Liquid-vacuum Interface Research Articles

Investigation of pyruvic acid photolysis at the air-liquid interface as a source of aqueous secondary organic aerosols

Pyruvic acid (PA) is a ubiquitous 2-oxocarboxylic acid in the atmosphere. Its photochemical process at the air-liquid (a-l) interface has been suggested as an important source of aqueous secondary organic aerosols. We investigated the photochemical reaction pathways of PA at the a-l interface using synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) microreactor. Results from mass spectral analysis and the determination of appearance energies (AEs) indicate that photolysis of PA can generate radicals, then they recombine with carboxylic acids and simple molecular oligomers. Furthermore, the preliminary products could form larger oligomers via radical reaction or esterification in the presence of hydroxyl and carboxyl functional groups. Mass spectral comparison shows that most photochemical reactions would complete within 4 h. The expanded photochemistry-driven reaction flowchart of PA is proposed based on the newly discovered products. Our results reveal that the interfacial PA photochemical reactions have different mechanisms from the bulk liquid due to the interfacial properties, such as molecular density, composition, and ion concentration. Our findings show that in situ mass spectral analysis with bright photon ionization is useful to elucidate the contribution of a-l interfacial reactions leading to aqSOA formation.

Electric-field-induced ion evaporation from the ionic liquid–vacuum interface

We studied ion evaporation from a planar interface between the room-temperature ionic liquid (RTIL) and vacuum under external electric fields by using molecular dynamics (MD) simulations. We calculated the ion evaporation rate (je) as a function of the electric field normal to the RTIL surface (En), and results under Langevin, dissipative particle dynamics (DPD), and Berendsen thermostats were compared. It was found that DPD thermostat is more suitable for simulating the ion evaporation phenomenon. We also compared results under different methods for applying the electric field (constant potential, constant charge, and constant field methods) and found that je-En curves from the three methods agree with each other. Temporal evolution of electric fields in vacuum was further analyzed, and variations of electric fields over time were traced to the induced electric field between the evaporated ion and RTIL film. This work could guide the selection of proper methods for MD simulations of electrospray in the pure ion regime and lays the foundation to study more complex electrospray phenomena using MD simulations.

Microscale Electrochemical Corrosion of Uranium Oxide Particles.

Understanding the corrosion of spent nuclear fuel is important for the development of long-term storage solutions. However, the risk of radiation contamination presents challenges for experimental analysis. Adapted from the system for analysis at the liquid-vacuum interface (SALVI), we developed a miniaturized uranium oxide (UO2)-attached working electrode (WE) to reduce contamination risk. To protect UO2 particles in a miniatured electrochemical cell, a thin layer of Nafion was formed on the surface. Atomic force microscopy (AFM) shows a dense layer of UO2 particles and indicates their participation in electrochemical reactions. Particles remain intact on the electrode surface with slight redistribution. X-ray photoelectron spectroscopy (XPS) reveals a difference in the distribution of U(IV), U(V), and U(VI) between pristine and corroded UO2 electrodes. The presence of U(V)/U(VI) on the corroded electrode surface demonstrates that electrochemically driven UO2 oxidation can be studied using these cells. Our observations of U(V) in the micro-electrode due to the selective semi-permeability of Nafion suggest that interfacial water plays a key role, potentially simulating a water-lean scenario in fuel storage conditions. This novel approach offers analytical reproducibility, design flexibility, a small footprint, and a low irradiation dose, while separating the α-effect. This approach provides a valuable microscale electrochemical platform for spent fuel corrosion studies with minimal radiological materials and the potential for diverse configurations.

Bis-polyethylene glycol-functionalized imidazolium ionic liquids: A multi-method approach towards bulk and surface properties

Adding to the versatile class of ionic liquids, we report a new series of hydrophilic polyethylene glycol-functionalized room-temperature ionic liquids, offering interesting thermo- and electrochemical behavior as well as remarkable surface properties. A scalable and generally applicable synthetic procedure for the preparation of N,N’-bis(polyethylene glycol)imidazolium salts, generally abbreviated as [(mPEGn)2Im][A] (n = 2‒6, A = I‒, OMs‒, PF6‒, NTf2‒) was developed. These ionic liquids were studied concerning their thermo- and electrochemical properties, such as phase transition behavior, decomposition temperature, viscosity, and density, as well as electrical conductivity and electrochemical stability, using i.a. differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Additionally, the surface properties were investigated by angle-resolved X-ray photoelectron spectroscopy (ARXPS) and the pendant drop method. Molecular dynamics simulations complement the studies and provide insight into the molecular structure of the ionic liquids and their specific orientation at the liquid-vacuum interface.

Studying Interfacial Dark Reactions of Glyoxal and Hydrogen Peroxide Using Vacuum Ultraviolet Single Photon Ionization Mass Spectrometry

Aqueous secondary organic aerosol (aqSOA) formation from volatile and semivolatile organic compounds at the air–liquid interface is considered as an important source of fine particles in the atmosphere. However, due to the lack of in situ detecting techniques, the detailed interfacial reaction mechanism and dynamics still remain uncertain. In this study, synchrotron-based vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) was coupled with the System for Analysis at the Liquid Vacuum Interface (SALVI) to investigate glyoxal dark oxidation products at the aqueous surface. Mass spectral analysis and determination of appearance energies (AEs) suggest that the main products of glyoxal dark interfacial aging are carboxylic acid related oligomers. Furthermore, the VUV SPI-MS results were compared and validated against those of in situ liquid time-of-flight secondary ion mass spectrometry (ToF-SIMS). The reaction mechanisms of the dark glyoxal interfacial oxidation, obtained using two different approaches, indicate that differences in ionization and instrument operation principles could contribute to their abilities to detect different oligomers. Therefore, the mechanistic differences revealed between the VUV SPI-MS and ToF-SIMS indicate that more in situ and real-time techniques are needed to investigate the contribution of the air–liquid interfacial reactions leading to aqSOA formation.

Interaction of volatile organic compounds acetone and toluene with room temperature ionic liquid at the bulk and the liquid-vacuum interface

Inventing the green method in capturing Volatile Organic Compounds (VOCs) is crucial for combating environmental pollution due to its unrestricted industrial emission and abundance in indoor air. Room temperature ionic liquids (RTILs) are known to be green solvents and having fascinating properties suitable for various industrial applications, including the capture of pollutants, like CO2, SO2, etc. To study the VOC capturing ability of the RTILs, we have performed molecular dynamics (MD) simulation of two VOCs (acetone and toluene) in an RTIL ([BMIM][PF6]). We have found sufficient evidence of having strong efficacy of the RTIL in capturing the VOCs. Various structural and dynamical properties are calculated for the simulated systems and have been understood in terms of molecular interaction between the VOCs and the ions of the RTIL. The VOCs are seen to have preferential absorption near the RTIL interfacial region. Simulated solvation free energy and the Henry's constant for the VOCs in RTIL further suggest that the VOC significantly absorbs in the RTILs. This study, therefore, puts forward an alternative green approach for VOC capture, vital for fighting against environmental pollution.

New Insights into Secondary Organic Aerosol Formation at the Air-Liquid Interface.

Air-liquid interfacial processing of volatile organic compound photooxidation has been suggested as an important source of secondary organic aerosols. However, owing to the lack of techniques for studying the air-liquid interface, the detailed interfacial mechanism remains speculative. To obviate this, we enabled in situ synchrotron-based vacuum ultraviolet single photon ionization mass spectrometry using the system for analysis at the liquid-vacuum interface microreactor to study glyoxal photooxidation at the air-liquid interface. Determination of reaction intermediates and new oxidation products, including polymers and oligomers, by mass spectral analysis and appearance energy measurements has been reported for the first time. Furthermore, an expanded reaction mechanism of photooxidation and free radical induced reactions as a source of aqueous secondary organic aerosol formation is proposed. Single photon ionization can provide new insights into interfacial chemistry.

Different Hydrogen Bond Changes Driven by Surface Segregation Behavior of Imidazolium-Based Ionic Liquid Mixture at the Liquid-Vacuum Interface.

In this work, molecular dynamics (MD) simulations were carried out to study the behaviors of a binary ionic liquid (IL) mixture consisting of equimolar [C2C1Im][BF4] and [C4C1Im][BF4], as well as two corresponding pure ILs, at the liquid-vacuum interface. Our simulation results show that the competition of nonpolar interactions between different alkyl chains of two cations results in an obvious surface segregation behavior of the IL mixture at the interface, indicating an enhanced aggregation of the [C4C1Im]+ cations but a weakened aggregation of the [C2C1Im]+ cations at the outermost surface. More interestingly, different hydrogen bond (HB) changes between two imidazolium cations at the interface can be driven by such surface segregation behavior, where the [C2C1Im]+ cations rather than the [C4C1Im]+ ones have more and stronger HBs with the [BF4]- anions by comparison with the corresponding pure ILs at the interface. Meanwhile, it is interesting to find that such a stronger HB would lower the rotations of the imidazolium rings of interfacial [C2C1Im]+ cations. By contrast, the [C4C1Im]+ cations at the outermost surface rotate faster owing to their weaker HB. In addition, the orientation analysis uncovers that there is a major decrease for the orderliness of interfacial [C2C1Im]+ cations, but a minor decrease for that of interfacial [C4C1Im]+ cations, from the pure IL to the IL mixture. Such distinct results are closely related to the surface segregation between the [C2C1Im]+ and [C4C1Im]+ cations in the IL mixture and their interfacial HB properties. Thus, our simulation results afford a deep insight into the surface segregation effect on the HB behavior of the imidazolium-based IL mixture at liquid-vacuum interface.

PH-Dependent Water Clusters in Photoacid Solution: Real-Time Observation by ToF-SIMS at a Submicropore Confined Liquid-Vacuum Interface.

Water clusters are ubiquitously formed in aqueous solutions by hydrogen bonding, which is quite sensitive to various environment factors such as temperature, pressure, electrolytes, and pH. Investigation of how the environment has impact on water structure is important for further understanding of the nature of water and the interactions between water and solutes. In this work, pH-dependent water structure changes were studied by monitoring the changes for the size distribution of protonated water clusters by in-situ liquid ToF-SIMS. In combination with a light illumination system, in-situ liquid ToF-SIMS was used to real-time measure the changes of a light-activated organic photoacid under different light illumination conditions. Thus, the proton transfer and pH-mediated water cluster changes were analyzed in real-time. It was found that higher concentration of free protons could lead to a strengthened local hydrogen bonding network as well as relatively larger protonated water clusters in both organic acid and inorganic acid. Besides, the accumulation of protons at the liquid-vacuum interface under light illumination was observed owing to the affinity of organic molecules to the low-pressure gas phase. The application of in-situ liquid ToF-SIMS analysis in combination with in-situ light illumination system opened up an avenue to real-time investigate light-activated reactions. Besides, the results regarding water structure changes in acidic solutions showed important insights in related atmospheric and physiochemical processes.

In Vivo Molecular Insights into Syntrophic Geobacter Aggregates.

Direct interspecies electron transfer (DIET) has been considered as a novel and highly efficient strategy in both natural anaerobic environments and artificial microbial fuel cells. A syntrophic model consisting of Geobacter metallireducens and Geobacter sulfurreducens was studied in this work. We conducted in vivo molecular mapping of the outer surface of the syntrophic community as the interface of nutrients and energy exchange. System for Analysis at the Liquid Vacuum Interface combined with time-of-flight secondary ion mass spectrometry was employed to capture the molecular distribution of syntrophic Geobacter communities in the living and hydrated state. Principal component analysis with selected peaks revealed that syntrophic Geobacter aggregates were well differentiated from other control samples, including syntrophic planktonic cells, pure cultured planktonic cells, and single population biofilms. Our in vivo imaging indicated that a unique molecular surface was formed. Specifically, aromatic amino acids, phosphatidylethanolamine components, and large water clusters were identified as key components that favored the DIET of syntrophic Geobacter aggregates. Moreover, the molecular changes in depths of the Geobacter aggregates were captured using dynamic depth profiling. Our findings shed new light on the interface components supporting electron transfer in syntrophic communities based on in vivo molecular imaging.

In situ, in vivo, and in operando imaging and spectroscopy of liquids using microfluidics in vacuum

This review offers a succinct overview of the development of a vacuum-compatible microfluidic reactor system for analysis at the liquid vacuum interface (SALVI), and its diverse applications in in situ, in vivo, and in operando imaging of liquid surfaces as well as the air-liquid (a-l), liquid-liquid (l-l), and solid-liquid (s-l) interfaces in the past decade. SALVI is one of the first microfluidics-based reactors that has enabled direct analysis of volatile liquids in vacuum surface tools such as scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Its integration into ambient and vacuum spectroscopy and microscopy is illustrated. Several applications are highlighted including (1) imaging nanoparticles in liquid using in situ SEM; (2) mapping the evolving l-l interface using in situ x-ray absorption spectroscopy and ToF-SIMS; (3) following complex a-l interfacial oxidation reaction products using in situ ToF-SIMS; (4) capturing biological interfaces of cells and microbes via in vivo multimodal and correlative imaging; and (5) monitoring the dynamic solid electrode and liquid electrolyte interface using in operando molecular imaging. Finally, outlook and recommendations are presented. Besides showing the holistic information volume obtained by real-time multiplexed imaging, this review intends to convey the importance of tool development in revolutionizing surface and interface analysis using vacuum platforms previously limited to solid surfaces. Microfluidics is manifested to be not limited to ambient conditions in many examples in this review. Moreover, fundamental interfacial phenomena underpinning mass and charge transfer can now be pursued in real time via innovated chemical imaging and spectroscopy.

In situ liquid SEM imaging analysis revealing particle dispersity in aqueous solutions.

A quantitative description on dispersity of boehmite (γ-AlOOH) particles, a key component for waste slurry at Hanford sites, can provide useful knowledge for understanding various physicochemical nature of the waste. In situ liquid scanning electron microscopy (SEM) was used to evaluate the dispersity of particles in aqueous conditions using a microfluidic sample holder, System for Analysis at Liquid Vacuum Interface (SALVI). Secondary electron (SE) images and image analyses were performed to determine particle centroid locations and the distance to the nearest neighbour particle centroid, providing reliable rescaled interparticle distances as a function of ionic strength in acidic and basic conditions. Our finding of the particle dispersity is consistent with physical insights from corresponding particle interactions under physicochemical conditions, demonstrating delicate changes in dispersity of boehmite particles based on novel in situ liquid SEM imaging and analysis. LAY DESCRIPTION: In situ liquid scanning electron microscopy (SEM) was used to determine the interparticle distance of boehmite (γ-AlOOH) particles, a key component for waste slurry at Hanford sites. This type of quantitative measurement is important to understand various physicochemical nature of the radiological waste containing boehmite. In situ liquid SEM was enabled by a unique vacuum compatible microfluidic cell, System for Analysis at Liquid Vacuum Interface (SALVI). We collected secondary electron (SE) images and performed image analyses to determine particle centroid locations and the distance to the nearest neighbour particle centroid to arrive at the interparticle distances in acidic and basic conditions. Our results show that delicate changes occur among boehmite particles under different pH conditions using novel in situ SEM imaging.

Revealing the Structural Evolution of Green Rust Synthesized in Ionic Liquids by In Situ Molecular Imaging

AbstractIonic liquids are green solvents that have wide applications in material synthesis, catalysis, and separation. A model switchable ionic liquid (SWIL) consisting of 1,8‐diazabicycloundec‐7‐ene (DBU) and 1‐hexanol with carbon dioxide (CO2) as the trigger gas is chosen to synthesize nanocrystalline green rust. Under anoxic conditions, by adding iron (II) acetate (Fe(C2H3O2)2) and methanol to the degassed SWIL, a nanoparticulate green rust with carbonate (nano‐GR) is synthesized. More importantly, the molecular structural change of the ionic liquid resulting in green rust crystallines is first characterized using in situ liquid using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) coupled with the system for analysis at the liquid vacuum interface (SALVI), a vacuum compatible microfluidic reactor in this work. Dimers and ionic clusters consisting ferric and ferrous ions are identified in liquid ToF‐SIMS spectra. Spectral principal component analysis is used to confirm that these ion pairs including dimers and cluster ions are different from nonionic liquids. The results show that liquid ToF‐SIMS can be a useful tool to study complex liquids at the molecular level providing insights into predicative synthesis of nanomaterials using environmentally friendly green solvents and giving unique visualization of the evolving material interface due to nucleation.

Proton Propensity and Orientation of Imidazolium Cation at Liquid Imidazole-Vacuum Interface: A Molecular Dynamics Simulation.

Imidazole has gained attention as an alternative to anhydrous proton conductor in high-temperature proton exchange membrane fuel cells. A detailed investigation of proton propensity and the orientation of the imidazolium cation at the liquid-vacuum interface is important for understanding the interfacial properties of imidazole-based proton-conductive materials. Here, we perform all-atom molecular dynamics simulation on a slab model of the liquid imidazole-vacuum interface. Proton transportation process between the imidazolium cation and neutral imidazole molecules is described by the multistate empirical valence bond model of imidazole developed previously. The imidazolium cation shows a tendency to stay in the bulk region rather than at the outermost surface, and the NN vectors and norm vectors of both the imidazolium cation and imidazole molecules are more probable to be perpendicular to the surface normal vector at the interface than in the bulk. The orientation of the hydrogen bond cluster shows the same tendency as the NN vectors, which indicates that proton transportation along the direction of the surface normal vector is hindered. The instantaneous surface analyses show that the fluctuation is depressed when the imidazolium cation is near the outermost surface, which makes it less favorable for the cation appearing at the interface.

Molecular-level insights into the structures, dynamics, and hydrogen bonds of ethylammonium nitrate protic ionic liquid at the liquid-vacuum interface.

A series of molecular dynamics simulations have been used to systematically explore the structures, dynamics and hydrogen bonds (HBs) of ethylammonium nitrate (EAN) protic ionic liquid (IL) and their mutual relationship at the liquid-vacuum interface. The simulation results clearly demonstrate that there exists a sandwich structure at the interface, with the double-layer of the EA+ cations on both sides and one intercalated layer of the NO3- anions in the middle. Wherein, the outermost cation layer prefers the orientation with the CH3 groups pointing to the vacuum phase due to the hydrophobic interactions, while the CH3 groups in the second layer direct to the bulk liquid phase owing to the HB formation between their NH3+ groups and the intercalated NO3- anions in the middle layer. On the other hand, the continuous HB strength of the cations in the outermost layer (denoted as Cation-1) is found to be almost identical with the counterpart of the cations in the second layer (denoted as Cation-2), whereas the intermittent HB strength of Cation-1 is much larger than that of Cation-2 at all temperatures. Furthermore, the rotational motion of Cation-1 with the normal vector of the C-C-N plane in the cation is faster than that of Cation-2 with the same vector, resulting from more free space in the outermost layer. On the contrary, the rotational motion of Cation-1 with the vector from the mass center of the cation to its N atom is much slower than that of Cation-2 with the same vector, which can be attributed to the combined effects of the stronger intermittent HBs of Cation-1 and the hydrophobic interactions of its CH3 group in the outermost layer.

Charging-driven coarsening and melting of a colloidal nanoparticle monolayer at an ionic liquid-vacuum interface.

We induce and investigate the coarsening and melting dynamics of an initially static nanoparticle colloidal monolayer at an ionic liquid-vacuum interface, driven by a focused, scanning electron beam. Coarsening occurs through grain interface migration and larger-scale motions such as grain rotations, often facilitated by sliding dislocations. The progressive decrease in area fraction that drives melting of the monolayer is explained using an electrowetting model whereby particles at the interface are solvated once their accumulating charge recruits sufficient counterions to subsume the particle. Subject to stochastic particle removal from the monolayer, melting is recapitulated in simulations with a Lennard-Jones potential. This new driving mechanism for colloidal systems, whose dynamical timescales we show can be controlled with the accelerating voltage, opens the possibility to manipulate particle interactions dynamically without need to vary particle intrinsic properties or surface treatments. Furthermore, the decrease in particle size availed by electron imaging presents opportunities to observe force and time scales in a lesser-explored regime intermediate between typical colloidal and molecular systems.

Understanding Time Dependence on Zinc Metal-Organic Framework Growth Using in Situ Liquid Secondary Ion Mass Spectrometry.

The abundance of novel metal-organic framework (MOF) materials continues to increase as more applications are discovered for these highly porous, well-ordered crystalline structures. The simplicity of constituents allows for the design of new MOFs with virtue of functionality and pore topology toward target adsorbates. However, the fundamental understanding of how these frameworks evolve during nucleation and growth is mostly limited to speculation from simulation studies. In this effort, we utilize a unique vacuum compatible system for analysis at the liquid vacuum interface (SALVI) microfluidic interface to analyze the formation and evolution of the benchmark MOF-74 framework using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Principal component analysis of the SIMS mass spectra, together with ex situ electron microscopy, powder X-ray diffractometry, and porosimetry, provides new insights into the structural growth, metal-oxide cluster formation, and aging process of Zn-MOF-74. Samples collected over a range of synthesis times and analyzed closely with in situ ToF-SIMS, transmission electron microscopy, and gas adsorption studies verify the developing pore structure during the aging process.

Probing a Ruthenium Coordination Complex at the Ionic Liquid–Vacuum Interface with Reactive-Atom Scattering, X-ray Photoelectron Spectroscopy, and Time-of-Flight Secondary Ion Mass Spectrometry

The speciation, conformation, and reactivity of transition metal complexes at the gas–liquid interface are poorly understood, yet the potential is high for observing chemistry unique to this anisot...

Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H2O)n-, n ≤ 200, by Electronic Absorption Spectroscopy.

Electronic absorption spectra of water cluster anions (H2O)n–, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid–vacuum interface.

Structure and diffusion of molten alkali carbonate salts at the liquid-vacuum interface

The liquid-vacuum interface of molten alkali carbonate salts is studied with molecular dynamics simulations. Three salts comprised of LixNayKzCO3 near their respective eutectic concentrations are considered to understand the distribution of ions relative to a liquid-vacuum interface and their diffusivity. These simulations show that each of the cations accumulate at the interface preferentially compared to carbonate. The cation ordering is found to inversely correspond to cation radius, with K being the most likely occupant at the surface, followed by Na, Li, and then the anion. Similar to other studies, the carbonate is found to diffuse more slowly than the cations, but we do observe small differences in diffusion between compositions that present opportunities to optimize ion transport. These results hold consequences for our understanding of ion behavior in molten carbonate salts and the performance of devices employ these electrolytes.