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1.
Trends Genet ; 2024 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-39277449

RESUMEN

Hydrothermal vents are unique habitats like an oases of life compared with typical deep-sea, soft-sediment environments. Most animals that live in these habitats are invertebrates, and they have adapted to extreme vent environments that include high temperatures, hypoxia, high sulfide, high metal concentration, and darkness. The advent of next-generation sequencing technology, especially the coming of the new era of omics, allowed more studies to focus on the molecular adaptation of these invertebrates to vent habitats. Many genes linked to hydrothermal adaptation have been studied. We summarize the findings related to these genetic adaptations and discuss which new techniques can facilitate studies in the future.

2.
Proc Natl Acad Sci U S A ; 121(28): e2403699121, 2024 Jul 09.
Artículo en Inglés | MEDLINE | ID: mdl-38954544

RESUMEN

Despite the ubiquity of thermal convection in nature and artificial systems, we still lack a unified formulation that integrates the system's geometry, fluid properties, and thermal forcing to characterize the transition from free to confined convective regimes. The latter is broadly relevant to understanding how convection transports energy and drives mixing across a wide range of environments, such as planetary atmospheres/oceans and hydrothermal flows through fractures, as well as engineering heatsinks and microfluidics for the control of mass and heat fluxes. Performing laboratory experiments in Hele-Shaw geometries, we find multiple transitions that are identified as remarkable shifts in flow structures and heat transport scaling, underpinning previous numerical studies. To unveil the mechanisms of the geometrically controlled transition, we focus on the smallest structure of convection, posing the following question: How free is a thermal plume in a closed system? We address this problem by proposing the degree of confinement [Formula: see text]-the ratio of the thermal plume's thickness in an unbounded domain to the lateral extent of the system-as a universal metric encapsulating all the physical parameters. Here, we characterize four convective regimes different in flow dimensionality and time dependency and demonstrate that the transitions across the regimes are well tied with [Formula: see text]. The introduced metric [Formula: see text] offers a unified characterization of convection in closed systems from the plume's standpoint.

3.
Proc Natl Acad Sci U S A ; 120(33): e2300491120, 2023 08 15.
Artículo en Inglés | MEDLINE | ID: mdl-37561785

RESUMEN

Alkaline hydrothermal vents have become a candidate setting for the origins of life on Earth and beyond. This is due to several key features including the presence of gradients of temperature, redox potential, pH, the availability of inorganic minerals, and the existence of a network of inorganic pore spaces that could have served as primitive compartments. Chemical gardens have long been used as experimental proxies for hydrothermal vents. This paper investigates-10pc]Please note that the spelling of the following author name in the manuscript differs from the spelling provided in the article metadata: Richard J. G. Löffler. The spelling provided in the manuscript has been retained; please confirm. a set of prebiotic interactions between such inorganic structures and fatty alcohols. The integration of a medium-chain fatty alcohol, decanol, within these inorganic minerals, produced a range of emergent 3 dimensions structures at both macroscopic and microscopic scales. Fatty alcohols can be considered plausible prebiotic amphiphiles that might have assisted the formation of protocellular structures such as vesicles. The experiments presented herein show that neither chemical gardens nor decanol alone promote vesicle formation, but chemical gardens grown in the presence of decanol, which is then integrated into inorganic mineral structures, support vesicle formation. These observations suggest that the interaction of fatty alcohols and inorganic mineral structures could have played an important role in the emergence of protocells, yielding support for the evolution of living cells.


Asunto(s)
Minerales , Origen de la Vida , Minerales/química
4.
Proc Natl Acad Sci U S A ; 120(45): e2306466120, 2023 Nov 07.
Artículo en Inglés | MEDLINE | ID: mdl-37903251

RESUMEN

The thermal state of mid-ocean ridges exerts a crucial modulation on seafloor spreading processes that shape ~2/3 of our planet's surface. Standard thermal models treat the ridge axis as a steady-state boundary layer between the hydrosphere and asthenosphere, whose thermal structure primarily reflects the local spreading rate. This framework explains the deepening of axial melt lenses (AMLs)-a proxy for the basaltic solidus isotherm-from ~1 to ~3 km from fast- to intermediate-spreading ridges but fails to account for shallow crustal AMLs documented at slow-ultraslow spreading ridges. Here, we show that these can be explained by a numerical model that decouples the potentially transient ridge magma supply from spreading rate, captures the essential physics of hydrothermal convection, and considers multiple modes of melt emplacement. Our simulations show that melt flux is a better thermal predictor than spreading rate. While multiple combinations of melt/dike emplacement modes, permeability structure, and temporal fluctuations of melt supply can explain shallow crustal AMLs at slow-ultraslow ridges, they all require elevated melt fluxes compared to most ridge sections of comparable spreading rates. This highlights the importance of along-axis melt focusing at slow-ultraslow ridges and sheds light on the natural variability of their thermal regimes.

5.
Proc Natl Acad Sci U S A ; 120(19): e2300687120, 2023 05 09.
Artículo en Inglés | MEDLINE | ID: mdl-37126695

RESUMEN

Metabolism constitutes the core chemistry of life. How it began on the early Earth and whether it had a cellular origin are still uncertain. A leading hypothesis for life's origins postulates that metabolism arose from geochemical CO2-fixing pathways, driven by inorganic catalysts and energy sources, long before enzymes or genes existed. The acetyl-CoA pathway and the reductive tricarboxylic acid cycle are considered ancient reaction networks that hold relics of early carbon-fixing pathways. Although transition metals can promote many steps of these pathways, whether they form a functional metabolic network in abiotic cells has not been demonstrated. Here, we formulate a nonenzymatic carbon-fixing network from these pathways and determine its functional feasibility in abiotic cells by imposing fundamental physicochemical constraints. Using first principles, we show that abiotic cells can sustain a steady carbon-fixing cycle that performs a systemic function over a relatively narrow range of conditions. Furthermore, we find that in all feasible steady states, the operation of the cycle elevates the osmotic pressure, leading to volume expansion. These results suggest that achieving homeostatic metabolic states under prebiotic conditions was possible, but challenging, and volume growth was a fundamental property of early metabolism.


Asunto(s)
Ciclo del Ácido Cítrico , Redes y Vías Metabólicas , Ciclo del Carbono , Homeostasis , Carbono/metabolismo
6.
Proc Natl Acad Sci U S A ; 119(44): e2210258119, 2022 11.
Artículo en Inglés | MEDLINE | ID: mdl-36279430

RESUMEN

The paleomagnetic record is an archive of Earth's geophysical history, informing reconstructions of ancient plate motions and probing the core via the geodynamo. We report a robust 3.25-billion-year-old (Ga) paleomagnetic pole from the East Pilbara Craton, Western Australia. Together with previous results from the East Pilbara between 3.34 and 3.18 Ga, this pole enables the oldest reconstruction of time-resolved lithospheric motions, documenting 160 My of both latitudinal drift and rotation at rates of at least 0.55°/My. Motions of this style, rate, and duration are difficult to reconcile with true polar wander or stagnant-lid geodynamics, arguing strongly for mobile-lid geodynamics by 3.25 Ga. Additionally, this pole includes the oldest documented geomagnetic reversal, reflecting a stably dipolar, core-generated Archean dynamo.


Asunto(s)
Fenómenos Geológicos , Australia Occidental
7.
Proc Natl Acad Sci U S A ; 119(30): e2205602119, 2022 07 26.
Artículo en Inglés | MEDLINE | ID: mdl-35862459

RESUMEN

Comprehensive knowledge of the distribution of active hydrothermal vent fields along midocean ridges is essential to understanding global chemical and heat fluxes and endemic faunal distributions. However, current knowledge is biased by a historical preference for on-axis surveys. A scarcity of high-resolution bathymetric surveys in off-axis regions limits vent identification, which implies that the number of vents may be underestimated. Here, we present the discovery of an active, high-temperature, off-axis hydrothermal field on a fast-spreading ridge. The vent field is located 750 m east of the East Pacific Rise axis and ∼7 km north of on-axis vents at 9° 50'N, which are situated in a 50- to 100-m-wide trough. This site is currently the largest vent field known on the East Pacific Rise between 9 and 10° N. Its proximity to a normal fault suggests that hydrothermal fluid pathways are tectonically controlled. Geochemical evidence reveals deep fluid circulation to depths only 160 m above the axial magma lens. Relative to on-axis vents at 9° 50'N, these off-axis fluids attain higher temperatures and pressures. This tectonically controlled vent field may therefore exhibit greater stability in fluid composition, in contrast to more dynamic, dike-controlled, on-axis vents. The location of this site indicates that high-temperature convective circulation cells extend to greater distances off axis than previously realized. Thorough high-resolution mapping is necessary to understand the distribution, frequency, and physical controls on active off-axis vent fields so that their contribution to global heat and chemical fluxes and role in metacommunity dynamics can be determined.


Asunto(s)
Respiraderos Hidrotermales , Biodiversidad , Ecosistema , Océano Pacífico
8.
Proc Natl Acad Sci U S A ; 119(14): e2115608119, 2022 04 05.
Artículo en Inglés | MEDLINE | ID: mdl-35349333

RESUMEN

SignificanceIn marine ecosystems, transmission of microbial symbionts between host generations occurs predominantly through the environment. Yet, it remains largely unknown how host genetics, symbiont competition, environmental conditions, and geography shape the composition of symbionts acquired by individual hosts. To address this question, we applied population genomic approaches to four species of deep-sea hydrothermal vent snails that live in association with chemosynthetic bacteria. Our analyses show that environment is more important to strain-level symbiont composition than host genetics and that symbiont strains show genetic variation indicative of adaptation to the distinct geochemical conditions at each vent site. This corroborates a long-standing hypothesis that hydrothermal vent invertebrates affiliate with locally adapted symbiont strains to cope with the variable conditions characterizing their habitats.


Asunto(s)
Respiraderos Hidrotermales , Bacterias/genética , Ecosistema , Respiraderos Hidrotermales/microbiología , Metagenómica , Simbiosis/genética
9.
J Struct Biol ; 216(4): 108126, 2024 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-39244170

RESUMEN

The global crystallographic texture of calcite and aragonite in the shells of the bivalves Bathymodiolus thermophilus, Mytilus galloprovincialis, M. edulis and M. trossulus was studied by means of neutron diffraction. It was revealed that the general appearance of pole figures isolines of both minerals coincides for the studied species. The crystallographic texture sharpness evaluated by means of pole density on the calcite pole figures ((0006), (101¯4)) and aragonite pole figures ((012)/(121), (040)/(221)) coincides or has close values for deep-sea hydrothermal species B. thermophilus and the studied shallow-water species of the genus Mytilus. The calcite pole figures (0006) and (101¯4) of B. thermophilus show a shift in the position of texture maximum values compared to corresponding pole figures of other mussels. The shell microstructure of all studied mollusks is similar, only the shape of the fibers of B. thermophilus differs. Global crystallographic texture is a stable feature of the family Mytilidae. The extreme habitat conditions of the hydrothermal biotope do not significantly affect the crystallographic texture of B. thermophilus.

10.
BMC Genomics ; 25(1): 162, 2024 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-38331729

RESUMEN

In this work, a novel isatin-Schiff base L2 had been synthesized through a simple reaction between isatin and 2-amino-5-methylthio-1,3,4-thiadiazole. The produced Schiff base L2 was then subjected to a hydrothermal reaction with cerium chloride to produce the cerium (III)-Schiff base complex C2. Several spectroscopic methods, including mass spectra, FT-IR, elemental analysis, UV-vis, 13C-NMR, 1H-NMR, Thermogravimetric Analysis, HR-TEM, and FE-SEM/EDX, were used to completely characterize the produced L2 and C2. A computer simulation was performed using the MOE software program to find out the probable biological resistance of studied compounds against the proteins in some types of bacteria or fungi. To investigate the interaction between the ligand and its complex, we conducted molecular docking simulations using the molecular operating environment (MOE). The docking simulation findings revealed that the complex displayed greater efficacy and demonstrated a stronger affinity for Avr2 effector protein from the fungal plant pathogen Fusarium oxysporum (code 5OD4) than the original ligand. The antibacterial activity of the ligand and its Ce3+ complex were applied in vitro tests against different microorganism. The study showed that the complex was found to be more effective than the ligand.


Asunto(s)
Cerio , Isatina , Simulación del Acoplamiento Molecular , Espectroscopía Infrarroja por Transformada de Fourier , Isatina/farmacología , Isatina/química , Cerio/farmacología , Bases de Schiff/farmacología , Bases de Schiff/química , Simulación por Computador , Ligandos , Antibacterianos/farmacología , Pruebas de Sensibilidad Microbiana
11.
Biochem Biophys Res Commun ; 712-713: 149938, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38640739

RESUMEN

Polymerization of nucleotides under prebiotic conditions simulating the early Earth has been extensively studied. Several independent methods have been used to verify that RNA-like polymers can be produced by hot wet-dry cycling of nucleotides. However, it has not been shown that these RNA-like polymers are similar to biological RNA with 3'-5' phosphodiester bonds. In the results described here, RNA-like polymers were generated from 5'-monophosphate nucleosides AMP and UMP. To confirm that the polymers resemble biological RNA, ribonuclease A should catalyze hydrolysis of the 3'-5' phosphodiester bonds between pyrimidine nucleotides to each other or to purine nucleotides, but not purine-purine nucleotide bonds. Here we show AFM images of specific polymers produced by hot wet-dry cycling of AMP, UMP and AMP/UMP (1:1) solutions on mica surfaces, before and after exposure to ribonuclease A. AMP polymers were unaffected by ribonuclease A but UMP polymers disappeared. This indicates that a major fraction of the bonds in the UMP polymers is indeed 3'-5' phosphodiester bonds. Some of the polymers generated from the AMP/UMP mixture also showed clear signs of cleavage. Because ribonuclease A recognizes the ester bonds in the polymers, we show for the first time that these prebiotically produced polymers are in fact similar to biological RNA but are likely to be linked by a mixture of 3'-5' and 2'-5' phosphodiester bonds.


Asunto(s)
ARN , Ribonucleasa Pancreática , ARN/química , ARN/metabolismo , Ribonucleasa Pancreática/química , Ribonucleasa Pancreática/metabolismo , Uridina Monofosfato/química , Uridina Monofosfato/metabolismo , Microscopía de Fuerza Atómica , Calor , Polímeros/química , Adenosina Monofosfato/química , Adenosina Monofosfato/metabolismo , Hidrólisis , Polimerizacion
12.
BMC Plant Biol ; 24(1): 502, 2024 Jun 05.
Artículo en Inglés | MEDLINE | ID: mdl-38840053

RESUMEN

BACKGROUND: Lentil is a significant legume that are consumed as a staple food and have a significant economic impact around the world. The purpose of the present research on lentil was to assess the hydrothermal time model's capacity to explain the dynamics of Lens culinaris L. var. Markaz-09 seed germination, as well as to ascertain the germination responses at various sub-optimal temperatures (T) and water potentials (Ψ). In order to study lentil seed germination (SG) behavior at variable water potentials (Ψs) and temperatures (Ts). A lab experiment employing the hydrothermal time model was created. Seeds were germinated at six distinct temperatures: 15 0С, 20 0С, 25 0С, 30 0С, 35 0С, and 40 0С, with five Ψs of 0, -0.3, -0.6, -0.9, and - 1.2 MPa in a PEG-6000 (Polyethylene glycol 6000) solution. RESULTS: The results indicated that the agronomic parameters like Germination index (GI), Germination energy (GE), Timson germination index (TGI), were maximum in 25 0C at (-0.9 MPa) and lowest at 40 0C in 0 MPa. On other hand, mean germination time (MGT) value was highest at 15 0C in -1.2 MPa and minimum at 40 0C in (-0.6 MPa) while Mean germination rate (MGR) was maximum at 40 0C in (0 MPa) and minimum at 15 0C in (-0.6 MPa). CONCLUSIONS: The HTT model eventually defined the germination response of Lens culinaris L. var. Markaz-09 (Lentil) for all Ts and Ψs, allowing it to be employed as a predictive tool in Lens culinaris L. var. Markaz-09 (Lentil) seed germination simulation models.


Asunto(s)
Germinación , Lens (Planta) , Semillas , Temperatura , Germinación/fisiología , Semillas/fisiología , Semillas/crecimiento & desarrollo , Lens (Planta)/fisiología , Lens (Planta)/crecimiento & desarrollo , Agua/metabolismo , Modelos Biológicos , Presión Osmótica
13.
Small ; 20(24): e2310587, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38546418

RESUMEN

The process of N-doping is frequently employed to enhance the properties of carbon quantum dots. However, the precise requirements for nitrogen precursors in producing high-quality N-doped carbon quantum dots (NCQDs) remain undefined. This research systematically examines the influence of various nitrogen dopants on the morphology, optical features, and band structure of NCQDs. The dots are synthesized using an efficient, eco- friendly, and rapid continuous hydrothermal flow technique. This method offers unparalleled control over synthesis and doping, while also eliminating convention-related issues. Citric acid is used as the carbon source, and urea, trizma base, beta-alanine, L-arginine, and EDTA are used as nitrogen sources. Notably, urea and trizma produced NCQDs with excitation-independent fluorescence, high quantum yields (up to 40%), and uniform dots with narrow particle size distributions. Density functional theory (DFT) and time-dependent DFT modelling established that defects and substituents within the graphitic structure have a more significant impact on the NCQDs' electronic structure than nitrogen-containing functional groups. Importantly, for the first time, this work demonstrates that the conventional approach of modelling single-layer structures is insufficient, but two layers suffice for replicating experimental data. This study, therefore, provides essential guidance on the selection of nitrogen precursors for NCQD customization for diverse applications.

14.
Small ; 20(29): e2400477, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38402438

RESUMEN

Utilizing the ionic flux to generate voltage output has been confirmed as an effective way to meet the requirements of clean energy sources. Different from ionic thermoelectric (i-TE) and hydrovoltaic devices, a new hydrothermal chemical generator is designed by amorphous FeCl3 particles dispersing in MWCNT and unique ferric chloride or water gate. In the presence of gate, the special ion behaviors enable the cell to present a constant voltage of 0.60 V lasting for over 96 h without temperature difference. Combining the differences of cation concentration, humidity and temperature between the right and left side of sample, the maximum short-circuit current and power output can be obtained to 168.46 µA and 28.11 µW, respectively. The generator also can utilize the low-grade heat to produce electricity wherein Seebeck coefficient is 6.79 mV K-1. The emerged hydrothermal chemical generator offers a novel approach to utilize the low-grade heat, water and salt solution resources, which provides a simple, sustainable and low-cost strategy to realize energy supply.

15.
Small ; 20(14): e2308127, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38009787

RESUMEN

Developing electronic skins (e-skins) with extraordinary perception through bionic strategies has far-reaching significance for the intellectualization of robot skins. Here, an artificial intelligence (AI)-motivated all-fabric bionic (AFB) e-skin is proposed, where the overall structure is inspired by the interlocked bionics of the epidermis-dermis interface inside the skin, while the structural design inspiration of the dielectric layer derives from the branch-needle structure of conifers. More importantly, AFB e-skin achieves intuition sensing in proximity mode and tactile sensing in pressure mode based on the fringing and iontronic effects, respectively, and is simulated and verified through COMSOL finite element analysis. The proposed AFB e-skin in pressure mode exhibits maximum sensitivity of 15.06 kPa-1 (<50 kPa), linear sensitivity of 6.06 kPa-1 (50-200 kPa), and fast response/recovery time of 5.6 ms (40 kPa). By integrating AFB e-skin with AI algorithm, and with the support of material inference mechanisms based on dielectric constant and softness/hardness, an intelligent material perception system capable of recognizing nine materials with indistinguishable surfaces within one proximity-pressure cycle is established, demonstrating abilities that surpass human perception.


Asunto(s)
Biónica , Dispositivos Electrónicos Vestibles , Humanos , Inteligencia Artificial , Intuición , Inteligencia , Percepción
16.
Small ; 20(33): e2400487, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38537118

RESUMEN

Hierarchical polyimides (PIs) not only show outstanding thermal stability and high mechanical strength but also have great advantages in terms of microstructure and surface area, which makes them highly valuable in various fields such as aerospace, microelectronics, adsorption, catalysis, and energy storage. However, great challenges still remain in the synthesis of hierarchical PIs with well-defined microstructure. Herein, polyamide acid salts (PAAS) with tunable ionization degree are synthesized first via the polymerization of dianhydride and diamine monomers in deionized water with 1,2-dimethylimidazole (DMIZ). Then cationic cetyltrimethylammonium chloride (CTAC) is added to the PAAS aqueous solution to induce the formation of polyelectrolyte-surfactant complexes based on electrostatic interaction. After a typical hydrothermal reaction (HTR) procedure, hierarchical PIs with different microstructures such as urchin-like PI microparticles, flower-like PI microparticles, and lamellar PI petals can be fabricated simply by changing the additive amount of DMIZ and CTAC. The nanostructure self-assemblies of PAAS are dominated by the charges on macromolecular chains and the formation of hierarchical structures of polymers is ascribed to a geometrical selection process during crystal growth. This work provides valuable insights into the self-assembly behaviors of polyelectrolyte systems for synthesizing well-defined hierarchical polymers.

17.
Small ; 20(27): e2310418, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38267816

RESUMEN

Antimony selenosulfide (Sb2(S,Se)3) is an emerging quasi-1D photovoltaic semiconductor with exceptional photoelectric properties. The low-symmetry chain structure contains complex defects and makes it difficult to improve electrical properties via doping method. This article reports a doping strategy to enhance the efficiency of Sb2(S,Se)3 solar cells by using alkali halide (CsI) as the hydrothermal reaction precursor. It is found that the Cs and I ions are effectively doped and atomically coordinate with Sb ions and S/Se ions. The CsI-doping Sb2(S,Se)3 absorbers exhibit enhanced grain morphologies and reduced trap densities. The consequential CsI-doping Sb2(S,Se)3 based solar cells demonstrate favorable band alignment, suppressed carrier recombination, and improved device performance. An efficiency as high as 10.05% under standard AM1.5 illumination irradiance is achieved. This precursor-based alkali halide doping strategy provides a useful guidance for high-efficiency antimony selenosulfide solar cells.

18.
Small ; : e2403247, 2024 Jul 23.
Artículo en Inglés | MEDLINE | ID: mdl-39039997

RESUMEN

AgSbS2-xSex is a promising light-harvesting material for thin film solar cells, characterized by nontoxicity, high chemical stability, and excellent optoelectronic properties. However, the complex chemical composition of AgSbS2-xSex poses significant challenges to thin film preparation, giving rise to an intensive dependence on multi-step preparation methods. Herein, a hydrothermal method is developed for depositing AgSbS2-xSex films and achieves one-step preparation of this kind of thin film materials for the first time. This method can provide sufficient energy for atomic nucleation and adsorption on the substrate surface to promote nuclei aggregation and grow into films. Meanwhile, it achieves control of the chemical kinetics of the deposition solution by introducing EDTA-2Na as an additive and suppressing the enrichment of Ag2Se impurities at the substrate interface. As a result, a high-purity AgSbS2-xSex film with compact and flat morphology is prepared and assembled into solar cells. The device delivers a power conversion efficiency of 3.04% under standard illumination, which is currently the highest efficiency for AgSbS2-xSex solar cells fabricated by the one-step method. This study provides a facile and promising method for the controllable preparation of high-quality AgSbS2-xSex thin films and promoting their application in solar cells.

19.
Small ; : e2405740, 2024 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-39240005

RESUMEN

Utilizing Diesel Oxidation Catalysts (DOC) to partially oxidize NO to NO2 is a crucial step in controlling NOx emissions from diesel engines. However, enhancing both catalytic activity and hydrothermal stability remains a significant challenge. Benefiting from abundant asymmetric oxygen vacancies and increased Mn4+ content, MnRE0.5Zr0.5 exhibits superior NO oxidation performance (T63 = 337 °C) and hydrothermal aging resistance (T52 = 340 °C) compared to the undoped sample (T53 = 365 °C). XPS, Raman, TPR, and XAS are employed to verify the elevation of oxygen vacancy concentration and Mn valence state modulation due to Zr introduction. Furthermore, compared to MnRE (1.36 eV), the formation energy of oxygen vacancies in MnRE0.5Zr0.5 is significantly reduced (0.17 eV). This work elucidates the dual regulatory role of Zr in the Mn-RE-Zr ternary system, providing theoretical support and guidance for the design of catalysts for atmospheric pollutant purification and industrial catalysis.

20.
Small ; : e2406294, 2024 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-39324306

RESUMEN

MEL type c is crucial for addressing energy and environmental crises, yet efficient synthesis remains a challenge due to thermodynamic and kinetic limitations. In this work, TS-2 as typical zeolite is successfully synthesized with high efficiency (12 h with 92% yield) by introducing titanate acid (TA) 2D nanosheet into a hydrothermal synthesis system. A newly defined TA/TS-2 heterostructure is precisely identified as being incorporated into the zeolite framework via a heterogeneous nucleation mechanism. Ab initio molecular dynamics simulations deeply revealed the nucleation and growth mechanisms of the TA/TS-2 heterostructure. The formation energy barrier of Ti─O─Si structural units (88 kJ mol-1) is much lower than that of Si─O─Si units (119 kJ mol-1), leading to more efficient growth of the Ti─O─Si structure. The polarized electronic properties of Ti─O─Si (negative LUMO orbital and larger polarization) further enhanced the reaction probability and stability of Ti─Si bonding. This obtained TA/TS-2 heterostructure also demonstrated superior activity for photocatalytic production of hydrogen peroxide, which can be attributed to the abundant conductive band holes and narrow bandgap. This research provides an effective strategy for using 2D nanosheets to accelerate zeolite production, as well as an in-depth molecular-level insight into the nucleation and growth processes.

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