Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “PEC”

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

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

At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Prediction of Feasibility of Polaronic OER on (110) Surface of Rutile TiO 2

The polaronic effects at the atomic level hold paramount significance for advancing the efficacy of transition metal oxides in applications pertinent to renewable energy. The lattice–distortion mediated localization of photoexcited carriers in the form of polarons plays a pivotal role in the photocatalysis. This investigation focuses on rutile TiO 2 , an important material extensively explored for solar energy conversion in artificial photosynthesis, specifically targeting the generation of green H 2 through photoelectrochemical (PEC) H 2 O splitting. By employing Hubbard-U corrected and hybrid density functional theory (DFT) methods, we systematically probe the polaronic effects in the catalysis of oxygen evolution reaction (OER) on the (110) surface of rutile TiO 2 . Theoretical understanding of polarons within the surface, coupled with simulations of OER at distinct titanium (Ti) and oxygen (O) active sites, reveals diverse polaron formation energies within the lattice sites with strong preference for bulk and surface bridge (O b ) oxygen sites. Moreover, we provide the evidence for the facilitative role of polarons in OER. Here, we find that hole polarons situated at the equatorial oxygen sites near the Ti–active site, along with bridge site hole polarons distal from the O b active site yield a small reduction in OER overpotential by ~0.06 eV and ~0.12 eV, respectively. However, subsurface, equatorial, and bridge site hole polarons significantly reduce the Ti-active site OER overpotential by ~0.4 eV through the peroxo–type oxygen pathway. We also observe that the presence of hole polarons stabilizes the *OH, *O, and *OOH intermediate species compared to the scenario without hole polarons. Overall, this study provides a detailed mechanistic insight into polaron–mediated OER, offering a promising avenue for improving the catalytic activity of transition metal oxide-based photocatalysts catering to renewable energy requisites.

14 SOLAR ENERGY↗
DOE OSTI2017

Atomically Altered Hematite for Highly Efficient Perovskite Tandem Water‐Splitting Devices

Abstract Photoelectrochemical (PEC) cells are attractive for storing solar energy in chemical bonds through cleaving of water into oxygen and hydrogen. Although hematite (α‐Fe 2 O 3 ) is a promising photoanode material owing to its chemical stability, suitable band gap, low cost, and environmental friendliness, its performance is limited by short carrier lifetimes, poor conductivity, and sluggish kinetics leading to low (solar‐to‐hydrogen) STH efficiency. Herein, we combine solution‐based hydrothermal growth and a post‐growth surface exposure through atomic layer deposition (ALD) to show a dramatic enhancement of the efficiency for water photolysis. These modified photoanodes show a high photocurrent of 3.12 mA cm −2 at 1.23 V versus RHE, (>5 times higher than Fe 2 O 3 ) and a plateau photocurrent of 4.5 mA cm −2 at 1.5 V versus RHE. We demonstrate that these photoanodes in tandem with a CH 3 NH 3 PbI 3 perovskite solar cell achieves overall unassisted water splitting with an STH conversion efficiency of 3.4 %, constituting a new benchmark for hematite‐based tandem systems.

Gurudayal↗
DOE OSTI2024

Ab initio exploration of low–lying electronic states of linear and bent MNX + (M = Ca, Sr, Ba, Ra; X = O, S, Se, Te, Po) and their origins

High-level multireference and coupled cluster quantum calculations were employed to analyze low-lying electronic states of linear-MNX + and side-bonded-M[NX] + (M = Ca, Sr, Ba, Ra; X = O, S, Se, Te, Po) species. Their full potential energy curves (PECs), dissociation energies (D e s), geometric parameters, excitation energies (T e s), and harmonic vibrational frequencies (ω e s) are reported. The first three chemically bound electronic states of MNX + and M[NX] + are 3 Σ – , 1 Δ, 1 Σ + and 3 A", 1 A', 1 A", respectively. The 3 Σ – , 1 Δ, 1 Σ + of MNX + originate from the M + ( 2 D) + NX( 2 Π) fragments, whereas the 3 A", 1 A', 1A" states of M[NX] + dissociate to M + ( 2 S) + NX( 2 Π) as a result of avoided crossings. The MNX + and M[NX] + are real minima on the potential energy surface and their interconversions are possible. The M 2+ NX – /M 2+ [NX] – ionic structure is an accurate representation for their low-lying electronic states. The D e s of MNX + species were found to depend on the dipole moment (μ) of the corresponding NX ligands and a linear relationship between these two parameters was observed.

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

Structure and properties of bottlebrush polyelectrolyte complexes

Abstract Structural variation of polyelectrolytes has been shown to play an important role in altering polyelectrolyte complex (PEC) properties in recent years. However, molecular‐level details such as polyelectrolyte architecture remain underdeveloped. Here, we use a combination of ring‐opening metathesis polymerization (ROMP), atom‐transfer radical polymerization (ATRP), and postpolymerization reactions to create densely branched bottlebrushes of poly(dimethylamino ethyl methcacrylate) and poly(tert‐butyl methacrylate) with high molecular weights (MDa), which we then convert into fully charged and densely branched bottlebrushes of poly(trimethylaminoethyl methacrylate) (PTMAEMA) and poly(methacrylic acid) (PAA). We investigate the structure and properties of bottlebrush polyelectrolyte complexes (BPECs) using optical microscopy, rheology, cryogenic transmission electron microscopy (Cryo‐TEM), and small‐angle X‐ray scattering (SAXS). Bottlebrush polyelectrolyte complexes are white solids, which exhibit gel‐like mechanical properties, which we attribute to sidechain interpenetration. Using a combination of Cryo‐TEM and SAXS, we are able to outline the structural development of BPECs, detailing how the network topology, sidechain conformation, and interdigitation spacing changes as a function of salt. Our results provide a foundation for further exploration of branched architectures within polyelectrolyte complexation.

Polymer Science↗
DOE OSTI2017

GaP/GaNP Heterojunctions for Efficient Solar‐Driven Water Oxidation

The growth and characterization of an n‐GaP/i‐GaNP/p + ‐GaP thin film heterojunction synthesized using a gas‐source molecular beam epitaxy (MBE) method, and its application for efficient solar‐driven water oxidation is reported. The TiO 2 /Ni passivated n‐GaP/i‐GaNP/p + ‐GaP thin film heterojunction provides much higher photoanodic performance in 1 m KOH solution than the TiO 2 /Ni‐coated n‐GaP substrate, leading to much lower onset potential and much higher photocurrent. There is a significant photoanodic potential shift of 764 mV at a photocurrent of 0.34 mA cm −2 , leading to an onset potential of ≈0.4 V versus reversible hydrogen electrode (RHE) at 0.34 mA cm −2 for the heterojunction. The photocurrent at the water oxidation potential (1.23 V vs RHE) is 1.46 and 7.26 mA cm −2 for the coated n‐GaP and n‐GaP/i‐GaNP/p + ‐GaP photoanodes, respectively. The passivated heterojunction offers a maximum applied bias photon‐to‐current efficiency (ABPE) of 1.9% while the ABPE of the coated n‐GaP sample is almost zero. Furthermore, the coated n‐GaP/i‐GaNP/p + ‐GaP heterojunction photoanode provides a broad absorption spectrum up to ≈620 nm with incident photon‐to‐current efficiencies (IPCEs) of over 40% from ≈400 to ≈560 nm. The high low‐bias performance and broad absorption of the wide‐bandgap GaP/GaNP heterojunctions render them as a promising photoanode material for tandem photoelectrochemical (PEC) cells to carry out overall solar water splitting.

Kargar, Alireza↗
DOE OSTI2014

Unimolecular and hydrolysis channels for the detachment of water from microsolvated alkaline earth dication (Mg2+, Ca2+, Sr2+, Ba2+) clusters

We examine theoretically the three channels that are associated with the detachment of a single water molecule from the aqueous clusters of the alkaline earth dications, [M(H2O)n]2+, M = Mg, Ca, Sr, Ba, n ≤ 6. These are the unimolecular water loss (M2+(H2O)n-1 + H2O) and the two hydrolysis channels resulting to the loss of hydronium ([MOH(H2O)n-2]+ + H3O+) and Zundel ([MOH(H2O)n-3]+ + H3O+(H2O)) cations. The Potential Energy Curves (PECs) corresponding to those three channels were constructed at the Møller-Plesset second order perturbation (MP2) level of theory with basis sets of double- and triple-ζ quality. We furthermore investigated the water and hydronium loss channels from the mono-hydroxide water clusters with up to four water molecules, [MOH(H2O)n]+, 1 ≤ n ≤ 4. Our results indicate the preference of the hydronium loss and possibly the Zundel cation loss channels for the smallest size clusters, whereas the unimolecular water loss channel is preferred for the larger ones as well as the mono-hydroxide clusters. Although the charge separation (hydronium and Zundel cation loss) channels produce more stable products when compared to the ones for the unimolecular water loss, they also require the surmounting of high energy barriers, a fact that makes the experimental observation of fragments related to these hydrolysis channels difficult.

Alkaline earth dication aqueous clusters↗
DOE OSTI2024

Performance evaluation of finned tube heat exchanger using curved wavy delta winglet vortex generators with circular perforations

Vortex generation is recognized as an effective passive approach to improve the heat transfer rate in fin and tube heat exchangers (FTHEs). The current study proposed innovative designs of curved wavy delta winglet vortex generators (CWDWVGs), both without and with circular perforations, to improve the heat transfer efficiency of FTHEs. There is potential to increase heat transfer performance further through various CWDWVG designs. Here, this study explores seven unique CWDWVG configurations, from 1-wave to 7-wave. A 3-D computational numerical model is utilized to evaluate the Thermo-hydraulic performance of FTHEs fitted with these different CWDWVG configurations across Reynolds numbers from 400 to 2000. This comparative analysis of the Thermo-hydraulic performance of FTHEs featuring four parallel circular tube layouts assesses configurations both with and without vortex generators (VGs) and various hole configurations. The evaluation of Thermo-hydraulic performance involves different parameters, including the London area goodness factor (LAGF), Colburn factor (j), friction factor (f), pressure drop (?P), and Nusselt number (Nu). Results demonstrate that the various CWDWVG configurations and the number of holes in them substantially affect the efficiency, as evaluated by the dimensionless Performance Evaluation Criteria (PEC). Notably, the 7-wave CWDWVGs surpassed other configurations, and integrating circular punched perforations further improved the thermal-hydraulic performance of FTHE. Specifically, the 7-wave CWDWVGs without holes demonstrated superior performance over other configurations, showing a significant increase in Nusselt number by 75.18% and 85.16% at Reynolds numbers of 2000 and 400, respectively, alongside an increase in pressure drop by 216.38% to 224.96%. Meanwhile, the 7-wave CWDWVGs with eight holes, in comparison to those without holes, exhibited a Nusselt number increase of 0.85%, a pressure drop decrease of 7.31%, and a reduction in the friction factor by 5.82%.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2017

A boundary integral method for numerical computation of radar cross section of 3D targets using hybrid BEM/FEM with edge elements

This contribution presents the boundary integral formulation for numerical computation of time-harmonic radar cross section for 3D targets. Method relies on hybrid edge element BEM/FEM to compute near field edge element coefficients that are associated with near electric and magnetic fields at the boundary of the computational domain. Special boundary integral formulation is presented that computes radar cross section directly from these edge element coefficients. Consequently, there is no need for near-to-far field transformation (NTFFT) which is common step in RCS computations. By the end of the paper it is demonstrated that the formulation yields accurate results for canonical models such as spheres, cubes, cones and pyramids. Method has demonstrated accuracy even in the case of dielectrically coated PEC sphere at interior resonance frequency which is common problem for computational electromagnetic codes. - Graphical abstract: - Highlights: • Hybrid edge element BEM/FEM is used to find edge element coefficients. • New formulation for RCS computation directly from edge element coefficients is presented. • Formulation is tested on canonical cases and on coated dielectric sphere at interior resonance frequency.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Memory-optimized shift operator alternating direction implicit finite difference time domain method for plasma

Through introducing the alternating direction implicit (ADI) technique and the memory-optimized algorithm to the shift operator (SO) finite difference time domain (FDTD) method, the memory-optimized SO-ADI FDTD for nonmagnetized collisional plasma is proposed and the corresponding formulae of the proposed method for programming are deduced. In order to further the computational efficiency, the iteration method rather than Gauss elimination method is employed to solve the equation set in the derivation of the formulae. Complicated transformations and convolutions are avoided in the proposed method compared with the Z transforms (ZT) ADI FDTD method and the piecewise linear JE recursive convolution (PLJERC) ADI FDTD method. The numerical dispersion of the SO-ADI FDTD method with different plasma frequencies and electron collision frequencies is analyzed and the appropriate ratio of grid size to the minimum wavelength is given. The accuracy of the proposed method is validated by the reflection coefficient test on a nonmagnetized collisional plasma sheet. The testing results show that the proposed method is advantageous for improving computational efficiency and saving computer memory. The reflection coefficient of a perfect electric conductor (PEC) sheet covered by multilayer plasma and the RCS of the objects coated by plasma are calculated by the proposed method and the simulation results are analyzed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Toward sustainable electrochemically mediated separations driven by renewable energy

Environmental pollution, water scarcity, resource shortage, and fossil fuel reliance have all represented threats to a sustainable future. Separation processes play a pivotal role in improving sustainability in fields such as industrial processes, resource recycling, wastewater treatment, and water desalination, among others. Electrochemical systems have gained increased attention as effective separation platforms, not only in performance but also as a potentially energy-efficient approach. However, the reliance on non-renewable energy sources, such as fossil fuels, for electricity generation limits the advancement toward a fully sustainable separation process. Integration of separation processes with eco-friendly renewable energy sources can increase overall sustainability and decrease carbon footprint. Here, in this review, we provide an overview of electrochemical separations and recent efforts to integrate them with renewable energy sources such as heat and solar energy. We discuss electrochemical separations, including electrosorption and electrodialysis, and research to transition these processes to thermoelectrochemical (TEC) and photoelectrochemical (PEC) platforms. Finally, we discuss current challenges and future prospects in direct integration of renewable energy sources with separation processes.

electrochemistry↗
DOE OSTI2014

Synthesis and characterization of Cr-doped ZnO nanorod-array photocatalysts with improved activity

Immobilized photocatalysts with high catalytic activity under UV light were prepared by growing Cr-doped ZnO nanorods on glass substrates by a hydrothermal method. The effects of Cr dopant on the surface texture, crystallinity, surface chemistry, and photoinduced charge separation and their relation with the photocatalytic degradation of Cr-doped ZnO were investigated by scanning electron microscopy, diffuse reflectance spectra, photoelectrochemical scanning electrochemical microscopy, and X-ray photoemission spectroscopy. Adding the appropriate amount of Cr dopant is a powerful way to enhance the separation of charge carriers in ZnO photocatalyst. The photocatalytic activity was improved due to the increase in surface oxygen vacancies, the separation of charge carriers, modification of the band gap, and the large surface area of the doped ZnO nanorod photocatalyst. - Graphical abstract: Photoinduced charge separation and its relation with the photocatalytic degradation activity of Cr-doped ZnO were investigated by photoelectrochemical scanning electrochemical microscopy. - Highlights: • Cr dopant enhances separation of charge carries in ZnO nanorod photocatalyst. • Photoinduced charge carries separation monitored by PEC-SECM. • The higher the photocurrent is, the higher the photocatalytic activity is. • Degradation of DB86 dye solutions under visible light finished within 50 min. • Higher activity due to more oxygen vacancy, tuned band gap and more surface area.

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

Fabrication and applications of copper sulfide (CuS) nanostructures

This review article presents different fabrication procedures (under the headlines of solvothermal routes, aerosol methods, solution methods and thermolysis), and applications (photocatalytic degradation, ablation of cancer cells, electrode material in lithium ion batteries and in gas sensing, organic solar cells, field emission properties, super capacitor applications, photoelectrochemical performance of QDSCs, photocatalytic reduction of organic pollutants, electrochemical bio sensing, enhanced PEC characteristics of pre-annealed CuS film electrodes) of copper sulfide (Covellite). - Highlights: • This review article presents the synthesis and applications of copper sulfide. • CuS has been used over the years for different applications in nanoscience. • Different synthetic protocols are followed for their preparation which help in the possible modifications in the morphology of CuS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Ternary CuInS{sub 2} photoelectrodes created using the sulfurization of Cu–In metal precursors for photoelectrochemical applications

Graphical abstract: At an irradiation of 100 mW/cm{sup 2} from a Xe lamp, the highest photo-enhancement current density of sample (f) obtained in this study was 5.81 mA/cm{sup 2} at an external potential of +0.4 V vs. an Ag/AgCl electrode in Na{sub 2}S (0.35 M) + K{sub 2}SO{sub 3} (0.25 M) solution. These results show that the physical properties of CuInS{sub 2} can be controlled by changing the [In]/[In + Cu] molar ratio in the metal precursors using the reactive sulfurization process with the sputtering of Cu–In metal precursors. - Highlights: • CuInS{sub 2} is deposited on substrates using sulfurization of Cu–In precursors. • Samples with [In]/[Cu + In] ratio of below 0.49 are p-type semiconductors. • Samples with [In]/[Cu + In] ratio of above 0.51 are n-type semiconductors. • Sample with [In]/[Cu + In] ratio of 0.53 has a maximum PEC response. - Abstract: Copper indium disulfide semiconductor layers are deposited onto glass substrates or fluorine-doped tin oxide-coated glass substrates with the reactive sulfurization and the sputtering of Cu–In metal precursors. X-ray diffraction patterns and energy dispersive analysis of X-ray results reveal that the samples change from the Cu-rich tetragonal CuInS{sub 2} to the In-rich CuInS{sub 2} phase with an increase in the [In]/[In + Cu] molar ratio in the metal precursors. The thicknesses and direct band gaps of the samples, determined from surface profile measurements and transmittance and reflectance spectra, are in the ranges of 0.82–1.29 μm and 1.39–1.53 eV, respectively. The carrier density and mobility of samples are in the ranges of 3.29 × 10{sup 14}–1.9 × 10{sup 20} cm{sup −3} and 0.58–17.41 cm{sup 2}/V s, respectively. A sample with an [In]/[In + Cu] molar ratio of 0.53 has a maximum photo enhancement current density of 5.81 mA/cm{sup 2} at an applied bias of 0.4 V vs. an Ag/AgCl electrode in aqueous Na{sub 2}S (0.35 M) + K{sub 2}SO{sub 3} (0.25 M) solution.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Fe{sub 2}O{sub 3} nanopowders prepared by a thermal plasma process for water oxidation

Highlights: • Hematite nanopowders with a high purity were synthesized by a DC thermal plasma process. • Fe{sub 3}O{sub 4} is formed during the formation of Fe{sub 2}O{sub 3} by thermal plasma with iron and oxygen sources. • Hematite nanopowders with a high purity show higher PEC performance compared to mixed oxides. - Abstract: Hematite (Fe{sub 2}O{sub 3}) nanopowders were synthesized from commercially available micro-sized iron powders by a DC thermal plasma process at atmospheric pressure. The micro-sized iron powders were vaporized in the plasma region, after which the plasma processing equipment was rapidly quenched, resulting in the formation of iron nanopowders with a size of less than 100 nm. Subsequently, the iron nanopowders were heated to convert hematite with a high purity, which was then formed into a thin film with a binder for preparation of electrodes for photoelectrochemical water oxidation. Iron oxide nanopowders were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), particle size analysis (PSA) and transmission electron microscopy (TEM). The photoelectrochemical properties of the Fe{sub 2}O{sub 3} film were characterized in 1 M NaOH under AM 1.5 conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Fabrication of CdSe nanoparticles sensitized TiO2 nanotube arrays via pulse electrodeposition for photoelectrochemical application

Highlights: • Anodization method approach for the synthesis of TiO{sub 2} nanotubes. • CdSe nanoparticle/TiO{sub 2} nanotube arrays were assembled via pulse electrochemical deposition technique. • Duty cycles were applied in order to enhance the properties of CdSe/TiO{sub 2} nanostructure. • PEC analysis verified that CdSe/TiO{sub 2} structure prepared at 50% duty cycle gave best photocurrent response. • Photoconversion efficiency of CdSe/TiO{sub 2} nanostructure was approximately 59 times greater than TiO{sub 2} nanotubes. - Abstract: Solar energy is an alternative sustainable energy resource that can be harvested using photoelectrochemical cell comprised of inorganic sensitized nanostructured oxide semiconductor electrode. In this work, pulse electrodeposition was used to deposit CdSe onto titanium dioxide nanotube arrays (TiO{sub 2} NTAs). TiO{sub 2} NTAs are commonly used in the nanostructured photoelectrochemical cells due to their high surface area, fewer interfacial grain boundaries and excellent charge transfer between interfaces. Duty cycle of pulse electrodeposition played an important role in the formation of CdSe nanoparticles. A significant enhancement in the photoelectrochemical performance was observed for the heterostructure of CdSe/TiO{sub 2} NTAs. CdSe/TiO{sub 2} NTAs prepared at 50% duty cycle exhibited maximum photocurrent of 1.94 mA cm{sup −2} and photoconversion efficiency of 1.18% which was 59 times higher than bare TiO{sub 2} NTAs. These results demonstrated that significant enhancement in the photoconversion efficiency could be obtained by incorporating CdSe as sensitizer into the TiO{sub 2} nanotube arrays via pulse electrodeposition technique.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Single and Dual-Solute Transport in Quaternary Ammonium-Functionalized Anion Exchange Membranes: Isolating the Impact of Water Volume Fraction

Membranes are essential components of photoelectrochemical CO 2 reduction cells (PEC-CRC), as they regulate solute transport and impact device efficiency. These cells are a promising approach for converting carbon dioxide into valuable chemicals. However, electrochemical reactions involve not just a single electrolyte; membrane transport typically includes multiple electrolytes. When a mixture of solutes is present, the presence of one solute in the membrane can impact the diffusion and sorption of other solutes. In complex systems where multiple solutes are diffusing simultaneously through a hydrated, dense polymer membrane, the resulting transport behavior is poorly understood. This study highlights the individual and two solute transport behavior of potassium formate, acetate, and bicarbonate ions in neutral membranes and quaternary ammonium-functionalized anion exchange membranes (AEMs) based on phenyl acrylate polymer backbones. By isolating the effect of water content, we emphasize how fixed charge density and solute-membrane interactions influence transport behavior. In neutral membranes, the diffusivity follows the order of potassium formate > potassium acetate > potassium bicarbonate. However, in AEMs, the order shifts due to changes in ion-membrane interactions, with potassium bicarbonate diffusivity surpassing that of potassium acetate. These results underscore the importance of ion exchange membranes and ion-membrane interaction in modulating transport properties, providing valuable insights for optimizing membranes in electrochemical applications.

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

Probing interfacial energetics and charge transfer kinetics in semiconductor nanocomposites: New insights into heterostructured TiO 2 /BiVO 4 photoanodes

Heterostructured nanocomposites offer promise for creating systems exhibiting functional properties that exceed those of the isolated components. For solar energy conversion, such combinations of semiconducting nanomaterials can be used to direct charge transfer along pathways that reduce recombination and promote efficient charge extraction. However, interfacial energetics and associated kinetic pathways often differ significantly from predictions derived from the characteristics of pure component materials, particularly at the nanoscale. Here, the emergent properties of TiO 2 /BiVO 4 nanocomposite photoanodes are explored using a combination of X-ray and optical spectroscopies, together with photoelectrochemical (PEC) characterization. Application of these methods to both the pure components and the fully assembled nanocomposites reveals unpredicted interfacial energetic alignment, which promotes ultrafast injection of electrons from BiVO 4 into TiO 2 . Physical charge separation yields extremely long-lived photoexcited states and correspondingly enhanced photoelectrochemical functionality. This work highlights the importance of probing emergent interfacial energetic alignment and kinetic processes for understanding mechanisms of solar energy conversion in complex nanocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Understanding the impact of SPMAK and PEGPEA in crosslinked PEGDA membranes: Methanol-carboxylate co-transport behavior and correlating structure-physicochemical-transport properties

Investigating multicomponent transport in dense, hydrated polymer membranes is necessary in applications such as fuel cells, electrolyzers, and desalination systems. Of particular interest are photoelectrochemical CO 2 reduction cells (PEC-CRC) which produce liquid products such as alcohols (methanol) and carboxylates (formate, acetate). Flux coupling and competitive sorption behavior of these products (solutes) have been found to affect permselectivity, thereby motivating us to investigate fundamental membrane structure-physicochemical-transport relationships. Past research has shown that systematic tuning of crosslinked cation exchange membranes (CEMs) with charge-neutral monoacrylate monomers containing alkyl and phenyl groups (i.e., poly(ethylene glycol) methacrylate (PEGMA), and poly(ethylene glycol) phenyl ether acrylate (PEGPEA)) can suppress acetate transport (permeability) in co-permeation with methanol. To further investigate this transport behavior and to enhance membrane ionic conductivities, 3-sulfopropyl methacrylate potassium (SPMAK), a sulfonated monoacrylate monomer is incorporated here. SPMAK content is varied with neutral PEGPEA and diacrylate crosslinker, poly (ethylene glycol) diacrylate (PEGDA) of two different chain lengths (n = 10 and 13) to prepare membranes of various compositions. Electrochemical and physicochemical properties including ionic conductivity, ion exchange capacity, and water uptake increase with increasing charged SPMAK content. Different states of water within hydrated membranes are probed using differential scanning calorimetry (DSC), where increasing intermediate (loosely bound) water is observed with increasing hydrophilic SPMAK content. The transport behavior of methanol and carboxylates (formate, acetate, propionate) are investigated, where permeabilities vary as methanol > formate > acetate ≈ propionate. Interestingly, permeabilities decrease with increasing PEGPEA content and are more dependent on solute diffusion than sorption. Permeabilities and diffusivities decrease while permselectivities increase with decreasing PEGDA chain length.

25 ENERGY STORAGE↗