Effects of cathode loadings and anode protection on the performance of lithium metal batteries.

While lithium-ion batteries (LIBs) are approaching their energy limits, lithium metal batteries (LMBs) are undergoing intensive investigation for higher energy density. Coupling LiNi0.8Mn0.1Co0.1O2(NMC811) cathode with lithium (Li) metal anode, the resultant Li||NMC811 LMBs are among the most promising technologies for future transportation electrification, which have the potential to realize an energy density two times higher than that of state-of-the-art LIBs. To maximize their energy density, the Li||NMC811 LMBs are preferred to have their cathode loading as high as possible while their Li anode as thin as possible. To this end, we investigated the effects of different cathode active material loadings (2-14 mg cm-2) on the performance of the Li||NMC811 LMBs. Our study revealed that the cathode loadings have remarkably affected the cell performance, in terms of capacity retention and sustainable capacity. Cells with high cathode loadings are more liable to fade in capacity, due to more severe formation of the CEI and more sluggish ion transport. In this study, we also verified that the protection of the Li anode is significant for achieving better cell performance. In this regard, our newly developed Li-containing glycerol (LiGL) via molecular layer deposition (MLD) is promising to help boost the cell performance, which was controllably deposited on the Li anode.

Using a Faculty-Developed Documentary-Style Film to Communicate Authentic Chemistry Research to a High School Audience.

Described is the creation, deployment, and evaluation of a video produced about the synthesis and applications of metal-organic frameworks (MOFs). The goal of this project was to gauge the impact of viewing the video on high school students' conceptions of authentic chemistry practices and applications. Additionally, comparisons were made between the use of the video and more traditional face-to-face presentations given by professional scientists. Observations, student surveys, and an interview with the high school chemistry teacher demonstrated the utility of such a video. Specifically, the students who viewed the video reported learning more about the nature of laboratory work in chemistry than other students who did not view the video. Students, regardless of whether they viewed the video or just received a presentation, reported growth in understandings of the applications of chemistry research and porous nanomaterial. Other research chemists are encouraged to consider ways that they could document on video the research that they are performing in order to introduce an untapped audience (high school students) to authentic chemistry research in a practically simple manner. During times of crisis, such as a pandemic, online videos could be a useful tool for high school chemistry teachers to use in collaboration with research faculty, particularly when schools are closed.

Two-Dimensional Water-Coupled Metallic MoS2 with Nanochannels for Ultrafast Supercapacitors.

MoS2 is a promising electrode material for energy storage. However, the intrinsic multilayer pure metallic MoS2 (M-MoS2) has not been investigated for use in supercapacitors. Here, an ultrafast rate supercapacitor with extraordinary capacitance using a multilayer M-MoS2-H2O system is first investigated. Intrinsic M-MoS2 with a monolayer of water molecules covering both sides of nanosheets is obtained through a hydrothermal method with water as solvent. The super electrical conductivity of the as-prepared pure M-MoS2 is beneficial to electron transport for high power supercapacitor. Meanwhile, nanochannels between the layers of M-MoS2-H2O with a distance of ∼1.18 nm are favorable for increasing the specific space for ion diffusion and enlarging the surface area for ion adsorption. By virtue of this, M-MoS2-H2O reaches a high capacitance of 380 F/g at a scan rate of 5 mV/s and still maintains 105 F/g at scan rate of 10 V/s. Furthermore, the specific capacitance of the symmetric supercapacitor based on M-MoS2-H2O electrodes retain a value as high as 249 F/g under 50 mV/s. These findings suggest that multilayered M-MoS2-H2O system with ion accessible large nanochannels and efficient charge transport provide an efficient energy storage strategy for ultrafast supercapacitors.

Investigation of electrically active defects in InGaAs quantum wire intermediate-band solar cells using deep-level transient spectroscopy technique.

InGaAs quantum wire (QWr) intermediate-band solar cell-based nanostructures grown by molecular beam epitaxy are studied. The electrical and interface properties of these solar cell devices, as determined by current-voltage (I-V) and capacitance-voltage (C-V) techniques, were found to change with temperature over a wide range of 20-340 K. The electron and hole traps present in these devices have been investigated using deep-level transient spectroscopy (DLTS). The DLTS results showed that the traps detected in the QWr-doped devices are directly or indirectly related to the insertion of the Si δ-layer used to dope the wires. In addition, in the QWr-doped devices, the decrease of the solar conversion efficiencies at low temperatures and the associated decrease of the integrated external quantum efficiency through InGaAs could be attributed to detected traps E1QWR_D, E2QWR_D, and E3QWR_D with activation energies of 0.0037, 0.0053, and 0.041 eV, respectively.

Physicochemical characteristics of pristine and functionalized graphene.

Graphene-based nanomaterials have received significant attention in the last decade due to their interesting properties. Its electrical and thermal conductivity and strength make graphene well suited for a variety of applications, particularly for use as a composite material in plastics. Furthermore, much work is taking place to utilize graphene as a biomaterial for uses such as drug delivery and tissue regeneration scaffolds. Owing to the rapid progress of graphene and its potential in many marketplaces, the potential toxicity of these materials has garnered attention. Graphene, while simple in its purest form, can have many different chemical and physical properties. In this paper, we describe our toxicity evaluation of pristine graphene and a functionalized graphene sample that has been oxidized for enhanced hydrophilicity, which was synthesized from the pristine sample. The samples were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, thermogravimetric analysis, zeta-potential, atomic force microscopy and electron microscopy. We discuss the disagreement between the size of imaged samples analyzed by atomic force microscopy and by transmission electron microscopy. Furthermore, the samples each exhibit quite different surface chemistry and structure, which directly affects their interaction with aqueous environments and is important to consider when evaluating the toxicity of materials both in vitro and in vivo. Copyright © 2017 John Wiley & Sons, Ltd.

Quantifying the distribution of nanodiamonds in pre-Younger Dryas to recent age deposits along Bull Creek, Oklahoma panhandle, USA.

High levels of nanodiamonds (nds) have been used to support the transformative hypothesis that an extraterrestrial (ET) event (comet explosion) triggered Younger Dryas changes in temperature, flora and fauna assemblages, and human adaptations [Firestone RB, et al. (2007) Proc Natl Acad Sci USA 104(41):16016-16021]. We evaluate this hypothesis by establishing the distribution of nds within the Bull Creek drainage of the Beaver River basin in the Oklahoma panhandle. The earlier report of an abundance spike of nds in the Bull Creek I Younger Dryas boundary soil is confirmed, although no pure cubic diamonds were identified. The lack of hexagonal nds suggests Bull Creek I is not near any impact site. Potential hexagonal nds at Bull Creek were found to be more consistent with graphene/graphane. An additional nd spike is found in deposits of late Holocene through the modern age, indicating nds are not unique to the Younger Dryas boundary. Nd distributions do not correlate with depositional environment, pedogenesis, climate perturbations, periods of surface stability, or cultural activity.

Defect-Free Self-Catalyzed GaAs/GaAsP Nanowire Quantum Dots Grown on Silicon Substrate.

The III-V nanowire quantum dots (NWQDs) monolithically grown on silicon substrates, combining the advantages of both one- and zero-dimensional materials, represent one of the most promising technologies for integrating advanced III-V photonic technologies on a silicon microelectronics platform. However, there are great challenges in the fabrication of high-quality III-V NWQDs by a bottom-up approach, that is, growth by the vapor-liquid-solid method, because of the potential contamination caused by external metal catalysts and the various types of interfacial defects introduced by self-catalyzed growth. Here, we report the defect-free self-catalyzed III-V NWQDs, GaAs quantum dots in GaAsP nanowires, on a silicon substrate with pure zinc blende structure for the first time. Well-resolved excitonic emission is observed with a narrow line width. These results pave the way toward on-chip III-V quantum information and photonic devices on silicon platform.

The effects of geometry and stability of solid-state nanopores on detecting single DNA molecules.

In this work we use a combination of 3D-TEM tomography, energy filtered TEM, single molecule DNA translocation experiments, and numerical modeling to show a more precise relationship between nanopore shape and ionic conductance and show that changes in geometry while in solution can account for most deviations between predicted and measured conductance. We compare the structural stability of ion beam sculpted (IBS), IBS-annealed, and TEM drilled nanopores. We demonstrate that annealing can significantly improve the stability of IBS made pores. Furthermore, the methods developed in this work can be used to predict pore conductance and current drop amplitudes of DNA translocation events for a wide variety of pore geometries. We discuss that chemical dissolution is one mechanism of the geometry change for SiNx nanopores and show that small modification in fabrication procedure can significantly increase the stability of IBS nanopores.

1.3-µm InAs/GaAs quantum-dot lasers monolithically grown on Si substrates using InAlAs/GaAs dislocation filter layers.

We compare InAlAs/GaAs and InGaAs/GaAs strained-layer superlattices (SLSs) as dislocation filter layers for 1.3-µm InAs/GaAs quantum-dot laser structures directly grown on Si substrates. InAlAs/GaAs SLSs are found to be more effective than InGaAs/GaAs SLSs in blocking the propagation of threading dislocations generated at the interface between the GaAs buffer layer and the Si substrate. Room-temperature lasing at ~1.27 µm with a threshold current density of 194 A/cm(2) and output power of ~77 mW has been demonstrated for broad-area lasers grown on Si substrates using InAlAs/GaAs dislocation filter layers.

Size-dependent reactivity of magnetite nanoparticles: a field-laboratory comparison.

Logistic challenges make direct comparisons between laboratory- and field-based investigations into the size-dependent reactivity of nanomaterials difficult. This investigation sought to compare the size-dependent reactivity of nanoparticles in a field setting to a laboratory analog using the specific example of magnetite dissolution. Synthetic magnetite nanoparticles of three size intervals, ∼ 6 nm, ∼ 44 nm, and ∼ 90 nm were emplaced in the subsurface of the USGS research site at the Norman Landfill for up to 30 days using custom-made subsurface nanoparticle holders. Laboratory analog dissolution experiments were conducted using synthetic groundwater. Reaction products were analyzed via TEM and SEM and compared to initial particle characterizations. Field results indicated that an organic coating developed on the particle surfaces largely inhibiting reactivity. Limited dissolution occurred, with the amount of dissolution decreasing as particle size decreased. Conversely, the laboratory analogs without organics revealed greater dissolution of the smaller particles. These results showed that the presence of dissolved organics led to a nearly complete reversal in the size-dependent reactivity trends displayed between the field and laboratory experiments indicating that size-dependent trends observed in laboratory investigations may not be relevant in organic-rich natural systems.

On the Structural and Molecular Properties of PEO and PEO-PPG Functionalized Chitosan Nanoparticles for Drug Delivery.

Chitosan nanoparticles (CS-NPs) are currently under investigation for a wide range of applications in nanomedicine. We investigated the structural, morphological, and molecular properties of CS-NPs synthesized via ionic gelation and designed specifically for drug delivery. The CS-NPs were prepared at concentrations ranging from 0.25 to 1.0% w/v. The 1.0% w/v CS-NPs were also functionalized with polyethylene oxide (PEO) alone and with a diblock copolymer of PEO and polypropylene glycol (PPG). The average nanoparticle size determined from TEM imaging is in the 11.3 to 14.8 nm range. The XRD and TEM analyses reveal a semi-crystalline structure with a degree of crystallinity dependent upon the nature of CS-NP functionalization. Functionalizing with PEO had no effect, whereas functionalizing with PEO-PPG resulted in a significant increase in the crystallinity of the 1.0% w/v CS-NPs. Additionally, the CS/TPP concentration (CS:TPP fixed at a 1:1 ratio) did not impact the degree of crystallinity of the CS-NPs. FTIR analysis confirmed the incorporation of TPP with CS and an increase in hydrogen bonding in more crystalline CS-NPs.

Tuning Exchange Coupling in NiO-Based Bimagnetic Heterostructured Nanocrystals.

A series of bimagnetic heterostructured nanocrystals having an antiferromagnetic NiO core and a ferrimagnetic MnxNi1-xO and/or FiM Mn3O4 island nanophase overgrowth has been synthesized under varying aqueous solution pH conditions. The two-step self-assembly process employs a thermal decomposition method to synthesize NiO nanoparticles, followed by growth of the MnxNi1-xO and/or Mn3O4 nanophase over the NiO core using hydrothermal synthesis at pH values ranging from 2.4-7.0. The environmentally benign hydrothermal process involves pH control of the protonation vs hydroxylation reactions occurring at the nanoparticle surface. TEM analysis and Rietveld refinement of XRD data show that three distinct types of heterostructured nanocrystals occur: NiO/MnxNi1-xO core-shell-like heterostructures at the pH of 2.4, mixed NiO/MnxNi1-xO and/or/Mn3O4 core-overgrowth structures for 2.4 < pH < 4.5, and predominantly NiO/Mn3O4 core-island structures for pH > 4.5. The magnetic coercivity and exchange bias of the heterostructured nanocrystals vary systematically with the pH of the aqueous solution used to synthesize the samples. The temperature-dependent magnetization and hysteresis loop data are consistent with the nature of overlayer coverage of the NiO core. Our DFT based calculations show that the MnxNi1-xO phase has ferrimagnetic properties with a stable spin orientation along the ⟨111⟩ orientation. Furthermore, the calculations show that the magnetic anisotropy constant (K1) of the Mn3O4 phase is considerably larger than that of the MnxNi1-xO phase, which is confirmed by our experimental results. The coercivity and exchange bias field are the largest for the NiO/Mn3O4 core-island nanocrystals, synthesized at a pH value of 5.0, with robust values of nearly 6 kOe and 3 kOe, respectively. This work demonstrates the tunability of hydrothermal deposition, and concomitant magnetic coercivity and exchange bias properties, of MnxNi1-xO and/or Mn3O4 nanophase overgrowth over a NiO core with pH, that makes these heterostructured nanocrystals potentially useful for magnetic device, biomedical, and other applications.

Probe metal binding mode of imine covalent organic frameworks: cycloiridation for (photo)catalytic hydrogen evolution from formate.

Metalation of covalent organic frameworks (COFs) is a critical strategy to functionalize COFs for advanced applications yet largely relies on the pre-installed specific metal docking sites in the network, such as porphyrin, salen, 2,2'-bipyridine, etc. We show in this study that the imine linkage of simple imine-based COFs, one of the most popular COFs, readily chelate transition metal (Ir in this work) via cyclometalation, which has not been explored before. The iridacycle decorated COF exhibited more than 10-fold efficiency enhancement in (photo)catalytic hydrogen evolution from aqueous formate solution than its molecular counterpart under mild conditions. This work will inspire more functional cyclometallated COFs to be explored beyond catalysis considering the large imine COF library and the rich metallacycle chemistry.

Tuning the Surface Plasmon Resonance of Gold Dumbbell Nanorods.

Gold has always fascinated humans, occupying an important functional and symbolic role in civilization. In earlier times, gold was predominantly used in jewelry; today, this noble metal's surface properties are taken advantage of in catalysis and plasmonics. In this article, the plasmon resonance of gold dumbbell nanorods is investigated. This unusual morphology was obtained by a seed-mediated growth method. The concentration of chemical precursors such as cetyltrimethylammonium bromide and silver nitrate plays a significant role in controlling the shape of the nanorods. Indeed, the aspect ratio of dumbbell nanostructures was varied from 2.6 to 4. UV-visible absorption spectra revealed a shift of the longitudinal surface plasmon resonance peak from 669 to 789 nm. Having the plasmon resonance in the near infrared region helps to use those nanostructures as photothermal agents.

Catalyst-Enabled In Situ Linkage Reduction in Imine Covalent Organic Frameworks.

New linkages for covalent organic frameworks (COFs) have been continuously pursued by chemists as they serve as the structure and property foundation for the materials. Developing new reaction types or modifying known linkages have been the only two methods to create new COF linkages. Herein, we report a novel strategy that uses H3PO3 as a bifunctional catalyst to achieve amine-linked COFs from readily available amine and aldehyde linkers. The acidic proton of H3PO3 catalyzes the imine framework formation, which is then in situ reduced to the amine COF by the reductive P-H moiety. The amine-linked COF outperforms its imine analogue in promoting Knoevenagel condensation because of the more basic sites and higher stability.

Pt(II)-Decorated Covalent Organic Framework for Photocatalytic Difluoroalkylation and Oxidative Cyclization Reactions.

A new covalent organic framework (COF) based on imine bonds was assembled from 2-(4-formylphenyl)-5-formylpyridine and 1,3,6,8-tetrakis(4-aminophenyl)pyrene, which showed an interesting dual-pore structure with high crystallinity. Postmetallation of the COF with Pt occurred selectively at the N donor (imine and pyridyl) in the larger pores. The metallated COF served as an excellent recyclable heterogeneous photocatalyst for decarboxylative difluoroalkylation and oxidative cyclization reactions.

Physicochemical properties of soy protein hydrolysate and its formulation and stability with encapsulated probiotic under in vitro gastrointestinal environment.

The objective of this study was to prepare protein isolate from defatted soybean and identify an optimal hydrolysis protocol to create improved hydrolysates and ascertain the optimum encapsulation technique for probiotics. Soy protein isolate (SPI) was prepared using an alkaline extraction procedure for solubility within a neutral, beverage-specific pH range. The soy protein hydrolysate (SPH) was prepared from aqueous extracted SPI using pepsin. The physicochemical properties of the SPH were investigated by solubility, degree of hydrolysis (DH), surface hydrophobicity, and electrophoresis. Hydrolysates from 2, 2.5, and 3 hr of hydrolysis time achieved the suitable DH between 2.5% to 5.0%. The 2.5 to 3 hr hydrolysates were also significantly more soluble than SPI at all pH levels from 85% to 95% solubility. Surface hydrophobicity of the hydrolysates ranged from 15 to 20 S0 values. Alginate (1%), resistant starch (2%), and probiotic culture (0.1%) were used as an encapsulation agent to protect probiotics. Alginate microcapsules were observed to be 1 mm in size using environmental scanning electron microscopy. The dried SPH and encapsulated probiotics with alginate in a dry powder formulation were tested for its gastrointestinal resistance and probiotic viability under in vitro simulated digestion. Approximately 1-log decrease was observed for all experimental groups after simulated digestion (final log colony forming units [CFU]/mL range: 6.55 to 6.19) with free probiotics having the lowest log CFU/mL (6.10 ± 0.10) value. No significant difference was observed among experimental groups for probiotic viability (P = 0.445). The findings of this research will provide an understanding of formulation for easily digestible protein and encapsulated probiotics. PRACTICAL APPLICATION: The findings of this research provide an understanding of improved formulation for more suitable soy protein hydrolysate and viability of encapsulated probiotics in gastrointestinal environment. Probiotics with the prebiotics in an encapsulated environment provide a technology for the enhancement of probiotics viability and for applications in suitable products for health and wellness.

Polydopamine Surface Coating Synergizes the Antimicrobial Activity of Silver Nanoparticles.

Metal nanoparticles, especially silver nanoparticles (AgNPs), have drawn increasing attention for antimicrobial applications. Most studies have emphasized on the correlations between the antibacterial potency of AgNPs and the kinetics of metallic to ionic Ag conversion, while other antimicrobial mechanisms have been underestimated. In this work, we focused on the surface effects of polydopamine (PDA) coating on the antimicrobial activity of AgNPs. A method of fast deposition of PDA was used to synthesize the PDA-AgNPs with controllable coating thickness ranging from 3 to 25 nm. The antimicrobial activities of the PDA-AgNPs were analyzed by fluorescence-based growth curve assays on Escherichia coli. The results indicated that the PDA-AgNPs exhibited significantly higher antibacterial activities than poly(vinylpyrrolidone)-passivated AgNPs (PVP-AgNPs) and PDA themselves. It was found that the PDA coating synergized with the AgNPs to prominently enhance the potency of the PDA-AgNPs against bacteria. The analysis of X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy elucidated that the synergistic effects could be originated from the interaction/coordination between Ag and catechol group on the PDA coating. The synergistic effects led to increased generation of reactive oxygen species and the consequent bacterial damage. These findings demonstrated the importance of the surface effects on the antimicrobial properties of AgNPs. The underlying molecular mechanisms have shined light on the future development of more potent metal nanoparticle-based antimicrobial agents.

(Thio)urea-Based Covalent Organic Framework as a Hydrogen-Bond-Donating Catalyst.

Two-dimensional urea- and thiourea-containing covalent organic frameworks (COFs) were synthesized at ambient conditions at large scale within 1 h in the absence of an acid catalyst. The site-isolated urea and thiourea in the COF showed enhanced catalytic efficiency as a hydrogen-bond-donating organocatalyst compared to the molecular counterparts in epoxide ring-opening reaction, aldehyde acetalization, and Friedel-Crafts reaction. The COF catalysts also had excellent recyclability.

Tuning Solid Electrolyte Interphase Layer Properties through the Integration of Conversion Reaction.

The solid electrolyte interphase (SEI) layer plays an important role in altering the ion transport and modifying the structural evolution of the Li metal anode during repeated cycling. While the fundamental understanding of the SEI properties has been continuously advanced in recent years, effectively tuning the SEI components, especially the inorganic constituents, is still challenging. In this work, tungsten trioxide, WO3, is found to promote the formation of inorganic salts, for example, LiF/Li2CO3 in SEI layers, thereby enhancing the SEI properties such as mechanical and chemical stabilities. Additionally, WO3 is simultaneously reduced to electronic W nanoparticles during the electrochemical process, mitigating the formation of "dead" Li, which otherwise is completely wrapped by the accumulated insulating SEI layers. The possibility of WO3 in catalyzing electrolyte decomposition, through favored reaction pathway, to produce robust SEI layers is discussed. This work provides new insights into the control of the SEI properties on Li metal surfaces.