Enhanced Catalytic Probe Design for Mapping Radical Density in the Plasma Afterglow.

The electrification of chemical processes using plasma generates an increasing demand for sensors, monitoring concentrations of plasma-activated species such as radicals. Radical probes are a low-cost in situ method for spatially resolved quantification of the radical density in a plasma afterglow using the heat from the exothermal recombination of radicals on a catalytic surface. However, distinguishing recombination heating from other heat fluxes in the system is challenging.

Unraveling NO Production in N-O Plasmas with 0D Kinetic Modeling and Experimental Validation.

This work presents a detailed investigation aimed at understanding the key mechanisms governing nitric oxide (NO) production in N-O discharges by systematically comparing experimental results to modeling data. The experimental phase capitalizes on radiofrequency (13.56 MHz) discharges, sustained at 5 mbar pressure conditions, featuring varying concentrations of oxygen, ranging from pure N plasma to air-like mixtures.

Scaling up BiVO Photoanodes on Porous Ti Transport Layers for Solar Hydrogen Production.

Commercialization of photoelectrochemical (PEC) water-splitting devices requires the development of large-area, low-cost photoanodes with high efficiency and photostability. Herein, we address these challenges by using scalable fabrication techniques and porous transport layer (PTLs) electrode supports. We demonstrate the deposition of W-doped BiVO on Ti PTLs using successive-ionic-layer-adsorption-and-reaction methods followed by boron treatment and chemical bath deposition of NiFeOOH co-catalyst.

Development of Electrode-Supported Proton Conducting Solid Oxide Cells and their Evaluation as Electrochemical Hydrogen Pumps.

Protonic ceramic solid oxide cells (P-SOCs) have gained widespread attention due to their potential for operation in the temperature range of 300-500 °C, which is not only beneficial in terms of material stability but also offers unique possibilities from a thermodynamic point of view to realize a series of reactions. For instance, they are ideal for the production of synthetic fuels by hydrogenation of carbon dioxide and nitrogen, upgradation of hydrocarbons, or dehydrogenation reactions. However, the development of P-SOC is quite challenging because it requires a multifront optimization in terms of material synthesis and fabrication procedures.

The Chemical Origins of Plasma Contraction and Thermalization in CO Microwave Discharges.

Thermalization of electron and gas temperature in CO microwave plasma is unveiled with the first Thomson scattering measurements. The results contradict the prevalent picture of an increasing electron temperature that causes discharge contraction. It is known that as pressure increases, the radial extension of the plasma reduces from ∼7 mm diameter at 100 mbar to ∼2 mm at 400 mbar.

Revisiting spontaneous Raman scattering for direct oxygen atom quantification.

In this Letter, the counterintuitive and largely unknown Raman activity of oxygen atoms is evaluated for its capacity to determine absolute densities in gases with significant O-density. The study involves ${\rm CO}_2$ microwave plasma to generate a self-calibrating mixture and establish accurate cross sections for the $^3{\!P_2}{\leftrightarrow ^3}{\!P_1}$ and $^3{\!P_2}{\leftrightarrow ^3}{\!P_0}$ transitions. The approach requires conservation of stoichiometry, confirmed within experimental uncertainty by a 1D fluid model.

High-Throughput Computational Screening of Cubic Perovskites for Solid Oxide Fuel Cell Cathodes.

It is a present-day challenge to design and develop oxygen-permeable solid oxide fuel cell (SOFC) electrode and electrolyte materials that operate at low temperatures. Herein, by performing high-throughput density functional theory calculations, oxygen vacancy formation energy, , data for a pool of all-inorganic ABO and AABO cubic perovskites is generated. Using data of perovskites, the area-specific resistance (ASR) data, which is related to both oxygen reduction reaction activity and selective oxygen ion conductivity of materials, is calculated.

Electrochemical Activation of Atomic Layer-Deposited Cobalt Phosphate Electrocatalysts for Water Oxidation.

The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented.

Charge carrier dynamics and photocatalytic activity of {111} and {100} faceted AgPO particles.

Silver orthophosphate is a highly promising visible light photocatalyst with high quantum yield for solar driven water oxidation. Recently, the performance of this material has been further enhanced using facet-controlled synthesis. The tetrahedral particles with {111} exposed facets demonstrate higher photocatalytic performance than the cubic particles with {100} exposed facets.

Observation of Nanoparticle Exsolution from Perovskite Oxides: From Atomic Scale Mechanistic Insight to Nanostructure Tailoring.

Understanding and controlling the formation of nanoparticles at the surface of functional oxide supports is critical for tuning activity and stability for catalytic and energy conversion applications. Here, we use a latest generation environmental transmission electron microscope to follow the exsolution of individual nanoparticles at the surface of perovskite oxides, with ultrahigh spatial and temporal resolution. Qualitative and quantitative analysis of the data reveals the atomic scale processes that underpin the formation of the socketed, strain-inducing interface that confers exsolved particles their exceptional stability and reactivity.

Solar Hydrogen Generation from Ambient Humidity Using Functionalized Porous Photoanodes.

Solar hydrogen is a promising sustainable energy vector, and steady progress has been made in the development of photoelectrochemical (PEC) cells. Most research in this field has focused on using acidic or alkaline liquid electrolytes for ionic transfer. However, the performance is limited by (i) scattering of light and blocking of catalytic sites by gas bubbles and (ii) mass transport limitations.

Electrochemistry of Sputtered Hematite Photoanodes: A Comparison of Metallic DC versus Reactive RF Sputtering.

The water splitting activity of hematite is sensitive to the film processing parameters due to limiting factors such as a short hole diffusion length, slow oxygen evolution kinetics, and poor light absorptivity. In this work, we use direct current (DC) magnetron sputtering as a fast and cost-effective route to deposit metallic iron thin films, which are annealed in air to obtain well-adhering hematite thin films on F:SnO-coated glass substrates. These films are compared to annealed hematite films, which are deposited by reactive radio frequency (RF) magnetron sputtering, which is usually used for depositing metal oxide thin films, but displays an order of magnitude lower deposition rate.

High and intermediate temperature sodium-sulfur batteries for energy storage: development, challenges and perspectives.

In view of the burgeoning demand for energy storage stemming largely from the growing renewable energy sector, the prospects of high (>300 °C), intermediate (100-200 °C) and room temperature (25-60 °C) battery systems are encouraging. Metal sulfur batteries are an attractive choice since the sulfur cathode is abundant and offers an extremely high theoretical capacity of 1672 mA h g upon complete discharge. Sodium also has high natural abundance and a respectable electrochemical reduction potential (-2.

Vibrational Kinetics in Plasma as a Functional Problem: A Flux-Matching Approach.

A new approach to calculate the vibrational distribution function of molecules in a medium providing energy for vibrational excitation is proposed and demonstrated. The approach is an improvement of solution methods based on the drift-diffusion Fokker-Planck (FP) equation for a double differentiable function representing the vibrational populations on a continuum internal energy scale. A self-consistent numerical solution avoids approximations used in previous analytical solutions.

How the alternating degeneracy in rotational Raman spectra of CO and CH reveals the vibrational temperature.

The contribution of higher vibrational levels to the rotational spectrum of linear polyatomic molecules with a center of symmetry (CO and CH) is assessed. An apparent nuclear degeneracy is analytically formulated by vibrational averaging and compared to numerical averaging over vibrational levels. It enables inferring the vibrational temperature of the bending and asymmetric stretching modes from the ratio of even to odd peaks in the rotational Raman spectrum.

Zeolites for CO-CO-O Separation to Obtain CO-Neutral Fuels.

Carbon dioxide release has become an important global issue due to the significant and continuous rise in atmospheric CO concentrations and the depletion of carbon-based energy resources. Plasmolysis is a very energy-efficient process for reintroducing CO into energy and chemical cycles by converting CO into CO and O utilizing renewable electricity. The bottleneck of the process is that CO remains mixed with O and residual CO.

Atomistic simulations of graphite etching at realistic time scales.

Hydrogen-graphite interactions are relevant to a wide variety of applications, ranging from astrophysics to fusion devices and nano-electronics. In order to shed light on these interactions, atomistic simulation using Molecular Dynamics (MD) has been shown to be an invaluable tool. It suffers, however, from severe time-scale limitations.

Oscillatory vapour shielding of liquid metal walls in nuclear fusion devices.

Providing an efficacious plasma facing surface between the extreme plasma heat exhaust and the structural materials of nuclear fusion devices is a major challenge on the road to electricity production by fusion power plants. The performance of solid plasma facing surfaces may become critically reduced over time due to progressing damage accumulation. Liquid metals, however, are now gaining interest in solving the challenge of extreme heat flux hitting the reactor walls.

Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface.

Self-Regulated Plasma Heat Flux Mitigation Due to Liquid Sn Vapor Shielding.

A steady-state high-flux H or He plasma beam was balanced against the pressure of a Sn vapor cloud for the first time, resulting in a self-regulated heat flux intensity near the liquid surface. A temperature response of the liquid surface characterized by a decoupling from the received heating power and significant cooling of the plasma in the neutral Sn cloud were observed. The plasma heat flux impinging on the target was found to be mitigated, as heat was partially dissipated by volumetric processes in the vapor cloud rather than wholly by surface effects.

Taming microwave plasma to beat thermodynamics in CO2 dissociation.

The strong non-equilibrium conditions provided by the plasma phase offer the opportunity to beat traditional thermal process energy efficiencies via preferential excitation of molecular vibrations. Simple molecular physics considerations are presented to explain potential dissociation pathways in plasma and their effect on energy efficiency. A common microwave reactor approach is evaluated experimentally with Rayleigh scattering and Fourier transform infrared spectroscopy to assess gas temperatures (exceeding 10(4) K) and conversion degrees (up to 30%), respectively.

Characterization of Nanocrystal Size Distribution using Raman Spectroscopy with a Multi-particle Phonon Confinement Model.

Analysis of the size distribution of nanocrystals is a critical requirement for the processing and optimization of their size-dependent properties. The common techniques used for the size analysis are transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence spectroscopy (PL). These techniques, however, are not suitable for analyzing the nanocrystal size distribution in a fast, non-destructive and a reliable manner at the same time.

Note: Rotational Raman scattering on CO₂ plasma using a volume Bragg grating as a notch filter.

We present a novel approach for filtering Rayleigh scattering and stray light from Raman scattering in a gas discharge, using a volume Bragg grating as a notch filter. For low frequency rotational Raman contributions, it is essential to filter out Rayleigh scattering and stray light at the laser wavelength to be able to measure an undisturbed Raman spectrum. Using the Bragg grating, having an optical density of 3.