as a catalyst for the reduction of model pollutant 4-nitrophenol. Our findings highlight the potential of CiP as a versatile platform for light-activated combinatorial cancer therapy and environmental pollutant remediation.


Subject(s)
Antineoplastic Agents , Cisplatin , Infrared Rays , Nitrophenols , Nitrophenols/chemistry , Cisplatin/chemistry , Cisplatin/pharmacology , Humans , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Line, Tumor , Oxidation-Reduction , Cell Survival/drug effects , Drug Screening Assays, Antitumor , Phototherapy , Cell Proliferation/drug effects
11.
Int J Biol Macromol ; 277(Pt 1): 133697, 2024 Oct.
Article in English | MEDLINE | ID: mdl-38996882

ABSTRACT

In this study, hydrogel beads were fabricated using alginate (Algt) polymer containing dispersed nickel phthalocyanine (NTC) nanomaterial. The viscous solution of Algt and NTC was poured dropwise into a divalent Ca2+ ions, resulting in the formation of hydrogel beads known as NTC@Algt-BDs. The surface of the NTC@Algt-BDs was further modified by coating them with different types of metal ions, yielding metal-coated M+/NTC@Algt-BDs. The adsorbed metal ions i.e., Cu+2, Ag+, Ni+2, Co+2, and Fe+3 were subsequently reduced to zero-valent metal nanoparticles (M0) by NaBH4. The prepared beads were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Initially, M0/NTC@Algt-BDs were examined for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). Among them, Cu0/NTC@Algt-BDs catalyst exhibited the highest reduction rate and therefore, investigated for reduction of different nitrophenols (NPs) and dyes, including 2-nitrophenol (2-NP), 2,6-dinitrophenol (2,6-DNP), methyl orange (MO), potassium ferrocyanide (PFC), congo red (CR), and acridine orange (ArO). The highest reduction rates of 2.019 and 1.394 min-1 were observed for MO and 2-NP, respectively. Furthermore, the fabricated catalysts were employed for the efficient production of H2 gas by NaBH4 methanolysis. Among which the Ag0/NTC@Algt-BDs catalyst showed excellent catalytic production of H2 gas, exhibiting the lowest activation energy (Ea) of 25.169 kJ/mol at ambient temperature. Furthermore, the impact of NaBH4 amount, and catalyst dosage on the reduction of 2-NP and H2 gas production was conducted whereas the effect of temperature on methanolysis of NaBH4 for evolution of H2 gas was studied. The amount of H2 gas was confirmed by GC-TCD system. Additionally, the recyclability of the catalyst was investigated, as it garnered significant research interest.


Subject(s)
Alginates , Hydrogen , Alginates/chemistry , Catalysis , Hydrogen/chemistry , Environmental Pollutants/chemistry , Indoles/chemistry , Surface Properties , Nitrophenols/chemistry , Microspheres , Hydrogels/chemistry , Adsorption
12.
Environ Sci Pollut Res Int ; 31(34): 47170-47188, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38987521

ABSTRACT

Anthropogenic activities have been one of the crucial driving factors for water pollution globally, thereby warranting a sustainable strategy for its redressal. In this study, we have developed a hydrogel-biochar nanocomposite for catalytic reduction of water pollutants. To begin with, green synthesis of nickel oxide nanoparticles (NiO NPs) was accomplished from waste kinnow peel extract via the environmentally benign microwave method. The formation of NiO NPs was affirmed from different analytical techniques namely ultraviolet-visible (UV-Vis), Fourier transform infrared (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy-dispersive spectroscopy (EDS). The FESEM images revealed spherical nature of NiO NPs. The average particle size was found to be 15.61 nm from XRD data. A novel hydrogel-biochar nanocomposite comprising the green NiO NPs, sunflower meal biochar and chitosan was prepared (Cs-biochar@ NiO) and explored as a nanocatalyst towards catalytic reduction of pollutants such as 4-nitrophenol, potassium hexacyanoferrate (III) and organic dyes methyl orange (MO), Congo red (CR), methylene blue (MB) in the presence of a reducing agent, i.e. NaBH4. Under optimized conditions, the reduction reactions were completed by 120 s and 60 s for 4-NP and potassium hexacyanoferrate (III) respectively and the rate constants were estimated to be 0.044 s-1 and 0.110 s-1. The rate of reduction was found to be faster for the dyes and the respective rate constants were 0.213 s-1 for MO, 0.213 s-1 for CR and 0.135 s-1 for MB. The assessment of the nanocatalyst in the reduction of binary dye systems depicted its selectivity towards the anionic dyes CR and MO. The nanocatalyst displayed effective reduction of dyes in real-water samples collected from different sources. Taken altogether, this study validates the design of sustainable hydrogel-biochar nanocatalyst for the efficient reduction of hazardous anthropogenic water pollutants.


Subject(s)
Charcoal , Chitosan , Nickel , Water Pollutants, Chemical , Nickel/chemistry , Water Pollutants, Chemical/chemistry , Catalysis , Charcoal/chemistry , Chitosan/chemistry , Hydrogels/chemistry , Green Chemistry Technology , Metal Nanoparticles/chemistry
13.
Int J Biol Macromol ; 275(Pt 1): 133633, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38964695

ABSTRACT

Conversion of toxic nitroarenes into less toxic aryl amines, which are the most suitable precursors for different types of compounds, is done with various materials which are costly or take more time for this conversion. In this regards, a silica@poly(chitosan-N-isopropylacrylamide-methacrylic acid) Si@P(CS-NIPAM-MAA) Si@P(CNM) core-shell microgel system was synthesized through free radical precipitation polymerization (FRPP) and then fabricated with palladium nanoparticles (Pd NPs) by in situ-reduction method to form Si@Pd-P(CNM) and characterized with XRD, TEM, FTIR, SEM, and EDX. The catalytic efficiency of Si@Pd-P(CNM) hybrid microgels was studied for reduction of 4-nitroaniline (4NiA) under diverse conditions. Different nitroarenes were successfully transformed into their corresponding aryl amines with high yields using the Si@Pd-P(CNM) system as catalyst and NaBH4 as reductant. The Si@Pd-P(CNM) catalyst exhibited remarkable catalytic efficiency and recyclability as well as maintaining its catalytic effectiveness over multiple cycles.


Subject(s)
Acrylamides , Chitosan , Metal Nanoparticles , Palladium , Silicon Dioxide , Palladium/chemistry , Catalysis , Silicon Dioxide/chemistry , Chitosan/chemistry , Metal Nanoparticles/chemistry , Acrylamides/chemistry , Microgels/chemistry , Oxidation-Reduction , Methacrylates/chemistry
14.
Environ Sci Technol ; 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-39013630

ABSTRACT

Renewing metal-poisoned NH3-SCR catalysts holds great potential for mitigating environmental pollution and utilizing hazardous wastes simultaneously. Ionic compounds containing heavy metals often exhibit limited solubility due to their high polarizability, making traditional washing techniques ineffective in removing heavy metal poisons. This study presents a gas-based method for regenerating heavy-metal-poisoned V2O5-WO3/TiO2 catalysts employed in NH3-SCR techniques. The regeneration is achieved by employing a masking and reconstruction strategy, which involves the in situ formation of NO2 to mediate the production of SO3. This enables the effective bonding of Pb and triggers the reconstruction of active VOx sites. In situ spectroscopy confirms that the sulfation of PbO restores acidity, while the occupied effect resulting from the sulfation of TiO2 promotes the formation of more polymeric VOx species. Consequently, the regenerated catalyst exhibits enhanced activity and superior resistance to metal poisons compared with the fresh catalyst. The innovative method offers a promising solution for extending the lifespan of poisoned catalysts, reducing waste generation, and enhancing the efficiency of NH3-SCR systems.

15.
Sensors (Basel) ; 24(13)2024 Jun 29.
Article in English | MEDLINE | ID: mdl-39001026

ABSTRACT

In the realm of electrochemical nitrite detection, the potent oxidizing nature of nitrite typically necessitates operation at high detection potentials. However, this study introduces a novel approach to address this challenge by developing a highly sensitive electrochemical sensor with a low reduction detection potential. Specifically, a copper metal nanosheet/carbon paper sensitive electrode (Cu/CP) was fabricated using a one-step electrodeposition method, leveraging the catalytic reduction properties of copper's high occupancy d-orbital. The Cu/CP sensor exhibited remarkable performance in nitrite detection, featuring a low detection potential of -0.05 V vs. Hg/HgO, a wide linear range of 10~1000 µM, an impressive detection limit of 0.079 µM (S/N = 3), and a high sensitivity of 2140 µA mM-1cm-2. These findings underscore the efficacy of electrochemical nitrite detection through catalytic reduction as a means to reduce the operational voltage of the sensor. By showcasing the successful implementation of this strategy, this work sets a valuable precedent for the advancement of electrochemical low-potential nitrite detection methodologies.

16.
BMC Chem ; 18(1): 124, 2024 Jul 02.
Article in English | MEDLINE | ID: mdl-38956730

ABSTRACT

One of the biggest issues affecting the entire world currently is water contamination caused by textile industries' incapacity to properly dispose their wastewater. The presence of toxic textile dyes in the aquatic environment has attracted significant research interest due to their high environmental stability and their negative effects on human health and ecosystems. Therefore, it is crucial to convert the hazardous dyes such as methyl orange (MO) azo dye into environmentally safe products. In this context, we describe the use of Copper Nitroprusside Chitosan (Cu/SNP/Cts) nanocomposite as a nanocatalyst for the chemical reduction of azodyes by sodium borohydride (NaBH4). The Cu/SNP/Cts was readily obtained by chemical coprecipitation in a stoichiometric manner. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FT-IR) spectroscopy were applied to investigate chemical, phase, composition, and molecular interactions. Additionally, Scanning electron microscope (SEM) was used to examine the nanomaterial's microstructure. UV-vis spectroscopy was utilized for studying the Cu Nitroprusside Chitosan's catalytic activity for the reduction of azodye. The Cu/SNP/Cts nanocomposite demonstrated outstanding performance with total reduction time 160 s and pseudo-first order constant of 0.0188 s-1. Additionally, the stability and reusability study demonstrated exceptional reusability up to 5 cycles with minimal activity loss. The developed Cu/SNP/Cts nanocomposite act as efficient nanocatalysts for the reduction of harmful Methyl orange azodye.

17.
Environ Sci Technol ; 2024 Jul 31.
Article in English | MEDLINE | ID: mdl-39083593

ABSTRACT

Mn-based catalysts are promising candidates for eliminating harmful nitrogen oxides (NOx) via selective catalytic reduction with ammonia (NH3-SCR) due to their inherent strong redox abilities. However, poor water tolerance and low N2 selectivity are still the main limitations for practical applications. Herein, we succeeded in preparing an active catalyst for NH3-SCR with improved water tolerance and N2 selectivity based on protecting MnOx with a secondary growth of a hydrophobic silicalite-1. This protection suppressed catalyst deactivation by water adsorption. Interestingly, impregnating MnOx on MesoTS-1 followed by silicalite-1 protection allowed for a higher dispersion of MnOx species, thus increasing the concentration of acid sites. Consequently, the level of N2O formation is decreased. These improvements resulted in a broader operating temperature of NOx conversion and a modification of the NH3-SCR mechanism. Diffuse reflectance infrared Fourier transform spectroscopy analysis revealed that unprotected Mn/MesoTS-1 mainly followed the Eley-Rideal mechanism, while Mn/MesoTS-1@S1 followed both Langmuir-Hinshelwood and Eley-Rideal mechanisms.

18.
Int J Biol Macromol ; 276(Pt 1): 133835, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39002901

ABSTRACT

Efficient treatment of toxic organic pollutants in water/wastewater by using innovative, cost efficient, and simple technologies has recently become an important issue worldwide. Remediation of these pollutants with chemical reduction in the presence of a nano-sized catalyst and a reducing agent is one of the most useful methodologies. In the present study, we have designed a promising heterogeneous catalyst system (Pd@CS-NiO) by easy and efficient stabilization of palladium nanoparticles on the surface of microspheres composed of chitosan (CS)-NiO particles (CS-NiO) for the reduction of organic pollutants. The nano-structure of the developed Pd@CS-NiO was successfully validated using FE-SEM, XRD, EDS, TEM, and FTIR/ATR and its particles size was determined as 10 nm. The catalytic power of Pd@CS-NiO was then assessed in the reduction of 4-nitro-o-phenylenediamine (4-NPDA), 4-nitrophenol (4-NP), 4-nitroaniline (4-NA), 2-nitroaniline (2-NA), and some organic dyes, namely methylene blue (MB), methyl orange (MO), and rhodamine B (RhB) in aqueous medium at room temperature. The reductions were thoroughly studied spectro-photometrically. The tests displayed that the synthesized Pd@CS-NiO was a highly active and useful catalyst that reduced these pollutants in 0-145 s. Moreover, the rate constants for 2-NA, 4-NP, 4-NA, 4-NPDA, MO, and RhB were found to be 0.017 s-1, 0.011 s-1, 0.006 s-1, 0.013 s-1, 0.023 s-1, and 0.03 s-1, respectively. Moreover, the recycling test indicated that Pd@CS-NiO may be recovered easily thanks to its micro size nature and could be used up to seven steps, confirming its practical application potential.


Subject(s)
Chitosan , Metal Nanoparticles , Nickel , Palladium , Chitosan/chemistry , Palladium/chemistry , Catalysis , Metal Nanoparticles/chemistry , Nickel/chemistry , Microspheres , Water Pollutants, Chemical/chemistry , Environmental Pollutants/chemistry , Particle Size , Water Purification/methods
19.
Biopolymers ; 115(5): e23608, 2024 Sep.
Article in English | MEDLINE | ID: mdl-38923469

ABSTRACT

The paper reports on the preparation of cellulose nanocrystals/reduced graphene oxide matrix loaded with cuprous oxide nanoparticles (CNC/rGO-Cu2O) through a simple solvothermal method and its application for 4-nitrophenol reduction to 4-aminophenol using sodium borohydride. The CNC/rGO-Cu2O nanocomposite was formed chemically by first mixing CNC and graphene oxide (GO) followed by complexation of the negatively charged functional groups of CNC/GO with Cu2+ ions and subsequent heating at 100°C. This resulted in the simultaneous reduction of GO to rGO and the formation of Cu2O nanoparticles. The as-elaborated nanocomposite was firstly characterized using different techniques such as atomic force microscopy, scanning electron microscopy, transmission electron microscopy, UV-Vis spectrophotometry, Raman spectroscopy and x-ray photoelectron spectroscopy. Then, it was successfully applied for efficient catalytic reduction of 4-nitrophenol to 4-aminophenol using sodium borohydride: the reduction was completed in about 6 min. After eight times use, the catalyst still maintained good catalytic performance. Compared to CNC/rGO, rGO/Cu2O and free Cu2O nanoparticles, the CNC/rGO-Cu2O nanocomposite exhibits higher catalytic activity even at lower copper loading.


Subject(s)
Cellulose , Copper , Graphite , Nitrophenols , Oxidation-Reduction , Graphite/chemistry , Nitrophenols/chemistry , Copper/chemistry , Cellulose/chemistry , Catalysis , Nanocomposites/chemistry , Aminophenols/chemistry , Borohydrides/chemistry , Photoelectron Spectroscopy , Nanoparticles/chemistry , Oxides/chemistry , Spectrum Analysis, Raman
20.
Bioprocess Biosyst Eng ; 47(9): 1515-1531, 2024 Sep.
Article in English | MEDLINE | ID: mdl-38904714

ABSTRACT

Hydrogel nanocatalyst composed of nickel oxide (NiO) nanoparticles embedded in PVA-alginate hydrogels were potentially explored toward the reduction of anthropogenic water pollutants. The NiO nanoparticles was accomplished via green method using waste pineapple peel extract. The formation of the nanoparticles was affirmed from different analytical techniques such as UV-Vis, FTIR, XRD, TGA, FESEM, and EDS. Spherical NiO nanoparticles were obtained having an average size of 11.5 nm. The nano NiO were then integrated into PVA-alginate hydrogel matrix forming a nanocomposite hydrogel (PVALg@ NiO). The integration of nano NiO rendered an improved thermal stability to the parent hydrogel. The PVALg@ NiO hydrogel was utilized as a catalyst in the reduction of 4-nitrophenol (4-NP), potassium hexacyanoferrate (III), rhodamine B (RhB), methyl orange (MO), and malachite green (MG) in the presence of a reducing agent, i.e., NaBH4. Under optimized conditions, the reduction reactions were completed by 4.0 min and 3.0 min for 4-NP and potassium hexacyanoferrate (III), respectively, and the rate constant was estimated to be 1.14 min-1 and 2.15 min-1. The rate of reduction was found to be faster for the dyes and the respective rate constants were be 0.17 s-1 for RhB, MG and 0.05 s-1 for MO. The PVALg@ NiO hydrogel nanocatalyst demonstrated a recyclability of four runs without any perceptible diminution in its catalytic mettle. The efficacy of the PVALg@ NiO hydrogel nanocatalyst was further examined for the reduction of dyes in real water samples collected from different sources and the results affirm its high catalytic potential. Thus, this study paves the path for the development of a sustainable hydrogel nanocatalyst for reduction of hazardous pollutants in wastewater treatment.


Subject(s)
Alginates , Hydrogels , Nickel , Water Pollutants, Chemical , Nickel/chemistry , Hydrogels/chemistry , Alginates/chemistry , Catalysis , Water Pollutants, Chemical/chemistry , Polyvinyl Alcohol/chemistry , Green Chemistry Technology , Metal Nanoparticles/chemistry , Water Purification/methods , Azo Compounds
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