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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Modulating Charge Transfer Efficiency of Hematite Photoanode with Hybrid Dual‐Metal–Organic Frameworks for Boosting Photoelectrochemical Water Oxidation

Abstract The glorious charge transfer efficiency of photoanode is an important factor for efficient photoelectrochemical (PEC) water oxidation. However, it is often limited by slow kinetics of oxygen evolution reaction. Herein, a dual transition metal‐based metal–organic frameworks (MOF) cocatalyst, Fe@Ni–MOF, is introduced into a titanium‐doped hematite (Fe 2 O 3 :Ti) photoanode. The combination of Ni and Fe can optimize the filling of 3d orbitals. Moreover, the introduction of Fe donates electrons to Ni in the MOF structure, thus, suppressing the irreversible (long‐life‐time) oxidation of Ni 2+ into Ni 3+ . The resulting Fe@Ni–MOF/Fe 2 O 3 :Ti photoanode exhibits ∼threefold enhancement in the photocurrent density at 1.23 V versus the reversible hydrogen electrode. Kinetic analysis of the PEC water oxidation processes indicates that this performance improvement is primarily due to modulating the charge transfer efficiency of hematite photoanode. Further results show that a single transition metal‐based MOF cocatalyst, Ni–MOF, exhibits slow charge transfer in spite of a reduction in surface charge recombination, resulting in a smaller charge transfer efficiency. These findings provide new insights for the development of photoelectrodes decorated with MOFs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

3D Printing of Aqueous Two-Phase Systems with Linear and Bottlebrush Polyelectrolytes

In this study, we formed core–shell-like polyelectrolyte complexes (PECs) from an anionic bottlebrush polymer with poly (acrylic acid) side chains with a cationic linear poly (allylamine hydrochloride). By varying the pH, the number of side chains of the polyanionic BB polymers (Nbb), the charge density of the polyelectrolytes, and the salt concentration, the phase separation behavior and salt resistance of the complexes could be tuned by the conformation of the BBs. By combining the linear/bottlebrush polyelectrolyte complexation with all-liquid 3D printing, flow-through tubular constructs were produced that showed selective transport across the PEC membrane comprising the walls of the tubules. These tubular constructs afford a new platform for flow-through delivery systems.

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

Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO-Mediated Oxidation of 5-Hydroxymethylfurfural

Motivated by replacing the kinetically unfavorable oxygen evolution reaction (OER) and producing value-added products in photoelectrochemical cells (PECs), we report that bismuth vanadate (BiVO 4 ) photoelectrodes modified with a cobalt phosphate (CoPi) overlayer facilitate 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated selective oxidation of 5-hydroxymethylfurfural (HMF). CoPi layers with sufficient thickness were found to reduce the potential required for TEMPO oxidation by 0.5 V, as well as increase charge injection efficiency sevenfold compared to BiVO 4 without CoPi. Furthermore, the undesired OER was completely suppressed when using the heterostructured photoanodes. Transient photocurrent measurements suggested that CoPi alleviates recombination losses resulting from the back reduction of oxidized TEMPO. The PECs with BiVO 4 /CoPi bilayer achieved 88 % yield to 2,5-furandicarboxylic acid (FDCA) from HMF oxidation under mild conditions, whereas <1 % FDCA was generated with BiVO 4 . In conclusion, these findings suggest that suppression of the back reduction process substantially improves the efficiency of the oxidation, giving a potential route to more efficient solar fuel/chemical production.

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

Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory

Here, we provide a theory to quantify the ionic current (i ion ) in nanochannels grafted with pH-responsive polyelectrolyte (PE) brushes. We consider the PE brushes to be modelled by our recently proposed augmented strong stretching theory (SST) model that improves the existing SST models by incorporating the effects of excluded volume interactions and an extended mass action law. Use of such augmented SST for this problem implies that this is the first study on computing i ion in PE-brush-grafted nanochannels accounting for the appropriate coupled con guration-electrostatic description of the PE brushes. i ion is obtained as functions of PE brush grafting density, medium pH and salt concentration (c ∞ ), and the density of polyelectrolyte chargeable sites (PECS). For large c ∞ , i ion increases linearly with c ∞ (as for such c ∞ , i ion becomes independent of the PE charge and is dominated by the bulk mobility and number density of the electrolyte ions), while iion is independent of c ∞ at small c ∞ (where the EDL electrostatics and the total number of ions in the system is dominated by the hydrogen ions). We further witness an enhancement of i ion for smaller pH and larger grafting density at low and moderate c ∞ , while there is little to no effect of the PECS density on the ionic current except for weakly grafted brushes at low c ∞ . We believe that this study will serve as a theoretical foundation for a large number of applications that are based on the brush-induced modification of the ionic current in a nanochannel.

42 ENGINEERING↗
DOE OSTI2019

Highly Ordered N-Doped Carbon Dots Photosensitizer on Metal–Organic Framework-Decorated ZnO Nanotubes for Improved Photoelectrochemical Water Splitting

In spite of having several advantages such as low cost, high chemical stability, and environmentally safe and benign synthetic as well as operational procedures, the full potential of carbon dots (CDs) are yet to be explored as photosensitizers due to the challenges associated with the fabrication of well-arrayed CDs with any other photocatalytic heterostructures. In the present study, a unique combination of Metal-organic frameworks (MOFs) decorated Zinc Oxide (ZnO) one-dimensional (1D) nanostructures as host and CDs as guest species have been explored on account of its potential applications in photoelectrochemical (PEC) water splitting performance. Our synthetic strategy to incorporate well-defined nitrogen-doped carbon dots (N-CDs) array onto zeolitic imidazolate framework-8 (ZIF-8) anchored on ZnO 1D nanostructures allows a facile unification of different components which subsequently plays a decisive role in improving the material’s PEC water splitting performance. Simple extension of such strategies is expected to offer significant advantages for the preparation of CDs-based heterostructures for photo(electro)catalytic and other related applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Optical, Structural and Photo Electrochemical Properties of Cd1-xZnxS Films Grown by Chemical Bath Deposition

Cd1-xZnxS (0 = x = 0.5) films were fabricated by chemical bath deposition method and characterized by grazing incidence X-ray diffraction (GIXRD), scanning electron microscopy (SEM), UV-visible spectroscopy and photoelectrochemical (PEC) cell. The flat band potential value was found to be tunable from -441 to -664 mV with increasing Zn2+ concentration in the reaction solution. GIXRD results indicate that the fabricated Cd1-xZnxS are hexagonally oriented and Zn2+ is successfully introduced into CdS. SEM results indicate that high Zn2+ doping concentration can form flake-like Cd1-xZnxS morphology. Furthermore, Zn2+ incorporation to the CdS was found to enhance the optical absorbing capability of CdS in visible region. The optical band gap was found to vary as the composition parameter changed from x = 0.0 to x = 0.5 in the reaction solution. The PEC cell results indicate that the Cd1-xZnxS thin films with x > 0.3 in the bath show the pinning of the Fermi level and cause VOC to decrease.

Chemical Bath Disposition, CBD, doping, thin film↗
DOE OSTI2016

In situ neutron scattering study of nanostructured PbTe-PbS bulk thermoelectric material

Nanostructures play an important role in thermoelectric materials. Their thermal stability, such as phase change and evolution at elevated temperatures, is thus of great interest to the thermoelectric community. In this study, in situ neutron diffraction was used to examine the phase evolution of nanostructured bulk PbTe-PbS materials fabricated using hot pressing and pulsed electrical current sintering (PECS). The PbS second phase was observed in all samples in the as-pressed condition. The temperature dependent lattice parameter and phase composition data show an initial formation of PbS precipitates followed by a redissolution during heating. The redissolution process started around 570 600 K, and completed at approximately 780 K. During cooling, the PECS sample followed a reversible curve while the heating/cooling behavior of the hot pressed sample was irreversible.

high temperature↗
DOE OSTI2012

Influence of Gas Flow Rate for Formation of Aligned Nanorods in ZnO Thin Films for Solar-Driven Hydrogen Production

ZnO thin films have been deposited in mixed Ar/N{sub 2} gas ambient at substrate temperature of 500 C by radiofrequency sputtering of ZnO targets. We find that an optimum N{sub 2}-to-Ar ratio in the deposition ambient promotes the formation of well-aligned nanorods. ZnO thin films grown in ambient with 25% N{sub 2} gas flow rate promoted nanorods aligned along c-axis and exhibit significantly enhanced photoelectrochemical (PEC) response, compared with ZnO thin films grown in an ambient with different N{sub 2}-to-Ar gas flow ratios. Our results suggest that chamber ambient is critical for the formation of aligned nanostructures, which offer potential advantages for improving the efficiency of PEC water splitting for H{sub 2} production.

14 SOLAR ENERGY↗
DOE OSTI2015

Approach on environmental risk assessment of nanosilver released from textiles

Based on the increased utilization of nanosilver (silver nanomaterials=AgNM) as antibacterial agent, there is the strong need to assess the potential environmental implication associated with its new application areas. In this study an exemplary environmental risk assessment (ERA) of AgNM applied in textiles was performed. Environmental exposure scenarios (via municipal sewage treatment plant (STP)) with wastewater supply from domestic homes) were developed for three different types of textiles equipped with AgNM. Based on these scenarios predicted environmental concentrations (PECs) were deduced for STPs and for the environmental compartments surface water, sediment as well as soil. These PECs were related to PNECs (predicted no effect concentrations). PNECs were deduced from results of ecotoxicity tests of a selected AgNM (NM-300K). Data on ecotoxicology were derived from various tests with activated sludge, cyanobacteria, algae, daphnids, fish, duckweed, macrophytes, chironomids, earthworms, terrestrial plants as well as soil microorganisms. Emission data for the AgNM NM-300K from textiles were derived from washing experiments. The performed ERA was based on the specifications defined in the ECHA Guidances on information requirements and chemical safety assessment. Based on the chosen scenarios and preconditions, no environmental risk of the AgNM NM-300K released from textiles was detected. Under conservative assumptions a risk quotient for surface water close to 1 indicated that the aquatic compartment may be affected by an increased emission of AgNM to the environment due to the high sensitivity of aquatic organisms to silver. Based on the successful retention of AgNM in the sewage sludge and the still ongoing continual application of sewage sludge on farmland it is recommended to introduce a threshold for total silver content in sewage sludge into the respective regulations. Regarding potential risk mitigation measures, it is emphasized to preferably directly introduce AgNM into the textile fiber since this will strongly minimize the release of AgNM during washing. If this is not possible due to technical limitations or other reasons, the introduction of a threshold level controlling the release of AgNM from textiles is suggested. It has to be noted that this study is a case study which is only valid for the investigated NM-300K and its potential application in textiles. - Highlights: • Washing: release rates of AgNM depend on furnishing in textiles. • Calculated PNECs for the aquatic compartment were low. • For the chosen scenarios no environmental risk of AgNM from textiles was observed. • AgNM is retained in sewage sludge. • In WWTP most of the silver adsorbs to sewage sludge and thus, may reach farmland.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Thyroid antagonists and thyroid indicators in U.S. pregnant women in the Vanguard Study of the National Children's Study

The sodium iodide-symporter (NIS) mediates uptake of iodide into thyroid follicular cells. This key step in thyroid hormone synthesis is inhibited by perchlorate, thiocyanate (SCN) and nitrate (NO{sub 3}) anions. When these exposures occur during pregnancy the resulting decreases in thyroid hormones may adversely affect neurodevelopment of the human fetus. Our objectives were to describe and examine the relationship of these anions to the serum thyroid indicators, thyroid stimulating hormone (TSH) and free thyroxine (FT4), in third trimester women from the initial Vanguard Study of the National Children's Study (NCS); and to compare urine perchlorate results with those in pregnant women from the National Health and Nutritional Examination Survey (NHANES). Urinary perchlorate, SCN, NO{sub 3}, and iodine, serum TSH, FT4, and cotinine were measured and a food frequency questionnaire (FFQ) was administered to pregnant women enrolled in the initial Vanguard Study. We used multiple regression models of FT4 and TSH that included perchlorate equivalent concentration (PEC, which estimates combined inhibitory effects of the anions perchlorate, SCN, and NO{sub 3} on the NIS). We used multiple regression to model predictors of each urinary anion, using FFQ results, drinking water source, season of year, smoking status, and demographic characteristics. Descriptive statistics were calculated for pregnant women in NHANES 2001–2012. The geometric mean (GM) for urinary perchlorate was 4.04 µg/L, for TSH 1.46 mIU/L, and the arithmetic mean for FT4 1.11 ng/dL in 359 NCS women. In 330 women with completed FFQs, consumption of leafy greens, winter season, and Hispanic ethnicity were significant predictors of higher urinary perchlorate, which differed significantly by study site and primary drinking water source, and bottled water was associated with higher urinary perchlorate compared to filtered tap water. Leafy greens consumption was associated with higher urinary NO{sub 3} and higher urinary SCN. There was no association between urinary perchlorate or PEC and TSH or FT4, even for women with urinary iodine <100 µg/L. GM urinary perchlorate concentrations in the full sample (n=494) of third trimester NCS women (4.03 µg/L) were similar to pregnant women in NHANES (3.58 µg/L). - Highlights: • Limited biomonitoring data are available in pregnant women. • We found no effect of perchlorate and related anions on thyroid indicators in third trimester women. • Leafy green vegetables were a dietary source for perchlorate, nitrate, and thiocyanate.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Effect of micro-fin tube geometry parameters on evaporator material savings

A Performance Evaluation Criteria (PEC) analysis is presented that explores the influence of the micro-fin tube geometry on the required material volume. The analysis was done using a local flow boiling model, which can quantify the effect of fin parameters and the tube diameter. The PEC was done while requiring that the compared surfaces satisfy the same heat duty and pressure drop. The following tube parameters and ranges were explored: tube diameter (3 mm ≤ D o ≤ 6 mm), fin base thickness (0.12 mm ≤ t bf ≤ 0.29 mm), helix angle (6° ≤ α ≤ 30°), fin apex angle (11° ≤ β ≤ 22°), total number of fins (43 ≤ n f ≤ 70), and the fin height (0.11 mm ≤ e ≤ 0.3 mm). The tube that provided the smallest material requirements within the examined parameter ranges had: D o = 3 mm, t bf = 0.12 mm, α = 6°, β = 11°, n f = 43, and e = 0.3 mm. In general, small D o and t bf and large n f and e provided the best performance and work to minimize the required material volume to provide a given heat duty and pressure drop. The helix and the fin-tip apex angles were found to have very little influence on the performance for the examined range of parameters and angles associated with the lowest production cost should be chosen.

Evaporation↗
DOE OSTI2011

Preparation of Pt deposited nanotubular TiO{sub 2} as cathodes for enhanced photoelectrochemical hydrogen production using seawater electrolytes

The purpose of this study was to develop effective cathodes to increase the production of hydrogen and use the seawater, an abundant resource in the earth as the electrolyte in photoelectrochemical systems. In order to fabricate the Pt/TiO{sub 2} cathodes, various contents of the Pt precursor (0-0.4 wt%) deposited by the electrodeposition method were used. On the basis of the hydrogen evolution rate, 0.2 wt% Pt/TiO{sub 2} was observed to exhibit the best performance among the various Pt/TiO{sub 2} cathodes with the natural seawater and two concentrated seawater electrolytes obtained from single (nanofiltration) and combined membrane (nanofiltration and reverse osmosis) processes. The surface characterizations exhibited that crystal structures and morphological properties of Pt and TiO{sub 2} found the results of XRD pattern and SEM/TEM images, respectively. - Graphical abstract: On the basis of photoelectrochemical hydrogen production, 0.2 wt% Pt/TiO{sub 2} was observed to exhibit the best performance among the various Pt/TIO{sub 2} cathodes with natural seawater. In comparison of hydrogen evolution rate with various seawater electrolytes, 0.2 wt% Pt/TiO{sub 2} was found to show the better performance as cathode with the concentrated seawater electrolytes obtained from membrane. Highlights: > Pt deposited TiO{sub 2} electrodes are used as cathode in PEC H{sub 2} production. > Natural and concentrated seawater by membranes are used as electrolytes in PEC. > Pt/TiO{sub 2} shows a good performance as cathode with seawater electrolytes. > H{sub 2} evolution rate increases with more concentrated seawater electrolyte. > Highly saline seawater is useful resource for H{sub 2} production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nanocrystalline immobilised ZnO photocatalyst for degradation of benzoic acid and methyl blue dye

Highlights: • ZnO thin films were successfully prepared with the help of chemical spray pyrolysis technique. • Study the effect of thickness variation(solution quantity) onto the various properties of film. • Film prepared at 1.65 μm thickness showsthe maximum photoelectrochemical performance in 0.1 M NaOH electrolyte. • The flat band potential of optimized ZnO thin film is –0.86 V/SCE. • Study degradation result of benzoic acidand methyl blue dye using ZnO photoelectrode under UV light illumination. - Abstract: ZnO thin films were deposited with different solution quantities using spray pyrolysis technique. The effect of thickness variations on photoelectrochemical (PEC), structural, morphological and optical properties are studied. PEC measurements showed maximum photo response about I{sub sc} = 0.485 mA and V{sub oc} = 632 mV at 1.65 μm film thickness. X-ray diffraction study confirms that the films are polycrystalline with hexagonal crystal structure. Hexagonal shaped grains are observed conformed from surface morphology. The estimated bandgap energy of ZnO films are varies between 3.23 to 3.29 eV. Finally large area (10 × 10 cm{sup 2}) deposited ZnO photoelectrode were used to study the photocatalytic and photoelectrocatalytic degradation of benzoic acid (BA) and methyl blue (MB) dye under UV radiation. Photoelectrocatalytic degradation result shows 65.7% degradation of BA and for colorant organic compound such as MB dye is about 98.1% is possible. The mineralization of pollutants are studied by measuring chemical oxygen demand (COD) values.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Broad Distribution of Local Polar States Generates Large Electrothermal Properties in Pb-Free Relaxor Ferroelectrics

Electrothermal energy conversion provides attractive solutions for global energy management, such as energy harvesting from waste heat using pyroelectric energy conversion (PEC) and efficient cooling of portable electronics or data servers using the electrocaloric effect. Relaxor ferroelectrics are attractive for electrothermal energy conversion because of their large pyroelectric coefficients over a wide temperature range. Although Pb-based relaxors are well-known, toxicity concerns have mandated the intense search for Pb-free alternatives. Here, we engineered (Ba,Ca)TiO 3 -based relaxors based on a multisite doping strategy, which show promising electrothermal performance, viz. a maximum PEC efficiency of 14% and electrocaloric refrigeration capacity of 115 J/kg. Using local-scale structural analysis, we provide an atomistic model for large electrothermal properties in the newly designed Pb-free ferroelectrics, whereby a temperature-independent continuous distribution of cation displacement directions creates easy pathways for microscopic polarization reorientation. This research provides key structural insight for future atomic-scale engineering of environmentally sustainable ferroelectrics in energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Semi Transparent Three-Dimensional Macroporous Quaternary Oxynitride Photoanodes for Photoelectrochemical Water Oxidation

Semi transparent three-dimensional macroporous (3DM) photoanodes based on quaternary oxynitrides have the potential to simultaneously realize superior light harvesting and efficient charge transfer in a tandem photoelectrochemical (PEC) cell. A 3DM CaTaO 2 N photoanode was prepared for the first time on a GaN/Al 2 O 3 substrate via a chemical route, and it exhibits a high transmittance of >60% in the wide solar spectrum and a photoresponse onset at −0.3 V versus the reversible hydrogen electrode (V RHE ) under simulated solar illumination. In particular, a plateau photocurrent density of 0.21 mA cm –2 was achieved at a low potential of 0.4 V RHE , which was 1.6-fold and more than 50-fold higher than a two-dimensional macroporous (2DM) CaTaO 2 N/GaN/Al 2 O 3 photoanode and a conventional particle-based CaTaO 2 N/GaN/Al 2 O 3 photoanode, respectively. The bicontinuous, interconnected pore structure within this 3DM film can improve charge carrier separation and collection by reducing the average diffusion distance for minority carriers toward the electrolyte. Optical measurements and simulations verified the enhanced sunlight harvesting in the 3DM photoanode, which was ascribed to the concentrated distribution of the electric field and multiple scattering. Furthermore, this study provides guidance for future synthesis of highly efficient semitransparent 3DM quaternary oxynitride-based photoanodes for a tandem PEC device.

Layers↗
DOE OSTI2024

Properties of NoO and YbO

Bond dissociation energies (BDEs) and spectroscopic parameters for the ground states of YbO and NoO were calculated at the Brueckner doubles (BD(T)) level and for NoO at the coupled cluster CCSD(T) level based on the closed-shell configurations Yb 2+ (4f 14 )O 2 – (2p 6 ) and No 2+ (5f 14 )O 2 – (2p 6 ). For YbO, the BD(T) BDE (3.93 eV) and vibrational frequency (686.3 cm –1 ) are consistent with the experiment; the BD(T) bond distance was 1.8492 Å, about 0.04 Å longer than the experiment. For NoO, the calculated BDEs are 3.07 eV (BD(T)) and 3.08 eV (CCSD(T)) and are expected to be good to ±3 kcal/mol (±0.13 eV). Potential energy curves (PECs) for the spin–orbit (Ω) states associated with the f 13 s 1 configurations of YbO and NoO were calculated at the SA-CASSCF/SO-CASPT2/aQ-DK level. PECs considering both the f 13 s 1 and f 14 configurations were calculated at this level, as the ground states are expected to contain both configurations. Due to a bias in the SA-CASSCF to the f 13 s 1 configurations, the f 14 configurations could not be properly described simultaneously with the f 13 s 1 ones. Finally, the natural population analysis based on the natural bond orbitals shows that YbO and NoO are quite ionic, with 5d orbitals being more important in YbO than the 6d orbitals in NoO.

basis sets↗
DOE OSTI2025

Redox Couples Control Band Bending, Photovoltage, and Quasi-Fermi Levels in Tungsten Oxide (WO 3 ) Photoanodes

Tungsten oxide (WO 3 ) is a well-known photoanode and photocatalyst for photoelectrochemical (PEC) water oxidation. Because the compound has a deep valence band, it can facilitate the oxygen evolution reaction without added cocatalysts, and it can drive the oxidation of species with much higher electrochemical potentials, including the conversion of water to hydrogen peroxide, sulfate to persulfate, and iodate to meta-periodate. Here, we use the liquid vibrating Kelvin probe surface photovoltage (liquid VK-SPV) technique in combination with open circuit potential (OCP) and photoelectrochemical (PEC) scans to assess the possibility of reaching such oxidizing potentials in aqueous electrolytes and at open circuit. Here, this is done by mapping the quasi-Fermi levels of electrons and holes at the interfaces as a function of the light intensity. Nanostructured WO 3 photoelectrodes for this purpose were fabricated by thermal annealing of a tungstic acid solution on fluorine-doped tin oxide. Electrochemical measurements are conducted at open circuit and 400 nm LED light illumination in electrolytes containing fast (O 2 /H 2 O 2 ), slow (O 2 /H 2 O), and very oxidizing (NaIO 4 /NaIO 3 ) redox couples. Photovoltage values scale with the light intensity and with the built-in potential for each redox couple and reach values up to 0.61 V under 20 mW cm –2 illumination for the NaIO 4 electrolyte. This shows that the photoelectrodes behave like Schottky-type diodes whose maximum possible energy output is determined mainly by the built-in voltage of each junction. For slow redox couples, the quasi-Fermi level of the holes increases with light intensity due to hole accumulation at the WO 3 –liquid interface. For example, for the O 2 /H 2 O electrolyte, interfacial hole accumulation and removal occur on the 90–300 s time scale. For the fast hole acceptor H 2 O 2 , on the other hand, the quasi-Fermi level of the photoholes is pinned to the electrochemical potential of the O 2 /H 2 O 2 couple. This limits the energy conversion efficiency of the electrode. Overall, these results reveal the influence of charge transfer thermodynamics and kinetics on the photovoltage of WO 3 . Furthermore, the work further establishes VK-SPV as a contactless method to observe the photovoltage, carrier dynamics, and quasi-Fermi levels of semiconductor-liquid junctions.

Electrodes↗
DOE OSTI2020

Effects of Non-Electrostatic Intermolecular Interactions on the Phase Behavior of pH-Sensitive Polyelectrolyte Complexes

Polyelectrolyte complexes (PECs) offer enormous material tunability and desirable functionalities, and consequently have found broad utility in biomedical and material industries. While poly(acrylic acid) (PAA) and poly( allylamine hydrochloride) (PAH) are a commonly used pairing, various aspects of the phase behavior of PAA-PAH complexes have not been sufficiently quantified. In this work, we present a comprehensive experimental study depicting the binodal phase boundaries for the PAA-PAH complexes prepared under acidic, neutral, and basic conditions using thermogravimetric analysis, turbidimetry, and optical microscopy. Under neutral and basic conditions, phase behaviors of the complexes were largely similar to one another and followed general expectations of PEC phase behavior, except for unusually high resistance to disruption of the complex with added salt. Stable complexes are observed up to 4 M NaCl concentrations. Under acidic conditions, strikingly different phase behaviors of the PAA-PAH complexes were observed. The polymer content in the complex phase increased initially, followed by an expected decrease as salt was added to the complexes. This behavior may result from a combination of associative phase separation of PAA and PAH chains, influenced by electrostatic interactions, and segregative phase separation, which can be ascribed to the influence of a combination of the hydrophobic interactions of the aliphatic polymer backbone and the interpolymer hydrogen bonding of unionized acrylic monomer units. Our systematic investigations over a range of pH detailing these discrepancies in the PAA-PAH phase behavior are expected to clarify the inconsistencies among the reports in the literature and provide the material design strategies for practical use of the PAA-PAH complexes and multilayer assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗