Surface Sensitive Spectroscopy Research Articles

A Strep-Tag Imprinted Polymer Platform for Heterogenous Bio(electro)catalysis.

Molecularly imprinted polymers (MIPs) are artificial receptors equipped with selective recognition sites for target molecules. One of the most promising strategies for protein MIPs relies on the exploitation of short surface-exposed protein fragments, termed epitopes, as templates to imprint binding sites in a polymer scaffold for a desired protein. However, the lack of high-resolution structural data of flexible surface-exposed regions challenges the selection of suitable epitopes. Here, we addressed this drawback by developing a polyscopoletin-based MIP that recognizes recombinant proteins via imprinting of the widely used Strep-tag II affinity peptide (Strep-MIP). Electrochemistry, surface-sensitive IR spectroscopy, and molecular dynamics simulations were employed to ensure an utmost control of the Strep-MIP electrosynthesis. The functionality of this novel platform was verified with two Strep-tagged enzymes: an O2-tolerant [NiFe]-hydrogenase, and an alkaline phosphatase. The enzymes preserved their biocatalytic activities after multiple utilization confirming the efficiency of Strep-MIP as a general biocompatible platform to confine recombinant proteins for exploitation in biotechnology.

Peeling-induced interfacial roughness and charging for enhanced triboelectric power generation

To date, there have been a lot of efforts to enhance the conversion efficiency of triboelectric nanogenerators (TENGs) via physical and chemical modifications of the polymer surface. Herein, we report that a facile peeling of polymer from a substrate can enhance the triboelectric power output. The peeling of spin-coated polydimethylsiloxane (PDMS) from glass and polytetrafluoroethylene (PTFE) substrates has revealed a considerable increase in interfacial roughness and lateral friction. Surface-sensitive X-ray photoemission spectroscopy and non-contact current measurements have also revealed the transfer of counter-material and interfacial charging. The surface roughness of peeled PDMS is significant for the PTFE substrate, while the surface charge is significant for the glass substrate. The triboelectric output power density for peeled PDMS from the substrate is similar, 10.3 µW/cm2, but significantly larger than that for as-grown PDMS (2.2 µW/cm2). The peeling strength of PDMS significantly increases for glass compared to PTFE after the oxygen plasma treatment of substrates. The triboelectric charge of peeled PDMS from a plasma-treated glass substrate is almost 1.3 times larger than that from a PTFE substrate. This work implies that peeling polymer from a rough substrate with a large adhesion force would be a facile and effective way to increase the triboelectric power output, without any delicate surface treatments.

Ultrathin Boron Growth onto Nanodiamond Surfaces via Electrophilic Boron Precursors.

Diamond as a templating substrate is largely unexplored, and the unique properties of diamond, including its large bandgap, thermal conductance, and lack of cytotoxicity, makes it versatile in emergent technologies in medicine and quantum sensing. Surface termination of an inert diamond substrate and its chemical reactivity are key in generating new bonds for nucleation and growth of an overlayer material. Oxidized high-pressure high temperature (HPHT) nanodiamonds (NDs) are largely terminated by alcohols that act as nucleophiles to initiate covalent bond formation when an electrophilic reactant is available. In this work, we demonstrate a templated synthesis of ultrathin boron on ND surfaces using trigonal boron compounds. Boron trichloride (BCl3), boron tribromide (BBr3), and borane (BH3) were found to react with ND substrates at room temperature in inert conditions. BBr3 and BCl3 were highly reactive with the diamond surface, and sheet-like structures were produced and verified with electron microscopy. Surface-sensitive spectroscopies were used to probe the molecular and atomic structure of the ND constructs' surface, and quantification showed the boron shell was less than 1 nm thick after 1-24 h reactions. Observation of the reaction supports a self-terminating mechanism, similar to atomic layer deposition growth, and is likely due to the quenching of alcohols on the diamond surface. X-ray absorption spectroscopy revealed that boron-termination generated midgap electronic states that were originally predicted by density functional theory (DFT) several years ago. DFT also predicted a negative electron surface, which has yet to be confirmed experimentally here. The boron-diamond nanostructures were found to aggregate in dichloromethane and were dispersed in various solvents and characterized with dynamic light scattering for future cell imaging or cancer therapy applications using boron neutron capture therapy (BNCT). The unique templating mechanism based on nucleophilic alcohols and electrophilic trigonal precursors allows for covalent bond formation and will be of interest to researchers using diamond for quantum sensing, additive manufacturing, BNCT, and potentially as an electron emitter.

Laser induced ultrafast Gd 4f spin dynamics at the surface of amorphous CoxGd100-x ferrimagnetic alloys

We have investigated the laser induced ultrafast dynamics of Gd 4f spins at the surface of CoxGd100-x alloys by means of surface-sensitive and time-resolved dichroic resonant Auger spectroscopy. We have observed that the laser induced quenching of Gd 4f magnetic order at the surface of the CoxGd100-x alloys occur on a much longer time scale than that previously reported in “bulk sensitive” time-resolved experiments. In parallel, we have characterized the static structural and magnetic properties at the surface and in the bulk of these alloys by combining Physical Property Measurement System (PPMS) magnetometry with X-ray Magnetic Circular Dichroism in absorption spectroscopy (XMCD) and X-Ray Photoelectron spectroscopy (XPS). The PPMS and XMCD measurements give information regarding the composition in the bulk of the alloys. The XPS measurements show non-homogeneous composition at the surface of the alloys with a strongly increased Gd content within the first layers compared to the nominal bulk values. Such larger Gd concentration results in a reduced indirect Gd 4f spin-lattice coupling. It explains the “slower” Gd 4f demagnetization we have observed in our surface-sensitive and time-resolved measurements compared to that previously reported by “bulk-sensitive” measurements.

Effect of template on the photoresponsivity of BaSi2 films grown on Ge(111) substrates by molecular beam epitaxy

Epitaxial growth of BaSi2 films on Si(111) has demonstrated that the BaSi2 template can serve as a seed crystal for BaSi2 overlayers by molecular beam epitaxy (MBE) and shows high photoresponsivity, but not yet on Ge(111) substrates. We have investigated the effect of various templates on the photoresponsivity of BaSi2 films grown on Ge(111) substrates. Samples with MBE-grown templates exhibited high a-axis orientation, but the surface was uneven, leading to partial oxidation of the BaSi2 film. On the other hand, the sample without such templates showed a smoother surface but was confirmed to be polycrystalline. When a template formed by the combination of solid phase epitaxy (SPE) and subsequent annealing for 30 min was used, a-axis-oriented BaSi2 together with 111-oriented Si appeared in the θ–2θ x-ray diffraction (XRD) patterns. The fact that no crystalline Si was detected by the surface-sensitive Raman spectroscopy and that the full width at half maximum of the XRD BaSi2 600 peak was increased to 2.686° in such samples suggests that Si aggregates were at the BaSi2/Ge interface. The photoresponsivity of the epitaxial BaSi2 film with MBE-grown templates reached 0.14 A W−1 at a wavelength of 790 nm. This is the highest photoresponsivity reported so far for BaSi2 films on Ge substrates. Even for samples without the MBE-grown templates, SPE-grown templates significantly increased the photoresponsivity up to 0.10 A W−1. These results confirm that the template has a significant impact on the photoresponsivity of BaSi2 films on Ge(111) substrates.

Series representation of differential elastic scattering cross section for electrons: Applications in theoretical models of electron transport in condensed matter

Series representation of differential elastic scattering cross section for electrons: Applications in theoretical models of electron transport in condensed matter

Spin polarized electron dynamics enhance water splitting efficiency by yttrium iron garnet photoanodes: a new platform for spin selective photocatalysis.

This work presents a spectroscopic and photocatalytic comparison of water splitting using yttrium iron garnet (Y3Fe5O12, YIG) and hematite (α-Fe2O3) photoanodes. Despite similar electronic structures, YIG significantly outperforms widely studied hematite, displaying more than an order of magnitude increase in photocurrent density. Probing the charge and spin dynamics by ultrafast, surface-sensitive XUV spectroscopy reveals that the enhanced performance arises from (1) reduced polaron formation in YIG compared to hematite and (2) an intrinsic spin polarization of catalytic photocurrents in YIG. Ultrafast XUV measurements show a reduction in the formation of surface electron polarons compared to hematite due to site-dependent electron-phonon coupling. This leads to spin polarized photocurrents in YIG where efficient charge separation occurs on the Td sub-lattice compared to fast trapping and electron/hole pair recombination on the Oh sub-lattice. These lattice-dependent dynamics result in a long-lived spin aligned hole population at the YIG surface, which is directly observed using XUV magnetic circular dichroism. Comparison of the Fe M2,3 and O L1-edges show that spin aligned holes are hybridized between O 2p and Fe 3d valence band states, and these holes are responsible for highly efficient, spin selective water oxidation by YIG. Together, these results point to YIG as a new platform for highly efficient, spin selective photocatalysis.

Investigating the Reaction Mechanism of Vinylene Carbonate Additive in Lithium Ion Batteries Using X-Ray Photoelectron Spectroscopy

The rechargeable Li-ion battery is an enabling technology which facilitates the electrification of the automotive industry and reduces the demand for fossil fuels. During the charge and discharge of a battery, a solid-electrolyte interphase (SEI) forms between the liquid electrolyte and the solid negative electrode as a result of electrolyte degradation. The chemical and physical stability and the functionality of the SEI is a key determining factor of battery performance. The chemical composition of the SEI is mainly controlled by the choice of solvent and salt used, but can be manipulated by the addition of electrolyte additives that influence the electrolyte degradation process.Vinylene carbonate (VC) is an additive used in many commercial Li-ion battery configurations. The addition of a small amount of VC to ethylene carbonate (EC) containing electrolytes has been demonstrated to drastically improve several performance metrics for batteries including cycle life, coulombic efficiencies, capacity retention and thermal stability. The success of VC is widely attributed to its ability to form a thinner, denser and more robust SEI, which better protects the electrode surface and prevents further electrolyte consumption. This improvement in stability has been linked to the presence of poly(VC) in the SEI, but the mechanism by which VC reacts in EC-containing electrolytes is still an area of ongoing study. Whilst computational methods have suggested several potential decomposition pathways of electrolytes containing VC, it is yet to be convincingly demonstrated experimentally. Whilst there is a general consensus about ‘What?’ forms in the SEI on the addition of VC to EC-containing solvent, this work aims to confirm ‘Where?’ these components are in the interface and the currently unanswered questions of ‘How?’ and ‘Why?’ they form.Using highly surface sensitive photoelectron spectroscopy (PES) measurements of the SEI deposited at various potentials, we identify the differences in composition and structure that result from the addition of VC additive to EC-containing electrolytes. The SEI formation is studied using a smooth Au surface as the model working electrode and a fluorine free EC:diethyl carbonate (DEC) (1:9) 1 M LiClO4 electrolyte in an attempt to isolate the impact of VC on the SEI. A potential step procedure allows analysis of the working electrode surface by PES at several progressively more negative potentials on the first charge. Through systematic variation of components such as the concentration of VC, the ratio of EC:DEC and swapping Au for other electrode materials such as Cu or Si, the interaction between VC, EC and the electrode surface is revealed. The differences in SEI composition and structure formed in each environment and at each potential step are correlated to quartz crystal microbalance (QCM) data in order to identify potential reaction mechanisms and formation processes. The results play a key role in understanding the reaction pathway of VC-containing electrolytes and will accelerate development of more efficient electrolyte additives.

Revealing ‘invisible’ subsurface structural change/damage in silicate glass made by ‘nearly-elastic contact’ with a spherical smooth surface

This research delves into the hypothesis that elastic contact with an external object can generate `invisible' surface defects, consequently reducing the apparent load to failure, or strength, of glass. This theory, while longstanding, has left the intricate details associated with such defects largely unknown. Utilizing vibrational spectroscopic techniques—with a depth sensitivity on the order of approximately 100 nm—and chemical etching, the study investigates subsurface structural alterations in and around the area subjected to nominally-elastic contact with a Hertzian indenter. Direct contact with the spherical indenter led to the recovery of over 99.96 % of the surface topography, suggesting a near-perfect post-indentation surface. However, surface-sensitive vibrational spectroscopy unveiled structural changes in the subsurface silicate network. Additionally, a shift in the vibrational spectrum was observed in areas that had experienced elastic deformation along with the contact region and fully recovered upon unloading. This shift indicates residual structural changes, even in these non-contacted regions. When the indenter tip was slid across the surface under loads much lower than the nominal yield strength, interfacial friction made the top-most region more susceptible to base-catalyzed hydrolysis. The depth affected by friction was significantly shallower than the length scale of the principal stress fields at maximum load during Hertzian indentation. Despite the glass surface maintaining its microscopic defect-free appearance, these subsurface structural changes—induced by indentation and friction—are proposed to be key factors responsile for the decrease in the apparent load to failure of glass.

Fully First-Principles Surface Spectroscopy with Machine Learning.

Our current understanding of the structure and dynamics of aqueous interfaces at the molecular level has grown substantially due to the continuous development of surface-specific spectroscopies, such as vibrational sum-frequency generation (VSFG). As in other vibrational spectroscopies, we must turn to atomistic simulations to extract all of the information encoded in the VSFG spectra. The high computational cost associated with existing methods means that they have limitations in representing systems with complex electronic structure or in achieving statistical convergence. In this work, we combine high-dimensional neural network interatomic potentials and symmetry-adapted Gaussian process regression to overcome these constraints. We show that it is possible to model VSFG signals with fully ab initio accuracy using machine learning and illustrate the versatility of our approach on the water/air interface. Our strategy allows us to identify the main sources of theoretical inaccuracy and establish a clear pathway toward the modeling of surface-sensitive spectroscopy of complex interfaces.

Studying Molecular Rearrangement of P1 Dye at a Passivating Alumina Surface Using Vibrational Sum-Frequency Generation Spectroscopy: Effect of Atomic-Level Roughness.

The effect of roughness and thickness of alumina layers, mimicking the passivation layer commonly used in dye-sensitized photoelectrodes, on the molecular adsorption of P1 dye, 4-(bi(4-(2,2-dicyano-vinyl)-thiophene-2-yl]-phenyl]-aminobenzoic acid) has been studied using surface-sensitive vibrational sum frequency generation(VSFG) spectroscopy. The VSFG spectra reveal the formation of poorly ordered dye layers on relatively rough surfaces where XPS measures a higher dye loading. Furthermore, these poorly ordered dye molecules are responsible for the generation of trapped electronic states as probed by successive photoluminescence (PL) measurements. Surface sensitive VSFG spectroscopy in combination with XPS and PL measurements provide complementary spectral information on ordering of the adsorbed dyes, their density on the surface and electronic states of the adsorbed monolayer which are prerequisite for improving our understanding of molecularly functionalized photoelectrodes and their further development.

Ion-Specific Interactions at a Mineral-Water Interface Revealed by Surface-Sensitive Spectroscopy under Flow Conditions

Ion-Specific Interactions at a Mineral-Water Interface Revealed by Surface-Sensitive Spectroscopy under Flow Conditions

Unraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO2 Electroreduction

Understanding the atomic and electronic changes of active sites promotes the whole new sight into electrochemical carbon dioxide reduction reaction (CO2RR), which provides a feasible strategy to achieve carbon neutrality. Here we employ operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) to track the structural evolution of Ni(II) phthalocyanine (NiPc), considered as the model catalysts with uniform Ni-N4-C8 moiety, during the CO2RR. The HERFD-XAS method is in favor of elucidating the interaction of the reactant/catalyst interface from the atomic electronic structure dimension, facilitating the establishment of the catalytic mechanism and the dynamic structure changes. Based on operando measurement, surface sensitive difference spectra (Δµ) and spectroscopy simulation, the interfacial interactions between the active sites of NiPc and reactants are monitored and the Ni species gradually reduced by increasing the applied potential is discovered. HERFD-XAS method offers an advanced and powerful tool for elucidating the complex catalytic mechanism in further various systems.

Interplay of field-induced molecular dipole alignment and compensating surface polarization in low-temperature P−V hysteresis of MAPbBr3(001)

We demonstrate the presence of a hysteresis in tunneling spectra acquired at 4.3 K on cleaved MA-Br terminated (001) surfaces of ${\mathrm{MAPbBr}}_{3}$ single crystals. Simulations of the tunneling spectra reveal an underlying polarization-voltage ($P\text{\ensuremath{-}}V$) hysteresis, which is caused by an interplay of subsurface field-induced rotation and alignment of the MA molecules, stabilized by dipole-dipole interactions, and an ion-lattice relaxation. The resulting subsurface polarization is counteracted by a compensating surface polarization, detectable by surface-sensitive tunneling spectroscopy.

Electronic Structure and Ultrafast Electron Dynamics in CuO Photocatalysts Probed by Surface Sensitive Femtosecond X-ray Absorption Near-Edge Structure Spectroscopy

CuO is often employed as a photocathode for H2 evolution and CO2 reduction, but observed efficiency is still far below the theoretical limit. To bridge the gap requires understanding the CuO electronic structure; however, computational efforts lack consensus on the orbital character of the photoexcited electron. In this study, we measure the femtosecond XANES spectra of CuO at the Cu M2,3 and O L1 edges to track the element-specific dynamics of electrons and holes. Results show that photoexcitation represents an O 2p to Cu 4s charge transfer state indicating the conduction band electron has primarily Cu 4s character. We also observe ultrafast mixing of Cu 3d and 4s conduction band states mediated by coherent phonons, with Cu 3d character of the photoelectron reaching a maximum of 16%. This is the first observation of the photoexcited redox state in CuO, and results provide a benchmark for theory where electronic structure modeling still relies heavily on model-dependent parametrization.

Interaction of Cyanoacrylate with Metal Oxide Surfaces (Cu, Al).

Cyanoacrylates are an extremely reactive class of adhesives. Despite their commercial use as instant adhesives, the adhesion mechanism, especially to technically relevant oxidized metal surfaces, has not yet been sufficiently investigated. In the present work, ultra-thin ethyl cyanoacrylate films are deposited on copper oxide and aluminum oxide by spin coating and cured there. Various surface sensitive spectroscopy methods are used to identify possible interactions. X-Ray photoelectron spectroscopy (XPS) indicates, among other information, hydrogen bonding of the carbonyl group to the oxidized surfaces. Metastable induced electron spectroscopy (MIES) measurements support the theory of this preferential molecular orientation. In addition, XPS shows the presence of an ionic carboxylate (COO- ) species at the interface. Infrared reflection adsorption spectroscopy (IRRAS) measurements confirm this ionic interaction and furthermore allow to investigate the influence of water on the reaction. A possible interaction mechanism of cyanoacrylates with metal oxides could be proposed. The formation of a carboxylate species probably occurs by hydrolysis of the ethyl group via the intermediate of a carboxyl (COOH) species.

Analysis of Ti nanolayers irradiated with Xeq＋ ions using synchrotron radiation based X-ray reflectometry

To characterize morphology and physicochemical properties of nanolayers the surface-sensitive X-ray spectroscopy techniques are often successfully applied. These techniques are still being developed in order to achieve better depth resolution and detection limits. In this article, we present measurements of morphology of Ti nanolayers (deposited on Si substrate) with thickness of 25 nm, 50 nm and 75 nm, unmodified and irradiated with Xeq＋ ions (where q is the charge state of the ion), which were carried out using synchrotron radiation (SR) based XRR technique. The nanolayers were irradiated with low-energy (of the order of hundreds of keV) highly charged Xeq＋ (q = 25, 30, 35) ions, at the Kielce EBIS facility (Jan Kochanowski University, Kielce, Poland). The SR-XRR measurements were performed at Elettra Synchrotron X-ray fluorescence beamline, using X-ray beam with energy of 6.0 keV. The obtained reflectivity curves were modelled by creating a structure consisting (from the bottom to the top) of silicon substrate (Si), main Ti layer, TiO2 layer, and TiO2(a) amorphous layer, with contamination of hydrocarbons, carboxylates or alkoxides. The experimental results obtained with the SR-XRR technique for the nanolayers, unmodified and irradiated with the Xeq＋, show the dependence of the TiO2 layers morphology on the Xe ions charge state. In the article the sample preparation, measurement using SR-XRR and the data analysis procedures are described in details and the advantages and disadvantages of the SR-XRR technique in the context of nanolayer studies are discussed.

Elucidating Electrocatalytic Oxygen Reduction Kinetics via Intermediates by Time-Dependent Electrochemiluminescence.

Facile evaluation of oxygen reduction reaction (ORR) kinetics for electrocatalysts is critical for sustainable fuel-cell development and industrial H2 O2 production. Despite great success in ORR studies using mainstream strategies, such as the membrane electrode assembly, rotation electrodes, and advanced surface-sensitive spectroscopy, the time and spatial distribution of reactive oxygen species (ROS) intermediates in the diffusion layer remain unknown. Using time-dependent electrochemiluminescence (Td-ECL), we report an intermediate-oriented method for ORR kinetics analysis. Owing to multiple ultrasensitive stoichiometric reactions between ROS and the ECL emitter, except for electron transfer numbers and rate constants, the potential-dependent time and spatial distribution of ROS were successfully obtained for the first time. Such exclusively uncovered information would guide the development of electrocatalysts for fuel cells and H2 O2 production with maximized activity and durability.

Nanostructured Silicon Matrix for Materials Engineering.

Tin-containing layers with different degrees of oxidation are uniformly distributed along the length of silicon nanowires formed by a top-down method by applying metalorganic chemical vapor deposition. The electronic and atomic structure of the obtained layers is investigated by applying nondestructive surface-sensitive X-ray absorption near edge spectroscopy using synchrotron radiation. The results demonstrated, for the first time, a distribution effect of the tin-containing phases in the nanostructured silicon matrix compared to the results obtained for planar structures at the same deposition temperatures. The amount and distribution of tin-containing phases can be effectively varied and controlled by adjusting the geometric parameters (pore diameter and length) of the initial matrix of nanostructured silicon. Due to the occurrence of intense interactions between precursor molecules and decomposition by-products in the nanocapillary, as a consequence of random thermal motion of molecules in the nanocapillary, which leads to additional kinetic energy and formation of reducing agents, resulting in effective reduction of tin-based compounds to a metallic tin state for molecules with the highest penetration depth in the nanostructured silicon matrix. This effect will enable clear control of the phase distributions of functional materials in 3D matrices for a wide range of applications.

Evidence of electron correlation and weak bulk plasmon in SrMoO3

We investigate the electronic structure of highly conducting perovskite SrMoO3 using valence band photoemission spectroscopy and electronic structure calculations. Large intensity corresponding to coherent feature close to Fermi level is captured by density functional theory (DFT) calculation. An additional satellite at ∼3 eV binding energy remains absent in DFT, hybrid functional (DFT-hybrid) and dynamical mean field theory (DFT + DMFT) calculations. Mo 4d spectra obtained with different surface sensitive photoemission spectroscopy suggest different surface and bulk electronic structures. DFT + DMFT spectral function is in excellent agreement with the coherent feature in the bulk Mo 4d spectra, revealing moderate electron correlation strength. A large plasmon satellite and signature of strong electron correlation are observed in the surface spectra, while the bulk spectra exhibits a weak plasmon satellite.