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1.
J Phys Condens Matter ; 34(47)2022 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-36179704

RESUMO

In developing nonvolatile valleytronic devices, ferromagnetic (FM) ferrovalley semiconductors are critically needed due to the existence of spontaneous valley polarization. At present, however, the known real materials have various drawbacks towards practical applications, including the in-plane FM ground state, low Curie temperature (TC), small valley polarization, narrow energy window with clean polarized valley, and indirect bandgap. From first-principles calculations, here we predict anideal ferrovalley semiconductor, honeycomb LaH2monolayer (ML), whose intrinsic properties can overcome all these shortcomings. We demonstrate that LaH2ML, having satisfied structural stability, is a FM half-semiconducting electrene (La3+2H-⋅e-) with its magnetic moments localized at the lattice interstitial sites rather than La atoms. At the same time, LaH2ML holds the following desired attributes: a robust out-of-plane FM ground state with a highTC(334 K), a sizable valley polarization (166 meV), a wide energy window (137 meV) harboring clean single-valley carriers, and a direct bandgap. These results identify a much needed ideal ferrovalley semiconductor candidate, holding the promising application potential in valleytronics and spintronics devices.

2.
Nano Lett ; 22(9): 3591-3597, 2022 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-35439017

RESUMO

Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here, we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of face-centered cubic (fcc)-Pd nanoplate templates with 12 nm plates giving fcc-Ru while 18-26 nm plates result in hexagonal closed-packed (hcp)-Ru. Although Ru overlayers with a metastable fcc- (high in bulk energy) or stable hcp-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp- (high in surface energy) and smooth fcc-facets (low in surface energy), respectively, on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The Pd@fcc-Ru outperforms the Pd@hcp-Ru nanoplates toward ethylene glycol and glycerol oxidation reactions.


Assuntos
Nanopartículas , Oxirredução , Fenômenos Físicos
3.
Adv Mater ; 34(1): e2102591, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34648198

RESUMO

Bimetallic Janus nanocrystals have received considerable interest in recent years owing to their unique properties and niche applications. The side-by-side distribution of two distinct metals provides a flexible platform for tailoring the optical and catalytic properties of nanocrystals. First, a brief introduction to the structural features of bimetallic Janus nanocrystals, followed by an extensive discussion of the synthetic approaches, is given. The strategies and experimental controls for achieving the Janus structure, as well as the mechanistic understandings, are specifically discussed. Then, a number of intriguing properties and applications enabled by the Janus nanocrystals are highlighted. Finally, this article is concluded with future directions and outlooks with respect to both syntheses and applications of this new class of functional nanomaterials.

4.
Angew Chem Int Ed Engl ; 60(36): 19643-19647, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-34128305

RESUMO

We report a simple route based upon seed-mediated growth to the synthesis of Pd@Aux Pd1-x (0.8≤x≤1) core-shell nanocubes. Benefiting from the well-defined {100} facets and an optimal Au/Pd ratio for the surface, the nanocubes bearing a shell made of Au0.95 Pd0.05 work as an efficient electrocatalyst toward H2 O2 production, with high selectivity of 93-100 % in the low-overpotential region of 0.4-0.7 V. When the Au0.95 Pd0.05 alloy is confined to a shell of only three atomic layers in thickness, the electrocatalyst is able to maintain its surface structure and elemental composition, endowing continuous and stable production of H2 O2 during oxygen reduction at a high rate of 1.62 mol g(Pd+Au) -1  h-1 . This work demonstrates a versatile route to the rational development of active and durable electrocatalysts based upon alloy nanocrystals.

5.
J Am Chem Soc ; 143(22): 8509-8518, 2021 06 09.
Artigo em Inglês | MEDLINE | ID: mdl-34043340

RESUMO

Despite extensive efforts devoted to the synthesis of Pt-Co bimetallic nanocrystals for fuel cell and related applications, it remains a challenge to simultaneously control atomic arrangements in the bulk and on the surface. Here we report a synthesis of Pt-Co@Pt octahedral nanocrystals that feature an intermetallic, face-centered tetragonal Pt-Co core and an ultrathin Pt shell, together with the dominance of {111} facets on the surface. When evaluated as a catalyst toward the oxygen reduction reaction (ORR), the nanocrystals delivered a mass activity of 2.82 A mg-1 and a specific activity of 9.16 mA cm-2, which were enhanced by 13.4 and 29.5 times, respectively, relative to the values of a commercial Pt/C catalyst. More significantly, the mass activity of the nanocrystals only dropped 21% after undergoing 30 000 cycles of accelerated durability test, promising an outstanding catalyst with optimal performance for ORR and related reactions.

6.
J Am Chem Soc ; 143(16): 6293-6302, 2021 04 28.
Artigo em Inglês | MEDLINE | ID: mdl-33852314

RESUMO

We report the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds. Specifically, Rh nanocrystals with cubic, cuboctahedral, and octahedral shapes can all be obtained from the same cubic seeds under suitable reduction kinetics for the precursor. The success of such a synthesis also relies on the use of a halide-free precursor to avoid oxidative etching, as well as the involvement of a sufficiently high temperature to remove Br- ions from the seeds while ensuring adequate surface diffusion. The availability of Rh nanocrystals with cubic and octahedral shapes allows for an evaluation of the facet dependences of their thermal and catalytic properties. The data from in situ electron microscopy studies indicate that the cubic and octahedral Rh nanocrystals can keep their original shapes up to 700 and 500 °C, respectively. When tested as catalysts for hydrazine decomposition, the octahedral nanocrystals exhibit almost 4-fold enhancement in terms of H2 selectivity relative to the cubic counterpart. As for ethanol oxidation, the order is reversed, with the cubic nanocrystals being about three times more active than the octahedral sample.

7.
Inorg Chem ; 2021 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-33522790

RESUMO

Improving the performance of noble-metal nanocrystals in various applications critically depends on our ability to manipulate their synthesis in a rational, robust, and controllable fashion. Different from a conventional trial-and-error approach, the reduction kinetics of a colloidal synthesis has recently been demonstrated as a reliable knob for controlling the synthesis of noble-metal nanocrystals in a deterministic and predictable manner. Here we present a brief Viewpoint on the recent progress in leveraging reduction kinetics for controlling and predicting the outcome of a synthesis of noble-metal nanocrystals. With a focus on Pd nanocrystals, we first offer a discussion on the correlation between the initial reduction rate and the internal structure of the resultant seeds. The kinetic approaches for controlling both nucleation and growth in a one-pot setting are then introduced with an emphasis on manipulation of the reduction pathways taken by the precursor. We then illustrate how to extend the strategy into a bimetallic system for the preparation of nanocrystals with different shapes and elemental distributions. Finally, the influence of speciation of the precursor on reduction kinetics is highlighted, followed by our perspectives on the challenges and future endeavors in achieving a controllable and predictable synthesis of noble-metal nanocrystals.

8.
Nano Lett ; 21(5): 2248-2254, 2021 03 10.
Artigo em Inglês | MEDLINE | ID: mdl-33599510

RESUMO

Platinum nanocrystals featuring a multiply twinned structure and uniform sizes below 5 nm are superb catalytic materials, but it is difficult to synthesize such particles owing to the high twin-boundary energy (166 mJ/m2) of Pt. Here, we report a simple route to the synthesis of such nanocrystals by selectively growing them from the vertices of Pd icosahedral seeds. The success of this synthesis critically depends on the introduction of Br- ions to slow the reduction kinetics of the Pt(II) precursor while limiting the surface diffusion of Pt adatoms by conducting the synthesis at 30 °C. Owing to the small size and multiply twinned structure of Pt dots, the as-obtained Pd-Pt nanocrystals show remarkably enhanced activity and durability toward oxygen reduction, with a mass activity of 1.23 A mg-1Pt and a specific activity of 0.99 mA cm-2Pt, which are 8.2 and 4.5 times as high as those of the commercial Pt/C.

9.
Angew Chem Int Ed Engl ; 60(18): 10384-10392, 2021 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-33600031

RESUMO

Janus nanocages with distinctive platinum-group metals on the outer and inner surfaces can naturally catalyze at least two different reactions. Here we report a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages. We have fabricated 11 different types of Janus nanocages characterized by a uniform size and well-defined {100} facets, together with porous, ultrathin, asymmetric walls up to 1.6 nm thick. When tested as dual-electrocatalysts toward oxygen reduction and evolution reactions, the Janus nanocages based on Pt and Ir exhibited superior activities depending on the thickness and relative position of the metal layer. Density functional theory studies suggest that the alloy composition and surface structure of the nanocages both play important roles in enhancing the electrocatalytic activities by modulating the stability of key reaction intermediates.

10.
Nano Lett ; 21(1): 875-886, 2021 01 13.
Artigo em Inglês | MEDLINE | ID: mdl-33395313

RESUMO

Monoclonal antibodies (mAb) have had a transformative impact on treating cancers and immune disorders. However, their use is limited by high development time and monetary cost, manufacturing complexities, suboptimal pharmacokinetics, and availability of disease-specific targets. To address some of these challenges, we developed an entirely synthetic, multivalent, Janus nanotherapeutic platform, called Synthetic Nanoparticle Antibodies (SNAbs). SNAbs, with phage-display-identified cell-targeting ligands on one "face" and Fc-mimicking ligands on the opposite "face", were synthesized using a custom, multistep, solid-phase chemistry method. SNAbs efficiently targeted and depleted myeloid-derived immune-suppressor cells (MDSCs) from mouse-tumor and rat-trauma models, ex vivo. Systemic injection of MDSC-targeting SNAbs efficiently depleted circulating MDSCs in a mouse triple-negative breast cancer model, enabling enhanced T cell and Natural Killer cell infiltration into tumors. Our results demonstrate that SNAbs are a versatile and effective functional alternative to mAbs, with advantages of a plug-and-play, cell-free manufacturing process, and high-throughput screening (HTS)-enabled library of potential targeting ligands.


Assuntos
Nanopartículas Multifuncionais , Células Supressoras Mieloides , Nanopartículas , Animais , Anticorpos Monoclonais , Humanos , Células Matadoras Naturais , Camundongos , Ratos
11.
Angew Chem Int Ed Engl ; 60(4): 1909-1915, 2021 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-33006809

RESUMO

Copper nanostructures are promising catalysts for the electrochemical reduction of CO2 because of their unique ability to produce a large proportion of multi-carbon products. Despite great progress, the selectivity and stability of such catalysts still need to be substantially improved. Here, we demonstrate that controlling the surface oxidation of Cu nanowires (CuNWs) can greatly improve their C2+ selectivity and stability. Specifically, we achieve a faradaic efficiency as high as 57.7 and 52.0 % for ethylene when the CuNWs are oxidized by the O2 from air and aqueous H2 O2 , respectively, and both of them show hydrogen selectivity below 12 %. The high yields of C2+ products can be mainly attributed to the increase in surface roughness and the generation of defects and cavities during the electrochemical reduction of the oxide layer. Our results also indicate that the formation of a relatively thick, smooth oxide sheath can improve the catalytic stability by mitigating the fragmentation issue.

12.
Chem Rev ; 121(2): 649-735, 2021 01 27.
Artigo em Inglês | MEDLINE | ID: mdl-32667792

RESUMO

The successful synthesis of noble-metal nanocrystals with controlled shapes offers many opportunities to not only maneuver their physicochemical properties but also optimize their figures of merit in a wide variety of applications. In particular, heterogeneous catalysis and surface science have benefited enormously from the availability of this new class of nanomaterials as the atomic structure presented on the surface of a nanocrystal is ultimately determined by its geometric shape. The immediate advantages may include significant enhancement in catalytic activity and/or selectivity and substantial reduction in materials cost while providing a well-defined model system for mechanistic study. With a focus on the monometallic system, this review article provides a comprehensive account of recent progress in the development of noble-metal nanocrystals with controlled shapes, in addition to their remarkable performance in a large number of catalytic and electrocatalytic reactions. We hope that this review article offers the impetus and roadmap for the development of next-generation catalysts vital to a broad range of industrial applications.

13.
Acc Chem Res ; 54(1): 1-10, 2021 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-33275422

RESUMO

ConspectusThe last two decades have witnessed the successful development of noble-metal nanocrystals with well-controlled properties for a variety of applications in catalysis, plasmonics, electronics, and biomedicine. Most of these nanocrystals are kinetically controlled products greatly deviated from the equilibrium state defined by thermodynamics. When subjected to elevated temperatures, their arrangements of atoms are expected to undergo various physical transformations, inducing changes to the shape, morphology (hollow vs solid), spatial distribution of elements (segregated vs alloyed/intermetallic), internal structure (twinned vs single-crystal), and crystal phase. In order to optimize the performance of these nanocrystals in various applications, there is a pressing need to understand and improve their thermal stability.By integrating in situ heating with transmission electron microscopy or X-ray diffraction, we have investigated the physical transformations of various types of noble-metal nanocrystals in real time. We have also explored the atomistic detail responsible for a physical transformation using first-principles calculations, providing insightful guidance for the development of noble-metal nanocrystals with augmented thermal stability. Specifically, solid nanocrystals were observed to transform into pseudospherical particles favored by thermodynamics by reducing the surface area while eliminating the facets high in surface energy. For nanocrystals of relatively large in size, a single-crystal lattice was more favorable than a twinned structure. When switching to core-shell nanocrystals, the elevation in temperature caused changes to the elemental distribution in addition to shape transformation. The compositional stability of a core-shell nanocrystal was found to be strongly dependent on the shape and thus the type of facet expressed on the surface. For hollow nanocrystals such as nanocages and nanoframes, their thermal stabilities were typically inferior to the solid counterparts, albeit their unique structure and large specific surface area are highly desired in applications such as catalysis. When a metastable crystal structure was involved, phase transition was also observed at a temperature close to that responsible for shape or compositional change. We hope the principles, methodologies, and mechanistic insights presented in this Account will help the readers achieve a good understanding of the physical transformations that are expected to take place in noble-metal nanocrystals when they are subjected to thermal activation. Such an understanding may eventually lead to the development of effective methods for retarding or even preventing some of the transformations.

14.
J Am Chem Soc ; 143(1): 149-162, 2021 01 13.
Artigo em Inglês | MEDLINE | ID: mdl-33370094

RESUMO

Bimetallic nanocrystals often outperform their monometallic counterparts in catalysis as a result of the electronic coupling and geometric effect arising from two different metals. Here we report a facile synthesis of Pd-Cu Janus nanocrystals with controlled shapes through site-selected growth by reducing the Cu(II) precursor with glucose in the presence of hexadecylamine and Pd icosahedral seeds. Specifically, at a slow reduction rate, the Cu atoms nucleate and grow from one vertex of the icosahedral seed to form a penta-twinned Janus nanocrystal in the shape of a pentagonal bipyramid or decahedron. At a fast reduction rate, in contrast, the Cu atoms can directly nucleate from or diffuse to the edge of the icosahedral seed for the generation of a singly twinned Janus nanocrystal in the shape of a truncated bitetrahedron. The segregation of two elements and the presence of twin boundaries on the surface make the Pd-Cu Janus nanocrystals effective catalysts for the electrochemical reduction of CO2. An onset potential as low as -0.7 VRHE (RHE: reversible hydrogen electrode) was achieved for C2+ products in 0.5 M KHCO3 solution, together with a faradaic efficiency approaching 51.0% at -1.0 VRHE. Density functional theory and Pourbaix phase diagram studies demonstrated that the high CO coverage on the Pd sites (either metallic or hydride form) during electrocatalysis enabled the spillover of CO to the Cu sites toward subsequent C-C coupling, promoting the formation of C2+ species. This work offers insights for the rational fabrication of bimetallic nanocrystals featuring desired compositions, shapes, and twin structures for catalytic applications.

15.
Chemistry ; 26(67): 15636-15642, 2020 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-32820552

RESUMO

Oleic acid (OAc) is commonly used as a surfactant and/or solvent for the oil-phase synthesis of metal nanocrystals but its explicit roles are yet to be resolved. Here, we report a systematic study of this problem by focusing on a synthesis that simply involves heating of Pt(acac)2 in OAc for the generation of Pt nanocrystals. When heated at 80 °C, the ligand exchange between Pt(acac)2 and OAc leads to the formation of a PtII -oleate complex that serves as the actual precursor to Pt atoms. Upon increasing the temperature to 120 °C, the decarbonylation of OAc produces CO, which can act as a reducing agent for the generation of Pt atoms and thus formation of nuclei. Afterwards, several catalytic reactions can take place on the surface of the Pt nuclei to produce more CO, which also serves as a capping agent for the formation of Pt nanocrystals enclosed by {100} facets. The emergence of Pt nanocrystals further promotes the autocatalytic surface reduction of PtII precursor to enable the continuation of growth. This work not only elucidates the critical roles of OAc at different stages in a synthesis of Pt nanocrystals, but also represents a pivotal step forward toward the rational synthesis of metal nanocrystals.

16.
Angew Chem Int Ed Engl ; 59(43): 19129-19135, 2020 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-32706132

RESUMO

We report a robust method for effectively removing the chemisorbed Br- ions, a capping agent, from the surface of Pd nanocubes to maximize their catalytic activity. The Br- ions can be removed by simply heating the sample in water, but the desorption of Br- ions will expose the underneath Pd atoms to the O2 from air for the formation of a relatively thick oxide layer. During potential cycling, the oxide layer evolves into detrimental features such as steps and terraces. By introducing a trace amount of hydrazine into the system, the Br- ions can be removed by heating without forming a thick oxide layer. The as-cleaned nanocubes show greatly enhanced activity toward formic acid oxidation. This cleaning method can also remove Br- ions from Rh nanocubes and it is expected to work for other combinations of nanocrystals and capping agents.

17.
Nanoscale ; 12(21): 11718-11727, 2020 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-32458949

RESUMO

We report a facile and scalable synthesis of Pt-Co truncated octahedral nanocrystals (TONs) by employing Pt(acac)2 and Co(acac)2 as precursors, together with CO molecules and Mn atoms derived from the decomposition of Mn2(CO)10 as a reductant and a {111} facet-directing agent, respectively. Both the composition and yield of the Pt-Co TONs could be varied through the introduction of CHCl3. When tested at 80 °C using membrane electrode assembly (MEA), the 4 nm Pt2.6Co TONs gave a mass activity of 294 A gPt-1 at beginning-of-life (BOL) and it increased to 384 A gPt-1 during recovery cycles. The mass activity at BOL only dropped by 24% after 30 000 voltage cycles at end-of-life (EOL) in a metal dissolution accelerated stress test. The Pt2.6Co/C catalyst outperformed the commercial TKK Pt3Co/C (230 A gPt-1 at BOL and 40% loss after 30 000 cycles at EOL) in terms of both activity and durability. Our systematic analysis suggested that the enhancement in activity can be attributed to the combination of small, uniform size and well-defined {111} facets. This new class of catalysts holds promise for applications in proton-exchange membrane fuel cells.

18.
Chemistry ; 25(71): 16397-16404, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31589785

RESUMO

Surface capping has been shown to play a pivotal role in controlling the evolution of metal nanocrystals into different shapes or morphologies. With the synthesis of Au@Pd concave nanocubes as an example, here we demonstrate that the capping agent can also impact the reduction kinetics of a precursor, and thereby its reduction pathway, for the formation of metal nanocrystals with distinct morphologies. A typical synthesis involves the reduction of a PdII precursor by ascorbic acid at room temperature in the presence of Au nanospheres as seeds, together with the use of hexadecyltrimethylammonium chloride (CTAC) or hexadecyltrimethylammonium bromide (CTAB) as the capping agent. In the case of CTAC, the PdII precursor prevails as PdCl4 2- , leading to the formation of Au@Pd concave nanocubes with a rough surface because of the fast reduction kinetics and thus the dominance of solution reduction pathway. When switched to CTAB, the PdII precursor changes to PdBr4 2- that features slow reduction kinetics and surface reduction pathway. Accordingly, the Au@Pd concave nanocubes take a smooth surface. This work demonstrates that both reduction kinetics and surface capping play important roles in controlling the morphology of metal nanocrystals and these two roles are often coupled to each other.

19.
Nano Lett ; 19(9): 6703-6708, 2019 09 11.
Artigo em Inglês | MEDLINE | ID: mdl-31449753

RESUMO

Heterodimers of metal nanoparticles are widely sought for applications in photonics, sensing, and catalysis. In this work, we demonstrate a general approach to the fabrication of heterodimers of metal nanoparticles by leveraging the concept of site-selected growth under the protection of an inert material. When styrene is polymerized in the presence of Au nanoparticles, the resultant polystyrene (PS) can be controlled to grow from only one portion of the surface of a nanoparticle. Free of PS, the remaining portion can serve as an active site for the heterogeneous nucleation and growth of the second metal. After dissolving the PS component, we obtain heterodimers of metal nanoparticles with tunable elemental compositions and controllable physical dimensions. The contact area between the two metals can also be maneuvered by adjusting the concentration of divinylbenzene used for copolymerization with styrene. Using this method, we have prepared Au-Ag, Au-Pd, and Au-Pt heterodimers and further investigated their plasmonic properties. The capability of this approach should be extendible to the fabrication of heterodimers with a broader range of compositions and properties.

20.
Nano Lett ; 19(8): 4997-5002, 2019 08 14.
Artigo em Inglês | MEDLINE | ID: mdl-31305086

RESUMO

Carbon-supported Pt nanoparticles are used as catalysts for a variety of reactions including the oxygen reduction reaction (ORR) key to proton-exchange membrane fuel cells, but their catalytic performance has long been plagued by detachment and sintering. Here we report the in situ growth of sub-2 nm Pt particles on a commercial carbon support via the galvanic reaction between a Pt(II) precursor and a uniform film of amorphous Se predeposited on the support. The residual Se could serve as a linker to strongly anchor the Pt nanoparticles to the carbon surface, leading to a catalytic system with extraordinary activity and durability toward ORR. Even after 20 000 cycles of accelerated durability test, the sub-2 nm Pt particles were still dispersed well on the carbon support and maintained a mass activity more than three-times as high as the pristine value of a commercial Pt/C catalyst.

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