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1.
Nano Lett ; 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-32048513

RESUMO

Pt-based alloy catalysts are promising candidates for fuel-cell applications, especially for cathodic oxygen reduction reaction (ORR) and anodic methanol oxidation reaction (MOR). The rational design of composition and morphology is crucial to promoting catalytic performances. Here, we report the synthesis of Pt-Co nanoframes via chemical etching of Co from solid rhombic dodecahedra. The obtained Pt-Co nanoframes exhibit excellent ORR mass activity in acidic electrolyte, which is as high as 0.40 A mgPt-1 initially and 0.34 A mgPt-1 after 10 000 potential cycles at 0.95 VRHE. Furthermore, their MOR mass activity in alkaline media is up to 4.28 A mgPt-1 and is 4-fold higher than that of commercial Pt/C catalyst. Experimental studies indicate that the weakened binding of intermediate carbonaceous poison contributes to the enhanced MOR behavior. More impressively, the Pt-Co nanoframes also demonstrate remarkable stability under long-term testing, which could be attributed to the negligible electrochemical Co dissolution.

2.
Nano Lett ; 19(8): 5388-5393, 2019 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-31306028

RESUMO

We present a new methodology that enables studies of the molecular structure of graphene-liquid interfaces with nanoscale spatial resolution. It is based on Fourier transform infrared nanospectroscopy (nano-FTIR), where the infrared (IR) field is plasmonically enhanced near the tip apex of an atomic force microscope (AFM). The graphene seals a liquid electrolyte reservoir while acting also as a working electrode. The photon transparency of graphene enables IR spectroscopy studies of its interface with liquids, including water, propylene carbonate, and aqueous ammonium sulfate electrolyte solutions. We illustrate the method by comparing IR spectra obtained by nano-FTIR and attenuated total reflection (which has a detection depth of a few microns) demonstrating that the nano-FTIR method makes it possible to determine changes in speciation and ion concentration in the electric double and diffuse layers as a function of bias.

3.
J Am Chem Soc ; 140(47): 16237-16244, 2018 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-30369234

RESUMO

Knowledge of the molecular composition and electronic structure of electrified solid-liquid interfaces is key to understanding elemental processes in heterogeneous reactions. Using X-ray absorption spectroscopy in the interface-sensitive electron yield mode (EY-XAS), first-principles electronic structure calculations, and multiscale simulations, we determined the chemical composition of the interfacial region of a polycrystalline platinum electrode in contact with aqueous sulfuric acid solution at potentials between the hydrogen and oxygen evolution reactions. We found that between 0.7 and 1.3 V vs Ag/AgCl the electrical double layer (EDL) region comprises adsorbed sulfate ions with hydrated hydronium ions in the next layer. No evidence was found for bisulfate or Pt-O/Pt-OH species, which have very distinctive spectral signatures. In addition to resolving the long-standing issue of the EDL structure, our work establishes interface- and element-sensitive EY-XAS as a powerful spectroscopic tool for studying condensed phase, buried solid-liquid interfaces relevant to various electrochemical processes and devices.

4.
J Phys Chem Lett ; 9(17): 4865-4871, 2018 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-30081626

RESUMO

Water-oxide surfaces are ubiquitous in nature and of widespread importance to phenomena like corrosion as well as contemporary industrial challenges such as energy production through water splitting. So far, a reasonably robust understanding of the structure of such interfaces under certain conditions has been obtained. Considerably less is known about how overlayer water modifies the inherent reactivity of oxide surfaces. Here we address this issue experimentally for rutile TiO2(110) using scanning tunneling microscopy and photoemission, with complementary density functional theory calculations. Through detailed studies of adsorbed water nanoclusters and continuous water overlayers, we determine that excess electrons in TiO2 are attracted to the top surface layer by water molecules. Measurements on methanol show similar behavior. Our results suggest that adsorbate-induced surface segregation of polarons could be a general phenomenon for technologically relevant oxide materials, with consequences for surface chemistry and the associated catalytic activity.

5.
J Am Chem Soc ; 140(21): 6575-6581, 2018 05 30.
Artigo em Inglês | MEDLINE | ID: mdl-29738671

RESUMO

We studied the structure of the copper-cobalt (CuCo) surface alloy, formed by Co deposition on Cu(110), in dynamic equilibrium with CO. Using scanning tunneling microscopy (STM), we found that, in vacuum at room temperature and at low Co coverage, clusters of a few Co atoms substituting Cu atoms form at the surface. At CO pressures in the Torr range, we found that up to 2.5 CO molecules can bind on a single Co atom, in carbonyl-like configurations. Based on high-resolution STM images, together with density functional theory calculations, we determined the most stable CuCo cluster structures formed with bound CO. Such carbonyl-like formation manifests in shifts in the binding energy of the Co core-level peaks in X-ray photoelectron spectra, as well as shifts in the vibrational modes of adsorbed CO in infrared reflection absorption spectra. The multiple CO adsorption on a Co site weakens the Co-CO bond and thus reduces the C-O bond scission probability. Our results may explain the different product distribution, including higher selectivity toward alcohol formation, when bimetallic CuCo catalysts are used compared to pure Co.

6.
J Phys Chem B ; 122(2): 401-404, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-29343070
7.
J Phys Chem B ; 122(2): 407-424, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-29343071
8.
J Phys Chem B ; 122(2): 405-406, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-29343072
9.
J Phys Chem Lett ; 9(4): 785-790, 2018 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-29376377

RESUMO

We investigated the X-ray absorption spectroscopy (XAS) fingerprint of EMImTFSI ionic liquid (IL) and its fragmentation products created by X-ray irradiation. To accomplish this, we used an open geometry where an IL droplet is directly exposed in the vacuum chamber and an enclosed geometry where the IL is confined in a cell covered by an X-ray transparent membrane. In the open geometry, the XAS signature was stable and consistent with experimental and theoretical spectra reported in the literature. In contrast, when the IL is enclosed, its XAS evolves continuously under X-ray illumination due to the accumulation of volatile fragmentation products inside the closed cell, while they evaporate in the open geometry. The changes in the XAS from the core levels of relevant elements (C, N, S, F) together with density functional theory calculations allowed us to identify the chemical nature of the fragment products and the chemical bonds most vulnerable to rupture under soft X-ray irradiation.

10.
J Phys Chem B ; 122(2): 737-744, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-28829130

RESUMO

Atmospheric pressure X-ray spectroscopy techniques based on soft X-ray excitation can provide powerful interface-sensitive chemical information about a solid surface immersed in a gas or liquid environment. However, X-ray illumination of such dense phases can lead to the generation of considerable quantities of radical species by radiolysis. Soft X-ray absorption measurements of Cu films in both air and aqueous alkali halide solutions reveal that this can cause significant evolution of the Cu oxidation state. In air and NaOH (0.1 M) solutions, the Cu is oxidized toward CuO, while the addition of small amounts of CH3OH to the solution leads to reduction toward Cu2O. For Ni films in NaHCO3 solutions, the oxidation state of the surface is found to remain stable under X-ray illumination and can be electrochemically cycled between a reduced and oxidized state. We provide a consistent explanation for this behavior based on the products of X-ray-induced radiolysis in these different environments and highlight a number of general approaches that can mitigate radiolysis effects when performing operando X-ray measurements.

11.
J Phys Chem B ; 122(2): 548-554, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-28749680

RESUMO

Using ambient pressure X-ray photoelectron spectroscopy (APXPS) and high pressure scanning tunneling microscopy (HPSTM), we show that in equilibrium with 0.01-0.2 Torr of methanol vapor, at room temperature, the Cu(100) surface is covered with methoxy species forming a c(2 × 2) overlayer structure. In contrast, no methoxy is formed if the surface is saturated with an ordered oxygen layer, even when the methanol pressure is 0.2 Torr. At oxygen coverages below saturation, methanol dissociates and reacts with the atomic oxygen, producing methoxy and formate on the surface, and formaldehyde that desorbs to the gas phase. Unlike the case of pure carbon monoxide and carbon dioxide, methanol does not induce the restructuring of the Cu(100) surface. These results provide insight into catalytic anhydrous production of aldehydes.

12.
J Phys Chem B ; 122(2): 649-656, 2018 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-28753310

RESUMO

We use scanning tunneling microscopy (STM) to investigate the spatial arrangement of carbon monoxide (CO) and hydrogen (H) coadsorbed on a model catalyst surface, Ru(0001). We find that at cryogenic temperatures, CO forms small triangular islands of up to 21 molecules with hydrogen segregated outside of the islands. Furthermore, whereas for small island sizes (3-6 CO molecules) the molecules adsorb at hcp sites, a registry shift toward top sites occurs for larger islands (10-21 CO molecules). To characterize the CO structures better and to help interpret the data, we carried out density functional theory (DFT) calculations of the structure and simulations of the STM images, which reveal a delicate interplay between the repulsions of the different species.

13.
Nano Lett ; 17(11): 6847-6854, 2017 11 08.
Artigo em Inglês | MEDLINE | ID: mdl-28968125

RESUMO

Many macroscopic properties such as collective chiral responses enhanced by coupled plasmonic nanoparticles require complex nanostructures. However, a key challenge is to directly assemble nanosized building blocks into functional entities with designed morphologies. For example, the DNA templated nanoparticle assembly has low scalability and requires aqueous conditions, while other approaches such as controlled drying and polymer templating access only simple 1-D, 2-D, and 3-D structures with limited assembly patterns. Here, we demonstrate a new self-assembly strategy that expands the diversity of 3-D nanoparticle assemblies. By subjecting supramolecular nanocomposites to cylindrical confinement, a range of new nanoparticle assemblies such as stacked rings and single and double helices can be readily obtained with a precisely defined morphology. Circular dichroism dark field scattering measurements on the single nanowire with Au helical ribbon-like assembly show chiral plasmonic response several orders of magnitude higher than that of natural chiral materials. The phase behavior of supramolecular nanocomposite under geometric constraints is quite different from that of block copolymer. It depends on the complex interplay among nanoparticle packing and phase behavior of parent block copolymers under confinement and can be governed by nanoparticle diffusion.

14.
J Phys Chem Lett ; 8(15): 3482-3487, 2017 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-28697599

RESUMO

Common experience shows that friction converts mechanical energy into heat. The first part of this process is vibrational excitation of atoms at the interface between rubbing bodies. The second part is the removal of the vibration energy by transferring it from the interface to the substrate. However, it is difficult to disentangle the excitation and energy transfer processes. We solved this by using a system consisting of a SiO2-terminated tip sliding over graphene deposited on mica with intercalated water between them. The intercalated water was found to increase friction by a factor of ∼3 relative to dry mica. Density functional theory calculations show that water broadens the spectral range of graphene vibrations-particularly the low-frequency flexural modes-thus providing new excitation channels and also by increasing the overlap with the atomic vibrations of the mica substrate, which facilitates coupling and energy transfer.

15.
Nat Mater ; 16(5): 558-564, 2017 05.
Artigo em Inglês | MEDLINE | ID: mdl-27992418

RESUMO

Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver-gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changes occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.

16.
J Am Chem Soc ; 138(40): 13246-13252, 2016 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-27599672

RESUMO

Using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), we studied the adsorption and reactions of CO2 and CO2 + H2 on the Ni(111) surface to identify the surface chemical state and the nature of the adsorbed species during the methanation reaction. In 200 mTorr CO2, we found that NiO is formed from CO2 dissociation into CO and atomic oxygen. Additionally, carbonate (CO32-) is present on the surface from further reaction of CO2 with NiO. The addition of H2 into the reaction environment leads to reduction of NiO and the disappearance of CO32-. At temperatures >160 °C, CO adsorbed on hollow sites, and atomic carbon and OH species are present on the surface. We conclude that the methanation reaction proceeds via dissociation of CO2, followed by reduction of CO to atomic carbon and its hydrogenation to methane.

17.
Nano Lett ; 16(8): 5001-9, 2016 08 10.
Artigo em Inglês | MEDLINE | ID: mdl-27328034

RESUMO

Heterogeneous catalysis occurs at the interface between a solid catalyst and the reactants. The structure of metal catalyst nanoparticles at the metal-gas interface is a key factor that determines catalytic selectivity and activity. Here we report that second-generation nanoclusters are formed on the initial catalyst nanoparticles as a result of interaction with the reactant molecules when the nanoparticles are in a gas phase at Torr pressure or higher. The formation of the second-generation nanoclusters is manifested by a decrease of the average coordination number of the metal atoms and a shift of their core level energies in the presence of gases. The formation of second-generation nanoclusters increases the number of undercoordinated sites, which are the most active for catalysis in many cases.

18.
Nat Commun ; 7: 11924, 2016 06 21.
Artigo em Inglês | MEDLINE | ID: mdl-27323904

RESUMO

The sensitivity of semiconductor photodetectors is limited by photocarrier recombination during the carrier transport process. We developed a new photoactive material that reduces recombination by physically separating hole and electron charge carriers. This material has a specific detectivity (the ability to detect small signals) of 5 × 10(17) Jones, the highest reported in visible and infrared detectors at room temperature, and 4-5 orders of magnitude higher than that of commercial single-crystal silicon detectors. The material was fabricated by sintering chloride-capped CdTe nanocrystals into polycrystalline films, where Cl selectively segregates into grain boundaries acting as n-type dopants. Photogenerated electrons concentrate in and percolate along the grain boundaries-a network of energy valleys, while holes are confined in the grain interiors. This electrostatic field-assisted carrier separation and percolation mechanism enables an unprecedented photoconductive gain of 10(10) e(-) per photon, and allows for effective control of the device response speed by active carrier quenching.

19.
J Am Chem Soc ; 138(26): 8207-11, 2016 07 06.
Artigo em Inglês | MEDLINE | ID: mdl-27280375

RESUMO

Ambient-pressure X-ray photoelectron spectroscopy (APXPS) and high-pressure scanning tunneling microscopy (HPSTM) were used to study the structure and chemistry of model Cu(100) and Cu(111) catalyst surfaces in the adsorption and dissociation of CO2. It was found that the (100) face is more active in dissociating CO2 than the (111) face. Atomic oxygen formed after the dissociation of CO2 poisons the surface by blocking further adsorption of CO2. This "self-poisoning" mechanism explains the need to mix CO into the industrial feed for methanol production from CO2, as it scavenges the chemisorbed O. The HPSTM images show that the (100) surface breaks up into nanoclusters in the presence of CO2 at 20 Torr and above, producing active kink and step sites. If the surface is precovered with atomic oxygen, no such nanoclustering occurs.

20.
Langmuir ; 32(22): 5526-31, 2016 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-27180868

RESUMO

The supramolecular self-assembly of copper(II) octaethylporphyrin (CuOEP) and octaethylporphyrin (H2OEP) on graphitic surfaces immersed in organic solvents (dichlorobenzene, dodecane) is studied using scanning tunneling microscopy (STM) and Raman spectroscopy. STM reveals that the self-assembled structure of CuOEP in 1,2-dichlorobenzene is significantly altered by dissolved oxygen within the solvent. Raman spectroscopy reveals that the presence of the oxygen alters the molecule-substrate interaction, which is attributed to the adsorption of oxygen on the Cu center of the CuOEP, which is facilitated by electron transfer from the graphitic surface. Such oxygen-induced changes are not observed for H2OEP, indicating that the metal center of CuOEP plays a critical role. When the solvent is dodecane, we find that solvation effects dominate. CuOEP adsorbed on graphitic surfaces provides a model system relevant to the study of the transport and activation of oxygen by enzymes and other complexes.

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