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At least 19 records

Modeling Mesoscale Processes of Scalable Synthesis (Final Report)

The main objective of the center is to develop tools that can help for the understanding of equilibrium and non-equilibrium properties of nanoparticles in aqueous electrolytes. To achieve this goal, we need to develop new computational methodologies that can integrate molecular level description such as the electronic structure analysis to mesoscale description such as generalized hydrodynamics. The challenge is to develop systematic coarse graining techniques that can adaptively choose the level of description needed for the particular task. For example, if bonding breaking is involved, then one should use appropriate models from quantum mechanics to accurately model the time scale and molecular mechanism for the breaking process. However, to model transport process or the process of self-assembly, much less detailed models can be used. There are two main components to this task. One is to develop accurate models that bridge different levels of description. The classical example is the QM/MM model that bridges quantum mechanics and molecular mechanics for studying chemical reactions of large molecules. This work was awarded the Nobel prize this year. For our purpose, we also need to develop methods that bridge molecular and continuum levels of description. Another main task is to develop systematic coarse-graining methods that can give rise to accurate mesoscale and macroscale models, starting from more detailed models at the atomic or molecular scale. None of these ideas are new. By now they have been fashionable topics for quite some time. But neither problem is satisfactorily resolved. The main problem is that uncontrolled approximations are used. As a result, we have very little idea about the validity and accuracy of these models. The main purpose of the center is to exploit the Mori-Zwanzig formalism to achieve the goals stated above. The Mori-Zwanzig formalism is a general tool for eliminating degrees of freedom from existing models. What is attractive about this formalism is its generality. The flip side is that it is also somewhat of a tautology. In order to make it a practical tool, one has to make approximations and this is where the trouble comes. Instead of focusing on Mori-Zwanzig formalism, the PI proposes to study the closely related renormalization group formalism (RG). Like Mori-Zwanzig, RG is a general strategy for eliminating small scale degrees of freedom in a model. Unlike Mori-Zwanzig, RG has the advantage that at least for some problems, one can write a PDE (partial differential equation) type of model for the exact RG flow, without any approximation. This gives us a solid starting point for discussing and analyzing approximations. The PI studied approximate RG flows for turbulent diffusion and related problems. However, extending it to more practical problems proved to be hard. The second line that the PI has pursued is to develop special numerical algorithms for studying particularly important events for dynamics processes in meso-scale systems. The PI succeeded in doing so for the problem of understanding phase transition in metallic systems.

97 MATHEMATICS AND COMPUTING↗

Modeling Mesoscale Processes of Scalable Synthesis. Final report

The newly developed solvers during the project address the coupling of multiple physics using both pure algebraic approach and analytic approach and provide optimal and scalable performance for wide-range numerical simulations. Such solvers and their theoretical framework are expected to have significant impact to other DoE-related multi-physics and multi-scale applications. Moreover, these solvers have been implemented in FASP package developed by the Penn State team.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Low-Frequency Carrier Kinetics in Perovskite Solar Cells

Hybrid organic–inorganic halide perovskite solar cells have emerged as leading candidates for third-generation photovoltaic technology. Despite the rapid improvement in power conversion efficiency (PCE) for perovskite solar cells in recent years, the low-frequency carrier kinetics that underlie practical roadblocks such as hysteresis and degradation remain relatively poorly understood. In an effort to bridge this knowledge gap, we perform here correlated low-frequency noise (LFN) and impedance spectroscopy (IS) characterization that elucidates carrier kinetics in operating perovskite solar cells. Specifically, we focus on planar cell geometries with a SnO2 electron transport layer and two different hole transport layers—namely, poly(triarylamine) (PTAA) and spiro-OMeTAD. PTAA and spiro-OMeTAD cells with moderate PCEs of 5–12% possess a Lorentzian feature at ~200 Hz in LFN measurements that corresponds to a crossover from electrode to dielectric polarization. In comparison, spiro-OMeTAD cells with high PCEs (>15%) show 4 orders of magnitude lower LFN amplitude and are accompanied by a cyclostationary process. Through a systematic study of more than a dozen solar cells, we establish a correlation with noise amplitude, PCE, and fill factor. Overall, this work establishes correlated LFN and IS as an effective methodology for quantifying low-frequency carrier kinetics in perovskite solar cells, thereby providing new physical insights that can rationally guide ongoing efforts to improve device performance, reproducibility, and stability.

14 SOLAR ENERGY↗

Effective Removal of Anionic Re(VII) by Surface-Modified Ti 2 CT x MXene Nanocomposites: Implications for Tc(VII) Sequestration

Environmental contamination by 99 Tc(VII) from radioactive wastewater streams is of particular concern due to the long half-life of 99 Tc and high mobility of pertechnetate. Here in this paper, we report a novel MXene-polyelectrolyte nanocomposite with three-dimensional networks for enhanced removal of perrhenate, which is pertechnetate simulant. The introduction of poly(diallyldimethylammonium chloride) (PDDA) regulates the surface charge and improves the stability of Ti 2 CT x nanosheet, resulting in Re(VII) removal capacity of up to 363 mg g –1 , and fast sorption kinetics. The Ti 2 CT x /PDDA nanocomposite furthermore exhibits good selectivity for ReO 4 – when competing anions (such as Cl – and SO 4 2– ) coexist at a concentration of 1800 times. The immobilization mechanism was confirmed as a sorption-reduction process by batch sorption experiments and X-ray photoelectron spectroscopy. The pH-dependent reducing activity of Ti 2 CT x /PDDA nanocomposite toward Re(VII) was clarified by X-ray absorption spectroscopy. As the pH increases, the local environment gradually changes from octahedral-coordinated Re(IV) to tetrahedral-coordinated Re(VII). The overall results suggest that Ti 2 CT x /PDDA nanocomposite may be a promising candidate for efficient elimination of Tc contamination. The reported surface modification strategy might result in applications of MXene-based materials in environmental remediation of other oxidized anion pollutants.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Electrochemical and Spectroscopic Analysis of the Ionogel–Electrode Interface

Ionogels, pseudo-solid-state electrolytes consisting of an ionic liquid electrolyte confined in a mesoporous inorganic matrix, have attracted interest recently due to their high ionic conductivity and physicochemical stability. These traits, coupled with their inherent solution processability, make them a viable solid electrolyte for solid-state battery systems. Despite the promising properties of ionogels, there have been very few investigations of the electrode–ionogel interface. In the present study, X-ray photoelectron spectroscopy, Raman spectroscopy, and electrochemical measurements were utilized to probe the surface reactions occurring at the electrode–ionogel interface for several electrode materials. Our results indicate that the sol acidity initiates breakdown of the organic constituents of the sol and reduction of the transition metals present in the electrode materials. This chemical attack forms an organic surface layer and affects the electrode composition, both of which can impede Li+ access. By modifying the silica sol–gel reaction via a two-step acid–base catalysis, these interfacial reactions can be avoided. Results are shown for a LiCoO 2 electrode in which a high Li-ion capacity and stable cycling were achieved.

36 MATERIALS SCIENCE↗

Toward Stable Deep-Blue Luminescent Colloidal Lead Halide Perovskite Nanoplatelets: Systematic Photostability Investigation

Colloidal lead halide perovskite nanocrystals and nanoplatelets have emerged as promising semiconductor nanomaterials because of their spectral tunability, facile processability, and bright emission with high color purity. In particular, strong quantum and dielectric confinement make atomically thin colloidal lead bromide perovskite nanoplatelets a favorable candidate for next-generation deep-blue-emitting (λ max = 437 nm) materials. However, poor photostability poses a critical challenge; colloidal nanoplatelets suffer from photobleaching or transformation into thicker, less-confined nanostructures with red-shifted emission upon UV irradiation. In this study, we synthesize deep-blue-emitting organic–inorganic hybrid perovskite nanoplatelets (formula: L 2 [ABX 3 ]BX 4 , L: butylammonium and octylammonium, A: methylammonium or formamidinium, B: lead, and X: bromide or iodide) with large lateral dimension (~1 μm) by ligand-assisted reprecipitation and systematically investigate the factors that affect the photostability of those nanoplatelets. We find that freshness of the prepared precursor solutions for ligand-assisted reprecipitation is critical to obtain better stability with high photoluminescence quantum yield of perovskite nanoplatelets. Photobleaching is found to result from intrinsic instability of the perovskite lattice against UV irradiation in nanoplatelets, whereas transformation into thicker nanostructures results from extrinsic factors—moisture, primarily. Furthermore, we observe that substitution of the organic cation from formamidinium to methylammonium and addition of excess alkylammonium bromide ligands significantly enhance both the ambient and photostability. Lastly, we demonstrate that the dropcast film of methylammonium lead bromide nanoplatelets with excess alkylammonium bromide ligands shows dramatically improved stability both under UV irradiation and under ambient conditions. Lastly, this study expands our understanding of the factors that affect perovskite nanoplatelet photostability and opens up new possibilities for the fabrication of stable perovskite nanoplatelet-based optoelectronic devices.

2D↗

Simultaneous Bottom-Up Interfacial and Bulk Defect Passivation in Highly Efficient Planar Perovskite Solar Cells using Nonconjugated Small-Molecule Electrolytes

Recent perovskite solar cell (PSC) advances have pursued strategies for reducing interfacial energetic mismatches to mitigate energy losses, as well as to minimize interfacial and bulk defects and ion vacancies to maximize charge transfer. In this work, nonconjugated multi-zwitterionic small-molecule electrolytes (NSEs) are introduced, which act not only as charge-extracting layers for barrier-free charge collection at planar triple cation PSC cathodes but also passivate charged defects at the perovskite bulk/interface via a spontaneous bottom-up passivation effect. Implementing these synergistic properties affords NSE-based planar PSCs that deliver a remarkable power conversion efficiency of 21.18% with a maximum V OC = 1.19 V, in combination with suppressed hysteresis and enhanced environmental, thermal, and light-soaking stability. Thus, this work demonstrates that the bottom-up, simultaneous interfacial and bulk trap passivation using NSE modifiers is a promising strategy to overcome outstanding issues impeding further PSC advances.

36 MATERIALS SCIENCE↗

All-Polymer Solar Cells: Recent Progress, Challenges, and Prospects

For over two decades bulk-heterojunction polymer solar cell (BHJ-PSC) research was dominated by donor:acceptor BHJ blends based on polymer donors and fullerene molecular acceptors. This situation has changed recently, with non-fullerene PSCs developing very rapidly. The power conversion efficiencies of non-fullerene PSCs have now reached over 15 %, which is far above the most efficient fullerene-based PSCs. Among the various non-fullerene PSCs, all-polymer solar cells (APSCs) based on polymer donor-polymer acceptor BHJs have attracted growing attention, due to the following attractions: 1) large and tunable light absorption of the polymer donor/polymer acceptor pair; 2) robustness of the BHJ film morphology; 3) compatibility with large scale/large area manufacturing; 4) long-term stability of the cell to external environmental and mechanical stresses. This Minireview highlights the opportunities offered by APSCs, selected polymer families suitable for these devices with optimization to enhance the performance further, and discusses the challenges facing APSC development for commercial applications.

bio-inspired↗

In Operando Visualization of the Electrochemical Formation of Liquid Polybromide Microdroplets

Zinc–bromine flow batteries are promising for stationary energy storage, and bromine-complexing agents have been used to form phase-separated liquid polybromide products. However, an understanding of the dynamics of polybromide nucleation is limited due to the beam sensitivity and complexity of polybromides. Here we report an in operando platform composed of dark-field light microscopy and a transparent electrochemical cell to reveal the dynamics of polybromide formation in their native environment. Using our platform, we confirm and reveal the liquid nature, chemical composition, pinning effect (strong interaction with Pt), residual effect (residual charge products on the surface), self-discharging, and over-oxidation of the polybromide products. Overall, the results provide insights into the role of complexing agents and guide the future design of zinc–bromine flow batteries. Furthermore, our in operando platform can potentially be used to study sensitive species and phases in other electrochemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ZIF-8 Membrane Separation Performance Tuning by Vapor Phase Ligand Treatment

Vapor phase ligand treatment (VPLT) of 2-aminobenzimidazole (2abIm) for 2-methylimidazole (2mIm) in ZIF-8 membranes prepared by two different methods (LIPS: ligand induced permselectivation and RTD: rapid thermal deposition) results in a notable shift of the molecular level cut-off to smaller molecules establishing selectivity improvements from ca. 1.8 to 5 for O 2 /N 2 ; 2.2 to 32 for CO 2 /CH 4 ; 2.4 to 24 for CO 2 /N 2 ; 4.8 to 140 for H 2 /CH 4 and 5.2 to 126 for H 2 /N 2 . Furthermore, stable (based on a one-week test) oxygen-selective air separation performance at ambient temperature, 7 bar(a) feed, and 1 bar(a) sweep-free permeate with a mixture separation factor of 4.5 and oxygen flux of 2.6×10 -3 mol m -2 s -1 is established. LIPS and RTD membranes exhibit fast and gradual evolution upon a 2abIm-VPLT, respectively, reflecting differences in their thickness and microstructure. Functional reversibility is demonstrated by showing that the original permeation properties of the VPLT-LIPS membranes can be recovered upon 2mIm-VPLT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Pivot-Hinge Installation to Evolve Topology in Rare-Earth Metal–Organic Frameworks

Linker desymmetrization has been witnessed as a powerful design strategy for the discovery of highly connected metal–organic frameworks (MOFs) with unprecedented topologies. Herein, we introduce molecular pivot-hinge installation as a linker desymmetrization strategy to evolve the topology of highly connected rare-earth (RE) MOFs, where a pivot group is placed in the center of a linker similar to a hinge. By tuning the composition of pivot groups and steric hindrances of the substituents on various linker rotamers, MOFs with various topologies can be obtained. The combination of L-SO 2 with C 2v symmetry and 12-connected RE9 clusters leads to the formation of a fascinating (4,12)-c dfs new topology. Interestingly, when replacing L-SO 2 with a tetrahedra linker L-O, the stacking behaviors of RE-organic layers switch from an eclipsed mode to a staggered stacking mode, leading to the discovery of an intriguing hjz topology. Additionally, the combination of the RE cluster and a linker [(L-(CH 3 ) 6 )] with more bulky groups gives rise to a flu topology with a new 8-c inorganic cluster. The diversity of these RE-MOFs was further enhanced through post-synthetic installation of linkers with various functional groups. Functionalization of each linker with acidic and basic units in the mesoporous RE-based PCN-90-SO 2 allows for efficient cascade catalytic transformation within the functionalized channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Pyrazine-Based Polymer for Fast-Charge Batteries

The lack of high-power and stable cathodes prohibits the development of rechargeable metal (Na, Mg, Al) batteries. Here, poly(hexaazatrinaphthalene) (PHATN), an environmentally benign, abundant and sustainable polymer, is employed as a universal cathode material for these batteries. In Na-ion batteries (NIBs), PHATN delivers a reversible capacity of 220 mAh g -1 at 50 mA g -1 , corresponding to the energy density of 440 Wh kg -1 , and still retains 100 mAh g -1 at 10 Ag -1 after 50 000 cycles, which is among the best performances in NIBs. Such an exceptional performance is also observed in more challenging Mg and Al batteries. PHATN retains reversible capacities of 110 mAh g -1 after 200 cycles in Mg batteries and 92 mAh g -1 after 100 cycles in Al batteries. DFT calculations, X-ray photoelectron spectroscopy, Raman, and FTIR show that the electron-deficient pyrazine sites in PHATN are the redox centers to reversibly react with metal ions.

25 ENERGY STORAGE↗

Steam-Induced Coarsening of Single-Unit-Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis

Commonly used methods to assess crystallinity, micro-/mesoporosity, Brønsted acid site density and distribution (in micro- vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two-dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Finally, superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro- and mesoporosity, and micropore reaction rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

[M(EtBTP) 3 ][BPh 4 ] 3 ∙3 CH 3 CN (M=Nd, Am; EtBTP=2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl 3 ∙ n H 2 O with EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M 3+ cations bound by tridentate EtBTP ligands to create a tricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution, single-crystal X-ray diffraction data also allowed reduction in bond lengths esd's, such that a slight contraction of Δ=0.0158(18) Å in the Am-N versus Nd-N bond lengths was observed, even though these cations ostensibly have matching ionic radii. Theoretical evaluation revealed enhanced metal–ligand bonding through back donation in the [Am(EtBTP) 3 ] 3+ complex that is absent in [Nd(EtBTP) 3 ] 3+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecularly Mixed Composite Membranes: Challenges and Opportunities

The fabrication of porous molecules, such as metal–organic polyhedra (MOPs), porous organic cages (POCs) and others, has given rise to the potential for creating “solid solutions” of molecular fillers and polymers. Such solid solutions circumvent longstanding interface issues associated with mixed matrix membranes (MMMs), and are referred to as molecularly mixed composite membranes (MMCMs) to distinguish them from traditional two-phase MMMs. Early investigations of MMCMs highlight the advantages of solid solutions over MMMs, including dispersion of the filler, anti-plasticization of the polymer network, and removal of deleterious interfacial issues. However, the exact microscopic structure as well as the transport modality in this new class of membrane are not well understood. Moreover, there are clear engineering challenges that need to be addressed for MMCMs to transition into the field. Finally in this Minireview, the authors outline several scientific and technological challenges associated with the aforementioned questions and their suggestions to tackle them.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Building Blocks for High-Efficiency Organic Photovoltaics: Interplay of Molecular, Crystal, and Electronic Properties in Post-Fullerene ITIC Ensembles

Accurate single-crystal X-ray diffraction data offer a unique opportunity to compare and contrast the atomistic details of bulk heterojunction photovoltaic small-molecule acceptor structure and packing, as well as provide an essential starting point for computational electronic structure and charge transport analysis. Herein, we report diffraction-derived crystal structures and computational analyses on the n-type semiconductors which enable some of the highest efficiency organic solar cells produced to date, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC) and seven derivatives (including three new crystal structures: 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-propylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC-C3), 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(3-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (m-ITIC-C6), and 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-butylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC-C4-4F). IDTT acceptors typically pack in a face-to-face fashion with π–π distances ranging from 3.28–3.95 Å. Additionally, edge-to-face packing is observed with S...π interactions as short as 3.21–3.24 Å. Moreover, ITIC end group identities and side chain substituents influence the nature and strength of noncovalent interactions (e.g. H-bonding, π–π) and thus correlate with the observed packing motif, electronic structure, and charge transport properties of the crystals. Furthermore, density functional theory (DFT) calculations reveal relatively large nearest-neighbor intermolecular π-π electronic couplings (5.85–56.8 meV) and correlate the nature of the band structure with the dispersion interactions in the single crystals and core–end group polarization effects. Overall, this combined experimental and theoretical work reveals key insights into crystal engineering strategies for indacenodithienothiophene (IDTT) acceptors, as well as general design rules for high-efficiency post-fullerene small molecule acceptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Branched Bio-Lubricant Base Oil Production through Aldol Condensation

Currently, lubricant base oils are derived from petroleum, a nonrenewable feedstock that contributes to greenhouse gas emissions. Bioderived, renewable lubricant base oils can mitigate environmental challenges and offer superior cold flow properties by incorporating branches to the base oil's hydrocarbon backbone with an appropriate synthetic strategy. A strategy was developed to synthesize branched alkanes for lubricant base oil in two steps from 12-tricosanone, obtained from bioderived fatty acids, and furfural, obtained from lignocellulosic biomass. The reaction pathway involves carbon–carbon coupling through aldol condensation followed by hydrodeoxygenation (HDO). Various solvents (non-polar, aprotic and polar, protic) and reaction conditions were screened to achieve a maximum yield of 94.3% of aldol condensation products, containing the majority of a C 33 furan (79.5%) followed by a C 28 furan (14.8%). Subsequent HDO of aldol condensation products over an Ir-ReO x /SiO 2 catalyst produced lubricant-ranged branched alkanes (C 28 and C 33 ) with 61.4% yield and small fractions (<11%) of alkanes with carbon numbers between C 15 and C 10 . The viscous properties of the produced bio-lubricant base oil were comparable to commercial petroleum-derived Group III and Group IV base oils. Overall, this approach serves as a potential stepping-stone to replace petroleumderived base oils and, in turn, reduce greenhouse gas emissions associated with current lubricant production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗