Influence of Cations on Direct CO2 Capture and Mineral Film Formation: The Role of KCl and MgCl2 at the Air/Electrolyte/Iron Interface.

Uncovering the mechanisms associated with CO2 capture through mineralization is vital for addressing rising CO2 levels. Iron in planetary soils, the mineral cycle, and atmospheric dust react with CO2 through complex surface chemistry. Here, the effect of cations on the growth of carbonate films on iron surfaces was investigated. In situ polarized modulated infrared reflection absorption spectroscopy was used to measure CO2 adsorption and oxidation of iron in MgCl2(aq) and KCl(aq), compared to FeCl2(aq) at the air/electrolyte/iron interface. The cation was found to influence the film composition and growth rates, as corroborated by infrared and photoelectron spectroscopy. In MgCl2(aq), a mixture of hydromagnesite, magnesite, and a Mg hydroxy carbonate film was grown on iron, while in KCl(aq), a potassium-rich bicarbonate film was grown. The cations were found to affect the rates of hydroxylation and carbonation, confirming a specific cation effect on carbonate film growth. In the submerged region, a heterogeneous mixture of lepidocrocite and iron hydroxy carbonate was produced, suggesting that Fe2+ dominates the surface products. Surface roughness measurements from in situ atomic force microscopy indicate iron initially corrodes faster in MgCl2(aq) than KCl(aq), due to the Cl- ions that initiate pitting and corrosion. In this region, cations were not found to affect the morphologies. This study shows surface corrosion is necessary to provide nucleation sites for film growth and that the cations influence the carbonate film, relevant for CO2 capture and planetary processes.

Effect of Cations on the Oxidation and Atmospheric Corrosion of Iron Interfaces to Minerals.

Surface corrosion involves a series of redox reactions that are catalyzed by the presence of ions. On infrastructure surfaces and in complex and natural environments, iron surfaces readily undergo redox reactions, impacting chemical processes. In this study, the effect of how cations influence the formation of the mineral scale on iron surfaces and its connection to surface corrosion was investigated in CaCl2(aq) and NaCl(aq) electrolytes. Polarized modulated-infrared reflection absorption spectroscopy (PM-IRRAS) measurements were used to measure the oxidation and formation of carbonates at the air/electrolyte/iron interface, which confirmed that the iron surface oxidized faster in CaCl2(aq) than in NaCl(aq). PM-IRRAS, attenuated total reflectance-Fourier transformed infrared spectroscopy, and X-ray photoelectron spectroscopy show that after the adsorption of atmospheric O2 and CO2, calcium carbonate (CaCO3) in the form of calcite and aragonite was produced on iron in the presence of CaCl2(aq), whereas siderite (FeCO3) was produced on the surface of iron in the presence of NaCl(aq). However, in either solution without gradual O2 and CO2 exposure, a heterogeneous mixture of lepidocrocite (γ-FeOOH) and an iron hydroxy carbonate (Fex(OH)yCO3) was grown on the iron surface. In situ liquid AFM was used to measure the surface roughness in CaCl2(aq) and NaCl(aq), as an estimation of the corrosion rate. In CaCl2(aq), Fe was found to corrode faster than Fe in NaCl(aq) due to more ions at equimolar concentrations. Surface physical changes, as measured by ex situ AFM, confirmed the presence of a heterogeneous mixture of γ-FeOOH and an Fex(OH)yCO3 in the submerged region. This indicates that the cation does not affect the type of mineral grown on the Fe surface in the region completely submerged in the electrolyte. These results suggest that the cations play a unique role in the initial stages of corrosion at the interface region, influencing the uptake of atmospheric CO2 and mineral nucleation. The knowledge gained from these interfacial reactions are important for understanding the connection between surface corrosion, mineral grown, and CO2 capture for sequestration.

In Situ PM-IRRAS at the Air/Electrolyte/Solid Interface Reveals Oxidation of Iron to Distinct Minerals.

Iron interfaces undergo redox and catalytic processes in various environments, on the surface of soils, dust, minerals, and materials that comprise industrial infrastructure. Measuring reactions at interfaces in complex environments is challenging, where adsorption of gases and interaction of aqueous species occur at the surface. This is due to the presence of several ionic species in solutions that catalyze surface oxidation and undergo ion exchange between the solution and the surface and from the influx of oxygen and other gases. Corrosion is an electrochemical redox reaction that is affected by the presence of oxygen and water, but accelerated by dissolved ions. Polarized modulated-infrared reflection absorption spectroscopy was used to measure in situ surface oxidation at the air/electrolyte/iron interface in semineutral NaCl(aq) and acidic HCl(aq) solutions using the meniscus method under ambient conditions. The iron interface was exposed to air, primarily oxygen, allowing for surface oxidation, where metallic iron was found to transform to siderite in NaCl(aq) and lepidocrocite in HCl(aq). Mechanisms are suggested for the transformation of iron to these corrosion products, which significantly impact our understanding of redox processes in the water cycle, material degradation, and energy applications.

New Approach to Simultaneous In Situ Measurements of the Air/Liquid/Solid Interface Using PM-IRRAS.

Vibrational spectroscopy techniques have evolved to measure gases, liquids, and solids at surfaces and interfaces. In the field of surface-sensitive vibrational spectroscopy, infrared spectroscopy measures the adsorption on surfaces and changes from reactions. Previous polarized modulated-infrared reflection-absorption spectroscopy (PM-IRRAS) measurements at the gas/solid interface were developed to observe catalytic reactions near reaction conditions. Other PM-IRRAS measurements use liquid cells where the sample is submerged and compressed against a prism that has traditionally been used for electrochemical reactions. This article presents a new method that is used to observe in situ adsorption of molecules using PM-IRRAS at the gas/liquid/solid interface. We demonstrate the meniscus method by measuring the adsorption of octadecanethiol on gold surfaces. Characterization of self-assembled monolayers (SAMs), the "gold standard" for PM-IRRAS calibration measurements, was measured in ethanol solutions. The condensed-phase (air/liquid) interface in addition to the liquid/solid interface was measured simultaneously in solution. These are compared with liquid attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy measurements to confirm the presence of the SAM and liquid ethanol. A model of the three-phase system is used to approximate the thickness of the liquid ethanol layer and correlate these values to signal attenuation using PM-IRRAS. This proof-of-concept study enables the measurement of reactions at the gas/liquid/solid interface that could be adapted for other reactions at the electrode and electrolyte interfaces with applications in environmental science and heterogeneous catalysis.

Investigation of N2 adsorption on Fe3O4(001) using ambient pressure X-ray photoelectron spectroscopy and density functional theory.

Reactions on iron oxide surfaces are prevalent in various chemical processes from heterogeneous catalysts to minerals. Nitrogen (N2) is known to dissociate on iron surfaces, a precursor for ammonia production in the Haber-Bosch process, where the dissociation of N2 is the limiting step in the reaction under equilibrium conditions. However, little is known about N2 adsorption on other iron-based materials, such as iron oxide surfaces that are ubiquitous in soils, steel pipelines, and other industrial materials. An atomistic description is reported for the binding of N2 on the Fe3O4(001) surface using first principles calculations with ambient pressure X-ray photoelectron spectroscopy. Two primary adsorption sites are experimentally identified from N2 dissociation on Fe3O4(001). The electronic signatures associated with the valence band region unambiguously show how the electronic structure of magnetite transforms near ambient pressures due to the binding of atomic nitrogen to different surface sites. Overall, the experimental and theoretical results of our study bridge the gap between ultra-high vacuum studies and reaction conditions to provide insight into other nitrogen-based chemistry on iron oxide surfaces that impact the agriculture and energy industries.

Antibacterial Properties of Mussel-Inspired Polydopamine Coatings Prepared by a Simple Two-Step Shaking-Assisted Method.

A simple two-step, shaking-assisted polydopamine (PDA) coating technique was used to impart polypropylene (PP) mesh with antimicrobial properties. In this modified method, a relatively large concentration of dopamine (20 mg ml-1) was first used to create a stable PDA primer layer, while the second step utilized a significantly lower concentration of dopamine (2 mg ml-1) to promote the formation and deposition of large aggregates of PDA nanoparticles. Gentle shaking (70 rpm) was employed to increase the deposition of PDA nanoparticle aggregates and the formation of a thicker PDA coating with nano-scaled surface roughness (RMS = 110 nm and Ra = 82 nm). Cyclic voltammetry experiment confirmed that the PDA coating remained redox active, despite extensive oxidative cross-linking. When the PDA-coated mesh was hydrated in phosphate saline buffer (pH 7.4), it was activated to generate 200 µM hydrogen peroxide (H2O2) for over 48 h. The sustained release of low doses of H2O2 was antibacterial against both gram-positive (Staphylococcus epidermidis) and gram-negative (Escherichia coli) bacteria. PDA coating achieved 100% reduction (LRV ~3.15) when incubated against E. coli and 98.9% reduction (LRV ~1.97) against S. epi in 24 h.

Spontaneous selective deposition of iron oxide nanoparticles on graphite as model catalysts.

Iron oxide nanomaterials participate in redox processes that give them ideal properties for their use as earth-abundant catalysts. Fabricating nanocatalysts for such applications requires detailed knowledge of the deposition and growth. We report the spontaneous deposition of iron oxide nanoparticles on HOPG in defect areas and on step edges from a metal precursor solution. To study the nucleation and growth of iron oxide nanoparticles, tailored defects were created on the surface of HOPG using various ion sources that serve as the target sites for iron oxide nucleation. After solution deposition and annealing, the iron oxide nanoparticles were found to nucleate and coalesce at 400 °C. AFM revealed that the particles on the sp3 carbon sites enabled the nanoparticles to aggregate into larger particles. The iron oxide nanoparticles were characterized as having an Fe3+ oxidation state and two different oxygen species, Fe-O and Fe-OH/Fe-OOH, as determined by XPS. STEM imaging and EDS mapping confirmed that the majority of the nanoparticles grown were converted to hematite after annealing at 400 °C. A mechanism of spontaneous and selective deposition on the HOPG surface and transformation of the iron oxide nanoparticles is proposed. These results suggest a simple method for growing nanoparticles as a model catalyst.

Specific cation effects at aqueous solution-vapor interfaces: Surfactant-like behavior of Li+ revealed by experiments and simulations.

It is now well established by numerous experimental and computational studies that the adsorption propensities of inorganic anions conform to the Hofmeister series. The adsorption propensities of inorganic cations, such as the alkali metal cations, have received relatively little attention. Here we use a combination of liquid-jet X-ray photoelectron experiments and molecular dynamics simulations to investigate the behavior of K+ and Li+ ions near the interfaces of their aqueous solutions with halide ions. Both the experiments and the simulations show that Li+ adsorbs to the aqueous solution-vapor interface, while K+ does not. Thus, we provide experimental validation of the "surfactant-like" behavior of Li+ predicted by previous simulation studies. Furthermore, we use our simulations to trace the difference in the adsorption of K+ and Li+ ions to a difference in the resilience of their hydration shells.

Reactivity of selectively terminated single crystal silicon surfaces.

As the cornerstone of multiple practical applications, silicon single crystal surfaces have attracted the interest of scientific and engineering communities for several decades. The most recent advances employ the surfaces precovered with a specific functionality to extend into the realm of organic and metal-organic films with well-defined interfaces, to protect the surfaces from oxidation and other contaminations, and to build the components of present and future molecular electronics and sensing devices. This critical review will focus on the reactivity of the selectively terminated Si(100) and Si(111) surfaces. The hydrogen and halogen-terminated surfaces are the most widely used and most heavily reviewed previously, thus only a brief summary will be given here with the emphasis of the most recent thermal approaches to functionalization of hydrogen-terminated silicon. The silicon surfaces precovered with NH(x) functionality are emerging as a very likely candidate both for the production of sharp interfaces and for coadsorption, co-assembly, and potential molecular templating of patterns on single crystalline surfaces. A brief overview of recent advances in achieving control over the hydroxyl-termination of silicon will be given. Some future directions for further development of chemistry, reactivity, and assembly on these surfaces, as well as potential applications, are highlighted in the last section (152 references).

Metallic nanostructure formation limited by the surface hydrogen on silicon.

Constant miniaturization of electronic devices and interfaces needed to make them functional requires an understanding of the initial stages of metal growth at the molecular level. The use of metal-organic precursors for metal deposition allows for some control of the deposition process, but the ligands of these precursor molecules often pose substantial contamination problems. One of the ways to alleviate the contamination problem with common copper deposition precursors, such as copper(I) (hexafluoroacetylacetonato) vinyltrimethylsilane, Cu(hfac)VTMS, is a gas-phase reduction with molecular hydrogen. Here we present an alternative method to copper film and nanostructure growth using the well-defined silicon surface. Nearly ideal hydrogen termination of silicon single-crystalline substrates achievable by modern surface modification methods provides a limited supply of a reducing agent at the surface during the initial stages of metal deposition. Spectroscopic evidence shows that the Cu(hfac) fragment is present upon room-temperature adsorption and reacts with H-terminated Si(100) and Si(111) surfaces to deposit metallic copper. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) are used to follow the initial stages of copper nucleation and the formation of copper nanoparticles, and X-ray energy dispersive spectroscopy (XEDS) confirms the presence of hfac fragments on the surfaces of nanoparticles. As the surface hydrogen is consumed, copper nanoparticles are formed; however, this growth stops as the accessible hydrogen is reacted away at room temperature. This reaction sets a reference for using other solid substrates that can act as reducing agents in nanoparticle growth and metal deposition.