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At least 433 records · Page 24

Comprehensive Efficiency Analysis of Current Source Inverter Based SPM Machine Drive System for Traction Applications

A current-source inverter (CSI) has the natural capability of boosting the output voltage which is a notable advantage over voltage source inverter (VSI) in traction drive applications. This paper investigates the voltage boosting feature of the CSI to improve the overall efficiency of the CSI-based surface permanent magnet (SPM) machine drive system in the constant power region. The effects of the boost function on the total system losses, including the machine copper loss, core loss, and magnet loss, as well as the device conduction and switching loss in the CSI and dc/dc converter, are described using analytical models. The operating characteristics of the machine and CSI are validated by 2-D finite-element analysis (FEA) and simulations. Based on the loss model, the effects of the modulation index on the overall drive system losses and power factor have been analyzed. A genetic algorithm has been used to optimize the CSI's boost ratio, demonstrating that the drive system efficiency can be increased by 1% to 2.5% along the constant-power regime envelope by using the boost function.

current source inverter, genetic algorithm, SPM ma↗

Single-Phase Jet Impingement Cooling for a Power-Dense Silicon Carbide Power Module

The adoption of silicon carbide (SiC) devices in the electric vehicle (EV) industry is increasing due to their superior performance over silicon devices. SiC devices enable further miniaturization of EV inverters, increasing their power density, which results in thermal management challenges. Here in this paper, the limits of single-phase jet impingement cooling are explored for an automotive SiC power module. We propose embedding pin fins in the direct-bonded-copper (DBC) substrate of the power module package using laser powder bed fusion additive manufacturing. The thermalhydraulic performance of the DBC-embedded pin fins is compared against folded fins that are directly soldered to the DBC substrate. A heat conduction analysis was conducted on a SiC package to determine the target heat transfer coefficient (HTC) for the heat sink. A water-ethylene glycol (WEG) jet impingement on the proposed concepts was studied using unit-cell models to achieve the target HTC. The studied designs put emphasis on the reliability and manufacturability requirements of the automotive industry. The thermal performance of DBC-embedded pin fins outperformed the DBC-soldered folded fins. The performance of the DBC-embedded pin fins is benchmarked against WEG-based cooling systems of commercial EVs. With the proposed cooling solution, we have shown a pathway of reducing the specific thermal resistance by 75% compared to BMW i3 thermal management system without any penalty on pressure drop or parasitic power.

33 ADVANCED PROPULSION SYSTEMS↗

Pseudocapacitive Charge Storage in Electrochromic Transition-Metal Oxide Thin Films

Electrochromic pseudocapacitive transition-metal oxide materials, such as tungsten oxide, which combine fast response, high energy density, and optical effects, can play a significant role as energy storage materials. Here we investigate the electrochemical kinetics of thin films of tungsten oxide, which turn transparent to sky-blue color in the lithiated state due to the reduction of W 6+ to W 5+ . In this study, we investigated the charge density, charge transfer, ion diffusion, and interfacial behavior upon Li + insertion/de-insertion in WO 3 . The electrochromic thin film's pseudocapacitive and electrical double layer mechanism was differentiated based on the power-law. Faradaic diffusion-controlled process dominates over the surface capacitive behavior at scan rates below 40 mV s –1 . These films exhibit an areal charge density of around 100 mC cm –2 and a capacitance of 80 mF cm –2 , superior to most comparable electrochromic materials and supercapacitors. This work combines electrochromics and energy storage properties and provides a fundamental understanding of pseudocapacitive and electrochromic mechanisms in WO 3 .

25 ENERGY STORAGE↗

Parameter-Varying Hydrodynamic Model of a Single Vane in a Variable-Geometry Oscillating Surge Wave Energy Converter

This paper presents a preliminary study on the parameter-varying hydrodynamic modeling of an individual vane of a variable-geometry oscillating surge wave energy converter (VGOSWEC). The WEC design incorporates controlled surfaces that can modify their orientation relative to the wave motion, reducing hydrodynamic pressure and related loads. This research focuses on characterizing the behavior of the oscillating WEC using a simplified model and three methods for achieving a continuous parameter-varying model: coarse hydrodynamic parameters, interpolation of hydrodynamic parameters, and a fitting function. The results of this study contribute to the understanding of parameter-varying hydrodynamic effects in variable geometry oscillating WECs. The findings provide insights into the potential for reducing structural loads and improving the overall performance of such devices. Further research and development in this area could lead to advancements in WEC technologies, enabling their integration into the competitive energy market.

analytical models↗

Advancements in High-Q development for novel medium-velocity 644 MHz 5-cell elliptical superconducting RF cavities for continuous-wave operation in heavy-ion linacs

The Facility for Rare Isotope Beams is a world-leading center for experimental nuclear physics research, and relies on a first-in-kind superconducting RF driver linac to supply 400 kW beams of a uniquely large range of particles, from protons through the heaviest uranium ions. The FRIB400 project proposes to double the end energy of the current superconducting FRIB linac for the heaviest uranium ions from 200 MeV per nucleon (MeV/u) to 400 MeV/u, which equates to approximately 1 GeV for protons. The increased rare isotope production from higher-energy drive beams would deliver new and exciting capabilities to FRIB users, which include extending the facility's reach along the neutron drip-line, greatly increasing the facility's rare isotope yield, and significantly improving the precision of parameter measurements for the nuclear matter equation of state, which is a particularly timely complement to the recent advent of multi-messenger astronomy, and the study of neutron star mergers. The unique set of design parameters defined by the 400 MeV/u (uranium) energy goal, the physical size, continuous-wave operation, and cryogenic capacity of the extant facilities at FRIB, requires development of a first-in-kind beta = v/c = 0.65, 644 MHz 5-cell elliptical superconducting RF (SRF) cavity, with field-leading efficiency, measured by the cavity's intrinsic quality factor, Q_0. The field of SRF has recently experienced a very active period of development, which demonstrated the potential to raise the Q_0 of 1.3 GHz cavities by factors of two to three or more. In addition to uncovering fascinating new properties of the fundamental physics of superconducting RF phenomena, these improvements suggest substantial improvements could be made over the minimum Q_0 of the proposed FRIB400 upgrade SRF cavities, if these new techniques can be adapted to the beta = 0.65, 644 MHz regime. This work presents the first validation of the the novel beta = 0.65, 644 MHz 5-cell elliptical superconducting RF cavity design, and the first results of both conventional and advanced RF surface preparation techniques. In particular, this work focuses on two recently-developed high-Q_0 recipes: N-doping, and furnace baking, setting the current world-record Q_0 for this type of resonant cavity at 3.8 x 10^10 at the FRIB400 operating gradient of 17.5 MV/m. We also find evidence that these results may be further improved upon, and make the case for further RF surface preparation recipe optimization. We then pair these high-power RF investigations with techniques borrowed from material science to try to better understand the ways in which specific properties of the niobium material, such as grain structure and superconducting flux pinning force, can be related to its superconducting RF performance. These experiments better elucidate the effects of high-temperature annealing on niobium samples, which suggest methods of further optimizing cavity flux expulsion and thus SRF performance.Read

McGee, Kellen E.↗

Improving robustness for model discerning synthesis process of uranium oxide with unsupervised domain adaptation

The quantitative characterization of surface structures captured in scanning electron microscopy (SEM) images has proven to be effective for discerning provenance of an unknown nuclear material. Recently, many works have taken advantage of the powerful performance of convolutional neural networks (CNNs) to provide faster and more consistent characterization of surface structures. However, one inherent limitation of CNNs is their degradation in performance when encountering discrepancy between training and test datasets, which limits their use widely. The common discrepancy in an SEM image dataset occurs at low-level image information due to user-bias in selecting acquisition parameters and microscopes from different manufacturers. Therefore, in this study, we present a domain adaptation framework to improve robustness of CNNs against the discrepancy in low-level image information. Furthermore, our proposed approach makes use of only unlabeled test samples to adapt a pretrained model, which is more suitable for nuclear forensics application for which obtaining both training and test datasets simultaneously is a challenge due to data sensitivity. Through extensive experiments, we demonstrate that our proposed approach effectively improves the performance of a model by at least 18% when encountering domain discrepancy, and can be deployed in many CNN architectures.

scanning electron microscopy↗

Wavelength Scaling of Widely-Tunable Terahertz Quantum-Cascade Metasurface Lasers

Terahertz (THz) external-cavity lasers based on quantum-cascade (QC) metasurfaces are emerging as widely-tunable, single-mode sources with the potential to cover the 1--6 THz range in discrete bands with milliwatt-level output power. By operating on an ultra-short cavity with a length on the order of the wavelength, the QC vertical-external-cavity surface-emitting-laser (VECSEL) architecture enables continuous, broadband tuning while producing high quality beam patterns and scalable power output. The methods and challenges for designing the metasurface at different frequencies are discussed. As the QC-VECSEL is scaled below 2 THz, the primary challenges are reduced gain from the QC active region, increased metasurface quality factor and its effect on tunable bandwidth, and larger power consumption due to a correspondingly scaled metasurface area. At frequencies above 4.5 THz, challenges arise from a reduced metasurface quality factor and the excess absorption that occurs from proximity to the Reststrahlen band. The results of four different devices — with center frequencies 1.8 THz, 2.8 THz, 3.5 THz, and 4.5 THz — are reported. Each device demonstrated at least 200 GHz of continuous single-mode tuning, with the largest being 650 GHz around 3.5 THz. The limitations of the tuning range are well modeled by a Fabry-Pérot cavity which accounts for the reflection phase of the metasurface and the effect of the metasurface quality factor on laser threshold. Lastly, the effect of different output couplers on device performance is studied, demonstrating a significant trade-off between the slope efficiency and tuning bandwidth.

47 OTHER INSTRUMENTATION↗

Tidal energy resource characterization measurements at Cook Inlet’s East Foreland: Velocity and turbulence

To characterize tidal current and turbulence at a top tidal energy site off the East Foreland in Cook Inlet, Alaska, United States, three moorings were deployed for two months between July and August 2021, and a transect survey was conducted over the course of two tidal cycles at the end of the deployment period. Measurements of velocity and turbulence were then analyzed to better understand the site's hydrodynamics and power potential. Analysis reveals that swift, north-flowing flood currents peak at 4~m/s, while south-flowing ebb currents reach just over 3~m/s. Turbulence intensity ranges from 23\% at the seafloor to 8\% near the surface, and the presence of the foreland creates more intense turbulence near-shore during ebb tide than flood. Power availability at the site could be as high as 720~MW, or 13~kW/m$^2$, though the energy available to a marine energy device will be smaller than this estimate because of water-to-wire efficiency and wake losses. The results from this measurement campaign will inform the validation of a high-resolution tidal hydrodynamic model, as well as early tidal energy projects that are beginning to move beyond the prototyping and demonstration stages to full-scale deployments.

McVey, James R.↗

Characterization of plasma catalytic decomposition of methane: role of atomic O and reaction mechanism

In this work, we investigated atmospheric pressure plasma jet (APPJ)-assisted methane oxidation over a Ni-SiO 2 /Al 2 O 3 catalyst. We evaluated possible reaction mechanisms by analyzing the correlation of gas phase, surface and plasma-produced species. Plasma feed gas compositions, plasma powers, and catalyst temperatures were varied to expand the experimental parameters. Real-time Fourier-transform infrared spectroscopy was applied to quantify gas phase species from the reactions. The reactive incident fluxes generated by plasma were measured by molecular beam mass spectroscopy using an identical APPJ operating at the same conditions. A strong correlation of the quantified fluxes of plasma-produced atomic oxygen with that of CH 4 consumption, and CO and CO 2 formation implies that O atoms play an essential role in CH 4 oxidation for the investigated conditions. With the integration of APPJ, the apparent activation energy was lowered and a synergistic effect of 30% was observed. We also performed in-situ diffuse reflectance infrared Fourier-transform spectroscopy to analyze the catalyst surface. The surface analysis showed that surface CO abundance mirrored the surface coverage of CH n at 25 °C. This suggests that CH n adsorbed on the catalyst surface as an intermediate species that was subsequently transformed into surface CO. We observed very little surface CH n absorbance at 500 °C, while a ten-fold increase of surface CO and stronger CO 2 absorption were seen. This indicates that for a nickel catalyst at 500 °C, the dissociation of CH 4 to CHn may be the rate-determining step in the plasma-assisted CH 4 oxidation for our conditions. We also found the CO vibrational frequency changes from 2143 cm –1 for gas phase CO to 2196 cm –1 for CO on a 25 °C catalyst surface, whereas the frequency of CO on a 500 °C catalyst was 2188 cm –1 . Here, the change in CO vibrational frequency may be related to the oxidation of the catalyst.

methane oxidation↗

Numerical Modelling of a Two-Body Point Absorber Featuring Variable Geometry

This work presents a novel wave energy converter (WEC) device concept that incorporates variable geometry modules into a two-body point absorber type WEC. The variable geometry modules consist of air inflatable bags in the surface float and a water inflatable ring in the reaction body. The variable geometry floats are able to provide greater control over the device hydrodynamics; they can be inflated or deflated to emphasize either power absorption or load shedding. The device geometry is controlled in a quasi-static fashion, while the power take-off (PTO) unit is controlled on a wave-to-wave timescale. The surface float is tethered directly to the submerged reaction body through PTO tether lines. A linear time-domain analysis, conducted using open-source Wave Energy Converter (WEC-Sim) software, was used to estimate the absorbed power of the WEC in sea states defined by the Wave Energy Prize. WEC power performance was weighted against the expected capital cost of building the load bearing structure of the device, providing an estimated ACE value. The inclusion of the variable geometry modules was shown to be effective in altering the device geometry to improve power capture with a near proportional increase in expected costs, providing a nearly constant power-to-cost ratio.

cost of energy↗

Double-sided electrodynamic screen films

An electrode film includes a first electrode pattern having a first set of parallel conductive electrodes and a second electrode pattern having a second set of parallel conductive electrodes disposed on a first surface of a transparent film, wherein elements of the first electrode pattern do not cross over elements of the second electrode pattern. A third electrode pattern having a third set of parallel conductive electrodes is disposed on a second surface of the transparent film, wherein the first, second and third sets of parallel conductive electrodes are arranged in an interlaced pattern. The electrode patterns are configured to be connected to respective power sources of electrical power supplying respective waveforms to generate a time-varying electric field pattern above a surface of the electrode film.

Tombs, Thomas Nathaniel↗

Fast-Charging and Ultrahigh-Capacity Lithium Metal Anode Enabled by Surface Alloying

Li metal anodes are going through a great revival but they still encounter grand challenges. One often neglected issue is that most reported Li metal anodes are only cyclable under relatively low current density (<5 mA cm -2 ) and small areal capacity (<5 mAh cm -2 ), which essentially limits their high-power applications and results in ineffective Li utilization (<1%). Herein, it is reported that surface alloyed Li metal anodes can enable reversible cycling with ultrafast rate and ultralarge areal capacity. Low-cost Si wafers are used and are chemically etched down to 20-30 mu m membranes. Simply laminating a Si membrane onto Li foil results in the formation of LixSi alloy film fused onto Li metal with mechanical robustness and high Li-ion conductivity. Symmetric cell measurements show that the surface alloyed Li anode has excellent cycling stability, even under high current density up to 25 mA cm -2 and unprecedented areal capacity up to 100 mAh cm -2 . Furthermore, the surface alloyed Li anode is paired with amorphous MoS 3 cathode and achieves remarkable full-cell performance.

36 MATERIALS SCIENCE↗

Experimental studies of a high-gradient X-band welded hard-copper split accelerating structure

We report on recent research on high-gradient radio frequency (RF) accelerating structures indicates that the use of hard copper alloys provides improvement in high gradient performance over annealed copper. Such structures are made by bonding individually manufactured parts. However, there are no well-established bonding techniques that preserve the hardness, surface finish and cleanliness required for high gradient operation. To preserve the copper hardness, RadiaBeam has developed a novel high-gradient split accelerating structure, based on electron beam welding joining technique. This technique provides efficient bonding with strong, clean welds and minimal thermal loading, while maintaining a clean inner RF environment. Our RF design and fabrication methodology limits the small heat affected zone to the outer cavity envelop, with virtually no distortions or thermal loading of critical RF surfaces. It also incorporates provisions to precisely control the gap despite conventional issues with weld joint shrinkage. To date we have manufactured and validated an RF accelerating structure joined by electron-beam welding that incorporates a novel open split design to significantly reduce the assembly complexity and cost. In this paper, we will present the electromagnetic design of this structure, discuss bonding, and present the results of high-power tests, where the accelerating gradients of 140 MV m -1 with surface peak fields of 400 MV m -1 were achieved for flat-top pulse length of 600 ns with an RF breakdown rate of 10 -4 1/(pulsecm).

43 PARTICLE ACCELERATORS↗

Evaluating software defined networking solutions to reduce the digital attack surface of nuclear security systems

Most nuclear security systems used today were not designed for today’s threat environment. Systems that were intended to be stand alone are now interconnected. Devices that have a single purpose are built on multi-purpose platforms and communication protocols that, while effective, have no ability to authenticate authorized versus unauthorized commands. These attributes provide an attacker significant ability to affect the system, pivot throughout the interconnected networks, and remain undetected if he/she is able to compromise a single node. Software defined networking (SDN) has been used for years by information technology (IT) cloud service providers to quickly provision or remove servers or other systems to meet changing demand. The same concept has recently been applied to operational technology (OT) systems to enable very fast failover on critical systems that have stringent and deterministic (<5ms) transmit/receive times. By carefully engineering the communication flows through a network using preplanned routes and specific pathways it is possible to achieve deterministic and extremely reliable message delivery even when components fail. This engineering approach to network design has added security benefits including securing the networking control plane, eliminating network scanning and mapping, inhibiting ARP spoofing and host masquerading, eliminating unauthorized network pivoting and enabling greater situational awareness on the network. SDN in OT environments is new but early testing in electrical power and other critical infrastructure has shown it to be a very powerful tool for building reliable networks and reducing the digital attack surface of the network. The authors tested a software defined network switch on a simple physical protection system with components commonly found in nuclear security systems and found improved mitigations to denial of service attacks, lateral movement and network reconnaissance. The paper details the tests and their results.

Cyber security, Nuclear security, software defined↗

Plasma catalysis: separating plasma and surface contributions for an Ar/N 2 /O 2 atmospheric discharge interacting with a Pt catalyst

Atmospheric pressure non-equilibrium plasmas can form nitrogen oxide (NO x ) compounds directly from nitrogen and oxygen without a catalyst, and at lower catalyst temperatures than would be possible without plasma. In this work, the oxidation of plasma-produced NO from an Ar/N 2 /O 2 non-equilibrium atmospheric-pressure plasma-jet (APPJ) over a platinum-on-alumina powder catalyst was investigated with in-situ infrared spectroscopy. Products downstream of the catalyst bed were analyzed along with catalyst surface species. The catalyst was exposed to plasma at both constant temperature and a cyclic temperature ramp in order to study long-lasting and transient surface changes. Primary incident reactive species to the catalyst were assessed to be NO and O 3 . Pt-Al 2 O 3 at 350 °C increased oxidation of NO relative to Al 2 O 3 or an empty chamber. The surface state of Pt-Al 2 O 3 evolves during plasma-effluent exposure and requires upwards of 20 min exposure for stabilization compared to Al 2 O 3 . Once stable surface conditions are achieved, thermal cycling reveals a repeatable hysteresis pattern in downstream products. At low temperature, oxygen and NO x accumulate on the catalyst surface and react at elevated temperatures to form NO 2 . Increasing plasma power and O 2 :N 2 ratio increases the hysteresis of the heating relative to the cooling curves in the pattern of NO 2 formation. The limitation on NO oxidation at high temperatures was assessed to be Pt-O which is depleted as the catalyst is heated. Once stored species have been depleted, NO oxidation rates are determined by incoming reactants. Two overlapping NO oxidation patterns are identified, one determined by surface reactants formed at low temperature, and the other by reactants arriving at the surface at high temperature. As a result, the plasma is responsible for providing the reactants to the catalyst surface, while the catalyst enables reaction at high temperature or storage at low temperature for subsequent reaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Laser Plasma Interaction in the MG Magnetic Field (Final Report)

Strong magnetic fields change properties of plasma. Employment of the magnetic fields can improve conditions for inertial confinement fusion. Compression and heating of the magnetized plasma is a base of the MagLIF pulsed power approach to the controlled fusion. Study of expansion and heating of plasma in the external magnetic fields, development of plasma instabilities, parametric and other effects are important for basic physics and applications. The main goal of the research for the grant was experimental investigation of laser produced plasma in the well characterized and controlled MG magnetic fields. We developed a platform for investigation of high intensity laser-plasma interaction (LPI) in the MG fields using a university-scale pulsed power machine. A Zebra machine at UNR generated transverse magnetic fields of 3 MG on the surface of the rod load and longitudinal fields of 1.4 MG in the coil loads. The magnetic fields were characterized with two-color Faraday rotation diagnostics. The pulsed power machine provided almost static magnetic fields for LPI compared to the much faster laser driven magnetic fields. We found that eddy currents in the rising magnetic field generate plasma on the metal targets. Eddy currents did not impact Si and CH dielectric targets. A Leopard laser with intensity in the focus up to 10 19 W/cm 2 produced plasma in the MG magnetic fields. The modified reflected Faraday diagnostics was used to study laser driven B-field at the MTW laser at Laboratory for Laser Energetics, UR. We demonstrated a slow dependence of the magnetic field in the coil on the applied laser intensity. The magnetic field increased by a factor of 2 if laser intensity increased by a factor of 30. This scaling is important for comparison of experiments at different laser facilities. Expansion of the plasma in the 2-3 MG external B-field was studied. Laser-produced plasma in the azimuthal magnetic field took the unique form of a thin disc expanding radially with a velocity of 250 km/s and confined in the vertical direction. A HYDRA MHD program at the University of Rochester was applied for simulations of LPI in the magnetic field B >3 MG. Simulations for the plasma disc parameters and the expansion dynamics were in a good agreement with experiments. Generation of narrow dense plasma jets in the longitudinal magnetic field of 0.6-0.8 MG was studied. Narrow plasma jets reached a length of 3-4 mm with the electron plasma density of (0.2-1.2)x10 20 cm -3 . A jet tip propagated with the velocity of 160-200 km/s. MHD simulations showed a good agreement of the dynamics of the formation of plasma jets with experiments. These jets are relevant to astrophysical jets. Simulations of K-shell spectra of Si plasma was performed for LPI in the B-field. The laser prepulse generated plasma near the laser target. A PrismSPECT model with a MeV electron beam produced by the laser was used. The spectral modelling showed the increased plasma density by a factor by 2-3 in the magnetic field. This was in agreement with the observed dynamics of the plasma plume confined by the axial magnetic field. The two-plasmon decay was studied in the 2.5-3 MG transversal magnetic fields. Strong 2-3.5 nm spectral widening and a 2-4 nm shifts of “red” and “blue” 3/2ω 0 spectral components were observed. The large shift and widening exceed the expected temperature and magnetic shift. PIC simulations are performing to clarify physics of this effect. The experimental research program for the grant is completed. New plasma effects in the MG fields were studied at the university-scale pulsed power generator. Two graduate and two undergraduate UNR and UR students carried experiments at the Zebra generator, supported and developed plasma diagnostics, provided data processing, and performed MHD simulations of LPI in the strong magnetic field. Research results are published in 9 referred papers and presented in 12 conferences. Program manager: Kramer U. Akli; Collaborators: R. C. Mancini and H. Sawada, University of Nevada, Reno (UNR); R. Betti and A. V. Maximov, University of Rochester (UR).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Two-Frequency RF Fields Induced Multipactor in Coaxial Transmission Lines

Multipactor is a nonlinear discharge phenomenon that occurs in vacuum RF systems, potentially leading to signal distortion, power loss, and even permanent damage to high-power components. This study presents a detailed investigation of two-surface multipactor in coaxial transmission lines under two-frequency excitation, using one-dimensional (1D) Monte Carlo simulations validated by three-dimensional (3D) Particle-in-Cell (PIC) results and experimental data. Introducing a second carrier mode is shown to suppress multipactor by reshaping and shrinking the susceptibility region, with the extent and location of suppression strongly dependent on the device aspect ratio and the relative phase of the second mode. Distinct suppression patterns emerge across different frequency–gap distance (fd) regimes, and in certain cases, susceptibility expansion is also observed. The study identifies and distinguishes pure and mixed multipactor modes in coaxial geometry, where analytical mode boundaries are not readily defined. Unlike planar systems, pure-mode regions in coaxial structures overlap with mixed-mode domains, complicating classification. Image charge forces are found to have minimal effect on susceptibility thresholds but do influence electron growth rates. These findings provide new insights into waveform-driven control of multipactor in high-power RF systems.

43 PARTICLE ACCELERATORS↗

In Situ Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes

In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗