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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.

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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Photoelectrochemical properties of MOF-induced surface-modified TiO 2 photoelectrode

Heteroatom doping and surface modification with oxides are both important strategies to improve the photoelectrochemical (PEC) activities of TiO 2 photoelectrodes. However, it is difficult to combine the two strategies into a single synthesis process. Herein, a simple one-pot synthesis method was developed to modify a TiO 2 photoelectrode surface by N-doping while simultaneously modifying the surface with In 2 O 3 and NiO. This method involved growing MOF onto a TiO 2 surface with N-containing organic ligands and In and Ni salts as metal precursors, followed by heat treatment at 600 °C. The roles of heteroatom doping and oxide modification are proposed as follows. (i) N-Doping extends the absorption edge of the TiO 2 to a longer wavelength region and enhances visible light absorption. (ii) N-Doping together with the passivation of TiO 2 surface trap states by oxide modification increases the donor density in TiO 2 . (iii) The generated suitable interfaces on the surface of TiO 2 facilitate photogenerated charge separation and transfer. In comparison with the pristine TiO 2 photoelectrode, the metal oxide- and heteroatom-modified TiO 2 photoelectrode exhibits superior photoelectrochemical performance under both simulated sunlight and visible light illumination. Suitable substrate of the electrode, appropriate size of the as-synthesized MOF precursors, and choice of ligands and metal ions are important factors for this strategy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Tungsten oxide nanostructures and nanocomposites for photoelectrochemical water splitting

Hydrogen production from photoelectrochemical (PEC) water splitting using semiconductor photocatalysts has attracted great attention to realize clean and renewable energy from solar energy. The visible light response of WO 3 with a long hole diffusion length (~150 nm) and good electron mobility (~12 cm 2 V –1 s –1 ) makes it suitable as the photoanode. Yet, WO 3 suffers from issues including rapid recombination of photoexcited electron–hole pairs, photo-corrosion during the photocatalytic process due to the formation of peroxo-species, sluggish kinetics of photogenerated holes, and slow charge transfer at the semiconductor/electrolyte interface. Our report highlights the approaches to overcome these drawbacks of WO 3 photoanodes, including: (i) the manipulation of nanostructured WO 3 photoanodes to decrease the nanoparticle size to promote hole migration to the WO 3 /electrolyte interface which benefits the charge separation; (ii) doping or introducing oxygen vacancies to improve electrical conductivity; exposing high energy crystal surfaces to promote the consumption of photogenerated holes on the high-active crystal face, thereby suppressing the recombination of photogenerated electrons and holes; (iii) decorating with co-catalysts to reduce the overpotential which inhibits the formation of peroxo-species; (iv) other methods such as coupling with narrow band semiconductors to accelerate the charge separation and controlling the crystal phase via annealing to reduce defects. These methods are reviewed with detailed examples.

08 HYDROGEN↗
DOE OSTI2019

Long-term stability studies of a semiconductor photoelectrode in three-electrode configuration

Improving the stability of semiconductor materials is one of the major challenges for sustainable and economic photoelectrochemical water splitting. N-terminated GaN nanostructures have emerged as a practical protective layer for conventional high efficiency but unstable Si and III–V photoelectrodes due to their near-perfect conduction band-alignment, which enables efficient extraction of photo-generated electrons, and N-terminated surfaces, which protects against chemical and photo-corrosion. In this paper, we demonstrate that Pt-decorated GaN nanostructures on an n + –p Si photocathode can exhibit an ultrahigh stability of 3000 h ( i.e. , over 500 days for usable sunlight ~5.5 h per day) at a large photocurrent density (>35 mA cm –2 ) in three-electrode configuration under AM 1.5G one-sun illumination. The measured applied bias photon-to-current efficiency of 11.9%, with an excellent onset potential of ~0.56 V vs. RHE, is one of the highest values reported for a Si photocathode under AM 1.5G one-sun illumination. This study provides a paradigm shift for the design and development of semiconductor photoelectrodes for PEC water splitting: stability is no longer limited by the light absorber, but rather by co-catalyst particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ultrathin alumina passivation for improved photoelectrochemical water oxidation catalysis of tin oxide sensitized by a phosphonate-functionalized perylene diimide first without, and then with, CoOy

Previously, a photoanode composed of nanostructured SnO 2 coated with the perylene diimide dye N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) plus photoelectrochemically deposited cobalt oxide (CoO y ) was shown to photoelectrochemically oxidize water at 31 ± 7% faradaic efficiency. A non-ideal part of that prior system is that the addition of the known CoO y water oxidation catalyst (WOC) resulted in a reduction of the total photocurrent rather than the anticipated increase, due to an increase in charge-carrier recombination. Herein, we show deposition of an ultrathin alumina overlayer applied by atomic layer deposition (ALD) on the SnO 2 /PMPDI photoanode can improve the photoactivity and catalytic activity of the system; the addition a ca. 1 nm-thick AlO x layer deposited on a 4000 nm (i.e., 4 micron) thick mesoporous anode system can and does have a positive, 2.5-fold improvement in the steady-state photocurrent with 29 ± 9% faradaic efficiency vs. the control anode without alumina passivation by reducing charge-carrier recombination. Moreover, ALD-deposited AlO x layer does help support the understanding of the “anti-catalysis” of co-depositing a CoO y WOC on the SnO 2 /PMPDI DS-PECs—specifically the picture of direct CoO y –SnO 2 contact-mediated recombination—but that AlO x layer was unable to improve the photocurrent in a net SnO 2 /PMPDI/AlO x (/CoO y ) system. We attribute the lack of a performance enhancement by CoOy WOC to incomplete coverage of each SnO 2 nanoparticle by the AlO x . Overall, we find the addition of an optimized ultrathin AlOx layer (0.6 nm thick; deposited at 85 °C) improves the SnO 2 /PMPDI/AlO x system's photoactivity by a factor of up to ca. 3-fold with reduced recombination. These results document that metal-oxide passivation by low-temperature ALD can be an effective strategy for improving the water oxidation performance of even nanostructured dye sensitized-photoelectrochemical cell.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Continuous-flow reactor with superior production rate and stability for CO 2 reduction using semiconductor photocatalysts

Semiconductor photocatalyst approaches for solar CO 2 reduction are attractive due to their simplicity but have lagged in efficiency compared to less-integrated photoelectrochemical (PEC) approaches and to electrolysis reactors. We identify poor mass transport and catalyst deactivation as key constraints. To address them, we have developed a continuous-flow photocatalytic reactor system allowing us to control the triple-phase interface on the photocatalyst surface using the liquid and reactant gas flow rates. With the goal of selectively producing CO, the reactor is optimized by controlling the pressure and flow rates of the reactant gas and electrolyte in contact with both sides with the intermediately placed catalyst. In comparison to batch reactors with an immobile photocatalyst bed and gas phase CO 2 or CO 2 purged water, 10–24 times higher production rates are achieved for photocatalysts such as TiO 2 , ZnO, C 3 N 4 , and CdS by simply changing to the designed flow-type photoreactor without any catalyst modification. In addition, CO selectivity (93.2%) and long-term stability (>780 min) using the designed reactor are significantly enhanced compared to using the batch reactors (71.7%, <180 min for reduced 50% activity). Here, we propose that the enhanced mass transport on the photocatalyst surface accelerates the desorption of the initial photolysis product, CO, and prevents the poisoning effect from deactivating photocatalyst activity. This study has the potential to facilitate the utilization of semiconductor-based photocatalytic reactions for achieving superior performance wih gaseous reactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ground and excited state properties of ThB − and ThB: a theoretical study

In the present work, we studied a series of electronic and spin–orbit states of ThB − and ThB using high-level multireference and coupled-cluster theories. We report the potential energy curves (PECs), equilibrium electron configurations, spectroscopic constants, energetics, and spin–orbit coupling effects of 17 and 19 electronic states of ThB − and ThB, respectively. The ground state of ThB − is a single-reference 1 3 Π with a 1σ 2 2σ 2 3σ 1 1π 3 electron configuration. Detachment of an electron from the doubly occupied 1π orbital of ThB − (1 3 Π) produces the single-reference ground electronic state of ThB (1 4 Σ − ). The ground spin–orbit states of ThB − and of ThB are 1 3 Π + 0 and 1 4 Σ − 3/2 , respectively. The vertical electron detachment energy (VDE) of ThB − and the adiabatic electron attachment energy (AEA) of ThB at our largest CBS-C-CCSD(T)+δT(Q)+δSO (complete basis set effect, spin–orbit effect, and triple and perturbative quadruple electron correlation effect added coupled-cluster theory with single, double, and perturbative triple excitations) level are 1.473 eV and 1.459, respectively. The reaction of Th( 3 F) + B( 2 P o ) produces the ground state of ThB with a bond energy of 2.843 eV. Finally, we estimated a heat of formation, Δ H 0 f (298 K), of 891.01 kJ mol −1 for the ThB molecule. The high-level findings of this work are expected to aid and motivate future experimental spectroscopic investigations of ThB and ThB − species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ground and excited state properties of ThBe and AcBe

In this work, the ground and excited states of ThBe and AcBe were investigated by performing high-level multireference and single-reference coupled-cluster quantum chemical calculations with large correlation consistent basis sets. Full potential energy curves (PECs), chemical bonding patterns, energetics, spectroscopic parameters (T e , r e , ω e , and ω e x e ), and spin–orbit effects of 13 and 8 electronic states of ThBe and AcBe, respectively, are reported. The ground electronic states of ThBe and AcBe are single-reference 1 3 Σ − (1σ 2 2σ 2 1π 2 ) and 1 2 Π (1σ 2 2σ 2 1π 1 ), respectively, and originate from their corresponding ground state fragments. The chemical bonding of ThBe (1 3 Σ − ) and AcBe (1 2 Π) are π-dative in character and are formed by d-electron transfers from Th/Ac to the empty 2p x and 2p y of the Be atom. The electron populations of the f-orbitals of both ThBe (1 3 Σ − ) and AcBe (1 2 Π) are minor which exhibit their “transition-metal-like” nature. The estimated bond energies of the spin–orbit ground states of ThBe (1 3 Σ − 0+ ) and AcBe (1 2 Π 1/2 ) are 12.79 and 11.02 kcal mol −1 , respectively. Finally, the bond energy of ThBe was used to estimate its heat of formation ΔH 0 f (298 K) of 869.61 ± 6 kJ mol −1 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Electronic properties of ThC − and ThC

The present study investigates the properties of low-lying states of ThC − and ThC using correlated wave function theories. To this end, we employed multireference calculations and various coupled-cluster approaches in combination with large correlation-consistent basis sets. These methods were applied to examine potential energy curves (PECs), electron configurations, energetics, spectroscopic constants, and spin–orbit coupling effects for 9 states of ThC − and 18 states of ThC. The ground states of ThC − and ThC were identified as single-reference 2 Σ + 1/2 (I) and $^3Σ^+_{0^-} (\textrm{I})$, respectively. Electron detachment from the 7s orbital of the Th center in ThC − [ 2 Σ + (I); 1σ 2 2σ1 3 σ2 1 π 4 ] yields ThC [ 3 Σ + (I); 1σ 2 2σ 1 3σ 1 1π 4 ]. The calculated adiabatic detachment energy (ADE) and vertical detachment energy (VDE) for this process are 1.591 and 1.604 eV, respectively. Furthermore, the dissociation energy (D 0 ) of ThC [$^3Σ^+_{0^-} (\textrm{I})$] is predicted to be 5.099 eV. The standard enthalpy of formation, $ΔH^{°}_{\textrm{f}}$ (298 K), of ThC is estimated to be 822.52 ± 6 kJ mol −1 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Synergetic effects of II-VI sensitization upon TiO{sub 2} for photoelectrochemical water splitting; a tri-layered structured scheme

World's energy demands are growing on a higher scale increasing the need of more reliable and long term renewable energy resources. Efficient photo-electrochemical (PEC) devices based on novel nano-structured designs for solar-hydrogen generation need to be developed. This study provides an insight of the tri-layered-TiO2 based nanostructures. Observing the mechanism of hydrogen production, the comparison of the structural order during the synthesis is pronounced. The sequence in the tri-layered structure affects the photogenerated electron (e{sup −}) and hole (h{sup +}) pair transfer and separation. It is also discussed that not only the semiconductors band gaps alignment is important with respect to the water redox potential but also the interfacial regions. Quasi-Fermi-level adjustment at the interfacial regions plays a key role in deciding the solar to hydrogen efficiency. More efficient multicomponent semiconductor nano-design (MCSN) could be developed with the approach given in this study.

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

Stability of the anodic growth porous tungsten oxide in different solutions

This article presents the study of the stability of the anodic growth porous tungsten oxide (WO{sub 3}) film in different solutions. As-anodized films are relatively stable in acidic electrolytes like sulphuric acid (H{sub 2}SO{sub 4}), hydrochloric acid (HCl) but not in oxalic acid. In higher pH solution, rate of dissolution of the WO{sub 3} film is higher. Annealing at 400 °C for 2 h transform the as-grown sample from amorphous phase to the crystalline phase and this significantly improve the stability of the film in high pH solution. Photocurrent measurements reveal that there is no significant difference of the electrolyte used (0.5 M H{sub 2}SO{sub 4}, 0.33 M H{sub 3}PO{sub 4}, 0.1 M sodium sulfate (Na{sub 2}SO{sub 4})) on the photocurrent. As-annealed films exhibit good stablility for the long photoelectrochemical (PEC) measurements (1700 s) in 0.5 M H{sub 2}SO{sub 4} and 0.1 M Na{sub 2}SO{sub 4}. There is no effect on the photocurrent for the variation of the concentration of the acidic solution (H{sub 2}SO{sub 4}). However, lower photocurrent was obtained as the concentration of Na{sub 2}SO{sub 4} was increased.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Dip coated nanocrystalline CdZnS thin films for solar cell application

Nanocrystalline cadmium sulfide (CdS) and zinc cadmium sulfide (ZnCdS) thin films have been grown via simple and low cost dip coating technique. The prepared films are characterized by X-ray diffraction (XRD), atomic force microscopic (AFM) and UV-VIS spectrophotometer techniques to reveal their structural, morphological and optical properties. XRD shows that both samples grown have zinc blende structure. The grain size is calculated as 6.2 and 8 nm using Scherrer’s formula. The band gap value of CdS and CdZnS film is estimated to be 2.58 and 2.69 eV respectively by UV-vis spectroscopy. Photoelectrochemical (PEC) investigations are carried out using cell configuration as n-CdZnS/(1M NaOH + 1M Na2S + 1M S)/C. The photovoltaic output characteristic is used to calculate fill-factor (FF) and solar conversion efficiency (η)

14 SOLAR ENERGY↗
DOE OSTI2016

Growth and surface topography of WSe{sub 2} single crystal

Tungsten Di-Selenide belongs to the family of TMDCs showing their potential applications in the fields of Optoelectronics and PEC solar cells. Here in the present investigation single crystals of WSe{sub 2} were grown by Direct Vapour Transport Technique in a dual zone furnace having temperature difference of 50 K between the two zones. These single crystals were characterized by EDAX which confirms the stiochiometry of the grown crystals. Surface topography of the crystal was studied by optical micrograph showing the left handed spirals on the surface of WSe{sub 2} crystals. Single crystalline nature of the crystals was confirmed by SAED.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

BiVO{sub 4} photoanodes for water splitting with high injection efficiency, deposited by reactive magnetron co-sputtering

Photoactive bismuth vanadate (BiVO{sub 4}) thin films were deposited by reactive co-magnetron sputtering from metallic Bi and V targets. The effects of the V-to-Bi ratio, molybdenum doping and post-annealing on the crystallographic and photoelectrochemical (PEC) properties of the BiVO{sub 4} films were investigated. Phase-pure monoclinic BiVO{sub 4} films, which are more photoactive than the tetragonal BiVO{sub 4} phase, were obtained under slightly vanadium-rich conditions. After annealing of the Mo-doped BiVO{sub 4} films, the photocurrent increased 2.6 times compared to undoped films. After optimization of the BiVO{sub 4} film thickness, the photocurrent densities (without a catalyst or a blocking layer or a hole scavenger) exceeded 1.2 mA/cm{sup 2} at a potential of 1.23 V{sub RHE} under solar AM1.5 irradiation. The surprisingly high injection efficiency of holes into the electrolyte is attributed to the highly porous film morphology. This co-magnetron sputtering preparation route for photoactive BiVO{sub 4} films opens new possibilities for the fabrication of large-scale devices for water splitting.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Efficient power combiner for THz radiation

Most dangerous explosive materials, both toxic and radioactive, contain nitrogen salts with resonant absorption lines in the frequency range 0.3-10 THz. Therefore, there has been growing interest in remotely detecting such materials by observing the spectrum of reflected signals when the suspicious material is interrogated by THz radiation. Practical portable THz sources available today generate only 20–40 mW output power. This power level is too low to interrogate suspicious material from a safe distance, especially if the material is concealed. Hence, there is a need for sources that can provide greater power in the THz spectrum. Generating and extracting high output power from THz sources is complicated and inefficient. The efficiency of vacuum electronic microwave sources is very low when scaled to the THz range and THz sources based on scaling down semiconductor laser sources have low efficiency as well, resulting in the well known “THz gap.” The reason for such low efficiencies for both source types is material losses in the THz band. In this article an efficient power combiner is described that is based on scaling to higher frequencies a microwave combiner that increases the output power in the THz range of interest in simulation studies. The proposed power combiner not only combines the THz power output from several sources, but can also form a Gaussian wavebeam output. A minimum conversion efficiency of 89% with cophased inputs in a lossy copper power combiner and maximum efficiency of 100% in a Perfect Electric Conductor (PEC)-made power combiner were achieved in simulations. Also, it is shown that the TE{sub 01} output mode is a reasonable option for THz applications due to the fact that conductive loss decreases for this mode as frequency increases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Discovery of the young L dwarf wise J174102.78-464225.5

We report the discovery of the L dwarf WISE J174102.78–464225.5, which was discovered as part of a search for nearby L dwarfs using the Wide-field Infrared Survey Explorer (WISE). The distinct triangular peak of the H-band portion of its near-infrared spectrum and its red near-infrared colors (J – K{sub S} = 2.35 ± 0.08 mag) are indicative of a young age. Via comparison to spectral standards and other red L dwarfs, we estimate a near-infrared spectral type of L7 ± 2 (pec). From a comparison to spectral and low-mass evolutionary models, we determine self-consistent effective temperature, log g, age, and mass values of 1450 ± 100 K, 4.0 ± 0.25 (cm s{sup –2}), 10-100 Myr, and 4-21 M {sub Jup}, respectively. With an estimated distance of 10-30 pc, we explore the possibility that WISE J174102.78–464225.5 belongs to one of the young nearby moving groups via a kinematic analysis and we find potential membership in the β Pictoris or AB Doradus associations. A trigonometric parallax measurement and a precise radial velocity can help to secure its membership in either of these groups.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

THE DISCOVERY OF Y DWARFS USING DATA FROM THE WIDE-FIELD INFRARED SURVEY EXPLORER (WISE)

We present the discovery of seven ultracool brown dwarfs identified with the Wide-field Infrared Survey Explorer (WISE). Near-infrared spectroscopy reveals deep absorption bands of H{sub 2}O and CH{sub 4} that indicate all seven of the brown dwarfs have spectral types later than UGPS J072227.51-054031.2, the latest-type T dwarf currently known. The spectrum of WISEP J182831.08+265037.8 is distinct in that the heights of the J- and H-band peaks are approximately equal in units of f{sub {lambda}}, so we identify it as the archetypal member of the Y spectral class. The spectra of at least two of the other brown dwarfs exhibit absorption on the blue wing of the H-band peak that we tentatively ascribe to NH{sub 3}. These spectral morphological changes provide a clear transition between the T dwarfs and the Y dwarfs. In order to produce a smooth near-infrared spectral sequence across the T/Y dwarf transition, we have reclassified UGPS 0722-05 as the T9 spectral standard and tentatively assign WISEP J173835.52+273258.9 as the Y0 spectral standard. In total, six of the seven new brown dwarfs are classified as Y dwarfs: four are classified as Y0, one is classified as Y0 (pec?), and WISEP J1828+2650 is classified as >Y0. We have also compared the spectra to the model atmospheres of Marley and Saumon and infer that the brown dwarfs have effective temperatures ranging from 300 K to 500 K, making them the coldest spectroscopically confirmed brown dwarfs known to date.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

DISCOVERY OF FOUR HIGH PROPER MOTION L DWARFS, INCLUDING A 10 pc L DWARF AT THE L/T TRANSITION {sup ,}

We discover four high proper motion L dwarfs by comparing the Wide-field Infrared Survey Explorer (WISE) to the Two Micron All Sky Survey. WISE J140533.32+835030.5 is an L dwarf at the L/T transition with a proper motion of 0.85 ± 0.''02 yr{sup –1}, previously overlooked due to its proximity to a bright star (V ≈ 12 mag). From optical spectroscopy we find a spectral type of L8, and from moderate-resolution J band spectroscopy we find a near-infrared spectral type of L9. We find WISE J140533.32+835030.5 to have a distance of 9.7 ± 1.7 pc, bringing the number of L dwarfs at the L/T transition within 10 pc from six to seven. WISE J040137.21+284951.7, WISE J040418.01+412735.6, and WISE J062442.37+662625.6 are all early L dwarfs within 25 pc, and were classified using optical and low-resolution near-infrared spectra. WISE J040418.01+412735.6 is an L2 pec (red) dwarf, a member of the class of unusually red L dwarfs. We use follow-up optical and low-resolution near-infrared spectroscopy to classify a previously discovered fifth object WISEP J060738.65+242953.4 as an (L8 Opt/L9 NIR), confirming it as an L dwarf at the L/T transition within 10 pc. WISEP J060738.65+242953.4 shows tentative CH{sub 4} in the H band, possibly the result of unresolved binarity with an early T dwarf, a scenario not supported by binary spectral template fitting. If WISEP J060738.65+242953.4 is a single object, it represents the earliest onset of CH{sub 4} in the H band of an L/T transition dwarf in the SpeX Library. As very late L dwarfs within 10 pc, WISE J140533.32+835030.5 and WISEP J060738.65+242953.4 will play a vital role in resolving outstanding issues at the L/T transition.

79 ASTRONOMY AND ASTROPHYSICS↗