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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Single- and Double-Site Substitutions in Mixed-Metal Oxides: Adjusting the Band Edges Toward the Water Redox Couples

New mixed-metal oxide solid solutions, i.e., the single-metal substituted Na 2 Ta 4–y Nb y O 11 (0 ≤ y ≤ 4) and the double-metal substituted Na 2–2x Sn x Ta 4–y Nb y O 11 (0 ≤ y ≤ 4; 0 ≤ x ≤ 0.35), were investigated and used to probe the impact of composition on their crystalline structures, optical band gaps, band energies, and photocatalytic properties. The Na 2 Ta 4 O 11 (y = 1) phase was prepared by flux-mediated synthesis, while the members of the Na 2 Ta 4–y Nb y O 11 solid solution (1 ≤ y ≤ 4) were prepared by traditional high-temperature reactions. The Sn(II)-containing Na 2–2x Sn x Ta 4–y Nb y O 11 (0 ≤ y ≤ 4) solid solutions were prepared by flux-mediated ion-exchange reactions of the Na 2 Ta 4–y Nb y O 11 solid solutions within a SnCl 2 flux. The crystalline structures of both solid solutions are based on the parent Na 2 B 4 O 11 (B = Nb, Ta) phases and consist of layers of edge-shared BO 7 pentagonal bipyramids that alternate with layers of isolated BO 6 octahedra surrounded by Na(I) cations. Rietveld refinements of the Na 2 Ta 4–y Nb y O 11 solid solution showed that Nb(V) cations were disordered equally over both the BO 7 and BO 6 atomic sites, with a symmetry-lowering distortion from R$\overline{3c}$ to C2/c occurring at ~67–75% Nb (y = ~2.7–3.0). A red-shift in the optical band gaps from ~4.3 to ~3.6 eV is observed owing to a new conduction band edge that arises from the introduction of the lower-energy Nb 4d-orbitals. Reactions of these phases within a SnCl 2 flux yielded the new Na 2–2x Sn x Ta 4–y Nb y O 11 solid solution with Sn-content varying from ~11% to ~21%. However, significant red-shifting of the band gap is found with increasing Nb-content, down to ~2.3 eV for Na 1.4 Sn 0.3 Nb 4 O 11 , because of the higher energy valence band edge upon incorporation of Sn(II) into the structure. Aqueous suspensions of the particles irradiated at ultraviolet–visible energies yielded the highest photocatalytic hydrogen production rates for Na 1.3 Sn 0.35 Ta 1.2 Nb 2.8 O 11 (~124 μmol H 2 ·g –1 ·h –1 ) and Na 1.4 Sn 0.3 Ta 3 NbO 11 (~105 μmol H 2 ·g –1 ·h –1 ), i.e., for the compositions with the highest Sn(II)-content. Further, polycrystalline films show n-type anodic photocurrents under ultraviolet–visible light irradiation. These results show that the valence and conduction band energies can be raised and lowered, respectively, using single-metal and double-metal substituted solid solutions. Furthermore, a novel approach is revealed for achieving smaller visible-light bandgap sizes and a closer bracketing of the water redox couples in order to drive total water splitting reactions that are critical for efficient solar energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Amplified Spontaneous Emission from Electron–Hole Quantum Droplets in Colloidal CdSe Nanoplatelets

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is <= 200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Finally, our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

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

Electron thermalization and relaxation in laser-heated nickel by few-femtosecond core-level transient absorption spectroscopy

Direct measurements of photoexcited carrier dynamics in nickel are made using few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy at the nickel M 2,3 edge. It is observed that the core-level absorption line shape of photoexcited nickel can be described by a Gaussian broadening (σ) and a red shift (ω s ) of the ground-state absorption spectrum. Theory predicts and the experimental results verify that after initial rapid carrier thermalization, the electron temperature increase (ΔT ) is linearly proportional to the Gaussian broadening factor σ, providing quantitative real-time tracking of the relaxation of the electron temperature. Measurements reveal an electron cooling time for 50 nm thick polycrystalline nickel films of 640 ± 80 fs. With hot thermalized carriers, the spectral red shift exhibits a power-law relationship with the change in electron temperature of ω s ∝ ΔT 1.5 . Rapid electron thermalization via carrier-carrier scattering accompanies and follows the nominal 4-fs photoexcitation pulse until the carriers reach a quasithermal equilibrium. Entwined with a <6 fs instrument response function, carrier thermalization times ranging from 34 fs to 13 fs are estimated from experimental data acquired at different pump fluences and it is observed that the electron thermalization time decreases with increasing pump fluence. Here, the study provides an initial example of measuring electron temperature and thermalization in metals in real time with XUV light, and it lays a foundation for further investigation of photoinduced phase transitions and carrier transport in metals with core-level absorption spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Enhanced Size Selection in Two-Photon Excitation for CsPbBr 3 Perovskite Nanocrystals

Here, cesium lead bromide (CsPbBr 3 ) perovskite nanocrystals (NCs), with large two-photon absorption (TPA) cross-section and bright photoluminescence (PL), have been demonstrated as stable two-photon-pumped lasing medium. With two-photon excitation, red-shifted PL spectrum and increased PL lifetime is observed compared with one-photon excitation. We have investigated the origin of such difference using time-resolved laser spectroscopies. We ascribe the difference to the enhanced size selection of NCs by two-photon excitation. Because of inherent nonlinearity, the size dependence of absorption cross-section under TPA is stronger. Consequently, larger size NCs are preferably excited, leading to longer excited-state lifetime and red-shifted PL emission. In a broad view, the enhanced size selection in two-photon excitation of CsPbBr 3 NCs is likely a general feature of the perovskite NCs and can be tuned via NC size distribution to influence their performance within NC-based nonlinear optical materials and devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Elucidating the Nanoparticle–Metal Organic Framework Interface of Pt@ZIF-8 Catalysts

Composites of metal nanoparticles encapsulated in metal–organic frameworks (NP@MOFs) have emerged as heterogeneous catalysts for regioselective reactions. While numerous NP@MOF composite combinations have been synthesized, characterization of the nanoparticle–MOF interface and the encapsulated nanoparticle surface have yet to be determined. In this work, Pt@ZIF-8 synthesized by the controlled encapsulation method was chosen as a representative NP@MOF, and in situ characterization methods coupled with density functional theory (DFT) calculations were used to probe the nanoparticle surface. CO adsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed that Pt@ZIF-8 exhibits red-shifted linear- and bridge-bound CO peaks and a linear peak associated with cationic Pt. DFT calculations and 1H NMR suggest that these sites arise from the binding and electronic donation of the MOF linker, 2-methylimidazole, to the Pt surface. DRIFTS under argon reveals that linker fragments may be present on the Pt nanoparticle surface, suggesting a reaction between the nanoparticle and the MOF linker during controlled encapsulation synthesis. Finally, CO oxidation reveals via DRIFTS that the red-shifted linear CO and bridging CO sites are active sites, while the cationic Pt is not. Overall, these results show that Pt@ZIF-8 contains unique Pt surface sites and indicate that the nanoparticle–MOF interface contains a heterogeneous mixture of framework 2-methylimidazole, free-standing 2-methylimidazole, and linker fragments. These findings expose the complex nature of the nanoparticle surface in NP@MOF composites and demonstrate the importance of characterizing their surface to understand their catalytic behavior.

Whitford, Cassandra L. (ORCID:0000000282237516)↗
DOE OSTI2021

Coupling between Emissive Defects on Carbon Nanotubes: Modeling Insights

Covalent functionalization of single-walled carbon nanotubes (SWCNTs) with organic molecules results in red-shifted emissive states associated with sp 3 -defects in the tube lattice, which facilitate their improved optical functionality, including single-photon emission. The energy of the defect-based electronic excitations (excitons) depends on the molecular adducts, the configuration of the defect, and concentration of defects. In this work, we model the interactions between two sp 3 -defects placed at various distances in the (6,5) SWCNT using time-dependent density functional theory. Calculations reveal that these interactions conform to the effective model of J-aggregates for well-spaced defects (>2 nm), leading to a red-shifted and optically allowed (bright) lowest energy exciton. H-aggregate behavior is not observed for any defect orientations, which is beneficial for emission. The splitting between the lowest energy bright and optically forbidden (dark) excitons and the pristine excitonic band are controlled by the single-defect configurations and their axial separation. These findings enable a synthetic design strategy for SWCNTs with tunable near-infrared emission.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Synthesis of highly water soluble tetrabenzoporphyrins and their application toward photodynamic therapy

Novel tetraaryl-(pyridinium-4-yl)-tetrabenzoporphyrins have been successfully synthesized via a Heck-based sequence reaction. These tetrabenzoporphyrins were substituted with eight pyridyl groups at the fused benzene rings. Methylation of the pyridyl groups with methyl iodide afforded highly water soluble tetrabenzoporphyrins carrying eight ionic groups. The extended π-conjugation broadened and red-shifted the absorption band of these porphyrins to 650–750 nm. Furthermore, these cationic tetrabenzoporphyrins showed non-toxicity in the dark up to 100 uM. High phototoxicity with IC 50 values lower than 18 μM were obtained for these tetrabenzoporphyrins.

DFT calculation photosensitizer↗
DOE OSTI2013

TiO{sub 2} nanocomposite with reduced graphene oxide through facile blending and its photocatalytic behavior for hydrogen evolution

Graphical abstract: - Highlights: • TRG-COOH nanocomposite as a photocatalyst for hydrogen evolution is prepared. • The reduction of graphene oxide reconstructs a part of conjugated structure. • The band gap is red-shifted due to the reconstruction of conjugated structure. • RG-COOH covered and anchored by P25 blocks the aggregation and the stacking. • The photocatalytic efficiency of TRG-COOH was increased under 500 W Xenon lamp. - Abstract: TRG-COOH nanocomposite is prepared as a photocatalyst for hydrogen evolution by blending TiO{sub 2} with reduced graphene oxide (RG-COOH). TRG-COOH is characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), and photoluminescent spectra. XPS result shows the reduction of monolayer graphene oxide (GO). The band gap is red-shifted from 3.25 eV for P25, which consists of 20% rutile and 80% anatase, to 2.95 eV for TGO and then to 2.80 eV for TRG-COOH due to the introduction of GO and the reconstruction of conjugated structure. TEM image illustrates that RG-COOH in TRG-COOH is covered and anchored by P25, which blocks the aggregation of TiO{sub 2} nanoparticles and the stacking of monolayer graphene. This allows RG-COOH to take a good role of electron-sink and electron-transporting bridge. The photocatalytic efficiency of TRG-COOH is respectively increased under Xenon lamp about 8.9 and 2.7 times compared to P25 and TGO.

36 MATERIALS SCIENCE↗
DOE OSTI2021

HJ-aggregates of donor–acceptor–donor oligomers and polymers

A vibronic exciton model is developed to account for the spectral signatures of HJ-aggregates of oligomers and polymers containing donor–acceptor–donor (DAD) repeat units. In (DAD) N π-stacks, J-aggregate-promoting intrachain interactions compete with H-aggregate promoting interchain interactions. The latter includes Coulombic coupling, which arises from “side-by-side” fragment transition dipole moments as well as intermolecular charge transfer (ICT), which is enhanced in geometries with substantial overlap between donors on one chain and acceptors on a neighboring chain. J-behavior is dominant in single (DAD)N chains with enhanced intrachain order as evidenced by an increased red-shift in the low-energy absorption band along with a heightened A 1 /A 2 peak ratio, where A 1 and A 2 are the oscillator strengths of the first two vibronic peaks in the progression sourced by the symmetric quinoidal–aromatic vibration. By contrast, the positive H-promoting interchain Coulomb interactions operative in aggregates cause the vibronic ratio to attenuate, similar to what has been established in H-aggregates of homopolymers such as P3HT. An attenuated A 1 /A 2 ratio can also be caused by H-promoting ICT which occurs when the electron and hole transfer integrals are out-of-phase. In this case, the A 1 peak is red-shifted, in contrast to conventional Kasha H-aggregates. With slight modifications, the ratio formula derived previously for P3HT aggregates is shown to apply to (DAD) N aggregates as well, allowing one to determine the effective free-exciton interchain coupling from the A 1 /A 2 ratio. Applications are made to polymers based on 2T-DPP-2T and 2T-BT-2T repeat units, where the importance of the admixture of the excited acceptor state in the lowest energy band is emphasized.

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

Infrared signature of micro-hydration in the organophosphate sarin: An ab initio study

The infrared (IR) spectra of micro-hydrated Sarin•(H 2 O) n clusters containing between one and four explicit waters have been studied using ab initio density functional theory (DFT) methods. The phosphate group P=O bond vibration region (~1270 to 1290 cm –1 ) revealed the largest frequency variation with hydration, with a frequency red shift reflecting the direct hydrogen bond formation between the P=O of Sarin and water. Small variations to the P-F stretch (~810 to 815 cm –1 ) and the C-O-P vibrational modes (~995 to 1004 cm –1 ) showed that the water interactions with these functional groups were minor, and that the structures of Sarin were not extensively perturbed in the hydrated complexes. Increasing the number of explicit hydration waters produced only small vibrational changes in the lowest free energy complexes. These minor changes were consistent with a single water-phosphate hydrogen bond being the dominant structure, though a second water-phosphate hydrogen bond was observed in some complexes and was identified by an additional red shift of the P=O bond vibration. As a result, the H 2 O•H 2 O vibrational modes (~3450 to 3660 cm –1 ) increased in complexity with higher hydration levels and reflect the extended hydrogen bonding networks formed between the explicit waters in the hydrated Sarin clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Lanthanide stannate pyrochlores Ln{sub 2}Sn{sub 2}O{sub 7} (Ln = Nd, Sm, Eu, Gd, Er, Yb) nanocrystals: Synthesis, characterization, and photocatalytic properties

Highlights: • Ln{sub 2}Sn{sub 2}O{sub 7} (Ln = Nd, Sm, Eu, Gd, Er, Yb) are synthesized by hydrothermal method. • Light absorption edge shows red shift with decreasing Ln{sup 3+} radius from Nd{sup 3+} to Yb{sup 3+}. • Ln{sub 2}Sn{sub 2}O{sub 7} shows increasing photocatalytic activity with the decease of Ln{sup 3+} radius. • Electronic configuration reaches 4f{sup 14} under light irradiation may decrease photocatalytic activity. • Hydroxyl radicals are detected to be the major reactive species. - Abstract: A series of lanthanide stannate pyrochlores Ln{sub 2}Sn{sub 2}O{sub 7} (Ln = Nd, Sm, Eu, Gd, Er, Yb) nanocrystals have been successfully synthesized via a facile hydrothermal route. With the decrease of Ln{sup 3+} radius, the light absorption edge of the as-prepared Ln{sub 2}Sn{sub 2}O{sub 7} shows a red shift from Nd{sup 3+} to Yb{sup 3+}. Their photocatalytic activities are found to be improved with the decrease of Ln{sup 3+} radius. However, the photocatalytic activity of Yb{sub 2}Sn{sub 2}O{sub 7} is a little lower than Er{sub 2}Sn{sub 2}O{sub 7}, although the Yb{sup 3+} radius is smaller than Er{sup 3+}, which may be attributed to the full-filled electronic configuration (4f{sup 14}) of surface Yb{sup 2+} intermediates (formed by Yb{sup 3+} trapping a photo-excited electron). The crystallite size and surface area play the most important role in determining the activities. Furthermore, hydroxyl radicals are detected to be the major reactive species during the photo-degradation process. Our findings provide insights in the fabrication of highly efficient stannate photocatalysts, thus enlarging the family of photocatalysts available.

36 MATERIALS SCIENCE↗
DOE OSTI2014

TiO{sub 2} nanobelts photocatalysts decorated with Bi{sub 2}WO{sub 6} nanocrystals: Preparation and enhanced photocatalytic activity

Highlights: • TiO{sub 2} nanobelts decorated with Bi{sub 2}WO{sub 6} nanocrystals have been prepared. • The introduction of Bi{sub 2}WO{sub 6} nanocrystals can induce red-shift of absorption edge. • The Bi{sub 2}WO{sub 6}/TiO{sub 2} composites show higher photocatalytic activity than TiO{sub 2} nanobelts. • The Bi{sub 2}WO{sub 6}/TiO{sub 2} composites have long-time recyclable ability of photodegradation. - Abstract: In this paper, the controllable preparation of one-dimensional TiO{sub 2} nanobelts decorated with Bi{sub 2}WO{sub 6} nanocrystals based on Ti foils was reported using two-step hydrothermal treatment method. X-ray photoelectron spectroscopy measurement results exhibited the binding energy changes of Ti and O elements, implying the strong adhesion of Bi{sub 2}WO{sub 6} nanocrystals onto the surface of TiO{sub 2} nanobelts. The ultraviolet–visible (UV–vis) absorption spectra showed that the introduction of Bi{sub 2}WO{sub 6} nanocrystals could induce the red-shift of absorption edge and exhibited a broad absorption band in the visible region, which extended the scope of absorption spectrum and help to improve the photocatalytic degradation efficiency. The photocatalytic experiment results revealed that Bi{sub 2}WO{sub 6}/TiO{sub 2} composites possess higher photocatalytic activities toward methyl orange than pure TiO{sub 2} nanobelts. The degradation efficiency of 90% after 5 cycles indicated that the as-prepared composite photocatalysts exhibited excellent long-time recyclable ability for the degradation of contaminants.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Height stabilization of GaSb/GaAs quantum dots by Al-rich capping

GaSb quantum dots (QDs) in a GaAs matrix are investigated with cross-sectional scanning tunneling microscopy (X-STM) and photoluminescence (PL). We observe that Al-rich capping materials prevent destabilization of the nanostructures during the capping stage of the molecular beam epitaxy (MBE) growth process and thus preserves the QD height. However, the strain induced by the absence of destabilization causes many structural defects to appear around the preserved QDs. These defects originate from misfit dislocations near the GaSb/GaAs interface and extend into the capping layer as stacking faults. The lack of a red shift in the QD PL suggests that the preserved dots do not contribute to the emission spectra. We suggest that a better control over the emission wavelength and an increase of the PL intensity is attainable by growing smaller QDs with an Al-rich overgrowth.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Anomalous two-photon Compton scattering

Abstract X-ray free-electron lasers can generate radiation pulses with extreme peak intensities at short wavelengths. This enables the investigation of laser–matter interactions in a regime of high fields, yet at a non-relativistic ponderomotive potential, where ordinary rules of light–matter interaction may no longer apply and nonlinear processes are starting to become observable. Despite small cross-sections, first nonlinear effects in the hard x-ray regime have recently been observed in solid targets, including x-ray-optical sum-frequency generation (XSFG), x-ray second harmonic generation (XSHG) and two-photon Compton scattering (2PCS). Nonlinear interactions of bound electrons in the x-ray range are fundamentally different from those dominating at optical frequencies. Whereas in the optical regime nonlinearities are predominantly caused by anharmonicities of the atomic potential in the chemical bonds, x-ray nonlinearities far above atomic resonances are expected to be due to nonlinear oscillations of quasi-free electrons, including inner-shell atomic electrons. While the quasi-free-electron model agrees reasonably well with the experimental data for XSFG and XSHG, 2PCS measurements have led to unexpected results: the energy of the nonlinearly scattered photons from non-relativistic electrons shows a substantial unexpected red shift in addition to the Compton shift that is well beyond that predicted by a nonlinear quantum electrodynamics model for free electrons. A potential explanation for the spectral broadening is based on a previously unexplored scattering process that involves the whole atom rather than just quasi-free electrons. A first simulation that includes the atomic binding potential was successful in describing a broadening of the spectrum of the nonlinearly scattered photons to longer wavelengths for soft x-rays. However, the same model does not show any broadening at hard x-ray wavelengths, which is in agreement with other simulation approaches. To this point no calculation has been able to reproduce the experimentally observed broadening. Here we present further experimental data of 2PCS for an extended parameter range using additional diagnostics. In particular, we present measurements of the electron momentum distribution during the interaction that strongly suggest that the spectral broadening is not caused by an increased plasma temperature. We extend our measurement of the magnitude of the red shift in beryllium to > 1.9 k e V in addition to the Compton shift expected for free electrons and expand the measurement of the angular distribution to include forward scattering angles. We also present first measurements of 2PCS from diamond.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2017

New Ligand Design Provides Delocalization and Promotes Strong Absorption throughout the Visible Region in a Ru(II) Complex

The new Ru(II)–anthraquinone complex [Ru(bpy) 2 (qdpq)](PF 6 ) 2 (Ru-qdpq; bpy = 2,2'-bipyridine; qdpq = 2,3-di(2-pyridyl)naphtho[2,3-f]quinoxaline-7,12-quinone) possesses a strong 1 MLCT Ru → qdpq absorption with a maximum at 546 nm that tails into the near-IR and is significantly red-shifted relative to that of the related complex [Ru(bpy) 2 (qdppz)](PF 6 ) 2 (Ru-qdppz; qdppz = naphtho[2,3-a]dipyrido[3,2-h:2',3'-f]phenazine-5,18-dione), with λ max = 450 nm. Ru-qdppz possesses electronically isolated proximal and distal qdppz-based excited states; the former is initially generated and decays to the latter, which repopulates the ground state with τ = 362 ps. In contrast, excitation of Ru-qdpq results in the population of a relatively long-lived (τ = 19 ns) Ru(dπ) → qdpq(π*) 3 MLCT excited state where the promoted electron is delocalized throughout the qdpq ligand. Ultrafast spectroscopy, used together with steady-state absorption, electrochemistry, and DFT calculations, indicates that the unique coordination modes of the qdpq and qdppz ligands impart substantially different electronic communication throughout the quinone-containing ligand, affecting the excited state and electron transfer properties of these molecules. As a result, these observations create a pathway to synthesize complexes with red-shifted absorptions that possess long-lived, redox-active excited states that are useful for various applications, including solar energy conversion and photochemotherapy.

14 SOLAR ENERGY↗
DOE OSTI2019

A2 and A2B2 Benzoporphyrins as sensitizers for dye-sensitized solar cells

The first example of A2B2 tetrabenzoporphyrin (KW-4) was synthesized, characterized and evaluated as a sensitizer for dye-sensitized solar cells. UV-vis and fluorescence spectroscopy revealed red-shifted and broadened absorption spectra of A2B2 tetrabenzoporphyrin as compared with its A2 dibenzo- and A2B2 dibenzoporphyrin analogues, which is a desired feature of dyes for dye-sensitized solar cells. DFT calculations also indicate favorable electron density distribution on the HOMO and LUMO of KW-4. However, the power conversion efficiency of the solar cell based on tetrabenzoporphyrin KW-4 displayed inferior performance than that of the solar cell based on A2 dibenzoporphyrin KW-2. The lower performance of the KW-4 cell was ascribed to two factors: the low lying LUMO energy level leading to less efficient electron injection and the “flat geometry” of the dye on TiO 2 surface facilitating charge recombination and decreasing dye loading. The investigation of anchoring group effect suggests that the acrylic acid group is a better anchoring group than pentadienyl carboxylic acid.

A2B2↗
NASA NTRS2012

ORIGIN: Metal Creation and Evolution from the Cosmic Dawn

ORIGIN is a proposal for the M3 mission call of ESA aimed at the study of metal creation from the epoch of cosmic dawn. Using high-spectral resolution in the soft X-ray band, ORIGIN will be able to identify the physical conditions of all abundant elements between C and Ni to red-shifts of z=10, and beyond. The mission will answer questions such as: When were the first metals created? How does the cosmic metal content evolve? Where do most of the metals reside in the Universe? What is the role of metals in structure formation and evolution? To reach out to the early Universe ORIGIN will use Gamma-Ray Bursts (GRBs) to study their local environments in their host galaxies. This requires the capability to slew the satellite in less than a minute to the GRB location. By studying the chemical composition and properties of clusters of galaxies we can extend the range of exploration to lower redshifts (z approx. 0.2). For this task we need a high-resolution spectral imaging instrument with a large field of view. Using the same instrument, we can also study the so far only partially detected baryons in the Warm-Hot Intergalactic Medium (WHIM). The less dense part of the WHIM will be studied using absorption lines at low redshift in the spectra for GRBs. The ORIGIN mission includes a Transient Event Detector (coded mask with a sensitivity of 0.4 photon/sq cm/s in 10 s in the 5-150 keV band) to identify and localize 2000 GRBs over a five year mission, of which approx.65 GRBs have a redshift >7. The Cryogenic Imaging Spectrometer, with a spectral resolution of 2.5 eV, a field of view of 30 arcmin and large effective area below 1 keV has the sensitivity to study clusters up to a significant fraction of the virial radius and to map the denser parts of the WHIM (factor 30 higher than achievable with current instruments). The payload is complemented by a Burst InfraRed Telescope to enable onboard red-shift determination of GRBs (hence securing proper follow up of high-z bursts) and also probes the mildly ionized state of the gas. Fast repointing is achieved by a dedicated Controlled Momentum Gyro and a low background is achieved by the selected low Earth orbit.

Kouveliotou, C.↗
DOE OSTI2019

Enhancing the Performance of a Fused-Ring Electron Acceptor by Unidirectional Extension

The unidirectional extension of a smaller fused-ring system into a larger one in a single direction will increase the conjugation length, allowing a fine-tuning of electronic properties. Here, we designed and synthesized a unidirectionally extended fused-8-ring-based nonfullerene acceptor, AOIC, and a bidirectionally extended fused-11-ring electron acceptor, IUIC2, and compared these with the parent fused-5-ring electron acceptor, F5IC. They share the same electron-accepting groups and alkylphenyl side chains but have different fused-ring electron-donating units. Core extension from 5 to 11 rings up-shifts the energy levels, red shifts the absorption spectra, and reduces bandgaps. The unidirectionally extended AOIC has the highest mobility (2.1 × 10$^{-3}$ cm$^2$ V$^{-1}$ s$^{-1}$) relative to the parent F5IC (1.0 × 10-3 cm2 V-1 s$^{-1}$) and the bidirectionally extended IUIC2 (4.7 × 10$^{-4}$ cm$^2$ V-1 s$^{-1}$). Upon blending with the donor PTB7-Th, AOIC-based organic photovoltaic cells show an efficiency of 13.7%, much better than that of F5IC-based cells (5.61%) and IUIC2-based cells (4.48%).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗