X-Ray Reflectometry of the Adsorption Octadecanamide Film at the Toluene-Water Interface
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A label-free high-performance electrochemical sensing of single nucleotide polymorphism in native genomic DNA samples from cancer tissues, in oncogene-specific complementary DNA and in amplicons has been carried out on bundles of few-walled carboxylated carbon nanotubes, surface of which was coated with electron-dense layer of probe DNA. High selectivity and sensitivity of the novel DNA-nanosensor are ensured by the following features. Firstly, a complementary-hybridization signal is enhanced by resonance between plasmons in carbon nanotubes and dipole oscillations of hydrated nucleic acids located in near-electrode Helmholtz double layer of the impedance sensor. Secondly, a decoration of carbon nanotubes by adhered metal atoms in a high-spin state leads to Fermi level stabilization for the carbon nanotube bundles.
A well-designed cathode catalyst layer with optimal ionomer distribution is critical to minimizing amount of Platinum (Pt) content in polymer electrolyte fuel cells (PEFCs). The impact of Pt loading, ionomer content and carbon support types on the catalyst/ionomer interface were also investigated at dry and wet conditions. Higher Pt loadings resulted in higher double layer capacity (C dl ) and similar electrochemical surface area (ECSA) due to well dispersed ionic phase material. Higher ionomer content resulted in higher ionic conductivity but also showed similar SO 3 − group coverage. High surface area (HSA) carbon support had larger ECSA and C dl at both dry and wet conditions, as less agglomerated Pt was well dispersed in the meso-pores of the support. Lower SO 3 − group coverages were observed for HSA carbon than for Vulcan carbon due to Pt particles being buried within the porous HSA carbon support. The effect of cell conditioning and voltage recovery on the PEFC cathode catalyst layer was shown to have minimal impact on SO 3 − group coverage despite a decrease in C dl and ECSA due to the size increase of Pt particles. At dry condition, a significant increases in SO 3 − group coverage were observed for all MEAs due to higher adsorptivity of ionomer in dry conditions.
This paper shows that oxide surface passivation coupled with optimum multilayer anti-reflective coating can provide approx. 3% (absolute) improvement in solar cell efficiency. Use of single-layer AR coating, without passivation, gives cell efficiencies in the range of 15 to 15.5% on high-quality, 4 ohm-cm as well as 0.1 to 0.2 ohm-cm float-zone silicon. Oxide surface passivation alone raises the cell efficiency to or = 17%. An optimum double-layer AR coating on oxide-passivated cells provides an additional approx. 5 to 10% improvement over a single-layer AR-coated cell, resulting in cell efficiencies in excess of 18%. Experimentally observed improvements are supported by model calculations and an approach to or = 20% efficient cells is discussed.
In the present model of multilayered stability stratification, aimed at obtaining the analytic eigensolutions of the vertical structure equation, each layer is characterized by its own static stability value. By requiring continuity of pressure and vertical velocity across each interface level, and by imposing suitable upper and lower boundary conditions, matching eigensolutions are obtained in terms of the Bessel functions. Attention is given to an explicit example of a double-layered stratified atmosphere which demonstrates the mathematical manipulations involved; the resultant vertical structure functions are used to check the accuracy of the numerical solutions by the finite difference and finite element methods.
Classical models of the electrochemical interface can be applied to complex and dynamic electrodes to understand important mechanisms that are relevant to device-level phenomena like calendar aging or cycle life. Here, we show that negative alloy electrodes with wide electrochemical windows cannot be assumed to have static interfaces throughout all states of charge. Under high states of charge, the interface -including the solid electrolyte interphase - has characteristics that resemble a highly polarized electrode far from the point of zero charge. Under these conditions, the interface can be understood through the Helmholtz model. At lower states of charge, the interface capacitance decreases and the space charge layer length increases. This transformation resembles a metal electrode approaching the point of zero charge which is understood through the Gouy-Chapman-Stern-Grahame model of the electrochemical interface. This transformation happens at both silicon and carbon-coated silicon interfaces. From voltage-limited cycling experiments, in the limit of the diffuse double layer, the silicon electrode impedance rises significantly in the first few cycles. This rise is related to the continuous electrochemical reduction of electrolyte components from an interface that is not electronically screened from the electrolyte. In other words, an electrode interface for batteries should resemble a 'Helmholtz-like' structure.
Metal ions found in the atmosphere above 60 km are the result of incoming meteoroid atmospheric ablation. Layers of metal ions are detected by sounding rocket in situ mass spectrometric sampling in the 80 to 130 km region, which coincides with the altitude region where meteors are observed. Enhancements of metal ion concentrations occur during meteor showers. Even outside of shower periods, the metal ion altitude profiles vary from measurement to measurement. Double layers are frequent at middle latitudes. More than 40 different meteoric atomic and molecular ions, including isotopes, have been detected. Atmospheric metal ions on average have an abundance that matches chrondritic material, the same composition as the early solar system. However there are frequently local departures from this composition due to differential ablation, species dependent chemistry and mass dependent ion transport. Metal ions react with atmospheric O2, O, O3, H2O and H2O2 to form oxygenated and hydrogenated ionic compounds. Metal atomic ions at high altitudes have long lifetimes. As a result, these ions, in the presence of Earth's magnetic field, are transported over long distances by upper atmospheric winds and ionospheric electric fields. Satellite measurements have detected metal ions as high as, approximately 1000 km and have revealed circulation of the ions on a global scale.
While water’s oxygen is the electron source in the industrially important oxygen evolution reaction, the strong absorber problem clouds our view of how the Stern layer water molecules orient themselves in response to applied potentials. Here, we report nonlinear optical measurements on nickel electrodes held at pH 13 indicating a disorder-to-order transition in the Stern layer water molecules before the onset of Faradaic current. A full water monolayer (1.1 × 10 15 centimeter −2 ) aligns with oxygen atoms pointing toward the electrode at +0.8 volt and the associated work is 80 kilojoule per mole. Our experiments identify water flipping energetics as a target for understanding overpotentials, advance molecular electrochemistry, provide benchmarks for electrical double layer models, and serve as a diagnostic tool for understanding electrocatalysis.
Electrolytes consisting of choline (Ch) salts with acetate (Ac) and oxalate (Ox) anions were studied in mixtures with ethylene glycol (EG), in comparison to chloride (Cl)- and bis(trifluorosulfonyl)imide (TFSI)-containing systems to understand the impact of anion size and charge density on the bulk electrolyte and interfacial properties. These represent hydrogen-bonded concentrated electrolytes where the Ch salts are the H-bond acceptors (HBAs) and EG is the H-bond donor (HBD) in 1:2 and 1:4 HBA:HBD ratios. Increased H-bonding in Ch 2 Ox with EG compacts the liquid compared to ChAc, consistent with the increased dissociation energies of the HBA:HBD clusters with Ox –2 calculated by density functional theory (DFT), thus leading to denser and more viscous liquids. Electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS) were used to investigate interfacial charge density and the electrode surface species. Differential capacitance curves demonstrate weak dependence on potential except for ChAc:EG, where Ac – is found to adsorb on the Au surface, in particular at +0.055 V vs Ag quasi-reference while no specific adsorption was observed on glassy carbon (GC). In situ SERS measurement confirms the formation of a surface layer in the ChAc:EG systems resulting from a Au–acetate interaction. Despite the structural similarities, Ox –2 did not show specific binding or any dependence of capacitance on potential as a result of strongly solvating EG molecules via H-bonds. Furthermore, this study shows that the charge density of the HBAs impacts both bulk properties and the electrical double-layer formation in concentrated H-bonded electrolytes that is relevant to electrochemical kinetics and morphology in electrodeposition processes and energy storage applications.
The bulk metallic electromagnetic levitation technique has a promising application prospect in condensed physics and materials science. In order to resolve the problem of weak levitation force and the small size of samples, an optimized solution based on finite element analysis (FEA) is developed to seek the best electromagnetic field distribution in the levitation zone. The influence of material properties on the distribution of magnetic flux density, surface pressure, and the Lorentz force were studied by the FEA method with various sample sizes of titanium and copper balls. The levitation capability of cylindrical coil system which consists of a single-layer coil with an inner diameter of 30 mm and the levitated object with a diameter of 20 mm was analyzed. To keep a balance between the turn number and increment efficiency of force, the best number of 7 turns is confirmed. Then, two types of optimized coils were predicted by numerical simulations, and the levitation force is improved drastically. The double-layer coil displays an outstanding levitation capability owing to the strong electromagnetic field generated by multilayer turns. In addition, 5 to 50 g aluminum, titanium, copper, and nickel are levitated by the above three kinds of coils and the levitation capacities are validated from the recorded data of the minimum operating current that can levitate the samples. The experimental results show good agreements with the simulation results, and the minimum current for optimized coils is reduced efficiently.
The degradation of the ionic pathway throughout the catalyst layer in proton exchange membrane fuel cells was studied under an accelerated stress test of catalyst support (potential hold at 1.2 V). Electrochemical behaviors of the cathode based on graphitic mesoporous carbon supported Pt catalyst were examined using electrochemical impedance spectroscopy and cyclic voltammetry. Impedance data were plotted and expressed in the complex capacitance form to determine useful parameters in the transmission line model: the double-layer capacitance, peak frequency, and ionic resistance. Electrochemical surface area and hydrogen crossover current through the membrane were estimated from cyclic voltammogram, while cathode Faradaic resistance was compared with ionic resistance as a function of test time. It was observed that during an accelerated stress test of catalyst support, graphitic mesoporous carbon becomes hydrophilic which increases interfacial area between the ionomer and the catalyst up to 100 h. However, the ionic resistance in the catalyst layer drastically increases after 100 h with further carbon support oxidation. The underlying mechanism has been studied and it was found that significant degradation of ionic pathway throughout the catalyst layer due to catalyst support corrosion induces uneven hydration and mechanical stress in the ionomer.
Three new heteroanionic oxypnictides, Ba 2 Zn 2 Sb 2 O, Ba 2 Zn 2 Bi 2 O, and the solid solution Ba 2 Zn 2 Sb 2−x Bi x O (x ≈ 1.1–1.6), have been synthesized and structurally characterized. They are isostructural with their Mn-bearing analog, adopting the Ba 2 Mn 2 Sb 2 O-type structure (space group P6 3 /mmc, No. 194), and feature a double-layered 2D $^{2}_{∞}$ [Zn 2 Pn 2 O] 2- substructure (Pn = Sb, Bi, Sb/Bi) composed of corner-sharing, distorted tetrahedral ZnPn 3 O units. Electronic structure calculations reveal a systematic progression from semiconducting Ba 2 Zn 2 Sb 2 O to metallic Ba 2 Zn 2 Bi 2 O as Bi content increases. These trends are corroborated by transport property measurements, with Ba 2 Zn 2 Sb 0.9(1) Bi 1.1 O exhibiting relatively low electrical resistivity, high Hall mobilities of ∼160 cm 2 /V·s, and large Seebeck coefficients from 69 to 132 μV K −1 over the 300–600 K temperature range. Comparison with structurally related Zintl pnictides, such as SrIn 2 As 2 and PrZn 3 As 3 phases, situates Ba 2 Zn 2 Pn 2 O (Pn = Sb, Bi) within a broader family of heteroanionic oxypnictide Zintl compounds, highlighting their structural flexibility and amenability to band engineering. Finally, electronic structure and bonding considerations point to tunable semiconducting behavior and underscore the relevance of these materials for thermoelectric and topological applications.
Single crystals of a new family of layered lanthanide oxychlorides, Ba 3 Ln 2 O 5 Cl 2 (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/ mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba 3 Ln 2 O 5 Cl 2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba 2 Ln 2 O 5 formed by corner-connected LnO 5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl 2 . A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.
The series of electrodes were fabricated by the scalable and manufacturable slot-die coating method for proton exchange membrane fuel cell (PEMFC) application. The inks with different amounts of solids were studied by rheological methods in order to establish a coating window with minimum manufacturing defects. The obtained electrodes were characterized by SEM, AFM, and optical microscopy, which showed that they were uniform and homogeneous with minimum defects. The electrochemical evaluation of the manufactured gas diffusion electrodes (GDE) showed that the main characteristics of the electrodes, like electrochemical surface area, proton resistivity, and double layer capacitance, were found to be close for all samples confirming the reproducibility of the slot-die process. Additionally, we studied the effects of membrane thickness on the performance of the GDE membrane electrode assemblies and determined that a decrease in membrane thickness favored the performance. Furthermore, the obtained results clearly demonstrated the applicability and feasibility of the approach for the Manufacturing of catalyst layers for the fuel cell application with potential for future mass production.
The adsorption energies of submonolayer amounts of one metal on the surface of another metal have been measured for decades by temperature programmed desorption. However, that method fails for metals that alloy. We report here the first measurement of the adsorption energy for any such metal-on-metal combination that forms a bulk alloy. The adsorption and interfacial energetics of vapor deposited Cu onto Pt(111) at 300 K has been studied herein using single crystal adsorption calorimetry (SCAC) and X-ray photoelectron spectroscopy (XPS). The Cu grows as 2D pseudomorphic islands in the first layer and its heat of adsorption decreased linearly from 358 to 339 kJ/mol. This is attributed to increasing lattice strain with island size, associated with the small lattice mismatch (8%). It adsorbs ~2 kJ/mol more weakly in the 2nd layer than above 3 ML, where it reaches the bulk heat of sublimation of Cu(solid), 337 kJ/mol. The adhesion energy of multilayer Cu onto Pt(111) is 3.76 J/m 2 . The extra stability of the first Cu monolayer compared to bulk Cu measured here is ~12 kJ/mol, compared to a difference of ~83 kJ/mol for underpotential deposition of Cu on a Pt(111) electrode, with the difference attributed to stronger bonding of Cu to the solvent and double layer compared to Pt.
This project aims at developing highly efficient perovskite/silicon tandem solar cells by developing efficient perovskite top cells, silicon bottom cells, and monolithically integrating the subcells for highly efficient tandem solar cells. The project focused on increasing the efficiency of perovskite solar cells to 20% and understanding related materials science and device physics, as well as developing a compatible bottom high-efficiency c-Si solar cell. The perovskite cells with a wide bandgap of 1.61 eV and 1.84 eV are fabricated by a low-cost, low-temperature, scalable solution process on lower bandgap silicon bottom cells. The bandgaps of perovskite top cells have been tuned between 1.61 eV and 1.84 eV by composition engineering mainly through controlling the halide mixing ratio in perovskite materials. The efficiencies of the wide bandgap perovskite solar cells have been improved to an excellent efficiency of 21.0% for perovskites with a bandgap of 1.63 eV with increased grain size, reduced energy disorder at cathode contact, and defect passivation. We invented a solvent annealing approach with solvent vapor during thermal annealing to enlarge grain size of perovskite film which reduces the charge trap density and improves the device efficiency. Moreover, we discovered that the non-wetting surface could further increase the grain size for perovskite films, because non-wetting surface could prevent the formation of too dense nuclei from heterogeneous nucleation process. We proposed to reduce the energy disorder of organic charge extraction layer to reduce the power loss in perovskite cells. We pioneered defect passivation concept and techniques to suppress the charge non-radiative recombination in perovskite solar cells to boost the efficiency. For the silicon bottom cell development, different from the conventional silicon cell work under full illumination, the light available for the silicon bottom cell in tandem structure is mainly NIR region. We developed a NIR enhanced silicon cell with efficiency of 21.2% by applying a double-layer antireflection coating at the front side and a MgF2 back reflector layer at the rear side. For the perovskite/silicon tandem device, we achieved a highest reported power conversion efficiency of 25.4% in 2018, and further increased the efficiency up to 26.0% in 2019. The research on tandem solar cells focused on reducing reflection loss to <5% at spectrum of 300-1100 nm by antireflection layer, tuning the bandgap of perovskite film for matched current density between sub-cells, and utilizing a ITO layer between perovskite top cell and silicon bottom cell as interconnect layer without Voc loss. Finally, we developed a blading technique to fabricate perovskite films which produces perovskite solar cells with comparable or even superior efficiency to those made by non-scalable spin coating method. This paves the way for scaling up perovskite/silicon tandem solar cells using solution approach.
We report that pseudocapacitive energy storage in supercapacitor electrodes differs significantly from the electrical double-layer mechanism of porous carbon materials, which requires a change from conventional thinking when choosing appropriate electrolytes. Here we show how simply changing the solvent of an electrolyte system can drastically influence the pseudocapacitive charge storage of the two-dimensional titanium carbide, Ti 3 C 2 (a representative member of the MXene family). Measurements of the charge stored by Ti 3 C 2 in lithium-containing electrolytes with nitrile-, carbonate- and sulfoxide-based solvents show that the use of a carbonate solvent doubles the charge stored by Ti 3 C 2 when compared with the other solvent systems. We find that the chemical nature of the electrolyte solvent has a profound effect on the arrangement of molecules/ions in Ti 3 C 2 , which correlates directly to the total charge being stored. Finally, having nearly completely desolvated lithium ions in Ti 3 C 2 for the carbonate-based electrolyte leads to high volumetric capacitance at high charge–discharge rates, demonstrating the importance of considering all aspects of an electrochemical system during development.