Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering.

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO2 (rutile and P25) with increasing oxygen deficiency and Ti3+ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti3+ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti3+ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.

Probing the Birth and Ultrafast Dynamics of Hydrated Electrons at the Gold/Liquid Water Interface via an Optoelectronic Approach.

The hydrated electron has fundamental and practical significance in radiation and radical chemistry, catalysis, and radiobiology. While its bulk properties have been extensively studied, its behavior at solid/liquid interfaces is still unclear due to the lack of effective tools to characterize this short-lived species in between two condensed matter layers. In this study, we develop a novel optoelectronic technique for the characterization of the birth and structural evolution of solvated electrons at the metal/liquid interface with a femtosecond time resolution. Using this tool, we record for the first time the transient spectra (in a photon energy range from 0.31 to 1.85 eV) in situ with a time resolution of 50 fs revealing several novel aspects of their properties at the interface. Especially the transient species show state-dependent optical transition behaviors from being isotropic in the hot state to perpendicular to the surface in the trapped and solvated states. The technique will enable a better understanding of hot electron driven reactions at electrochemical interfaces.

Polyvinylpyrrolidone-Coordinated Single-Site Platinum Catalyst Exhibits High Activity for Hydrogen Evolution Reaction.

The essence of developing a Pt-based single-atom catalyst (SAC) for hydrogen evolution reaction (HER) is the preparation of well-defined and stable single Pt sites with desired electrocatalytic efficacy. Herein, we report a facile approach to generate uniformly dispersed Pt sites with outstanding HER performance via a photochemical reduction method using polyvinylpyrrolidone (PVP) molecules as the key additive to significantly simplify the synthesis and enhance the catalytic performance. The as-prepared catalyst displays remarkable kinetic activities (20 times higher current density than the commercially available Pt/C) with excellent stability (76.3 % of its initial activity after 5000 cycles) for HER. EXAFS measurements and DFT calculations demonstrate a synergetic effect, where the PVP ligands and the support together modulate the electronic structure of the Pt atoms, which optimize the hydrogen adsorption energy, resulting in a considerably improved HER activity.

Resolving the chemical identity of H2SO4 derived anions on Pt(111) electrodes: they're sulfate.

Understanding how electrolyte composition controls electrocatalytic reactions requires molecular-level insight into electrode/electrolyte interaction. Perhaps the most basic aspect of this interaction, the speciation of the interfacial ion, is often controversial for even relatively simple systems. For example, for Pt(111) in 0.5 M H2SO4 it has long been debated whether the adsorbed anion is SO42-, HSO4- or an H3O+SO42- ion pair. Here we apply interface-specific vibrational sum frequency (VSF) spectroscopy and theory to this problem and perform an isotope exchange study: we collect VSF spectra of Pt(111) in H2SO4(H2O) and D2SO4(D2O) as a function of bias and show that at all potentials they are identical. This is the most direct spectroscopic evidence to date that SO42- is the dominant adsorbate, despite the fact that at 0.5 M H2SO4 bulk solution is dominated by HSO4-. This approach is based on the unique selection rule of the VSF spectroscopy and thus offers a new way of accessing general electrode/electrolyte interaction in electrocatalysis.

Hydrophobic Water Probed Experimentally at the Gold Electrode/Aqueous Interface.

Quantitative description of reaction mechanisms in aqueous phase electrochemistry requires experimental characterization of local water structure at the electrode/aqueous interface and its evolution with changing potential. Gaining such insight experimentally under electrochemical conditions is a formidable task. The potential-dependent structure of a subpopulation of interfacial water with one OH group pointing towards a gold working electrode is characterized using interface specific vibrational spectroscopy in a thin film electrochemical cell. Such free-OH groups are the molecular level observable of an extended hydrophobic interface. This free-OH interacts only weakly with the Au surface at all potentials, has an orientational distribution that narrows approaching the potential of zero charge, and disappears on oxidation of the gold electrode.

Experimentally probing the libration of interfacial water: the rotational potential of water is stiffer at the air/water interface than in bulk liquid.

Most properties of liquid water are determined by its hydrogen-bond network. Because forming an aqueous interface requires termination of this network, one might expect the molecular level properties of interfacial water to markedly differ from water in bulk. Intriguingly, much prior experimental and theoretical work has found that, from the perspective of their time-averaged structure and picosecond structural dynamics, hydrogen-bonded OH groups at an air/water interface behave the same as hydrogen-bonded OH groups in bulk liquid water. Here we report the first experimental observation of interfacial water's libration (i.e. frustrated rotation) using the laser-based technique vibrational sum frequency spectroscopy. We find this mode has a frequency of 834 cm(-1), ≈165 cm(-1) higher than in bulk liquid water at the same temperature and similar to bulk ice. Because libration frequency is proportional to the stiffness of water's rotational potential, this increase suggests that one effect of terminating bulk water's hydrogen bonding network at the air/water interface is retarding rotation of water around intact hydrogen bonds. Because in bulk liquid water the libration plays a key role in stabilizing reaction intermediates and dissipating excess vibrational energy, we expect the ability to probe this mode in interfacial water to open new perspectives on the kinetics of heterogeneous reactions at aqueous interfaces.

Phase transition behaviors of the supported DPPC bilayer investigated by sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM).

The phase transition behaviors of a supported bilayer of dipalmitoylphosphatidyl-choline (DPPC) have been systematically evaluated by in situ sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM). By using an asymmetric bilayer composed of per-deuterated and per-protonated monolayers, i.e., DPPC-d75/DPPC and a symmetric bilayer of DPPC/DPPC, we were able to probe the molecular structural changes during the phase transition process of the lipid bilayer by SFG spectroscopy. It was found that the DPPC bilayer is sequentially melted from the top (adjacent to the solution) to bottom leaflet (adjacent to the substrate) over a wide temperature range. The conformational ordering of the supported bilayer does not decrease (even slightly increases) during the phase transition process. The conformational defects in the bilayer can be removed after the complete melting process. The phase transition enthalpy for the bottom leaflet was found to be approximately three times greater than that for the top leaflet, indicating a strong interaction of the lipids with the substrate. The present SFG and AFM observations revealed similar temperature dependent profiles. Based on these results, the temperature-induced structural changes in the supported lipid bilayer during its phase transition process are discussed in comparison with previous studies.

Characterization of water dissociation on α-Al2O3(11[combining macron]02): theory and experiment.

The interaction of water with α-alumina (i.e. α-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with α-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined α-Al2O3(11[combining macron]02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1-4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schrödinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm(-1). Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.

Optically probing Al-O and O-H vibrations to characterize water adsorption and surface reconstruction on α-alumina: an experimental and theoretical study.

Oxide/water interfaces are ubiquitous in a wide variety of applications and the environment. Despite this ubiquity, and attendant decades of study, gaining molecular level insight into water/oxide interaction has proven challenging. In part, this challenge springs from a lack of tools to concurrently characterize changes in surface structure (i.e., water/oxide interaction from the perspective of the solid) and O-H population and local environment (i.e., water/oxide interaction from the water perspective). Here, we demonstrate the application of surface specific vibrational spectroscopy to the characterization of the interaction of the paradigmatic α-Al2O3(0001) surface and water. By probing both the interfacial Al-O (surface phonon) and O-H spectral response, we characterize this interaction from both perspectives. Through electronic structure calculation, we assign the interfacial Al-O response and rationalize its changes on surface dehydroxylation and reconstruction. Because our technique is all-optical and interface specific, it is equally applicable to oxide surfaces in vacuum, ambient atmospheres and at the solid/liquid interface. Application of this approach to additional alumina surfaces and other oxides thus seems likely to significantly expand our understanding of how water meets oxide surfaces and thus the wide variety of phenomena this interaction controls.

Enzyme-catalyzed hydrolysis of the supported phospholipid bilayers studied by atomic force microscopy.

Atomic force microscopy (AFM) is employed to reveal the morphological changes of the supported phospholipid bilayers hydrolyzed by a phospholipase A(2) (PLA(2)) enzyme in a buffer solution at room temperature. Based on the high catalytic selectivity of PLA(2) toward l-enantiomer phospholipids, five kinds of supported bilayers made of l- and D-dipalmitoylphosphatidylcholines (DPPC), including l-DPPC (upper leaflet adjacent to solution)/l-DPPC (bottom leaflet) (or l/l in short), l/d, d/l, d/d, and racemic ld/ld, were prepared on a mica surface in gel-phase, to explicate the kinetics and mechanism of the enzyme-induced hydrolysis reaction in detail. AFM observations for the l/l bilayer show that the hydrolysis rate for l-DPPC is significantly increased by PLA(2) and most of the hydrolysis products desorb from substrate surface in 40 min. As d-enantiomers are included in the bilayer, the hydrolysis rate is largely decreased in comparison with the l/l bilayer. The time used to hydrolyze the as-prepared bilayers by PLA(2) increases in the sequence of l/l, l/d, ld/ld, and d/l (d/d is inert to the enzyme action). d-enantiomers in the enantiomer hybrid bilayers remain on the mica surface at the end of the hydrolysis reaction. It was confirmed that the hydrolysis reaction catalyzed by PLA(2) preferentially occurs at the edges of pits or defects on the bilayer surface. The bilayer structures are preserved during the hydrolysis process. Based on these observations, a novel kinetics model is proposed to quantitatively account for the PLA(2)-catalyzed hydrolysis of the supported phospholipid bilayers. The model simulation demonstrates that PLA(2) mainly binds with lipids at the perimeter of defects in the upper leaflet and leads to a hydrolysis reaction, yielding species soluble to the solution phase. The lipid molecules underneath subsequently flip up to the upper leaflet to maintain the hydrophilicity of the bilayer structure. Our analysis shows that d-enantiomers in the hybrid bilayers considerably reduce the hydrolysis rate by its ineffective binding with PLA(2).

Interfacial structure of soft matter probed by SFG spectroscopy.

Sum frequency generation (SFG) vibrational spectroscopy, an interface-specific technique in contrast to, for example, attenuated total reflectance spectroscopy, which is only interface sensitive, has been employed to investigate the surface and interface structure of soft matter on a molecular scale. The experimental arrangement required to carry out SFG spectroscopy, with particular reference to soft matter, and the analytical methods developed to interpret the spectra are described. The elucidation of the interfacial structure of soft matter systems is an essential prerequisite in order to understand and eventually control the surface properties of these important functional materials.

Integration of conventional surface science techniques with surface-sensitive azimuthal and polarization dependent femtosecond-resolved sum frequency generation spectroscopy.

Experimental insight into the elementary processes underlying charge transfer across interfaces has blossomed with the wide-spread availability of ultra-high vacuum (UHV) setups that allow the preparation and characterization of solid surfaces with well-defined molecular adsorbates over a wide range of temperatures. Within the last 15 years, such insights have extended to charge transfer heterostructures containing solids overlain by one or more atomically thin two dimensional materials. Such systems are of wide potential interest both because they appear to offer a path to separate surface reactivity from bulk chemical properties and because some offer completely novel physics, unrealizable in bulk three dimensional solids. Thick layers of molecular adsorbates or heterostructures of 2D materials generally preclude the use of electrons or atoms as probes. However, with linear photon-in/photon-out techniques, it is often challenging to assign the observed optical response to a particular portion of the interface. We and prior workers have demonstrated that by full characterization of the symmetry of the second order nonlinear optical susceptibility, i.e., the χ(2), in sum frequency generation (SFG) spectroscopy, this problem can be overcome. Here, we describe an UHV system built to allow conventional UHV sample preparation and characterization, femtosecond and polarization resolved SFG spectroscopy, the azimuthal sample rotation necessary to fully describe χ(2) symmetry, and sufficient stability to allow scanning SFG microscopy. We demonstrate these capabilities in proof-of-principle measurements on CO adsorbed on Pt(111) and on the clean Ag(111) surface. Because this setup allows both full characterization of the nonlinear susceptibility and the temperature control and sample preparation/characterization of conventional UHV setups, we expect it to be of great utility in the investigation of both the basic physics and applications of solid, 2D material heterostructures.

Effect of functional group on the monolayer structures of biodegradable quaternary ammonium surfactants.

The monolayer structures and conformational ordering of cationic surfactants including the biodegradable quaternary ammonium molecules have been systematically characterized by π-A isotherm, surface potential, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and sum frequency generation (SFG) vibrational spectroscopy. It was found that the monolayer of the typical dialkyl dimethylammonium on the water surface was less densely packed along with many conformational gauche defects. The packing density and ordering of these monolayers were improved as halide ions were added to the subphase. A similar condensation effect was also observed when amide or ester groups are present in the alkyl tails of the surfactant. These results are discussed on the basis of the repulsive electrostatic interactions between the terminal ammonium moieties, the hydrogen bonding between the functional groups in the alkyl chains, as well as the flexibility of the alkyl chains in these surfactants. The present study is crucial to understanding the relationship between the interfacial structures and the functionalities of the biodegradable quaternary ammonium surfactants.

Probing the effect of the solution environment around redox-active moieties using rigid anthraquinone terminated molecular rulers.

Herein, we report the influence of the position and the solution environment around surface-bound redox-active moieties on their redox reaction. The study was made possible by using rigid norbornylogous bridges, which possess anthraquinone (AQ) moieties. An L-shaped norbornylogous bridge (L-NB) and straight-shaped norbornylogous bridge (S-NB) were used to situate AQ moieties at well-defined position and environments above a mixed alkanethiol self-assembled monolayer (SAM) on Au (111) surfaces. Sum frequency generation (SFG) vibrational spectroscopy was employed to evaluate the interaction between the S-NB and L-NB with diluent molecules in the mixed SAMs. The SFG measurements demonstrated that hydrogen-bonding interactions were formed between AQ moieties of L-NB and diluent molecules terminated by hydroxyl group within a suitable separation. The SFG observations provided information about the relative position of the AQ moieties in each SAM, which significantly affects the thermodynamics and the kinetics of the electron transfer on the electrode/solution interface. The rate constant (k(et)) of the electron transfer between the AQ moiety and the gold surface and the apparent formal potential (E(0')) were studied using cyclic voltammetry (CV), alternating current voltammetry (ACV), and electrochemical impedance spectroscopy (EIS). It was found that the k(et) increases and E(0') shifts to more anodic values as the distance between the AQ moiety and the surface of the diluent was increased, for both methyl and hydroxyl terminated diluent. These results are discussed in relation to H-bonding interactions with water surrounding the AQ moieties.

Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges.

Herein, we describe the synthesis of straight (S) and L-shaped (L) norbornylogous bridges (NBs) with an anthraquinone moiety at the distal end as the redox-active head group and two thiol feet at the proximal end, by which the molecules assemble on gold surfaces. The NB molecules were shown to form self-assembled monolayers (SAMs) with a well-behaved surface redox process. The SAMs were characterized by using in situ IR spectroscopy, cyclic voltammetry, scanning tunnelling microscopy and electrochemical impedance spectroscopy. The surface selection rules associated with the IR band intensities allowed the estimation of the position of the anthraquinone moiety with respect to the surface and the tilt of the bridge with respect to the surface normal, both in pure and diluted monolayers. It is shown that the S- and L-NBs hold the plane of the anthraquinone moiety close to the surface normal or the surface tangent, respectively. Neither NB molecule changes its orientation if spaced by diluents on the surface. The difference in the structure of the S- and L-NB SAMs provides a suitable framework for the investigation of factors that govern electron transfer of anthraquinone moieties across self-assembled monolayers with limited structural ambiguity, as compared with the commonly used structurally flexible alkanethiol monolayers.

Characterizing the photoinduced switching process of a nitrospiropyran self-assembled monolayer using in situ sum frequency generation spectroscopy.

Sum frequency generation (SFG) vibrational spectroscopy is employed to investigate the reversible, photoinduced spiro→merocyanine isomerization of a self-assembled monolayer, the result of attachment of nitrospiropyran to a gold surface using a dithiolane anchoring group. The attachment of these molecular "alligator clips" to spiropyran molecules provide an easily accessible method to self-assemble a robust monolayer of spiropyran on a gold surface, which allows photoswitching of the spiropyran units. Probing the symmetric and antisymmetric stretching modes of the nitro group allows the determination of the structural orientation of the charged moiety with respect to the surface normal as well as the isomerization rates under photoinduced switching conditions. The photoisomerization of the spiropyran SAM on the gold surface is much faster than the rates of switching spiropyrans in a solid crystalline form, and the rate of thermal relaxation of the opened to closed form in this study is found to be on the same time scale as the relaxation of spiropyran when present in solutions with polar solvents.

Tailoring electronic-ionic local environment for solid-state Li-O2 battery by engineering crystal structure.

Solid-state Li-O2 batteries (SSLOBs) have attracted considerable attention because of their high energy density and superior safety. However, their sluggish kinetics have severely impeded their practical application. Despite efforts to design highly efficient catalysts, efficient oxygen reaction evolution at gas-solid interfaces and fast transport pathways in solid-state electrodes remain challenging. Here, we develop a dual electronic-ionic microenvironment to substantially enhance oxygen electrolysis in solid-state batteries. By designing a lithium-decorative catalyst with an engineering crystal structure, the coordinatively unsaturated sites and high concentration of defects alleviate the limitations of electronic-ionic transport in solid interfaces and create a balanced gas-solid microenvironment for solid-state oxygen electrolysis. This strategy facilitates oxygen reduction reaction, mediates the transport of reaction species, and promotes the decomposition of the discharge products, contributing to a high specific capacity with a stable cycling life. Our work provides previously unknown insight into structure-property relationships in solid-state electrolysis for SSLOBs.

Preferential adsorption of amino-terminated silane in a binary mixed self-assembled monolayer.

The composition and structure of a binary mixed self-assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APS, NH(2)(CH(2))(3)Si(OCH(2)CH(3))(3)) and octadecyltrimethoxysilane (ODS, CH(3)(CH(2))(17)Si(OCH(3))(3)) on a silicon oxide surface have been characterized by water contact-angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. XPS demonstrated that APS in the mixed SAM is significantly enriched in comparison to that in solution, indicating the preferential adsorption of APS during the SAM formation. AFM observations showed that the mixed SAM becomes rougher. SFG revealed that the coadsorption of APS induced a conformation disordering in the ODS molecules present in the mixed SAM. The surface enrichment of APS has been explained in terms of differences in the surface adsorption rates of the two components as well as in the self-congregation states of APS molecules in the bulk solution. Furthermore, the structure of the water molecules on the mixed SAM surface in contact with the aqueous solutions at different pH's has also been studied. The results indicate that the mixed-SAM modified surface is positively charged at pH < 5 and negatively charged at pH > 7.

Mechanistic Insights into the Structural Modulation of Transition Metal Selenides to Boost Potassium Ion Storage Stability.

Atomic-level structure engineering is an effective strategy to reduce mechanical degradation and boost ion transport kinetics for battery anodes. To address the electrode failure induced by large ionic radius of K+ ions, herein we synthesized Mn-doped ZnSe with modulated electronic structure for potassium ion batteries (PIBs). State-of-the-art analytical techniques and theoretical calculations were conducted to probe crystalline structure changes, ion/electron migration pathways, and micromechanical stresses evolution mechanisms. We demonstrate that the heterogeneous adjustment of the electronic structure can relieve the potassiumization-induced internal strain and improve the structural stability of battery anodes. Our work highlights the importance of the correlation between doping chemistry and mechanical stability, inspiring a pathway of structural engineering strategy toward a highly stable PIBs.

Self-assembled monolayers formed using zero net curvature norbornylogous bridges: the influence of potential on molecular orientation.

A new class of electroactive norbornylogous bridges, with no net curvature, that form self-assembled monolayers on gold electrodes were studied by electrochemistry and in situ infrared spectroscopy. The influence of the electrode potential on the structure and conformation of the self-assembled monolayers (SAMs) was investigated. This was performed using two different lengths of rigid norbornylogous bridges with terminal ferrocene moieties and ω-hydroxyalkanethiols. It was found that single component monolayers of the rigid norbornylogous bridges changed their tilt angle with their transition from the ferrocene to ferricinium. However, when the norbornylogous SAMs were diluted with ω-hydroxyalkanethiols the tilt angle remained unchanged upon oxidation of ferrocene to ferricinium. It was also observed that the tilt angle of the diluent, ω-hydroxyalkanethiols changed at potentials exceeding 500 mV.