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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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(9[beta]H)-Pimaranes and Derivatives from the Tuber of Icacina trichantha
Abstract not provided
Entropy-Driven Charge Separation: A Potential Explanation for the Low Energy Loss Found in OPVs with Non-fullerene Acceptors
The recent development of non-fullerene acceptors (NFA) has led to an abrupt increase in the organic photovoltaic (OPV) efficiency from ~12% to ~20%. NFA OPVs can generate photocurrent efficiently without much energy loss, which contrasts with the large energy loss often needed for generating free charges from excitons in fullerene OPVs. Here, we argue that entropy-driven charge separation, which allows excitons to spontaneously gain heat from the environment, is responsible for the exceptionally low energy loss found in NFA OPVs. The entropic driving force is maximized when the delocalized electron and hole wave functions in the CT exciton intersect each other via pointlike junctions. Furthermore, these pointlike junctions are abundant in the polymer/NFA bulk heterojunction which consists of intertwined, stringlike donor and acceptor domains in which electron delocalizes anisotropically. Such microstructure favors entropy-driven charge separation, which can enable charge separation with a minimal energy loss.
Long-Lived Charge-Transfer Excitons in a Graphene–PTCDI–TiOPc Trilayer Heterostructure
Excitation transfer across the interfaces between graphene, perylenetetracarboxylic diimide (PTCDI), and titanyl phthalocyanine (TiOPc) was studied by using transient absorption and photoluminescence spectroscopy. Both photoluminescence quenching and transient absorption measurements confirm the presence of a type-II interface between PTCDI and TiOPc. While the graphene/PTCDI interface is expected to exhibit type-I behavior, transient absorption measurements indicate that only electrons transfer from PTCDI to graphene, with no evidence of hole transfer. Density functional theory calculations reveal significant ground-state electron transfer from graphene to PTCDI, resulting in band bending that prevents excited holes from transferring from PTCDI to graphene. This feature is exploited in a trilayer heterostructure of graphene/PTCDI/TiOPc, where the spatial separation of photoexcited electrons and holes in graphene and TiOPc, respectively, leads to the formation of long-lived photoexcitations with a lifetime of approximately 500 ps. Furthermore, spatially resolved transient absorption measurements reveal the immobile nature of these excitations, confirming that they are charge-transfer excitons rather than free electrons and holes. Furthermore, these results provide valuable insights into the complex interlayer photoexcitation transfer properties and demonstrate precise control over the layer population and the recombination lifetime of photocarriers in such hybrid heterostructures.
Charge Separation at Organic Interfaces with Near-Zero Energy Offset: A Step toward Designing Inorganic-like Organic Semiconductors
For organic semiconductors, it is often presumed that an energy level offset at the donor–acceptor (D-A) interface is required to provide the driving force for charge separation (CS). This energy level offset unavoidably leads to a voltage loss in organic photovoltaics. In this work, by using zinc phthalocyanine (ZnPc) and fluorinated zinc phthalocyanine (F 4 ZnPc) as a model D/A interface, we found that spontaneous CS, with an enthalpy increase of ∼0.3–0.4 eV, can occur even with an interfacial energy offset as small as ∼0.1 eV. This enthalpy-increase CS process is driven by entropy. The entropic driving force can be enhanced by two factors: (1) a point-like spatial contact between the delocalized electron and hole wave function in the charge transfer exciton; (2) a small band bending near the interface originating from long-range electrostatic interaction. Our work demonstrates that effective CS can occur at interfaces with a near-zero energy level offset, which means that the energy loss at the D/A interface can be avoided.
Modulation of Electrostatic Potential in 2D Crystal Engineered by an Array of Alternating Polar Molecules
The moiré potential in rotationally misfit two-dimensional (2D) heterostructures has been used to build artificial exciton and electron lattices, which have become platforms for realizing exotic electronic phases. Here, we demonstrate a different approach to create a superlattice potential in 2D crystals by using the near field of an array of polar molecules. Here, a bilayer of titanyl phthalocyanine (TiOPc), consisting of alternating out-of-plane dipoles, is deposited on monolayer MoS 2 . Time-resolved two-photon photoemission spectroscopy reveals a pair of interlayer exciton states with an energy difference of ~0.1 eV, which is consistent with the electrostatic potential modulation induced by the TiOPc bilayer as determined by density functional theory calculations. Because the symmetry and the period of this potential superlattice can be changed readily by using molecules of different shapes and sizes, molecule/2D heterostructures can be promising platforms for designing artificial exciton and electron lattices.
Origins of Irreversibility in Layered NaNi x Fe y Mn z O 2 Cathode Materials for Sodium Ion Batteries
Layered NaNi x Fe y Mn z O 2 cathode (NFM) is of great interest in sodium ion batteries due to its high theoretical capacity and utilization of abundant, low-cost, environmentally-friendly raw materials. Nevertheless, there remains insufficient understanding on the concurrent local environment evolution in each transition metal (TM) that largely influences the reversibility of the cathode materials upon cycling. In this work, we investigate the reversibility of TM ions in layered NFMs with varying Fe contents and potential windows. Utilizing ex situ synchrotron X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) of pre-cycled samples the valence and bonding evolution of the TMs are elucidated. It is found that Mn is electrochemically inactive as indicated by the insignificant change of Mn valence and Mn-O bonding distance. Fe is electrochemically inactive after the first five cycles. The Ni redox couple contributes most of the charge compensation for NFMs. Ni redox is quite reversible in the cathodes with less Fe contents. Furthermore, the Ni redox couple shows significant irreversibility with high Fe content of 0.8. The electrochemical reversibility of the NFM cathode becomes increasingly enhanced with the decrease of either Fe content or with lower upper charge cutoff potential.
Neutralization Short-Circuiting with Weak Electrolytes Erodes the Efficiency of Bipolar Membranes
Bipolar membranes (BPMs) are critical components of a variety of electrochemical energy technologies. Many electrochemical applications require the use of buffers to maintain stable, nonextreme pH environments, yet the impact of buffers or weak acids/bases on the electrochemical behavior of BPMs remains poorly understood. Here, our data for a cell containing weak electrolytes is consistent with internal pH gradients within the anion exchange membrane (AEM) or cation exchange membrane (CEM) component of the BPM that form via ionic short-circuiting processes at open-circuit. Short-circuiting results from the coupling of co-ion crossover and parasitic neutralization and leads to buffering of the bipolar interface. This phenomenon, which we term neutralization short-circuiting, serves to erode BPM efficiency by attenuating the open-circuit membrane voltage and introducing parasitic reverse bias currents associated with weak acid/base dissociation at the interface. These findings establish a mechanistic basis for the operation of BPM cells in the presence of weak acid/base electrolytes.
Coalescence-Induced Spontaneous Shedding of Microdroplets on Superhydrophobic Surfaces Featuring Enclosed Micropillars with Hierarchical Roughness
This study investigated water vapor condensation on superhydrophobic surfaces (SHSs) featuring micropillars enclosed by wall lattices and having three-tier hierarchical roughness. A total of five samples were created with three (NW-J, W200-J and W400-J samples) having large micropillar depth (~6 μm) and two (NW-S and W200-S samples) having small micropillar depth (~1 μm). Two distinct condensate removal modes were observed during condensation: coalescence-induced jumping on samples with large micropillar depth and coalescence-induced shedding on samples with small micropillar depth. The results showed that the diameter of the shedding droplet on the W200-S sample having small micropillar depth could be as small as 107 μm, as compared to the theoretical critical diameter of 267 μm for gravitational shedding on the same sample. The enhanced functionality of the three-tier nanotextures on the W200-S sample could effectively suppress localized pinning of the three-phase contact line and Wenzel neck formation during the growth of condensate droplets. Consequently, during multidroplet coalescence, the released surface energy easily overcomes the solid–liquid adhesion, leading to spontaneous shedding of merged droplets. The inclusion of the wall lattice aids condensate growth by the droplet self-alignment along the walls and promoting coalescence. As a result, the W200-S sample exhibited the highest condensate collection as well. In conclusion, the proposed surface design has great potential for scaling up and implementation in heating, ventilation, and air-conditioning equipment due to the simplicity of the surface morphology and the facile spray-coating method used to achieve hierarchical roughness.
Modularly Constructed Polyhedral Oligomeric Silsesquioxane-Based Giant Molecules for Unconventional Nanostructure Fabrication
Controlled assembly of nanoscale building blocks is a promising approach to obtain functional materials with unique properties. In this paper, we report a way to manipulate the supramolecular structures of giant molecules based on discotic triangle cores and isobutyl polyhedral oligomeric silsesquioxanes (BPOSS) nanoparticles (NPs). It is found that depending upon the number of BPOSS at the periphery of the discotic cores, the packing of these nanoscale components (discotic core and POSS) could be manipulated into either cylindrical or Frank–Kasper (F–K) A15 ($Pm\overline 3n$) phases. The formation of these supramolecular nanostructures is mandated by the balance between the stacking of the discotic cores and the steric hindrance effect of the BPOSS NPs. This strategy to manipulate the packing of nanoscale building blocks for different supramolecular nanostructures including the fabrication of cylindrical structures and A15 ($Pm\overline 3n$) phases may be extended to other nanoscale building blocks for future development of materials with complex structures as well as tailored functionalities and properties.
Photooxidation of Organic Sulfide Enhanced by Heavy Atom Effect in Porphyrin Metal–Organic Frameworks with a Sea Topology
The photoactivity of three porphyrin-based metal-organic frameworks (PMOFs) incorporating Al, Ga, and In nodes was systematically evaluated using the photooxidation of an organic sulfide (2-chloroethyl ethyl sulfide, or CEES; a mustard gas simulant). Faster photodegradation of CEES was observed for PMOFs with heavier metal nodes, placing In-PMOF as the most efficient photocatalyst in the series. Guided by this insight, we developed CSLA-10, a MOF integrating In nodes and Sn-doped porphyrin linker to synergistically amplify heavy-atom effects at both the nodes and ligand levels. CSLA-10 exhibited the fastest reported CEES photooxidation to date, achieving a half-life of 38 s in methanol under blue LED irradiation. When grafted onto textiles, CSLA-10 enabled solvent-free CEES degradation in air/O 2 with a half-life of 2.7 min and complete conversion within 7 min, representing the most rapid full degradation reported under solvent-free conditions. Furthermore, this work establishes a dual heavy-atom strategy for enhancing intersystem crossing and singlet oxygen generation in porphyrin MOFs, providing a rational design principle for next-generation photocatalysts for the degradation of toxic organic sulfides.
NH 3 -Mediated Reactive Capture and Conversion: Integrating CO 2 Absorption from Flue Gas with CO Production via NH 4 HCO 3 Electrolysis
Efficient carbon capture and utilization require strategies that minimize energy penalties of CO 2 regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO 2 from simulated flue gas (10% v/v CO 2 in N 2 ) with electroreduction of NH 4 HCO 3 to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO 2 capture with C/N ratio of 0.65 was achieved using 2.5 M NH 3 from simulated flue gas. Electrolysis of the resulting NH 4 HCO 3 on the Ni- SAC delivered an 85% CO Faradaic efficiency at 100 mA/cm 2 with excellent tolerance to NH 3 /NH 4 + as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.
Atomic-Scale Insights into the Lateral and Vertical Epitaxial Growth in Two-Dimensional Pd 2 Se 3 –MoS 2 Heterostructures
Two-dimensional (2D) materials form heterostructures in both the lateral and vertical directions when two different materials are interfaced, but with totally different bonding mechanisms of covalent in-plane to van der Waal’s layered interactions. Understanding how the competition between lateral and vertical forces influences the epitaxial growth is important for future materials development of complex mixed layered heterostructures. In this study, we use atomic-resolution annular dark-field scanning transmission electron microscopy to study the detailed atomic arrangements at mixed 2D heterostructure interfaces composed of two semiconductors with distinctly different crystal symmetry and elemental composition, Pd 2 Se 3 :MoS 2 , in order to understand the role of different chemical bonds on the resultant epitaxy. Pd 2 Se 3 is grown off the step edge in bilayer MoS 2 , and the vertical and lateral epitaxial relationships of the Pd 2 Se 3 –MoS 2 heterostructures are investigated. We find that the similarity of geometry at the interface with one metal (Pd or Mo) atoms bonded with two chalcogens (S or Se) are the crucial factors to make the atomically stitched lateral junction of 2D heterostructures. In addition, the vertical van der Waal interactions that are normally dominant in layered materials can be overcome by in-plane forces if the interfacial atomic stitching is high in quality and low in defect density. This knowledge should help guide the approaches for improving the epitaxy in mixed 2D heterostructures and seamless stitching of in-plane 2D heterostructures with various complex monolayer structures.