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The nanoscale structure and dynamics of proteins on surfaces has been extensively studied using various imaging techniques, such as transmission electron microscopy and atomic force microscopy (AFM) in liquid environments. These powerful imaging techniques, however, can potentially damage or perturb delicate biological material and do not provide chemical information, which prevents a fundamental understanding of the dynamic processes underlying their evolution under physiological conditions. Here, we use a platform developed in our laboratory that enables acquisition of infrared (IR) spectroscopy and AFM images of biological material in physiological liquids with nanometer resolution in a cell closed by atomically thin graphene membranes transparent to IR photons. In this work, we studied the self-assembly process of S-layer proteins at the graphene-aqueous solution interface. The graphene acts also as the membrane separating the solution containing the proteins and Ca2+ ions from the AFM tip, thus eliminating sample damage and contamination effects. The formation of S-layer protein lattices and their structural evolution was monitored by AFM and by recording the amide I and II IR absorption bands, which reveal the noncovalent interaction between proteins and their response to the environment, including ionic strength and solvation. Our measurement platform opens unique opportunities to study biological material and soft materials in general.
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Glicoproteínas de Membrana , Microscopia de Força Atômica , Nanotecnologia , Espectrofotometria Infravermelho , Amidas/química , Cálcio , Grafite/química , Glicoproteínas de Membrana/química , Glicoproteínas de Membrana/metabolismo , Glicoproteínas de Membrana/ultraestrutura , Concentração Osmolar , Fótons , Solventes/química , Água/químicaRESUMO
Understanding the chemical environment and interparticle dynamics of nanoparticle electrocatalysts under operating conditions offers valuable insights into tuning their activity and selectivity. This is particularly important to the design of Cu nanocatalysts for CO2 electroreduction due to their dynamic nature under bias. Here, we have developed operando electrochemical resonant soft X-ray scattering (EC-RSoXS) to probe the chemical identity of active sites during the dynamic structural transformation of Cu nanoparticle (NP) ensembles through 1 µm thick electrolyte. Operando scattering-enhanced X-ray absorption spectroscopy (XAS) serves as a powerful technique to investigate the size-dependent catalyst stability under beam exposure while monitoring the potential-dependent surface structural changes. Small NPs (7 nm) in aqueous electrolyte were found to experience a predominant soft X-ray beam-induced oxidation to CuO despite only sub-second X-ray exposure. In comparison, large NPs (18 nm) showed improved resistivity to beam damage, which allowed the reliable observation of surface Cu2O electroreduction to metallic Cu. Small-angle X-ray scattering (SAXS) statistically probes the particle-particle interactions of large ensembles of NPs. This study points out the need for rigorous examination of beam effects for operando X-ray studies on electrocatalysts. The strategy of using EC-RSoXS that combines soft XAS and SAXS can serve as a general approach to simultaneously investigate the chemical environment and interparticle information on nanocatalysts.
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Dióxido de Carbono , Catálise , Espalhamento a Baixo Ângulo , Difração de Raios X , Raios XRESUMO
Undercoordinated metal nanoclusters have shown great promise for various catalytic applications. However, their activity is often limited by the covalently bonded ligands, which could block the active surface sites. Here, we investigate the ligand removal process for Au25 nanoclusters using both thermal and electrochemical treatments, as well as its impact on the electroreduction of CO2 to CO. The Au25 nanoclusters are synthesized with 2-phenylethanethiol as the capping agent and anchored on sulfur-doped graphene. The thiolate ligands can be readily removed under either thermal annealing at ≥180°C or electrochemical biasing at ≤-0.5 V vs reversible hydrogen electrode, as evidenced by the Cu underpotential deposition surface area measurement, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. However, these ligand-removing treatments also trigger the structural evolution of Au25 nanoclusters concomitantly. The thermally and electrochemically treated Au25 nanoclusters show enhanced activity and selectivity for the electrochemical CO2-to-CO conversion than their pristine counterpart, which is attributed to the exposure of undercoordinated Au sites on the surface after ligand removal. This work provides facile strategies to strip away the staple ligands from metal nanoclusters and highlights its importance in promoting the catalytic performances.
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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 10â¯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.
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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.
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Electrode/electrolyte interfaces play a vital role in various electrochemical systems, but in situ characterization of such buried interfaces remains a major challenge. Several efforts to develop techniques or to modify existing techniques to study such interfaces are showing great promise to overcome this challenge. Successful examples include electrochemical scanning tunneling microscopy (EC-STM), surface-sensitive vibrational spectroscopies, environmental transmission electron microscopy (E-TEM), and surface X-ray scattering. Other techniques such as X-ray core-level spectroscopies are element-specific and chemical-state-specific, and are being widely applied in materials science research. Herein we showcase four types of newly developed strategies to probe electrode/electrolyte interfaces in situ with X-ray core-level spectroscopies. These include the standing wave approach, the meniscus approach, and two liquid cell approaches based on X-ray photoelectron spectroscopy and soft X-ray absorption spectroscopy. These examples demonstrate that with proper modifications, many ultra-high-vacuum based techniques can be adapted to study buried electrode/electrolyte interfaces and provide interface-sensitive, element- and chemical-state-specific information, such as solute distribution, hydrogen-bonding network, and molecular reorientation. At present, each method has its own specific limitations, but all of them enable in situ and operando characterization of electrode/electrolyte interfaces that can provide important insights into a variety of electrochemical systems.
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Efficient conversion of photonic to plasmonic energy is important for nano-optical applications, particularly imaging and spectroscopy. Recently a new generation of photonic/plasmonic transducers, the 'campanile' probes, has been developed that overcomes many shortcomings of previous near-field probes by efficiently merging broadband field enhancement with bidirectional coupling of far- to near-field electromagnetic modes. In this work we compare the properties of the campanile structure with those of current NSOM tips using finite element simulations. Field confinement, enhancement, and polarization near the apex of the probe are evaluated relative to local fields created by conical tapered tips in vacuum and in tip-substrate gap mode. We show that the campanile design has similar field enhancement and bandwidth capabilities as those of ultra-sharp metallized tips, but without the substrate and sample restrictions inherent in the tip-surface gap mode operation often required by those tips. In addition, we show for the first time that this campanile probe structure also significantly enhances the radiative rate of any dipole emitter located near the probe apex, quantifying the enhanced decay rate and demonstrating that over 90% of the light radiated by the emitter is "captured" by this probe. This is equivalent to collecting the light from a solid angle of ~3.6 pi. These advantages are crucial for performing techniques such as Raman and IR spectroscopy, white-light nano-ellipsometry and ultrafast pump-probe studies at the nanoscale.
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Desenho Assistido por Computador , Ressonância de Plasmônio de Superfície/instrumentação , Transdutores , Simulação por Computador , Desenho de Equipamento , Análise de Falha de Equipamento , Luz , Modelos Teóricos , Espalhamento de RadiaçãoRESUMO
Polyvinylpyrollidone (PVP)-capped platinum nanoparticles (NPs) are found to change shape from spherical to flat when deposited on mesoporous silica substrates (SBA-15). Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) analyses are used in these studies. The SAXS results indicate that, after deposition, the 2 nm NPs have an average gyration radius 22% larger than in solution, while the EXAFS measurements indicate a decrease in first neighbor co-ordination number from 9.3 to 7.4. The deformation of these small capped NPs is attributed to interactions with the surface of the SBA-15 support, as evidenced by X-ray absorption near-edge structure (XANES).
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We have demonstrated hyperspectral tip-enhanced Raman imaging on dielectric substrates using linearly polarized light and nanofabricated coaxial antenna tips. A full Raman spectrum was acquired at each pixel of a 256 by 256 pixel contact-mode atomic force microscope image of carbon nanotubes grown on a fused silica microscope coverslip, allowing D and G mode intensity and D-mode peak shifts to be measured with â¼20 nm spatial resolution. Tip enhancement was sufficient to acquire useful Raman spectra in 50-100 ms. Coaxial scan probes combine the efficiency and enhanced, ultralocalized optical fields of plasmonically coupled antennae with the superior topographical imaging properties of sharp metal tips. The yield of the coaxial tip fabrication process is close to 100%, and the tips are sufficiently durable to support hours of contact-mode force microscope imaging. Our coaxial probes avoid the limitations associated with the "gap-mode" imaging geometry used in most tip-enhanced Raman studies to date, where a sharp metal tip is held â¼1 nm above a metallic substrate with the sample located in the gap.
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To understand corrosion, energy storage, (electro)catalysis, etc., obtaining chemical information on the solid-liquid interface is crucial but remains extremely challenging. Here, X-ray absorption spectroscopy (XAS) is used to study the solid-liquid interface between TiO2 and H2O. A thin film (6.7 nm) of TiO2 is deposited on an X-ray-transparent SiNx window, acting as the working electrode in a three-electrode flow cell. The spectra are collected based on the electron emission resulting from the decay of the X-ray-induced core-hole-excited atoms, which we show is sensitive to the solid-liquid interface within a few nm. The drain currents measured at the working and counter electrodes are identical but of opposite sign. With this method, we found that the water layer next to anatase is spectroscopically similar to ice. This result highlights the potential of electron-yield XAS to obtain chemical and structural information with a high sensitivity for the species at the electrode-electrolyte interface.
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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.
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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.
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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.
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Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.
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Grafite/química , Pressão Atmosférica , Tamanho da Partícula , Espectroscopia Fotoeletrônica , Propriedades de SuperfícieRESUMO
Two-dimensional monolayer transition metal dichalcogenide semiconductors are ideal building blocks for atomically thin, flexible optoelectronic and catalytic devices. Although challenging for two-dimensional systems, sub-diffraction optical microscopy provides a nanoscale material understanding that is vital for optimizing their optoelectronic properties. Here we use the 'Campanile' nano-optical probe to spectroscopically image exciton recombination within monolayer MoS2 with sub-wavelength resolution (60 nm), at the length scale relevant to many critical optoelectronic processes. Synthetic monolayer MoS2 is found to be composed of two distinct optoelectronic regions: an interior, locally ordered but mesoscopically heterogeneous two-dimensional quantum well and an unexpected â¼300-nm wide, energetically disordered edge region. Further, grain boundaries are imaged with sufficient resolution to quantify local exciton-quenching phenomena, and complimentary nano-Auger microscopy reveals that the optically defective grain boundary and edge regions are sulfur deficient. The nanoscale structure-property relationships established here are critical for the interpretation of edge- and boundary-related phenomena and the development of next-generation two-dimensional optoelectronic devices.