Development of Transition Metal Carbide and Nitride Electrocatalysts for Chemical Energy Storage and CO2 Conversion

The rapid influx of solar energy and the desire to utilize carbon dioxide (CO2) will require large-scale energy storage and CO2 conversion technologies. Electrocatalytic devices can substantially impact both challenges, but improvements to electrocatalyst cost, activity, and selectivity are needed. Transition metal carbides provide a unique framework to reduce the loading of expensive catalyst metals while tuning the electrocatalytic activity and selectivity. Transition metal nitrides have many similar properties as carbides, and their synthesis inherently avoids the unwanted carbonaceous overlayer associated with carbide synthesis. Here it is shown that carbides and nitrides enable lower platinum-group metal (PGM) loadings and improve the activity and selectivity of electrocatalysts for reactions of water electrolysis and electrochemical CO2 reduction. Atom-thick layers of Pt were deposited onto niobium carbide (NbC) thin films to assess hydrogen evolution reaction (HER) activity. The Pt/NbC thin film, with one monolayer of Pt on NbC, performed similarly to bulk Pt. This correlated well with density functional theory (DFT) calculations of the hydrogen binding energy on the Pt/NbC surface. Potential applications of transition metal nitrides as electrocatalyst support materials were explored by synthesizing thin film nitrides of niobium and tungsten. The stability of each nitride was evaluated across broad potential-pH regimes to create a pseudo-Pourbaix diagram for each one. The films were each modified with atom-thick layers of Pt and were evaluated for HER performance in acid and alkaline electrolyte. Thin layers of Pt on WN and NbN showed Pt-like HER performance in acid and are promising candidates for high-surface area catalysts. To address the issue of high iridium (Ir) loading for the oxygen evolution reaction (OER) at the water electrolyzer anode, core-shell Ir-metal nitride particles were synthesized that contained 50% of the Ir mass loading of benchmark IrO¬2 particles. Iridium-iron nitride (Ir/Fe4N) showed increased activity on a mass-Ir basis and on a per-site basis, compared to IrO2. The core-shell morphology and stability under reaction conditions were confirmed with electron microscopy and in-situ X-ray absorption spectroscopy. Electrochemical reduction of CO2 to a mixture of CO and H¬2 (synthesis gas) was achieved on the palladium hydride (PdH) electrocatalyst. The product mixture can then be used as feedstock for the Fischer–Tropsch process and methanol synthesis. The syngas production performance was optimized by evaluating shape controlled PdH particles, bimetallic PdH, and PdH supported on transition metal carbides. At each step, the phase transition from Pd to PdH was monitored under reaction conditions with synchrotron-based X-ray absorption spectroscopy and X-ray diffraction. We also performed an overall carbon balance for catalytic transformation of CO2 to methanol via four reaction schemes, including one relying on electrocatalytic syngas production. The analysis revealed that hybrid electrocatalytic/thermocatalytic processes are most promising for resulting in overall CO2 reduction, but current densities of recently reported electrocatalysts need to increase to make the process economically feasible

CALIPSO Lidar Level 3 Aerosol Profile Product: Version 3 Algorithm Design

The CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) level 3 aerosol profile product reports globally gridded, quality-screened, monthly mean aerosol extinction profiles retrieved by CALIOP (the Cloud-Aerosol Lidar with Orthogonal Polarization). This paper describes the quality screening and averaging methods used to generate the version 3 product. The fundamental input data are CALIOP level 2 aerosol extinction profiles and layer classification information (aerosol, cloud, and clear-air). Prior to aggregation, the extinction profiles are quality-screened by a series of filters to reduce the impact of layer detection errors, layer classification errors, extinction retrieval errors, and biases due to an intermittent signal anomaly at the surface. The relative influence of these filters are compared in terms of sample rejection frequency, mean extinction, and mean aerosol optical depth (AOD). The extinction QC flag filter is the most influential in preventing high-biases in level 3 mean extinction, while the misclassified cirrus fringe filter is most aggressive at rejecting cirrus misclassified as aerosol. The impact of quality screening on monthly mean aerosol extinction is investigated globally and regionally. After applying quality filters, the level 3 algorithm calculates monthly mean AOD by vertically integrating the monthly mean quality-screened aerosol extinction profile. Calculating monthly mean AOD by integrating the monthly mean extinction profile prevents a low bias that would result from alternately integrating the set of extinction profiles first and then averaging the resultant AOD values together. Ultimately, the quality filters reduce level 3 mean AOD by 24 and 31 % for global ocean and global land, respectively, indicating the importance of quality screening

Adapting CALIPSO Climate Measurements for Near Real Time Analyses and Forecasting

The Cloud-Aerosol Lidar and Infrared Pathfinder satellite Observations (CALIPSO) mission was originally conceived and designed as a climate measurements mission, with considerable latency between data acquisition and the release of the level 1 and level 2 data products. However, the unique nature of the CALIPSO lidar backscatter profiles quickly led to the qualitative use of CALIPSO?s near real time (i.e., ? expedited?) lidar data imagery in several different forecasting applications. To enable quantitative use of their near real time analyses, the CALIPSO project recently expanded their expedited data catalog to include all of the standard level 1 and level 2 lidar data products. Also included is a new cloud cleared level 1.5 profile product developed for use by operational forecast centers for verification of aerosol predictions. This paper describes the architecture and content of the CALIPSO expedited data products. The fidelity and accuracy of the expedited products are assessed via comparisons to the standard CALIPSO data products

Strategies for Improved CALIPSO Aerosol Optical Depth Estimates

In the spring of 2010, the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) project will be releasing version 3 of its level 2 data products. In this paper we describe several changes to the algorithms and code that yield substantial improvements in CALIPSO's retrieval of aerosol optical depths (AOD). Among these are a retooled cloud-clearing procedure and a new approach to determining the base altitudes of aerosol layers in the planetary boundary layer (PBL). The results derived from these modifications are illustrated using case studies prepared using a late beta version of the level 2 version 3 processing code

A PWWP Domain-Containing Protein Targets the NuA3 Acetyltransferase Complex via Histone H3 Lysine 36 trimethylation to Coordinate Transcriptional Elongation at Coding Regions

Post-translational modifications of histones, such as acetylation and methylation, are differentially positioned in chromatin with respect to gene organization. For example, although histone H3 is often trimethylated on lysine 4 (H3K4me3) and acetylated on lysine 14 (H3K14ac) at active promoter regions, histone H3 lysine 36 trimethylation (H3K36me3) occurs throughout the open reading frames of transcriptionally active genes. The conserved yeast histone acetyltransferase complex, NuA3, specifically binds H3K4me3 through a plant homeodomain (PHD) finger in the Yng1 subunit, and subsequently catalyzes the acetylation of H3K14 through the histone acetyltransferase domain of Sas3, leading to transcription initiation at a subset of genes. We previously found that Ylr455w (Pdp3), an uncharacterized proline-tryptophan-tryptophan-proline (PWWP) domain-containing protein, copurifies with stable members of NuA3. Here, we employ mass-spectrometric analysis of affinity purified Pdp3, biophysical binding assays, and genetic analyses to classify NuA3 into two functionally distinct forms: NuA3a and NuA3b. Although NuA3a uses the PHD finger of Yng1 to interact with H3K4me3 at the 5′-end of open reading frames, NuA3b contains the unique member, Pdp3, which regulates an interaction between NuA3b and H3K36me3 at the transcribed regions of genes through its PWWP domain. We find that deletion of PDP3 decreases NuA3-directed transcription and results in growth defects when combined with transcription elongation mutants, suggesting NuA3b acts as a positive elongation factor. Finally, we determine that NuA3a, but not NuA3b, is synthetically lethal in combination with a deletion of the histone acetyltransferase GCN5, indicating NuA3b has a specialized role at coding regions that is independent of Gcn5 activity. Collectively, these studies define a new form of the NuA3 complex that associates with H3K36me3 to effect transcriptional elongation. MS data are available via ProteomeXchange with identifier PXD001156

Excess membrane cholesterol is an early contributing reversible aspect of skeletal muscle insulin resistance in C57BL/6NJ mice fed a Western-style high-fat diet

Skeletal muscle insulin resistance manifests shortly after high-fat feeding, yet mechanisms are not known. Here we set out to determine whether excess skeletal muscle membrane cholesterol and cytoskeletal derangement known to compromise glucose transporter (GLUT)4 regulation occurs early after high-fat feeding. We fed 6-wk-old male C57BL/6NJ mice either a low-fat (LF, 10% kcal) or a high-fat (HF, 45% kcal) diet for 1 wk. This HF feeding challenge was associated with an increase, albeit slight, in body mass, glucose intolerance, and hyperinsulinemia. Liver analyses did not reveal signs of hepatic insulin resistance; however, skeletal muscle immunoblots of triad-enriched regions containing transverse tubule membrane showed a marked loss of stimulated GLUT4 recruitment. An increase in cholesterol was also found in these fractions from HF-fed mice. These derangements were associated with a marked loss of cortical filamentous actin (F-actin) that is essential for GLUT4 regulation and known to be compromised by increases in membrane cholesterol. Both the withdrawal of the HF diet and two subcutaneous injections of the cholesterol-lowering agent methyl-β-cyclodextrin at 3 and 6 days during the 1-wk HF feeding intervention completely mitigated cholesterol accumulation, cortical F-actin loss, and GLUT4 dysregulation. Moreover, these beneficial membrane/cytoskeletal changes occurred concomitant with a full restoration of metabolic responses. These results identify skeletal muscle membrane cholesterol accumulation as an early, reversible, feature of insulin resistance and suggest cortical F-actin loss as an early derangement of skeletal muscle insulin resistance

CALIOP Calibration: Version 4.0 Algorithm Updates

The Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) lidar, onboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite, has been providing a near continuous record of high-resolution vertical profiles of clouds and aerosols properties since the summer of 2006. Key to the generation of these vertical profiles is proper calibration of the 532 nm and 1064 nm channels. This abstract summarizes improvements to the calibration techniques used to calibrate the 532 nm and 1064 nm signals for the recent version 4 (V4) Lidar Level 1 data release