Coordination-Assisted Precise Construction of Metal Oxide Nanofilms for High-Performance Solid-State Batteries.

The application of solid-state batteries (SSBs) is challenged by the inherently poor interfacial contact between the solid-state electrolyte (SSE) and the electrodes, typically a metallic lithium anode. Building artificial intermediate nanofilms is effective in tackling this roadblock, but their implementation largely relies on vapor-based techniques such as atomic layer deposition, which are expensive, energy-intensive, and time-consuming due to the monolayer deposited per cycle. Herein, an easy and low-cost wet-chemistry fabrication process is used to engineer the anode/solid electrolyte interface in SSBs with nanoscale precision. This coordination-assisted deposition is initiated with polyacrylate acid as a functional polymer to control the surface reaction, which modulates the distribution and decomposition of metal precursors to reliably form a uniform crack-free and flexible nanofilm of a large variety of metal oxides. For demonstration, artificial Al2O3 interfacial nanofilms were deposited on a ceramic SSE, typically garnet-structured Li6.5La3Zr1.5Ta0.5O12 (LLZT), that led to a significant decrease in the Li/LLZT interfacial resistance (from 2079.5 to 8.4 Ω cm2) as well as extraordinarily long cycle life of the assembled SSBs. This strategy enables the use of a nickel-rich LiNi0.83Co0.07Mn0.1O2 cathode to deliver a reversible capacity of 201.5 mAh g-1 at a considerable loading of 4.8 mg cm-2, featuring performance metrics for an SSB that is competitive with those of traditional Li-ion systems. Our study demonstrates the potential of solution-based routes as an affordable and scalable manufacturing alternative to vapor-based deposition techniques that can accelerate the development of SSBs for practical applications.

Manipulating Particle Chemistry for Hollow Carbon-based Nanospheres: Synthesis Strategies, Mechanistic Insights, and Electrochemical Applications.

Hollow carbon-based nanospheres (HCNs) have been demonstrated to show promising potential in a large variety of research fields, particularly electrochemical devices for energy conversion/storage. The current synthetic protocols for HCNs largely rely on template-based routes (TBRs), which are conceptually straightforward in creating hollow structures but challenged by the time-consuming operations with a low yield in product as well as serious environmental concerns caused by hazardous etching agents. Meanwhile, they showed inadequate ability to build complex carbon-related architectures. Innovative strategies for HCNs free from extra templates thus are highly desirable and are expected to not only ensure precise control of the key structural parameters of hollow architectures with designated functionalities, but also be environmentally benign and scalable approaches suited for their practical applications.In this Account, we outline our recent research progress on the development of template-free protocols for the creation of HCNs with a focus on the acquired mechanical insight into the hollowing mechanism when no extra templates were involved. We demonstrated that carbon-based particles themselves could act as versatile platforms to create hollow architectures through an effective modulation of their inner chemistry. By means of reaction control, the precursor particles were synthesized into solid ones with a well-designed inhomogeneity inside in the form of different chemical parameters such as molecular weight, crystallization degree, and chemical reactivity, by which we not only can create hollow structures inside particles but also have the ability to tune the key features including compositions, porosity, and dimensional architectures. Accordingly, the functionalities of the prepared HCNs could be systematically altered or optimized for their applications. Importantly, the discussed synthesis approaches are facile and environmentally benign processes with potential for scale-up production.The nanoengineering of HNCs is found to be of special importance for their application in a large variety of electrochemical energy storage and conversion systems where the charge transfer and structural stability become a serious concern. Particular attention in this Account is therefore directed to the potential of HCNs in battery systems such as sodium ion batteries (NIBs) and potassium ion batteries (KIBs), whose electrochemical performances are plagued by the destructive volumetric deformation and sluggish charge diffusion during the intercalation/deintercalation of large-size Na+ or K+. We demonstrated that precise control of the multidimensional factors of the HCNs is critical to offer an optimized design of sufficient reactive sites, excellent charge and mass transport kinetics, and resilient electrode structure and also provide a model system suitable for the study of complicated metal-ion storage mechanisms, such as Na+ storage in a hard carbon anode. We expect that this Account will spark new endeavors in the development of HCNs for various applications including energy conversion and storage, catalysis, biomedicine, and adsorption.

Dendritic organic molecular gel coating with molecular shape selectivity and its application in selective separation by liquid chromatography.

Dendritic organic molecular gels are a promising class of three-dimensional network compounds. Here, we have synthesized a new type of dendritic organic molecular gel stationary phase (SiO2-G3) by using benzyl alcohol as raw material and dimethyl 5-hydroxyisophthalate as growth unit to synthesize a third-generation organic molecular gel G3, which grafted onto the silica surface by cyanogen chloride (CC). The developed stationary phase not only exhibits high molecular shape selectivity but also has a RPLC/HILIC/IEC mixed-mode characteristic for HPLC due to the ordered structure, the multiple strong π-π stacking interactions and the introduction of a hydrophilic triazine fraction during the grafting process. Compared with a commercial C18 column, the developed column exhibited flexible selectivity, enhanced separation performance and excellent separation of monosubstituted benzene, polycyclic aromatic hydrocarbons (PAHs), positional isomers, nucleosides and nucleobases, benzoic acid and aniline compounds. In addition, the new column provided baseline separation of polycyclic aromatic hydrocarbon contaminants in Yellow River water, verifying its potential for application in the analysis of real samples.

Molecular characterization and analysis of the association of growth hormone 1 gene with growth traits in Chinese indigenous yak (Bos grunniens).

This study aimed to investigate the effects of polymorphisms in growth hormone 1 (GH1) gene on the growth traits in Chinese indigenous yak. Using the polymerase chain reaction-restriction fragment length polymorphism (PCR-PFLP) approach, one novel single-nucleotide polymorphism (SNP), termed as g.1721G>A, was identified in the exon 4 of GH1 gene in 423 individuals of yak population. Based on the chi-square (χ2) test, the frequencies of g.1721G>A alleles agreed with Hardy-Weinberg equilibrium (HWE) (P < 0.05). A significant association was observed between this SNP and several growth traits (P < 0.01 or P < 0.05), in which the genotype GG exhibited the best values. The present study suggested that the identified SNP was a useful genetic marker for the improvement of growth traits in Chinese indigenous yak.

A General Synthesis Strategy for Hollow Metal Oxide Microspheres Enabled by Gel-Assisted Precipitation.

Hollow metal oxide microspheres (HMMs) have drawn enormous attention in different research fields. Reliable and scalable synthetic protocols applicable for a large variety of metal oxides are in emergent demand. Here we demonstrated that polymer hydrogel, such as the resorcinol formaldehyde (RF) one, existed as an efficient synthetic platform to build HMMs. Specifically, the RF gel forms stacked RF microspheres enlaced with its aqueous phase, where the following evaporation of the highly dispersed water leads to a gel-assisted precipitation (GAP) of the dissolved metal precursor onto the embedded polymeric solids suited for the creation of HMMs. By taking advantage of the structural features of hydrogel, this synthesis design avoids the delicate control on the usually necessitated coating process and provides a simple and effective synthetic process versatile for functional HMMs, particularly Nb2 O5 as a high-performance electrode material in Li-ion intercalation pseudocapacitor.

Spherical Mesoporous Metal Oxides with Tunable Orientation Enabled by Growth Kinetics Control.

Recent advances in spherical mesoporous metal oxides (SMMOs) have demonstrated their enormous potential in a large variety of research fields. However, a direct creation of these materials with precise control on their key shape features, particularly pore architectures, remains a major challenge as compared to the widely explored counterpart of silica. Here, using Al2O3 as an example, we identified that deposition kinetics in solution played an essential role in the construction of different SMMOs. Specifically, a controlled Al3+ precipitation is critical to maintaining the electrostatic interaction between the inorganic precursors and the molecular templates, thereby achieving a designable assembly of these two components toward uniform mesoporous Al2O3-based nanospheres. We demonstrated that such a synthesis strategy is not only able to precisely control the channel orientations from concentric to radial and dendritic, a synthesis capability impeded so far for SMMOs, but is readily applicable to other metal oxides. Our study showed that the growth-kinetics control is a simple but powerful synthesis protocol and opened up a multifunctional platform to achieve systematic design of SMMOs for their future applications.

Effects of oxygen concentrations on developmental competence and transcriptomic profile of yak oocytes.

Oxygen concentration influences oocyte quality and subsequent embryo development, but it remains unclear whether oxygen concentrations affect the developmental competence and transcriptomic profile of yak oocytes. In this study, we investigated the effects of different oxygen concentrations (5% versus 20%) on the developmental competence, reactive oxygen species (ROS) levels, glutathione (GSH) content, and transcriptomic profile of yak oocytes. The results showed that a low oxygen concentration significantly increased the maturation rate of yak oocytes (81.2 ± 2.2% vs 75.9 ± 1.3%) and the blastocyst quality of yak in vitro fertilized embryos. Analysis of ROS and GSH showed that a low oxygen concentration reduced ROS levels and increased the content of GSH (75.05 ± 7.1 ng/oocyte vs 50.63 ± 5.6 ng/oocyte). Furthermore, transcriptomic analysis identified 120 differentially expressed genes (DEGs) between the two groups of oocytes. Gene enrichment analysis of the DEGs indicated multiple cellular processes, including oxidative phosphorylation, transcription regulation, mitochondrial regulation, oestrogen signalling pathway, HIF-1 signalling pathway, TNF signalling pathway, were involved in the response to oxygen concentration alterations. Taken together, these results indicated that a low oxygen concentration improved the developmental competence of yak oocytes.

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine.

In this work, a series of Cu-ZSM-5 catalysts with different SiO2/Al2O3 ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N2, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N2 selectivity was impacted by the Brønsted acidity and the isolated Cu2+ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.

A Hollow Multi-Shelled Structure for Charge Transport and Active Sites in Lithium-Ion Capacitors.

The lithium-ion capacitor (LIC) has attracted tremendous research interest because it meets both the requirement on high energy and power densities. The balance between effective surface areas and mass transport is highly desired to fabricate the optimized electrode material for LIC. Now, triple-shelled (3S) Nb2 O5 hollow multi-shelled structures (HoMSs) were synthesized for the first time through the sequential templating approach and then applied for the anode of LIC. The unique structure of HoMSs, such as large efficient surface area, hierarchical pores, and multiple shells, provides abundant reaction sites, decreases the electron transport resistance, and increases the diffusion rate for ion transport. In this case, the best combination performance has been achieved among all the reported Nb2 O5 -based materials, which delivered an excellent energy and power densities simultaneously, and superb cycling stability.

Phase Control on Surface for the Stabilization of High Energy Cathode Materials of Lithium Ion Batteries.

The development of high energy electrode materials for lithium ion batteries is challenged by their inherent instabilities, which become more aggravated as the energy densities continue to climb, accordingly causing increasing concerns on battery safety and reliability. Here, taking the high voltage cathode of LiNi0.5Mn1.5O4 as an example, we demonstrate a protocol to stabilize this cathode through a systematic phase modulating on its particle surface. We are able to transfer the spinel surface into a 30 nm shell composed of two functional phases including a rock-salt one and a layered one. The former is electrochemically inert for surface stabilization while the latter is designated to provide necessary electrochemical activity. The precise synthesis control enables us to tune the ratio of these two phases, and achieve an optimized balance between improved stability against structural degradation without sacrificing its capacity. This study highlights the critical importance of well-tailored surface phase property for the cathode stabilization of high energy lithium ion batteries.

Precise Surface Engineering of Cathode Materials for Improved Stability of Lithium-Ion Batteries.

As lithium-ion batteries continue to climb to even higher energy density, they meanwhile cause serious concerns on their stability and reliability during operation. To make sure the electrode materials, particularly cathode materials, are stable upon extended cycles, surface modification becomes indispensable to minimize the undesirable side reaction at the electrolyte-cathode interface, which is known as a critical factor to jeopardizing the electrode performance. This Review is targeted at a precise surface control of cathode materials with focus on the synthetic strategies suitable for a maximized surface protection ensured by a uniform and conformal surface coating. Detailed discussions are taken on the formation mechanism of the designated surface species achieved by either wet-chemistry routes or instrumental ones, with attention to the optimized electrochemical performance as a result of the surface control, accordingly drawing a clear image to describe the synthesis-structure-performance relationship to facilitate further understanding of functional electrode materials. Finally, perspectives regarding the most promising and/or most urgent developments for the surface control of high-energy cathode materials are provided.

Genetic variants in the SIRT6 transcriptional regulatory region affect gene activity and carcass quality traits in indigenous Chinese beef cattle (Bos taurus).

BACKGROUND: The aim of this study was to analyze potential influences of polymorphisms within the regulatory region of the bovine SIRT6 gene on carcass quality traits. Expression analyses suggested that SIRT6 gene is predominately expressed in kidney, compared with other tissues. In 535 indigenous Chinese beef cattle, two novel single nucleotide polymorphisms (SNPs) were identified within the promoter region of the SIRT6 gene. RESULTS: Association analysis indicated that G allele of the c.-1100 A > G had a positive effect on fat deposition, and the Hap4/4 diplotype had more favourable results than other dipoltypes with respect to the evaluation of carcass quality traits. Furthermore, promoter activity associated with the Hap3 haplotype was measured at higher levels than the Hap1 haplotype, which would be in agreement with the previously described association analysis. CONCLUSION: The SIRT6 promoter variants significantly affect transcriptional levels and subsequently significantly influence bovine intramscular fat content.

Engineering Hollow Carbon Architecture for High-Performance K-Ion Battery Anode.

K-ion batteries (KIBs) are now drawing increasing research interest as an inexpensive alternative to Li-ion batteries (LIBs). However, due to the large size of K+, stable electrode materials capable of sustaining the repeated K+ intercalation/deintercalation cycles are extremely deficient especially if a satisfactory reversible capacity is expected. Herein, we demonstrated that the structural engineering of carbon into a hollow interconnected architecture, a shape similar to the neuron-cell network, promised high conceptual and technological potential for a high-performance KIB anode. Using melamine-formaldehyde resin as the starting material, we identify an interesting glass blowing effect of this polymeric precursor during its carbonization, which features a skeleton-softening process followed by its spontaneous hollowing. When used as a KIB anode, the carbon scaffold with interconnected hollow channels can ensure a resilient structure for a stable potassiation/depotassiation process and deliver an extraordinary capacity (340 mAh g-1 at 0.1 C) together with a superior cycling stability (no obvious fading over 150 cycles at 0.5 C).

Controlling the Reaction of Nanoparticles for Hollow Metal Oxide Nanostructures.

Hollow nanostructures of metal oxides have found broad applications in different fields. Here, we reported a facile and versatile synthetic protocol to prepare hollow metal oxide nanospheres by modulating the chemical properties in solid nanoparticles. Our synthesis design starts with the precipitation of urea-containing metal oxalate, which is soluble in water but exists as solid nanospheres in ethanol. A controlled particle hydrolysis is achieved through the heating-induced urea decomposition, which transforms the particle composition in an outside-to-inside style: The reaction starts from the surface and then proceeds inward to gradually form a water-insoluble shell of basic metal oxalate. Such a reaction-induced solubility difference inside nanospheres becomes highly efficient to create a hollow structure through a simple water wash process. A following high temperature treatment forms hollow nanospheres of different metal oxides with structural features suited to their applications. For example, a high performance anode for Li-ion intercalation pseudocapacitor was demonstrated with the hollow and mesoporous Nb2O5 nanospheres.

Controlling the Compositional Chemistry in Single Nanoparticles for Functional Hollow Carbon Nanospheres.

Hollow carbon nanostructures have inspired numerous interests in areas such as energy conversion/storage, biomedicine, catalysis, and adsorption. Unfortunately, their synthesis mainly relies on template-based routes, which include tedious operating procedures and showed inadequate capability to build complex architectures. Here, by looking into the inner structure of single polymeric nanospheres, we identified the complicated compositional chemistry underneath their uniform shape, and confirmed that nanoparticles themselves stand for an effective and versatile synthetic platform for functional hollow carbon architectures. Using the formation of 3-aminophenol/formaldehyde resin as an example, we were able to tune its growth kinetics by controlling the molecular/environmental variables, forming resin nanospheres with designated styles of inner constitutional inhomogeneity. We confirmed that this intraparticle difference could be well exploited to create a large variety of hollow carbon architectures with desirable structural characters for their applications; for example, high-capacity anode for potassium-ion battery has been demonstrated with the multishelled hollow carbon nanospheres.

Microbial-Phosphorus-Enabled Synthesis of Phosphide Nanocomposites for Efficient Electrocatalysts.

Transition-metal phosphides have recently been identified as low-cost and efficient electrocatalysts that are highly active for the hydrogen evolution reaction. Unfortunately, to achieve a controlled phosphidation of nonprecious metals toward a desired nanostructure of metal phosphides, the synthetic processes usually turned complicated, high-cost, and even dangerous due to the reaction chemistry related to different phosphorus sources. It becomes even more challenging when considering the integration of those active metal phosphides with the structural engineering of their conductive matrix toward a favorable architecture for optimized catalytic performance. Herein, we identified that the biomass itself could act as an effective synthetic platform for the construction of supported metal phosphides by recovering its inner phosphorus upon reacting with transition-metals ions, forming well-dispersed, highly active nanoparticles of metal phosphides incorporated in the nanoporous carbon matrix, which promised high catalytic activity in the hydrogen evolution reaction. Our synthetic protocol not only provides a simple and effective strategy for the construction of a large variety of highly active nanoparticles of metal phosphides but also envisions new perspectives on an integrated utilization of the essential ingredients, particularly phosphorus, together with the innate architecture of the existing biomass for the creation of functional nanomaterials toward sustainable energy development.

3D Copper Tetrathiafulvalene Redox-Active Network with 8-Fold Interpenetrating Diamond-like Topology.

A tetrathiafulvalene derivative has been incorporated into a diamond-like structure for the first time. The coordination network shows highly unusual 8-fold interpenetration with redox-active and photoelectric properties.

Levels of polybrominated diphenyl ethers in settled house dust from urban dwellings with resident preschool-aged children in Nanjing, China.

We investigated the levels and possible determinants of polybrominated diphenyl ethers (PBDEs) in the settled house-dust (SHD) of urban dwellings with resident preschool-aged children in Nanjing, China. The possible neurodevelopmental effects of house-dust PBDEs were also explored. SHD was collected from 216 urban houses. Levels of 8 PBDEs were measured by gas chromatography-negative chemical ionization mass spectrometry. The Child Behavior Checklist and the Gesell Development Inventory were used to evaluate the child's development. BDE47, BDE99, BDE153, BDE18, and BDE209 were detected in the SHD of >90 % of houses, of which BDE209 predominated. Most PBDEs were found at significantly greater levels in indoor than in outdoor dust (P < 0.05). Levels of BDE28 and BDE154 in houses with solid-wood floors were significantly greater than those in houses with plywood floors (P < 0.05). BDE154 levels in houses with wallpaper were significantly greater than those without wallpaper (P < 0.05). Greater BDE47 concentrations were found in houses with less natural ventilation time (linear trend P < 0.05). After dichotomization at the geometric mean concentration, BDE209 and total BDEs showed significant risks for depressed behavior problems and lower personal social developmental quotients (DQs); BDE99 and BDE153 indicated a risk for lower personal social DQs. In conclusion, PBDEs (especially BDE209) are ubiquitous in urban SHD in Nanjing residences. Natural ventilation and floor materials potentially influence PBDE levels in SHD. The potential adverse effect of postnatal exposure to PBDEs on the behavior and neurodevelopment of preschool-age children requires follow-up in larger studies.

Effect of metal coordination on photocurrent response properties of a tetrathiafulvalene organogel film.

Organic low molecular weight gelators with a tetrathiafulvalene (TTF) unit have received considerable attention because the formed gels usually exhibit redox active response and conducting or semiconducting properties. However, to our knowledge, metal coordination systems have not been reported for TTF-derived gels up to date. We have designed and synthesized a series of TTF derivatives with a diamide-diamino moiety that can coordinate to specific metal ions with square coordination geometry. Gelation properties and morphologies of the films prepared by the gelators in different hydrophobic solvents are characterized. The TTF derivative with a dodecyl group shows effective gelation properties, and electrodes with the organogel films are prepared. The effect of the Ni(II) and Cu(II) coordination on the photocurrent response property of the electrodes is examined. The metal square coordination significantly increases the photocurrent response. This gel system is the first metal coordination related TTF-gel-based photoelectric material. The mechanism of the metal coordination-improved photocurrent response property is discussed based on the crystal structural analysis and theoretical calculations.

Role of the coordination center in photocurrent behavior of a tetrathiafulvalene and metal complex dyad.

Small organic molecule-based compounds are considered to be promising materials in photoelectronics and high-performance optoelectronic devices. However, photoelectron conversion research based on functional organic molecule and metal complex dyads is very scarce. We design and prepare a series of compounds containing a tetrathiafulvalene (TTF) moiety substituted with pyridylmethylamide groups of formulas [Ni(acac)2L]·2CH3OH (1), [Cu2I2L2]·THF·2CH3CN (2), and [MnCl2L2]n·2nCH3CH2OH (3) (L = 4,5-bis(3-pyridylmethylamide)-4',5'-bimethylthio-tetrathiafulvalene, acac = acetylacetone) to study the role of the coordination center in photocurrent behavior. Complex 1 is a mononuclear species, and complex 2 is a dimeric species. Complex 3 is a two-dimensional (2-D) coordination polymer. Spectroscopic and electrochemical properties of these complexes indicate that they are electrochemically active materials. The tetrathiafulvalene ligand L is a photoelectron donor in the presence of electron acceptor methylviologen. The effect of metal coordination centers on photocurrent response behavior is examined. The redox-active metal coordination centers should play an important role in improvement of the photocurrent response property. The different morphologies of the electrode films reflect the dimensions in molecular structures of the coordination compounds.