Enhanced photoactivity of CdS nanorods by MXene and ZnSnO3: Application in photoelectrochemical biosensor for the effect of environmental pollutants on DNA hydroxymethylation in wheat tissues

The photoactivity of CdS nanorods was greatly improved by amino functionalized accordion-like MXene and spherical ZnSnO₃. MXene possesses good electron transfer capability and ZnSnO₃ presents matched energy band with CdS, which deeply accelerate the electron transfer and prevent the recombination of photogenerated electron-hole pair, leading to a strong photoelectrochemical (PEC) response. Taking the merit of the improved photoactivity of CdS nanorods, a novel PEC biosensor was constructed for DNA hydromethylation detection based on immune recognition of target molecule, where 5-hydroxymethyl-2′-deoxycytidine triphosphate (5hmdCTP) was employed as detect target, CdS/MXene was used as photoactive material, and ZnSnO₃ was adopted as signal amplification unit. Under enzymatic covalent reaction of –CH₂OH of 5hmdCTP with –NH₂ of MXene, 5hmdCTP was specifically recognized and captured. Then, taking advantages of the covalent reaction between phosphate group of 5hmdCTP and ZnSnO₃, the signal amplification unit was captured. Under the optimum conditions, this PEC biosensor presents wide linear range of 0.008–100 nM and low detection limit of 4.21 pM (3σ). The applicability of the developed method was evaluated by investigating the effect of Cd²⁺ and perfluorohexane compound pollutant on 5-hydroxymethylcytosine content in the genomic DNA of the roots and leaves of wheat seedlings.     

Metal-facilitated Photocatalytic Nanohybrids: Rational Design and Promising Environmental Applications

As a promising technique to potentially address the energy crisis and environmental issues, photocatalysis has been reported widely to exhibit various outstanding behaviors in production of new fuels/chemicals and treatment of contaminants. The photocatalytic performance is extremely dependent on the used photocatalysts, so that the design and preparation of efficient photocatalysts are critically important for significantly improving the photocatalytic activity. Among various strategies, the hybridization of metal with semiconductors has recently been attracting more and more research interest owing to their expended spectral absorption, promoted transferring rate of charge carriers and Plasmon-enhanced effect. In this minireview, the metal-facilitated hybrid photocatalysts are overviewed comprehensively to first reveal unique functions of metals in improvement of photoactivity and summarize the emerging metal-involved hybrid systems. Subsequently, the synthetic methods towards hybrid photocatalysts are introduced and their practical applications are emphasized in environmental remediation including degradation of organic pollutants, conversion of harmful gases, treatment of heavy metal ions and sterilization of bacteria. At the end, the challenges for industrializing these hybrid photocatalysts are discussed carefully and future development is suggested rationally.     

Recent Progress in High-Performance Lithium Sulfur Batteries: The Emerging Strategies for Advanced Separators/Electrolytes Based on Nanomaterials and Corresponding Interfaces

Lithium-sulfur (Li−S) batteries, possessing excellent theoretical capacities, low cost and nontoxicity, are one of the most promising energy storage battery systems. However, poor conductivity of elemental S and the “shuttle effect” of lithium polysulfides hinder the commercialization of Li−S batteries. These problems are closely related to the interface problems between the cathodes, separators/electrolytes and anodes. The review focuses on interface issues for advanced separators/electrolytes based on nanomaterials in Li−S batteries. In the liquid electrolyte systems, electrolytes/separators and electrodes system can be decorated by nano materials coating for separators and electrospinning nanofiber separators. And, interface of anodes and electrolytes/separators can be modified by nano surface coating, nano composite metal lithium and lithium nano alloy, while the interface between cathodes and electrolytes/separators is designed by nano metal sulfide, nanocarbon-based and other nano materials. In all solid-state electrolyte systems, the focus is to increase the ionic conductivity of the solid electrolytes and reduce the resistance in the cathode/polymer electrolyte and Li/electrolyte interfaces through using nanomaterials. The basic mechanism of these interface problems and the corresponding electrochemical performance are discussed. Based on the most critical factors of the interfaces, we provide some insights on nanomaterials in high-performance liquid or state Li−S batteries in the future.     

Earth-abundant Metal-catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis

Nitrogen-containing compounds, as an important class of chemicals, have been used widely in pharmaceuticals, materials synthesis. Transition metal-catalyzed reductive amination of an aldehyde or a ketone with ammonia or an amine has been proved to be an efficient and practical method for the preparation of nitrogen-containing compounds in academia and industry for a century. Given the above, several effective methods using transition metals have been developed in recent years. Noble transition metals like Pd, Pt, and Au-based catalysts have been predominately used in reductive amination. Because of their high prices, strict official regulations of residues in pharmaceuticals, and deleterious effects on the biological system, their industrial applications are severely hampered. With the increasing sustainable and environmental problems, the Earth-abundant transition metals including Ti, Fe, Co, Ni, and Zr have also been investigated for the reductive amination reaction and showed great potential to the advancement of sustainable and cost-effective reductive amination processes. This critical review will mainly summarize the work using Earth-abundant metals. The effects of different transition metals used in catalytic reduction amination were discussed and compared, and some suggestions were given. The last section highlights the catalytic activities of bi- and tri-metallic catalysts. Indeed, this latter family is very promising and simultaneously benefits from increased stability, and selectivity, compared to monometallic NPs, due to synergistic substrate activation. Few comprehensive reviews focusing on Earth-abundant transition metals catalyst has been published since 1948, although several authors reported some summaries dealing with one or the other part of this aspect. It is hoped that this critical review will inspire researchers to develop new efficient and selective earth-abundant metal catalysts for highly, environmentally sustainable reductive amination methods, as well as improve the pharmaceutical industry and related chemical synthesis company traditional method with the utilization of the green method widely.     

Polymer Electrolytes – New Opportunities for the Development of Multivalent Ion Batteries

Batteries, as highly concerned energy conversion system, have a great development prospect in various fields, especially in the field of energy powered vehicles. Multivalent ion batteries are getting more attention due to their low cost, high abundance in earth crust, high capacity and safety compared with Lithium batteries. Despite above advantages, several problems still need to be solved before multivalent ion batteries achieve large-scale application, such as interfacial parasitic reaction, anode passivation, and dendrites. The replacement of liquid electrolytes with gel polymer electrolytes (GPEs) which pose high safety, high mechanical strength and simplified battery system, is an effective strategy to inhibit dendrite growth and improve electrochemical performance. This review mainly discusses the advantages and challenges of multivalent ion batteries including zinc, magnesium, calcium and aluminum batteries. Meanwhile, the major targets of this review are introducing the recent developments and making a summary of the future trends of GPEs in the multivalent ion batteries.     

Predicting Dinitrogen Activation via Transition-Metal-Involved [4+2] Cycloaddition Reaction

As the strongest triple bond in nature, the N≡N triple bond activation has always been a challenging project in chemistry. On the other hand, since the award of the Nobel Prize in Chemistry in 1950, the Diels-Alder reaction has served as a powerful and widely applied tool in the synthesis of natural products and new materials. However, the application of the Diels-Alder reaction to dinitrogen activation remains less developed. Here we first demonstrate that a transition-metal-involved [4+2] Diels-Alder cycloaddition reaction could be used to activate dinitrogen without an additional reductant by density functional theory calculations. Further study reveals that such a dinitrogen activation by 1-metalla-1,3-dienes screened out from a series of transition metal complexes (38 species) according to the effects of metal center, ligand, and substituents can become favorable both thermodynamically (with an exergonicity of 28.2 kcal mol⁻¹) and kinetically (with an activation energy as low as 13.8 kcal mol⁻¹). Our findings highlight an important application of the Diels-Alder reaction in dinitrogen activation, inviting experimental chemists’ verification.     

全自动电位滴定法测定锂电池原料碳酸锂中主成分的含量

采用全自动电位滴定法测定锂电池原料碳酸锂中主成分的含量,用盐酸标准溶液进行滴定,考虑自动电位滴定仪的灵敏性和准确度,通过多次对比实验,确定了仪器的最佳工作参数、滴定剂浓度和样品称样量等滴定条件;对两个不同品位试样分别进行了11次平行测定,相对标准偏差(RSD)均小于1%。在碳酸锂试样中加入基准物质无水碳酸钠进行碳酸根的加标回收实验,碳酸根的加标回收率在99.4%~100%。与传统的酸碱滴定法相比,全自动电位滴定法方便、快捷,同时方法测定结果准确、可靠、精密度高,适合大批量样品快速分析。     

Development of Magnesium Anode-Based Transient Primary Batteries

Biodegradable primary batteries, also known as transient batteries, are essential to realize autonomous biodegradable electronic devices with high performance and advanced functionality. In this work, magnesium, copper, iron, and zinc – metals that exist as trace elements in the human body – were tested as materials for biomedical transient electronic devices. Different full cell combinations of Mg and X (where X = Cu, Fe, and Zn and the anodized form of the metals) with phosphate buffered saline (PBS) as electrolyte were studied. To form the cathodes, metal foils were anodized galvanostatically at a current density of 2.0 mA cm⁻² for 30 mins. Electrochemical measurements were then conducted for each electrode combination to evaluate full cell battery performance. Results showed that the Mg−Cu_anodized chemistry has the highest power density at 0.99 mW/cm². Nominal operating voltages of 1.26 V for the first 0.50 h and 0.63 V for the next 3.7 h were observed for Mg−Cu_anodized which was discharged at a current density of 0.70 mA cm⁻². Among the materials tested, Mg−Cu_anodized exhibited the best discharge performance with an average specific capacity of 2.94 mAh cm⁻², which is comparable to previous reports on transient batteries.     

Nonflammable nonaqueous electrolytes for lithium batteries

As the energy density of state-of-the-art lithium (Li)-ion batteries (LIBs) increases, the safety concern of LIBs using liquid electrolytes is drawing increasing attention. Flammability of electrolytes is a critical link of the overall safety performance of LIBs and Li metal batteries. For this reason, intensive efforts have been devoted to suppressing the flammability of liquid electrolytes. In this short review, the common approaches to reduce the flammability of the nonaqueous liquid electrolytes will be summarized. The advantages and limitations of these approaches will also be discussed.     

Metal Sulfide Nanoparticle Synthesis with Ionic Liquids – State of the Art and Future Perspectives

Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.