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1.
Angew Chem Int Ed Engl ; : e202406750, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38651747

RESUMEN

Electrocatalytic reduction of nitrate to ammonia provides a green alternate to the Haber-Bosch method, yet it suffers from sluggish kinetics and a low yield rate. The nitrate reduction follows a tandem reaction of nitrate reduction to nitrite and subsequent nitrite hydrogenation to generate ammonia, and the ammonia Faraday efficiency (FE) is limited by the competitive hydrogen evolution reaction. Herein, we design a heterostructure catalyst to remedy the above issues, which consists of Ni nanosphere core and Ni(OH)2 nanosheet shell (Ni/Ni(OH)2). In-situ Raman spectroscopy reveals Ni and Ni(OH)2 are interconvertible according to the applied potential, facilitating the cascade nitrate reduction synergistically. Consequently, it attains superior electrocatalytic nitrate reduction performance with an ammonia FE of 98.50% and a current density of 0.934 A cm-2 at -0.476 V versus reversible hydrogen electrode, and exhibits an average ammonia yield rate of 84.74 mg h-1 cm-2 during the 102-hour stability test, which is highly superior to the reported catalysts tested under similar conditions. Density functional theory calculations corroborate the synergistic effect of Ni and Ni(OH)2 in the tandem reaction of nitrate reduction. Moreover, the Ni/Ni(OH)2 catalyst also possesses good capability for methanol oxidation and thus is used to establish a system coupling with nitrate reduction.

2.
Nanoscale ; 16(16): 7786-7824, 2024 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-38568434

RESUMEN

Nanozymes, as a type of nanomaterials with enzymatic catalytic activity, have demonstrated tremendous potential in cancer treatment owing to their unique biomedical properties. However, the heterogeneity of tumors and the complex tumor microenvironment pose significant challenges to the in vivo catalytic efficacy of traditional nanozymes. Drawing inspiration from natural enzymes, scientists are now using biomimetic design to build nanozymes from the ground up. This approach aims to replicate the key characteristics of natural enzymes, including active structures, catalytic processes, and the ability to adapt to the tumor environment. This achieves selective optimization of nanozyme catalytic performance and therapeutic effects. This review takes a deep dive into the use of these biomimetically designed nanozymes in cancer treatment. It explores a range of biomimetic design strategies, from structural and process mimicry to advanced functional biomimicry. A significant focus is on tweaking the nanozyme structures to boost their catalytic performance, integrating them into complex enzyme networks similar to those in biological systems, and adjusting functions like altering tumor metabolism, reshaping the tumor environment, and enhancing drug delivery. The review also covers the applications of specially designed nanozymes in pan-cancer treatment, from catalytic therapy to improved traditional methods like chemotherapy, radiotherapy, and sonodynamic therapy, specifically analyzing the anti-tumor mechanisms of different therapeutic combination systems. Through rational design, these biomimetically designed nanozymes not only deepen the understanding of the regulatory mechanisms of nanozyme structure and performance but also adapt profoundly to tumor physiology, optimizing therapeutic effects and paving new pathways for innovative cancer treatment.


Asunto(s)
Materiales Biomiméticos , Nanoestructuras , Neoplasias , Humanos , Neoplasias/tratamiento farmacológico , Neoplasias/metabolismo , Neoplasias/terapia , Materiales Biomiméticos/química , Materiales Biomiméticos/uso terapéutico , Nanoestructuras/química , Nanoestructuras/uso terapéutico , Catálisis , Antineoplásicos/química , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico , Animales , Microambiente Tumoral/efectos de los fármacos , Biomimética
3.
Heliyon ; 10(3): e24676, 2024 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-38314290

RESUMEN

Enterprises are facing the superimposed challenges of digitalization and greening. The shift from reactive green technology innovation (RGT) to proactive green technology innovation (PGT) has special significance for sustainable economic development. Which strategies will companies choose? Can digital transformation (DT) motivate companies to transform their green innovation strategies? Enterprises' green innovation strategy choices must be explained with regard to digitalization. The purpose of this paper is to reveal how digitalization affects the choice of green innovation strategies and to provide a realistic basis for the sustainable development of heavily polluting enterprises. We formulated a "DT-capability-strategy" theoretical framework incorporating external constraints and internal attitudes to empirically test the microdata of 505 heavily polluting enterprises. The results show that: (1) DT can shift the heavily polluting enterprises' green innovation strategies from RGT to PGT. Endogenous tests and robustness tests support this conclusion. (2) A mechanism test shows that environmental regulations cannot significantly regulate a green innovation strategy. Only a company's capabilities and attitudes can influence PGT but their effects on RGT are not statistically significant. (3) The influence of DT on green innovation strategies shows multi-dimensional heterogeneity in the digital infrastructure, scale, and innovation level of the enterprise. The conclusions provide implications for enterprises to integrate their digital and green behaviors.

4.
Nat Commun ; 15(1): 1116, 2024 Feb 06.
Artículo en Inglés | MEDLINE | ID: mdl-38321072

RESUMEN

Stretchable electronics that prevalently adopt chemically inert metals as sensing layers and interconnect wires have enabled high-fidelity signal acquisition for on-skin applications. However, the weak interfacial interaction between inert metals and elastomers limit the tolerance of the device to external friction interferences. Here, we report an interfacial diffusion-induced cohesion strategy that utilizes hydrophilic polyurethane to wet gold (Au) grains and render them wrapped by strong hydrogen bonding, resulting in a high interfacial binding strength of 1017.6 N/m. By further constructing a nanoscale rough configuration of the polyurethane (RPU), the binding strength of Au-RPU device increases to 1243.4 N/m, which is 100 and 4 times higher than that of conventional polydimethylsiloxane and styrene-ethylene-butylene-styrene-based devices, respectively. The stretchable Au-RPU device can remain good electrical conductivity after 1022 frictions at 130 kPa pressure, and reliably record high-fidelity electrophysiological signals. Furthermore, an anti-friction pressure sensor array is constructed based on Au-RPU interconnect wires, demonstrating a superior mechanical durability for concentrated large pressure acquisition. This chemical modification-free approach of interfacial strengthening for chemically inert metal-based stretchable electronics is promising for three-dimensional integration and on-chip interconnection.

5.
ACS Appl Mater Interfaces ; 15(51): 59454-59462, 2023 Dec 27.
Artículo en Inglés | MEDLINE | ID: mdl-38102993

RESUMEN

Atomically dispersed single-atom catalysts are intriguing catalysts in the field of electrocatalysis for nearly 100% exploitation of metal atoms. However, they are still far from practical usage due to the scaling relationship limit and metal loading limit. Generation of a diatomic complex would offer superior catalytic performance through the cooperation of two neighboring atoms as active sites. Herein, Fe/Co dual atomic sites embedded in a tube-on-plate hollow structure are designed and fabricated for an efficient electrochemical oxygen reduction reaction (ORR). The unique structure composed of ultrathin nanotube building blocks dramatically maximizes the surface area for copious active site exposure. Thanks to the synergetic interaction between Fe/Co pairs, the obtained FeCo/NC exhibits outstanding ORR activity and stability in alkaline media. Furthermore, density functional theory calculations have revealed that the remarkable activity is attributed to the electron-deficient Fe sites in FeCoN6. This work may pave the way for the innovative design of highly dispersed dual-site catalysts for broader applications in the realm of electrochemical catalysis.

7.
Nano Lett ; 23(4): 1573-1581, 2023 Feb 22.
Artículo en Inglés | MEDLINE | ID: mdl-36724081

RESUMEN

Metal-oxygen bonds significantly affect the oxygen reaction kinetics of metal oxide-based catalysts but still face the bottlenecks of limited cognition and insufficient regulation. Herein, we develop a unique strategy to accurately tailor metal-oxygen bond structure via amorphous/crystalline heterojunction realized by ion-exchange. Compared with pristine amorphous CoSnO3-y, iron ion-exchange induced amorphous/crystalline structure strengthens the Sn-O bond, weakens the Co-O bond strength, and introduces additional Fe-O bond, accompanied by abundant cobalt defects and optimal oxygen defects with larger pore structure and specific surface area. The optimization of metal-oxygen bond structure is dominated by the introduction of crystal structure and further promoted by the introduction of Fe-O bond and rich Co defect. Remarkably, the Fe doped amorphous/crystalline catalyst (Co1-xSnO3-y-Fe0.021-A/C) demonstrates excellent oxygen evolution reaction and oxygen reduction reaction activities with a smaller potential gap (ΔE = 0.687 V), and the Zn-air battery based with Co1-xSnO3-y-Fe0.021-A/C exhibits excellent output power density, cycle performance, and flexibility.

8.
Small ; 18(17): e2106396, 2022 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-35344277

RESUMEN

Control of structural ordering in noble metals is very important for the exploration of their properties and applications, and thus it is highly desired to have an in-depth understanding of their structural transitions. Herein, through high-pressure treatment, the mutual transformations between crystalline and amorphous phases are achieved in Pd nanosheets (NSs) and nanoparticles (NPs). The amorphous domains in the amorphous/crystalline Pd NSs exhibit pressure-induced crystallization (PIC) phenomenon, which is considered as the preferred structural response of amorphous Pd under high pressure. On the contrary, in the spherical crystalline@amorphous core-shell Pd NPs, pressure-induced amorphization (PIA) is observed in the crystalline core, in which the amorphous-crystalline phase boundary acts as the initiation site for the collapse of crystalline structure. The distinct PIC and PIA phenomena in two different heterophase Pd nanostructures might originate from the different characteristics of Pd NSs and NPs, including morphology, amorphous-crystalline interface, and lattice parameter. This work not only provides insights into the phase transition mechanisms of amorphous/crystalline heterophase noble metal nanostructures, but also offers an alternative route for engineering noble metals with different phases.

9.
Soft Matter ; 18(13): 2522-2527, 2022 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-35311841

RESUMEN

The electrochemical performance and safe operation of the separator plays an important role in lithium-ion batteries. The introduction of inorganic nanoparticles into the separators with organic matter as the matrix effectively improves the thermal stability and wettability of the composite separators, but it also blocks some pores and adversely affects the electrochemical performance. Herein, vermiculite and laponite nanoparticles are introduced into a poly(vinylidene fluoride) matrix to prepare organic-inorganic composite separators for lithium-ion batteries and the synergistic effect of the two inorganic nanofillers is explored. By adding the same amount of the two nanoparticles into the polymer matrix, the prepared separator has the highest ionic conductivity (0.72 mS cm-1) at room temperature and the lowest interfacial impedance (283 Ω). It has an initial discharge capacity of 161.2 mA h g-1 at a rate of 0.5C, a coulombic efficiency of 99.5% after 100 cycles, and a high capacity retention rate of 98.4%, which shows excellent rate performance. The results show that the two clay nanoparticles exert their respective advantages and exhibit a synergistic enhancement effect on the battery performance, which inspires new ideas for the preparation of new organic-inorganic composite separators.

10.
Adv Mater ; 34(1): e2106115, 2022 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-34601769

RESUMEN

The crystal phase of nanomaterials is one of the key parameters determining their physicochemical properties and performance in various applications. However, it still remains a great challenge to synthesize nanomaterials with different crystal phases while maintaining the same composition, size, and morphology. Here, a facile, one-pot, wet-chemical method is reported to synthesize Pd3 Sn nanorods with comparable size and morphology but different crystal phases, that is, an ordered intermetallic and a disordered alloy with L12 and face-centered cubic (fcc) phases, respectively. The crystal phase of the as-synthesized Pd3 Sn nanorods is easily tuned by altering the types of tin precursors and solvents. Moreover, the approach can also be used to synthesize ternary PdCuSn nanorods with the L12 crystal phase. When used as electrocatalysts, the L12 Pd3 Sn nanorods exhibit superior electrocatalytic performance toward the ethanol oxidation reaction (EOR) compared to their fcc counterpart. Impressively, compared to the L12 Pd3 Sn nanorods, the ternary L12 PdCuSn nanorods exhibit more enhanced electrocatalytic performance toward the EOR, yielding a high mass current density up to 6.22 A mgPd -1 , which is superior to the commercial Pd/C catalyst and among the best reported Pd-based EOR electrocatalysts.

11.
J Mol Graph Model ; 110: 108069, 2022 01.
Artículo en Inglés | MEDLINE | ID: mdl-34773872

RESUMEN

Chiral organophosphorus agents are distributed ubiquitously in the environment, but the neuroactivity of these asymmetric chemicals to humans remains uncertain. This scenario was to explore the stereoselective neurobiological response of human acetylcholinesterase (AChE) to chiral pyraclofos at the enantiomeric scale, and then decipher the microscopic basis of enantioselective neurotoxicity of pyraclofos enantiomers. The results indicated that (R)-/(S)-pyraclofos can form the bioconjugates with AChE with a stoichiometric ratio of 1:1, but the neuronal affinity of (R)-pyraclofos (K = 6.31 × 104 M-1) with AChE was larger than that of (S)-pyraclofos (K = 1.86 × 104 M-1), and significant enantioselectivity was existed in the biochemical reaction. The modes of neurobiological action revealed that pyraclofos enantiomers were situated at the substrate binding domain, and the strength of the overall noncovalent bonds between (S)-pyraclofos and the residues was weaker than that of (R)-pyraclofos, resulting in the high inhibitory effect of (R)-pyraclofos toward the activity of AChE. Dynamic enantioselective biointeractions illustrated that the intervention of inherent conformational flexibility in the AChE-(R)-pyraclofos was greater than that of the AChE-(S)-pyraclofos, which arises from the big spatial displacement and the conformational flip of the binding domain composed of the residues Thr-64~Asn-89, Gly-122~Asp-134, and Thr-436~Tyr-449. Energy decomposition exhibited that the Gibbs free energies of the AChE-(R)-/(S)-pyraclofos were ΔG° = ï¼37.4/-30.2 kJ mol-1, respectively, and the disparity comes from the electrostatic energy during the stereoselective neurochemical reactions. Quantitative conformational analysis further confirmed the atomic-scale computational chemistry conclusions, and the perturbation of (S)-pyraclofos on the AChE's ordered conformation was lower than that of (R)-pyraclofos, which is germane to the interaction energies of the crucial residues, e.g. Tyr-124, Tyr-337, Asp-74, Trp-86, and Tyr-119. Evidently, this attempt will contribute mechanistic information to uncovering the neurobiological effects of chiral organophosphates on the body.


Asunto(s)
Acetilcolinesterasa , Simulación de Dinámica Molecular , Acetilcolinesterasa/metabolismo , Inhibidores de la Colinesterasa , Humanos , Simulación del Acoplamiento Molecular , Organotiofosfatos , Análisis Espectral , Estereoisomerismo
12.
Nanoscale ; 14(2): 289-298, 2022 Jan 06.
Artículo en Inglés | MEDLINE | ID: mdl-34932057

RESUMEN

Reservoir computing (RC), as a brain-inspired neuromorphic computing algorithm, is capable of fast and energy-efficient temporal data analysis and prediction. Hardware implementation of RC systems can significantly reduce the computing time and energy, but it is hindered by current physical devices. Recently, dynamic memristors have proved to be promising for hardware implementation of such systems, benefiting from their fast and low-energy switching, nonlinear dynamics, and short-term memory behavior. In this work, we review striking results that leverage dynamic memristors to enhance the data processing abilities of RC systems based on resistive switching devices and magnetoresistive devices. The critical characteristic parameters of memristors affecting the performance of RC systems, such as reservoir size and decay time, are identified and discussed. Finally, we summarize the challenges this field faces in reliable and accurate task processing, and forecast the future directions of RC systems.

13.
Small Methods ; 5(11): e2100871, 2021 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-34927975

RESUMEN

Electrolyzers coupling electrocatalytic hydrogen evolution with oxidation reactions of small organic molecules have the merits of reducing cell voltage and generating high-value products. Herein, an electrolyzer is designed and optimized that can simultaneously achieve efficient hydrogen generation at the cathode, CO2 absorption by the catholyte, and methanol upgrading to formate at the anode. For these purposes, transition metal phosphides are used as the low-cost catalysts. The unique electrolyzer exhibits a low working voltage of 1.1 V at 10 mA cm-2 . Under optimal conditions, the Faraday efficiencies of hydrogen evolution and formic acid conversion reactions, which are the reaction products at the cathode and anode, respectively, are nearly 100% at various current densities from 10 to 400 mA cm-2 . Meanwhile, the CO2 absorption rate is about twice that of the hydrogen generation rate, which is close to the theoretical value. An innovative and energy-efficient strategy is presented in this work to realize simultaneous hydrogen production and CO2 capture based on low-cost catalyst materials.

14.
J Colloid Interface Sci ; 602: 859-867, 2021 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-34171750

RESUMEN

Aqueous zinc-ion batteries are recognized as one of the most potential neutral aqueous batteries because of the high energy density, high specific capacity, low cost, and low pollution. However, the applications of zinc-ion batteries are seriously limited by the capacity fading, easy-corrosion, side reaction, and hydrogen evolution. Herein, we report a uniform halloysite nanotubes (HNTs) coating which can guide Zn2+ ions stripping/plating on the HNTs/Zn interfaces and protect the Zn anode. The HNTs coating significantly suppresses the corrosion of Zn anode and effectively reduces the hydrogen evolution and the formation of by-product. Furthermore, the HNTs-Zn anode exhibits lower resistance than bare Zn. Compared with the bare Zn anode batteries, HNTs-Zn/MnO2 batteries exhibit good capacity retention and can increase the discharge capacity to 79% at 3 C after 400 cycles. The novel design of interfacial coating based on halloysite nanotubes through electrophoretic deposition method provides a new way to fabricate economic and stable aqueous zinc-ion batteries.

15.
Sci Adv ; 7(13)2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-33762332

RESUMEN

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H2O in the HER.

16.
J Am Chem Soc ; 143(11): 4387-4396, 2021 Mar 24.
Artículo en Inglés | MEDLINE | ID: mdl-33703893

RESUMEN

Phase engineering of nanomaterials (PEN) enables the preparation of metal nanomaterials with unconventional phases that are different from their thermodynamically stable counterparts. These unconventional-phase nanomaterials can serve as templates to construct precisely controlled metallic heterostructures for wide applications. Nevertheless, how the unconventional phase of templates affects the nucleation and growth of secondary metals still requires systematic explorations. Here, two-dimensional (2D) square-like Au nanosheets with an unconventional 2H/face-centered cubic (fcc) heterophase, composing of two pairs of opposite edges with 2H/fcc heterophase and fcc phase, respectively, and two 2H/fcc heterophase basal planes, are prepared and then used as templates to grow one-dimensional (1D) Rh nanorods. The effect of different phases in different regions of the Au templates on the overgrowth of Rh nanorods has been systematically investigated. By tuning the reaction conditions, three types of 1D/2D Rh-Au heterostructures are prepared. In the type A heterostructure, Rh nanorods only grow on the fcc defects including stacking faults and/or twin boundaries (denoted as fcc-SF/T) and 2H phases in two 2H/fcc edges of the Au nanosheet. In the type B heterostructure, Rh nanorods grow on the fcc-SF/T and 2H phases in two 2H/fcc edges and two 2H/fcc basal planes of the Au nanosheet. In the type C heterostructure, Rh nanorods grow on four edges and two basal planes of the Au nanosheet. Furthermore, the type C heterostructure shows promising performance toward the electrochemical hydrogen evolution reaction (HER) in acidic media, which is among the best reported Rh-based and other noble-metal-based HER electrocatalysts.

17.
Adv Mater ; 33(9): e2006711, 2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-33491810

RESUMEN

Heterogeneous noble-metal-based catalysis plays an essential role in the production of fine chemicals. Rh-based catalysts are one of the most active candidates for indole synthesis. However, it is still highly desired to develop heterogeneous Rh-based catalysts with high activity and selectivity. In this work, a general, facile wet-chemical method is reported to synthesize ultrathin amorphous/crystalline heterophase Rh and Rh-based bimetallic alloy nanosheets (NSs), including RhCu, RhZn, and RhRu. Impressively, the amorphous/crystalline heterophase Rh NSs exhibit enhanced catalytic activity toward the direct synthesis of indole compared to the crystalline counterpart. Importantly, the obtained amorphous/crystalline heterophase RhCu alloy NSs can further enhance the selectivity to indole of >99.9% and the conversion is 100%. This work demonstrates the importance of phase engineering and metal alloying in the rational design and synthesis of tandem heterogeneous catalysts toward fine chemical synthesis.

18.
Adv Mater ; 33(1): e2007140, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33241576

RESUMEN

Phase engineering of nanomaterials is an effective strategy to tune the physicochemical properties of nanomaterials for various promising applications. Herein, by using the 4H-Au nanoribbons as templates, four novel magnetic nanostructures, namely 4H-Au @ 14H-Co nanobranches, 4H-Au @ 14H-Co nanoribbons, 4H-Au @ 2H-Co nanoribbons, and 4H-Au @ 2H-Ni nanoribbons, are synthesized based on the quasi-epitaxial growth. Different from the conventional epitaxial growth of metal nanomaterials, the obtained Co and Ni nanostructures possess different crystal phases from the Au template. Due to the large lattice mismatch between Au and the grown metals (i.e., Co and Ni), ordered misfit dislocations are generated at the Co/Au and Ni/Au interfaces. Notably, a new super-structure of Co is formed, denoted as 14H. Both 4H-Au @ 14H-Co nanobranches and nanoribbons are ferromagnetic at room temperature, showing similar Curie temperature. However, their magnetic behaviors exhibit distinct temperature dependence, resulting from the competition between spin and volume fluctuations as well as the unique geometry. This work paves the way to the templated synthesis of nanomaterials with unconventional crystal phases for the exploration of phase-dependent properties.

19.
Spectrochim Acta A Mol Biomol Spectrosc ; 249: 119286, 2021 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-33340959

RESUMEN

Low-weight components of coal macromolecule were subjected to pyrolysis and condensation when magmatic rock intruded into coal measure, eventually, the residual condensed aromatic components can transform into microcrystalline graphite (coaly graphite). To study the structural transformation from anthracite to natural coaly graphite, ten samples with different graphitization degrees from Xinhua and Lutang of Hunan Province, China were characterized by organic geochemical analysis, X-ray diffraction (XRD), Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM). The geochemical parameters (proximate and ultimate analyses) and structural features (XRD, Raman, and HRTEM) of the series naturally graphitized coals exhibit a progressive change as the samples' locations closing to the intrusion. The series naturally graphitized coal samples were classified into four categories, including anthracite, meta-anthracite, semi-graphite, and coaly graphite. But, single parameter cannot classify the series metamorphosed coals well, multi parameters including ash free-basis volatile matter, petrographic features, and carbon structural parameters (based on XRD and Raman spectroscopy) should be considered, additionally, the lattice fringe change observed under HRTEM from anthracite to coaly graphite can verify for the classification. The relatively lower metamorphic grade samples (anthracite and meta-anthracite) have small crystalline sizes, prominent disorders, and amorphous carbon structure, whereas the crystallite structure of highest grade samples (coaly graphite) is three-dimensional crystalline order (testified by XRD and HRTEM), indicating a totally structural transformation from amorphous carbon of anthracite to highly ordered crystalline carbon of coaly graphite in the course of natural graphitization. The carbon structural evolution of coal under natural graphitization process will probably be helpful for synthetic graphite using coal to replace the expensive petroleum coke in the future.

20.
J Am Chem Soc ; 142(44): 18971-18980, 2020 11 04.
Artículo en Inglés | MEDLINE | ID: mdl-33086784

RESUMEN

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO2RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochemical cells.

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