C-O bond activation using ultralow loading of noble metal catalysts on moderately reducible oxides
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99 GENERAL AND MISCELLANEOUS↗
SEARCH · Engineering Papers
Results for “multifunction”
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Allosteric regulation of lysosomal enzyme recognition by the cation-independent mannose 6-phosphate receptor
Abstract not provided
Olson, Linda J.↗
Carbon mineralization pathways in interfacial adsorbed water nanofilms
Carbon mineralization in humidified carbon dioxide offers a promising route to mitigate anthropogenic emissions in a world stressed by water security. Despite its technological importance, our understanding of carbonation in water-poor environments lags, as traditional dissolution-precipitation pathways struggle to explain the adsorbed water nanofilm-mediated reactivity. Here, we utilize in operando X-ray diffraction (XRD) and advanced molecular simulations to investigate nanoconfined reactions driving forsterite carbonation, the magnesium-rich olivine. By examining magnesium ion dissolution and transport in atomistic simulations of the forsterite-water-carbon dioxide interface and comparing these with the in operando XRD activation energies, we identify both processes as rate-limiting at saturation. Our simulations reveal a mechanistic view of interfacial carbonation, where dissolution and precipitation are mediated by anomalous quasi two-dimensional diffusion. The transport process involves intermittent diffusive hopping in the desorbed state, separated by crawling events that are spatially short but temporally long. This understanding transcends carbon mineralization, with implications for understanding the transport of contaminants in geosystems, the design of multifunctional materials, water desalination, and molecular recognition systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Crystallization of binary nanocrystal superlattices and the relevance of short-range attraction
The synthesis of binary nanocrystal superlattices (BNSLs) enables the targeted integration of orthogonal physical properties, such as photoluminescence and magnetism, into a single superstructure, unlocking a vast design space for multifunctional materials. However, the formation mechanism of BNSLs remains poorly understood, restricting the prediction of the structure and properties of superlattices. Here we use a combination of in situ scattering and molecular simulation to elucidate the self-assembly of two common BNSLs (AlB 2 and NaZn 13 ) through emulsion templating. Our self-assembly experiments reveal that no intermediate structures precede the formation of the final binary phases, indicating that their formation proceeds through classical nucleation. Using simulations, we find that, despite the formation of AlB 2 and NaZn 13 typically being attributed to entropy, their self-assembly is most consistent with the nanocrystals possessing short-range interparticle attraction, which we find can accelerate nucleation kinetics in BNSLs. Here, we also find homogeneous, classical nucleation in simulations, corroborating our experiments. These results establish a robust correspondence between experiment and theory, paving the way towards prediction of BNSLs.
36 MATERIALS SCIENCE↗
Bio-inspired multiscale design for perovskite solar cells
Metal halide perovskite semiconductors have attractive light-harvesting and charge-carrier transport properties for photovoltaics. Perovskite solar cells (PSCs) and modules have demonstrated their commercial promise with high power conversion efficiencies, but still face stability challenges. In this Review, we explore how biomaterials offer design inspiration for the development of durable and efficient PSCs at three different scales. At the molecular level, bio-inspired molecular interactions are harnessed towards crystallization control and degradation prevention, which offers an enhancement in long-term maximum-power-point tracking stability. At the microstructural level, self-healing and strength-enhancing strategies, utilizing dynamic bonds and interfacial reinforcement, can help PSCs to recover from physical damage and maintain high performance. At the device level, macroscopic functionalities, such as moth-eye-inspired structures tailored to different layers, can collectively enable antireflection, radiative cooling and self-cleaning to optimize light management, heat dissipation and encapsulation in PSCs. Bio-inspired PSC research can combine improved efficiency and lifetime, with abundant, biocompatible alternatives to conventional stabilizers. Future efforts should focus on screening bioinspired molecules to optimize film crystallization and stability, developing self-healing mechanisms triggered by operational stress, designing cost-efficient biomicrostructures, and integrating multifunctional encapsulation to enhance the efficiency and lifespan of PSCs.
Duan, Tianwei↗
Chapter 3: Ultrathin Oxides for Solar Cells
This chapter discusses the many uses of ultrathin oxide layers across a broad range of photovoltaic (PV) technologies. The chapter is broken down into six sections, working from the solar absorber outwards: passivation layers, selective contact/buffer layers, recombination layers, barrier layers, anti-reflective coatings, and anti-soiling layers. The goal is to introduce the layer function, outline the scientific mechanisms behind each function, and provide illustrative examples from academic literature and industry. One theme in this chapter is the multifunctionality of oxide layers in the PV device stack, that is, a single layer rarely has only one purpose and therefore certain ideas will build upon other sections. The chapter covers a wide range of material and the discussions and examples are by no means exhaustive. The best efforts have been made to capture the central concepts for each topic and direct the reader to additional resources that have been found by the authors to be useful and relevant.
anti-reflection coatings↗
Photoelectron spectroscopy and computational investigations of the electronic structures and noncovalent interactions of cyclodextrin-closo-dodecaborate anion complexes x-CD·B12X122- (x = a, ß, y; X = H, F)
We report a joint negative ion photoelectron spectroscopy (NIPES) and computational study on the electronic structures and noncovalent interactions of a series of cyclodextrin-closo-dodecaborate dianion complexes, ?-CD·B12X122- (? = a, ß, ?; X = H, F). The measured vertical / adiabatic detachment energies (VDEs / ADEs) are 1.15/0.93, 3.55/3.20, 3.90/3.60, and 3.85/3.60 eV for B12H122- and its a-, ß-, ?-CD complexes, respectively; while the corresponding values are 1.90/1.70, 4.00/3.60, 4.33/3.95, and 4.30/3.85 eV for the X = F case. These results show that the inclusion of B12X122- into the CD cavities greatly increase the electronic stability of the dianions. The effect of electronic stabilization for ß-CD is roughly the same as for ?-CD, both being considerably stronger than that for a-CD. Density functional theory (DFT) based geometry optimization reveals that B12X122- are inserted into CDs increasingly deeper from a-CD to ?-CD. The calculated VDEs and ADEs agree with the experiments well, particularly, reproducing the electron binding energy (EBE) trends. The molecular orbital analyses indicate that the most loosely bound photodetached electrons origin from the guest B12X122- moieties. In addition to a shift of all signals to larger EBE, significant changes in the signal patterns are observed. At low EBE, this is due to the splitting of highly degenerate B12X122- orbitals, while at high EBE, photodetachment from CD oxygens contributes to the new bands. The guest B12X122- and host CD nocovalent, size-specific interaction based on the independent gradient model (IGM) and energy decomposition analysis (EDA), is dominated by electrostatic interactions. The analysis further unravels unambiguiously the existence of dihydrogen bonding and how it affects the total energy that stabilizes the host-guest complexes of CDs·B12H122- compared to the general hydrogen bonding interaction in CDs·B12F122-. This work clearly exhibits strong influences on the electronic structures of dodecaborates upon clustering with CDs, with both size (a-, ß-, ?-) and molecular (X = H or F) specificities, thus providing critical molecular-level information on the cyclodextrin-closo-dodecaborate interactions of interest to medical applications, e.g. Boron neutron capature therapy. The NIPES experiments done at PNNL were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Bioscience (X.-B.W.) and was performed at the EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. H.S. and Z.S. acknowledge the funding support of National Natural Science Foundation of China (Nos.11727810, 61720106009 and 21603074), the Science and Technology Commission of Shanghai Municipality (Nos. 19JC1412200), and the Program of Introducing Talents of Discipline to Universities 111 project (B12024). Z. L. thanks the China Scholarship Council (CSC) for financial support. We acknowledge the ECNU Multifunctional Platform for Innovation (001) and HPC Research Computing Team for providing computational and storage resources. J.W. acknowledges support from the Alexander von Humboldt foundation (Feodor Lynen Fellowship and Rückkehrerstipendium), a Freigeist fellowship of the Volkswagenfoundation and Prof. Vladimir A. Azov for helpful discussions.
Li, Zhipeng↗
Effect of lattice mismatch and shell thickness on strain in core@shell nanocrystals
Abstract not provided
Gamler, Jocelyn T.L.↗
Hybrid magnetic nanoparticles as efficient nanoheaters in biomedical applications
Heating at the nanoscale is the basis of several biomedical applications, including magnetic hyperthermia therapies and heat-triggered drug delivery. The combination of multiple inorganic materials in hybrid magnetic nanoparticles provides versatile platforms to achieve an efficient heat delivery upon different external stimuli or to get an optical feedback during the process. However, the successful design and application of these nanomaterials usually require intricate synthesis routes and their magnetic response is still not fully understood. In this review we give an overview of the novel systems reported in the last few years, which have been mostly obtained by organic phase-based synthesis and epitaxial growth processes. Since the heating efficiency of hybrid magnetic nanoparticles often relies on the exchange-interaction between their components, we discuss various interface-phenomena that are responsible for their magnetic properties. Finally, followed by a brief comment on future directions in the field, we outline recent advances on multifunctional nanoparticles that can boost the heating power with light and combine heating and temperature sensing in a single nanomaterial.
36 MATERIALS SCIENCE↗
Exploring phase transitions and magnetoelectric coupling of epitaxial asymmetric multilayer heterostructures
Magnetoelectric (ME) heterostructures can exhibit higher magnetic and ferroelectric ordering temperatures along with large ME coupling compared to single-phase multiferroic materials. We synthesized Pb(Fe 0.5 Nb 0.5 )O 3 (PFN)/Ni 0.65 Zn 0.35 Fe 2 O 4 (NZFO)/Pb(Fe 0.5 Nb 0.5 )O 3 (PFN)/Ni 0.65 Zn 0.35 Fe 2 O 4 (NZFO)/Pb(Fe 0.5 Nb 0.5 )O 3 (PFN) multilayer heterostructures having dimensions of 40/10/40/10/40 nm. High quality epitaxial growth of these heterostructures was confirmed via X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns. These nanostructures show well saturated polarization (~52 μC cm -2 ) and magnetization (~62 emu cm -3 ) at room temperature (RT). The magnetic and ferroelectric transitions occur well above RT. These heterostructures exhibit relaxor behavior and undergo 2nd order ferroelectric phase transition. Magnetodielectric measurements show significant coupling between the magnetic and electrical order parameters at RT. These characteristics of the heterostructures make them suitable as potential candidates for ultra-low power memory, spintronics, and different multifunctional (micro)nanoscale device applications.
36 MATERIALS SCIENCE↗
Synthesis of (hemi)cellulosic lubricant base oils via catalytic coupling and deoxygenation pathways
The past decade has witnessed a significant growth in bioproduct development due to the strong interest in creating a more diverse energy supply, environmental sustainability, and a carbon neutral bioeconomy. The initial biorefinery strategy, which focused mainly on the production of low carbon number drop-in bioproducts, has recently shifted its focus on the production of high carbon number and high performance bioproducts with unique properties and value propositions. One such product is lubricant base oil (LBO), which represents over $150 billion global lubricant market and is used for various industrial, automotive, marine, metal-working, consumer, and specialized applications. The application landscape of lubricants has changed significantly over the past decade because of environmental regulations and the growing demand for sustainable lubricants to mitigate regulatory challenges and improve carbon footprint. Currently, only 3% LBOs are produced from bio-based triglycerides/fatty acids. Because of low oxidation stability and high hydrolytic susceptibility, these bio-based LBOs have limited applications. Thus, research and development and commercialization efforts for (hemi)cellulosic LBOs to meet the market demand have received momentum over the past few years. This review describes strategies to produce (hemi)cellulosic LBOs via carbon–carbon coupling and hydrodeoxygenation chemistries. We emphasize the coupling strategies to create LBOs with a branched architecture to surrogate petroleum-based poly-α-olefins. Here, a structure–property relationship for tuning the key specifications of LBOs as a function of molecular architecture is illustrated. Mechanistic understanding and molecular interactions of multi-furan substrates with the active sites of complex multifunctional catalysts are described. Furthermore, techno-economic and life-cycle analysis is summarized along with standing challenges and future opportunities.
09 BIOMASS FUELS↗
One-step fabrication of robust lithium ion battery separators by polymerization-induced phase separation
Conventional lithium ion battery separators are microporous polyolefin membranes that play a passive role in the electrochemical cell. Next generation separators should offer significant performance enhancements, while being fabricated through facile, low cost approaches with the ability to readily tune physicochemical properties. This study presents a single-step manufacturing technique based on UV-initiated polymerization-induced phase separation (PIPS), wherein microporous separators are fabricated from multifunctional monomers and ethylene carbonate (EC), which functions as both the pore-forming agent (porogen) and electrolyte component in the electrochemical cell. By controlling the ratio of the 1,4-butanediol diacrylate (BDDA) monomer to ethylene carbonate, monolithic microporous membranes are readily prepared with 25 μm thickness and pore sizes and porosities ranging from 6.8 to 22 nm and 15.4% to 38.5%, respectively. With 38.5% apparent porosity and an average pore size of 22 nm, the poly(1,4-butanediol diacrylate) (pBDDA) separator takes up 127% liquid electrolyte, resulting in an ionic conductivity of 1.98 mS cm –1 , which is greater than in conventional Celgard 2500. Lithium ion battery half cells consisting of LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathodes and pBDDA separators were shown to undergo reversible charge/discharge cycling with an average discharge capacity of 142 mA h g –1 and a capacity retention of 98.4% over 100 cycles – comparable to cells using state-of-the-art separators. Moreover, similar discharge capacities were achieved in rate performance tests due to the high ionic conductivity and electrolyte uptake of the film. Finally, the pBDDA separators were shown to be thermally stable to 374 °C, lack low temperature thermal transitions that can compromise cell safety, and exhibit no thermal shrinkage up to 150 °C.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Light–ferroelectric interaction in two-dimensional lead iodide perovskites
The unique physical properties of two-dimensional (2D) metal halide perovskites (MHPs) such as nonlinear optics, anisotropic charge transport, and ferroelectricity have made these materials promising candidates for multifunctional applications. Recently, fluorine derivatives such as 4,4-difluoropiperidinium lead iodide perovskite or (4,4-DFPD, C 5 H 10 F 2 N) 2 PbI 4 have shown strong ferroelectricity as compared to other 2D MHPs. Although it was previously addressed that the ferroelectricity in MHPs can be affected by illumination, the underlying physical mechanisms of light–ferroelectricity interaction in 2D MHPs are still lacking. Here, we explore the electromechanical responses in 4,4-(DFPD) 2 PbI 4 thin films using advanced scanning probe microscopy techniques revealing ferroelectric domain structures. In this work, hysteretic ferroelectric loops measured by contact-Kelvin probe force microscopy are dependent on domain structures under dark conditions, while ferroelectricity weakens under illumination. The X-ray diffraction patterns exhibit significant changes in preferential orientation of individual lattice planes under illumination. Particularly, the reduced intensity of the (1 1 1) lattice plane under illumination leads to transitioning from a ferroelectric to a paraelectric phase. The instability of positive ions, especially molecular organic cations, is observed under illumination by time-of-flight secondary ion mass spectrometry. The combination of crystallographic orientation and chemical changes under illumination clearly contributes to the origin of light–ferroelectricity interaction in 2D (4,4-DFPD, C 5 H 10 F 2 N) 2 PbI 4 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ferroic phase transitions and magnetoelectric coupling in cobalt doped BaTiO 3
Magnetoelectric (ME) materials exhibit interesting physics with cross coupling between ferroelectric and magnetic order parameters and thus strong potential to be utilized in memory, spintronics and other multifunctional electronic/magnetic devices. Doping of suitable transition metals in ferroelectrics can induce magnetism and ME coupling and modify the physical properties. Here, we report the structural, electronic, magnetic and ME coupling of 3.5, 5 and 7.5 mol% cobalt doped BaTiO 3 (BTO) ceramics. X-ray diffraction and Raman spectroscopy indicate that the samples are single phase having a tetragonal crystal structure with P4mm symmetry. The tetragonality ratio is found to decrease with increasing cobalt content. We observed a Fano-like asymmetric peak in the [A 1 (LO 1 )] Raman mode at ~173 cm -1 in all the cobalt doped BTO samples. The cobalt dopants are shown to be uniformly distributed throughout the surface of the samples. We observed a lowering of the ferroelectric transition temperature and increasing diffusivity parameter with increasing cobalt concentration. The electrical properties of all the samples have been investigated in detail by impedance spectroscopy and ac conductivity studies before and after the ferroelectric phase transitions. All the samples show hysteretic ferroelectric behavior with a clear saturation state that decreases with increasing cobalt content. The observed ferroelectricity in these samples is intrinsic in nature. The 3.5% cobalt doped BTO sample exhibits paramagnetic behavior whereas the 5 and 7.5% cobalt doped BTO samples show ferromagnetic ordering below 43 K. The 7.5% cobalt doped BTO samples show significant ME coupling.
36 MATERIALS SCIENCE↗
Unusual electronic transport in (1 - x )Cu 2 Se-( x )CuInSe 2 hierarchical composites
The ability to control the relative density of electronic point defects as well as their energy distribution in semiconductors could afford a systematic modulation of their electronic, optical, and optoelectronic properties. Using a model binary hybrid system Cu 2 Se–CuInSe 2 , we have investigated the correlation between phase composition, microstructure, and electronic transport behavior in the synthesized composites. We found that both Cu 2 Se and CuInSe 2 phases coexist at multiple length scales, ranging from sub-ten nanometer to several micrometers, leading to the formation of a hybrid hierarchical microstructure. Astonishingly, the electronic phase diagram of the (1 - x)Cu 2 Se–(x)CuInSe 2 (15% ≤ x ≤ 100%) hierarchical composites remarkably deviates from the trend normally expected for composites between a heavily doped semiconductor (Cu 2 Se) and a poorly conducting phase (CuInSe 2 ). A sudden 3-fold increase in the electrical conductivity and carrier concentration along with a marginal increase in the carrier mobility is observed for composites at the vicinity of equimolar composition (48% ≤ x ≤ 52%). The carrier concentration increases from ~1.5 × 10 20 cm -3 for the composites with x ≤ 45% to 5.0 × 10 20 cm -3 for x = 50%, and remains constant at 4.5 × 10 20 cm -3 with x value in the range of 52% < x ≤ 90%, then quickly drops to 8 × 10 18 cm -3 for pristine CuInSe 2 phase (x = 100%). The atypical electronic behavior was rationalized in the light of the formation of an inter-band (IB) within the band gap, which arises from the hybridization of native electronic point defects from both Cu 2 Se and CuInSe 2 phases in the resulting hierarchical composites. The result points to a new strategy to modulate the electronic structure of semiconductor composites to maximize interaction and coupling between two fundamentally contrasting properties enabling access to electronic hybrid systems with potential applications as interactive and stimuli-responsive multifunctional materials.
36 MATERIALS SCIENCE↗
Self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars
Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, e.g., hyperbolic optical properties. Herein, self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO 2 matrix were fabricated using a one-step self-assembly process. The film crystallinity and pillar uniformity can be obviously improved by adding an ultra-thin TiN-Au buffer layer during the growth. Here, the HfO 2 -Au hybrid VAN films show an obvious plasmonic resonance at 480 nm, which is much lower than the typical plasmonic resonance wavelength of Au nanostructures, and is attributed to the well-aligned ultra-fine Au nanopillars. Coupled with the broad hyperbolic dispersion ranging from 1050 nm to 1800 nm in wavelength, and unique dielectric HfO 2 , this nanoscale hybrid plasmonic metamaterial presents strong potential for the design of future integrated optical and electronic switching devices.
36 MATERIALS SCIENCE↗
Design of a multi-functional gel polymer electrolyte with a 3D compact stacked polymer micro-sphere matrix for high-performance lithium metal batteries
We report lithium metal batteries (LMBs) are considered as promising high energy density batteries. However, they still suffer from poor cyclability due to the instability of solid electrolyte interphases (SEIs) and Li dendrite issues. Herein, a novel 3D densely packed multifunctional crosslinked gel polymer electrolyte (PHGPE) has been synthesized by in situ copolymerization of pentaerythritol tetraacrylate and 2-hydroxyethyl acrylate in a liquid electrolyte via a thermal initiation method. Due to intermolecular hydrogen bonding in the frameworks, the PHGPE exhibits a 3D compact-stacked and crosslinked micro-sphere structure, which benefits the construction of homogeneous Li + flux, enabling uniform Li plating/stripping and formation of robust SEIs onto the lithium electrode. Benefiting from the above advantages, symmetric Li cells in the PHGPE deliver excellent cyclabilities of 6000 h at a current density of 1 mA cm -2 (1 mA h cm -2 ) and 7700 h at 0.5 mA cm -2 (2 mA h cm -2 ). Moreover, the PHGPE has such a wide electrochemical window that it is compatible with both high-voltage LiNi 0.8 Co 0.1 Mn 0.1 O 2 and sulfur cathodes to realize long cycle life. Additionally, a LiFePO 4 based pouch size LMB also presents promising performance. Therefore, this study of the PHGPE has opened a new avenue for high-performance LMBs with excellent versatility and practicality.
25 ENERGY STORAGE↗
Carbon nanomaterials–polymer composites for perovskite solar cells: preparation, properties and applications
Perovskite solar cells (PSCs) are a rising star in the photovoltaic industry, which achieved an enormous breakthrough in terms of efficiency from an initial 3.8% in 2009 to 25.7% in 2021. Here, the major challenge to bring perovskite solar cells commercially available is the poor long-term device stability. The defects in perovskite and energy loss originating from charge recombination limit the efficiency of perovskite solar cells. Carbon–polymer composites, which feature superb electrical conductivity, outstanding carrier mobility, remarkable flexibility and superior heat and moisture stability, have attracted considerable attention to tackle these issues. With their multifunctional properties, carbon–polymer composites can play various roles in almost every component in the perovskite solar cell architecture. In this review article, recent progress concerning the utilization of carbon–polymer composites in different components in PSCs (i.e., perovskite additives, electrodes, encapsulation layers and charge transport layers) is comprehensively overviewed. Then, future research directions and opportunities toward high-performance perovskite solar cells utilizing carbon–polymer composites are presented.
36 MATERIALS SCIENCE↗