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1.
Nanomaterials (Basel) ; 13(19)2023 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-37836313

RESUMO

The interaction between metal particles and the oxide support, the so-called metal-support interaction, plays a critical role in the performance of heterogenous catalysts. Probing the dynamic evolution of these interactions under reactive gas atmospheres is crucial to comprehending the structure-performance relationship and eventually designing new catalysts with enhanced properties. Cobalt supported on TiO2 (Co/TiO2) is an industrially relevant catalyst applied in Fischer-Tropsch synthesis. Although it is widely acknowledged that Co/TiO2 is restructured during the reaction process, little is known about the impact of the specific gas phase environment at the material's surface. The combination of soft and hard X-ray photoemission spectroscopies are used to investigate in situ Co particles supported on pure and NaBH4-modified TiO2 under H2, O2, and CO2:H2 gas atmospheres. The combination of soft and hard X-ray photoemission methods, which allows for simultaneous probing of the chemical composition of surface and subsurface layers, is one of the study's unique features. It is shown that under H2, cobalt particles are encapsulated below a stoichiometric TiO2 layer. This arrangement is preserved under CO2 hydrogenation conditions (i.e., CO2:H2), but changes rapidly upon exposure to O2. The pretreatment of the TiO2 support with NaBH4 affects the surface mobility and prevents TiO2 spillover onto Co particles.

2.
Nanoscale ; 15(4): 1739-1753, 2023 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-36598381

RESUMO

2D ultrathin metal nanostructures are emerging materials displaying distinct physical and chemical properties compared to their analogues of different dimensionalities. Nanosheets of fcc metals are intriguing, as their crystal structure does not favour a 2D configuration. Thanks to their increased surface-to-volume ratios and the optimal exposure of low-coordinated sites, 2D metal nanostructures can be advantageously exploited in catalysis. Synthesis approaches to ultrathin nanosheets of pure platinum are scarce compared to other noble metals and to Pt-based alloys. Here, we present the selective synthesis of Pt ultrathin nansosheets by a simple seeded-growth method. The most crucial point in our approach is the selective synthesis of Pt seeds comprising planar defects, a main driving force for the 2D growth of metals with fcc structure. Defect engineering is employed here, not in order to disintegrate, but for conserving the defect comprising seeds. This is achieved by in situ elimination of the principal etching agent, chloride, which is present in the PtCl2 precursor. As a result of etching suppression, twinned nuclei, that are selectively formed during the early stage of nucleation, survive and grow to multipods comprising planar defects. Using the twinned multipods as seeds for the subsequent 2D overgrowth of Pt from Pt(acac)2 yields ultrathin dendritic nanosheets, in which the planar defects are conserved. Using phenylacetylene hydrogenation as a model reaction of selective hydrogenation, we compared the performance of Pt nanosheets to that of a commercial Pt/C catalyst. The Pt nanosheets show better stability and much higher selectivity to styrene than the commercial Pt/C catalyst for comparable activity.

3.
Angew Chem Int Ed Engl ; 61(35): e202207301, 2022 08 26.
Artigo em Inglês | MEDLINE | ID: mdl-35708117

RESUMO

Magnetic nanoparticles (NPs) are attractive both for their fundamental properties and for their potential in a variety of applications ranging from nanomedicine and biology to micro/nanoelectronics and catalysis. While these fields are dominated by the use of iron oxides, reduced metal NPs are of interest since they display high magnetization and adjustable anisotropy according to their size, shape and composition. The use of organometallic precursors makes it possible to adjust the size, shape (sphere, cube, rod, wire, urchin, …) and composition (alloys, core-shell, composition gradient, dumbbell, …) of the resulting NPs and hence their magnetic properties. We discuss here the synthesis of magnetic metal NPs from organometallic precursors carried out in Toulouse, as well as their associated properties and their potential in applications.


Assuntos
Magnetismo , Nanopartículas Metálicas , Anisotropia , Fenômenos Magnéticos , Nanomedicina/métodos
4.
Nano Lett ; 21(8): 3664-3670, 2021 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-33847503

RESUMO

Single crystalline magnetic FeCo nanostars were prepared using an organometallic approach under mild conditions. The fine-tuning of the experimental conditions allowed the direct synthesis of these nano-octopods with body-centered cubic (bcc) structure through a one-pot reaction, contrarily to the seed-mediated growth classically used. The FeCo nanostars consist of 8 tetrahedrons exposing {311} facets, as revealed by high resolution transmission electron microscopy (HRTEM) imaging and electron tomography (ET), and exhibit a high magnetization comparable with the bulk one (Ms = 235 A·m2·kg-1). Complex 3D spin configurations resulting from the competition between dipolar and exchange interactions are revealed by electron holography. This spin structures are stabilized by the high aspect ratio tetrahedral branches of the nanostars, as confirmed by micromagnetic simulations. This illustrates how magnetic properties can be significantly tuned by nanoscale shape control.

5.
ACS Appl Nano Mater ; 3(7): 7076-7087, 2020 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-32743352

RESUMO

Magnetically induced catalysis using magnetic nanoparticles (MagNPs) as heating agents is a new efficient method to perform reactions at high temperatures. However, the main limitation is the lack of stability of the catalysts operating in such harsh conditions. Normally, above 500 °C, significant sintering of MagNPs takes place. Here we present encapsulated magnetic FeCo and Co NPs in carbon (Co@C and FeCo@C) as an ultrastable heating material suitable for high-temperature magnetic catalysis. Indeed, FeCo@C or a mixture of FeCo@C:Co@C (2:1) decorated with Ni or Pt-Sn showed good stability in terms of temperature and catalytic performances. In addition, consistent conversions and selectivities regarding conventional heating were observed for CO2 methanation (Sabatier reaction), propane dehydrogenation (PDH), and propane dry reforming (PDR). Thus, the encapsulation of MagNPs in carbon constitutes a major advance in the development of stable catalysts for high-temperature magnetically induced catalysis.

6.
ACS Nano ; 13(3): 2870-2878, 2019 03 26.
Artigo em Inglês | MEDLINE | ID: mdl-30822381

RESUMO

Magnetic nanoparticles are important tools for biomedicine, where they serve as versatile multifunctional instruments for a wide range of applications. Among these applications, magnetic hyperthermia is of special interest for the destruction of tumors and triggering of drug delivery. However, many applications of magnetic nanoparticles require high-quality magnetic nanoparticles displaying high specific absorption rates (SARs), which remains a challenge today. We report here the functionalization and stabilization in aqueous media of highly magnetic 15 nm iron carbide nanoparticles featuring excellent heating power through magnetic induction. The challenge of achieving water solubility and colloidal stability was addressed by designing and using specific dopamine-based ligands. The resulting nanoparticles were completely stable for several months in water, phosphate, phosphate-buffered saline, and serum-containing media. Iron carbide nanoparticles displayed high SARs in water and viscous media (water/glycerol mixtures), even after extended exposition to water and oxygen (SAR up to 1000 W·g-1 in water at 100 kHz, 47 mT). The cytotoxicity and cellular uptake of iron carbide nanoparticles could be easily tuned and were highly dependent on the chemical structure of the ligands used.


Assuntos
Materiais Biocompatíveis/química , Compostos Inorgânicos de Carbono/química , Compostos de Ferro/química , Nanopartículas de Magnetita/química , Água/química , Materiais Biocompatíveis/síntese química , Compostos Inorgânicos de Carbono/síntese química , Dopamina/síntese química , Dopamina/química , Glicerol/química , Células HeLa , Humanos , Compostos de Ferro/síntese química , Ligantes , Estrutura Molecular , Oxigênio/química
7.
Nanoscale ; 11(12): 5402-5411, 2019 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-30854537

RESUMO

Heating magnetic nanoparticles with high frequency magnetic fields is a topic of interest for biological applications (magnetic hyperthermia) as well as for heterogeneous catalysis. This study shows why FeC NPs of similar structures and static magnetic properties display radically different heating power (SAR from 0 to 2 kW g-1). By combining results from Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS) and static and time-dependent high-frequency magnetic measurements, we propose a model describing the heating mechanism in FeC nanoparticles. Using, for the first time, time-dependent high-frequency hysteresis loop measurements, it is shown that in the samples displaying the larger heating powers, the hysteresis is strongly time dependent. More precisely, the hysteresis area increases by a factor 10 on a timescale of a few tens of seconds. This effect is directly related to the ability of the nanoparticles to form chains under magnetic excitation, which depends on the presence or not of strong dipolar couplings. These differences are due to different ligand concentrations on the surface of the particles. As a result, this study allows the design of a scalable synthesis of nanomaterials displaying a controllable and reproducible SAR.

8.
Nano Lett ; 19(2): 1379-1386, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30645938

RESUMO

Single-crystalline FeCo nanoparticles with tunable size and shape were prepared by co-decomposing two metal-amide precursors under mild conditions. The nature of the ligands introduced in this organometallic synthesis drastically affects the reactivity of the precursors and, thus, the chemical distribution within the nanoparticles. The presence of the B2 short-range order was evidenced in FeCo nanoparticles prepared in the presence of HDAHCl ligands, combining 57Fe Mössbauer, zero-field 59Co ferromagnetic nuclear resonance (FNR), and X-ray diffraction studies. This is the first time that the B2 structure is directly formed during synthesis without the need of any annealing step. The as-prepared nanoparticles exhibit magnetic properties comparable with the ones for the bulk ( Ms = 226 Am2·kg-1). Composite magnetic materials prepared from these FeCo nanoparticles led to a successful proof-of-concept of the integration on inductor-based filters (27% enhancement of the inductance value at 100 MHz).

9.
Nanoscale ; 10(48): 22730-22736, 2018 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-30500037

RESUMO

Supported nanocrystals of original shapes are highly desirable for the development of optimized catalysts; however, conventional methods for the preparation of supported catalysts do not allow shape control. In this work, we have synthesized concave platinum nanocubes exposing {110} crystallographic facets at 20 °C. In the presence of a crystallographically oriented Pt(111) support in the reaction medium, the concave nanocubes grow epitaxially on the support, producing macroscopic nanostructured surfaces. Higher reaction temperature produces a mixture of different nanostructures in solution; however, only the nanostructures growing along the 111 direction are obtained on the Pt(111) support. Therefore, the oriented surface acts as a template for a selective immobilization of specific nanostructures out of a mixture, which can be regarded as an "epitaxial resolution" of an inhomogeneous mixture of nanocrystals. Thus, a judicious choice of the support crystallographic orientation may allow the isolation of original nanostructures that cannot be obtained in a pure form.

13.
Angew Chem Int Ed Engl ; 57(33): 10579-10583, 2018 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-29893037

RESUMO

The Fischer-Tropsch synthesis (FTS) is a structure-sensitive exothermic reaction that enables catalytic transformation of syngas to high quality liquid fuels. Now, monolithic cobalt-based heterogeneous catalysts were elaborated through a wet chemistry approach that allows control over nanocrystal shape and crystallographic phase, while at the same time enables heat management. Copper and nickel foams have been employed as supports for the epitaxial growth of hcp-Co nanowires directly from a solution containing a coordination compound of cobalt and stabilizing ligands. The Co/Cufoam catalyst was tested for Fischer-Tropsch synthesis in a fixed-bed reactor, showing stability and significantly superior activity and selectivity towards C5+ compared to a Co/SiO2 -Al2 O3 reference catalyst under the same conditions.

14.
Front Chem ; 6: 609, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30619818

RESUMO

This paper deals with the synthesis of high-magnetization porous silicon-based nanocomposites. Using well-controlled organometallic synthesis of ferromagnetic FeCo nanoparticles, the impregnation of mesoporous silicon has been performed by immersion of porous silicon in a colloidal solution. The technique was optimized by controlling the temperature, the immersion duration, and the solvent nature. The characterization of the nanocomposites showed a homogeneous filling of the pores and a high magnetization of 135 emu/cm3. Such composites present a great interest for many applications including data storage, medical instrumentations, catalysis, or electronics.

15.
Sci Rep ; 7(1): 4752, 2017 07 06.
Artigo em Inglês | MEDLINE | ID: mdl-28684848

RESUMO

Detecting biomarkers from complex sample solutions is the key objective of molecular diagnostics. Being able to do so in a simple approach that does not require laborious sample preparation, sophisticated equipment and trained staff is vital for point-of-care applications. Here, we report on the specific detection of the breast cancer biomarker sHER2 directly from serum and saliva samples by a nanorod-based homogeneous biosensing approach, which is easy to operate as it only requires mixing of the samples with the nanorod probes. By careful nanorod surface engineering and homogeneous assay design, we demonstrate that the formation of a protein corona around the nanoparticles does not limit the applicability of our detection method, but on the contrary enables us to conduct in-situ reference measurements, thus further strengthening the point-of-care applicability of our method. Making use of sandwich assays on top of the nanorods, we obtain a limit of detection of 110 pM and 470 pM in 10-fold diluted spiked saliva and serum samples, respectively. In conclusion, our results open up numerous applications in direct protein biomarker quantification, specifically in point-of-care settings where resources are limited and ease-of-use is of essence.


Assuntos
Biomarcadores Tumorais/sangue , Técnicas Biossensoriais , Nanopartículas/química , Nanotubos/química , Coroa de Proteína/análise , Receptor ErbB-2/sangue , Anticorpos/química , Biomarcadores Tumorais/genética , Desenho de Equipamento , Humanos , Imunoensaio , Limite de Detecção , Sistemas Automatizados de Assistência Junto ao Leito , Receptor ErbB-2/genética , Padrões de Referência , Saliva/química
16.
Angew Chem Int Ed Engl ; 55(51): 15894-15898, 2016 12 19.
Artigo em Inglês | MEDLINE | ID: mdl-27873427

RESUMO

The use of magnetic nanoparticles to convert electromagnetic energy into heat is known to be a key strategy for numerous biomedical applications but is also an approach of growing interest in the field of catalysis. The heating efficiency of magnetic nanoparticles is limited by the poor magnetic properties of most of them. Here we show that the new generation of iron carbide nanoparticles of controlled size and with over 80 % crystalline Fe2.2 C leads to exceptional heating properties, which are much better than the heating properties of currently available nanoparticles. Associated to catalytic metals (Ni, Ru), iron carbide nanoparticles submitted to magnetic excitation very efficiently catalyze CO2 hydrogenation in a dedicated continuous-flow reactor. Hence, we demonstrate that the concept of magnetically induced heterogeneous catalysis can be successfully applied to methanation of CO2 and represents an approach of strategic interest in the context of intermittent energy storage and CO2 recovery.

17.
J Am Chem Soc ; 138(27): 8422-31, 2016 07 13.
Artigo em Inglês | MEDLINE | ID: mdl-27300493

RESUMO

The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray absorption spectroscopy-small-angle X-ray scattering (XAS-SAXS). The supercrystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long-chain amine and a long-chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom-by-atom anisotropic growth, and a slower oriented attachment process that continues well after cobalt reduction is complete. Smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized superlattices, which can be regarded as mesocrystals.

18.
Sensors (Basel) ; 16(6)2016 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-27275824

RESUMO

The growing availability of biomarker panels for molecular diagnostics is leading to an increasing need for fast and sensitive biosensing technologies that are applicable to point-of-care testing. In that regard, homogeneous measurement principles are especially relevant as they usually do not require extensive sample preparation procedures, thus reducing the total analysis time and maximizing ease-of-use. In this review, we focus on homogeneous biosensors for the in vitro detection of biomarkers. Within this broad range of biosensors, we concentrate on methods that apply magnetic particle labels. The advantage of such methods lies in the added possibility to manipulate the particle labels by applied magnetic fields, which can be exploited, for example, to decrease incubation times or to enhance the signal-to-noise-ratio of the measurement signal by applying frequency-selective detection. In our review, we discriminate the corresponding methods based on the nature of the acquired measurement signal, which can either be based on magnetic or optical detection. The underlying measurement principles of the different techniques are discussed, and biosensing examples for all techniques are reported, thereby demonstrating the broad applicability of homogeneous in vitro biosensing based on magnetic particle label actuation.


Assuntos
Biomarcadores/análise , Técnicas Biossensoriais/métodos , Patologia Molecular/métodos , Humanos , Campos Magnéticos , Magnetismo
19.
ACS Appl Mater Interfaces ; 8(14): 8893-9, 2016 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-27023370

RESUMO

Studying protein interactions is of vital importance both to fundamental biology research and to medical applications. Here, we report on the experimental proof of a universally applicable label-free homogeneous platform for rapid protein analysis. It is based on optically detecting changes in the rotational dynamics of magnetically agitated core-shell nanorods upon their specific interaction with proteins. By adjusting the excitation frequency, we are able to optimize the measurement signal for each analyte protein size. In addition, due to the locking of the optical signal to the magnetic excitation frequency, background signals are suppressed, thus allowing exclusive studies of processes at the nanoprobe surface only. We study target proteins (soluble domain of the human epidermal growth factor receptor 2 - sHER2) specifically binding to antibodies (trastuzumab) immobilized on the surface of our nanoprobes and demonstrate direct deduction of their respective sizes. Additionally, we examine the dependence of our measurement signal on the concentration of the analyte protein, and deduce a minimally detectable sHER2 concentration of 440 pM. For our homogeneous measurement platform, good dispersion stability of the applied nanoprobes under physiological conditions is of vital importance. To that end, we support our measurement data by theoretical modeling of the total particle-particle interaction energies. The successful implementation of our platform offers scope for applications in biomarker-based diagnostics as well as for answering basic biology questions.


Assuntos
Anticorpos Imobilizados/química , Nanotubos/química , Receptor ErbB-2/metabolismo , Trastuzumab/química , Anticorpos Imobilizados/metabolismo , Humanos , Magnetismo , Modelos Moleculares , Tamanho da Partícula , Ligação Proteica , Mapas de Interação de Proteínas/genética , Receptor ErbB-2/química , Trastuzumab/uso terapêutico
20.
Chem Commun (Camb) ; 51(93): 16691-4, 2015 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-26430906

RESUMO

Ultrathin Au-Ag alloy nanorods and nanowires of different lengths and ca. 1.9 nm diameter are prepared through a low-temperature decomposition of the precursor [Au2Ag2(C6F5)4(OEt2)2]n in oleic acid. This nanostructure formation has been studied through TEM, HRTEM, EDS, HS-SPME-GC-MS and (19)F NMR spectroscopy. The UNRs and UNWs display a length-dependent broad band in the mid-IR region that is related to the longitudinal mode of the surface plasmon resonance of the ultrathin nanostructures.

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