RESUMEN
Upgrading excess CO2 toward the electrosynthesis of formic acid is of significant research and commercial interest. However, simultaneously achieving high selectivity and industrially relevant current densities of CO2-to-formate conversion remains a grand challenge for practical implementations. Here, an electrically conductive zeolite support is strategically designed by implanting Sn ions into the skeleton structure of a zeolite Y, which impregnates ultrasmall In0.2Sn0.8 alloy nanoclusters into the supercages of the tailored 12-ring framework. The prominent electronic and geometric interactions between In0.2Sn0.8 nanoalloy and zeolite support lead to the delocalization of electron density that enhances orbital hybridizations between In active site and *OCHO intermediate. Thus, the energy barrier for the rate-limiting *OCHO formation step is reduced, facilitating the electrocatalytic hydrogenation of CO2 to formic acid. Accordingly, the developed zeolite electrocatalyst achieves an industrial-level partial current density of 322 mA cm-2 and remarkable Faradaic efficiency of 98.2% for formate production and stably maintains Faradaic efficiency above 93% at an industrially relevant current density for over 102 h. This work opens up new opportunities of conductive zeolite-based electrocatalysts for industrial-level formic acid electrosynthesis from CO2 electrolysis and toward practically accessible electrocatalysis and energy conversion.
RESUMEN
The metal-support interaction is crucial for the performance of Cu-based catalysts. However, the distinctive properties of the support metal element itself are often overlooked in catalyst design. In this paper, a sheet Cu-Zn-Ce with [Ce3+-OV-Ce4+] located on the surface was designed by the sol-gel method. Through EPR and X-ray photoelectron spectroscopy (XPS), the relationship between the content of oxygen vacancies and Ce was revealed. Ce itself induces the generation of [Ce3+-OV-Ce4+]. Through ICP-MS, XPS, and SEM-mapping, the Ce-induced formation of [Ce3+-OV-Ce4+] located on the catalyst surface was demonstrated. CO2-TPD and DFT calculations further revealed that [Ce3+-OV-Ce4+] enhanced CO2 adsorption, leading to a 10% increase in methanol selectivity compared to Cu-Zn-Ce synthesized via the coprecipitation method.
RESUMEN
Catalyst supports play an essential role in catalytic reactions, hinting at pronounced metal-support effects. Zeolites are a propitious support in heterogeneous catalysts, while their use in the electrocatalytic CO2 reduction reaction has been limited as yet because of their electrically insulating nature and serious competing hydrogen evolution reaction (HER). Enlightened by theoretical prediction, herein, we implant zinc ions into the structural skeleton of a zeolite Y to strategically tailor a favorable electrocatalytic platform with remarkably enhanced electronic conduction and strong HER inhibition capability, which incorporates ultrafine cadmium oxide nanoclusters as guest species into the supercages of the tailored 12-ring window framework. The metal d-bandwidth tuning of cadmium by skeletal zinc steers the extent of substrate-molecule orbital mixing, enhancing the stabilization of the key intermediate *COOH while weakening the CO poisoning effect. Furthermore, the strong cadmium-zinc interplay causes a considerable thermodynamic barrier for water dissociation in the conversion of H+ to *H, potently suppressing the competing HER. Therefore, we achieve an industrial-level partial current density of 335 mA cm-2 and remarkable Faradaic efficiency of 97.1% for CO production and stably maintain Faradaic efficiency above 90% at the industrially relevant current density for over 120 h. This work provides a proof of concept of tailored conductive zeolite as a favorable electrocatalytic support for industrial-level CO2 electrolysis and will significantly enhance the adaptability of conductive zeolite-based electrocatalysts in a variety of electrocatalysis and energy conversion applications.
RESUMEN
The demand for aromatics, especially benzene, toluene, and xylene, has been increased in recent years as the crucial feedstocks of coatings and pharmaceutical industry. In this work, a modified Fischer-Tropsch synthesis (FTS) catalyst FeNaMg was fabricated via a sol-precipitation method and integrated with an HZSM-5 aromatization catalyst for the aromatics synthesis from syngas by a one-step process. Syngas was first converted to lower olefins as intermediates on the active component of the FeNaMg catalyst followed by aromatization on zeolite. Different characterization approaches, such as BET, XRD, XPS, hydrogen temperature-programmed reduction, temperature-programmed desorption of CO, TG, and SEM, revealed that Mg efficiently optimized physicochemical properties of the Fe-based catalyst by generating a MgFe2O4 spinel structure. Further investigation demonstrated that the MgFe2O4 spinel structure could increase the syngas adsorption area, facilitating the reduction and carburization of the Fe phase, while Mg decreased CO2 selectivity (31.26 to21%) by restraining the water-gas shift reaction and improved the utilization efficiency of carbon. At the same time, alkali metal Na changed the surface electronic environment of the FTS catalyst to enhance CO adsorption as an electronic promoter, which suppressed methane formation by restraining over hydrogenation. Therefore, the synergism that existed between Mg and Na during the reaction escalated the CO conversion and aromatics selectivity to 96.19 and 51.38%, respectively.
RESUMEN
Deposition of carbonaceous compounds was used to improve the propylene selectivity of ZSM-5 by deactivating some acid sites meanwhile maintaining the high activity for methanol conversion. The carbonaceous species of pre-coked samples before and after MTP reactions were investigated by elementary analysis and thermogravimetric analysis (TGA). The results showed that pre-coke formed at low temperature (250°C) was unstable and easy to transform into polyaromatics species at the high reacting temperature, while combining 5% pre-coking process with 95% steam treatment at high temperature (480°C) was effective in inhibiting the formation of coke deposits and presented a significant improvement in the propylene selectivity.
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Southern root-knot nematode (Meloidogyne incognita) is a biotrophic parasite, causing enormous loss in global crop production annually. Abamectin (Abm) is a biological and high-efficiency pesticide against Meloidogyne incognita. In this study, a powerful method, flash nanoprecipitation (FNP), was adopted to successfully produce Abm-loaded nanoparticle suspensions with high drug loading capacity (>40%) and encapsulation efficiency (>95%), where amphiphilic block copolymers (BCPs) poly(lactic-co-glycolic acid)-b-poly(ethylene glycol) (PLGA-b-PEG), poly(d,l-lactide)-b-poly(ethylene glycol) (PLA-b-PEG), or poly(caprolactone)-b-poly(ethylene glycol) (PCL-b-PEG) were used as the stabilizer to prevent the nanoparticles from aggregation. The effect of the drug-to-stabilizer feed ratio on the particle stability were investigated. Moreover, the effect of the BCP composition on the morphology of Abm-loaded nanoparticles for controlling Meloidogyne incognita were discussed. Notably, spindle-like nanoparticles were obtained with PCL-b-PEG as the stabilizer and found significantly more efficient (98.4% mortality at 1 ppm particle concentration) than spherical nanoparticles using PLGA-b-PEG or PLA-b-PEG as the stabilizer. This work provides a more rapid and powerful method to prepare stable Abm-loaded nanoparticles with tunable morphologies and improved effectiveness for controlling Meloidogyne incognita.
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OBJECTIVE: Inflammation and oxidative stress play a key role in the initiation, propagation, and development of atherosclerosis. Arterial baroreflex (ABR) dysfunction induced by sinoaortic denervation (SAD) promoted the development of atherosclerosis in ApoE-/- mice. The present work was designed to examine whether ABR deficiency affected inflammation and oxidative stress via α7 nicotinic acetylcholine receptor (α7nAChR) leading to the aggravation of atherosclerosis in mice. METHODS AND RESULTS: ApoE-/- mice were fed with a high-cholesterol diet for 6weeks and half of the mice received sinoaortic denervation that destroyed ABR. We studied the expression of vesicular acetylcholine transporter (VAChT), α7nAChR and levels of inflammatory response and oxidative stress. The results showed that baroreflex dysfunction could promote atherosclerosis, meanwhile, decrease the expression of VAChT and α7nAChR and significantly increase the levels of oxidative stress and inflammation in SAD mice. After treated with PNU-282987 (a selective α7nAChR agonist, 0.53mg/kg/day) for 6weeks in SAD and Sham mice, we found that PNU-282987 could attenuate atherosclerosis and significantly decreased oxidative stress and inflammation after SAD. In addition, α7nAChR+/+ and α7nAChR-/- mice fed with a high-cholesterol diet for 8weeks were co-treated with ketanserin (0.6mg/kg/day), a drug that can enhance baroreflex sensitivity (BRS). Ketanserin could alleviate atherosclerosis and markedly decrease oxidative stress and inflammation in α7nAChR+/+ mice. But there were no effects in α7nAChR knockout mice. CONCLUSIONS: Our results demonstrate that ABR dysfunction aggravates atherosclerosis in mice via the vagus-ACh-α7nAChR-inflammation and oxidative stress pathway.
Asunto(s)
Aterosclerosis/patología , Barorreflejo/fisiología , Inflamación/patología , Receptor Nicotínico de Acetilcolina alfa 7/metabolismo , Animales , Apolipoproteínas E/genética , Arterias/fisiología , Benzamidas/farmacología , Compuestos Bicíclicos con Puentes/farmacología , Modelos Animales de Enfermedad , Ketanserina/farmacología , Ratones , Ratones Noqueados , Estrés Oxidativo/fisiología , Receptor Nicotínico de Acetilcolina alfa 7/genéticaAsunto(s)
Glucósidos/farmacología , Glucósidos/uso terapéutico , Compuestos Heterocíclicos con 2 Anillos/farmacología , Compuestos Heterocíclicos con 2 Anillos/uso terapéutico , Hiperalgesia/tratamiento farmacológico , Umbral del Dolor/efectos de los fármacos , Dolor/tratamiento farmacológico , Analgésicos/química , Analgésicos/farmacología , Analgésicos/uso terapéutico , Análisis de Varianza , Animales , Modelos Animales de Enfermedad , Relación Dosis-Respuesta a Droga , Formaldehído , Glucósidos/química , Compuestos Heterocíclicos con 2 Anillos/química , Ratones , Ratones Endogámicos ICR , Morfina/uso terapéutico , Dolor/inducido químicamente , Dimensión del Dolor , Factores de TiempoRESUMEN
Nitric oxide (NO) plays an important role in the pathogenesis of endotoxic shock. This work tested the hypothesis that ketanserin could attenuate endotoxic shock by inhibiting the expression of inducible NO synthase (iNOS). The results demonstrated that ketanserin could inhibit iNOS expression in the heart, lungs, liver, and kidneys and nitrate production in the serum upon endotoxic shock in mice. In RAW264.7 cells, ketanserin significantly inhibited the expression of iNOS and decreased the production of NO, TNFα, IL-6, and reactive oxygen species upon lipopolysaccharide (LPS) challenge. Ketanserin also increased the level of ATP and mitochondrial membrane potential in RAW264.7 cells upon LPS exposure. LPS-induced iNOS expression was inhibited by the 5-HT2A receptor antagonist ritanserin and not the α1 receptor antagonist prazosin. Knockdown of 5-HT2A receptor by siRNA abolished the inhibitory effect of ketanserin on the expression of iNOS. These results indicated that the inhibitory effect of ketanserin on the expression of iNOS is mediated by blocking the 5-HT2A receptor. Furthermore, ketanserin significantly inhibited the activation of ERK1/2 and NF-κB signal. Pretreatment with PD184352, a specific inhibitor of ERK1/2, blocked the inhibitory effect of ketanserin on the expression of iNOS and NO production, indicating a critical role for the MEK/ERK1/2 signaling pathway. Collectively, our findings indicate that inhibition of the expression of iNOS via the MEK/ERK pathway mediates the protective effects of ketanserin against LPS-induced shock in mice.