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1.
Clin Shoulder Elb ; 27(3): 345-352, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-39138940

RESUMEN

BACKGROUND: Several studies have investigated factors affecting patient satisfaction after arthroscopic rotator cuff repair (ARCR); however, it is unknown if these factors vary according to age. Therefore, this study aimed to evaluate the factors associated with satisfaction of ARCR in individuals 70 years and older versus younger patients. METHODS: Among 319 consecutive patients who underwent ARCR, 173 were included. Patients were divided into an old age group (≥70 years) and a young age group (<70 years), and the two age groups were further divided into satisfied and unsatisfied subgroups. Patient satisfaction was evaluated at the final follow-up visit using a binary question (yes or no). Clinical outcomes were assessed preoperatively and at the final follow-up. RESULTS: Satisfaction rates in the older and younger age groups were 75.41% and 79.47%, respectively. Mean changes in Constant and American Shoulder and Elbow Surgeons scores were significantly different between the satisfied and unsatisfied subgroups (P=0.031 and P=0.012, respectively) in the young patients. In the old patients, there was a significant difference in the mean change in depression subscale of the Hospital Anxiety and Depression Scale (P=0.031) and anxiety subscale of the Hospital Anxiety and Depression Scale (P=0.044) scores between the satisfied and unsatisfied subgroups. CONCLUSIONS: Factors affecting patient satisfaction after ARCR differed according to age. Psychological improvement was more important to elderly patients, whereas restoration of function was more important to younger patients. Pain relief was important for both age groups. Level of evidence: III.

2.
Angew Chem Int Ed Engl ; : e202406273, 2024 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-39076060

RESUMEN

The chlorine evolution reaction (CER) is a crucial anode reaction in the chlor-alkali industrial process. Precious metal-based dimensionally stable anodes (DSAs) are commonly used as catalysts for CER but are constrained by their high cost and low selectivity. Herein, a Pt dual singe-atom catalyst (DSAC) dispersed on fluorine-doped carbon nanotubes (F-CNTs) is designed for an efficient and robust CER process. The prepared Pt DSAC demonstrates excellent CER activity with a low overpotential of 21 mV to achieve a current density of 10 mA cm-2 and a remarkable mass activity of 3802.6 A gpt-1 at an overpotential around 30 mV, outperforming those of commercial DSA and Pt single-atom catalysts. The excellent CER performance of Pt DSAC is attributed to the high atomic utilization and improved intrinsic activity. Notably, introducing fluorine atoms on CNTs increases the oxidation and chlorination resistance of Pt DSAC, and reduces the demetalization ratio of Pt atoms, resulting in excellent long-term CER stability. Theoretical calculations reveal that several Pt DSAC configurations with optimized first-shell ligands and interatomic distance display lower energy barriers for Cl intermediates generation and weaker ionic Pt-Cl bond interaction, which are favorable for the CER process.

3.
Medicina (Kaunas) ; 60(7)2024 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-39064561

RESUMEN

Background and Objectives: Chronic hepatitis C (CHC) can be cured with direct-acting antiviral (DAA) therapy. In Korea, sofosbuvir (SOF) and ledipasvir (LDV)/SOF were launched in 2016. Patients who achieve a sustained virologic response (SVR) following DAA treatment are predicted to have a favorable prognosis. Nevertheless, little is known regarding the prognosis of Korean CHC patients who receive SOF-based treatment and achieve SVR. Therefore, the purpose of this study was to look into the long-term outcomes for these patients. Materials and Methods: This was a prospective, multicenter observational study. CHC patients were enrolled who, following SOF or LDV/SOF treatment, had achieved SVR. The last day for follow-up was December 2023. The primary endpoint was HCC occurrence, which was checked at least once per year. Results: A total of 516 patients were included in this analysis, with a median follow-up duration of 39.0 months. Among them, 231 were male patients (44.8%), with a median age of 62.0 years. Genotypes were 1 (90, 17.4%), 2 (423, 82.0%), and 3 (3, 0.6%). The combination of SOF plus ribavirin was the most common treatment (394, 76.4%). In total, 160 patients were cirrhotic (31.0%), and the mean Child-Pugh score was 5.1. Within a maximum of 7 years, 21 patients (4.1%) developed HCC. Patients with HCC were older (69 vs. 61 years, p = 0.013) and had a higher cirrhosis incidence (81.0 vs. 28.9%, p < 0.001), higher AFP (6.0 vs. 3.3, p = 0.003) and higher APRI (0.8 vs. 0.5, p = 0.005). Age over 65 (p = 0.016) and cirrhosis (p = 0.005) were found to be significant risk factors for HCC by Cox regression analysis. Conclusions: Patients who achieved SVR with SOF-based treatment had a relatively favorable prognosis. However, the risk of HCC was not eliminated, especially in older and cirrhotic patients. Therefore, routine follow-up, surveillance, and early treatment are required.


Asunto(s)
Antivirales , Hepatitis C Crónica , Sofosbuvir , Respuesta Virológica Sostenida , Humanos , Masculino , Hepatitis C Crónica/tratamiento farmacológico , Hepatitis C Crónica/complicaciones , Sofosbuvir/uso terapéutico , Femenino , Persona de Mediana Edad , Estudios Prospectivos , Antivirales/uso terapéutico , República de Corea/epidemiología , Anciano , Pronóstico , Adulto , Neoplasias Hepáticas/epidemiología , Carcinoma Hepatocelular/epidemiología
4.
Nat Commun ; 15(1): 6047, 2024 Jul 18.
Artículo en Inglés | MEDLINE | ID: mdl-39025876

RESUMEN

Currently, conventional dimethoxymethane synthesis methods are environmentally unfriendly. Here, we report a photo-redox catalysis system to generate dimethoxymethane using a silver and tungsten co-modified blue titanium dioxide catalyst (Ag.W-BTO) by coupling CO2 reduction and CH3OH oxidation under mild conditions. The Ag.W-BTO structure and its electron and hole transfer are comprehensively investigated by combining advanced characterizations and theoretical studies. Strikingly, Ag.W-BTO achieve a record photocatalytic activity of 5702.49 µmol g-1 with 92.08% dimethoxymethane selectivity in 9 h of ultraviolet-visible irradiation without sacrificial agents. Systematic isotope labeling experiments, in-situ diffuse reflectance infrared Fourier-transform analysis, and theoretical calculations reveal that the Ag and W species respectively catalyze CO2 conversion to *CH2O and CH3OH oxidation to *CH3O. Subsequently, an asymmetric carbon-oxygen coupling process between these two crucial intermediates produces dimethoxymethane. This work presents a CO2 photocatalytic reduction system for multi-carbon production to meet the objectives of sustainable economic development and carbon neutrality.

5.
Nano Lett ; 24(26): 7999-8007, 2024 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-38900975

RESUMEN

The rapid increase in data storage worldwide demands a substantial amount of energy consumption annually. Studies looking at low power consumption accompanied by high-performance memory are essential for next-generation memory. Here, Graphdiyne oxide (GDYO), characterized by facile resistive switching behavior, is systematically reported toward a low switching voltage memristor. The intrinsic large, homogeneous pore-size structure in GDYO facilitates ion diffusion processes, effectively suppressing the operating voltage. The theoretical approach highlights the remarkably low diffusion energy of the Ag ion (0.11 eV) and oxygen functional group (0.6 eV) within three layers of GDYO. The Ag/GDYO/Au memristor exhibits an ultralow operating voltage of 0.25 V with a GDYO thickness of 5 nm; meanwhile, the thicker GDYO of 29 nm presents multilevel memory with an ON/OFF ratio of up to 104. The findings shed light on memory resistive switching behavior, facilitating future improvements in GDYO-based devices toward opto-memristors, artificial synapses, and neuromorphic applications.

6.
ACS Infect Dis ; 10(6): 1890-1895, 2024 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-38738652

RESUMEN

Currently used visible light catalysts either operate with high-power light sources or require prolonged periods of time for catalytic reactions. This presents a limitation regarding facile application in indoor environments and spaces frequented by the public. Furthermore, this gives rise to elevated power consumption. Here, we enhance photocatalytic performance with blue TiO2 and WO3 complexes covalently coupled through an organic molecule, 3-mercaptopropionic acid, under indoor light. Antibacterial experiments against 108 CFU/mL Escherichia coli (E. coli) suspensions were conducted under indoor light exposure conditions. They showed a sterilization effect of almost 90% within 70 min and nearly 100% after 110 min. The complex generates reactive oxygen species (ROS), such as •OH and O2•-, under natural air conditions. We also showed that h+ and •OH are important for sterilizing E. coli using common scavengers. This research highlights the potential of these complexes to generate ROS, effectively playing a crucial role in antibacterial effects under indoor light.


Asunto(s)
Antibacterianos , Escherichia coli , Luz , Especies Reactivas de Oxígeno , Titanio , Tungsteno , Escherichia coli/efectos de los fármacos , Escherichia coli/efectos de la radiación , Titanio/química , Titanio/farmacología , Antibacterianos/farmacología , Antibacterianos/química , Tungsteno/química , Tungsteno/farmacología , Catálisis , Especies Reactivas de Oxígeno/metabolismo , Óxidos/farmacología , Óxidos/química , Pruebas de Sensibilidad Microbiana
7.
ACS Nano ; 18(22): 14742-14753, 2024 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-38770934

RESUMEN

Transition metal single-atom catalysts (SACs) have been regarded as possible alternatives to platinum-based materials due to their satisfactory performance of the oxygen reduction reaction (ORR). By contrast, main-group metal elements are rarely studied due to their unfavorable surface and electronic states. Herein, a main-group Sn-based SAC with penta-coordinated and asymmetric first-shell ligands is reported as an efficient and robust ORR catalyst. The introduction of the vertical oxygen atom breaks the symmetric charge balance, modulating the binding strength to oxygen intermediates and decreasing the energy barrier for the ORR process. As expected, the prepared Sn SAC exhibits outstanding ORR activity with a high half-wave potential of 0.912 V (vs RHE) and an excellent mass activity of 13.1 A mgSn-1 at 0.850 V (vs RHE), which surpasses that of commercial Pt/C and most reported transition-metal-based SACs. Additionally, the reported Sn SAC shows excellent ORR stability due to the strong interaction between Sn sites and the carbon support with oxygen atom as the bridge. The excellent ORR performance of Sn SAC was also proven by both liquid- and solid-state zinc-air battery (ZAB) measurements, indicating its great potential in practical applications.

8.
Chemistry ; 30(2): e202302843, 2024 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-37768323

RESUMEN

Ammonia is vital for fertilizer production, hydrogen storage, and alternative fuels. The conventional Haber-Bosch process for ammonia production is energy-intensive and environmentally harmful. Designing environmentally friendly and low-energy consumption strategies for electrocatalytic N2 reduction reaction (ENRR) in mild conditions is meaningful. Single-atom catalysts (SACs) have been studied extensively for NRR due to their high atomic utilization and unique electronic structure but are limited by their poor faradic efficiency and low ammonia formation yield. Dual single-atom catalysts (DSACs) have recently emerged as a promising solution for the effective activation of molecular N2 , providing diverse active sites and synergistic interactions between adjacent atoms. In this review, we summarize the latest advances in metal DSACs for electrochemical ENRR based on both theoretical calculations and experimental studies, including aspects such as their variety, coordination, support, N2 adsorption and activity mechanisms, the characterization of NRR and electrochemical cell Configuration. We also address challenges and prospects in this rapidly evolving field, providing a comprehensive overview of DSACs for ENRR.

9.
J Foot Ankle Surg ; 63(2): 127-131, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-37898330

RESUMEN

The anterior inferior tibiofibular ligament (AITFL) avulsion fracture accompanying an ankle fracture can compromise ankle stability, necessitating accurate evaluation and a clear understanding of its pathophysiology.. The aim of this study was to investigate the association between AITFL avulsion fracture and Lauge-Hansen, Wagstaffe classification. A retro-prospective study was conducted at a university-affiliated tertiary care medical center. We selected 128 patients who underwent surgery at our institution between January 2013 and July 2017 and analyzed the association between AITFL avulsion fracture and the foot position. According to the modified Wagstaffe classification system, there were 39 cases of type II, followed by 9 cases of type III and 8 cases of type IV. Of the7 pronation-abduction fractures, 3 were AITFL avulsion fracture (43%), while of the 21 pronation-external rotation fractures, 9 were AITFL avulsion fracture (43%). Of the 95 supination-external rotation fractures, there were 56 cases (59%) of AITFL avulsion fractures. Of the pronation fractures, 0% were fibular avulsion fractures and 43% were tibial avulsion fractures. Of the supination fractures, 44% were fibular avulsion fractures and 16% were tibial avulsion fracture. The difference in the ratio of fibular to tibial avulsion fractures between pronation and supination fractures was significant (p < .001). These results suggest that tibial avulsion fractures of type IV in the modified Wagstaffe classification and pronation fractures occur due to collision with the anterolateral corners of the distal bone when the talus externally rotates. Moreover, in cases of pronation fractures, a new type of AITFL avulsion fracture has been observed.


Asunto(s)
Fracturas de Tobillo , Fracturas por Avulsión , Ligamentos Laterales del Tobillo , Fracturas de la Tibia , Humanos , Fracturas de Tobillo/complicaciones , Fracturas de Tobillo/diagnóstico por imagen , Fracturas de Tobillo/cirugía , Fracturas por Avulsión/complicaciones , Fracturas por Avulsión/diagnóstico por imagen , Fracturas por Avulsión/cirugía , Ligamentos Laterales del Tobillo/cirugía , Estudios Prospectivos , Estudios Retrospectivos , Fijación Interna de Fracturas/métodos
10.
ACS Nano ; 18(1): 874-884, 2024 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-38112494

RESUMEN

Controllable metal-support interaction (MSI) modulations have long been studied for improving the performance of catalysts supported on metal oxides. However, the corresponding in-depth study for metal1-metal2 (M1-M2) composited configurations is rarely achieved due to the lack of reliable models and manipulation mechanisms of MSI modifications. We modeled ruthenium on copper support (Ru-Cu) metal catalysts with negligible interfacial contact potential (e0.06 V) and investigated MSI-dependent hydrogen evolution reaction (HER) catalysis kinetics induced by an electronic hydroxyl (HO-) modifier. Comprehensive simulations and characterizations confirmed that adjusting the HO- coverage can readily realize the tailorable improvement of MSI, facilitating charge migration at the Ru-Cu interface and optimizing the overall HER pathway on active Ru. As a result, a 5/10 monolayer (ML) HO-modified catalyst (5/10 ML) exhibits superior HER activity and durability owing to the relatively stronger MSI. This catalyst also ensured sustainable and efficient hydrogen generation in a urea electrolyzer with significant energy savings. Our work provides a valuable reference for optimizing the MSI-activity relationship in M1-M2 catalysts that target more than just HER.

11.
ACS Appl Mater Interfaces ; 15(48): 56084-56094, 2023 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-38058106

RESUMEN

Currently, most carbon monoxide (CO) gas sensors work at high temperatures of over 150 °C. Developing CO gas sensors that operate at room temperature is challenging because of the sensitivity trade-offs. Here, we report an ultrasensitive CO gas sensor at room temperature using fluorine-graphdiyne (F-GDY) in which electrons are increased by light. The GDY films used as channels of field-effect transistors were prepared by using chemical vapor deposition and were characterized by using various spectroscopic techniques. With exposure to UV light, F-GDY showed a more efficient photodoping effect than hydrogen-graphdiyne (H-GDY), resulting in a larger negative shift in the charge neutral point (CNP) to form an n-type semiconductor and an increase in the Fermi level from -5.27 to -5.01 eV. Upon CO exposure, the negatively shifted CNP moved toward a positive shift, and the electrical current decreased, indicating electron transfer from photodoped GDYs to CO. Dynamic sensing experiments demonstrated that negatively charged F-GDY is remarkably sensitive to an electron-deficient CO gas, even with a low concentration of 200 parts per billion. This work provides a promising solution for enhancing the CO sensitivity at room temperature and expanding the application of GDYs in electronic devices.

12.
Nano Lett ; 23(17): 7927-7933, 2023 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-37647420

RESUMEN

Transition metal dichalcogenides (TMDs) benefit electrical devices with spin-orbit coupling and valley- and topology-related properties. However, TMD-based devices suffer from traps arising from defect sites inside the channel and the gate oxide interface. Deactivating them requires independent treatments, because the origins are dissimilar. This study introduces a single treatment to passivate defects in a multilayer MoS2 FET. By applying back-gate bias, protons from an H-TFSI droplet are injected into the MoS2, penetrating deeply enough to reach the SiO2 gate oxide. The characterizations employing low-temperature transport and deep-level transient spectroscopy (DLTS) studies reveal that the trap density of S vacancies in MoS2 drops to the lowest detection level. The temperature-dependent mobility plot on the SiO2 substrate resembles that of the h-BN substrate, implying that dangling bonds in SiO2 are passivated. The carrier mobility on the SiO2 substrate is enhanced by approximately 2200% after the injection.

13.
ACS Appl Mater Interfaces ; 15(35): 41708-41719, 2023 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-37621110

RESUMEN

The sp-hybridized carbon network in single- or few-layer γ-graphyne (γ-GY) has a polarized electron distribution, which can be crucial in overcoming biosafety issues. Here, we report the low-temperature synthesis, electronic properties, and amyloid fibril nanostructures of electrostatic few-layer γ-GY. ABC stacked γ-GY is synthesized by layer-by-layer growth on a catalytic copper surface, exhibiting intrinsic p-type semiconducting properties in few-layer γ-GY. Thickness-dependent electronic properties of γ-GY elucidate interlayer interactions by electron doping between electrostatic layers and layer stacking-involved modulation of the band gap. Electrostatic few-layer γ-GY induces high electronic sensitivity and intense interaction with amyloid beta (i.e., Aß40) peptides assembling into elongated mature Aß40 fibrils. Two-dimensional biocompatible nanostructures of Aß40 fibrils/few-layer γ-GY enable excellent cell viability and high neuronal differentiation of living cells without external stimulation.


Asunto(s)
Péptidos beta-Amiloides , Carbono , Temperatura , Catálisis , Supervivencia Celular
14.
Small ; : e2304560, 2023 Aug 06.
Artículo en Inglés | MEDLINE | ID: mdl-37544918

RESUMEN

Atomic-scale electrocatalysts greatly improve the performance and efficiency of water splitting but require special adjustments of the supporting structures for anchoring and dispersing metal single atoms. Here, the structural evolution of atomic-scale electrocatalysts for water splitting is reviewed based on different synthetic methods and structural properties that create different environments for electrocatalytic activity. The rate-determining step or intermediate state for hydrogen or oxygen evolution reactions is energetically stabilized by the coordination environment to the single-atom active site from the supporting material. In large-scale practical use, maximizing the loading amount of metal single atoms increases the efficiency of the electrocatalyst and reduces the economic cost. Dual-atom electrocatalysts with two different single-atom active sites react with an increased number of water molecules and reduce the adsorption energy of water derived from the difference in electronegativity between the two metal atoms. In particular, single-atom dimers induce asymmetric active sites that promote the degradation of H2 O to H2 or O2 evolution. Consequently, the structural properties of atomic-scale electrocatalysts clarify the atomic interrelation between the catalytic active sites and the supporting material to achieve maximum efficiency.

15.
Adv Sci (Weinh) ; 10(25): e2300925, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37424035

RESUMEN

Graphdiyne (GDY), a new 2D material, has recently proven excellent performance in photodetector applications due to its direct bandgap and high mobility. Different from the zero-gap of graphene, these preeminent properties made GDY emerge as a rising star for solving the bottleneck of graphene-based inefficient heterojunction. Herein, a highly effective graphdiyne/molybdenum (GDY/MoS2 ) type-II heterojunction in a charge separation is reported toward a high-performance photodetector. Characterized by robust electron repulsion of alkyne-rich skeleton, the GDY based junction facilitates the effective electron-hole pairs separation and transfer. This results in significant suppression of Auger recombination up to six times at the GDY/MoS2 interface compared with the pristine materials owing to an ultrafast hot hole transfer from MoS2 to GDY. GDY/MoS2 device demonstrates notable photovoltaic behavior with a short-circuit current of -1.3 × 10-5 A and a large open-circuit voltage of 0.23 V under visible irradiation. As a positive-charge-attracting magnet, under illumination, alkyne-rich framework induces positive photogating effect on the neighboring MoS2 , further enhancing photocurrent. Consequently, the device exhibits broadband detection (453-1064 nm) with a maximum responsivity of 78.5 A W-1 and a high speed of 50 µs. Results open up a new promising strategy using GDY toward effective junction for future optoelectronic applications.

16.
Sci Adv ; 9(25): eadg2324, 2023 Jun 23.
Artículo en Inglés | MEDLINE | ID: mdl-37343104

RESUMEN

Organic systems often allow to create two triplet spin states (triplet excitons) by converting an initially excited singlet spin state (a singlet exciton). An ideally designed organic/inorganic heterostructure could reach the photovoltaic energy harvest over the Shockley-Queisser (S-Q) limit because of the efficient conversion of triplet excitons into charge carriers. Here, we demonstrate the molybdenum ditelluride (MoTe2)/pentacene heterostructure to boost the carrier density via efficient triplet transfer from pentacene to MoTe2 using ultrafast transient absorption spectroscopy. We observe carrier multiplication by nearly four times by doubling carriers in MoTe2 via the inverse Auger process and subsequently doubling carriers via triplet extraction from pentacene. We also verify efficient energy conversion by doubling the photocurrent in the MoTe2/pentacene film. This puts a step forward to enhancing photovoltaic conversion efficiency beyond the S-Q limit in the organic/inorganic heterostructures.

17.
ACS Appl Bio Mater ; 6(5): 1970-1980, 2023 05 15.
Artículo en Inglés | MEDLINE | ID: mdl-37134284

RESUMEN

In this study, we report a one-step direct synthesis of molybdenum disulfide (MoS2) and tungsten disulfide (WS2) quantum dots (QDs) through a solvothermal reaction using only alcohol solvents and efficient Escherichia coli (E. coli) decompositions as photocatalytic antibacterial agents under visible light irradiation. The solvothermal reaction gives the scission of molybdenum-sulfur (Mo-S) and tungsten-sulfur (W-S) bonding during the synthesis of MoS2 and WS2 QDs. Using only alcohol solvent does not require a residue purification process necessary for metal intercalation. As the number of the CH3 groups of alcohol solvents among ethyl, isopropyl, and tert(t)-butyl alcohols increases, the dispersibility of MoS2/WS2 increases. The CH3 groups of alcohols minimize the surface energy, leading to the effective exfoliation and disintegration of the bulk under heat and pressure. The bulky t-butyl alcohol with the highest number of methyl groups shows the highest exfoliation and yield. MoS2 QDs with a lateral size of about 2.5 nm and WS2 QDs of about 10 nm are prepared, exhibiting a strong blue luminescence under 365 nm ultraviolet (UV) light irradiation. Their heights are 0.68-3 and 0.72-5 nm, corresponding to a few layers of MoS2 and WS2, respectively. They offer a highly efficient performance in sterilizing E. coli as the visible-light-driven photocatalyst.


Asunto(s)
Puntos Cuánticos , Puntos Cuánticos/química , Molibdeno/química , Solventes , Escherichia coli , Etanol , Antibacterianos/farmacología , Azufre
18.
ACS Nano ; 17(8): 7406-7416, 2023 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-37042711

RESUMEN

Single-atom catalysts have already been widely investigated for the nitrogen reduction reaction (NRR). However, the simplicity of a single atom as an active center encounters the challenge of modulating the multiple reaction intermediates during the NRR process. Moving toward the single-atom-dimer (SAD) structures can not only buffer the multiple reaction intermediates but also provide a strategy to modify the electronic structure and environment of the catalysts. Here, a structure of a vanadium SAD (V-O-V) catalyst on N-doped carbon (O-V2-NC) is proposed for the electrochemical nitrogen reduction reaction, in which the vanadium dimer is coordinated with nitrogen and simultaneously bridged by one oxygen. The oxygen-bridged metal atom dimer that has more electron deficiency is perceived to be the active center for nitrogen reduction. A loop evolution of the intermediate structure was found during the theoretical process simulated by density functional theory (DFT) calculation. The active center V-O-V breaks down to V-O and V during the protonation process and regenerates to the original V-O-V structure after releasing all the nitrogen species. Thus, the O-V2-NC structure presents excellent activity toward the electrochemical NRR, achieving an outstanding faradaic efficiency (77%) along with the yield of 9.97 µg h-1 mg-1 at 0 V (vs RHE) and comparably high ammonia yield (26 µg h-1 mg-1) with the FE of 4.6% at -0.4 V (vs RHE). This report synthesizes and proves the peculiar V-O-V dimer structure experimentally, which also contributes to the library of SAD catalysts with superior performance.

19.
Chem Commun (Camb) ; 59(6): 756-759, 2023 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-36541631

RESUMEN

Epoxidation of dicyclopentadiene (DCPD) is studied on a series of TiO2 catalysts using hydrogen peroxide as an oxidant. DCPD derivatives have applications in several areas including polymer, pharmaceutical and pesticide products. The control of selectivity leading to the desired product is important for many of these applications. Using experimental and computational studies, we show that the surface crystalline phases of TiO2 play crucial roles not only in the formation of peroxo species but also in the selective epoxidation of two different CC double bonds in DCPD.


Asunto(s)
Peróxido de Hidrógeno , Titanio , Peróxido de Hidrógeno/química , Catálisis
20.
ACS Appl Mater Interfaces ; 14(48): 53603-53614, 2022 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-36404762

RESUMEN

Band-edge modulation of halide perovskites as photoabsorbers plays significant roles in the application of photovoltaic and photochemical systems. Here, Lewis acidity of dopants (M) as the new descriptor of engineering the band-edge position of the perovskite is investigated in the gradiently doped perovskite along the core-to-surface (CsPbBr3-CsPb1-xMxBr3). Reducing M-bromide bond strength with an increase in hardness of acidic M increases the electron ability of basic Br, thus strengthening the Pb-Br orbital coupling in M-Pb-Br, noted as the inductive effect of dopants. Especially, the highly hard Lewis acidic Mg localized in the outer position of the perovskite induces the increase of work function and then shifts band edge upward along the core-to-surface of the perovskite. Thus, charge separation driven by the dopant-induced internal electric field induces the slow annihilation of the excited holes, improving the slow aromatic Csp3-H dissociation in the photocatalytic oxidation process by ∼211% (491.39 µmol g-1 h-1) enhancements, compared with undoped nanocrystals.

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