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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spatiotemporal Formation and Growth Kinetics of Polyelectrolyte Complex Micelles with Millisecond Resolution

We have directly observed the in situ self-assembly kinetics of polyelectrolyte complex (PEC) micelles by synchrotron time-resolved small-angle X-ray scattering, equipped with a stopped-flow device that provides millisecond temporal resolution. A synthesized neutral-charged diblock polycation and homopolyanion that we have previously investigated as a model charge-matched, core-shell micelle system were selected for this work. The initial micellization of the oppositely charged polyelectrolytes was completed within the dead time of mixing of 100 ms, followed by micelle growth and equilibration up to several seconds. By combining the structural evolution of the radius of gyration (R-g) with complementary molecular dynamics simulations, we show how the self-assemblies evolve incrementally in size over time through a two-step kinetic process: first, oppositely charged polyelectrolyte chains pair to form nascent aggregates that immediately assemble into spherical micelles, and second, these PEC micelles grow into larger micellar entities. Furthermore, this work has determined one possible kinetic pathway for the initial formation of PEC micelles, which provides useful physical insights for increasing fundamental understanding self-assembly dynamics, driven by polyelectrolyte complexation that occurs on ultrafast time scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Rapid Flame-Annealed CuFe 2 O 4 as Efficient Photocathode for Photoelectrochemical Hydrogen Production

Copper ferrite (CuFe 2 O 4 ) possesses an indirect bandgap in the range of 1.54–1.95 eV. It is used as an attractive p-type photocathode in photoelectrochemical (PEC) water splitting, and theoretically it can yield a maximum photocurrent density of ~27 mA/cm 2 and a maximum solar-to-hydrogen conversion efficiency of ~33%. To date, only a few reports have been published on CuFe 2 O 4 photocathodes with very low-photocurrent densities, with a maximum value of 0.4 mA/cm2 at 0.4 V vs RHE. Herein, we prepared a CuFe 2 O 4 photocathode on FTO glass with the sol–gel method followed by either high-temperature flame annealing or furnace annealing. We found that the flame-annealed CuFe 2 O 4 photocathode generated a photocurrent density of 1.82 mA/cm 2 at 0.4 V vs RHE that is approximately 3.5 times higher than the furnace-annealed CuFe 2 O 4 (0.52 mA/cm 2 ). This photocurrent density is also higher than those of all the reported CuFe 2 O 4 photocathodes, and any Cu containing ternary oxide (Cu–M–O, M: Fe, Bi, V, and Nb) photocathode (0.1–1.3 mA/cm 2 at 0.4 V vs RHE). An improved PEC performance of the flame-annealed CuFe 2 O 4 photocathode is elicited owing to the beneficial effects of flame annealing on the physical, optical, and electrical properties of CuFe 2 O 4 . Flame annealing enhances the light absorption property of the CuFe 2 O 4 photocathode by slightly reducing the bandgap, and by forming a thicker film with increased porosity. Flame annealing also reduces the oxygen vacancy concentration in CuFe 2 O 4 , thus facilitating charge transport and interfacial charge transfer processes. Moreover, flame annealing requires only 16 min, which is much shorter than the time required for furnace annealing (~9 h). Furthermore, these results demonstrate that flame annealing is a rapid and effective means for fabricating metal oxide photoelectrodes with an enhanced PEC water splitting performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Perspectives on the Development of Oxide-Based Photocathodes for Solar Fuel Production

Photoelectrochemical cells (PECs), which use semiconductor electrodes (photoelectrodes) to absorb solar energy and perform chemical reactions, constitute one of the most attractive strategies to produce chemical fuels using renewable energy sources. Oxide-based photoelectrodes specifically have been intensively investigated for the construction of PECs due to their relatively inexpensive processing costs and better stability in aqueous media compared with other types of photoelectrodes. Although there have been many advancements in the development of oxide-based photoanodes, our understanding of oxide-based photocathodes remains limited. The goal of this Perspective is to examine the recent progress made in the field of oxide-based photocathodes and discuss future research directions. The photocathode systems considered here include binary and ternary Cu-based photocathodes and ternary Fe-based photocathodes. Here, we assessed the characteristics and major advantages and drawbacks of each system and identified the most critical research gaps. The insights and discussions provided in this Perspective will serve as useful resources for the design of future studies, leading to the development of more efficient and practical PECs.

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

Reliable bi-functional nickel-phosphate /TiO2 integration enables stable n-GaAs photoanode for water oxidation under alkaline condition

Abstract Hydrogen is one of the most widely used essential chemicals worldwide, and it is also employed in the production of many other chemicals, especially carbon-free energy fuels produced via photoelectrochemical (PEC) water splitting. At present, gallium arsenide represents the most efficient photoanode material for PEC water oxidation, but it is known to either be anodically photocorroded or photopassivated by native metal oxides in the competitive reaction, limiting efficiency and stability. Here, we report chemically etched GaAs that is decorated with thin titanium dioxide (~30 nm-thick, crystalline) surface passivation layer along with nickel-phosphate (Ni-Pi) cocatalyst as a surface hole-sink layer. The integration of Ni-Pi bifunctional co-catalyst results in a highly efficient GaAs electrode with a ~ 100 mV cathodic shift of the onset potential. In this work, the electrode also has enhanced photostability under 110 h testing for PEC water oxidation at a steady current density J ph > 25 mA·cm −2 . The Et-GaAs/TiO 2 /Ni-Pi║Ni-Pi tandem configuration results in the best unassisted bias-free water splitting device with the highest J ph (~7.6 mA·cm −2 ) and a stable solar-to-hydrogen conversion efficiency of 9.5%.

08 HYDROGEN↗
DOE OSTI2025

Solar-driven selective conversion of millimolar dissolved carbon to fuels with molecular flux generation

Abstract The direct utilization of dissolved inorganic carbon in seawater for CO 2 conversion promises chemical production on-demand and with zero carbon footprint. Photoelectrochemical (PEC) CO 2 reduction (CO 2 R) devices promise the sustainable conversion of dissolved carbon in seawater to carbon products using sunlight as the only energy input. However, the diffusion-dominant transport mechanism and the near-zero concentration of CO 2 (aq) (CO 2 dissolved in aqueous solution) in static seawater has made it extremely challenging to achieve high solar-to-fuel (STF) efficiency and high carbon-product selectivity. Here, where CO 2 (aq) as a reactant generated in situ by acidification of HCO 3 - flows continuously from BiVO 4 photoanodes to Si photocathodes, enabling a single-step conversion of dissolved carbon into products. Our PEC device significantly increases the CO selectivity from 3% to 21%, which approaches the 30% theoretical limit according to multi-physics modeling. Meanwhile, the Si/BiVO 4 PEC CO 2 R device achieved a STF efficiency of 0.71%. Such flow engineering achieves flow-dependent selectivity, rate, and stability in simulated seawater, thus promising practical solar fuel production at scale.

Liu, Bin↗
DOE OSTI2015

Methods of photoelectrode characterization with high spatial and temporal resolution

Here, materials and photoelectrode architectures that are highly efficient, extremely stable, and made from low cost materials are required for commercially viable photoelectrochemical (PEC) water-splitting technology. A key challenge is the heterogeneous nature of real-world materials, which often possess spatial variation in their crystal structure, morphology, and/or composition at the nano-, micro-, or macro-scale. Different structures and compositions can have vastly different properties and can therefore strongly influence the overall performance of the photoelectrode through complex structure–property relationships. A complete understanding of photoelectrode materials would also involve elucidation of processes such as carrier collection and electrochemical charge transfer that occur at very fast time scales. We present herein an overview of a broad suite of experimental and computational tools that can be used to define the structure–property relationships of photoelectrode materials at small dimensions and on fast time scales. A major focus is on in situ scanning-probe measurement (SPM) techniques that possess the ability to measure differences in optical, electronic, catalytic, and physical properties with nano- or micro-scale spatial resolution. In situ ultrafast spectroscopic techniques, used to probe carrier dynamics involved with processes such as carrier generation, recombination, and interfacial charge transport, are also discussed. Complementing all of these experimental techniques are computational atomistic modeling tools, which can be invaluable for interpreting experimental results, aiding in materials discovery, and interrogating PEC processes at length and time scales not currently accessible by experiment. In addition to reviewing the basic capabilities of these experimental and computational techniques, we highlight key opportunities and limitations of applying these tools for the development of PEC materials.

08 HYDROGEN↗
DOE OSTI2016

Synthesis and characterization of (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with a wide range of compositions

We describe the synthesis and characterization of wurtzite (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with a wide range of compositions and a focus on properties relevant for solar fuel generation. (Ga 1-x Zn x )(N 1-x O x ), a solid solution of GaN and ZnO, is an intriguing material because it exhibits composition-dependent visible absorption even though the parent semiconductors absorb in the UV. When functionalized with co-catalysts, (Ga 1-x Zn x )(N 1-x O x ) is also capable of water splitting under visible irradiation. Here, we examine the synthesis of (Ga 1-x Zn x )(N 1-x O x ) nanocrystals to understand how they form by nitridation of ZnO and ZnGa 2 O 4 nanocrystalline precursors. We find that the ZnO precursor is critical for the formation of crystalline (Ga 1-x Zn x )(N 1-x O x ) at 650 °C, consistent with a mechanism in which wurtzite (Ga 1-x Zn x )(N 1-x O x ) nucleates topotactically on wurtzite ZnO at an interface with ZnGa 2 O 4 . Using this information, we expand the range of compositions from previously reported 0.30 ≤ x ≤ 0.87 to include the low-x and high-x ends of the range. The resulting compositions, 0.06 ≤ x ≤ 0.98, constitute the widest range of (Ga 1-x Zn x )(N 1-x O x ) compositions obtained by one synthetic method. We then examine how the band gap depends on sample composition and find a minimum of 2.25 eV at x = 0.87, corresponding to a maximum possible solar-to-H 2 power conversion efficiency of 12%. Finally, we examine the photoelectrochemical (PEC) oxidation behavior of thick films of (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with x = 0.40, 0.52, and 0.87 under visible illumination. (Ga 1-x Zn x )(N 1-x O x ) nanocrystals with x = 0.40 exhibit solar PEC oxidation activity that, while too low for practical applications, is higher than that of bulk (Ga 1-x Zn x )(N 1-x O x ) of the same composition. The highest photocurrents are observed at x = 0.52, even though x = 0.87 absorbs more visible light, illustrating that the observed photocurrents are a result of an interplay of multiple parameters which remain to be elucidated. This set of characterizations provides information useful for future studies of composition-dependent PEC properties of nanoscale (Ga 1-x Zn x )(N 1-x O x ).

36 MATERIALS SCIENCE↗
DOE OSTI2023

Codesign of an integrated metal–insulator–semiconductor photocathode for photoelectrochemical reduction of CO 2 to ethylene

Photoelectrochemical carbon-dioxide reduction (PEC CO 2 R) is a potentially attractive means for producing chemicals and fuels using sunlight, water, and carbon dioxide; however, this technology is in its infancy. To date, most studies of PEC CO 2 R have reported products containing one carbon atom (C 1 products) but the production of valuable products containing two or more carbons (C 2+ products), such as ethylene, ethanol, etc., is rarely demonstrated. Metal–semiconductor–insulator (MIS) photocathode/catalyst structures offer a promising approach for this purpose, since they integrate the functions of light absorption, charge separation, and catalysis. In this study, we have investigated a Cu/TiO 2 /p-Si photocathode/catalyst structure with the aim of establishing the effects of semiconductor–insulator interactions on the performance of the photocathode and the influence of the direction of illumination of the MIS structure on the total current density and the distribution of products formed by on the Cu catalyst. Here, we have also examined the influence of ionomer coatings deposited on the Cu surface on the total current density and the distribution of products formed. A major finding is that for a fixed Cu potential the distribution of products formed by PEC CO 2 R are the same, irrespective of the direction of illumination, and are identical to those obtained by electrochemical reduction of CO 2 (EC CO 2 R). Another important finding is that the total current density and the faradaic efficiency to ethylene are enhanced significantly by deposition of a thin bilayer of Sustainion/Nafion onto the surface of the Cu.

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

Polyelectrolyte complex scaffoldings for photocrosslinked hydrogels

Photocrosslinkable precursors (small molecules or polymers) undergo rapid crosslinking upon photoirradiation, forming covalently crosslinked hydrogels. The spatiotemporally controlled crosslinking, which can be achieved in situ, encourages the utility of photocrosslinked hydrogels in biomedicine as bioadhesives, bioprinting inks, and extracellular matrix mimics. However, the low viscosity of the precursor solutions results in unwanted flows and dilution, leading to handling difficulties and compromised strength of the photocrosslinked hydrogels. Here, we introduce oppositely charged triblock polyelectrolytes as additives for precursor solutions that transform them into self-assembled polyelectrolyte complex (PEC) hydrogels with enhanced shear strength and viscosity, providing interim protection against precursor dilution and mitigating secondary flows. The PEC network also augments the properties of the photocrosslinked hydrogels. Crosslinking of the precursors upon photoirradiation results in the formation of interpenetrating polymer network hydrogels with PEC and covalently-linked networks that exhibit shear moduli exceeding the linear combination of the moduli of the constituent networks and overcome the tensile strength–extensibility tradeoff that restricts the performance of covalently-linked hydrogels. In conclusion, the reinforcement approach is shown to be compatible with four types of photocrosslinkable precursors, does not require any modification of the precursors, and introduces minimal processing steps, paving the way for a broader translation of photocrosslinkable materials for biomedical applications.

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

Accurate potential energy curve of the LiH{sup +} molecule calculated with explicitly correlated Gaussian functions

Very accurate calculations of the ground-state potential energy curve (PEC) of the LiH{sup +} ion performed with all-electron explicitly correlated Gaussian functions with shifted centers are presented. The variational method is employed. The calculations involve optimization of nonlinear exponential parameters of the Gaussians performed with the aid of the analytical first derivatives of the energy determined with respect to the parameters. The diagonal adiabatic correction is also calculated for each PEC point. The PEC is then used to calculate the vibrational energies of the system. In that calculation, the non-adiabatic effects are accounted for by using an effective vibrational mass obtained by the minimization of the difference between the vibrational energies obtained from the calculations where the Born-Oppenheimer approximation was not assumed and the results of the present calculations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Ionization satellites of the ArHe dimer

Ionization satellites are key ingredients in the control of post ionization processes such as molecular dissociation and interatomic Coulombic decay. Here, using the high-level ab initio method of multi-reference configuration interaction up to triple excitations, we study the potential energy curves (PECs) of the ionization satellites of the ArHe dimer. With this model system, we demonstrate that the simple model used in alkaline earth metal and rare gas complexes to describe the satellites as a Rydberg electron moving on top of a dicationic core does not fully hold for the rare gas clusters. The more complex valence structure in the rare gas atom leads to the mixing of different electronic configurations of the dimer. This prevents one from assigning a single dicationic parent state to some of the ionization satellites. We further analyze the structure of the different PECs, demonstrating how the density of the Rydberg electron is reflected in the structure of the PEC wherever the simple model is applicable.

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

Interplay of light transmission and catalytic exchange current in photoelectrochemical systems

We develop an analytic current-voltage expression for a variable junction photoelectrochemical (PEC) cell and use it to investigate and illustrate the influence of the optical and electrical properties of catalysts on the optoelectronic performance of PEC devices. Specifically, the model enables a simple, yet accurate accounting of nanostructured catalyst optical and electrical properties through incorporation of an optical transmission factor and active catalytic area factor. We demonstrate the utility of this model via the output power characteristics of an exemplary dual tandem solar cell with indium gallium phosphide and indium gallium arsenide absorbers with varying rhodium catalyst nanoparticle loading. The approach highlights the importance of considering interactions between independently optimized components for optimal PEC device design.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Zero photoelastic and water durable ZnO–SnO–P{sub 2}O{sub 5}–B{sub 2}O{sub 3} glasses

We report properties of zero birefringent xZnO–(67–x)SnO–(33–y)P{sub 2}O{sub 5}–y B{sub 2}O{sub 3} glasses, within 18.5 ≤ x ≤ 22 and y = 0, 3, and 10 mol. %. These compositions of boro-phosphate glasses provide both zero photoelastic constant (PEC) and improved water durability. x = 19 and y = 3 compositions show minimum PEC of −0.002 × 10{sup −12} Pa{sup −1}, which can contribute to candidate material for fiber current sensor devise without lead. The structures of zero photoelastic glasses were investigated by Raman scattering and nuclear magnetic resonance spectroscopies. Compositions of zero PEC glasses are explained by the empirical model proposed by Zwanziger et al. [Chem. Mater. 19, 286-290 (2007)].

36 MATERIALS SCIENCE↗
DOE OSTI2015

A study of potential energy curves from the model space quantum Monte Carlo method

We report on the first application of the model space quantum Monte Carlo (MSQMC) to potential energy curves (PECs) for the excited states of C{sub 2}, N{sub 2}, and O{sub 2} to validate the applicability of the method. A parallel MSQMC code is implemented with the initiator approximation to enable efficient sampling. The PECs of MSQMC for various excited and ionized states are compared with those from the Rydberg-Klein-Rees and full configuration interaction methods. The results indicate the usefulness of MSQMC for precise PECs in a wide range obviating problems concerning quasi-degeneracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Enhanced ferroelectric photoelectrochemical properties of polycrystalline BiFeO{sub 3} film by decorating with Ag nanoparticles

Polycrystalline BiFeO{sub 3} (BFO) films are fabricated on Pt/Ti/SiO{sub 2}/Si(100) substrate as photoelectrode using sol-gel method. The microstructure, optical, and photoelectrochemical (PEC) properties of the films are characterized and optimized by controlling the film thickness. Moreover, the PEC properties of the BFO films are dependent on ferroelectric polarization, which is mainly ascribed to the modulation of band structure at the BFO/electrolyte interface by the polarization. Further enhancement of PEC properties is obtained by decorating the samples with appropriate amounts of Ag nanoparticles, which is attributed to the reduced electron-hole recombination, and localized surface plasmon resonance effect of Ag nanoparticles.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Photophysics of α-furil at room temperature and 77 K: Spectroscopic and quantum chemical studies

Steady state and time resolved spectroscopic measurements have been exploited to assign the emissions from different conformations of α-furil (2, 2′-furil) in solution phase at room temperature as well as cryogen (liquid nitrogen, LN{sub 2}) frozen matrices of ethanol and methylcyclohexane. Room temperature studies reveal a single fluorescence from the trans-planar conformer of the fluorophore or two fluorescence bands coming from the trans-planar and the relaxed skew forms depending on excitation at the nπ{sup ∗} or the ππ{sup ∗} absorption band, respectively. Together with the fluorescence bands, the LN{sub 2} studies in both the solvents unambiguously ascertain two phosphorescence emissions with lifetimes 5 ± 0.3 ms (trans-planar triplet) and 81 ± 3 ms (relaxed skew triplet). Quantum chemical calculations have been performed using density functional theory at CAM-B3LYP/6-311++G{sup ∗∗} level to prop up the spectroscopic surveillance. The simulated potential energy curves (PECs) illustrate that α-furil is capable of giving two emissions from each of the S{sub 1} and the T{sub 1} states—one corresponding to the trans-planar and the other to the relaxed skew conformation. Contrary to the other 1,2-dicarbonyl molecular systems like benzil and α-naphthil, α-furil does not exhibit any fluorescence from its second excited singlet (S{sub 2}) state. This is ascribed to the proximity of the minimum of the PEC of the S{sub 2} state and the hill-top of the PEC of the S{sub 1} state.

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

On the design and performance of InGaN/Si double-junction photocathodes

Via a combined theoretical and experimental study, we have investigated the synthesis and performance characteristics of InGaN/Si double-junction photoelectrochemical (PEC) water splitting devices, which promise a theoretical solar-to-hydrogen conversion efficiency ~30% under AM 1.5G one-sun illumination. The double-junction photocathodes consist of a p + -InGaN top light absorber and a Si bottom p-n junction, which are connected through a nanowire tunnel junction. The effect of indium composition of the top light absorber as well as the impact of p-type Mg dopant incorporation on the PEC performance was studied. Experimentally, the sample with 32% indium composition showed a maximum photocurrent density of ~9 mA/cm 2 at 0.4 mV vs reverse hydrogen electrode (RHE) with applied bias photon-to-current efficiency (ABPE) of ~9.5%. An optimum p-type doping level ~1 × 10 17 cm -3 was also identified, which results in the best device performance as a result of optimum surface band bending as well as vertical charge carrier (hole) transport. These results also show a good agreement with our theoretical analysis. This work provides significant insights in advancing the design and development of high efficiency PEC devices for artificial photosynthesis using industry ready materials, e.g., Si and GaN, to achieve large-scale, low-cost onsite hydrogen fuel production.

42 ENGINEERING↗
DOE OSTI2021

A perspective on ordered vacancy compound and parent chalcopyrite thin film absorbers for photoelectrochemical water splitting

Chalcopyrites could fill the gap between the low-cost, poor-efficiency single junction metal oxide photoelectrochemical (PEC) water splitting cells and the high efficiency, yet costly III–V tandems. In this Perspective, we first review the key barriers that must be addressed by the community to enable economical chalcopyrite-based PEC water splitting. Then, we highlight how theoretical modeling can be used to identify promising ordered vacancy compound absorbers with improved energetics compared to their chalcopyrite parents. Finally, we describe how advanced spectroscopic analysis performed on chalcopyrite photocathodes after PEC testing uncovered a new passivation layer candidate for prolonged durability.

08 HYDROGEN↗