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1.
Proc Natl Acad Sci U S A ; 121(43): e2411613121, 2024 Oct 22.
Artículo en Inglés | MEDLINE | ID: mdl-39418306

RESUMEN

Hydraulic energy is a key component of the global energy mix, yet there exists no practical way of harvesting it at small scales, from flows with low Reynolds number. This has triggered a search for alternative hydroelectric conversion methodologies, leading to unconventional proposals based on droplet triboelectricity, water evaporation, osmotic energy, or flow-induced ionic Coulomb drag. Yet, these approaches systematically rely on ions as intermediate charge carriers, limiting the achievable power density. Here, we predict that the kinetic energy of small-scale "waste" flows can be directly and efficiently converted into electricity thanks to the hydroelectronic drag effect, by which an ion-free liquid induces an electronic current in the solid wall along which it flows. This effect originates in the fluctuation-induced coupling between fluid motion and electron transport. We develop a nonequilibrium thermodynamic formalism to assess the efficiency of such hydroelectric energy conversion, dubbed hydronic energy. We find that hydronic energy conversion is analogous to thermoelectricity, with the efficiency being controlled by a dimensionless figure of merit. However, in contrast to its thermoelectric analogue, this figure of merit combines independently tunable parameters of the solid and the liquid, and can thus significantly exceed unity. Our findings suggest strategies for blue energy harvesting without electrochemistry, and for waste flow mitigation in membrane-based filtration processes.

2.
Proc Natl Acad Sci U S A ; 121(14): e2318777121, 2024 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-38547057

RESUMEN

A concept of solar energy convertible zinc-air battery (SZAB) is demonstrated through rational design of an electrode coupled with multifunction. The multifunctional electrode is fabricated using nitrogen-substituted graphdiyne (N-GDY) with large π-conjugated carbonous network, which can work as photoresponsive bifunctional electrocatalyst, enabling a sunlight-promoted process through efficient injection of photoelectrons into the conduction band of N-GDY. SZAB enables direct conversion and storage of solar energy during the charging process. Such a battery exhibits a lowered charge voltage under illumination, corresponding to a high energy efficiency of 90.4% and electric energy saving of 30.3%. The battery can display a power conversion efficiency as high as 1.02%. Density functional theory calculations reveal that the photopromoted oxygen evolution reaction kinetics originates from the transition from the alkyne bonds to double bonds caused by the transfer of excited electrons, which changes the position of highest occupied molecular orbital and lowest unoccupied molecular orbital, thus greatly promoting the formation of intermediates to the conversion process. Our findings provide conceptual and experimental confirmation that batteries are charged directly from solar energy without the external solar cells, providing a way to manufacture future energy devices.

3.
Proc Natl Acad Sci U S A ; 120(38): e2311412120, 2023 Sep 19.
Artículo en Inglés | MEDLINE | ID: mdl-37695893

RESUMEN

I propose that there exists in natural and artificial environments a class of resonant oscillations that can be excited directly by a steady, zero-frequency force such as that of wind, water, electric field. A member of this class comprises two normally independent oscillating modes of a system, for example, a building or bridge, which, separately, cannot be driven by a zero-frequency force. Agreeing on terms of collaboration, the two modes engage in a joint oscillation powered by the steady zero-frequency force in which they drive each other, one directly and the other parametrically. I observed a bimodal vibration belonging to this class in a home shower where the two modes are the pendulum excursion and the torsional twisting of a freely suspended showerhead which break into a joint oscillation above a threshold value of the water flow rate. I advance a theoretical model which predicts and explains the main features of the observations. The model constitutes an extension to two modes of a proposal and demonstration in 1883 by Lord Rayleigh and Michael Faraday for the excitation of a single resonant mode by modulating a system parameter at twice the resonance frequency. The proposal is credited with the launching of parametric physics. The Experiments section of this report consists of three linked video clips photographed in the home shower which support the basic theoretical assumptions. The ubiquity of zero-frequency forces, such as that of wind, and their direct conversion to alternating on-resonance system vibrations endows the class with an amplified destructive potential with implications for structural stability.

4.
Proc Natl Acad Sci U S A ; 120(15): e2220333120, 2023 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-37011201

RESUMEN

Hot carrier-based energy conversion systems could double the efficiency of conventional solar energy technology or drive photochemical reactions that would not be possible using fully thermalized, "cool" carriers, but current strategies require expensive multijunction architectures. Using an unprecedented combination of photoelectrochemical and in situ transient absorption spectroscopy measurements, we demonstrate ultrafast (<50 fs) hot exciton and free carrier extraction under applied bias in a proof-of-concept photoelectrochemical solar cell made from earth-abundant and potentially inexpensive monolayer (ML) MoS2. Our approach facilitates ultrathin 7 Å charge transport distances over 1 cm2 areas by intimately coupling ML-MoS2 to an electron-selective solid contact and a hole-selective electrolyte contact. Our theoretical investigations of the spatial distribution of exciton states suggest greater electronic coupling between hot exciton states located on peripheral S atoms and neighboring contacts likely facilitates ultrafast charge transfer. Our work delineates future two-dimensional (2D) semiconductor design strategies for practical implementation in ultrathin photovoltaic and solar fuel applications.

5.
Proc Natl Acad Sci U S A ; 120(26): e2303262120, 2023 Jun 27.
Artículo en Inglés | MEDLINE | ID: mdl-37339215

RESUMEN

Graphene nanoribbons (GNRs) are widely recognized as intriguing building blocks for high-performance electronics and catalysis owing to their unique width-dependent bandgap and ample lone pair electrons on both sides of GNR, respectively, over the graphene nanosheet counterpart. However, it remains challenging to mass-produce kilogram-scale GNRs to render their practical applications. More importantly, the ability to intercalate nanofillers of interest within GNR enables in-situ large-scale dispersion and retains structural stability and properties of nanofillers for enhanced energy conversion and storage. This, however, has yet to be largely explored. Herein, we report a rapid, low-cost freezing-rolling-capillary compression strategy to yield GNRs at a kilogram scale with tunable interlayer spacing for situating a set of functional nanomaterials for electrochemical energy conversion and storage. Specifically, GNRs are created by sequential freezing, rolling, and capillary compression of large-sized graphene oxide nanosheets in liquid nitrogen, followed by pyrolysis. The interlayer spacing of GNRs can be conveniently regulated by tuning the amount of nanofillers of different dimensions added. As such, heteroatoms; metal single atoms; and 0D, 1D, and 2D nanomaterials can be readily in-situ intercalated into the GNR matrix, producing a rich variety of functional nanofiller-dispersed GNR nanocomposites. They manifest promising performance in electrocatalysis, battery, and supercapacitor due to excellent electronic conductivity, catalytic activity, and structural stability of the resulting GNR nanocomposites. The freezing-rolling-capillary compression strategy is facile, robust, and generalizable. It renders the creation of versatile GNR-derived nanocomposites with adjustable interlay spacing of GNR, thereby underpinning future advances in electronics and clean energy applications.

6.
Biochem J ; 481(7): 499-514, 2024 Apr 10.
Artículo en Inglés | MEDLINE | ID: mdl-38572757

RESUMEN

Respiratory complex I is a redox-driven proton pump. Several high-resolution structures of complex I have been determined providing important information about the putative proton transfer paths and conformational transitions that may occur during catalysis. However, how redox energy is coupled to the pumping of protons remains unclear. In this article, we review biochemical, structural and molecular simulation data on complex I and discuss several coupling models, including the key unresolved mechanistic questions. Focusing both on the quinone-reductase domain as well as the proton-pumping membrane-bound domain of complex I, we discuss a molecular mechanism of proton pumping that satisfies most experimental and theoretical constraints. We suggest that protonation reactions play an important role not only in catalysis, but also in the physiologically-relevant active/deactive transition of complex I.


Asunto(s)
Complejo I de Transporte de Electrón , Protones , Complejo I de Transporte de Electrón/química , Complejo I de Transporte de Electrón/metabolismo , Antiportadores/metabolismo , Electrones , Simulación de Dinámica Molecular , Oxidación-Reducción , Benzoquinonas
7.
Proc Natl Acad Sci U S A ; 119(36): e2206946119, 2022 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-36037378

RESUMEN

Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in seawater electrolysis reactions. In this report, the heterostructures of graphdiyne-RhOx-graphdiyne (GDY/RhOx/GDY) were constructed by in situ-controlled growth of GDY on RhOx nanocrystals. A double layer interface of sp-hybridized carbon-oxide-Rhodium (sp-C∼O-Rh) was formed in this system. The microstructures at the interface are composed of active sites of sp-C∼O-Rh. The obvious electron-withdrawing surface enhances the catalytic activity with orders of magnitude, while the GDY outer of the metal oxides guarantees the stability. The electron-donating and withdrawing sp-C∼O-Rh structures enhance the catalytic activity, achieving high-performance overall seawater electrolysis with very small cell voltages of 1.42 and 1.52 V at large current densities of 10 and 500 mA cm-2 at room temperatures and ambient pressures, respectively. The compositional and structural superiority of the GDY-derived sp-C-metal-oxide active center offers great opportunities to engineer tunable redox properties and catalytic performance for seawater electrolysis and beyond. This is a typical successful example of the rational design of catalytic systems.

8.
Proc Natl Acad Sci U S A ; 119(27): e2123090119, 2022 07 05.
Artículo en Inglés | MEDLINE | ID: mdl-35759670

RESUMEN

Energy-converting NADH:ubiquinone oxidoreductase, respiratory complex I, is essential for cellular energy metabolism coupling NADH oxidation to proton translocation. The mechanism of proton translocation by complex I is still under debate. Its membrane arm contains an unusual central axis of polar and charged amino acid residues connecting the quinone binding site with the antiporter-type subunits NuoL, NuoM, and NuoN, proposed to catalyze proton translocation. Quinone chemistry probably causes conformational changes and electrostatic interactions that are propagated through these subunits by a conserved pattern of predominantly lysine, histidine, and glutamate residues. These conserved residues are thought to transfer protons along and across the membrane arm. The distinct charge distribution in the membrane arm is a prerequisite for proton translocation. Remarkably, the central subunit NuoM contains a conserved glutamate residue in a position that is taken by a lysine residue in the two other antiporter-type subunits. It was proposed that this charge asymmetry is essential for proton translocation, as it should enable NuoM to operate asynchronously with NuoL and NuoN. Accordingly, we exchanged the conserved glutamate in NuoM for a lysine residue, introducing charge symmetry in the membrane arm. The stably assembled variant pumps protons across the membrane, but with a diminished H+/e- stoichiometry of 1.5. Thus, charge asymmetry is not essential for proton translocation by complex I, casting doubts on the suggestion of an asynchronous operation of NuoL, NuoM, and NuoN. Furthermore, our data emphasize the importance of a balanced charge distribution in the protein for directional proton transfer.


Asunto(s)
Membrana Celular , Complejo I de Transporte de Electrón , Proteínas de Escherichia coli , NADH Deshidrogenasa , Sustitución de Aminoácidos , Membrana Celular/química , Secuencia Conservada , Complejo I de Transporte de Electrón/química , Complejo I de Transporte de Electrón/genética , Proteínas de Escherichia coli/química , Proteínas de Escherichia coli/genética , Glutamatos/química , Glutamatos/genética , Lisina/química , Lisina/genética , NADH Deshidrogenasa/química , NADH Deshidrogenasa/genética , Protones , Quinonas/química
9.
Nano Lett ; 24(35): 10987-10994, 2024 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-39171754

RESUMEN

Plasmonic nanomaterials such as Au, Ag, and Cu are widely recognized for their strong light-matter interactions, making them promising photothermal materials for solar steam generation. However, their practical use in water evaporation is significantly limited by the trade-off between high costs and poor stability. In this regard, we introduce a novel, nonmetallic dual plasmonic TiN/MoO3-x composite. This composite features a three-dimensional, urchin-like biomimetic structure, with plasmonic TiN nanoparticles embedded within a network of plasmonic MoO3-x nanorods. As a solar absorber, the TiN/MoO3-x composite achieves a high evaporation rate of ∼2.05 kg m-2 h-1 with an energy efficiency up to 106.7% under 1 sun illumination, outperforming the state-of-the-art plasmonic systems. The high photothermal stability and unique dual plasmonic nanostructure of the TiN/MoO3-x composite are demonstrated by advanced in situ laser-heating transmission electron microscopy and photon-induced near-field electron microscopy/electron energy-loss spectroscopy, respectively. This work provides new inspiration for the design of plasmonic materials.

10.
Nano Lett ; 24(6): 1916-1922, 2024 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-38215312

RESUMEN

Electrochemistry has extended from reactions at solid/liquid interfaces to those at solid/solid interfaces. However, photoelectrochemistry at solid/solid interfaces has been hardly reported. In this study, we achieve a stable photoelectrochemical reaction at the semiconductor-electrode/solid-electrolyte interface in a Nb-doped anatase-TiO2 (a-TiO2:Nb)/Li3PO4 (LPO)/Li all-solid-state cell. The oxidative currents of a-TiO2:Nb/LPO/Li increase upon light irradiation when a-TiO2:Nb is located at a potential that is more positive than its flat-band potential. This is because the photoexcited electrons migrate to the current collector due to the bending of the conduction band minimum toward the negative potential. The photoelectrochemical reaction at the semiconductor/solid-electrolyte interface is driven by the same principle as those at semiconductor/liquid-electrolyte interfaces. Moreover, oxidation under light irradiation exhibits reversibility with reduction in the dark. Thus, we extend photoelectrochemistry to all-solid-state systems composed of solid/solid interfaces. This extension would enable us to investigate photoelectrochemical phenomena uncleared at solid/liquid interfaces because of low stability and durability.

11.
Small ; 20(28): e2310099, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38342694

RESUMEN

Metal telluride (MTe)-based nanomaterials have emerged as a potential alternative for efficient, highly conductive, robust, and durable electrodes in energy storage/conversion applications. Significant progress in the material development of MTe-based electrodes is well-sought, from the synthesis of its nanostructures, integration of MTes with supporting materials, synthesis of their hybrid morphologies, and their implications in energy storage/conversion systems. Herein, an extensive exploration of the recent advancements and progress in MTes-based nanomaterials is reviewed. This review emphasizes elucidating the fundamental properties of MTes and providing a systematic compilation of its wet and dry synthesis methods. The applications of MTes are extensively summarized and discussed, particularly, in energy storage and conversion systems including batteries (Li-ion, Zn-ion, Li-S, Na-ion, K-ion), supercapacitor, hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and CO2 reduction. The review also emphasizes the future prospects and urgent challenges to be addressed in the development of MTes, providing knowledge for researchers in utilizing MTes in energy storage and conversion technologies.

12.
Small ; 20(33): e2311684, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38533989

RESUMEN

Carbonate-superstructured solid fuel cells (CSSFCs) are an emerging type of fuel cells with high flexibility of fuels. However, using ethane fuel for solid fuel cells is a great challenge due to serious degradation of their anodes. Herein, this critical issue is solved by creating a novel gradient functional layer anode for CSSFCs. First, a finer-scale anode with a larger surface area is demonstrated to provide more active sites for the internal reforming reaction of ethane, achieving a 60% higher ethane conversion rate and 40% lower polarization resistance than conventional anodes. Second, incorporating a gradient functional layer into the anode results in an additional 50% enhancement in the peak power density of CSSFCs to a record high value (up to 241 mW cm-2) with dry ethane fuel at a low temperature of 550 °C, which is even comparable to the power density of conventional solid oxide fuel cells above 700 °C. Furthermore, the CSSFC with the gradient anode exhibits excellent durability for over 200 h. This finding provides a new strategy to develop efficient anodes for hydrocarbon fuels.

13.
Small ; 20(43): e2403162, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-38934346

RESUMEN

Electrocatalysis is a crucial method for achieving global carbon neutrality, serving as an essential means of energy conversion, and electrocatalyst is crucial in the process of electrocatalysis. Because of the abundant active sites, the multi-component synergistic effect of high-entropy materials has a wide application prospect in the field of electrocatalysis. Moreover, due to the special structure of high-entropy materials, it is possible to obtain almost continuous adsorption energy distribution by regulating the composition, which has attracted extensive attention of researchers. This paper reviews the properties and types of high-entropy materials, including alloys and compounds. The synthesis strategies of high-entropy materials are systematically introduced, and the solid phase synthesis, liquid-phase synthesis, and gas-phase synthesis are classified and summarized. The application of high-entropy materials in electrocatalysis is summarized, and the promotion effect of high-entropy strategy in various catalytic reaction processes is summarized. Finally, the current progress of high-entropy materials, the problems encountered, and the future development direction are reviewed. It is emphasized that the strategy of high flux density functional theory calculation guiding high-entropy catalyst design will be of great significance to electrocatalysis.

14.
Small ; : e2405870, 2024 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-39396387

RESUMEN

2D transition metal borides (MBenes) have garnered significant attention from researchers due to their exceptional electrical conductivity, strong mechanical rigidity, excellent dynamic and thermodynamic stability, which stimulates the enthusiasm of researchers for the study of MBenes. Over the past few years, extensive research efforts have been dedicated to the study of MBenes, resulting in a growing number of synthesis methods being developed. However, there remains a scarcity of comprehensive reviews on MBenes, particularly in relation to the synthesis techniques employed. To address this gap, this review aims to provide a comprehensive summary of the latest research findings on MBenes. An exhaustive exploration of the crystal structure types of MBenes is presented, highlighting the greater structural diversity compared to MXenes. Furthermore, a comprehensive review of the recent advancements in MBenes synthesis methodologies is provided. The review also delves into the physical and chemical properties of MBenes, while elucidating their applications in the realms of energy conversion and energy storage. Lastly, this review concludes by summarizing and offering insights on MBenes from three angles: synthesis, structure-property relationships, and application prospects.

15.
Small ; : e2403347, 2024 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-39118562

RESUMEN

Plastics are widely used in daily lives, but unfortunately, their inadequate recycling practices have led to the accumulation of microplastics in the environment, posing a threat to public health. The existing methods for treating microplastics are energy-intensive and environmentally damaging. In this context, photoreforming has emerged as a sustainable solution to address the microplastic crisis by simultaneously recycling them into value-added chemicals. This review presents a comprehensive overview of the application of photoreforming for upcycling microplastic. The underlying mechanisms of photoreforming reaction are discussed, followed by the exploration of recent advancements and innovative strategies in photoreforming techniques with particular emphasis on their real-world applications and potential for large-scale implementation. Also, critical factors influencing the efficiency of microplastic photoreforming are identified, providing guidance for further research and optimization.

16.
Small ; 20(20): e2309119, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38126651

RESUMEN

Carbon neutrality is an important goal for humanity . As an eco-friendly technology, electrocatalytic clean energy conversion technology has emerged in the 21st century. Currently, metal-organic framework (MOF)-based electrocatalysis, including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR), are the mainstream energy catalytic reactions, which are driven by electrocatalysis. In this paper, the current advanced characterizations for the analyses of MOF-based electrocatalytic energy reactions have been described in details, such as density function theory (DFT), machine learning, operando/in situ characterization, which provide in-depth analyses of the reaction mechanisms related to the above reactions reported in the past years. The practical applications that have been developed for some of the responses that are of application values, such as fuel cells, metal-air batteries, and water splitting have also been demonstrated. This paper aims to maximize the potential of MOF-based electrocatalysts in the field of energy catalysis, and to shed light on the development of current intense energy situations.

17.
Small ; 20(1): e2305009, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37641184

RESUMEN

As a high energy density power system, lithium-carbon dioxide (Li-CO2 ) batteries play an important role in addressing the fossil fuel crisis issues and alleviating the greenhouse effect. However, the sluggish transformation kinetic of CO2 and the difficult decomposition of discharge products impede the achievement of large capacity, small overpotential, and long life span of the batteries, which require exploring efficient catalysts to resolve these problems. In this review, the main focus is on the hot spot regulation strategies of the catalysts, which include the modulation of the active sites, the designing of microstructure, and the construction of composition. The recent progress of promising catalysis with hot spot regulated strategies is systematically addressed. Critical challenges are also presented and perspectives to provide useful guidance for the rational design of highly efficient catalysts for practical advanced Li-CO2 batteries are proposed.

18.
Small ; 20(6): e2305568, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-37752749

RESUMEN

Droplet well-controlled directional motion being an essential function has attracted much interest in academic and industrial applications, such as self-cleaning, micro-/nano-electro-mechanical systems, drug delivery, and heat-transferring. Conventional understanding has it that a droplet impacted on an anisotropic surface tends to bounce along the microstructural direction, which is mainly dictated by surface properties rather than initial conditions. In contrast to previous findings, it demonstrates that the direction of a droplet's rebound on an anisotropic surface can be switched by designing the initial impacting velocity. With an increase in impacting height from 2 to 10 cm, the droplet successively shows a backward, vertical, and forward motion on anisotropic surfaces. Theoretical demonstrations establish that the transition of droplet bouncing on the anisotropic surface is related to its dynamic wettability during impacting process. Characterized by the liquid-solid interaction, it is demonstrated that the contact state at small and large impacting heights induces an opposite resultant force in microstructures. Furthermore, energy balance analysis reveals that the energy conversion efficiency of backward motion is almost three times as that of traditional bouncing. This work, including experiments, theoretical models, and energy balance analysis provides insight view in droplet motions on the anisotropic surfaces and opens a new way for the droplet transport.

19.
Small ; : e2404012, 2024 Jul 18.
Artículo en Inglés | MEDLINE | ID: mdl-39022999

RESUMEN

Despite recent revolutionary advancements in photovoltaic (PV) technology, further improving cell efficiencies toward their Shockley-Queisser (SQ) limits remains challenging due to inherent optical, electrical, and thermal losses. Currently, most research focuses on improving optical and electrical performance through maximizing spectral utilization and suppressing carrier recombination losses, while there is a serious lack of effective opto-electro-thermal coupled management, which, however, is crucial for further improving PV performance and the practical application of PV devices. In this article, the energy conversion and loss processes of a PV device (with a specific focus on perovskite solar cells) are detailed under both steady-state and transient processes through rigorous opto-electro-thermal coupling simulation. By innovatively coupling multi-physical behaviors of photon management, carrier/ion transport, and thermodynamics, it meticulously quantifies and analyzes energy losses across optical, electrical, and thermal domains, identifies heat components amenable to regulation, and proposes specific regulatory means, evaluates their impact on device efficiency and operating temperature, offering valuable insights to advance PV technology for practical applications.

20.
Small ; : e2403996, 2024 Jul 16.
Artículo en Inglés | MEDLINE | ID: mdl-39011953

RESUMEN

Triboelectric nanogenerators (TENGs) as an avant-garde technology that transforms mechanical energy into electrical energy, offering a new direction for green energy and sustainable development. By means of high-efficiency TENGs, conventional materials as new triboelectric materials have exhibited multi-attribute characteristics, achieving innovative applications in the field of micro-nano energy harvesting and self-powered sensing. The progress of TENGs technology with the triboelectric materials is complementary and mutually promoting. On the one hand, one of the cruxes of TENGs lies in the triboelectric materials, which have a decisive impact on their performance. On the other hand, as the research and application of TENGs continue to deepen, higher demands are placed on triboelectric materials, which in turn promotes the advancement of the entire material system as well as the fields of materials science and physics. This work aims to delve into the characteristics, types, preferred choices, and modification treatments of triboelectric materials on the performances of TENGs, hoping to provide guidance and insights for future research and applications.

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