Search NASA⌕ Search

SEARCH · Search NASA

Results for “H- source”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Measurement of the Hubble constant with high-energy neutrinos

Measuring distances in the Universe is one of the hardest problems in physics and astronomy. Almost every distance probe relies on photons, whose propagation across cosmic distances introduces extinction, absorption, scattering, and radiative-transfer effects. Neutrinos suffer none of these and propagate unattenuated through dust, intergalactic medium, and dense source environments alike. We introduce a new distance-ladder method for measuring the Hubble constant $H_0$ using high-energy astrophysical neutrinos from point sources as standardizable candles, and report its first observational realization. Using 12 X-ray-selected Seyfert galaxies for which IceCube reports significant per-source neutrino excesses in its 14-year public point-source release, we exploit the disk-corona correlation $L_ν= κ\, L_X^β$ between neutrino and X-ray luminosities to construct a neutrino distance ladder anchored by non-redshift distances to NGC 1068 (Cepheid + TRGB). We find $H_0 = 49^{+40}_{-30}\,\mathrm{km\,s^{-1}\,Mpc^{-1}}$ and $β= 0.67^{+0.16}_{-0.25}$ (68% credible intervals), with the corona slope disfavoring the calorimetric limit $β= 1$ at ${\sim}2σ$. The result is consistent with existing $H_0$ determinations from Planck and SH0ES within 1$σ$. While the uncertainty on $H_0$ is large, the measurement is free of electromagnetic propagation systematics and demonstrates the viability of neutrinos as a novel cosmographical probe.

Herrera, Gonzalo [MIT, MKI; Harvard U.] (ORCID:000↗
NASA NTRS2019

Directional limits on persistent gravitational waves using data from Advanced LIGO’s first two observing runs

We perform an unmodeled search for persistent, directional gravitational wave (GW) sources using data from the first and second observing runs of Advanced LIGO. We do not find evidence for any GW signals. We place limits on the broadband GW flux emitted at 25 Hz from point sources with a power law spectrum at F(α;Θ) < (0.05–25) × 10^(−8) erg/sq. cmsHz and the (normalized) energy density spectrum in GWs at 25 Hz from extended sources at Ω(α)(Θ) < (0.19–2.89) × 10^(−8) per sr where α is the spectral index of the energy density spectrum. These represent improvements of 2.5–3× over previous limits. We also consider point sources emitting GWs at a single frequency, targeting the directions of Sco X-1, SN 1987A, and the Galactic center. The best upper limits on the strain amplitude of a potential source in these three directions range from h(0) < (3.6–4.7) × 10^(−25), 1.5× better than previous limits set with the same analysis method. We also report on a marginally significant outlier at 36.06 Hz. This outlier is not consistent with a persistent gravitational-wave source as its significance diminishes when combining all of the available data.

B. P. Abbott↗
DOE OSTI2013

THE COMPACT, TIME-VARIABLE RADIO SOURCE PROJECTED INSIDE W3(OH): EVIDENCE FOR A PHOTOEVAPORATED DISK?

We present new Karl G. Jansky Very Large Array (VLA) observations of the compact ({approx}0.''05), time-variable radio source projected near the center of the ultracompact H II region W3(OH). The analysis of our new data as well as of VLA archival observations confirms the variability of the source on timescales of years and for a given epoch indicates a spectral index of {alpha} = 1.3 {+-} 0.3 (S{sub {nu}}{proportional_to}{nu}{sup {alpha}}). This spectral index and the brightness temperature of the source ({approx}6500 K) suggest that we are most likely detecting partially optically thick free-free radiation. The radio source is probably associated with the ionizing star of W3(OH), but an interpretation in terms of an ionized stellar wind fails because the detected flux densities are orders of magnitude larger than expected. We discuss several scenarios and tentatively propose that the radio emission could arise in a static ionized atmosphere around a fossil photoevaporated disk.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

THE ALFALFA H I ABSORPTION PILOT SURVEY: A WIDE-AREA BLIND DAMPED Ly{alpha} SYSTEM SURVEY OF THE LOCAL UNIVERSE

We present the results of a pilot survey for neutral hydrogen (H I) 21 cm absorption in the Arecibo Legacy Fast Arecibo L-Band Feed Array (ALFALFA) Survey. This project is a wide-area 'blind' search for H I absorption in the local universe, spanning -650 km s{sup -1} < cz < 17, 500 km s{sup -1} and covering 517.0 deg{sup 2} (7% of the full ALFALFA survey). The survey is sensitive to H I absorption lines stronger than 7.7 mJy (8983 radio sources) and is 90% complete for lines stronger than 11.0 mJy (7296 sources). The total redshift interval sensitive to all damped Ly{alpha} (DLA) systems (N{sub H{sub i}}{>=}2 Multiplication-Sign 10{sup 20} cm{sup -2}) is {Delta}z = 7.0 (129 objects, assuming T{sub s} = 100 K and covering fraction unity); for super-DLAs (N{sub H{sub i}}{>=}2 Multiplication-Sign 10{sup 21} cm{sup -2}) it is {Delta}z = 128.2 (2353 objects). We re-detect the intrinsic H I absorption line in UGC 6081 but detect no intervening absorption line systems. We compute a 95% confidence upper limit on the column density frequency distribution function f(N{sub H{sub i}},X) spanning four orders of magnitude in column density, 10{sup 19} (T{sub s} /100 K) (1/f) cm{sup -2}<N{sub H{sub I}}<10{sup 23}(Ts/100 K)(1/f) cm{sup -2}, that is consistent with previous redshifted optical DLA surveys and the aggregate H I 21 cm emission in the local universe. The detection rate is in agreement with extant observations. This pilot survey suggests that an absorption line search of the complete ALFALFA survey-or any higher redshift, larger bandwidth, or more sensitive survey, such as those planned for Square Kilometer Array pathfinders or a low-frequency lunar array-will either make numerous detections or will set a strong statistical lower limit on the typical spin temperature of neutral hydrogen gas.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Temperature effects on prevalent structures of hydrated Fe{sup +} complexes: Infrared spectroscopy and DFT calculations of Fe{sup +}(H{sub 2}O){sub n} (n = 3–8)

Hydrated Fe{sup +} ions are produced in a laser-vaporization cluster source of a triple quadrupole mass spectrometer. The Fe{sup +}(H{sub 2}O){sub n} (n = 3–8) complexes are mass-selected and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region. Density functional theory (DFT) calculations are also carried out for analyzing the experimental IR spectra and for evaluating thermodynamic quantities of low-lying isomers. Solvation through H-bonding instead of direct coordination to Fe{sup +} is observed already at n = 3, indicating the completion of the first hydration shell with two H{sub 2}O molecules. Size dependent variations in the spectra for n = 5–7 provide evidence for the second-shell completion at n = 6, where a linearly coordinated Fe{sup +}(H{sub 2}O){sub 2} subunit is solvated with four H{sub 2}O molecules. Overall spectral features for n = 3–8 agree well with those predicted for 2-coordinated structures. DFT calculations predict that such 2-coordinated structures are lowest in energy for smaller n. However, 4-coordinated isomers are predicted to be more stable for n = 7 and 8; the energy ordering is in conflict with the IR spectroscopic observation. Examination of free energy as a function of temperature suggests that the ordering of the isomers at warmer temperatures can be different from the ordering near 0 K. For n = 7 and 8, the 4-coordinated isomers should be observed at low temperatures because they are lowest in enthalpy. Meanwhile, outer-shell waters in the 2-coordinated structures are bound less rigidly; their contribution to entropy is rather large. The 2-coordinated structures become abundant at warmer temperatures, owing to the entropy effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A Herschel/HIFI legacy survey of HF and H{sub 2}O IN the galaxy: Probing diffuse molecular cloud chemistry

We combine Herschel observations for a total of 12 sources to construct the most uniform survey of HF and H{sub 2}O in our Galactic disk. Both molecules are detected in absorption along all sight lines. The high spectral resolution of the Heterodyne Instrument for the Far-infrared (HIFI) allows us to compare the HF and H{sub 2}O distributions in 47 diffuse cloud components sampling the disk. We find that the HF and H{sub 2}O velocity distributions follow each other almost perfectly and establish that HF and H{sub 2}O probe the same gas-phase volume. Our observations corroborate theoretical predictions that HF is a sensitive tracer of H{sub 2} in diffuse clouds, down to molecular fractions of only a few percent. Using HF to trace H{sub 2} in our sample, we find that the N(H{sub 2}O)-to-N(HF) ratio shows a narrow distribution with a median value of 1.51. Our results further suggest that H{sub 2}O might be used as a tracer of H{sub 2}—within a factor of 2.5—in the diffuse interstellar medium (ISM). We show that the measured factor of ∼2.5 variation around the median is driven by true local variations in the H{sub 2}O abundance relative to H{sub 2} throughout the disk. The latter variability allows us to test our theoretical understanding of the chemistry of oxygen-bearing molecules in the diffuse gas. We show that both gas-phase and grain-surface chemistry are required to reproduce our H{sub 2}O observations. This survey thus confirms that grain surface reactions can play a significant role in the chemistry occurring in the diffuse ISM (n{sub H} ⩽ 1000 cm{sup −3}).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

DISCOVERY OF A HOT CORINO IN THE BOK GLOBULE B335

We report the first evidence of a hot corino in a Bok globule. This is based on ALMA observations in the 1.2 mm band toward the low-mass Class 0 protostar IRAS 19347+0727 in B335. Saturated complex organic molecules (COMs), CH{sub 3}CHO, HCOOCH{sub 3}, and NH{sub 2}CHO, are detected in a compact region within a few 10 au around the protostar. Additionally, CH{sub 3}OCH{sub 3}, C{sub 2}H{sub 5}OH, C{sub 2}H{sub 5}CN, and CH{sub 3}COCH{sub 3} are tentatively detected. Carbon-chain related molecules, CCH and c-C{sub 3}H{sub 2}, are also found in this source, whose distributions are extended over a scale of a few 100 au. On the other hand, sulfur-bearing molecules CS, SO, and SO{sub 2} have both compact and extended components. Fractional abundances of the COMs relative to H{sub 2} are found to be comparable to those in known hot corino sources. Though the COMs lines are as broad as 5–8 km s{sup −1}, they do not show obvious rotation motion in the present observation. Thus, the COMs mainly exist in a structure whose distribution is much smaller than the synthesized beam (0.″58 × 0.″52).

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1985

Star formation in the inner Galaxy - A far-infrared and radio study of two H II regions

Far-infrared and radio continuum maps have been made of two inner-Galaxy H II region complexes, G30.8-0.0 and G25.4-0.2, along with radio and molecular line measurements at selected positions. The far-IR emission from each region is dominated by two sources. For both G25.4 and G30.8, the distribution of the emission is similar to that of the radio emission, indicating that OB stars provide most of the heating. There is evidence that extinction plays an important role in G30.8, even in the far-IR. A near-IR point source has been detected in G30.8 at the position of peak far-IR color temperature. This source may be the ionizing star for the core of G30.8. Measurement of forbidden S III 9532 A from G25.4SE indicates that the extinction toward this source is very low, which is difficult to reconcile with previously determined distance measurements to this source.

Lester, D. F.↗
DOE OSTI2025

A sound horizon-free measurement of H 0 in DESI 2024

The physical size of the sound horizon at recombination is a powerful source of information for early-time measurements of the Hubble constant H 0 , and many proposed solutions to the Hubble tension therefore involve modifications to this scale. In light of this, there has been growing interest in measuring H 0 independently of the sound horizon. We present the first such measurement to use data from the Dark Energy Spectroscopic Instrument (DESI), jointly analyzing the full-shape galaxy power spectra of DESI luminous red galaxies, emission line galaxies, quasars, and the bright galaxy sample, in a total of six redshift bins. Information from the sound horizon scale is removed from our constraints via a rescaling procedure at the power spectrum level, with our sound horizon-marginalized measurement being driven instead primarily by the matter-radiation equality scale. This measurement is then combined with additional sound horizon-free information from Planck+ACT CMB lensing, uncalibrated type Ia supernovae, and the DESI Lyman-α forest. We agnostically combine with the DESY5, Pantheon+, and Union3 supernova datasets, with our tightest respective constraints being H 0 = 66.7 +1.7 -1.9 , 67.9 +1.9 -2.1 , and 67.8 +2.0 -2.2 km s -1 Mpc -1 . This corresponds to a sub-3% sound horizon-free constraint of the Hubble constant, and is the most precise measurement of its kind to date. Even without including information from the sound horizon, our measurement is still in 2.2-3.0σ tension with SH0ES. Additionally, the consistency between our result and other measurements that do rely on the sound horizon scale provides no evidence for new early-Universe physics (e.g. early dark energy). Future DESI data releases will allow unprecedented measurements of H 0 and place strong constraints on models that use beyond-ΛCDM physics to ameliorate the Hubble tension.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

( Chandra Chandra) counterparts of CANDELS GOODS-S sources

Improving the capabilities of detecting faint X-ray sources is fundamental for increasing the statistics on faint high-z active galactic nuclei (AGNs) and star-forming galaxies (SFGs). We performed a simultaneous maximum likelihood point-spread function fit in the [0.5–2] keV and [2–7] keV energy bands of the 4 Ms Chandra Deep Field South (CDFS) data at the position of the 34,930 CANDELS H-band selected galaxies. For each detected source we provide X-ray photometry and optical counterpart validation. We validated this technique by means of a ray-tracing simulation. We detected a total of 698 X-ray point sources with a likelihood L>4.98 (i.e., >2.7σ). We show that prior knowledge of a deep sample of optical–NIR galaxies leads to a significant increase in the detection of faint (i.e., ∼10{sup −17} cgs in the [0.5–2] keV band) sources with respect to “blind” X-ray detections. By including previous X-ray catalogs, this work increases the total number of X-ray sources detected in the 4 Ms CDFS, CANDELS area to 793, which represents the largest sample of extremely faint X-ray sources assembled to date. Our results suggest that a large fraction of the optical counterparts of our X-ray sources determined by likelihood ratio actually coincides with the priors used for the source detection. Most of the new detected sources are likely SFGs or faint, absorbed AGNs. We identified a few sources with putative photometric redshift z > 4. Despite the low number statistics and the uncertainties on the photo z, this sample significantly increases the number of X-ray-selected candidate high-z AGNs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

THE ABUNDANCE OF H{sub 2}O AND HDO IN ORION KL FROM HERSCHEL/HIFI

Using a broadband, high spectral resolution survey toward the Orion Kleinmann-Low nebula acquired with Herschel/HIFI as part of the Herschel Observations of Extra-Ordinary Sources key program, we derive the abundances of H{sub 2}O and HDO in the different spatial/velocity components associated with this massive star-forming region: the Hot Core, Compact Ridge, and Plateau. A total of 20 transitions of H{sub 2} {sup 18}O, 14 of H{sub 2} {sup 17}O, 37 of HD{sup 16}O, 6 of HD{sup 18}O, and 6 of D{sub 2}O are used in the analysis, spanning from ground state transitions to over 1200 K in upper-state energy. Low-excitation lines are detected in multiple components, but the highest-excitation lines (E{sub u} > 500 K) are well modeled as emitting from a small ({approx}2'') clump with a high abundance of H{sub 2}O ({chi} = 6.5 Multiplication-Sign 10{sup -4} relative to H{sub 2}) and a HDO/H{sub 2}O ratio of 0.003. Using high spatial resolution (1.''5 Multiplication-Sign 1.''1) images of two transitions of HDO measured by the Atacama Large Millimeter/Submillimeter Array as part of its science verification phase, we identify this component as located near, but not directly coincident with, known continuum sources in the Hot Core region. Significant HDO/H{sub 2}O fractionation is also seen in the Compact Ridge and Plateau components. The outflowing gas, observed with both emission and absorption components, has a lower HDO/H{sub 2}O ratio than the compact components in Orion Kleinmann-Low, which we propose could be due to modification by gas-phase shock chemistry.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Simulation of Gas Production from Multilayered Hydrate-Bearing Media with Fully Coupled Flow, Thermal, Chemical and Geomechanical Processes Using TOUGH + Millstone. Part 1: Numerical Modeling of Hydrates

TOUGH + Millstone has been developed for the analysis of coupled flow, thermal and geomechanical processes associated with the formation and/or dissociation of CH4-hydrates in geological media. It is composed of two constituent codes: (a) a significantly enhanced version of the TOUGH + HYDRATE simulator, V2.0, that accounts for all known flow, physical, thermodynamic and chemical processes associated with the behavior of hydrate-bearing systems undergoing changes and includes the most recent advances in the description of the system properties, coupled seamlessly with (b) Millstone V1.0, a new code that addresses the conceptual, computational and mathematical shortcomings of earlier codes used to describe the geomechanical response of these systems. The capabilities of TOUGH + Millstone are demonstrated in the simulation and analysis of the system flow, thermal and geomechanical behavior during gas production from a realistic complex offshore hydrate deposit. In the first paper of this series, we discuss the physics underlying the T + H hydrate simulator, the constitutive relationships describing the physical, chemical (equilibrium and kinetic) and thermal processes, the states of the CH 4 + H 2 O system and the sources of critically important data, as well as the mathematical approaches used for the development of the of mass and energy balance equations and their solution. Finally, we provide verification examples of the hydrate code against numerical results from the simulation of laboratory and field experiments.

58 GEOSCIENCES↗
DOE OSTI2015

H{sup +} and Na{sup +} are involved in flagellar rotation of the spirochete Leptospira

Leptospira is a spirochete possessing intracellular flagella. Each Leptospira flagellar filament is linked with a flagellar motor composed of a rotor and a dozen stators. For many bacterial species, it is known that the stator functions as an ion channel and that the ion flux through the stator is coupled with flagellar rotation. The coupling ion varies depending on the species; for example, H{sup +} is used in Escherichia coli, and Na{sup +} is used in Vibrio spp. to drive a polar flagellum. Although genetic and structural studies illustrated that the Leptospira flagellar motor also contains a stator, the coupling ion for flagellar rotation remains unknown. In the present study, we analyzed the motility of Leptospira under various pH values and salt concentrations. Leptospira cells displayed motility in acidic to alkaline pH. In the presence of a protonophore, the cells completely lost motility in acidic to neutral pH but displayed extremely slow movement under alkaline conditions. This result suggests that H{sup +} is a major coupling ion for flagellar rotation over a wide pH range; however, we also observed that the motility of Leptospira was significantly enhanced by the addition of Na{sup +}, though it vigorously moved even under Na{sup +}-free conditions. These results suggest that H{sup +} is preferentially used and that Na{sup +} is secondarily involved in flagellar rotation in Leptospira. The flexible ion selectivity in the flagellar system could be advantageous for Leptospira to survive in a wide range of environment. - Highlights: • This is a study on input energy for motility in the spirochete Leptospira. • Leptospira biflexa exhibited active motility in acidic to alkaline pH. • Both H{sup +} and Na{sup +} are involved in flagellar rotation in Leptospira. • H{sup +} is a primary energy source, but Na{sup +} can secondarily enhance motility.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Preparation of amorphous copper - chromium oxides catalysts for selective oxidation of cyclohexane

In this work, amorphous copper-chromium catalysts with different Cu/Cr molar ratios have been prepared by a sol-gel method and were used in the oxidation of cyclohexane to KA-oil. The catalysts have been characterized by a variety of analytical techniques including XRD, XPS, Raman, FT-IR, BET, TEM and SEM. XRD results confirmed that the formation of amorphous structure. Here, the XPS and Raman results indicated that most of Cu species existed in well-dispersed tetrahedral coordination before calcination. After calcination, the tetrahedrally coordinated Cu ions are transformed into octahedral coordination and the activity of catalyst is significantly reduced. The results show that the tetrahedrally coordinated Cu ions play the synergistic catalytic role with Cr ions. Interestingly, oxidation of cyclohexane is more inclined to produce cyclohexanol with uncalcined catalyst due to the presence of the tetrahedrally coordinated Cu ions; however, the appearance of surface lattice oxygen makes the reaction more conducive to cyclohexanone after calcination. After optimizing conditions, Cu-Cr oxide catalyst with the molar ratio 1:1 shows the highest activity, which obtains 62.2% yield and 92.4% selectivity for KA-oil using H 2 O 2 as oxygen source.

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

An investigation on the structural stability of $\mathrm{ZIF}$-8 in water versus water-derived oxidative species in aqueous environment

We report the zeolitic-imidazolate-framework-8 (ZIF-8) is one of the extensively studied metal-organic frameworks (MOF) materials because of its unique structure. For its potential applicability in numerous fields, it becomes crucial to have detailed studies on the structural stability of ZIF-8, especially in aqueous environments. A number of studies have been conducted to investigate the breakdown process of the ZIF-8 structure in water; which is known as the hydrolysis of ZIF-8. However, those studies reported different opposing experimental observations on the role of water on the structural stability of ZIF-8, which created obscurity in understanding this phenomenon. This study explored the effects of different water-derived species on the structural stability of ZIF-8; specifically, examined the effects of only water and water with different oxidative species that may be generated by water molecules' dissociation under external energy or catalyst presence. To this effort, we experimentally probed the physical and chemical structural changes of ZIF-8 in DI water and three different solutions of hydrogen peroxides (H 2 O 2 ); taking H 2 O 2 as the source of oxidative species. To assess the changes in elemental compositions, chemical bonds, functional groups, crystal structure, and morphology, all the samples were analyzed by X-ray photoelectron spectroscopy (XPS), energy-dispersive x-ray (EDX) spectroscopy, Fourier Transform Infrared (FTIR) spectroscope, X-ray diffractometer (XRD), and scanning electron microscope (SEM). Significant structural changes in ZIF-8 occurred mainly in the presence of oxidative species in water. Notably, oxidative species' concentration exceeding 1 M heightened the deformation of the ZIF-8 structure.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Graphene-Immobilized fac -Re(bipy)(CO) 3 Cl for Syngas Generation from Carbon Dioxide

We report herein the synthesis of fac -M(4-amino-bipy)(CO) 3 X (M = Mn and X = Br or M = Re and X = Cl, with bipy = 2,2'-bipyridine), their immobilization on graphene oxide (GrO) via diazonium grafting, and the use of Re-functionalized GrO for electrocatalytic syngas production. Infrared (IR) spectroscopy, X-ray absorption fine structure (XAFS) spectroscopy, and electrocatalysis indicated successful grafting of the Re catalyst onto GrO. Re-functionalized GrO was then deposited onto a glassy carbon electrode (GCE) for CO 2 reduction. Investigation of the Re-functionalized GCE for syngas production was performed in a CO 2 -saturated acetonitrile solution with 3.1 M H 2 O as the proton source and 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF 6 ) as the supporting electrolyte. Cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatography (GC) were employed to determine its CO 2 -to-CO conversion performance. The Re catalyst shows a turnover frequency (TOF) for generating CO up to 4.44 s –1 with a CO/H 2 ratio of 7:5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Selective CO 2 Reduction by Bis(bipyridine)cobalt(II) Catalysts: The Role of Pendant Pyridine as a Proton Acceptor

Electrochemical CO 2 reduction reaction (CO 2 RR) catalyzed by molecular earth-abundant metal catalysts is a promising strategy to convert CO 2 into value-added products. One recent trend in this field has been focusing on the rational design of catalysts by incorporating redox-active ligands and modifying the secondary coordination sphere (SCS) to achieve efficient and selective CO 2 RR. Herein, we report a series of Co bis­(bipyridine) catalysts featuring various dangling groups, such as pyridine, tertiary amine, or butyl, in the secondary coordination sphere (Co-PyMe, Co-Py, Co-PrN, and Co-Bu). Efficient, selective electrocatalytic CO 2 RR was achieved by the complexes after the generation of triply reduced intermediate consisting of a Co I center and a dianionic ligand, producing CO as the major product and trace amount of H 2 . Strong correlations with the identity of dangling groups and turnover frequency (TOF) have been observed, in which Co-PyMe displayed the highest TOF (1086 s –1 in MeCN/H 2 O). Mechanistic studies indicated that the acceleration of CO 2 RR with pyridine-functionalized catalysts were derived from the protonation of pyridine dangling groups which participated as weak acids in the H-bonding network with exogenous proton sources, stabilizing CO 2 -bound intermediates and facilitating proton transfer. In addition, precatalytic CO 2 binding and activation at the third reduction (−2.1 V) was revealed by CV and SEC-IR studies. The resultant doubly reduced CO-bound species acted as a trapping state which inhibited CO 2 RR electrocatalysis. Regeneration of active species was accessed via reductive dissociation of CO at a more negative potential. In conclusion, this study highlights the combined effects of redox-active ligands and pyridine/pyridinium as SCS groups on CO 2 RR catalysis and provides design principles for future development of CO 2 RR catalysts utilizing pyridine/pyridiniums as SCS functional groups to fine-tune the catalytic activity.

CO2 reduction↗
DOE OSTI2018

Partial Surface Selenization of Cobalt Sulfide Microspheres for Enhancing the Hydrogen Evolution Reaction

Electrocatalysis of water is a scalable and easily available source of the production of hydrogen (H 2 ), the future energy carrier. This drive for clean energy inspired us to develop an inexpensive, readily producible, highly active, and stable catalyst to replace current state of the art platinum catalysts. Building on the promising hydrogen evolution reaction (HER) activity of many pyrites, their structural tuning by different metals and nonmetals has been found to be effective in several instances. We present here one such effort by partial surface selenization of mesoporous cobalt sulfide material, which displayed long-term operational stability (for at least 25 h) besides attaining a current density of 100 mA cm –2 at an overpotential of 160 mV versus the reversible hydrogen electrode (RHE) (in acidic media). A low Tafel slope (of 52 mV dec –1 ) and high exchange current density ( j 0 ) (of 70 μA cm –2 ) make our catalyst better to most existing systems. More importantly, using a variety of analytical techniques, electrochemical measurements, and theoretical calculations, we have analyzed the morphology of the material and rationalized the key to the enhanced intrinsic activity (as compared to the meso-CoS 2 ) per active site. This study is expected to explain similar systems and modify approaches to enhancing the electrochemical activity of metal chalcogenides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗