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1.
Artigo em Inglês | MEDLINE | ID: mdl-32463648

RESUMO

Thermionic emission relies on the low work function and negative electron affinity of the, often functionalized, surface of the emitting material. However, there is little understanding of the interplay between thermionic emission and temperature-driven dynamic surface transformation processes as these are not represented on the traditional Richardson-Dushman equation for thermionic emission. Here, we show a new model for thermionic emission that can reproduce the effect of dynamic surface changes on the electron emission and correlate the components of the thermionic emission with specific surface reconstruction phases on the surface of the emitter. We use hydrogenated <100> single-crystal and polycrystalline diamonds as thermionic emitters to validate our model, which shows excellent agreement with the experimental data and could be applicable to other emitting materials. Furthermore, we find that tailoring the coverage of specific structures of the C(100)-(2 × 1):H surface reconstruction could increase the thermionic emission of diamond by several orders of magnitude.

2.
Nat Commun ; 11(1): 41, 2020 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-31900396

RESUMO

The development of programmable microscale materials with cell-like functions, dynamics and collective behaviour is an important milestone in systems chemistry, soft matter bioengineering and synthetic protobiology. Here, polymer/nucleotide coacervate micro-droplets are reconfigured into membrane-bounded polyoxometalate coacervate vesicles (PCVs) in the presence of a bio-inspired Ru-based polyoxometalate catalyst to produce synzyme protocells (Ru4PCVs) with catalase-like activity. We exploit the synthetic protocells for the implementation of multi-compartmentalized cell-like models capable of collective synzyme-mediated buoyancy, parallel catalytic processing in individual horseradish peroxidase-containing Ru4PCVs, and chemical signalling in distributed or encapsulated multi-catalytic protocell communities. Our results highlight a new type of catalytic micro-compartment with multi-functional activity and provide a step towards the development of protocell reaction networks.


Assuntos
Células Artificiais/química , Catalase/química , Rutênio/química , Compostos de Tungstênio/química , Catalase/síntese química , Catálise , Peroxidase do Rábano Silvestre/química
3.
Nanotechnology ; 30(28): 285701, 2019 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-30901765

RESUMO

The photoemission electron microscopy and x-ray photoemission spectroscopy were utilized for the study of anodized epitaxial graphene (EG) on silicon carbide as a fundamental aspect of the oxygen evolution reaction on graphitic materials. The high-resolution analysis of surface morphology and composition quantified the material transformation during the anodization. We investigated the surface with lateral resolution <150 nm, revealing significant transformations on the EG and the role of multilayer edges in increasing the film capacitance.

4.
Langmuir ; 35(8): 2983-2988, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30695647

RESUMO

We compare electrochemically modified or thiol-functionalized single-crystal samples of the topological insulator (TI) Bi2Te0.9Se2.1 to freshly cleaved/air-exposed control samples and use X-ray photoelectron spectroscopy (XPS) to investigate the extent of any surface oxidation. XPS spectra for a TI sample maintained at an appropriate potential for 2 h demonstrate the feasibility of protecting the TI surface from oxidation while working in an electrochemical environment. Deliberate electrochemical oxidation, in contrast, generates prominent Bi, Te, and Se peaks associated with oxidation. However, this change is reversible, as further XPS spectra following electrochemical reduction are similar to those measured for an in situ cleaved sample. XPS also shows that adsorption of pentanedithiol (PDT) protects the TI surface from oxidation. Cyclic voltammetry shows that PDT adsorption suppresses electrochemical oxidation and reduction, while electrochemical impedance spectroscopy shows that it increases the charge transfer resistance significantly. Our work demonstrates the ability to control and characterize the surface chemistry of single-crystal TIs in an electrochemical environment for the first time.

5.
iScience ; 9: 36-46, 2018 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-30384132

RESUMO

The performance of Cu2ZnSn(S,Se)4 thin-film solar cells, commonly referred to as kesterite or CZTSSe, is limited by open-circuit voltage (VOC) values less than 60% of the maximum theoretical limit. In the present study, we employ energy-filtered photoemission microscopy to visualize nanoscale shunting paths in solution-processed CZTSSe films, which limit the VOC of cells to approximately 400 mV. These studies unveil areas of local effective work function (LEWF) narrowly distributed around 4.9 eV, whereas other portions show hotspots with LEWF as low as 4.2 eV. Localized valence band spectra and density functional theory calculations allow rationalizing the LEWF maps in terms of the CZTSSe effective work function broadened by potential energy fluctuations and nanoscale Sn(S,Se) phases.

6.
Nanotechnology ; 29(48): 485201, 2018 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-30192742

RESUMO

Graphene and h-BN are grown by chemical vapor deposition in ultra high vacuum conditions on the Pt(110) surface. Scanning tunneling microscopy measurements and low-energy electron diffraction data indicate that graphene forms a variety of differently oriented incommensurate domains although with a strong preference to align its [Formula: see text] direction with the [Formula: see text] direction of Pt. Meanwhile, h-BN exhibits a c(8 × 10) commensurate superstructure, which presents a high level of defectivity that implies local variation of the periodicity (i.e. mixed c(8 × 10) and c(8 × 12) patches) and the introduction of local defects. The combination of advanced photoemission spectroscopy data (angle-resolved photoemission spectroscopy from the valence band) and ab initio calculations indicates that both 2D materials interact weakly with the substrate: graphene exhibits neutral doping and is morphologically flat, even if it nucleates on the relatively highly corrugated rectangular (110) surface. In the case of h-BN, the interaction is slightly stronger and is characterized by a small electron transfer from surface Pt atoms to nitrogen atoms. The (110) termination of Pt is therefore a quite interesting surface for the growth of 2D materials because given its low symmetry, it may favor the growth of selectively oriented domains but does not affect their pristine electronic properties.

7.
Nanomaterials (Basel) ; 8(6)2018 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-29882781

RESUMO

Chemically modified graphene⁻based materials (CMG) are currently attracting a vast interest in their application in different fields. In particular, heteroatom-doped graphenes have revealed great potentialities in the field of electrocatalysis as substitutes of fuel cell noble metal⁻based catalysts. In this work, we investigate an innovative process for doping graphene nanostructures. We optimize a novel synthetic route based on aerosol preparation, which allows the simultaneous doping, crumpling, and reduction of graphene oxide (GO). Starting from aqueous solutions containing GO and the dopant precursors, we synthesize N- and N,S-dual-doped 3D graphene nanostructures (N-cGO and N,S-cGO). In the aerosol process, every aerosol droplet can be considered as a microreactor where dopant precursors undergo thermal decomposition and react with the GO flakes. Simultaneously, thanks to the relatively high temperature, GO undergoes crumpling and partial reduction. Using a combination of spectroscopic and microscopic characterization techniques, we investigate the morphology of the obtained materials and the chemical nature of the dopants within the crumpled graphene sheets. This study highlights the versatility of the aerosol process for the design of new CMG materials with tailored electrocatalytic properties.

8.
Nanomaterials (Basel) ; 8(5)2018 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-29702567

RESUMO

In this paper, a perspective on the application of Spatially- and Angle-Resolved PhotoEmission Spectroscopy (ARPES) for the study of two-dimensional (2D) materials is presented. ARPES allows the direct measurement of the electronic band structure of materials generating extremely useful insights into their electronic properties. The possibility to apply this technique to 2D materials is of paramount importance because these ultrathin layers are considered fundamental for future electronic, photonic and spintronic devices. In this review an overview of the technical aspects of spatially localized ARPES is given along with a description of the most advanced setups for laboratory and synchrotron-based equipment. This technique is sensitive to the lateral dimensions of the sample. Therefore, a discussion on the preparation methods of 2D material is presented. Some of the most interesting results obtained by ARPES are reported in three sections including: graphene, transition metal dichalcogenides (TMDCs) and 2D heterostructures. Graphene has played a key role in ARPES studies because it inspired the use of this technique with other 2D materials. TMDCs are presented for their peculiar transport, optical and spin properties. Finally, the section featuring heterostructures highlights a future direction for research into 2D material structures.

9.
Phys Chem Chem Phys ; 18(48): 33233-33239, 2016 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-27892576

RESUMO

In this paper, we study the magnetic and chemical properties of Fe/graphene vertically stacked ultrathin films by means of X-ray magnetic circular dichroism and X-ray photoelectron spectroscopy. We compare two systems: an iron layer deposited directly on top of the Pt(111) surface, and an intercalated Fe film sandwiched between graphene and Pt(111). The system composed of a submonolayer Fe deposited directly on Pt(111) maintains an out-of-plane easy magnetization axis, even if it has been covered by graphene that quenches effectively the magnetic orbital moment of Fe. However, when the Fe coverage is increased above 1 ML the easy magnetization axis flips in the in-plane direction.

10.
Nanoscale ; 8(41): 17843-17853, 2016 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-27714142

RESUMO

By a combination of scanning tunneling microscopy, X-ray spectroscopic techniques and density functional theory calculations, we prove the formation of extended patterns of parallel, graphene nanoribbons with alternate zig-zag and armchair edges and selected width by surface-assisted Ullmann coupling polymerization and dehydrogenation of 1,6-dibromopyrene (C16H8Br2). Besides the relevance of these nanostructures for their possible application in nanodevices, we demonstrate the peculiarity of halogenated pyrene derivatives for the formation of nanoribbons, in particular on Ag(110). These results open the possibility of tuning the shape and dimension of nanoribbons (and hence the correlated electronic properties) by choosing suitably tailored or on-purpose designed molecular precursors.

11.
ACS Nano ; 10(4): 4543-9, 2016 04 26.
Artigo em Inglês | MEDLINE | ID: mdl-27054462

RESUMO

By means of a combination of surface-science spectroscopies and theory, we investigate the mechanisms ruling the catalytic role of epitaxial graphene (Gr) grown on transition-metal substrates for the production of hydrogen from water. Water decomposition at the Gr/metal interface at room temperature provides a hydrogenated Gr sheet, which is buckled and decoupled from the metal substrate. We evaluate the performance of Gr/metal interface as a hydrogen storage medium, with a storage density in the Gr sheet comparable with state-of-the-art materials (1.42 wt %). Moreover, thermal programmed reaction experiments show that molecular hydrogen can be released upon heating the water-exposed Gr/metal interface above 400 K. The Gr hydro/dehydrogenation process might be exploited for an effective and eco-friendly device to produce (and store) hydrogen from water, i.e., starting from an almost unlimited source.

12.
ACS Appl Mater Interfaces ; 7(46): 25685-92, 2015 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-26517577

RESUMO

Aerosol processing enables the preparation of hierarchical graphene nanocomposites with special crumpled morphology in high yield and in a short time. Using modular insertion of suitable precursors in the starting solution, it is possible to synthesize different types of graphene-based materials ranging from heteroatom-doped graphene nanoballs to hierarchical nanohybrids made up by nitrogen-doped crumpled graphene nanosacks that wrap finely dispersed MoS2 nanoparticles. These materials are carefully investigated by microscopic (SEM, standard and HR TEM), diffraction (grazing incidence X-ray diffraction (GIXRD)) and spectroscopic (high resolution photoemission, Raman and UV-visible spectroscopy) techniques, evidencing that nitrogen dopants provide anchoring sites for MoS2 nanoparticles, whereas crumpling of graphene sheets drastically limits aggregation. The activity of these materials is tested toward the photoelectrochemical production of hydrogen, obtaining that N-doped graphene/MoS2 nanohybrids are seven times more efficient with respect to single MoS2 because of the formation of local p-n MoS2/N-doped graphene nanojunctions, which allow an efficient charge carrier separation.

13.
Chem Commun (Camb) ; 51(63): 12593-6, 2015 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-26154619

RESUMO

The surface-assisted synthesis of gold-organometallic hybrids on the Au(111) surface both by thermo- and light-initiated dehalogenation of bromo-substituted tetracene is reported. Combined X-ray photoemission (XPS) and scanning tunneling microscopy (STM) data reveal a significant increase of the surface order when mild reaction conditions are combined with 405 nm light irradiation.

14.
Chemistry ; 21(15): 5826-35, 2015 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-25711882

RESUMO

Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions.

15.
Nanotechnology ; 26(7): 075501, 2015 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-25627790

RESUMO

Polyvinyl alcohol (PVA) electrospun nanofibers containing Ag nanoparticles (NPs) have been deposited on glass substrates. The aim of the work was to test the feasibility of this approach for the detection of biogenic amines by using either the Ag localized surface plasmon resonance quenching caused by the adsorption of amines on Ag NPs or by detecting the amines by surface enhanced Raman spectroscopy (SERS) after adsorption, from the gas phase, on the metal NPs. Two different approaches have been adopted. In the first one an ethanol/water solution containing AgNO3 was used directly in the electrospinning apparatus. In this way, a simple heat treatment of the nanofibers mat was sufficient to obtain the formation of Ag NPs inside the nanofibers and a partial cross-link of PVA. In the second procedure, the Ag NPs were deposited on PVA nanofibers by using the supersonic cluster beam deposition method, so that a beam of pure Ag NPs of controlled size was obtained. Exposure of the PVA mat to the beam produced a uniform distribution of the NPs on the nanofibers surface. Ethylendiamine vapors and volatile amines released from fresh shrimp meat were chemisorbed on the nanofibers mats. A SERS spectrum characterized by a diagnostic Ag-N stretching vibration at 230 cm(-1) was obtained. The results allow to compare the two different approaches in the detection of ammines.


Assuntos
Aminas/química , Nanopartículas Metálicas/química , Nanotecnologia/métodos , Álcool de Polivinil/química , Prata/química , Análise Espectral Raman/métodos , Adsorção , Animais , Reagentes para Ligações Cruzadas/química , Etanol/química , Etilenodiaminas/química , Análise de Alimentos/métodos , Gases , Vidro , Temperatura Alta , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Nanofibras , Penaeidae , Alimentos Marinhos , Termogravimetria , Água/química
16.
J Am Chem Soc ; 137(5): 1802-8, 2015 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-25582946

RESUMO

We report on a stepwise on-surface polymerization reaction leading to oriented graphene nanoribbons on Au(111) as the final product. Starting from the precursor 4,4″-dibromo-p-terphenyl and using the Ullmann coupling reaction followed by dehydrogenation and C-C coupling, we have developed a fine-tuned, annealing-triggered on-surface polymerization that allows us to obtain an oriented nanomesh of graphene nanoribbons via two well-defined intermediate products, namely, p-phenylene oligomers with reduced length dispersion and ordered submicrometric molecular wires of poly(p-phenylene). A fine balance involving gold catalytic activity in the Ullmann coupling, appropriate on-surface molecular mobility, and favorable topochemical conditions provided by the used precursor leads to a high degree of long-range order that characterizes each step of the synthesis and is rarely observed for surface organic frameworks obtained via Ullmann coupling.

17.
ACS Appl Mater Interfaces ; 6(22): 20130-6, 2014 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-25321080

RESUMO

The Ce4+↔Ce3+ redox switch is at the basis of an all-inorganic catalytic cycle that is capable of mimicking the activity of several natural redox enzymes. The efficiency of these artificial enzymes (nanozymes) strongly depends on the Ce4+/Ce3+ ratio. By capitalizing on the results obtained on oxide/oxide model systems, we implemented a simple and effective procedure to obtain conformal TiO2@CeOx core-shell nanoparticles whose thickness is controlled with single-layer precision. Since the Ce3+ species are stabilized only at the interface by the electronic hybridization with the TiO2 states, the modulation of the shell thickness offers a simple method to tailor the Ce4+/Ce3+ ratio and therefore the catalytic properties. The activity of these nanoparticles as artificial peroxidase-like enzymes was tested, showing exceptional performances, even better than natural horseradish peroxidase enzyme. The main advantage with respect to other oxide/oxide nanozymes is that our nanoparticles, having a tunable Ce4+/Ce3+ ratio, are efficient already at low H2O2 concentrations.


Assuntos
Materiais Biocompatíveis/metabolismo , Cério/química , Nanopartículas Metálicas/química , Titânio/química , Materiais Biocompatíveis/química , Catálise , Peroxidase do Rábano Silvestre/química , Peroxidase do Rábano Silvestre/metabolismo , Peróxido de Hidrogênio , Oxirredução
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