Systematic electrochemical oxidative doping of P3HT to probe interfacial charge transfer across polymer-fullerene interfaces
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solar (photovoltaic), electrodes - solar, charge t↗
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Results for “process synthesis”
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Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks
Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. In this work, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal–organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal–organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Lastly and most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.
36 MATERIALS SCIENCE↗
Hot Carrier and Surface Recombination Dynamics in Layered InSe Crystals
Layered indium selenide (InSe) is a van der Waals solid that has emerged as a promising material for high-performance ultrathin solar cells. The optoelectronic parameters that are critical to photoconversion efficiencies, such as hot carrier lifetime and surface recombination velocity, are however largely unexplored in InSe. Here, these key photophysical properties of layered InSe are measured with femtosecond transient reflection spectroscopy. The hot carrier cooling process is found to occur through phonon scattering. The surface recombination velocity and ambipolar diffusion coefficient are extracted from fits to the pump energy-dependent transient reflection kinetics using a free carrier diffusion model. The extracted surface recombination velocity is approximately an order of magnitude larger than that for methylammonium lead-iodide perovskites, suggesting that surface recombination is a principal source of photocarrier loss in InSe. The extracted ambipolar diffusion coefficient is consistent with previously reported values of InSe carrier mobility.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Large-Scale Synthesis of Colloidal Si Nanocrystals and Their Helium Plasma Processing into Spin-On, Carbon-Free Nanocrystalline Si Films
This study describes a simple approach to the large-scale synthesis of colloidal Si nanocrystals and their processing into spin-on carbon-free nanocrystalline Si films. The synthesized silicon nanoparticles are capped with decene, dispersed in hexane, and deposited on silicon substrates. The deposited films are exposed to nonoxidizing room-temperature He plasma to remove the organic ligands without adversely affecting the silicon nanoparticles to form crack-free thin films. We further show that the reactive ion etching rate in these films is 1.87 times faster than that for single-crystalline Si, consistent with a simple geometric argument that accounts for the nanoscale roughness caused by the nanoparticle shape.
36 MATERIALS SCIENCE↗
Cation-Dependent Stabilization of Electrogenerated Naphthalene Diimide Dianions in Porous Polymer Thin Films and Their Application to Electrical Energy Storage
Porous polymer networks (PPNs) are attractive materials for capacitive energy storage because they offer high surface areas for increased double-layer capacitance, open structures for rapid ion transport, and redox-active moieties that enable faradaic (pseudocapacitive) energy storage. Here we demonstrate a new attractive feature of PPNs—the ability of their reduced forms (radical anions and dianions) to interact with small radii cations through synergistic interactions arising from densely packed redox-active groups, only when prepared as thin films. When naphthalene diimides (NDIs) are incorporated into PPN films, the carbonyl groups of adjacent, electrochemically generated, NDI radical anions and dianions bind strongly to K+, Li+, and Mg2+, shifting the formal potentials of NDI’s second reduction by 120 and 460 mV for K+ and Li+-based electrolytes, respectively. In the case of Mg2+, NDI’s two redox waves coalesce into a single two-electron process with shifts of 240 and 710 mV, for the first and second reductions, respectively, increasing the energy density by over 20 % without changing the polymer backbone. In contrast, the formal reduction potentials of NDI derivatives in solution are identical for each electrolyte, and this effect has not been reported for NDI previously. This study illustrates the profound influence of the solid-state structure of a polymer on its electrochemical response, which does not simply reflect the solution-phase redox behavior of its monomers.
36 MATERIALS SCIENCE↗
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↗
Highly Porous Thermoelectric Nanocomposites with Low Thermal Conductivity and High Figure of Merit from Large-Scale Solution-Synthesized Bi 2 Te 2.5 Se 0.5 Hollow Nanostructures
To enhance the performance of thermoelectric materials and enable access to their widespread applications, it is beneficial yet challenging to synthesize hollow nanostructures in large quantities, with high porosity, low thermal conductivity (κ) and excellent figure of merit ($z$T). Herein we report a scalable (ca. 11.0 g per batch) and low-temperature colloidal processing route for Bi 2 Te 2.5 Se 0.5 hollow nanostructures. They are sintered into porous, bulk nanocomposites (phi 10 mm×h 10 mm) with low κ (0.48 W m -1 K -1 ) and the highest z T (1.18) among state-of-the-art Bi 2 Te 3-x Se x materilas. Additional benefits of the unprecedented low relative density (68–77 %) are the large demand reduction of raw materials and the improved portability. This method can be adopted to fabricate other porous phase-transition and thermoelectric chalcogenide materials and will pave the way for the implementation of hollow nanostructures in other fields.
36 MATERIALS SCIENCE↗
Mechanistic investigation of the Zn/Pd/C catalyzed cleavage and hydrodeoxygenation of lignin
While current biorefinery processes use lignin only for its heat value, the conversion of lignin to high value chemicals is an area of increasing interest. In this article we present a detailed mechanistic study of the hydrodeoxygenation (HDO) of lignin by using a synergistic Pd/C and Zn II catalyst through use of both lignin model compounds and lignocellulosic biomass. Spectroscopic data coupled with the study of lignin model compounds suggest that Zn II activates and facilitates removal of the hydroxyl group at the Cγ position of the β-O-4 ether linkage. Activation is proposed to occur through formation of a six-membered ring complex of Zn II coordinated to the oxygen atoms at Cα and Cγ of the lignin model compound guaiacylglycerol-β-guaiacyl.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomistic Simulation Derived Insight on the Irreversible Structural Changes of Si Electrode during Fast and Slow Delithiation
Quantifying the irreversible chemical and structural changes of Si during cycling remains challenging. In this study, a continuous reactive molecular dynamics delithiation algorithm, with well-controlled potential gradient and delithiation rate, was developed and used to investigate the “natural” delithiation responses of an aluminum-oxide coated silicon thin-film. Fast delithiation led to the formation of dense Si network near the surface and nanoporosity inside the a-Li x Si, resulting in 141% volume dilation and significant amount of Li trapped inside (a-Li 1.2 Si) at the end of delithiation process. In contrast, slow delithiation allowed the a-Li x Si to shrink by near-equilibrium condition, demonstrating no permanent inner pore with nearly Li-free structure (a-Li 0.2 Si) and minimal volume dilation (44%). However, even without trapped Li, the delithiated a-LixSi still exhibited higher volume (lower density) than the equilibrium structure with the same Li concentration, despite delithiation rate. The origin of this excess volume is the loss of directly bonded Si–Si pairs, which made the subsequent relithiation faster. On the basis of the atomistic modeling and the quantified degradation mechanism, battery operating guidelines, including the delithiation rate and the depth of charge to avoid trapped Li and coating delamination, were suggested to improve the durability Si electrodes.
25 ENERGY STORAGE↗
A Review of Biorefinery Separations for Bioproduct Production via Thermocatalytic Processing
With technological advancement of thermocatalytic processes for valorizing renewable biomass carbon, development of effective separation technologies for selective recovery of bioproducts from complex reaction media and their purification becomes essential. The high thermal sensitivity of biomass intermediates and their low volatility and high reactivity, along with the use of dilute solutions, make the bioproducts separations energy intensive and expensive. Novel separation techniques, including solvent extraction in biphasic systems and reactive adsorption using zeolite and carbon sorbents, membranes, and chromatography, have been developed. In parallel with experimental efforts, multiscale simulations have been reported for predicting solvent selection and adsorption separation. We discuss various separations that are potentially valuable to future biorefineries and the factors controlling separation performance. Particular emphasis is given to current gaps and opportunities for future development.
bio-inspired↗
Self-generated concentration and modulus gradient coating design to protect Si nano-wire electrodes during lithiation
Surface coatings as artificial solid electrolyte interphases have been actively pursued as an effective way to improve the cycle efficiency of nanostructured Si electrodes for high energy density lithium ion batteries, where the mechanical stability of the surface coatings on Si is as critical as Si itself. However, the chemical composition and mechanical property change of coating materials during the lithiation and delithiation process imposed a grand challenge to design coating/Si nanostructure as an integrated electrode system. In our work, we first developed reactive force field (ReaxFF) parameters for Li–Si–Al–O materials to simulate the lithiation process of Si-core/Al 2 O 3 -shell and Si-core/SiO 2 -shell nanostructures. With reactive dynamics simulations, we were able to simultaneously track and correlate the lithiation rate, compositional change, mechanical property evolution, stress distributions, and fracture. A new mechanics model based on these varying properties was developed to determine how to stabilize the coating with a critical size ratio. Furthermore, we discovered that the self-accelerating Li diffusion in Al 2 O 3 coating forms a well-defined Li concentration gradient, leading to an elastic modulus gradient, which effectively avoids local stress concentration and mitigates crack propagation. Finally, based on these results, we propose a modulus gradient coating, softer outside, harder inside, as the most efficient coating to protect the Si electrode surface and improve its current efficiency.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Simulation of the Effect of Contact Area Loss in All-Solid-State Li-Ion Batteries
Maintaining the physical contact between the solid electrolyte and the electrode is important to improve the performance of all-solid-state batteries. Imperfect contact can be formed during cell fabrication and will be worsened due to cycling, resulting in degradation of the battery performance. In this paper, the effect of imperfect contact area was incorporated into a 1-D Newman battery model by assuming the current and Li concentration will be localized at the contacted area. Constant current discharging processes at different rates and contact areas were simulated for a film-type Li|LiPON|LiCoO 2 all-solid-state Li-ion battery. The capacity drop was correlated with the contact area loss. It was found at lower cutoff voltage, the correlation is almost linear with a slope of 1; while at a higher cutoff voltage, the dropping rate is slower. To establish the relationship between the applied pressure and the contact area, Persson's contact mechanics theory was applied, as it uses self-affined surfaces to simplify the multi-length scale contacts in all-solid-state batteries. The contact area and pressure were computed for both film-type and bulk-type all-solid-state Li-ion batteries. The model is then used to suggest how much pressures should be applied to recover the capacity drop due to contact area loss.
25 ENERGY STORAGE↗
3D Wettable Framework for Dendrite-Free Alkali Metal Anodes
The infinite volume change and dendritic behavior in alkali metal anodes lead to low Coulombic efficiency and short-circuit issues that significantly hamper renewed efforts at commercialization. In this study, a dendrite-free alkali metal anode, made by thermally preloading molten Li or Na into a 3D framework with high alkali wettability, is reported. In the mechanically robust 3D framework, carbon fiber (CF) serves as an electrical highway that provides fast charge transfer for the redox reaction. Through a facile solution-based process, a SnO 2 coating is introduced to modify the poor wetting behavior of the carbon framework and drastically improve both the electrochemical performance and reliability. The kinetic barrier to adhesion of molten alkali metals on the CF framework is eliminated by the mixed reaction with SnO 2 . The growth of dendrites is effectively repressed under the decreased local current density of the 3D framework. In full-cell configurations with LiFePO 4 cathodes, the Li–CF electrode shows reduced polarization and 90% capacity retention after 500 cycles in traditional carbonate electrolyte. Comparable improvements are also observed in 3D electrodes for Na metal batteries. These findings on a stable 3D carbon framework with improved wetting behavior provide significant practical implications for achieving safe and commercially viable alkali metal anodes.
25 ENERGY STORAGE↗
A synergistic biorefinery based on catalytic conversion of lignin prior to cellulose starting from lignocellulosic biomass
Current biomass utilization processes do not make use of lignin beyond its heat value. Here we report on a bimetallic Zn/Pd/C catalyst that converts lignin in intact lignocellulosic biomass directly into two methoxyphenol products, leaving behind the carbohydrates as a solid residue. Genetically modified poplar enhanced in syringyl (S) monomer content yields only a single product, dihydroeugenol. Lignin-derived methoxyphenols can be deoxygenated further to propylcyclohexane. In this work the leftover carbohydrate residue is hydrolyzed by cellulases to give glucose in 95% yield, which is comparable to lignin-free cellulose (solka floc). New conversion pathways to useful fuels and chemicals are proposed based on the efficient conversion of lignin into intact hydrocarbons.
09 BIOMASS FUELS↗
Investigation of the effects of ternary deep eutectic solvent composition on pretreatment of sorghum stover
Biomass‐derived deep eutectic solvents (DESs) have been introduced as promising pretreatment and fractionation solvents because of their mild processing conditions, easy synthesis, and green solvent components from biomass. In recent DES studies, solvent‐based third constituents like water, ethanol, and others improve the processibility of typical binary DESs. However, the impacts of these components are not well understood. Here, two solvent‐based constituents, including water and ethylene glycol, were applied to 3,4‐dihydroxybenzoic acid (DHBA)‐based DES system for improving the conversion efficiency of cellulose‐rich fraction and the properties of lignin fraction. Chemical composition, enzymatic digestibility, degree of polymerization of cellulose and physicochemical properties of lignin were used to evaluate the impact of each third constituent on biomass processing. Ternary ChCl‐DHBA DESs exhibited better performances in delignification, fermentable sugar production, and preservation of β‐O‐4 ether linkage in lignin compared with binary ChCl‐DHBA DES.
09 BIOMASS FUELS↗
Anti-melanogenic activity of schaftoside in Rhizoma Arisaematis by increasing autophagy in B16F1 cells
Highlights: • Rhizoma Arisaematis extract (RA) suppressed the melanogenesis. • Inhibition of autophagy reduced the anti-melanogenic activity of RA. • Schaftoside was identified as an effector molecule of RA. • Schaftoside has anti-melanogenic effect and induced autophagy activation. Skin pigmentation involves multiple processes, including melanin synthesis, transport, and melanosome release. Melanin content determines skin color and protects against UV radiation-induced damage. Autophagy is a cooperative process between autophagosomes and lysosomes that degrades cellular components and organelles. In the present study, B16F1 cells were treated with Rhizoma Arisaematis extract (RA) and assessed for pigmentation and autophagy regulation. RA treatment suppressed the α-MSH-stimulated increase of melanogenesis and down-regulated the expression of tyrosinase and TRP1 proteins in B16F1 cells. In addition, autophagy was activated in RA-treated cells. Inhibition of autophagy reduced the anti-melanogenic activity of RA in α-MSH-treated B16F1 cells. We identified schaftoside as an effector molecule by LC-MS analysis of RA. Consistently, treatment of schaftoside showed anti-melanogenic effect and induced autophagy activation in B16F1 cells. Inhibition of autophagy by 3 MA treatment reduced the anti-melanogenic effect of the schaftoside and recovered expression level of melanogenesis regulators in α-MSH-treated B16F1 cells. Taken together, our results suggest that schaftoside from RA inhibits skin pigmentation through modulation of autophagy.
60 APPLIED LIFE SCIENCES↗
Stability of Zeolitic Imidazolate Frameworks in NO 2
The use of nanoporous zeolitic imidazolate frameworks (ZIFs) in separation processes is promising, but the presence of acid gases such as SO x or NO x in process streams can have detrimental results. Although we have recently developed a mechanistic picture of SO x –ZIF interactions, here we describe the remarkably different effects of NO 2 on ZIFs. ZIFs with a representative range of SO x stabilities are all unstable—as defined by loss of crystallinity and porosity—in dry and humid NO 2 , whereas most ZIFs are stable in dry SO x and some even in humid SO x . A detailed mechanism is developed based on Fourier transform infrared spectroscopy and density functional theory calculations. H-abstraction by free radical NO 2 and subsequent acidic species formation are the major degradation pathways, while adsorbed HNO 3 formation in humid conditions is an additional pathway in hydrophilic ZIFs. These findings strongly suggest that new strategies to stabilize ZIFs/metal–organic frameworks toward NO 2 attack are required.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coherent Dynamics of Mixed Frenkel and Charge-Transfer Excitons in Dinaphtho[2,3- b :2'3'- f ]thieno[3,2- b ]-thiophene Thin Films: The Importance of Hole Delocalization
Charge-transfer states in organic semiconductors play crucial roles in processes such as singlet fission and exciton dissociation at donor/acceptor interfaces. Recently, a time-resolved spectroscopy study of dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene (DNTT) thin films provided evidence for the formation of mixed Frenkel and charge-transfer excitons after the photoexcitation. In this study, we investigate optical properties and excitation dynamics of the DNTT thin films by combining ab initio calculations and a stochastic Schrödinger equation. Our theory predicts that the low-energy Frenkel exciton band consists of 8–47% CT character. The quantum dynamics simulations show coherent dynamics of Frenkel and CT states in 50 fs after the optical excitation. Lastly, we demonstrate the role of charge delocalization and localization in the mixing of CT states with Frenkel excitons as well as the role of their decoherence.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗