Design Principles and Mechanistic Understandings of Non-Noble-Metal Bifunctional Electrocatalysts for Zinc-Air Batteries

Zinc-air batteries(ZABs)are promising energy storage systems because of high theoretical energy density,safety,low cost,and abundance of zinc.However,the slow multi-step reaction of oxygen and heavy reliance on noble-metal catalysts hinder the practical applications of ZABs.Therefore,feasible and advanced non-noble-metal elec-trocatalysts for air cathodes need to be identified to promote the oxygen catalytic reaction.In this review,we initially introduced the advancement of ZABs in the past two decades and provided an overview of key developments in this field.Then,we discussed the work-ing mechanism and the design of bifunctional electrocatalysts from the perspective of morphology design,crystal structure tuning,interface strategy,and atomic engineering.We also included theoretical studies,machine learning,and advanced characterization technologies to provide a comprehensive understanding of the structure-performance relationship of electrocatalysts and the reaction pathways of the oxygen redox reactions.Finally,we discussed the challenges and prospects related to designing advanced non-noble-metal bifunctional electrocatalysts for ZABs.

Fabrication and anti-corrosion performance of superhydrophobic silane film on sintered NdFeB

An eco-friendly superhydrophobic protective film(DTMS/TEOS silane film)was fabricated on sintered NdFeB substrate through the utilization of electrochemically assisted deposition technology.The structure,properties,and film-forming mechanism of dodecyltrime-thoxysilane(DTMS)/tetraethoxysilane(TEOS)silane films were comprehensively analyzed using Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS).Based on the test results,it can be determined that this film has a superhydrophobic property with a hydrophobicity angle of 152°.This special property can be attributed to the long alkyl chains in the DTMS molecule,the rough morphology,and the low surface energy of the DTMS/TEOS silane film.The surface of sintered NdFeB is coated with a layered three-dimensional network silane film that forms through the condensation of silanol substances.This film provides excellent corrosion resistance to the sintered NdFeB substrate,reducing its corrosion current density to 2.02×10~(-6)A/cm~2.Moreover,the impact of film on the magnetic characteristics of sintered NdFeB was assessed and found to be minimal.

Hydrogen release of NaBH_(4) below 60 ℃ with binary eutectic mixture of xylitol and erythritol additive

NaBH_(4) was widely regarded as a low-cost hydrogen storage material due to its high-mass hydrogen capacity of approximately 10.8%(mass)and high volumetric hydrogen capacity of around 115 g·L^(–1).However,it exhibits strong stability and requires temperatures above 500℃ for hydrogen release in practical applications.In this study,two polyhydric alcohols,xylitol and erythritol(XE),were prepared as a binary eutectic sugar alcohol through a grinding-melting method.This binary eutectic sugar alcohol was used as a proton-hydrogen carrier to destabilize NaBH_(4).The 19NaBH_(4)-16XE composite material prepared by ball milling could start releasing hydrogen at 57.5℃,and the total hydrogen release can reach over 88.8%(4.45%(mass))of the theoretical capacity.When the 19NaBH_(4)-16XE composite was pressed into solid blocks,the volumetric hydrogen capacity of the block-shaped composite could reach 67.2 g·L^(–1).By controlling the temperature,the hydrogen desorption capacity of the NaBH_(4)-XE composite material was controllable,which has great potential for achieving solid-state hydrogen production from NaBH_(4).

Efficient Polytelluride Anchoring for Ultralong-Life Potassium Storage: Combined Physical Barrier and Chemisorption in Nanogrid-in-Nanofiber

Metal tellurides(MTes) are highly attractive as promising anodes for high-performance potassium-ion batteries. The capacity attenuation of most reported MTe anodes is attributed to their poor electrical conductivity and large volume variation. The evolution mechanisms, dissolution properties, and corresponding manipulation strategies of intermediates(K-polytellurides, K-pTe_(x)) are rarely mentioned. Herein,we propose a novel structural engineering strategy to confine ultrafine CoTe_(2) nanodots in hierarchical nanogrid-in-nanofiber carbon substrates(CoTe_(2)@NC@NSPCNFs) for smooth immobilization of K-pTe_(x) and highly reversible conversion of CoTe_(2) by manipulating the intense electrochemical reaction process. Various in situ/ex situ techniques and density functional theory calculations have been performed to clarify the formation, transformation, and dissolution of K-pTe_(x)(K_(5)Te_(3) and K_(2)Te), as well as verifying the robust physical barrier and the strong chemisorption of K_(5)Te_(3) and K_(2)Te on S, N co-doped dual-type carbon substrates. Additionally, the hierarchical nanogrid-in-nanofiber nanostructure increases the chemical anchoring sites for K-pTe_(x), provides sufficient volume buffer space, and constructs highly interconnected conductive microcircuits, further propelling the battery reaction to new heights(3500 cycles at 2.0 A g^(-1)). Furthermore, the full cells further demonstrate the potential for practical applications. This work provides new insights into manipulating K-pTe_(x) in the design of ultralong-cycling MTe anodes for advanced PIBs.

Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium

Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.

Effect of VC addition on the microstructure and properties of Ti(C,N)-based nano cermets

In this paper, Ti（C,N）-based nano cermets were prepared by nano particles, and the effect of VC addition on the micmstructure and properties of Ti（C,N）-based nano cermets was investigated. The results showed that there existed black-core grayish-rim strucmre as well as gray-core grayish-rim structure in VC-doped Ti（C,N）-based nano cermets. With the increase of VC addition, the number of gray cores in- creased, the lattice parameter of Ti（C,N） phase increased, the grain size decreased, the hardness and fracture toughness of Ti（C,N）-based nano cermets were enhanced, and nearly full densification could be achieved. However, excessive addition of VC to 1 wt% resulted in slight decrease in hardness and fracture toughness. Some deep dimples were found in the fracture surface of cermets with VC addition, which corresponded to ductile fracture.

Enhanced Potassium‑Ion Storage of the 3D Carbon Superstructure by Manipulating the Nitrogen‑Doped Species and Morphology

Potassium-ion batteries(PIBs)are attractive for gridscale energy storage due to the abundant potassium resource and high energy density.The key to achieving high-performance and large-scale energy storage technology lies in seeking eco-efficient synthetic processes to the design of suitable anode materials.Herein,a spherical sponge-like carbon superstructure(NCS)assembled by 2D nanosheets is rationally and efficiently designed for K+storage.The optimized NCS electrode exhibits an outstanding rate capability,high reversible specific capacity(250 mAh g^(−1) at 200 mA g^(−1) after 300 cycles),and promising cycling performance(205 mAh g^(−1) at 1000 mA g^(−1) after 2000 cycles).The superior performance can be attributed to the unique robust spherical structure and 3D electrical transfer network together with nitrogen-rich nanosheets.Moreover,the regulation of the nitrogen doping types and morphology of NCS-5 is also discussed in detail based on the experiments results and density functional theory calculations.This strategy for manipulating the structure and properties of 3D materials is expected to meet the grand challenges for advanced carbon materials as high-performance PIB anodes in practical applications.

Preparation and Characterization of Novel Ti-doped M-site Deficient Olivine LiFePO_4

A novel Ti-doped M-site deficient olivine LiFePO4, i.e. Li0.95Fe0.95Ti0.05PO4, was synthesized by a solid-state reaction method. XRD and VTR were used to characterize the as-prepared samples. As a cathode material for lithium-ion batteries, Li0.95Fe0.95Ti0.05PO4 exhibited improved rate capability.

Preparation and Photochemical Behavior of a Cationic Azobenzene Dye-Montmorillonite Intercalation Compound

Montmorillonite/cationic azobenzene dye（p-（δ-triethylammoniobutoxy）-p＇-methyl- azobenzene bromide） intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure cationic azo-dye, the thermal stability of the intercalated dye was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated dye shifted towards longer wave length by 38 nm. This could be ascribed to the strong conjugation of cationic azo-dye supramolecular order structure（J cluster） confined in a nanoscale space of montmorillonite interlayer gallery. UV/vis spectra data show that the intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and daylight cis-to-trans back reaction. FTIR indicates the successful intercalation of cationic azo-dye into the montmorillonite interlayer.

Effects of postthermal treatment and UV irradiation on the structure of titania-polyacrylate nanocomposites

The effects of postthermal treatment and irradiation time on the structure and thermal stability of TiO2/polyacrylate nanocomposites by a sol-gel process in reverse micelles and subsequent rapid photopolymerization were investigated, and the hybrid films were characterized by thermal gravimetry analysis （TGA）, X-ray photoelectron spectrum （XPS）, and atomic force microscopy （AFM）. XPS data suggested that the prolongation of irradiation time and the postthermal treatment promoted titania formation, with the former affecting more remarkably. TGA data showed that TiO2-hybrid films could upgrade the decomposition onset temperature （Tonset） as well as the temperature at which there is a maximum mass loss rate （Tmax）. AFM data demonstrated that the inorganic titania particles with a mean diameter of 25.26-28.84 nm were homogeneously distributed in the organic matrix.

Preparation and properties of GAGG:Ce/glass composite scintillation material

The translucent GGAG:Ce/glass composites are prepared successfully by ball-milling,tableting,and pressureless sintering.The thickness of composites is about 400μm.The x-ray diffraction(XRD),differential scanning calorimetry(DSC),density of composite materials are measured and discussed systematically.The scanning electron microscopy(SEM)and energy dispersive spectrometer(EDS)elemental mapping are employed to analyze the particle size,the shape of powders,and the distribution of GGAG:Ce particles in the glass matrix,respectively.The decay time,ultraviolet,(UV),x-ray excitation luminescence spectra,and temperature spectra are studied.The results show that the composite materials have high light output,good thermostability,and short decay time.The method adopted in this work is an effective method to reduce the preparation time and cost of the sample.The ultralow afterglow indicates that the composite materials have an opportunity to be used for x-ray detection and imaging.

Cure Behaviors and Water Up-take Evaluation of a New Waterborne Epoxy Resin

Cure behaviors and water up-take evaluation of a low cost, ecofriendly and water soluble epoxy resin prepared by reaction between epichlorohydrin and PEG400, PEG600 and PEG1000, respectively, were investigated using non-isothermal differential scanning calorimetry （DSC） and gravimetrical method, respectively. Factors affecting the cure behaviors as well as water up-take of waterborne epoxy resins, such as amount of triethylenetetramine （TETA） and triethylene diamine （TEDA）, PEG molecular weight, curing temperature, were systematically investigated. The prepared water soluble epoxy resins can be cured under room temperature with the shape of the curing curves similar to that expected for an autocatalytic reaction.

Synthesis of CdTe/SiO_2 Composites and Their Fluorescence Properties

Thioglycolic acid（TGA）-stabilized CdTe nanocrystals（NCs） were prepared with sodium tellurite as tellurium source,which avoids the cumbersome processes associated with H2Te or NaHTe sources.Fluorescent CdTe/SiO2 composites were synthesized by a sol-gel method without the exchange of surface ligands.The phase structure of CdTe NCs was investigated by X-ray diffractometry.For comparison,some characterizations were done for both the CdTe NCs and the composites.CdTe NCs and CdTe/SiO2 composites were characterized with TEM,digital camera and fluorescence spectrophotometer.The stability of CdTe NCs and the composites were investigated in phosphate-buffered saline（PBS） buffer and the fluorescent properties of the composites were discussed in detail.

Preparation of a cationic azobenzene dye-montmorillonite intercalation compound and its photochemical behavior

Montmorillonite/cationic azobenzene dye （GTL） intercalation compounds were prepared by the conventional ion exchange method. As compared with that of pure GTL, the thermal stability of the intercalated GTL was greatly enhanced, and the absorption band corresponding to azobenzene group in intercalated GTL shifted towards a longer wavelength by 55 nm, which could be ascribed to the strong conjugation of GTL supramolecular order structure （J cluster） confined in a nanoscale space of montmorillonite interlayer gallery. The microstructures of the resulting intercalation compounds could be successfully controlled by varying the amount of dye loaded as evidenced by the basal spacing of the intercalation compounds. The intercalated azo dye in the montmorillonite interlayer space exhibited reversible trans-to-cis photoisomerization and thermal cis-to-trans reaction. FTIR proved the successful intercalation of GTL into the silicate layer.

A Highly Efficient and Selective Water-Soluble Bimetallic Catalyst for Hydrogenation of Chloronitrobenzene to Chloroaniline

Selective hydrogenation of chloronitrobenzene(CNB) to chloroaniline(CAN) catalyzed by water-soluble Ru/Pt bimetallic catalyst in an aqueous-organic biphasic system was studied. It was found that the catalytic activity increased obviously due to the addition of platinum. Ru/Pt bimetallic catalysts exhibited a strong synergistic effect when the molar ratio of Pt was in the range of 5%—80%. Under the mild conditions including a temperature of 25 ℃, a hydrogen pressure of 1.0 MPa and a Pt molar ratio of 20%, the conversion of p-chloronitrobenzene(p-CNB) reached 99.9%, with the selectivity to p-chloroaniline(p-CAN) equating to 99.4%. The Ru/Pt catalyst also showed high activity and selectivity for the hydrogenation of other chloro- and dichloro-nitrobenzenes with different substituted positions. In addition, the catalyst can be recycled five times without significant loss of activity.

Effects of ECAE processing temperature on the microstructure, mechanical properties, and corrosion behavior of pure Mg

A two-step equal channel angular extrusion（ECAE） procedure was used to process pure Mg. The effects of ECAE processing temperature on the microstructure, mechanical properties, and corrosion behavior of pure Mg were studied. The results show that the average grain size of pure Mg decreases with decreasing extrusion temperature. After ECAE processing at 473 K, fine and equiaxed grains（~9 μm） are obtained. The sample processed at 473 K exhibits the excellent mechanical properties, whereas the sample processed at 633 K has the lowest corrosion rate. The improved corrosion resistance and mechanical properties of pure Mg by ECAE are ascribed to grain refinement and microstructural modification.

New insight into the design of highly dispersed Pt supported CeO_(2)-TiO_(2) catalysts with superior activity for VOCs low-temperature removal

A series of CeO_(2)-TiO_(2)mixed oxides supports with various Ce/Ti molar ratio were synthesized by modified coprecipitation method. The corresponding Pt loaded(0.5 wt% Pt) catalysts were prepared by electronless deposition method and evaluated for the deep oxidation of n-hexane as a model VOCs. The results show that the CeO_(2)and TiOxnanoparticles can highly disperse into each other and form Ce_(2)Ti_(2)O_(7)solid solution with appropriate Ce/Ti molar ratio, which significantly improves their redox ability by enhancing the interaction between CeO_(2)and TiO_(x). The dispersibility of Pt species can also be adjusted by altering the Ce/Ti molar ratio, and Pt/CeTi-2/1 catalyst with Ce/Ti molar ratio of 2:1 exhibits the best Pt dispersibility that Pt species mainly exist as Pt single atoms. The high dispersion of Pt species in the Pt/CeO_(2)-TiO_(2)catalysts would promote the catalytic activity of VOCs oxidation with low T90% values(1000 ppm, GHSV = 15,000 h^(-1)), such as for n-hexane degradation with T90% of 139℃. The characterizations reveal that the superior activity is mainly related to possessing the more Pt2+species,adsorbed oxygen species and higher low-temperature reducibility owing to the strong interaction between highly dispersed Pt species and CeO_(2)-TiO_(2)as well as the promoted migration of lattice oxygen by the formation of more Ce_(2)Ti_(2)O_(7)species. Furthermore, the Pt/CeTi-2/1 catalyst also exhibits excellent stability for chlorinated and other non-chlorinated VOCs oxidation, making it very promising for real application under various operating conditions.

Source and yearly distribution of PAHs in the snow from the Hailuogou glacier of Mountain Gongga, China

Snow samples were collected over a 3-year period from 2012 to 2014 at the Hailuogou glacier of Mountain Gongga(Mt. Gongga) and analyzed for 16 priority polycyclic aromatic hydrocarbons(PAHs) using Gas Chromatography–Mass Spectrometry(GC–MS). The results show that total average levels of the 16 PAHs ranged from 452 to 290 ng·L^(-1) with a possible declining trend from 2012 to 2014. Distances between the sampling sites and the emission sources were estimated at typically less than 500 km. The results suggest that the major source of PAHs was from coal combustion, while contributions from automobile exhaust played an important role in more recent years. This finding was in agreement with the characteristics of presence of local industry, residence, and recent development of tourism of the surrounding areas.

Preparation of Ammonium Tungstophosphate-Calcium Alginate Composite Adsorbent and the Separation of Rubidium and Potassium

As a kind of rare metals,rubidium is often used to prepare special glass,photomultiplier tubes,thermoelectric converter,organic catalysts and antidepressants.Rubidium forms no minerals of its own,hence,it often coexists with

Thermodynamics Phase Equilibria for the Salt- Water System of Potassium and Rubidium Ions

1 Introduction Brines,containing a variety of useful components,such as alkali metal(IA),alkaline earth metal(type IIA),halogen elements(such as VIIA),are naturally occurring complex electrolyte solution.Although rubidium is not the main component of the brine,while in the brine exploiting process,rubidium ion is continuously enriched in the