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1.
J Environ Sci (China) ; 147: 487-497, 2025 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-39003064

RESUMEN

Dissolved copper and iron ions are regarded as friendly and economic catalysts for peroxymonosulfate (PMS) activation, however, neither Cu(II) nor Fe(III) shows efficient catalytic performance because of the slow rates of Cu(II)/Cu(I) and Fe(III)/Fe(II) cycles. Innovatively, we observed a significant enhancement on the degradation of organic contaminants when Cu(II) and Fe(III) were coupled to activate PMS in borate (BA) buffer. The degradation efficiency of Rhodamine B (RhB, 20 µmol/L) reached up to 96.3% within 10 min, which was higher than the sum of individual Cu(II)- and Fe(III)- activated PMS process. Sulfate radical, hydroxyl radical and high-valent metal ions (i.e., Cu(III) and Fe(IV)) were identified as the working reactive species for RhB removal in Cu(II)/Fe(III)/PMS/BA system, while the last played a predominated role. The presence of BA dramatically facilitated the reduction of Cu(II) to Cu(I) via chelating with Cu(II) followed by Fe(III) reduction by Cu(I), resulting in enhanced PMS activation by Cu(I) and Fe(II) as well as accelerated generation of reactive species. Additionally, the strong buffering capacity of BA to stabilize the solution pH was satisfying for the pollutants degradation since a slightly alkaline environment favored the PMS activation by coupling Cu(II) and Fe(III). In a word, this work provides a brand-new insight into the outstanding PMS activation by homogeneous bimetals and an expanded application of iron-based advanced oxidation processes in alkaline conditions.


Asunto(s)
Cobre , Peróxidos , Contaminantes Químicos del Agua , Cobre/química , Contaminantes Químicos del Agua/química , Peróxidos/química , Catálisis , Hierro/química , Rodaminas/química , Oxidación-Reducción
2.
J Environ Sci (China) ; 149: 221-233, 2025 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-39181637

RESUMEN

Catalytic reduction of nitrate over bimetallic catalysts has emerged as a technology for sustainable treatment of nitrate-containing groundwater. However, the structure of bimetallic has been much less investigated for catalyst optimization. Herein, two main types of Pd-Cu bimetallic nanocrystal structures, heterostructure and intermetallic, were prepared and characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results show that two individual Pd and Cu nanocrystals with a mixed interface exist in the heterostructure nanocrystals, while Pd and Cu atoms are uniformly distributed across the intermetallic Pd-Cu nanocrystals. The catalytic nitrate reduction experiments were carried out in a semibatch reactor under constant hydrogen flow. The nitrate conversion rate of the heterostructure Pd-Cu nanocrystals supported on α-Al2O3, γ-Al2O3, SBA-15, and XC-72R exhibited 3.82-, 6.76-, 4.28-, 2.44-fold enhancements relative to the intermetallic nanocrystals, and the nitrogen and nitrite were the main products for the heterostructure and intermetallic Pd-Cu nanocrystals, respectively. This indicates that the catalytic nitrate reduction over Pd-Cu catalyst is sensitive to the bimetallic structures of the catalysts, and heterostructure bimetallic nanocrystals exhibit better catalytic performances on both the activity and selectivity, which may provide new insights into the design and optimization of catalysts to improve catalytic activity and selectivity for nitrate reduction in water.


Asunto(s)
Cobre , Nitratos , Oxidación-Reducción , Paladio , Catálisis , Cobre/química , Paladio/química , Nitratos/química , Nanopartículas del Metal/química , Nanopartículas/química , Contaminantes Químicos del Agua/química , Modelos Químicos
3.
Chemosphere ; : 143341, 2024 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-39278323

RESUMEN

In this paper, we report the successful application of a patent-pending reduced bimetallic nanoparticle catalytic system developed for the remediation of polychlorinated biphenyl (PCB)-contaminated sediment and aquatic media. The formation of bimetallic nanoparticles associated with the granular activated carbon (GAC) were confirmed by high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy showed the presence of the bimetallic matrix in reduced, albeit mixed, states. In the degradation studies, the bimetallic nanoparticles were deposited on a GAC substrate and utilized to treat both a surrogate PCB, 2-Chlorobiphenyl (2-CBP) in water and contaminated bottom-river sediments collected from a site with mixed-congener PCB contamination. The degradation studies on non-degassed water contaminated with 2-CBP at room temperature showed a high yield of 2-CBP degradation to biphenyl and phenol. Results from the bottom-river sediments contaminated with PCBs (tested in laboratory environment at ambient temperature and atmospheric conditions, not degassed) have indicated the bimetallic catalyst has great promise for remedial application in sediment and aquatic media. Results illustrate that this newly-developed and patent-pending catalytic system degrades PCBs through stepwise dichlorination, with expected byproducts such as biphenyl and phenol leading to mineralization of the PCBs.

4.
Nanomaterials (Basel) ; 14(17)2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39269084

RESUMEN

Hydrogen has garnered considerable attention as a promising energy source for addressing contemporary environmental degradation and energy scarcity challenges. Electrocatalytic water splitting for hydrogen production has emerged as an environmentally friendly and versatile method, offering high purity. However, the development of cost-effective electrocatalytic catalysts using abundant and inexpensive materials is crucial. In this study, we successfully synthesized nitrogen-doped Co6Mo6C supported on nitrogen-doped graphene (N-Co6Mo6C/NC). The catalyst exhibited high performance and durability in alkaline electrolytes (1.0 M KOH) for hydrogen evolution, showcasing an overpotential of 185 mV at a current density of 100 mA cm-2 and a Tafel slope of 80 mV dec-1. These findings present a novel avenue for the fabrication of efficient bimetallic carbide catalysts.

5.
Int J Biol Macromol ; 278(Pt 3): 134573, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39214840

RESUMEN

The utilization efficiency of palladium-based catalysts has sharply increased in many catalytic reactions. However, numerous studies have shown that preparing alloys of palladium with other metals has superior catalytic activity than pure palladium. Additionally, hierarchical porous carbon has gradually developed into an excellent carrier for loading bimetallic nanoparticles. In this study, we firstly pyrolyzed chitosan, sodium bicarbonate and nickel nitrate to create highly dispersed porous carbon materials doped with Ni NPs. The carbon materials were then grafted with silane coupling agent (APTMS) to afford them with amino groups on the surface. Taking advantage of the fact that Pd2+ can react with Ni in spontaneous reduction reaction, Pd was deposited on the surface of Ni to produce PdNi bimetallic-loaded carbon catalysts containing amino groups. The resulting catalysts were examined by a series of characterizations and were found to have a hierarchically porous structure and large specific surface area, which increased the number of active sites of the catalysts. In comparison to other Pd catalysts, the PdNi/HPCS-NH2 catalysts displayed remarkable activity for Suzuki coupling reaction and hydro reduction of nitroaromatics, which exhibited a high turnover frequency value (TOF) of 37,857 h-1 and 680.9 h-1, respectively. These were mainly due to the high dispersion of the PdNi NPs and the superior structure of the carriers. Moreover, the catalysts did not experience a significant decline in activity after ten cycles. All in all, this investigation has created a new approach for the fabrication of novel carriers for Pd catalysts, which is in line with the concept of green chemistry and recyclable.


Asunto(s)
Carbono , Quitosano , Níquel , Paladio , Quitosano/química , Catálisis , Porosidad , Paladio/química , Níquel/química , Carbono/química , Nanopartículas del Metal/química
6.
ACS Appl Mater Interfaces ; 16(29): 37963-37971, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-38984437

RESUMEN

Dodecahydro-N-ethylcarbazole (12H-NEC) is regarded as the most promising liquid organic hydrogen carrier for hydrogen storage and transportation. Understanding the mechanism of 12H-NEC dehydrogenation and developing cost-effective catalysts are significant. Pd is a high-performance catalyst for 12H-NEC but is not cost-effective, and Ni is just the opposite. How to understand the whole process of full dehydrogenation and improve the performance of Ni become two key questions. Herein, we systematically investigated the mechanism of the full dehydrogenation of 12H-NEC on Pd(111) and Ni(111) for the first time. By calculating all the barriers in the whole dehydrogenation process, we identified that 3H-NEC to 2H-NEC is the rate-determining step and Ni is catalytically less effective than Pd, which is attributed to its narrower d-band distribution and a 0.32 eV higher d-band center than that of Pd. To improve the performance of Ni, we further introduced dopants of Au, Ag, Cu, Pd, Pt, Ru, Rh, Zn, and Al. We found that Ag doping brings a downshift of the d-band center from -1.29 to -1.67 eV and reduces the barrier of 4H-NEC to NEC from 0.94 to 0.76 eV. This study provides new insights into the catalytic mechanism and performance-tuning strategy to help future experimental synthesis.

7.
Molecules ; 29(11)2024 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-38893516

RESUMEN

A series of bimetallic NixCuy catalysts with different metal molar ratios, supported on nitric acid modified rice husk-based porous carbon (RHPC), were prepared using a simple impregnation method for the liquid-phase hydrogenation of furfural (FFA) to tetrahydrofurfuryl alcohol (THFA). The Ni2Cu1/RHPC catalyst, with an average metal particle size of 9.3 nm, exhibits excellent catalytic performance for the selective hydrogenation of FFA to THFA. The 100% conversion of FFA and the 99% selectivity to THFA were obtained under mild reaction conditions (50 °C, 1 MPa, 1 h), using water as a green reaction solvent. The synergistic effect of NiCu alloy ensures the high catalytic activity. The acid sites and oxygen-containing functional groups on the surface of the modified RHPC can enhance the selectivity of THFA. The Ni2Cu1/RHPC catalyst offers good cyclability and regenerability. The current work proposes a simple method for preparing an NiCu bimetallic catalyst. The catalyst exhibits excellent performance in the catalytic hydrogenation of furfural to tetrahydrofurfuryl alcohol, which broadens the application of non-noble metal bimetallic nanocatalysts in the catalytic hydrogenation of furfural.

8.
Nanomaterials (Basel) ; 14(10)2024 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-38786778

RESUMEN

Carbon nanotube (CNT) is an excellent field emission material. However, uniformity and stability are the key issues hampering its device application. In this work, a bimetallic W-Co alloy was adopted as the catalyst of CNT in chemical vapor deposition process. The high melting point and stable crystal structure of W-Co helps to increase the grown CNT diameter uniformity and homogeneous crystal structure. High-crystallinity CNTs were grown on the W-Co bimetallic catalyst. Its field emission characteristics demonstrated a low turn-on field, high current density, stable current stability, and uniform emission distribution. The Fowler-Nordheim (FN) and Seppen-Katamuki (SK) analyses revealed that the CNT grown on the W-Co catalyst has a relatively low work function and high field enhancement factor. The high crystallinity and homogeneous crystal structure of CNT also reduce the body resistance and increase the emission current stability and maximum current. The result provides a way to synthesis a high-quality CNT field emitter, which will accelerate the development of cold cathode vacuum electronic device application.

9.
Adv Sci (Weinh) ; 11(24): e2309865, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38634577

RESUMEN

Copper-based bimetallic heterojunction catalysts facilitate the deep electrochemical reduction of CO2 (eCO2RR) to produce high-value-added organic compounds, which hold significant promise. Understanding the influence of copper interactions with other metals on the adsorption strength of various intermediates is crucial as it directly impacts the reaction selectivity. In this review, an overview of the formation mechanism of various catalytic products in eCO2RR is provided and highlight the uniqueness of copper-based catalysts. By considering the different metals' adsorption tendencies toward various reaction intermediates, metals are classified, including copper, into four categories. The significance and advantages of constructing bimetallic heterojunction catalysts are then discussed and delve into the research findings and current development status of different types of copper-based bimetallic heterojunction catalysts. Finally, insights are offered into the design strategies for future high-performance electrocatalysts, aiming to contribute to the development of eCO2RR to multi-carbon fuels with high selectivity.

10.
Chem Asian J ; 19(11): e202400292, 2024 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-38639574

RESUMEN

Cu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation-gel method and studied for the selective hydrogenation of syngas or biomass-based diethyl malonate (DEM) to valuable 1,3-propanediol (1,3-PDO). The Ga-promoted 70Cu6Ga/SiO2 catalyst was found to exhibit the highest catalytic performance, achieving 100 % DEM conversion and 76.6 % 1,3-PDO selectivity under reaction conditions of 160 °C and 8 MPa H2. The 70Cu6Ga/SiO2 bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO2 catalyst in a continuous flow reactor over 180 h time-on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu2+ species, and thus increased the proportion of Cu+ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu0 and Cu+ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO2 bimetallic catalysts.

11.
Chemosphere ; 352: 141333, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38336036

RESUMEN

Persulfate-based advanced oxidation processes (PS-AOPs) show a bright prospect in sewage purification. The development of efficient catalysts with simple preparation process and eco-friendliness is the key for their applying in practical water treatment. Herein, a bimetallic Cu-Fe metal organic framework (MOF) was simply synthesized by using one-pot solvothermal methods and employed for activating peroxymonosulfate (PMS) to degrade organic pollutants in water. The Cu-Fe-MOF/PMS exhibited excellent degradation efficiencies (over 95% in 30 min) for a variety of pollutants, including phenol, bisphenol A, 2,4-dichlorophenol, methyl blue, rhodamine B, tetracycline and sulfamethoxazole. The degradation efficiency was impacted by dosages of Cu-Fe-MOF, PMS concentrations, reaction temperature, solution pH and anionic species. Phenol could be efficiently decomposed in a wide pH range of 5-9, with the highest degradation and mineralization efficiency of nearly 100% and 70%, respectively. Free radicals and non-free radicals participated in degrading of phenol at the same time, with dominantly free radical process, because sulfate radicals (SO4·-) and hydroxyl radicals (·OH) were the primary active substances by contribution calculation. Cu-Fe-MOF was acted as electron shuttle between molecules of phenol and PMS, and the cooperation effect of Fe and Cu on the Cu-Fe-MOF promoted the electron transfer, achieving the high degradation efficiency of phenol. Thus, Cu-Fe-MOF is an ideal catalyst for activating PMS, which is conducive to promote the applying of catalyst-activated PMS processes for practical wastewater treatments.


Asunto(s)
Contaminantes Ambientales , Estructuras Metalorgánicas , Hierro/química , Contaminantes Ambientales/química , Electrones , Peróxidos/química , Fenoles
12.
Environ Sci Pollut Res Int ; 31(14): 22187-22197, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38403826

RESUMEN

The study focused on the efficacious performance of bimetallic Fe-Zn loaded 3A zeolite in catalytic ozonation for the degradation of highly toxic veterinary antibiotic enrofloxacin in wastewater of the pharmaceutical industry. Batch experiments were conducted in a glass reactor containing a submerged pump holding catalyst pellets at suction. The submerged pump provided the agitation and recirculation across the solution for effective contact with the catalyst. The effect of ozone flow (0.8-1.55 mg/min) and catalyst dose (5-15 g/L) on the enrofloxacin degradation and removal of other conventional pollutants COD, BOD5, turbidity was studied. In batch experiments, 10 g of Fe-Zn 3A zeolite efficiently removed 92% of enrofloxacin, 77% of COD, 69% BOD5, and 61% turbidity in 1 L sample of pharmaceutical wastewater in 30 min at 1.1 mg/min of O3 flow. The catalytic performance of Fe-Zn 3A zeolite notably exceeded the removal efficiencies of 52%, 51%, 52%, and 59% for enrofloxacin, COD, BOD5, and turbidity, respectively, achieved with single ozonation process. Furthermore, an increase in the biodegradability of treated pharmaceutical industrial wastewater was observed and made biodegradable easily for subsequent treatment.


Asunto(s)
Ozono , Drogas Veterinarias , Contaminantes Químicos del Agua , Purificación del Agua , Zeolitas , Aguas Residuales , Enrofloxacina , Contaminantes Químicos del Agua/análisis
13.
Comb Chem High Throughput Screen ; 27(12): 1830-1839, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38305403

RESUMEN

BACKGROUND: Bisoprolol (BIS) is a selective beta-blocker. It has been successfully used to treat hypertension and angina pectoris. An overdose of BIS can lead to serious complications. An overdose is a medical emergency that requires immediate medical attention to overcome the adverse effects of the overdose. Hence, sensitive, reliable, and cost-effective methods are required for the determination of BIS. METHODS: In this work, a new electrochemical sensing platform based on a bimetallic catalyst was developed for the determination of BIS. The Cu-Co nanocatalyst was easily synthesized by galvanic displacement onto a carbon paste electrode (CPE). Then, field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), and cyclic voltammetry (CV) were utilized for the characterization of the Cu-Co catalyst. RESULTS: The galvanic displacement of Cu metal significantly affected the electro-catalytic behavior of the Cu-Co catalyst and the Cu-Co/CPE electrode displayed a very sensitive and accurate response towards BIS. Under optimized conditions, the response was linear in the 3 to 120 µM concentration range, sensitivity of 631.1 µA mM-1 and a detection limit of as low as 0.4 µM using cyclic voltammetry. The simple proposed method was also successfully employed in the analysis of BIS in biological and pharmaceutical samples. The advantages of Cu-Co/CPE are its fast and simple manufacturing and the possibility of a repeated surface regeneration of the sensing platform, as well as its application for the detection of BIS in tablets and biological samples, making Cu-Co significant promise for use in clinical diagnostics. Besides, the synthesized catalysts showed excellent reusability and stability. CONCLUSION: The presence of Cu metal due to galvanic displacement increased the sensitivity. These findings suggest that the new nanocatalyst has potential applications in sensors and electronics.


Asunto(s)
Bisoprolol , Cobalto , Cobre , Técnicas Electroquímicas , Cobre/química , Catálisis , Cobalto/química , Bisoprolol/análisis , Bisoprolol/química , Humanos , Electrodos , Límite de Detección
14.
Bioresour Technol ; 395: 130378, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38281546

RESUMEN

A novel manganese cobalt metal-organic framework based carbon nanofiber electrode (MnCo/CNF) was prepared and used as microbial fuel cell (MFC) anode. Pyrite was introduced into the anode chamber (MnCoPy_MFC). Synergistic function between pyrite and MnCo/CNF facilitated the pollutants removal and energy generation in MnCoPy_MFC. MnCoPy_MFC showed the highest chemical oxygen demand removal efficiency (82 ± 1%) and the highest coulombic efficiency (35 ± 1%). MnCoPy_MFC achieved both efficient electricity generation (maximum voltage: 658 mV; maximum power density: 3.2 W/m3) and total antimony (Sb) removal efficiency (99%). The application of MnCo/CNF significantly enhanced the biocatalytic efficiency of MnCoPy_MFC, attributed to its large surface area and abundant porous structure that provided ample attachment sites for electroactive microorganisms. This study revealed the synergistic interaction between pyrite and MnCo/CNF anode, which provided a new strategy for the application of composite anode MFC in heavy metal removal and energy recovery.


Asunto(s)
Fuentes de Energía Bioeléctrica , Hierro , Nanofibras , Compuestos de Nitrosourea , Sulfuros , Carbono , Manganeso , Antimonio , Cobalto , Fuentes de Energía Bioeléctrica/microbiología , Electricidad , Electrodos , Bacterias/química
15.
ACS Appl Mater Interfaces ; 16(1): 17-29, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38118131

RESUMEN

Bimetallic glucose oxidation electrocatalysts were synthesized by two electrochemical reduction reactions carried out in series onto a titanium electrode. Nickel was deposited in the first synthesis stage followed by either silver or copper in the second stage to form Ag@Ni and Cu@Ni bimetallic structures. The chemical composition, crystal structure, and morphology of the resulting metal coating of the titanium electrode were investigated by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy. The electrocatalytic performance of the coated titanium electrodes toward glucose oxidation was probed using cyclic voltammetry and amperometry. It was found that the unique high surface area bimetallic structures have superior electrocatalytic activity compared to nickel alone. The resulting catalyst-coated titanium electrode served as a nonenzymatic glucose sensor with high sensitivity and low limit of detection for glucose. The Cu@Ni catalyst enables accurate measurement of glucose over the concentration range of 0.2-12 mM, which includes the full normal human blood glucose range, with the maximum level extending high enough to encompass warning levels for prediabetic and diabetic conditions. The sensors were also found to perform well in the presence of several chemical compounds found in human blood known to interfere with nonenzymatic sensors.


Asunto(s)
Técnicas Biosensibles , Cobre , Humanos , Cobre/química , Níquel/química , Titanio , Técnicas Biosensibles/métodos , Glucosa/química , Electrodos , Técnicas Electroquímicas
16.
J Colloid Interface Sci ; 656: 424-439, 2024 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-38000254

RESUMEN

Manipulating metal valence states and porosity in the metal-organic framework (MOF) by alloying has been a unique tool for creating high-valent metal sites and pore environments in a structure that are inaccessible by other methods, favorable for accelerating the catalytic activity towards sensing applications. Herein, we report Fe3+-driven formation of catalytic active Ni3+ species in the amine-crafted benzene-dicarboxylate (BDC-NH2)-based MOF as a high-performance electrocatalyst for glucose sensing. This work took the benefit of different bonding stability between BDC-NH2 ligand, and Fe3+ and Ni2+ metal precursor ions in the heterometallic NixFe(1-x)-BDC-NH2 MOF. The FeCl3 that interacts weakly with ligand, oxidizes the Ni2+ precursor to Ni3+-based MOF owing to its Lewis acidic behavior and was subsequently removed from the structure supported by Ni atoms, during solvothermal synthesis. This enables to create mesopores within a highly stable Ni-MOF structure with optimal feed composition of Ni0.7Fe0.3-BDC-NH2. The Ni3+-based Ni0.7Fe0.3-BDC-NH2 demonstrates superior catalytic properties towards glucose sensing with a high sensitivity of 13,435 µA mM-1 cm-2 compared to the parent Ni2+-based Ni-BDC-NH2 (10897 µA mM-1cm-2), along with low detection limit (0.9 µM), short response time (≤5 s), excellent selectivity, and higher stability. This presented approach for fabricating high-valent nickel species, with a controlled quantity of Fe3+ integrated into the structure allowing pore engineering of MOFs, opens new avenues for designing high-performing MOF catalysts with porous framework for sensing applications.

17.
Chemosphere ; 349: 140958, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38104735

RESUMEN

A novel 3D bimetallic metal-organic framework (MOF(Fe-Co)) was successfully prepared and its performance on sulfamethoxazole (SMX) removal in advanced oxidation process (AOP) based on peracetic acid (PAA) was evaluated. MOF(Fe-Co) exhibited an efficient catalytic performance on PAA activation for SMX degradation under neutral condition. Increasing PAA concentration could enhance SMX removal, while the variation of MOF(Fe-Co) dosage from 0.05 to 0.2 g/L had an inappreciable effect on SMX removal. According to the results of inductively coupled plasma mass spectrometry analyses and X-ray photoelectron spectroscopy, catalytic reactions mainly occurred on the surface of MOF(Fe-Co). Organic radicals (i.e., CH3C(O)OO• and CH3C(O)O•) were demonstrated to be the predominant reactive radicals for SMX degradation by MOF(Fe-Co)/PAA through radical quenching experiments. The presence of Cl- could enhance the degradation of SMX by MOF(Fe-Co)/PAA, while HCO3- and natural organic matter inhibited SMX degradation severely. Five identified degradation products were detected in this system and four possible SMX transformation pathways were proposed, including amino oxidation, S-N bond cleavage, coupling reaction and hydroxylation.


Asunto(s)
Estructuras Metalorgánicas , Contaminantes Químicos del Agua , Ácido Peracético , Sulfametoxazol/química , Contaminantes Químicos del Agua/análisis , Oxidación-Reducción , Peróxido de Hidrógeno/química
18.
Environ Sci Pollut Res Int ; 31(4): 6332-6349, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-38147249

RESUMEN

This research endeavors to address the pressing challenge of reducing sulfur content in fuels, an environmental imperative. It does so by employing bimetallic catalysts to enhance the efficiency of oxidative desulfurization (ODS) processes. This involves utilizing successive impregnation and co-impregnation methods to prepare a MoO3-V2O5/Al2O3. The catalysts underwent characterization using various techniques including X-ray diffraction (XRD), N2 adsorption-desorption, UV-vis (DRS), temperature-programmed desorption (NH3-TPD), Raman, Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), and energy dispersive spectrum (EDS). The catalyst was utilized for the evaluation of the ODS process of dibenzothiophene (DBT). The effects of oxidants, namely H2O2 and t-butyl hydroperoxide (TBHP), were studied in the ODS. The catalyst prepared using the co-impregnation method (5M-15V-co) demonstrated significant acidic sites and exhibited remarkable efficiency in oxidative desulfurization. Remarkably, this catalyst achieved 100% oxidation of sulfur components within 30 min (min). To assess the catalyst's performance further, competitive compounds including nitrogen-containing compounds (NCCs) and saturated and unsaturated hydrocarbon compounds (HCs) were employed in the ODS. Initially, the introduction of NCCs led to a decrease in the sulfur removal rate; however, the catalyst successfully oxidized DBT completely within 60 min. When cyclohexene was present as an olefinic hydrocarbon compound, the catalyst oxidized DBT by approximately 75%, whereas DBT oxidation reached 100% within 20 min when p-xylene was introduced to the catalytic reactor. Additionally, as the O/S ratio increased from 2/5 to 10, the sulfur removal rate improved from 30 to 90%, indicating that HCs and NCCs compete with sulfur in terms of oxidant consumption.


Asunto(s)
Peróxido de Hidrógeno , Compuestos de Nitrógeno , Oxidación-Reducción , Temperatura , Estrés Oxidativo , Azufre/química
19.
Molecules ; 28(24)2023 Dec 18.
Artículo en Inglés | MEDLINE | ID: mdl-38138634

RESUMEN

The water-gas shift (WGS) performance was investigated over 5%Ni/CeO2, 5%Ni/Ce0.95Pr0.05O1.975, and 1%Re4%Ni/Ce0.95Pr0.05O1.975 catalysts to decrease the CO amount and generate extra H2. CeO2 and Pr-doped CeO2 mixed oxides were synthesized using a combustion method. After that, Ni and Re were loaded onto the ceria support via an impregnation method. The structural and redox characteristics of monometallic Ni and bimetallic NiRe materials, which affect their water-gas shift performance, were investigated. The results show that the Pr addition into Ni/ceria increases the specific surface area, decreases the ceria crystallite size, and improves the dispersion of Ni on the CeO2 surface. Furthermore, Re addition results in the enhancement of the WGS performance of the Ni/Ce0.95Pr0.05O1.975 catalyst. Among the studied catalysts, the ReNi/Ce0.95Pr0.05O1.975 catalyst showed the highest catalytic activity, reaching 96% of CO conversion at 330°. It was established that the occurrence of more oxygen vacancies accelerates the redox process at the ceria surface. In addition, an increase in the Ni dispersion, Ni surface area, and surface acidity has a positive effect on hydrogen generation during the water-gas shift reaction due to favored CO adsorption.

20.
Environ Sci Pollut Res Int ; 30(48): 105885-105896, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37718361

RESUMEN

Pt-V bimetallic catalysts maybe promising substitutes to precious metal catalysts for selective catalytic oxidation (SCO) of NH3. But it remains a major challenge for Pt-V bimetallic catalysts to pursue high NH3 conversion rate and N2 selectivity simultaneously. In this work, both Cu and Er were adopted to modify V0.5/Pt0.04/TiO2 catalyst (denoted as V/PT), and the influences of Cu and Er doping amounts on NH3-SCO performance of V/PT catalysts were investigated systematically. The results indicated that the co-modification of Cu and Er imposed little influence on NH3 conversion efficiency, but significantly boosted N2 selectivity. Compared with other Cu-Er-modified V/PT catalysts, CEV/PT-4 catalyst exhibited outstanding NH3-SCO performance, which attained completely 100% NH3 conversion efficiency and > 90% N2 selectivity in the temperature range of 225-450 °C. It was significantly superior to the NH3-SCO performance of most previously reported catalysts. The characterization results indicated that the adequate doping amounts of Cu and Er resulted in an obvious enhancement on redox property and surface acidity of CEV/PT-4 catalyst. It also led to abundant Pt0 and surface chemisorbed oxygen species on catalyst surface, which facilitated the oxidation of NH3 to NOx and enhanced i-SCR reactions. In situ DRIFTS results showed that -NH2 species on the surface of CEV/PT-4 catalyst could actively react with nitrate species to generate N2 and H2O.


Asunto(s)
Amoníaco , Titanio , Oxidación-Reducción , Nitratos , Catálisis
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