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1.
Int J Mol Sci ; 25(19)2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-39408913

RESUMEN

Acetylene and methylacetylene are impurities commonly found in the raw materials used for the production of polymers such as polypropylene and polyethylene. Experimental evidence indicates that both acetylene and methylacetylene can decrease the productivity of the Ziegler-Natta catalyst and alter the properties of the resulting polymer. However, there is still a lack of understanding regarding the mechanisms through which these substances affect this process. Therefore, elucidating these mechanisms is crucial to develop effective solutions to this problem. In this study, the inhibition mechanisms of the Ziegler-Natta catalyst by acetylene and methylacetylene are presented and compared with the incorporation of the first propylene monomer (chain initiation) to elucidate experimental effects. The Density Functional Theory (DFT) method was used, along with the B3LYP-D3 functional and the 6-311++G(d,p) basis set. The recorded adsorption energies were -11.10, -13.99, and -0.31 kcal mol-1, while the activation energies were 1.53, 2.83, and 28.36 kcal mol-1 for acetylene, methylacetylene, and propylene, respectively. The determined rate constants were 4.68 × 1011, 5.29 × 1011, and 2.3 × 10-8 M-1 s-1 for acetylene, methylacetylene, and propylene, respectively. Based on these values, it is concluded that inhibition reactions are more feasible than propylene insertion only if an ethylene molecule has not been previously adsorbed, as such an event reinforces propylene adsorption.


Asunto(s)
Acetileno , Alquenos , Polimerizacion , Alquenos/química , Catálisis , Acetileno/química , Acetileno/análogos & derivados , Alquinos/química , Alquinos/farmacología , Termodinámica , Teoría Funcional de la Densidad
2.
Molecules ; 29(19)2024 Oct 08.
Artículo en Inglés | MEDLINE | ID: mdl-39407679

RESUMEN

The influence of residual cuts on the deactivation of hierarchical Y zeolite-based catalysts during the co-processing of vacuum gas oil (VGO) with atmospheric residue (ATR) was investigated. The experiments were conducted in a laboratory-scale MAT-type reactor. The conversion of VGO, ATR, and their 70:30 (mass basis) mixture was examined using two composite catalysts: Cat.Y.0.00 and Cat.Y.0.20. The operating conditions closely resembled those of the commercial catalytic cracking process (550 °C and contact times of 10 to 50 s). When ATR was processed individually, the conversion remained below 50 wt%. However, significant improvements in conversion rates were achieved and catalyst deactivation was mitigated when ATR was co-processed with VGO. Notably, the BET surface area and average mesopore volume were adversely impacted by ATR, which also led to the accumulation of high levels of metals and nitrogen on the spent catalyst, detrimentally affecting its acidic and structural properties. Moreover, substantial coke deposition occurred during ATR cracking. The soluble and insoluble coke analysis revealed H/C ratio values of up to 0.36, indicative of polycondensed coke structures with more than ten aromatic rings. The nature of the coke was confirmed through TPO and FTIR analyses. Interestingly, the CatY.0.20 catalyst exhibited less activity loss, retaining superior acid and structural properties. Co-processing Colombian atmospheric residue with ATR loadings of 30 wt% (higher than the typical 20 wt%) in catalysts formulated with hierarchical zeolites presents a promising alternative for commercial applications. This research opens avenues for optimizing catalytic cracking processes.

3.
Artículo en Inglés | MEDLINE | ID: mdl-39333433

RESUMEN

This work aimed to evaluate the effect of niobium addition on nickel-based catalysts and their performance in dry reforming reactions to produce syngas (H2 and CO). Different quantities of Nb2O5 (5, 10, and 20% w/w) were used to prepare the catalysts, while a fixed content of Ni was applied (20%). The catalysts were supported on MCM-41. Physical, chemical, and morphological analyses were conducted to assess the characteristics of the materials. The produced Nb-Ni catalysts were applied in dry reforming reactions at 800 °C for 12 h. The dry reforming results indicated that the catalyst with 10% Nb-Ni demonstrated the best conversion of CH4 and CO2 (> 97%) and a significant H2 production (40%), with good stability during 12 h of reaction, while the catalyst with 5% Nb-Ni showed lower conversions and did not present good stability during the reaction. The catalyst with 5% Nb-Ni exhibited the highest production of H2 (44%), and the lowest of CO (50.87%), probably due to the presence of parallel reactions that increased H2 content and caused carbon (coke) formation. The characterization results of this material revealed the greatest formation of carbon on its surface. The presence of coke can prejudice the efficiency of the catalyst during a reaction and significantly reduce its lifetime. The catalyst with 10% Nb-Ni did not present coke formation, while the catalyst with 20% Nb-Ni showed carbon presence. The good dispersion of Ni on supports (Nb2O5 and SiO2/MCM-41) can explain the best behavior of 10% Nb-Ni for dry reforming reactions. X-ray diffractometry of the solids suggests the contribution of both metals (Ni and Nb) to the reforming process. From the obtained results, the catalyst with 10% Nb-Ni was indicated as the most favorable for dry reforming reactions among the studied materials, displaying good stability and conversion along with resistance to carbon formation.

4.
Heliyon ; 10(18): e37813, 2024 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-39315141

RESUMEN

This study investigated the deactivation and regeneration of hierarchical zeolites in vacuum gas oil conversion, aiming to reach the equilibrium state seen in fluidized bed catalytic cracking (FCC). The research utilized various characterization techniques to analyze the properties of zeolites before and after coking and regeneration. Zeolite Y-0.20-S was found to have the highest gasoline selectivity and quality, mirroring industrial yields, and displayed notable stability across deactivation/regeneration cycles. Higher mesopore concentration in zeolites led to increased coke selectivity and better resistance to deactivation. The study observed a dominance of aromatic coke with a higher degree of condensation in these zeolites. Despite coke deposition affecting acid and textural properties, the regeneration process effectively restored these characteristics, proving its efficiency. The zeolites with greater mesoporosity retained their fundamental properties responsible for activity and selectivity, highlighting the importance of selecting materials that provide high conversions and maintain stability and product selectivity over multiple cycles. The Y-0.20-S zeolite, in particular, was identified as a promising candidate for commercial catalyst development for gasoline production, contributing to the FCC process's energy efficiency.

5.
J Mol Model ; 30(8): 278, 2024 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-39034330

RESUMEN

CONTEXT: This study investigates the ethylene insertion reaction mechanism for polymerization catalysis, aiming to discern differences between Ni-α-imine ketone-type catalyst and their SiO2-supported counterpart. The reaction force analysis unveils a more intricate mechanism with SiO2 support, shedding light on unexplored factors and elucidating the observed lower catalytic activity. Furthermore, reactivity indexes suggest earlier ethylene activation in the supported catalyst, potentially enhancing overall selectivity. Finally, the reaction electronic flux analysis provides detailed insights into the electronic activity at each step of the reaction mechanism. In sum, this study offers a comprehensive understanding of the ethylene insertion reaction mechanism in both molecular and supported catalysts, underscoring the pivotal role of structural and electronic factors in catalytic processes. METHODS: Density functional theory (DFT) calculations were conducted using the ωB97XD functional and the 6-31 + G(d,p) basis sets with Gaussian16 software. Computational techniques utilized in this study encompassed the IRC method, reaction force analysis, and evaluation of electronic descriptors such as electronic chemical potential, molecular hardness, and electrophilicity reactivity indexes. Additionally, reaction electronic flux analysis was employed to investigate electronic activity along the reaction coordinate.

6.
Molecules ; 29(13)2024 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-38999037

RESUMEN

The performance of catalysts prepared from hierarchical Y zeolites has been studied during the conversion of vacuum gas oil (VGO) into higher-value products. Two different catalysts have been studied: CatY.0.00 was obtained from the standard zeolite (Y-0.00-M: without alkaline treatment) and CatY.0.20 was prepared from the desilicated zeolite (Y-0-20-M: treated with 0.20 M NaOH). The cracking tests were carried out in a microactivity test (MAT) unit with a fixed-bed reactor at 550 °C in the 20-50 s reaction time range, with a catalyst mass of 3 g and a mass flow rate of VGO of 2.0 g/min. The products obtained were grouped according to their boiling point range in dry gas (DG), liquefied petroleum gas (LPG), naphtha, and coke. The results showed a greater conversion and selectivity to gasoline with the CatY.0.20 catalyst, along with improved quality (RON) of the C5-C12 cut. Conversely, the CatY.0.00 catalyst (obtained from the Y-0.00-M zeolite) showed greater selectivity to gases (DG and LPG), attributable to the electronic confinement effect within the microporous channels of the zeolite. The nature of coke has been studied using different analysis techniques and the impact on the catalysts by comparing the properties of the fresh and deactivated catalysts. The coke deposited on the catalyst surfaces was responsible for the loss of activity; however, the CatY.0.20 catalyst showed greater resistance to deactivation by coke, despite showing the highest selectivity. Given that the reaction occurs in the acid sites of the zeolite and not in the matrix, the increased degree of mesoporosity of the zeolite in the CatY.0.20 catalyst facilitated the outward diffusion of products from the zeolitic channels to the matrix, thereby preserving greater activity.

7.
Artículo en Inglés | MEDLINE | ID: mdl-39075825

RESUMEN

In this contribution, nanocatalysts with rather diverse architectures were designed to promote different intimacy degrees between Cu and SiO2 and consequently tune distinct Cu-SiO2 interactions. Previously synthesized copper nanoparticles were deposited onto SiO2 (NPCu/SiO2) in contrast to ordinarily prepared supported Cu/SiO2. NPCu@SiO2 and SiO2@Cu core-shell nanocatalysts were also synthesized, and they were all bulk and surface characterized by XRD, TGA, TEM/HRTEM, H2-TPR, XANES, and XPS. It was found that Cu0 is the main copper phase in NPCu/SiO2 while Cu2+ rules the ordinary Cu/SiO2 catalyst, and Cu0 and electron-deficient Cuδ+ species coexist in the core-shell nanocatalysts as a consequence of a deeper metal-support interaction. Catalytic performance could not be associated with the physical properties of the nanocatalysts derived from their architectures but was associated with the more refined chemical characteristics tuned by their design. Cu/SiO2 and NPCu/SiO2 catalysts led to the formation of furfuryl alcohol, evidencing that catalysts holding weak or no metal-support interaction have no significant impact on product distribution even in the aqueous phase. The establishment of such interactions through advanced catalyst architecture, allowing the formation of electron-deficient Cuδ+ moieties, particularly Cu2+ and Cu+ as unveiled by spectroscopic investigations, is critical to promoting the hydrogenation-ring rearrangement cascade mechanism leading to cycloketones.

8.
Environ Sci Pollut Res Int ; 31(32): 44965-44982, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38954345

RESUMEN

Sulfate radical-based advanced oxidation processes (SR-AOPs) are renowned for their exceptional capacity to degrade refractory organic pollutants due to their wide applicability, cost-effectiveness, and swift mineralization and oxidation rates. The primary sources of radicals in AOPs are persulfate (PS) and peroxymonosulfate (PMS) ions, sparking significant interest in their mechanistic and catalytic aspects. To develop a novel nanocatalyst for SR-AOPs, particularly for PMS activation, we synthesized carbon-coated FeCo nanoparticles (NPs) using solvothermal methods based on the polyol approach. Various synthesis conditions were investigated, and the NPs were thoroughly characterized regarding their structure, morphology, magnetic properties, and catalytic efficiency. The FeCo phase was primarily obtained at [OH-] / [Metal] = 26 and [Fe] / [Co] = 2 ratios. Moreover, as the [Fe]/[Co] ratio increased, the degree of xylose carbonization to form a carbon coating (hydrochar) on the NPs also increased. The NPs exhibited a spherical morphology with agglomerates of varying sizes. Vibrating-sample magnetometer analysis (VSM) indicated that a higher proportion of iron resulted in NPs with higher saturation magnetization (up to 167.8 emu g-1), attributed to a larger proportion of FeCo bcc phase in the nanocomposite. The best catalytic conditions for degrading 100 ppm Rhodamine B (RhB) included 0.05 g L-1 of NPs, 2 mM PMS, pH 7.0, and a 20-min reaction at 25 °C. Notably, singlet oxygen was the predominant specie formed in the experiments in the SR-AOP, followed by sulfate and hydroxyl radicals. The catalyst could be reused for up to five cycles, retaining over 98% RhB degradation, albeit with increased metal leaching. Even in the first use, dissolved Fe and Co concentrations were 0.8 ± 0.3 and 4.0 ± 0.5 mg L-1, respectively. The FeCo catalyst proved to be effective in dye degradation and offers the potential for further refinement to minimize Co2+ leaching.


Asunto(s)
Nanocompuestos , Peróxidos , Nanocompuestos/química , Peróxidos/química , Contaminantes Químicos del Agua/química , Catálisis , Oxidación-Reducción , Hierro/química , Carbono/química
9.
Front Chem ; 12: 1383443, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38783898

RESUMEN

In this work, the electrochemical oxidation of carbohydrates (glucose, fructose, and sucrose) was induced at the interface of Pt-nanoparticles supported on different carbon-based materials as carbon vulcan (C) and carbon black (CB). It was found that the support plays an important role during carbohydrates electro-oxidation as demonstrated by electrochemical techniques. In this context, current-concentration profiles of the redox peaks show the behavior of the pathways at carbohydrates-based solutions. Herein, the trend of current measured was glucose > sucrose > fructose, attributed to differences in the organic functional groups and chain-structure. Raman, XRD, SEM-EDS and XPS put in clear important structural, morphological, and electronic differences linked with the intrinsic nature of the obtained material. Differential Electrochemical Mass Spectroscopy (DEMS) indicated that the selectivity and the conversion of the formed reaction products during oxidation is linked with the catalyst nature (distribution, particle size) and the interaction with the carbon-based support.

10.
J Mol Model ; 30(6): 183, 2024 May 24.
Artículo en Inglés | MEDLINE | ID: mdl-38782773

RESUMEN

CONTEXT: The activation of C-H bonds is a fundamental process in synthetic organic chemistry, which enables their replacement by highly reactive functional groups. Coordination compounds serve as effective catalysts for this purpose, as they facilitate chemical transformations by interacting with C-H bonds. A comprehensive understanding of the mechanism of activation of this type of bond lays the foundation for the development of efficient protocols for cross-coupling reactions. We explored the activation of C(sp2)-H bonds in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives with CH3, OCH3, and NO2 substituents in the para position of the phenyl ring, using palladium acetate as catalyst. The studied reaction is the first step for subsequent conjugation of the triazoles with naphthoquinones in a Heck-type reaction to create a C-C bond. The basic nitrogen atoms of the 1,2,3-triazole coordinate preferentially with the cationic palladium center to form an activated species. A concerted proton transfer from the terminal vinyl carbon to one of the acetate ligands with low activation energy is the main step for the C(sp2)-H activation. This study offers significant mechanistic insights for enhancing the effectiveness of C(sp2)-H activation protocols in organic synthesis. METHODS: All calculations were performed using the Gaussian 09 software package and density functional theory (DFT). The structures of all reaction path components were fully optimized using the CAM-B3LYP functional with the Def2-SVP basis set. The optimized geometries were analyzed by computing the second-order Hessian matrix to confirm that the corresponding minimum or transition state was located. To account for solvent effects, the Polarizable Continuum Model of the Integral Equation Formalism (IEFPCM) with water as the solvent was used.

11.
Angew Chem Int Ed Engl ; 63(34): e202406701, 2024 Aug 19.
Artículo en Inglés | MEDLINE | ID: mdl-38740950

RESUMEN

Stable homogeneous two-electron water oxidation electrocatalysts are highly demanded to understand the precise mechanism and reaction intermediates of electrochemical H2O2 production. Here we report a tetranuclear manganese complex with a cubane structure which can electrocatalyze water oxidation to hydrogen peroxide under alkaline and neutral conditions. Such a complex demonstrates an optimal Faradaic efficiency (FE) of 87 %, which is amongst (if not) the highest FE(H2O2) of reported homogeneous and heterogeneous electrocatalysts. In addition, active species were identified and co-catalysts were excluded through ESI-MS characterization. Furthermore, we identified water binding sites and isolated one-electron oxidation intermediate by chemical oxidation of the catalyst in the presence of water substrates. It is evident that efficient proton-accepting electrolytes avoid rapid proton building-up at electrode and substantially improve reaction rate and selectivity. Accordingly, we propose a two-electron catalytic cycle model for water oxidation to hydrogen peroxide with the bioinspired molecular electrocatalyst. The present work is expected to provide an ideal platform to elucidate the two-electron WOR mechanism at the atomic level.

12.
Methods Protoc ; 7(2)2024 Mar 23.
Artículo en Inglés | MEDLINE | ID: mdl-38668135

RESUMEN

This research focuses on the development of a state observer for performing indirect measurements of the main variables involved in the soybean oil transesterification reaction with a guishe biochar-based heterogeneous catalyst; the studied reaction takes place in a batch reactor. The mathematical model required for the observer design includes the triglycerides' conversion rate, and the reaction temperature. Since these variables are represented by nonlinear differential equations, the model is linearized around an operation point; after that, the pole placement and linear quadratic regulator (LQR) methods are considered for calculating the observer gain vector L(x). Then, the estimation of the conversion rate and the reaction temperature provided by the observer are used to indirectly measure other variables such as esters, alcohol, and byproducts. The observer performance is evaluated with three error indexes considering initial condition variations up to 30%. With both methods, a fast convergence (less than 3 h in the worst case) of the observer is remarked.

13.
Adv Sci (Weinh) ; 11(25): e2402234, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38629782

RESUMEN

Protein structure plays an essential role on their stability, functionality, and catalytic activity. In this work, the interplay between the ß-sheet structure and its catalytic implications to the design of enzyme-inspired materials is investigated. Here, inspiration is drawn from the active sites and ß-sheet rich structure of the highly efficient multicopper oxidase (MCO) to engineer a bio-inspired electrocatalyst for water oxidation utilizing the abundant metal, copper. Copper ions are coordinated to poly-histidine (polyCuHis), as they are in MCO active sites. The resultant polyCuHis material effectively promotes water oxidation with low overpotentials (0.15 V) in alkaline systems. This activity is due to the 3D structure of the poly-histidine backbone. By increasing the prevalence of ß-sheet structure and decreasing the random coil nature of the polyCuHis secondary structures, this study is able to modulates the electrocatalytic activity of this material is modulated, shifting it toward water oxidation. These results highlight the crucial role of the local environment at catalytic sites for efficient, energy-relevant transformations. Moreover, this work highlights the importance of conformational structure in the design of scaffolds for high-performance electrocatalysts.


Asunto(s)
Oxidación-Reducción , Agua , Agua/química , Catálisis , Polímeros/química , Cobre/química , Estructura Secundaria de Proteína , Oxidorreductasas/química , Oxidorreductasas/metabolismo , Histidina
14.
Molecules ; 29(5)2024 Feb 29.
Artículo en Inglés | MEDLINE | ID: mdl-38474584

RESUMEN

The integration of clean energy generation with wastewater treatment holds promise for addressing both environmental and energy concerns. Focusing on photocatalytic hydrogen production and wastewater treatment, this study introduces PdIn/TiO2 catalysts for the simultaneous removal of the pharmaceutical contaminant paracetamol (PTM) and hydrogen production. Physicochemical characterization showed a high distribution of Pd and In on the support as well as a high interaction with it. The Pd and In deposition enhance the light absorption capability and significantly improve the hydrogen evolution reaction (HER) in the absence and presence of paracetamol compared to TiO2. On the other hand, the photoelectroxidation of PTM at TiO2 and PdIn/TiO2 follows the full mineralization path and, accordingly, is limited by the adsorption of intermediate species on the electrode surface. Thus, PdIn-doped TiO2 stands out as a promising photoelectrocatalyst, showcasing enhanced physicochemical properties and superior photoelectrocatalytic performance. This underscores its potential for both environmental remediation and sustainable hydrogen production.

15.
Sci Rep ; 14(1): 7299, 2024 Mar 27.
Artículo en Inglés | MEDLINE | ID: mdl-38538652

RESUMEN

In polymer membrane fuel cells (PEMFC), the pore microstructure and the effective diffusion coefficient ( D eff ) of the catalytic layer have a significant impact on the overall performance of the fuel cell. In this work, numerical methods to simulate PEMFC catalytic layers were used to study the effect of isotropy ( I xy ) on the D eff . The proposed methodology studies reconstructed systems by Simulated Annealing imaging with different surface fractions of microstructures composed by two diffusive phases: agglomerates and pores. The D eff is determined numerically by the Finite Volume Method solved for Fick's First Law of Diffusion. The results show that the proposed methodology can effectively quantify the effect of isotropy on the D eff for both diffusion phases. Two trends were obtained in the magnitude of the D eff concerning the change in isotropy: (1) an analytical equation is proposed in this article for D eff ≥ 5 % D 0 and (2) numerical solutions are determined for D eff < 5 % D 0 . In our analytical equation are both a lineal and a logarithmic sweep. When the surface fraction is ∅ = 50%, the D eff decreases more linearly than ∅ = 10 % at the beginning of the isotropy change, which indicates that small changes in isotropy in the particulate material modify it drastically; under these conditions the diffusion coefficient in the pore is predominant. (3) When the surface fraction is less than 50%, the D eff decreases more exponentially at the beginning and more linearly at the end of the isotropy change, which shows that small isotropy changes in the bar-aligned material drastically alter it. In this trend, diffusion in the agglomerate is less affected by isotropy. The proposed methodology can be used as a design tool to improve the mass transport in porous PEMFC electrodes.

16.
Polymers (Basel) ; 16(5)2024 Feb 23.
Artículo en Inglés | MEDLINE | ID: mdl-38475289

RESUMEN

This study outlines the investigation into how the compounds CO2, CO, and O2 interact with the active center of titanium (Ti) on the surface of MgCl2 and how these interactions impact the productivity of the Ziegler-Natta catalyst, ultimately influencing the thermal stability of the produced polypropylene. The calculations revealed that the adsorption energies of Ti-CO2-CO and O2 were -9.6, -12.5, and -2.32 Kcal/mol, respectively. Using the density functional theory in quantum calculations, the impacts of electronic properties and molecular structure on the adsorption of CO, O2, and CO2 on the Ziegler-Natta catalyst were thoroughly explored. Additionally, the Gibbs free energy and enthalpy of adsorption were examined. It was discovered that strong adsorption and a significant energy release (-16.2 kcal/mol) during CO adsorption could explain why this gas caused the most substantial reductions in the ZN catalyst productivity. These findings are supported by experimental tests showing that carbon monoxide has the most significant impact on the ZN catalyst productivity, followed by carbon dioxide, while oxygen exerts a less pronounced inhibitory effect.

17.
Environ Sci Pollut Res Int ; 31(5): 8072-8081, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-38175508

RESUMEN

Cigarette filters were utilized as carbon source for the production of solid carbon acid catalysts. In this study, the process of carbonization and simultaneous sulfonation via hydrothermal treatment was employed. The catalysts were prepared by mixing cigarette filters and sulfuric acid at temperatures of 100, 150, and 190 °C for durations ranging from 2 to 8 h. It was observed that the highest conversion of oleic acid occurred when the catalyst was synthesized at 190 °C for 4 h. The optimized conditions for the esterification reaction using this catalyst included an oleic acid to methanol molar ratio of 1:12, a catalyst loading of 5 wt%, and a temperature of 100 °C for 1 h. Additionally, the catalyst was successfully reused four times without significantly impacting the reaction yield. These findings highlight a promising approach for the utilization of waste materials, with immediate implications for waste management practices and positive environmental impacts.


Asunto(s)
Biocombustibles , Ácido Oléico , Esterificación , Temperatura , Catálisis , Carbono
18.
Angew Chem Int Ed Engl ; 63(4): e202315146, 2024 Jan 22.
Artículo en Inglés | MEDLINE | ID: mdl-37953459

RESUMEN

The chiral-induced spin selectivity effect (CISS) is a breakthrough phenomenon that has revolutionized the field of electrocatalysis. We report the first study on the electron spin-dependent electrocatalysis for the oxygen reduction reaction, ORR, using iron phthalocyanine, FePc, a well-known molecular catalyst for this reaction. The FePc complex belongs to the non-precious catalysts group, whose active site, FeN4, emulates catalytic centers of biocatalysts such as Cytochrome c. This study presents an experimental platform involving FePc self-assembled to a gold electrode surface using chiral peptides (L and D enantiomers), i.e., chiro-self-assembled FePc systems (CSAFePc). The chiral peptides behave as spin filters axial ligands of the FePc. One of the main findings is that the peptides' handedness and length in CSAFePc can optimize the kinetics and thermodynamic factors governing ORR. Moreover, the D-enantiomer promotes the highest electrocatalytic activity of FePc for ORR, shifting the onset potential up to 1.01 V vs. RHE in an alkaline medium, a potential close to the reversible potential of the O2 /H2 O couple. Therefore, this work has exciting implications for developing highly efficient and bioinspired catalysts, considering that, in biological organisms, biocatalysts that promote O2 reduction to water comprise L-enantiomers.

19.
Artículo en Inglés | MEDLINE | ID: mdl-38141124

RESUMEN

There is high interest in the development of water pollution remediation technologies. Advanced oxidation processes (AOPs) are a promising alternative for the degradation of organic compounds; however, these technologies have been limited mainly by high operating costs and, in some cases, by forming byproducts, which can be more hazardous than the original pollutants. Activated carbon (AC) is a porous material that can be combined with AOP systems in various ways, given its adsorbent and catalytic characteristics. In addition, AC is a flexible, adaptable, and low-cost material. This article presents a bibliometric analysis of AOPs incorporating CA in scientific research and patents; the Scopus database was used to obtain patents and Orbit Express for patents. The most investigated AOPs incorporating AC are photocatalysis processes, Fenton processes, persulfate-based AOP, electrochemical processes, and ozonation. However, it is the persulfate-based AOP that has seen the greatest growth in scientific publications in recent years; this great interest can be related to the synergy that the process has with AC, allowing the degradation of contaminants via radical and non-radical. According to the maturity analysis of scientific publications, photocatalysis, Fenton, electrochemistry, ozonation, and persulfate technologies are in a growth stage and will reach maturity in 2034, 2042, 2040, 2034, and 2035, respectively; these technologies coupled with AC are expected to generate a greater number of patents when they reach maturity.

20.
Molecules ; 28(24)2023 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-38138472

RESUMEN

This study presents the synthesis of a basic heterogeneous catalyst based on sodium functionalized biochar. The murici biochar (BCAM) support used in the process was obtained through the pyrolysis of the murici seed (Byrsonimia crassifolia), followed by impregnation of the active phase in amounts that made it possible to obtain concentrations of 6, 9, 12, 15 and 18% of sodium in the final composition of the catalyst. The best-performing 15Na/BCAM catalyst was characterized by Elemental Composition (CHNS), Thermogravimetric Analysis (TG/DTG), X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), and Energy Dispersion X-ray Spectroscopy (EDS). The catalyst 15Na/BCAM was applied under optimal reaction conditions: temperature of 75 °C, reaction time of 1.5 h, catalyst concentration of 5% (w/w) and MeOH:oil molar ratio of 20:1, resulting in a biodiesel with ester content of 97.20% ± 0.31 in the first reaction cycle, and maintenance of catalytic activity for five reaction cycles with ester content above 65%. Furthermore, the study demonstrated an effective catalyst regeneration process, with the synthesized biodiesels maintaining ester content above 75% for another five reaction cycles. Thus, the data indicate a promising alternative to low-cost residual raw materials for the synthesis of basic heterogeneous catalysts.


Asunto(s)
Biocombustibles , Aceites de Plantas , Aceites de Plantas/química , Biocombustibles/análisis , Espectroscopía Infrarroja por Transformada de Fourier , Biomasa , Esterificación , Catálisis , Ésteres , Sodio
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