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Hybrid nanowire networks of electron donors and acceptors were achieved by the combination of phase separation, interfacial segregation, and crystallization in multicomponent blends.
Our research program was aimed at elucidating the nature of proton transport in ionomer membranes by means of a combination of analytical theory and molecular modeling. There were two broad thrusts. The first of these was directed towards understanding the equilibrium structure of Nafion and related polymers at various levels of hydration. The second thrust was concerned with the transport of protons through a membrane of this type. The research on structure proceeded by building on existing work, but with the introduction of some novel techniques, among which is a hybrid Molecular Dynamics--Monte Carlo approach. This method permits rapid computations by temporarily decoupling the motion of the polar side chains from that of the perfluorinated backbone, while still retaining the essential aspects of the constraint that phase separation can only continue to a very limited degree. Competition between an elastic energy due to this constraint and the tendency to phase separation lead to the equilibrium structure, which turns out to be qualitatively different at different levels of hydration.
The ornately geometric walls of pollen grains have inspired scientists for decades. Here, we show that the evolved diversity of these patterns is entirely recapitulated by a biophysical model in which an initially uniform polysaccharide layer in the extracellular space, mechanically coupled to the cell membrane, phase separates to a spatially modulated state. Experiments reveal this process occurring in living cells. We observe that in ~10% of extant species, this phase separation reaches equilibrium during development such that individual pollen grains are identical and perfectly reproducible. About 90% of species undergo an arrest of this process prior to equilibrium such that individual grains are similar but inexact copies. Equilibrium patterns have appeared multiple times during the evolution of seed plants, but selection does not favor these states. This framework for pattern development provides a route to rationalizing the surface textures of other secreted structures, such as cell walls and insect cuticle.
2,3-Butanediol (BDO) is a bio-derived building block available from biomass through biochemical methods in high titers (>120 g L-1) making it an attractive target for production and further upgrading to chemical products and fuels such as sustainable aviation fuel. A key challenge to enable the adoption of BDO as a precursor is the effective separation and isolation of this molecule from the fermentation broth. 2,3-Butanediol has a boiling point higher than that of water (177 degrees C), and as a consequence, separation via distillation methods is an energy-intensive and therefore costly approach. We have improved the BDO separation through conversion to a 1,3-dioxolane directly in fermentation broth via reaction with bio-derived aldehydes catalyzed by a solid acid catalyst. The resulting dioxolane phase separates from the fermentation broth, allowing for easy decantation and isolation in >90% isolated yield. Isolated dioxolane can be used directly as a compression iginition fuel, trans-acetalized to recover high-purity BDO or used directly in a catalytic process as a BDO synthon to produce methyl ethyl ketone with aldehyde recovery in near quantitative yield.
Multiferroic materials have driven significant research interest due to their promising technological potential. Developing new room-temperature multiferroics and understanding their fundamental properties are important to reveal unanticipated physical phenomena and potential applications. Here, a new room temperature multiferroic nanocomposite comprised of an ordered ferrimagnetic spinel α-LiFe 5 O 8 (LFO) and a ferroelectric perovskite BiFeO 3 (BFO) is presented. It is observed that lithium (Li)-doping in BFO favors the formation of LFO spinel as a secondary phase during the synthesis of Li x Bi 1-x FeO 3 ceramics. Multimodal functional and chemical imaging methods are used to map the relationship between doping-induced phase separation and local ferroic properties in both the BFO-LFO composite ceramics and self-assembled nanocomposite thin films. The energetics of phase separation in Li doped BFO and the formation of BFO-LFO composites are supported by first principles calculations. These findings shed light on Li's role in the formation of a functionally important room temperature multiferroic and open a new approach in the synthesis of light element doped nanocomposites for future energy, sensing, and memory applications.
Ternary organic solar cells (OSCs), which blend two donors and fullerene derivatives with different absorption ranges, are a promising potential strategy for high-power conversion efficiencies (PCEs). In this study, inverted ternary OSCs are fabricated by blending a highly crystalline small molecule BDT-3T-CNCOO in a low band gap polymer PBDTTT-C-T:PC71BM. As the small molecule is introduced, the overall PCEs increase from 7.60% to 8.58%. The morphologies of ternary blends are studied by combining transmission electron microscopy and X-ray scattering techniques at different length scales. Hierarchical phase separation is revealed in the ternary blend, which is composed of domains with sizes of ≈88, ≈50, and ≈20 nm, respectively. The hierarchical phase separation balances the charge separation and transport in ternary OSCs. As a result, the fill factors of the devices significantly improve from 58.4% to 71.6%. Thus, ternary blends show higher hole mobility and higher fill factor than binary blends, which demonstrates a facile strategy to increase the performance of OSCs.
It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.
Here, we report how the superconducting phase forms in pseudo-single-crystal K x Fe 2-y Se 2 . In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition. It should be emphasized that the phase separation in pseudo-single-crystal K x Fe 2-y Se 2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.
Metal-free organic semiconductors have emerged as a kind of promising star material in photocatalysis. However, their photocatalytic efficacy is impeded by the great recombination rate of the photogenerated charge carriers. Herein, we demonstrate the devising of solution-processable organic semiconductor bulk heterojunction (BHJ) systems with varying ratios by using BP3DT and PC 61 BM as the donor (D) and acceptor (A) candidates, respectively, for enhanced selective CO production from CO 2 photoreduction. The prepared BP3DT/PC 61 BM BHJs are solution-processed on both glass substrates (GS) and molecular sieves (MS) via a drop-casting technique to form an active thin film and porous photocatalysts to catalyze CO production. All BP3DT/PC 61 BM BHJs efficiently produce CO as the primary product in the existence of trace-level TEA/H 2 O (0.5 mL). Our results show that the photocatalytic efficiency depended on the D/A w% ratios and its nanoscale phase separation morphology within the BHJ, contributing to the promotion of exciton dissociation. Additionally, the BHJ undergoes an ostensible morphological transition from large-scale phase-separation to a fine mixed homogeneous nanoscale by varying the BP3DT/PC 61 BM blend ratio from 30/70 w% to 70/30 w%, which increases the interfacial area and shortens the distance of the exciton to the D/A surface, and promotes charge carrier separation, corroborated by photo-optical and photoelectrochemical experimental results. Accordingly, the resulting BP3DT/PC 61 BM BHJ@MS with a D/A ratio of 70/30 w% achieves a CO yield of 819 μmol·g cat -1 h -1 , surpassing those of pure PC 61 BM (126 μmol·g cat -1 h -1 ) and BP3DT (72 μmol·g cat -1 h -1 ) by 6.5- to 11.3-fold and also exceeding that of metal-free linear conjugated polymer-based organocatalysts reported to date. Specifically, this is the first work to develop an organic-semiconductor-based BHJ photocatalyst, which may offer a nascent way to design more efficient organocatalysts for CO 2 reduction.
Microgravity poses many challenges to the designer of spacecraft tanks. Chief among these are the lack of phase separation and the need to supply vapor-free liquid or liquidfree vapor to the spacecraft processes that require fluid. One of the principal problems of phase separation is the creation of liquid jets. A jet can be created by liquid filling, settling of the fluid to one end of the tank, or even closing a valve to stop the liquid flow. Anyone who has seen a fountain knows that jets occur in normal gravity also. However, in normal gravity, the gravity controls and restricts the jet flow. In microgravity, with gravity largely absent, surface tension forces must contain jets. To model this phenomenon, a numerical method that tracks the fluid motion and the surface tension forces is required. Jacqmin has developed a phase model that converts the discrete surface tension force into a barrier function that peaks at the free surface and decays rapidly away. Previous attempts at this formulation were criticized for smearing the interface. This can be overcome by sharpening the phase function, double gridding the fluid function, and using a higher order solution for the fluid function. The solution of this equation can be rewritten as two coupled Poisson equations that also include the velocity. After the code was implemented in axisymmetric form and verified by several test cases at the NASA Glenn Research Center, the drop tower runs of Aydelott were modeled. Work last year with a laminar model was found to overpredict Aydelott's results, except at the lowest Reynolds number conditions of 400. This year, a simple turbulence model was implemented by adding a turbulent viscosity based on the mixing-length hypothesis and empirical measurements of previous works. Predictions made after this change was implemented have been much closer to experimentally observed flow patterns and geyser heights. Two model runs is shown. The first, without any turbulence correction, breaks through the free surface and strikes the far end of the tank. In the second, the turbulence spreads the jet momentum over more of the free surface, enabling the surface tension forces to turn the jet back into the bulk liquid. The model geyser height with the second model is 1.1 cm. This is quite close to the 1.5-cm geyser height measured by Aydelott.
Studies of active particle systems have demonstrated that particle anisotropy can impact the collective behavior of a system, motivating a systematic study. Here, we report a systematic computational investigation of the role of anisotropy in shape and active force director on the collective behavior of a two-dimensional active colloidal system. We find that shape and force anisotropy can combine to produce critical densities both lower and higher than those of disks. Furthermore, we demonstrate that changing particle anisotropy tunes what we define as a “collision efficiency” of inter-particle collisions in leading to motility-induced phase separation (MIPS) of the system. We use this efficiency to determine the relative critical density across systems. Additionally, we observe that local structure in phase-separated clusters is the same as the particle's equilibrium densest packing, suggesting a general connection between equilibrium behavior and non-equilibrium cluster structure of self-propelled anisotropic particles. In engineering applications for active colloidal systems, shape-controlled steric interactions such as those described here may offer a simple route for tailoring emergent behaviors.
Tension in Microgravity Modeled Microgravity poses many challenges to the designer of spacecraft tanks. Chief among these are the lack of phase separation and the need to supply vapor-free liquid or liquidfree vapor to the spacecraft processes that require fluid. One of the principal problems of phase separation is the creation of liquid jets. A jet can be created by liquid filling, settling of the fluid to one end of the tank, or even closing a valve to stop the liquid flow. Anyone who has seen a fountain knows that jets occur in normal gravity also. However, in normal gravity, the gravity controls and restricts the jet flow. In microgravity, with gravity largely absent, jets must be contained by surface tension forces. Recent NASA experiments in microgravity (Tank Pressure Control Experiment, TPCE, and Vented Tank Pressure Experiment, VTRE) resulted in a wealth of data about jet behavior in microgravity. VTRE was surprising in that, although it contained a complex geometry of baffles and vanes, the limit on liquid inflow was the emergence of a liquid jet from the top of the vane structure. Clearly understanding the restraint of liquid jets by surface tension is key to managing fluids in low gravity. To model this phenomenon, we need a numerical method that can track the fluid motion and the surface tension forces. The fluid motion is modeled with the Navier-Stokes equation formulated for low-speed incompressible flows. The quantities of velocity and pressure are placed on a staggered grid, with velocity being tracked at cell faces and pressure at cell centers. The free surface is tracked via the introduction of a color function that tracks liquid as 1/2 and gas as -1/2. A phase model developed by Jacqmin is used. This model converts the discrete surface tension force into a barrier function that peaks at the free surface and decays rapidly. Previous attempts at this formulation have been criticized for smearing the interface. However, by sharpening the phase function, double gridding the fluid function, and using a higher order solution for the fluid function, interface smearing is avoided. These equations can be rewritten as two coupled Poisson equations that also include the velocity. The method of solution is as follows: first, the phase equations are solved from this solution, a velocity field is generated, then a successive overrelaxation scheme is used to solve for a pressure field consistent with the velocity solution. After the code was implemented in axisymmetric form and verified by several test cases, the drop tower runs of Aydelott were modeled. The model handed the free-surface deformation quite nicely, even to the point of modeling geyser growth in the regime where the free surface was no longer restrained. A representative run is shown.
Microgravity poses many challenges to the designer of spacecraft tanks. Chief among these are the lack of phase separation and the need to supply vapor-free liquid or liquid-free vapor to the spacecraft processes that require fluid. One of the principal problems of phase separation is the creation of liquid jets. A jet can be created by liquid filling, settling of the fluid to one end of the tank, or even closing a valve to stop the liquid flow. Anyone who has seen a fountain knows that jets occur in normal gravity also. However, in normal gravity, the gravity controls and restricts the jet flow. In microgravity, with gravity largely absent, surface tension forces must be used to contain jets. To model this phenomenon, a numerical method that tracks the fluid motion and the surface tension forces is required. Jacqmin has developed a phase model that converts the discrete surface tension force into a barrier function that peaks at the free surface and decays rapidly away. Previous attempts at this formulation were criticized for smearing the interface. This can be overcome by sharpening the phase function, double gridding the fluid function, and using a higher-order solution for the fluid function. The solution of this equation can be rewritten as two coupled Poisson equations that also include the velocity.
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The mass transport mechanisms of Ti in TiO 2 :SiO 2 and Ge in GeO 2 :SiO 2 direct ink write, additively manufactured glasses were studied. Due to the low solubility of Ti in SiO2 and high melting point of TiO 2 relative to SiO 2 , Ti transport was found to occur via solid state interdiffusion between adjoining SiO 2 and TiO 2 precursor particles. The diffusivity of titanium in SiO 2 measured over typical sintering temperatures (1000-1300 °C) using Rutherford backscattering spectrometry was D = 9.1 × 10 -7 [m2/sec] exp ($\frac{378[\frac{kJ}{mol}]}{RT}$. This provides an estimate of ~30 nm for the diffusion length under typical sintering conditions (2 hrs. at 1200 °C). Although Ti and Ge have similar diffusivities in SiO 2 glass at low concentrations, GeO 2 was found to be much more mobile during the sintering of printed GeO 2 :SiO 2 green bodies. This was evident in glasses with phase separated GeO 2 regions over length scales of ~10 μm and in experiments involving binary xerogels in which GeO 2 migrated over ~10 μm through cracked, porous SiO 2 layers. Large phase separated regions and long transport lengths in GeO 2 :SiO 2 suggest that the transport of GeO 2 occurs prior to the densification of the SiO 2 matrix via an alternative mechanism such as capillary flow. These results inform important considerations in the design of index modifying inks for the direct ink write process, namely initial precursor phase, mutual solubility with the base SiO 2 glass, and mass transport throughout the sintering process.
Inverse design methods are powerful computational approaches for creating colloidal systems which self-assemble into a target morphology by reverse engineering the Hamiltonian of the system. Despite this, these optimization procedures tend to yield Hamiltonians which are too complex to be experimentally realized. An alternative route to complex structures involves the use of several different components, however, conventional inverse design methods do not explicitly account for the possibility of phase separation into compositionally distinct structures. We present an inverse design scheme for multicomponent colloidal systems by combining active learning with a method to directly compute their ground state phase diagrams. This explicitly accounts for phase separation and can locate stable regions of Hamiltonian parameter space which grid-based surveys are prone to miss. Using this we design low-density, binary structures with Lennard-Jones-like pairwise interactions that are simpler than in the single component case and potentially realizable in an experimental setting. This reinforces the concept that ground states of simple, multicomponent systems might be rich with previously unappreciated diversity, enabling the assembly of non-trivial structures with only few simple components instead of a single complex one.
The ecofriendly synthesis of organic semiconductors with heterojunctions is of interest and requires surfactants to stabilize colloidal nanoparticles (NPs) in aqueous solution. The use of conventional surfactants results in p-n heterostructured NPs, in which both p- and n-type semiconductors are phase separated and confined within a core surrounded by the surfactant shell. The performances of these devices, however, are not comparable to those of solid organic semiconductor films. Further efforts are required to understand and control the morphological structure of the nanoparticles to improve their performances. Here, by using a new class of polyethyleneglycol-based surfactant, PEG-C60, we synthesized unique p-n heterostructured water-borne NPs that comprise a p-type semiconductor core and an n-type PEG-C60 shell. We demonstrate that the morphology gives rise to charge separation superior to conventional water-borne NPs. These PEG-C60-based water-borne NPs can, thus, provide a new paradigm in the current field of water-based organic semiconductor colloids.
Conjugated polyelectrolytes (CPEs) have the potential to serve as building blocks of artificial light-harvesting systems. This is primarily due to their delocalized electronic states and potential for hierarchical self-assembly. We showed previously that inter-CPE complexes composed of oppositely charged exciton-donor and exciton-acceptor CPEs displayed efficient electronic energy transfer. However, near ionic charge equivalence, complexed CPE chains become net-neutral and thus experience a precipitous drop in aqueous solubility. To increase the stability and to rationally manipulate the phase behavior of inter-CPE complexes, we synthesized a series of highly water-soluble exciton-donor CPEs composed of alternating ionic and polar nonionic fluorene monomers. The nonionic monomer contained oligo(ethyleneglycol) sidechains of variable length. We then formed exciton donor-acceptor complexes and investigated their relative energy transfer efficiencies in the presence of a fixed exciton-acceptor CPE. We find that, even when the polar nonionic sidechains become quite long (nine ethyleneglycol units), the energy transfer efficiency is hardly affected so long as the inter-CPE network retains a net polyelectrolyte charge. However, near the onset of spontaneous phase separation, we observe a clear influence of the length of the oligo(ethyleneglycol) sidechains on the photophysics of the complex. Our results have implications for the use of polyelectrolyte phase separation to produce aqueous light-harvesting soft materials.