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At least 451 records · Page 25

In-plane thermal conductivity and the applicability of the Wiedemann–Franz law in dilute AlCu thin films

The Wiedemann–Franz (WF) law correlates heat and charge transport in metals. However, the validity of this correlation remains an open-ended question, especially in the context of inelastic scattering at room temperature. To address this gap in knowledge, we perform independent measurements of the in-plane thermal and electrical conductivities across four AlCu (0.5% Cu) films [thickness (⁠h⁠) ≈ 174, 98, 53, and 24 nm] using optical pump–probe metrologies and four-point probe techniques, respectively. For in-plane thermal conductivity measurements, we utilize time-domain thermoreflectance, in both concentric and beam-offset configurations, and the time-resolved magneto-optic Kerr effect. Our results show that the WF law overpredicts the thermal conductivity by at least ∼10% in all films, thus demonstrating modest deviations in predicted thermal conductivity when applying the WF law to dilute AlCu films. Using infrared variable angle spectroscopic ellipsometry, we demonstrate increased electron scattering rates in the thinnest film (⁠⁠h⁠ ≈ 24 nm), indicating electron-boundary scattering drives the reduction in in-plane thermal conductivity. Furthermore, this is generally an elastic scattering process, which is supported by our thermal conductivity measurements and analysis.

Electrical conductivity↗

Probing ultrafast excited-state dynamics using EUV-IR six-wave-mixing emission spectroscopy

Non-linear processes such as four-wave-mixing have become instrumental in attosecond EUV spectroscopy. Using EUV high harmonics in conjunction with collinear near-infrared and mid-infrared fields, we extended this approach to high-order-mixing between three colors. Specifically, we find that atomic resonances in neon exhibit a significant cross section for six-wave mixing. The MIR probe frequency tunability in our multicolor scheme is employed to access several optically dark resonances and probe the quantum beat of a coherent electronic wavepacket using background-free EUV emission as a diagnostic. This technique can be easily extended to other atomic and molecular systems, and opens the door to multi-dimensional non-linear spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗

Gamma-Ray Emission from Galaxies Hosting Molecular Outflows

Many star-forming galaxies and those hosting active galactic nuclei show evidence of massive outflows of material in a variety of phases including ionized, neutral atomic, and molecular. Molecular outflows in particular have been the focus of recent interest as they may be responsible for removing gas from the galaxy, thereby suppressing star formation. As material is ejected from the cores of galaxies, interactions of the outflowing material with the interstellar medium can accelerate cosmic rays and produce high-energy gamma rays. In this work, we search for gamma-ray emission from a sample of local galaxies known to host molecular outflows using data collected by the Fermi Large Area Telescope. We employ a stacking technique in order to search for and characterize the average gamma-ray emission properties of the sample. Gamma-ray emission is detected from the galaxies in our sample at the 4.4σ level with a power-law photon index of Γ ≈ 2 in the 1–800 GeV energy range. The emission is found to correlate with tracers of star formation activity, namely the 8–1000 μm infrared luminosity. We also find that the observed signal can be predominantly attributed to H II galaxies hosting energy-driven outflows. While we do not find evidence suggesting that the outflows are accelerating charged particles directly, galaxies with molecular outflows may produce more gamma rays than galaxies without outflows. In particular, the set consisting of gamma-ray-detected galaxies with molecular outflows are nearly perfect calorimeters and may be future targets for searches of high-energy neutrinos.

79 ASTRONOMY AND ASTROPHYSICS↗

Gifts from anomalies: Exact results for Landau phase transitions in metals

Non-Fermi liquid phenomena arise naturally near critical points of Landau ordering transitions in metallic systems, where strong fluctuations of a bosonic order parameter destroy coherent quasiparticles. Despite progress in developing controlled perturbative techniques, much of the low energy physics of such metallic quantum critical points remains poorly understood. We demonstrate that exact, non-perburbative results can be obtained for both optical transport and static susceptibilities in “Hertz-Millis” theories of Fermi surfaces coupled to critical bosons. Such models possess a large emergent symmetry and anomaly structure, which we leverage to fix these quantities. In particular, we show that in the infrared limit, the boson self energy at zero wave vector, \mathbf{q}=0 𝐪 = 0 , is a constant independent of frequency, and the real part of the optical conductivity, \sigma(\omega) σ ( ω ) , is purely a delta function Drude peak with no other corrections. Therefore, further frequency dependence in the boson self energy or optical conductivity can only come from irrelevant operators in a clean system. Exact relations between Fermi liquid parameters as the critical point is approached from the disordered phase are also obtained. The absence of a universal, power law frequency dependence in the boson self energy contrasts with previous perturbative calculations, and we explain the origin of this difference.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Vapor-phase grafting of a model aminosilane compound to Al 2 O 3 , ZnO, and TiO 2 surfaces prepared by atomic layer deposition

Atomic layer deposition (ALD) is a highly versatile surface functionalization technique that can conformally coat both planar and porous substrates. Here we use ALD metal oxide layers to establish a well-defined starting surface for vapor-phase surface organic modification. Vapor-phase (3-aminopropyl)triethoxysilane (APTES) surface silanization of ALD Al 2 O 3 , ZnO and TiO 2 surfaces were studied at 100 °C, 150 °C and 200 °C. In situ quartz crystal microbalance (QCM) and Fourier-transform infrared (FTIR) spectroscopy measurements, and ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) measurements showed uniform monolayer silane formation through self-limiting APTES reaction. We observed a higher surface density of grafted APTES species following silanization at 100 °C compared to 200 °C, and we attribute this to the temperature-dependent reactivity of the surface hydroxyls and changes in the mode of APTES reaction. The FTIR and XPS measurements revealed that APTES reacts with Al 2 O 3 and ZnO exclusively through metal siloxy bond formation. However, APTES reacts with TiO 2 through both siloxy bond formation and ammonium salt formation via the amine group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low Cost (CAPEX and variable): Tool design for cell and module fabrication with thin, free-standing silicon wafers

This project aimed to develop technologies that can potentially enable free-standing thin (<80 μm) wafer in today’s manufacturing lines with high production yield, and thereby reduce capex barriers of silicon photovoltaics cells and modules. One of the major benefits is that thin wafer dramatically reduces the amount of polysilicon required. As a result, it can lead to reduction in the capital expenditures associated with polysilicon refining and wafer fabrication, which together are more than half of the total capital expenditure to manufacture Si PV module. We focused our efforts on developing the tools needed to enable high yield fabrication of wafer, cell, and module with thin silicon wafers. However, as the wafer thickness reduces, the major challenge is that wafer breakage increases significantly. Three technological areas were explored in this project to improve the production yield of the silicon wafer, namely detection of edge cracks via dark-field near-infrared (NIR) scattering; (2) wafer handling using controlled temperature profiles; (3) manufacturable low-stress cell interconnection for multiwire. First, the formation of wafer cracks in submillimeter length is one of the reasons that causes wafer breakages. Crack detection tools are needed to enable us to locate and track the wafer crack during manufacturing, so that we can improve the process to reduce initialization. The state-of-the-art crack detection technique cannot fulfill the need for measuring submillimeter edge cracks detrimental for thin wafers. The prototype developed in this project demonstrates the scanning of microcracks near wafer edges. With a semi-automatic laboratory setup, the submillimeter cracks were reliably detected near the edges in multi-Si wafers. The smallest detectable crack is 200 µm in length in slow scans; and submillimeter cracks are detected in high-throughput scans at the scan speed of >0.5 m/s, which is compatible with the inline detection of a manufacturing line at least 1 sec/wafer. This detection limit is a significant advancement in comparison to the benchmarked industrial tool. Second, wafer handling with the well-controlled temperature profile was thought to be the solution to reduce crack initiation and propagation during the manufacturing. However, without crack detection being widely adopted in production line, we did not find a strong industrial pull toward this technology. We did an initial literature survey and then diverted our efforts to the other tasks. Third, the innovation on low-stress multi-wire interconnection tackles a fundamental problem in the standard interconnection scheme. The standard over-under “zig-zag” interconnection induces a significant amount of stress into the soldering point on the cell whenever PV module is under stress, e.g., thermal cycling, transportation, and installation. Therefore, the interconnection process was re-designed in this project to allow for significant movement between adjacent solar cells, e.g., due to thermal expansion, without building up stresses on the solar cells or solder joints. The new interconnection method with the cross-connect wire also simplifies the tabbing and stringing process by replacing the standard over-under method with an off-cell interconnect from top to bottom. A manual tabbing and stringing tool for this new process was prototyped in the lab to demonstrate the fabrication of this new interconnection design. During the test with brass sheets as our “testing cells”, it was found that the mechanical cycling test only broke the interconnection after more than 50,000 cycles, which is equivalent to more than 130 years of the day-and-night thermal cycles. Lastly, throughout the project, we continuously analyzed the PV market with techno-economic analysis to identify the opportunity for thin Si adoption. Even though the drastic cost reduction has already happened in the past five years, our analysis results indicated that we can still save quite significantly in both manufacturing cost and factory capex, Particularly, in order to grow the PV manufacturing capacity to multi-terawatt level, reducing the thickness of silicon wafer is one of the most effective ways to quickly reduce factory capex, and sustain the high growth rate. The technologies developed in this project are readily available to provide some assistances in tackling the production yield problem.

14 SOLAR ENERGY↗

Rapid and high-throughput determination of sorghum ( Sorghum bicolor ) biomass composition using near infrared spectroscopy and chemometrics

Compositional characterization of biomass is vital for the biofuel industry. Traditional wet chemistry-based methods for analyzing biomass composition are laborious, time-consuming, and require extensive use of chemical reagents as well as highly skilled personnel. In this study, near-infrared (NIR) spectroscopy was used to quickly assess the composition of above-ground vegetative biomass from 113 diverse, photoperiod-sensitive, biomass-type sorghum (Sorghum bicolor) accessions cultivated under field conditions in Central Illinois. Biomass samples were analyzed using NIR spectra collected in the spectral range of 867–2536 nm, with their chemical compositions determined following the National Renewable Energy Laboratory (NREL) protocol. Advanced spectral pre-treatment and band selection techniques were utilized to develop calibration models using partial least squares regression (PLSR). The models’ effectiveness was assessed through cross-validation and independent data tests. The predictions for moisture, ash, extractives, glucan, xylan, acid-soluble lignin (ASL), acid-insoluble lignin (AIL), and total lignin were accurate and reliable, demonstrating the capability of NIR spectroscopy to provide rapid and precise characterization of sorghum biomass. The results demonstrated that NIR spectroscopy is an efficient tool for rapidly characterizing sorghum biomass, making it a sustainable option for screening desirable feedstock for biofuel or bioproduct production.

09 BIOMASS FUELS↗

Optical spectroscopy of molten fluorides: Methods, electronic and vibrational data, structural interpretation, and relevance to radiative heat transfer

In this study, to help address the need for predicting radiative heat transfer (RHT) behavior of molten salts, we conducted a comprehensive review of methods and data from optical spectroscopic measurements on molten fluoride salts. Transmittance, reflectance, and trans-reflectance experimental methods are discussed, along with the corresponding data reduction methodology and the limitations of each technique. Optical spectroscopy is a convenient indirect probe for changes in structural parameters with temperature and composition. Electronic and vibrational absorption data for transition-metal, lanthanide, and actinide solutes and vibrational absorption data for alkali and alkaline earth fluoride solvents are compiled, and the corresponding structural interpretation is discussed and compared with other experimental and theoretical work. We find that solvent and solute vibrational absorption can be significant in the mid-infrared, resulting in near-infrared edges of significance to RHT. Extrapolation and averaging of existing edge data leads to estimated gray absorption coefficient values at 700 °C of 546 m —1 for FLiBe and 276 m —1 for FLiNaK, both within the range of 1 – 6000 m —1 identified to be of engineering relevance for radiative heat transfer analysis.

36 MATERIALS SCIENCE↗

XMM–Newton study of the Sculptor dwarf spheroidal galaxy

ABSTRACT We analysed observations with XMM–Newton in the field of the Sculptor dwarf spheroidal galaxy (dSph). The aim of the study was the classification of X-ray binaries and accreting white dwarfs belonging to the Sculptor dSph. Using different methods of X-ray timing and spectral analyses, together with an extensive multiwavelength study of the optical and infrared counterparts of the X-ray sources, we classified the sources detected with XMM–Newton in the field of the Sculptor dSph. The long-term variability of the sources has been studied over two XMM–Newton observations. None of the members of the Sculptor dSph show significant long-term variability over these two observations. We also searched for periodicity and pulsation using the Lomb–Scargle and Rayleigh Z$^{2}_{n}$ techniques. No signals of pulsation or periodicity have been found for the X-ray sources. The results show the presence of a noticeable number of background X-ray sources in the field of this galaxy. We classified 43 sources as active galactic nuclei, galaxies, and galaxy candidates. Three Galactic foreground stars have been identified in the field of the Sculptor dSph, and one of them is an M-dwarf candidate. Moreover, we classified four symbiotic-star candidates and three quiescent low-mass X-ray binary candidates in the Sculptor dSph. The luminosity of these X-ray sources is ∼1033−35 erg s−1.

79 ASTRONOMY AND ASTROPHYSICS↗

Data for Rapid and High-Throughput Determination of Sorghum ( Sorghum bicolor ) Biomass Composition using Near Infrared Spectroscopy and Chemometrics

Compositional characterization of biomass is vital for the biofuel industry. Traditional wet chemistry-based methods for analyzing biomass composition are laborious, time-consuming, and require extensive use of chemical reagents as well as highly skilled personnel. In this study, near-infrared (NIR) spectroscopy was used to quickly assess the composition of above-ground vegetative biomass from 113 diverse, photoperiod-sensitive, biomass-type sorghum ( Sorghum bicolor ) accessions cultivated under field conditions in Central Illinois. Biomass samples were analyzed using NIR spectra collected in the spectral range of 867–2536 nm, with their chemical compositions determined following the National Renewable Energy Laboratory (NREL) protocol. Advanced spectral pre-treatment and band selection techniques were utilized to develop calibration models using partial least squares regression (PLSR). The models’ effectiveness was assessed through cross-validation and independent data tests. The predictions for moisture, ash, extractives, glucan, xylan, acid-soluble lignin (ASL), acid-insoluble lignin (AIL), and total lignin were accurate and reliable, demonstrating the capability of NIR spectroscopy to provide rapid and precise characterization of sorghum biomass. The results demonstrated that NIR spectroscopy is an efficient tool for rapidly characterizing sorghum biomass, making it a sustainable option for screening desirable feedstock for biofuel or bioproduct production.

Biomass Analytics↗

Label-free nanoscopy of cell metabolism by ultrasensitive reweighted visible stimulated Raman scattering

Nanoscopic imaging of cell metabolism is hindered by the incompatibility of small metabolites with fluorescent dyes and the limited resolution of imaging mass spectrometry. We present ultrasensitive reweighted visible stimulated Raman scattering (URV-SRS), a label-free vibrational nanoscopy technique that enables multiplexed detection of metabolic nanostructures within cells. We developed an extensively chirped spectral focusing visible SRS microscope that achieves a detection limit of 4,000 molecules and introduced a self-supervised learning-based denoiser to robustly suppress non-independent SRS noise by over 7.2 dB. The instrumentation-based signal enhancement and computation-based noise suppression synergistically improved the detection sensitivity by 50 times over near-infrared SRS. Leveraging this enhanced sensitivity, we further pushed the resolution to nanoscopic levels by introducing Fourier reweighting to amplify sub-100 nm spatial frequencies previously overwhelmed by noise. Validated by Fourier ring correlation, URV-SRS achieves a lateral resolution of 86 nm in cellular imaging. Here, we applied URV-SRS to elucidate the reprogramming of metabolic nanostructures associated with virus replication in Vero E6 host cells and to compositionally delineate subcellular fatty acid synthesis in engineered Escherichia coli, demonstrating its capability towards nanoscopic spatial metabolomics.

59 BASIC BIOLOGICAL SCIENCES↗

A Reduced-Temperature Process for Preparing Atomically Clean Si(100) and SiGe(100) Surfaces with Vapor HF

Silicon processing techniques such as atomic precision advanced manufacturing (APAM) and epitaxial growth require surface preparations that activate oxide desorption (typically >1000 °C) and promote surface reconstruction toward atomically clean, flat, and ordered Si(100)-2 × 1. Here, in this study, we compare the aqueous and vapor phase cleaning of Si and Si/SiGe surfaces to prepare APAM-ready and epitaxy-ready surfaces at lower temperatures. Angle resolved X-ray photoelectron spectroscopy (ARXPS) and Fourier transform infrared (FTIR) spectroscopy indicate that vapor hydrogen fluoride (VHF) cleans dramatically reduce carbon surface contamination and allow the chemically prepared surface to reconstruct at lower temperatures, 600 °C for Si and 580 °C for a Si/Si 0.7 Ge 0.3 heterostructure, into an ordered atomic terrace structure indicated by scanning tunneling microscopy (STM). After thermal treatment and vacuum hydrogen termination, we demonstrate STM hydrogen desorption lithography (HDL) on VHF-treated Si samples, creating reactive zones that enable area-selective chemistry by using a thermal budget similar to CMOS process flows. We anticipate that these results will establish new pathways to integrate APAM with Si foundry processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine Learning Enabled Sensor Fusion for In-Situ Defect Detection in Laser Powder Bed Fusion

Laser Powder Bed Fusion (L-PBF) Additive Manufacturing (AM) is among the metal 3D printing technologies most broadly adopted by the manufacturing industry. The current industry qualification paradigm for critical-application L-PBF parts relies heavily on expensive non-destructive inspection techniques such as X-Ray Computed Tomography (XCT), which significantly limits the use-cases of L-PBF. In situ monitoring of the process promises a less expensive alternative to ex situ testing, but existing sensor technologies and data analysis techniques struggle to detect sub-surface flaws (e.g., porosity and cracking) on production-scale L-PBF printers. RTX Technologies Research Center (RTRC) has licensed ORNL’s Peregrine software package – a printer- and camera-agnostic data analytics tool designed specifically for detecting process anomalies using in situ data collected during powder bed printing. The goal of this project was to feed temporally rich, multi-modal sensor data, including visible light, integrated near infrared (NIR), and spatially mapped co-axial melt pool thermal emission data into Peregrine to enable detection of subsurface flaws. XCT data was used as ground truth training data to allow Peregrine’s deep learning algorithms to recognize anomalies in these complex data streams in both test artifacts and industrially relevant geometries. Completion of this program has seen the successful implementation of multi-modal, multi-layer sensor data footprints for training of machine learning models in Peregrine. Flaws detected in XCT data have been successfully detected directly from this in situ data footprint, and initial analyses of the in situ probability-of-detection has been conducted, showing performance levels commensurate with traditional non-destructive evaluation (NDE) methods. The in situ monitoring methodology was then applied to an industrially relevant component that was using post-build NDE, highlighting the utility of the proposed method for hard-to-inspect AM components. As a direct result of this program, two journal manuscripts [1], [2] have been published in Additive Manufacturing, with additional manuscripts planned following program completion.

36 MATERIALS SCIENCE↗

Evidence of hexagonal germanium grains on annealed monolayer MoS 2

Growing three-dimensional (3D) materials on two-dimensional (2D) van der Waals surface has shown its effectiveness in overcoming materials incompatibility for stacking transferrable membranes toward advanced device manufacturing. Herein, we demonstrate that the nucleation of hexagonal germanium (Ge) grains within a continuous crystalline film, which has been unfeasible through traditional epitaxy techniques, is realized by chemical vapor deposition on top of n-type monolayer molybdenum disulfide (MoS 2 ) substrates. Suggested by quantum molecular dynamics calculation, the hexagonal Ge nucleation is thermodynamically preferable to cubic Ge when growing on monolayer MoS 2 with sulfur vacancies. The strained hexagonal Ge grains have been confirmed by transmission electron microscopy analyses from both real space and reciprocal space. Scanning probe microscopy shows that the hexagonal Ge film possesses higher reflectivity in infrared spectral range, implying a higher carrier concentration resulted from the narrower band gap, as compared to cubic Ge.

36 MATERIALS SCIENCE↗

Trapping light in air with membrane metasurfaces for vibrational strong coupling

Optical metasurfaces can manipulate electromagnetic waves in unprecedented ways at ultra-thin engineered interfaces. Specifically, in the mid-infrared (mid-IR) region, metasurfaces have enabled numerous biochemical sensing, spectroscopy, and vibrational strong coupling (VSC) applications via enhanced light-matter interactions in resonant cavities. However, mid-IR metasurfaces are usually fabricated on solid supporting substrates, which degrade resonance quality factors (Q) and hinder efficient sample access to the near-field electromagnetic hotspots. Besides, typical IR-transparent substrate materials with low refractive indices, such as CaF 2 , NaCl, KBr, and ZnSe, are usually either water-soluble, expensive, or not compatible with low-cost mass manufacturing processes. Here, we present novel free-standing Si-membrane mid-IR metasurfaces with strong light-trapping capabilities in accessible air voids. We employ the Brillouin zone folding technique to excite tunable, high-Q quasi-bound states in the continuum (qBIC) resonances with our highest measured Q-factor of 722. Leveraging the strong field localizations in accessible air cavities, we demonstrate VSC with multiple quantities of PMMA molecules and the qBIC modes at various detuning frequencies. Our new approach of fabricating mid-IR metasurfaces into semiconductor membranes enables scalable manufacturing of mid-IR photonic devices and provides exciting opportunities for quantum-coherent light-matter interactions, biochemical sensing, and polaritonic chemistry. The authors introduce a mid-IR metasurface fabricated by decorating a free-standing Si-membrane with air holes. The enhanced light-matter interactions in such air cavities enable vibrational strong coupling and advanced biochemical sensing.

infrared spectroscopy↗

Chemical and spectroscopic characterization of plutonium tetrafluoride

Anhydrous plutonium tetrafluoride is an important intermediate in the production of metallic Pu. This historically important compound is also known to exist in at least two distinct, yet understudied hydrate forms, PuF 4 ·xH 2 O(s) (0.5 ≤ x ≤ 2) and PuF 4 ·2.5H 2 O(s). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) are the most common tools used to characterize these materials, often in a context for studying structural and morphological changes that arise from aging or calcination. However, fundamental electronic and vibrational spectroscopic information is rather scarce. Here, in this study, we measured the visible and shortwave infrared (SWIR) diffuse reflectance, Fourier transform infrared (FTIR), fluorescence and Raman spectra of PuF 4 (s) and PuF 4 ·xH 2 O(s) to obtain a better electronic and vibrational fingerprint. Our work provides clear indication of the polymeric structure of anhydrous PuF 4 , consistent with the Raman spectrum of UF 4 (s) and its hydrates. This is supplemented with XRD, TGA and SEM analysis. Findings in this study indicate that the spectra are modified by particle size, which in turn is influenced by synthetic technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large active-area superconducting microwire detector array with single-photon sensitivity in the near-infrared

Superconducting nanowire single photon detectors (SNSPDs) are the highest-performing technology for time-resolved single-photon counting from the UV to the near-infrared. The recent discovery of single-photon sensitivity in micrometer-scale superconducting wires is a promising pathway to explore for large active area devices with application to dark matter searches and fundamental physics experiments. We present 8-pixel $1 mm^2$ superconducting microwire single photon detectors (SMSPDs) with $1\,\mathrm{\mu m}$-wide wires fabricated from WSi and MoSi films of various stoichiometries using electron-beam and optical lithography. Devices made from all materials and fabrication techniques show saturated internal detection efficiency at 1064 nm in at least one pixel, and the best performing device made from silicon-rich WSi shows single-photon sensitivity in all 8 pixels and saturated internal detection efficiency in 6/8 pixels. This detector is the largest reported active-area SMSPD or SNSPD with near-IR sensitivity published to date, and the first report of an SMSPD array. By further optimizing the photolithography techniques presented in this work, a viable pathway exists to realize larger devices with $cm^2$-scale active area and beyond.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Tracing the transient reaction kinetics of adsorbed species by in situ/operando infrared spectroscopy

The dynamic reaction behavior (i.e., transient responses) of IR-observable adsorbed species and gaseous products obtained from transient kinetic studies provide valuable kinetic and mechanistic information, namely: the abundance of active intermediates and their reactivity distribution, the chemical structure of IR-observable active and spectator species, the sequence of their formation, and the kinetically significant and rate-determining step under reaction conditions of practical catalysis. We discuss the use of transient response data to elucidate the reaction mechanisms of several gas-solid reactions: CO/H 2 , CO/H 2 /C 2 H 4 , photocatalytic oxidation of ethanol, and the CO 2 -amine reaction. The IR coupled with transient kinetic techniques is especially useful for investigating the mechanisms of photocatalytic reactions because both photogenerated electrons and many adsorbed species are IR-active (exhibiting measurable IR bands), and their evolution occurs on a time scale of seconds at ambient temperature. We highlight the key features and limitations of in situ IR with transient kinetics, as well as their significance in catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗