Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 42
Filtrar
Más filtros













Base de datos
Intervalo de año de publicación
1.
Animals (Basel) ; 14(6)2024 Mar 19.
Artículo en Inglés | MEDLINE | ID: mdl-38540053

RESUMEN

The purpose of this study was to determine the efficacy of tannic acid on the antioxidative function, immunity, and intestinal barrier of broilers co-infected with coccidia and Clostridium perfringens (CCP). A total of 294 1-day-old arbor acres(AA) broilers were divided into three groups: control group (CON), CCP co-infected group (CCP), and 1000 mg/kg TA + CCP co-infected group (CTA). This trial lasted for 28 days. The results showed that the CCP group decreased the activity of glutathione peroxidase (GSH-Px), total superoxide dismutase (T-SOD), catalase (CAT), and total antioxidant capacity (T-AOC) levels and increased the contents of hydrogen peroxide (H2O2) and malondialdehyde (MDA) in the jejunum (p < 0.05). The mRNA levels of GSH-Px3 and CAT in the liver and jejunum, and the mRNA levels of GSH-Px3, SOD, HO-1, and NAD(P)H quinone oxidoreductase I (NQO1) in the liver were down-regulated by CCP challenge (p < 0.05). In addition, the Keap1 and Nrf2 mRNA levels in the liver and jejunum, jejunal glutathione S-transferase (GST), and heme-oxygenase-1 (HO-1) were upregulated in the CCP group compared with CON (p < 0.05). The mRNA levels of interleukin 8 (IL-8), IL-1ß, inducible nitric oxide synthase (iNOS), and interferon γ (IFN-γ) in the jejunum were elevated, and jejunal mRNA levels of IL-10, zonula occludens protein1 (ZO-1), claudin-1, claudin-2, and occludin were decreased in the CCP treatment (p < 0.05). Dietary supplementation with 1000 mg/kg TA increased the activity of GSH-Px, T-SOD, CAT, and T-AOC and decreased the contents of H2O2 and MDA in the jejunum (p < 0.05). Compared with the CCP group, TA decreased the mRNA level of Keap1 and Nrf2 in the liver and jejunum, increased the GSH-Px3, SOD, and CAT mRNA in the liver, and alleviated the rise of IL-8, IL-1ß, iNOS, and IFN-γ and decrease in IL-10, occludin gene expression in the jejunum (p < 0.05). In conclusion, the addition of 1000 mg/kg TA to the diet improved the jejunal barrier, mitigated the jejunal inflammation, and increased the antioxidant capacity of the liver and jejunum through the activation of the transcription factor Nrf2 downstream of the Nrf2-Keap1 pathway in broilers with NE condition.

2.
J Am Chem Soc ; 146(4): 2426-2434, 2024 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-38228289

RESUMEN

The molecular details of an electrocatalytic interface play an essential role in the production of sustainable fuels and value-added chemicals. Many electrochemical reactions exhibit strong cation-dependent activities, but how cations affect reaction kinetics is still elusive. We report the effect of cations (K+, Li+, and Ba2+) on the interfacial water structure using second-harmonic generation (SHG) and classical molecular dynamics (MD) simulation. The second- (χH2O(2)) and third-order (χH2O(3)) optical susceptibilities of water on Pt are smaller in the presence of Ba2+ compared to those of K+, suggesting that cations can affect the interfacial water orientation. MD simulation reproduces experimental SHG observations and further shows that the competition between cation hydration and interfacial water alignment governs the net water orientation. The impact of cations on interfacial water supports a cation hydration-mediated mechanism for hydrogen electrocatalysis; i.e., the reaction occurs via water dissociation followed by cation-assisted hydroxide/water exchange on Pt. Our study highlights the role of interfacial water in electrocatalysis and how innocent additives (such as cations) can affect the local electrochemical environment.

3.
J Hazard Mater ; 453: 131383, 2023 07 05.
Artículo en Inglés | MEDLINE | ID: mdl-37080023

RESUMEN

Recently, the cryogel as a special type of hydrogel was widely used in the field of medicine due to its porous structure and good biocompatibilit. However, great challenges existed for its irregular pore size and incompressible property, limiting its application in other fields. In this study, a novel silk fibroin-based cryogel (named SF@PVA/CS) with regulable pore size, excellent elasticity and durability was constructed using a green dual-directional crosslink strategy. The SF@PVA/CS was prepared by using silk fibroin (SF) as bone scaffold, and chitosan (CS) and polyvinyl alcohol (PVA) as polymer hydrogel which was introduced into the inner bone scaffold of SF. Such a brand-new cryogel possessed three-dimensional dual network structure, which can overcome the shortcoming of unregulatable pore size and incompressibility of traditional cryogel. Additionally, the developed SF@PVA/CS membrane was used for water purification for the first time, which exhibited superior selective permeation, excellent anti-fouling and brilliant self-cleaning property, and it can achieve the purification of both oil/water emulsion and methylene blue solution. This study expanded the application of SF-based cryogel, providing a novel routine for designing new-type composite cryogel and widening the application of dual-directional crosslink strategy developed in this study for facilitating the purification of wastewater.


Asunto(s)
Quitosano , Fibroínas , Purificación del Agua , Fibroínas/química , Criogeles , Quitosano/química , Alcohol Polivinílico/química
4.
Nat Mater ; 22(4): 503-510, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36781952

RESUMEN

When an electrode contacts an electrolyte, an interfacial electric field forms. This interfacial field can polarize the electrode's surface and nearby molecules, but its effect can be countered by an applied potential. Quantifying the value of this countering potential ('potential of zero charge' (pzc)) is, however, not straightforward. Here we present an optical method for determining the pzc at an electrochemical interface. Our approach uses phase-sensitive second-harmonic generation to determine the electrochemical potential where the interfacial electric field vanishes at an electrode-electrolyte interface with Pt-water as a model experiment. Our method reveals that the pzc of the Pt-water interface is 0.23 ± 0.08 V versus standard hydrogen electrode (SHE) and is pH independent from pH 1 to pH 13. First-principles calculations with a hybrid explicit-implicit solvent model predict the pzc of the Pt(111)-water interface to be 0.23 V versus SHE and reveal how the interfacial water structure rearranges as the electrode potential is moved above and below the pzc. We further show that pzc is sensitive to surface modification; deposition of Ni on Pt shifts the interfacial pzc in the cathodic direction by ~360 mV. Our work demonstrates a materials-agnostic approach for quantifying the interfacial electrical field and water orientation at an electrochemical interface without requiring probe molecules and confirms the long-held view that the interfacial electric field is more intense during hydrogen electrocatalysis in alkaline than in acid.

5.
Front Vet Sci ; 9: 1037046, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-36337182

RESUMEN

A total of 480 one-day-old AA broiler chicks were randomly allocated to one of four treatments in a 2 × 2 factorial to investigate the effects of tannic acid (TA) on growth performance, relative organ weight, antioxidant capacity, and intestinal health in broilers dietary exposed to aflatoxin B1 (AFB1). Treatments were as follows: (1) CON, control diet; (2) TA, CON + 250 mg/kg TA; (3) AFB1, CON + 500 µg/kg AFB1; and (4) TA+AFB1, CON + 250 mg/kg TA + 500 µg/kg AFB1. There were 10 replicate pens with 12 broilers per replicate. Dietary AFB1 challenge increased the feed conversion ratio during days 1 to 21 (P < 0.05). The TA in the diet did not show significant effects on the growth performance of broilers during the whole experiment period (P > 0.05). The liver and kidney relative weight was increased in the AF challenge groups compared with the CON (P < 0.05). The addition of TA could alleviate the relative weight increase of liver and kidney caused by AFB1 (P < 0.05). Broilers fed the AFB1 diets had lower activity of glutathione peroxidase, catalase, total superoxide dismutase, S-transferase, and total antioxidant capacity in plasma, liver and jejunum, and greater malondialdehyde content (P < 0.05). Dietary supplemented with 250 mg/kg TA increased the activities of antioxidative enzymes, and decreased malondialdehyde content (P < 0.05). In addition, AFB1 significantly reduced the villus height and crypt depth ratio in the ileum on day 42 (P < 0.05). In conclusion, supplementation with 250 mg/kg TA could partially protect the antioxidant capacity and prevent the enlargement of liver in broilers dietary challenged with 500 µg/kg AFB1.

6.
Inorg Chem ; 61(37): 14824-14832, 2022 Sep 19.
Artículo en Inglés | MEDLINE | ID: mdl-36074721

RESUMEN

Basal plane-functionalized NbS2 nanosheets were obtained using in situ photolysis to generate the coordinatively unsaturated organometallic fragment cyclopentadienyl manganese(I) dicarbonyl (CpMn(CO)2). Under UV irradiation, a labile carbonyl ligand dissociates from the tricarbonyl complex, creating an open coordination site for bonding between the Mn atom and the electron-rich sulfur atoms on the surface of the NbS2 nanosheets. In contrast, no reaction is observed with 2H-MoS2 nanosheets under the same reaction conditions. This difference in reactivity is consistent with the electronic structure calculations, which indicate stronger bonding of the organometallic fragment to electron-poor, metallic NbS2 than to semiconducting, electron-rich MoS2. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectroscopy, and powder X-ray diffraction (PXRD) were used to characterize the bonding between Mn and S atoms on the surface-functionalized nanosheets.

7.
Chem Rev ; 122(6): 6117-6321, 2022 03 23.
Artículo en Inglés | MEDLINE | ID: mdl-35133808

RESUMEN

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.


Asunto(s)
Suministros de Energía Eléctrica , Protones , Hidrógeno/química , Oxígeno/química , Agua
9.
Microbiome ; 9(1): 145, 2021 06 25.
Artículo en Inglés | MEDLINE | ID: mdl-34172092

RESUMEN

BACKGROUND: Modification of the gut microbiota has been reported to reduce the incidence of type 1 diabetes mellitus (T1D). We hypothesized that the gut microbiota shifts might also have an effect on cognitive functions in T1D. Herein we used a non-absorbable antibiotic vancomycin to modify the gut microbiota in streptozotocin (STZ)-induced T1D mice and studied the impact of microbial changes on cognitive performances in T1D mice and its potential gut-brain neural mechanism. RESULTS: We found that vancomycin exposure disrupted the gut microbiome, altered host metabolic phenotypes, and facilitated cognitive impairment in T1D mice. Long-term acetate deficiency due to depletion of acetate-producing bacteria resulted in the reduction of synaptophysin (SYP) in the hippocampus as well as learning and memory impairments. Exogenous acetate supplement or fecal microbiota transplant recovered hippocampal SYP level in vancomycin-treated T1D mice, and this effect was attenuated by vagal inhibition or vagotomy. CONCLUSIONS: Our results demonstrate the protective role of microbiota metabolite acetate in cognitive functions and suggest long-term acetate deficiency as a risk factor of cognitive decline. Video Abstract.


Asunto(s)
Disfunción Cognitiva , Diabetes Mellitus Experimental , Microbioma Gastrointestinal , Acetatos/farmacología , Animales , Bacterias/genética , Encéfalo , Ratones
10.
ACS Appl Mater Interfaces ; 13(9): 11260-11267, 2021 Mar 10.
Artículo en Inglés | MEDLINE | ID: mdl-33625826

RESUMEN

Flexible textile displays can be revolutionary for information transmission at any place and any time. Typically, textile displays are fabricated by traditional rigid electronics that sacrifice mechanical flexibility of devices or by flexible electronics that do not have an appropriate choice to arbitrarily control single pixels. This work reports on an electroluminescent fabric woven by ultrastretchable fibers (electroluminescent fibers up to 400% stretch, electrode fibers up to 250% stretch), which can exhibit the pixel-based arbitrarily controllable pattern display by a mobile phone application. To realize ultrastretchability, we made these fibers by encapsulating liquid metals on a polyurethane core (high elasticity). To realize arbitrary control, the design shows a plain-woven structure comprising ZnS-based electroluminescent fibers and perpendicular electrode fibers. The cross-points between the electroluminescent fiber and the electrode fiber form pixels that can be switched on or off independently and can further form the pixel-based arbitrarily controllable pattern display. By doping with different elements, ZnS-based electroluminescent fibers can emit green, blue, or yellow lights. Meanwhile, the fabrication of these fibers employs dip-coating, a scalable manufacturing method without high temperature or vacuum atmosphere. These fabrics show great potential in a wide range of applications such as wearable electronic devices, healthcare, and fashion design.

11.
Neurochem Int ; 143: 104941, 2021 02.
Artículo en Inglés | MEDLINE | ID: mdl-33333211

RESUMEN

Type 1 diabetes (T1D) has been reported to cause cognitive decline, but brain metabolic changes during this process are still far from being fully understood. Here, we found that streptozotocin (STZ)-induced T1D mice exhibited impaired learning and memory at 11 weeks after STZ treatment but not at 3 weeks. Therefore, we studied metabolic alterations in six different brain regions of T1D mice with and without cognitive decline, and attempted to identify key metabolic pathways related to diabetic cognitive dysfunction. The results demonstrate that lactate had already increased in all brain regions of T1D mice prior to cognitive decline, but a decreased TCA cycle was only observed in hippocampus, cortex and striatum of T1D mice with cognitive impairment. Reduced N-acetylaspartate and choline were found in all brain regions of T1D mice, irrespective of cognitive decline. In addition, disrupted neurotransmitter metabolism was noted to occur in T1D mice before cognitive deficit. Of note, we found that the level of uridine was significantly reduced in cerebellum, cortex, hypothalamus and midbrain of T1D mice when cognitive decline was presented. Therefore, brain region-specific metabolic alterations may comprise possible biomarkers for the early-diagnosis and monitoring of diabetic cognitive decline. Moreover, down-regulated TCA cycle and pyrimidine metabolism could be closely related to T1D-associated cognitive impairment.


Asunto(s)
Encéfalo/metabolismo , Disfunción Cognitiva/metabolismo , Diabetes Mellitus Experimental/metabolismo , Diabetes Mellitus Tipo 1/metabolismo , Animales , Disfunción Cognitiva/inducido químicamente , Disfunción Cognitiva/psicología , Diabetes Mellitus Experimental/inducido químicamente , Diabetes Mellitus Experimental/psicología , Diabetes Mellitus Tipo 1/inducido químicamente , Diabetes Mellitus Tipo 1/psicología , Masculino , Aprendizaje por Laberinto/fisiología , Ratones , Ratones Endogámicos C57BL , Estreptozocina
12.
J Phys Chem Lett ; 11(19): 8216-8221, 2020 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-32880461

RESUMEN

The interaction between molecular species and charged interfaces plays an indispensable role in a multitude of electrochemical devices. Yet, very little is understood about the nature of this interaction, in particular, the interfacial electric field. Second-order nonlinear spectroscopy such as second-harmonic generation (SHG) can provide chemical information on these interfacial interactions; however, the phase information has received limited attention in electrochemical SHG studies. Here, we demonstrate that the phase of the SHG is essential to the measurement of the electric field at the electrode-electrolyte interface. Our in situ SHG experiment provides strong evidence in support of the parabolic model with complex nonlinear susceptibilities. We conclude that if the absolute phase of the total SHG signal with both χ(2) and χ(3) contributions can be obtained, it would be possible to measure the potential of zero charge of any electrochemical material.

13.
J Proteome Res ; 18(11): 3944-3954, 2019 11 01.
Artículo en Inglés | MEDLINE | ID: mdl-31553190

RESUMEN

Antibiotic-induced microbial perturbations alter host metabolism and affect host physiology. In this study, we aimed to investigate the effects of vancomycin (Vanc) and ciprofloxacin/metronidazole (CiMe) exposures on the gut microbiome and metabolome in the colonic content and tissue samples from advanced-stage type 1 diabetic (AST1D) rats and age-matched controls (AMCs) using 16S ribosomal RNA gene sequencing and nuclear magnetic resonance-based metabolomics. The results show that antibiotic effects on the gut microbiota were stronger in AMC rats relative to AST1D rats. These microbial alterations were accompanied by a series of metabolic changes, including energy metabolism, short-chain fatty acid metabolism, and amino acid metabolism. We found that AMC rats had a more notable metabolic response to antibiotic exposure than AST1D rats. Additionally, Vanc had a stronger impact on the gut microbiota and host metabolic phenotype versus CiMe. Therefore, our results reveal that antibiotic-induced shifts in the gut microbiome and metabolome are different between AST1D and AMC rats. If confirmed in human studies, these findings suggest that diabetic patients may need a specific strategy for antibiotic use in clinical practice.


Asunto(s)
Antibacterianos/farmacología , Diabetes Mellitus Tipo 1/metabolismo , Microbioma Gastrointestinal/efectos de los fármacos , Metaboloma/efectos de los fármacos , Metabolómica/métodos , Animales , Bacterias/clasificación , Bacterias/genética , Colon/efectos de los fármacos , Colon/metabolismo , Metabolismo Energético/efectos de los fármacos , Heces/microbiología , Microbioma Gastrointestinal/genética , Humanos , Masculino , Fenotipo , ARN Ribosómico 16S/genética , Ratas Sprague-Dawley
14.
mSystems ; 4(4)2019 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-31164448

RESUMEN

The gut microbiota has the capability to regulate homeostasis of the host metabolism. Since antibiotic exposure can adversely affect the microbiome, we hypothesized that antibiotic effects on the gut microbiota and host metabolism are sex dependent. In this study, we examined the effects of antibiotic treatments, including vancomycin (Vanc) and ciprofloxacin-metronidazole (CiMe), on the gut microbiome and metabolome in colonic contents and tissues in both male and female mice. We found that the relative abundances and structural composition of Firmicutes were significantly reduced in female mice after both Vanc and CiMe treatments but in male mice only after treatment with Vanc. However, Vanc exposure considerably altered the relative abundances and structural composition of representatives of the Proteobacteria especially in male mice. The levels of short-chain fatty acids (SCFAs; acetate, butyrate, and propionate) in colonic contents and tissues were significantly decreased in female mice after both antibiotic treatments, while these reductions were detected in male mice only after Vanc treatment. However, another SCFA, formate, exhibited the opposite tendency in colonic tissues. Both antibiotic exposures significantly decreased the levels of alanine, branched-chain amino acids (BCAAs; leucine, isoleucine, and valine) and aromatic amino acids (AAAs; phenylalanine and tyrosine) in colonic contents of female mice but not in male mice. Additionally, female mice had much greater correlations between microbe and metabolite than male mice. These findings suggest that sex-dependent effects should be considered for antibiotic-induced modifications of the gut microbiota and host metabolism.IMPORTANCE Accumulating evidence shows that the gut microbiota regulates host metabolism by producing a series of metabolites, such as amino acids, bile acids, fatty acids, and others. These metabolites have a positive or negative effect on host health. Antibiotic exposure can disrupt the gut microbiota and thereby affect host metabolism and physiology. However, there are a limited number of studies addressing whether antibiotic effects on the gut microbiota and host metabolism are sex dependent. In this study, we uncovered a sex-dependent difference in antibiotic effects on the gut microbiota and metabolome in colonic contents and tissues in mice. These findings reveal that sex-dependent effects need to be considered for antibiotic use in scientific research or clinical practice. Moreover, this study will also give an important direction for future use of antibiotics to modify the gut microbiome and host metabolism in a sex-specific manner.

15.
J Proteome Res ; 18(3): 1218-1227, 2019 03 01.
Artículo en Inglés | MEDLINE | ID: mdl-30592618

RESUMEN

Alzheimer's disease (AD) is regarded as a metabolic disorder, and more attention has been paid to brain metabolism. However, AD may also affect metabolism in the peripheral organs beyond the brain. In this study, therefore, we investigated metabolic changes in the liver, kidney, and heart of amyloid precursor protein/presenilin 1 (APP/PS1) mice at 1, 5, and 10 months of age by using 1H NMR-based metabolomics and chemometrics. Metabolomic results reveal that the liver was the earliest affected organ in APP/PS1 mice during amyloid pathology progression, followed by the kidney and heart. Moreover, a hypometabolic state was found in the liver of APP/PS1 mice at 5 months of age, and the disturbed metabolites were mainly involved in energy metabolism, amino acid metabolism, nucleic acid metabolism, as well as ketone and fatty acid metabolism. In conclusion, our results suggest that AD is a systemic metabolic dysfunction, and hepatic metabolic abnormality may reflect amyloid pathology progression.


Asunto(s)
Enfermedad de Alzheimer/genética , Encefalopatías Metabólicas/genética , Hígado/metabolismo , Presenilina-1/metabolismo , Enfermedad de Alzheimer/complicaciones , Enfermedad de Alzheimer/metabolismo , Enfermedad de Alzheimer/patología , Precursor de Proteína beta-Amiloide/genética , Precursor de Proteína beta-Amiloide/metabolismo , Animales , Encefalopatías Metabólicas/complicaciones , Encefalopatías Metabólicas/metabolismo , Encefalopatías Metabólicas/patología , Modelos Animales de Enfermedad , Humanos , Riñón/metabolismo , Hígado/patología , Metabolómica/métodos , Ratones , Miocardio/metabolismo , Especificidad de Órganos/genética , Presenilina-1/genética
16.
J Am Chem Soc ; 140(37): 11647-11654, 2018 09 19.
Artículo en Inglés | MEDLINE | ID: mdl-30145888

RESUMEN

In water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs), charge recombination competes with catalytic water oxidation to determine the overall efficiency of the system. The kinetics of these processes have been difficult to understand because transient absorbance (TA) experiments typically show nearly complete charge recombination on the submillisecond time scale; in contrast, electrochemical measurements such as open circuit photovoltage decay suggest a charge recombination time scale that is 2-3 orders of magnitude longer. Here we explore these processes with dye-sensitized nanocrystalline TiO2 and TiO2/Ta2O5 core-shell photoanodes in aqueous electrolytes using TA spectroscopy, intensity-modulated photovoltage spectroscopy (IMVS), and photoelectrochemical impedance spectroscopy (PEIS). The fast recombination rates measured by TA result from strong laser excitation that leads to high electron occupancy in TiO2, whereas IMVS modulates the concentration of charge-separated states near solar irradiance levels. The recombination processes measured by electrochemical methods such as IMVS, PEIS, and transient photovoltage are the discharging of injected electrons in TiO2, as evidenced by the close agreement between the nearly first-order recombination rates probed by IMVS and the RC time constants derived from PEIS data. However, IMVS measurements at variable probe light intensity reveal that the reaction orders for the recombination of injected electrons with oxidized sensitizer molecules are far from unity. This kinetic analysis is relevant to understanding steady-state recombination rates in full WS-DSPECs in which molecular and nanoparticle catalysts are used to oxidize water.


Asunto(s)
Colorantes/química , Técnicas Electroquímicas , Agua/química , Cinética , Oxidación-Reducción , Procesos Fotoquímicos , Análisis Espectral
17.
Chem Commun (Camb) ; 54(57): 7971-7974, 2018 Jul 12.
Artículo en Inglés | MEDLINE | ID: mdl-29961797

RESUMEN

Core-shell architectures are used to modulate injection and recombination in dye-sensitized photoelectrochemical cells. Here, we demonstrate that exposing SnO2-core/ZrO2-shell films to acid permits photoinduced electron transfer through ZrO2-shells at least 4 nm thick. A novel mechanism of charge transfer is proposed where protonic defects permit ultrafast trap-assisted tunneling of electrons.

18.
Proc Natl Acad Sci U S A ; 115(27): 6946-6951, 2018 07 03.
Artículo en Inglés | MEDLINE | ID: mdl-29915092

RESUMEN

Water oxidation has long been a challenge in artificial photosynthetic devices that convert solar energy into fuels. Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) provide a modular approach for integrating light-harvesting molecules with water-oxidation catalysts on metal-oxide electrodes. Despite recent progress in improving the efficiency of these devices by introducing good molecular water-oxidation catalysts, WS-DSPECs have poor stability, owing to the oxidation of molecular components at very positive electrode potentials. Here we demonstrate that a solid-state dye-sensitized solar cell (ss-DSSC) can be used as a buried junction for stable photoelectrochemical water splitting. A thin protecting layer of TiO2 grown by atomic layer deposition (ALD) stabilizes the operation of the photoanode in aqueous solution, although as a solar cell there is a performance loss due to increased series resistance after the coating. With an electrodeposited iridium oxide layer, a photocurrent density of 1.43 mA cm-2 was observed in 0.1 M pH 6.7 phosphate solution at 1.23 V versus reversible hydrogen electrode, with good stability over 1 h. We measured an incident photon-to-current efficiency of 22% at 540 nm and a Faradaic efficiency of 43% for oxygen evolution. While the potential profile of the catalyst layer suggested otherwise, we confirmed the formation of a buried junction in the as-prepared photoelectrode. The buried junction design of ss-DSSs adds to our understanding of semiconductor-electrocatalyst junction behaviors in the presence of a poor semiconducting material.

19.
ACS Appl Mater Interfaces ; 10(3): 2810-2818, 2018 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-29303245

RESUMEN

Monolayer WS2 has interesting properties as a direct bandgap semiconductor, photocatalyst, and electrocatalyst, but it is still a significant challenge to prepare this material in colloidal form by liquid-phase exfoliation (LPE). Here, we report the preparation of 1-2 layer semiconducting WS2 nanosheets in a yield of 18-22 wt % by a modified LPE method that involves preintercalation with substoichometric quantities of n-butyllithium. The exfoliated WS2 nanosheeets are n-type, have a bandgap of ∼1.78 eV, and act as a cocatalyst with CdS nanorods in photocatalytic hydrogen evolution using lactate as a sacrificial electron donor. Up to a 26-fold increase in H2 evolution rate was observed with WS2/CdS hybrids compared with their pure CdS counterpart, and an absorbed photon quantum yield (AQE) of >60% was measured with the optimized photocatalyst.

20.
RSC Adv ; 8(18): 9871-9878, 2018 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-35540842

RESUMEN

The group VIb dichalcogenides (MX2, M = Mo, W; X= S, Se) have a layered molybdenite structure in which M atoms are coordinated by a trigonal prism of X atoms. Ternary solid solutions of MS x Se2-x were synthesized, microcrystals were grown by chemical vapor transport, and their morphologies and structures were characterized by using synchrotron X-ray diffraction, Rietveld refinement, DIFFaX simulation of structural disorder, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Double aberration corrected scanning transmission electron microscopy was used to determine the anion distributions in single-layer nanosheets exfoliated from the microcrystals. These experiments indicate that the size difference between S and Se atoms does not result in phase separation, consistent with earlier studies of MX2 monolayer sheets grown by chemical vapor deposition. However, stacking faults occur in microcrystals along the layering axis, particularly in sulfur-rich compositions of MS x Se2-x solid solutions.

SELECCIÓN DE REFERENCIAS
DETALLE DE LA BÚSQUEDA