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NASA NTRS1992

The Use of Subcarriers in Future DSN Missions

The performance of deep space telemetry signals that employ a residual carrier modulation technique is compared in the presence and absence of a subcarrier. When the subcarrier is present, the performance for the resulting pulse-coded modulation/phase-shift keyed/phase-modulated (PCM/PSK/PM) scheme is evaluated for both sine wave and square wave subcarriers and non-return-to zero (NRZ) data. When the subcarrier is absent, the performance for the resulting PCM/PM technique is evaluated for both the NRZ and the bi-phase data format. The comparison is based on telemetry performance as well as bandwidth efficiency. The first criterion is characterized in terms of the symbol error rate (SER) as a function of symbol SNR, loop bandwidth-to-data rate ratio, and modulation index. The bandwidth efficiency is characterized by the occupancy factor. The results of both the analysis and measurements show that when the interference-to-carrier ratio (ICR) is less than -15 dB, the performance degradation in the absence of a subcarrier is negligible. Various combinations of loop bandwidth-to-data rate ratios and modulation indices that achieve this performance are derived and listed. Bandwidth occupancy comparison indicates that PCM/PM/NRZ is the most efficient in this regard. Therefore, by eliminating the subcarrier and using the PCM/PM/NRZ scheme, many advantages can be realized without any sacrifice in performance.

Shihabi, M. M.↗
NASA NTRS1994

A Comparison of Telemetry Signals in the Presence and Absence of a Subcarrier

The performance of deep-space telemetry signals that employ a residual carrier modulation technique is compared in the presence and absence of a subcarrier. When the subcarrier is present, the performance for the resulting pulse-coded modulation/phase-shift keyed/phase-modulated (PCM/PSK/PM) scheme is evaluated for both sine-wave and square-wave subcarriers and Non-Return-to Zero (NRZ) data. When the subcarrier is absent, the performance for the resulting PCM/PM technique is evaluated for both the NRZ and the bi-phase data format. The comparison is based on telemetry performance as well as bandwidth efficiency. The first criterion is characterized in terms of the Symbol Error Rate (SER) as a function of symbol SNR, loop bandwidth-to-data rate ratio, and modulation index. The bandwidth efficiency is characterized by the occupancy factor. The results of both the analysis and measurements show that when the Interference-to-Carrier Ratio (ICR) is less than -20 dB, the performance degradation in the absence of a subcarrier is negligible. Various combinations of loop bandwidth-to-data rate ratios and modulation indices that achieve this performance are derived and listed. Bandwidth occupancy comparison indicates that PCM/PM/NRZ is the most efficient in this regard. Therefore, by eliminating the subcarrier and using the PCM/PM/NRZ scheme, many advantages can be realized without any sacrifice in performance.

Shihabi, Mazen M.↗
NASA NTRS2010

Challenges in Transitioning Research Data to Operations: The SPoRT Paradigm

Established in 2002 to demonstrate the weather and forecasting application of real-time EOS measurements, the NASA Short-term Prediction Research and Transition (SPoRT) program has grown to be an end-to-end research to operations activity focused on the use of advanced NASA modeling and data assimilation approaches, nowcasting techniques, and unique high-resolution multispectral data from EOS satellites to improve short-term weather forecasts on a regional and local scale. With the ever-broadening application of real-time high resolution satellite data from current EOS and planned NPP, JPSS, and GOES-R sensors to weather forecast problems, significant challenges arise in the acquisition, delivery, and integration of the new capabilities into the decision making process of the operational weather community. For polar orbiting sensors such as MODIS, AIRS, VIIRS, and CRiS, the use of direct broadcast ground stations is key to the real-time delivery of the data and derived products in a timely fashion. With the ABI on the geostationary GOES-R satellite, the data volume will likely increase by a factor of 5- 10 from current data streams. However, the high data volume and limited bandwidth of end user facilities presents a formidable obstacle to timely access to the data. This challenge can be addressed through the use of subsetting techniques, innovative web services, and the judicious selection of data formats. Many of these approaches have been implemented by SPoRT for the delivery of real-time products to NWS forecast offices and other weather entities. Once available in decision support systems like AWIPS II, these new data and products must be integrated into existing and new displays that allow for the integration of the data with existing operational products in these systems. SPoRT is leading the way in demonstrating this enhanced capability. This paper will highlight the ways SPoRT is overcoming many of the challenges presented by the enormous data volumes of current and future satellite systems to get unique high quality research data into the operational weather environment.

Jedloved, Gary J.↗
NASA NTRS2013

SPoRT: Transitioning NASA and NOAA Experimental Data to the Operational Weather Community

Established in 2002 to demonstrate the weather and forecasting application of real-time EOS measurements, the NASA Short-term Prediction Research and Transition (SPoRT) program has grown to be an end-to-end research to operations activity focused on the use of advanced NASA modeling and data assimilation approaches, nowcasting techniques, and unique high-resolution multispectral data from EOS satellites to improve short-term weather forecasts on a regional and local scale. With the ever-broadening application of real-time high resolution satellite data from current EOS, Suomi NPP, and planned JPSS and GOES-R sensors to weather forecast problems, significant challenges arise in the acquisition, delivery, and integration of the new capabilities into the decision making process of the operational weather community. For polar orbiting sensors such as MODIS, AIRS, VIIRS, and CRiS, the use of direct broadcast ground stations is key to the real-time delivery of the data and derived products in a timely fashion. With the ABI on the geostationary GOES-R satellite, the data volumes will likely increase by a factor of 5-10 from current data streams. However, the high data volume and limited bandwidth of end user facilities presents a formidable obstacle to timely access to the data. This challenge can be addressed through the use of subsetting techniques, innovative web services, and the judicious selection of data formats. Many of these approaches have been implemented by SPoRT for the delivery of real-time products to NWS forecast offices and other weather entities. Once available in decision support systems like AWIPS II, these new data and products must be integrated into existing and new displays that allow for the integration of the data with existing operational products in these systems. SPoRT is leading the way in demonstrating this enhanced capability. This paper will highlight the ways SPoRT is overcoming many of the challenges presented by the enormous data volumes of current and future satellite systems to get unique high quality research data into the operational weather environment.

Jedlovec, Gary J.↗
NASA NTRS2014

True Emission Factors for Forest Fires and the Role of Non-Fire NOx

True Emission Factors for Forest Fires and the Role of Non-Fire NOx Robert B. Chatfield and Meinrat Andreae The standard way to estimate biomass burning emissions factors from airborne, surface, or laboratory data is to relate the emitted pollutant concentration to the carbon burned, C(sub tot), and liberated to the air, mostly CO2. We approximate total emitted carbon C(sub tot) ~ (CO2 + CO). Emission ratios that are based on CO, describing burning effects, delta-parameter delta-CO, are often used to quantify fire emissions. These are not as useful as emission factors, for they often complicate analyses, since delta-CO delta-CO2 may vary by unto tenfold, and can have bias artifacts of similar magnitude. We present a methodology that estimates both emission factors and a reasonable description of background C(sub tot). High O3 values require a history of the balanced interaction of two pollutant types, nitrogen oxides (NOx) and a radical source, VOCs. However, high VOC NOx ratios seen in many plumes, especially from smoldering-dominated fires, make substantial O3 formation less likely. One particularly intense fire we analyzed, the notorious Rim Fire of 2013, near Yosemite, California. It produced notable quantities of free NOx and (both gas- and particle-phase) Cl species. Consequently, we also outline a quantitative way to assess the effects of anthropogenic or lightning NOx. We provide the example of California burning emissions using measurements of HCHO, NO, and the photolysis rate j(sub HCHO).

Chatfield, Robert B.↗
DOE OSTI2021

Heat shock induces the nuclear accumulation of YAP1 via SRC

Highlights: • YAP1 enters the nucleus in response to heat shock. • YAP1 spontaneously returns to the cytoplasm after heat shock. • SRC is involved in the nuclear accumulation of YAP1. • HSP90 is involved in the return to the cytoplasm of YAP1. • YAP1 cross-talks with NF-κB signaling in response to heat shock. Yes-associated protein 1 (YAP1), a co-transcription activator, shuttles between the cytoplasm and the nucleus. Phosphorylation by large tumor suppressor kinases (LATS1/2) is the major determinant of YAP1 subcellular localization. Unphosphorylated YAP1 interacts with transcription factors in the nucleus and regulates gene transcription, while phosphorylated YAP1 is trapped in the cytoplasm and is degraded. We found that when U2OS and HeLa cells are exposed to 42 °C, YAP1 enters the nucleus within 30 min and returns to the cytoplasm at 4 h. SRC and HSP90 are involved in nuclear accumulation and return to the cytoplasm, respectively. Upon heat shock, LATS2 forms aggregates including protein phosphatase 1 and is dephosphorylated and inactivated. SRC activation is necessary for the formation of aggregates, while HSP90 is required for their dissociation. YAP1 is involved in heat shock-induced NF-κB signaling. Mechanistically, YAP1 is implicated in strengthening the interaction between RELA and DPF3, a component of SWI/SNF chromatin remodeling complex, in response to heat shock. Thus, YAP1 plays a role as a thermosensor.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Waste to worth: A high-temperature water-gas shift magnetite catalyst with encapsulated core-shell structure from coal fly ash

In this paper, we demonstrate the synthesis of magnetite-based, encapsulated catalyst with a core-shell structure from coal fly ash, an industrial solid waste, and its application to industrially important high temperature water-gas shift reaction (HT-WGSR). The catalyst precursor was first synthesized through a leaching-precipitation-hydrothermal process, leading to the formation of a nanosheet-like hematite precursor consisting of Fe 3+ as primary element and minor cations including Al 3+ , Mg 2+ and other cations (e.g. Ca 2+ and Ti 4+ ). During the WGSR, the nanosheets broke into smaller particles with a core of magnetite with a diameter of ~20 nm, whereas the inherent impurity elements were activated and migrated to the outer surface forming a shell with a thickness of ~4 nm. Due to the protection of shell, the as-synthesized catalyst exhibited improved activity, thermal stability and long-term durability for HT-WGSR at 400 °C and 450 °C. Compared to the pure hematite, this catalyst exhibited much higher activity and stability, i.e., increased CO conversion and decreased deactivation rate constant, by a factor of four and three, respectively. Additionally, through a bottom-up reverse synthesis, we have confirmed that Al 3+ functioned as a textual promoter enhancing the interfacial area of the catalyst. On the other hand, the presence of minor impurity elements, in particular 2.58 wt% Mg 2+ and 0.18 wt% Ti 4+ , were found to increase the basicity, and promote the adsorption rate of CO, the redox of catalysts, and the alteration of the reaction mechanism from regenerative to associative with the formation of a strong intermediate formate. Finally, this study not only opens a new direction on the valorization of solid waste into high-value catalysts, promoting the sustainability of solid waste management, but also provides an alternative, cost-effective and scalable approach for the design and fine-tuning of encapsulated catalysts.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

The Three Hundred Project: Modeling baryon and hot-gas fraction evolution in simulated clusters

The baryon fraction of galaxy clusters, expressed as the ratio between the mass in baryons (including both stars and cold or hot gas) and the total mass, is a powerful tool to provide information on the cosmological parameters, while the hot-gas fraction provides indications on the physics of the intracluster plasma and its interplay with the processes that drive galaxy formation. Using cosmological hydrodynamical simulations of about 300 simulated massive galaxy clusters with a median mass M 500 ≈ 7 × 10 14 M ⊙ at z = 0, we model the relations between total mass and either baryon fraction or the hot gas fractions at overdensities Δ = 2500, 500, and 200 with respect to the cosmic critical density, and their evolution from z ∼ 0 to z ∼ 1.3. We utilized the simulated galaxy clusters from the Three Hundred project, which include star formation and feedback from both supernovae and active galactic nuclei. We fit the simulation results for such scaling relations against three analytic forms (linear, quadratic, and logarithmic in a logarithmic plane) and three forms for the redshift dependence, and we considered as a variable both the inverse of the cosmic scale factor, (1 + z), and the Hubble expansion rate, E(z). We show that power-law dependencies on cluster mass poorly describe the investigated relations. A power law fails to simultaneously capture the flattening of the total baryon and gas fractions at high masses, their drop at low masses, and the transition between these two regimes. The other two functional forms provide a more accurate description of the curvature in mass scaling. The fractions measured within smaller radii exhibit a stronger evolution than those measured within larger radii. From the analysis of these simulations, we evince that as long as we include systems in the mass range herein investigated, the baryon or gas fraction can be accurately related to the total mass through either a parabola or a logarithm in the logarithmic plane. The trends are common to all modern hydro simulations, although the amplitude of the drop at low masses might differ. Being able to observationally determine the gas fraction in groups will thus provide constraints on the baryonic physics.

galaxy clusters↗
DOE OSTI2023

Deciphering the molecular components of the quorum sensing system in the fungus Ophiostoma piceae

Quorum sensing (QS) is a complex cell-cell communication mechanism that coordinates population-level behaviors in microbes. In eukaryotes, this phenomenon has been extensively described in the dimorphic yeast Candida albicans as its main QS molecule, the sesquiterpene alcohol farnesol, is responsible for various phenotypic (i.e., inhibition of yeast-to-hyphae transition, biofilm formation, and, hence, pathogenesis) and metabolic (i.e., induction of oxidative stress and apoptosis) changes. Ophiostoma piceae CECT 20416 is a dimorphic saprotrophic ascomycete with biotechnological interest that also produces farnesol as QS molecule, but in this case, the alcohol promotes the morphological transition to the mycelial form, biofilm formation, enzyme secretion, and melanin production. Here, we characterized the physiological response of Ophiostoma piceae to farnesol, the molecular components of the QS system of this fungus have been investigated using a “multiomics” approach that involved genomic, transcriptomic, and proteomic analyses. Some genes identified in this work are proposed as key factors in farnesol transport and signaling. We have also cataloged the genes undergoing major transcriptional changes triggered by the presence of the autoinducer, such as cell-wall remodeling, reactive oxygen species (ROS) protection, and melanin biosynthesis, using self-organizing maps. This analysis could be useful for applications in the forestry industry, for enzymes production, and for the valorization of residues. Furthermore, it might as well help to investigate the QS mechanisms of clinically relevant fungi phylogenetically related to Ophiostoma.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1983

Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

Newsom, H. E.↗
NASA NTRS1991

Interaction of a finite-length ion beam with a background plasma - Reflected ions at the quasi-parallel bow shock

The coupling of a finite-length, field-aligned, ion beam with a uniform background plasma is investigated using one-dimensional hybrid computer simulations. The finite-length beam is used to study the interaction between the incident solar wind and ions reflected from the earth's quasi-parallel bow shock, where the reflection process may vary with time. The coupling between the reflected ions and the solar wind is relevant to ion heating at the bow shock and possibly to the formation of hot, flow anomalies and re-formation of the shock itself. Consistent with linear theory, the waves which dominate the interaction are the electromagnetic right-hand polarized resonant and nonresonant modes. However, in addition to the instability growth rates, the length of time that the waves are in contact with the beam is also an important factor in determining which wave mode will dominate the interaction. It is found that interaction will result in strong coupling, where a significant fraction of the available free energy is converted into thermal energy in a short time, provided the beam is sufficiently dense or sufficiently long.

Onsager, T. G.↗
NASA NTRS1994

Nonlinear instability of accelerating shock waves with application to supernovae

We consider the stability of a planar accelerating shock front in an exponential atmosphere, a situation that can be described by a self-similar solution. A previous linear instability analysis showed that there are three regimes, depending on the wavelength of the perturbation along the direction of the shock front: at long wavelengths the shock is unstable, at intermediate wavelengths it is overstable, and at short wavelenghts it is stable, where the characteristic length is set by the initial density scale height. We have carried out numerical simulations of such an accelerating shock front and have confirmed the results of the semianalytic linear analysis in the linear regime. In the nonlinear regime, the evolution again depends on the three wavelength domains. At long wavelengths, the instability continuously grows but the flow remains smooth, and at short wavelengths, the flow is stable. The intermediate wavelength, overstable regime shows more complex evolution. The growing linear oscillations saturate soon after entering the nonlinear regime and the oscillations continue with the same approximate period. The shock front develops moving points of intersection, which generate weak shock fronts and density and pressure structure in the immediate postshock flow. The density fluctuations, with a contrast of a factor of 2-3, become frozen into the downstream flow. The growth of the instability is slow, so substantial initial perturbations are needed; thesemay be present in Type II supernovae with red supergiant progenitor stars which have outer convective regions. The clumping in the outer supernova atmosphere may affect spectral line formation and may play a role in the formation of fast knots.

Luo, Ding↗
NASA NTRS1992

X-ray Novae and Related Systems

Accretion disk thermal instability models have been successful in accounting for the basic observations of dwarf novae and the steady behavior of nova-like systems. Models for the dwarf-nova like variability of the old nova and intermediate polar GK Per give good agreement with the burst amplitude, profile and recurrence time in the optical and UV. A month-long 'precursor plateau' in the UV is predicted for the expected 1992 outburst prior to the rise to maximum in the optical and UV. The models for the time scales of the outbursts and corresponding UV spectra at maximum are consistent with the inner edge of the accretion disk being essentially constant between quiescence and outburst and a factor of four larger than the co-rotation radius. These conclusions represent a challenge to the standard theory of magnetic accretion. Disk instability models have also given a good representation of the soft X-ray and optical outbursts of the X-ray novae A0620-00 and GS2000+25. Formation of coronae above the disk, heated by magneto-acoustic flux from the disk, may account for the temporal and spectral properties of the hard X-ray and gamma ray emission of related sources such as Cyg X-1, GS 2023+33 (V404 Cyg), IE 1740.7-2942 (the 'Galactic Center' Einstein Source), and GS 1124-683 (Nova Muscae).

Wheeler, J. Craig↗
NASA NTRS1999

Effects of Spaceflight on Bone: The Rat as an Animal Model for Human Bone Loss

The loss of weight bearing during spaceflight results in osteopenia in humans. Decrements in bone mineral reach 3-10% after as little as 75-184 days in space. Loss of bone mineral during flight decreases bone strength and increases fracture risk. The mechanisms responsible for, and the factors contributing to, the changes in bone induced by spaceflight are poorly understood. The rat has been widely used as an animal model for human bone loss during spaceflight. Despite its potential usefulness, the results of bone studies performed in the rat in space have been inconsistent. In some flights bone formation is decreased and cancellous bone volume reduced, while in others no significant changes in bone occur. In June of 1996 Drs. T. Wronski, S. Miller and myself participated in a flight experiment (STS 78) to examine the effects of glucocorticoids on bone during weightlessness. Technically the 17 day flight experiment was flawless. The results, however, were surprising. Cancellous bone volume and osteoblast surface in the proximal tibial metaphysis were the same in flight and ground-based control rats. Normal levels of cancellous bone mass and bone formation were also detected in the lumbar vertebrae and femoral neck of flight rats. Furthermore, periosteal bone formation rate was found to be identical in flight and ground-based control rats. Spaceflight had little or no effect on bone metabolism! These results prompted us to carefully review the changes in bone observed in, and the flight conditions of previous spaceflight missions.

Halloran, B.↗
NASA NTRS2006

Spectral Measurements of PMCs from SBUV/2 Instruments

The SBUV/2 (Solar Backscattered Ultraviolet, model 2) instrument is designed to monitor ozone stratospheric profile and total column ozone using measurements of the Earth's backscattered ultraviolet albedo. We have previously demonstrated that the normal radiance measurements from SBUV/2 instruments, which sample 12 discrete wavelengths between 252 and 340 nm during each scan, can be used to identify polar mesospheric clouds (PMCs). Some SBUV/2 instruments also periodically view the earth in continuous scan mode, covering the wavelength range 160-400 nm with 0.15 nm sampling. Analysis of these data show PMC occurrence rates similar to the normal discrete scan results, although the observation technique reduces the number of daily measurements by a factor of six. PMC observed by SBUV/2 instruments show a monotonic variation in the residual spectral albedo over the wavelength range 250 300 nm, with maximum enhancements of 10 15% at 250 nm. This result is consistent with microphysical model predictions from Jensen [1989. A numerical model of polar mesospheric cloud formation and evolution, Ph. D. Thesis, University of Colorado]. We find no evidence for a systematic localized increase in PMC residual albedo for wavelengths near 260 nm, in contrast to the recently reported results from the MSX UVISI instrument [Carbary J.F., et al., 2004. Evidence for bimodal particle distribution from the spectra of polar mesospheric clouds. Geophysics Research. Letters 31, L13108]. This result is observed for three different SBUV/2 instruments in both Northern and Southern Hemisphere data over a 13-year span. Our Mie scattering calculations show that the location and magnitude of the 260 nm hump feature is dependent upon the specific scattering angles appropriate to the MSX measurements. Although it explains the MSX spectrum, the bimodal size distribution proposed by Carbary et al. (2004), cannot explain the lack of scattering angle dependence of the SBUV/2 spectral shapes. The spectral signature of the SBUV/2 continuous scan PMC data is thus inconsistent with the bimodal particle size distribution suggested by Carbary et al. (2004).

DeLand, Matthew T.↗
NASA NTRS2014

Low Temperature Double-Layer Capacitors Using Asymmetric and Spiro-Type Quaternary Ammonium Salts

Double-layer capacitors capable of operating at extremely low temperatures (e.g., as low as -80.degree. C.) are disclosed. Electrolyte solutions combining a base solvent (e.g., acetonitrile) and a cosolvent are employed to lower the melting point of the base electrolyte. Example cosolvents include methyl formate, ethyl acetate, methyl acetate, propionitrile, butyronitrile, and 1,3-dioxolane. A quaternary ammonium salt including at least one of triethylmethylammonium tetrafluoroborate (TEMATFB) and spiro-(1,1')-bipyrrolidium tetrafluoroborate (SBPBF.sub.4), is used in an optimized concentration (e.g., 0.10 M to 0.75 M), dissolved into the electrolyte solution. Conventional device form factors and structural elements (e.g., porous carbon electrodes and a polyethylene separator) may be employed.

Brandon, Erik J.↗
DOE OSTI2024

Understanding the Origin of Negative Temperature Dependence and Activity of N-Coordinated Cobalt Sites During Ethylene Dimerization

The on-demand production of short-chain linear alpha olefins (LAOs; C4-C8) via C2H4 dimerization and oligomerization is industrially attractive, prompting extensive research on designing active, selective, and stable catalysts for industrial use. Cobalt supported on ammoniated carbon (Co(NH3)x/C) catalysts have shown remarkable activity and selectivity in this process. However, critical aspects such as the active phase, active site structure, the role of the catalyst support, cobalt loading effects, and the inverse correlation of the reaction rate with temperature remain inadequately understood. This study systematically explores these factors using a combination of steady-state differential catalytic tests, in situ molecular characterization including diffuse reflectance UV-Vis (DR-UV-Vis), Infrared, and Raman spectroscopies, and ex situ X-ray diffraction (XRD) and high annular aberration-corrected dark field transmission electron microscopy (HAADF-STEM). Various supports (SiO2, Al2O3, NH4-ZSM-5, g-C3N4, and C) and cobalt loadings (1.0-3.0 Co nm-2) were studied to determine the optimal catalyst composition and identify the active phase and sites. Carbon-supported catalysts uniquely produce C4-8 LAOs during C2H4 dimerization, with site-time-yield remaining constant (~10-3 s-1) for 1.0-4.0 Co nm-2 at prolonged reaction times (24-48?h time-on-stream). At higher loadings of 6.0 Co nm-2, the formation of crystalline CoO and Co3O4 phases reduces catalytic activity and LAO selectivity. Our findings show that active catalysts lack crystalline cobalt oxides and instead feature dispersed Co2+ sites, tetra-coordinated to a mix of N/NH3 and O/H2O ligands, which catalyze C2H4 dimerization via the Cossee-Arlman mechanism, exhibiting 1st order dependence on C2H4 concentration. The observed inverse rate-temperature correlation is attributed to compensation effects (i.e., presence of Cremer-Constable relationship) linked to changes in adsorption enthalpic and entropic factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interfacial Connections between Organic Perovskite/n + Silicon/Catalyst that Allow Integration of Solar Cell and Catalyst for Hydrogen Evolution from Water

Abstract The rapidly increasing solar conversion efficiency (PCE) of hybrid organic–inorganic perovskite (HOIP) thin‐film semiconductors has triggered interest in their use for direct solar‐driven water splitting to produce hydrogen. However, application of these low‐cost, electronic‐structure‐tunable HOIP tandem photoabsorbers has been hindered by the instability of the photovoltaic‐catalyst‐electrolyte (PV+E) interfaces. Here, photolytic water splitting is demonstrated using an integrated configuration consisting of an HOIP/n + silicon single junction photoabsorber and a platinum (Pt) thin film catalyst. An extended electrochemical (EC) lifetime in alkaline media is achieved using titanium nitride on both sides of the Si support to eliminate formation of insulating silicon oxide, and as an effective diffusion barrier to allow high‐temperature annealing of the catalyst/TiO 2 ‐protected‐n + silicon interface necessary to retard electrolytic corrosion. Halide composition is examined in the (FA 1‐x Cs x )PbI 3 system with a bandgap suitable for tandem operation. A fill factor of 72.5% is achieved using a Spiro‐OMeTAD‐hole‐transport‐layer (HTL)‐based HOIP/n + Si solar cell, and a high photocurrent density of −15.9 mA cm −2 (at 0 V vs reversible hydrogen electrode) is attained for the HOIP/n + Si/Pt photocathode in 1 m NaOH under simulated 1‐sun illumination. While this thin‐film design creates stable interfaces, the intrinsic photo‐ and electro‐degradation of the HOIP photoabsorber remains the main obstacle for future HOIP/Si tandem PEC devices.

08 HYDROGEN↗