Effects of Alumina Bubble Addition on the Properties of Corundum-Spinel Castables Containing Cr2O3.

Purging plugs made of corundum-spinel castables containing Cr2O3 have been widely utilized in secondary refining process. However, their poor thermal shock resistance has greatly limited the improvement of their service life. Aiming to enhance their properties, we introduced alumina bubbles (ABs) to corundum-spinel castables, and the effects of the AB addition on the properties of the castables are studied in this manuscript. The results indicate that the apparent porosity, permanent linear change, cold strength, and hot strength all increased with an increasing AB amount. The thermal shock resistance of the samples with the AB addition was improved; the residual strength and residual strength ratio of the sample with 4 wt% ABs was the best. The effects of ABs on the tabular alumina aggregate distribution and relationship between the cold strength of the samples and the AB content was evaluated via the box dimension method. With the increments of AB content, the box dimension value of the tabular alumina within the samples significantly decreased, indicating that the tabular alumina aggregate distribution was related to the amount of ABs. In addition, the relationship between the box dimension and the strength was also established.

A first-principles study of 2D single-layer SiP as anode materials for lithium-ion batteries and sodium-ion batteries.

The promotion of lithium-ion batteries and sodium-ion batteries is limited by the deficiency of suitable anode materials with desired electrochemical properties. In this work, the models of 2D single-layer SiP are constructed to explore its potential as an anode material for LIBs and SIBs using density functional theory (DFT). The diffusion of Li in bulk SiP is anisotropic. There is a low diffusion energy barrier of 0.28 eV along the X-axis. The low surface exfoliation energy suggests that there is a high probability of preparing 2D single-layer SiP experimentally. Its structure stability is verified by ab initio molecular dynamics (AIMD) simulations at 300 K and 400 K. The intercalation and diffusion behaviors of Li/Na on 2D single-layer SiP indicate that Li/Na tends to diffuse along the X-axis direction of 2D single-layer SiP. The diffusion energy barrier of Li/Na on 2D single-layer SiP is lower compared to that of bulk SiP. The conductivity of 2D single-layer SiP is improved after lithiation due to the upshift of Fermi levels. 2D single-layer SiP has a lower average open circuit voltage (1.50 V for LIBs and 1.08 V for SIBs) and a high theoretical capacity (520 mA h g-1). Hence, 2D single-layer SiP can be an ideal anode material for LIBs and SIBs.

Large-Scale Fabrication of SiC-TiC@C Powders via Modified Molten Salt Shielding Synthesis Technique and Their Effect on the Properties of Al2O3-MgO Castables.

Graphite flakes are commonly used to fabricate carbon-based refractories owing to their superior properties, including better corrosion resistance and thermal shock resistance (TSR); unfortunately, their insufficient water-wettability has remarkably hindered their application in castables. Aiming to enhance their water-wettability, a facile and low-cost technique for fabricating carbides coated in graphite was proposed in this work. Firstly, SiC-TiC coated graphite (SiC-TiC@C) powders were prepared via modified molten salt shielding synthesis in an air atmosphere using graphite flake, Si and Ti powders as raw materials and NaCl-KCl as the molten salt shielding medium. Water-wettability and oxidation resistance of SiC-TiC@C powders were significantly improved. Compared to the Al2O3-MgO castables with graphite flakes, the water demand of the castables with SiC-TiC@C was noticeably decreased from 6.85% to 4.89%, thereby decreasing the apparent porosity of the castables with 5% SiC-TiC@C (from 20.3% to 13%), enhancing the cold strength, hot strength and oxidation resistance of the castables. Such enhancements are ascribed to continuous and crack-free SiC-TiC coatings on graphite surfaces ensuring that the castables have outstanding properties.

A novel insight into the microwave induced catalytic reduction mechanism in aqueous Cr(VI) removal over ZnFe2O4 catalyst.

Aqueous Cr(VI) pollution is an emerging environmental issue. Herein, a sphere-like ZnFe2O4 catalyst with a size of ∼430 nm was prepared by a solvothermal method, by which the aqueous Cr(VI) in a 50 mL solution with concentration of 50 mg/L was completely removed after 10 min-microwave (MW) irradiation. "Surface temperature visualization" tests and COMSOL simulations showed that the surface temperature of the as-prepared ZnFe2O4 catalysts could be as high as > 1000 °C only after 300 s MW irradiation, and the work function calculations and scavenging experiments demonstrated that the excited electrons derived by the "hot spots" effect of the ZnFe2O4 catalysts reduced the Cr(VI) to Cr(III). Kinetic reaction process of the reduction of *Cr2O72- to *CrO3H3 over the ZnFe2O4 catalysts was clarified by using DFT calculation, and the results indicated that *Cr2O72- adsorbed on the Fe atoms was more easily to be reduced, and that Fe atoms played more significant roles than the Zn and O atoms in ZnFe2O4 catalysts. The present study not only proves that the MW induced ZnFe2O4 catalytic reduction was promising for ultrafast remediation of toxic Cr(VI), but also provides a new insight into the corresponding mechanism.

Preparation of B4Cp/Al Composites via Selective Laser Melting and Their Tribological Properties.

B4C-particle-reinforced Al (B4Cp/Al) composites are widely used in various areas, e.g., armors, electronic packaging and fuel storage, owing to their several outstanding properties including high specific rigidity, excellent wear resistance and light weight. Selective laser melting (SLM) is favored in manufacturing complex components because of its high raw material utilization rate and high efficiency. In this work, a B4Cp/Al composite was successfully synthesized by SLM, and the effects of one of the most important parameters, scanning speed (100-700 mm/s), on the phase composition, density, microhardness and tribological properties of the samples were investigated. The microhardness, relative density and dry-sliding wear resistance of as-prepared B4Cp/Al composites were improved with the decrease in scanning speed, and the sample fabricated at a scanning speed of 100 mm/s exhibited a relative density as high as about 97.1%, and a maximum microhardness of ~180 HV0.1 (approximately six times more than that of the SLM-formed pure Al sample, 31 HV0.1), a minimum wear rate of 4.2 × 10-5 mm3·N-1·m-1 and a corresponding friction coefficient of 0.41. In addition, abrasive wear, adhesive wear and oxidation wear were found to be behind the overall wear behavior of as-prepared B4Cp/Al composites.

Excellent Catalytic Performance of ISOBAM Stabilized Co/Fe Colloidal Catalysts toward KBH4 Hydrolysis.

Recently, developing a cost-effective and high-performance catalyst is regarded as an urgent priority for hydrogen generation technology. In this work, ISOBAM-104 stabilized Co/Fe colloidal catalysts were prepared via a co-reduction method and used for the hydrogen generation from KBH4 hydrolysis. The obtained ISOBAM-104 stabilized Co10Fe90 colloidal catalysts exhibit an outstanding catalytic activity of 37,900 mL-H2 min-1 g-Co-1, which is far higher than that of Fe or Co monometallic nanoparticles (MNPs). The apparent activation energy (Ea) of the as-prepared Co10Fe90 colloidal catalysts is only 14.6 ± 0.7 kJ mol-1, which is much lower than that of previous reported noble metal-based catalysts. The X-ray photoelectron spectroscopy results and density functional theory calculations demonstrate that the electron transfer between Fe and Co atoms is beneficial for the catalytic hydrolysis of KBH4.

A robust air superhydrophilic/superoleophobic diatomite porous ceramic for high-performance continuous separation of oil-in-water emulsion.

Three-dimensional (3D) porous architecture has attracted considerable attention in remediation of oil/water emulsion. In present work, an air superhydrophilic/superoleophobic diatomite porous ceramic (AS-DC) was prepared, using SiO2 whiskers modified diatomite ceramic as the substrate and FS-50 as the modifier. The interconnected SiO2 whiskers intertwined on the skeleton of ceramic block forming a 3D network structure, which not only improved the wettability of AS-DC, but also reinforced its mechanical property (about 2.5 MPa of compressive strength). The as-prepared AS-DC with intrinsically superoleophobicity (154°) and superhydrophilicity (0°) exhibited an underwater oil contact angle of 161°, suggesting a multifunctional separation capability. By simply assembling AS-DC with pipes and a pump, it could not only separate the surfactant-stabilized oil-in-water emulsion in a permeation flux as high as 107.8 kg min-1 m-2 with a selectivity of >95%, but also collect the clean water from the floating oil/water mixture in a flux of 197.4 kg min-1 m-2 and a selectivity of ∼99%. In addition, the AS-DC was resistant to the salt/acid/alkaline corrosion and temperature fluctuation. The mechanical/chemical firmness of AS-DC renders it tremendous potential as a robust 3D architecture in real application for purification of oil/water mixture.

In situ synthesized α-Fe2O3/BCN heterojunction for promoting photocatalytic CO2 reduction performance.

The conversion of CO2 into clean fuels by utilizing solar energy is still limited by a low photoconversion efficiency, and heterojunction photocatalysts are considered a very effective way to solve this problem. Herein, a heterojunction system consisting of hematite (α-Fe2O3) and boron carbonitride (BCN) was fabricated through a one-pot ionothermal method. α-Fe2O3 nanoparticles were grown in situ on the surface of BCN nanosheets, forming an α-Fe2O3/BCN heterojunction (FBCN) with tiny amounts of α-Fe2O3 (less than 2 wt%). The as-synthesized FBCN catalyst with 1.46 wt% α-Fe2O3 provides the highest CO2 photoreduction activity (55.1 µmol g-1 for CO) without any cocatalyst or sacrificial reagents, which is 3.9 times higher than that obtained for pure BCN. The enhanced CO2 reduction activity can be attributed to the high surface area and effective interface-contacted heterostructure, which endows the catalyst with broadband visible light absorption, suppressed separation of photogenerated electron holes, and promoted charge transfer. Meanwhile, cycling experiments demonstrate that the FBCN photocatalyst shows good reusability and stability. This work can assist in the design and preparation of BCN-based heterojunctions with effective CO2 reduction performance.

Kinetically Accelerated Lithium Storage in High-Entropy (LiMgCoNiCuZn)O Enabled By Oxygen Vacancies.

High-entropy oxides (HEOs) are gradually becoming a new focus for lithium-ion battery (LIB) anodes due to their vast element space/adjustable electrochemical properties and unique single-phase retention ability. However, the sluggish kinetics upon long cycling limits their further generalization. Here, oxygen vacancies with targeted functionality are introduced into rock salt-type (MgCoNiCuZn)O through a wet-chemical molten salt strategy to accelerate the ion/electron transmission. Both experimental results and theoretical calculations reveal the potential improvement of lithium storage, charge transfer, and diffusion kinetics from HEO surface defects, which ultimately leads to enhanced electrochemical properties. The currently raised strategy offers a modular approach and enlightening insights for defect-induced HEO-based anodes.

Bimetallic Co-Mo sulfide/carbon composites derived from polyoxometalate encapsulated polydopamine-decorated ZIF nanocubes for efficient hydrogen and oxygen evolution.

The increased call for carbon neutrality by 2050 makes it compelling to develop emission-free alternative energy sources. Green hydrogen produced from water electrolyzers using renewable electricity is of great importance, and the development of efficient transition-metal-based materials for hydrogen production by electrolysis is highly desirable. In this report, a new approach to produce defect-rich and ultra-fine bimetallic Co-Mo sulfides/carbon composites from polyoxometalates@ZIF-67@polydopamine nanocubes via carbonization/sulfurization, which are highly active for hydrogen and oxygen evolution reactions (HER and OER), have been successfully developed. The coating of polydopamine (PDA) on the surface of the acid-sensitive ZIF-67 cubes can prevent the over-dissociation of ZIF-67 caused by the encapsulated phosphomolybdic acid (PMA) etching through PDA chelating with the PMA molecules. Meanwhile, the partially dissociated Co2+ from ZIF-67 can be captured by the coated PDA via chelation, resulting in more evenly dispersed active sites throughout the heterogeneous composite after pyrolysis. The optimized bimetallic composite CoMoS-600 exhibits a prominent improvement in HER (with an overpotential of -0.235 V vs. RHE at a current density of 10 mA cm-2) and OER performance (with an overpotential of 0.350 V vs. RHE at a current density of 10 mA cm-2), due to the synergistic effect of ultra-fine defect-rich Co-Mo-S nanoparticle active sites and N,S-codoped porous carbons in the composites. Moreover, this synthesis approach can be readily expanded to other acidic polyoxometalates to produce HER and OER active bimetallic Co-W sulfide/carbon composites by replacing PMA with phosphotungstic acid. This new synthesis strategy to modify acid-sensitive ZIFs with selected compounds offers an alternative approach to develop novel transition metal sulfide/carbon composites for various applications.

Research Progress on Coating Structure of Silicon Anode Materials for Lithium-Ion Batteries.

Silicon, which has been widely studied by virtue of its extremely high theoretical capacity and abundance, is recognized as one of the most promising anode materials for the next generation of lithium-ion batteries. However, silicon undergoes tremendous volume change during cycling, which leads to the destruction of the electrode structure and irreversible capacity loss, so the promotion of silicon materials in commercial applications is greatly hampered. In recent years, many strategies have been proposed to address these shortcomings of silicon. This Review focused on different coatings materials (e. g., carbon-based materials, metals, oxides, conducting polymers, etc.) for silicon materials. The role of different types of materials in the modification of silicon-based material encapsulation structure was reviewed to confirm the feasibility of the protective layer strategy. Finally, the future research direction of the silicon-based material coating structure design for the next-generation lithium-ion battery was summarized.

One-Pot Synthesis of Alumina-Titanium Diboride Composite Powder at Low Temperature.

Alumina-titanium diboride (Al2O3-TiB2) composite powders were synthesised via aluminothermic reduction of TiO2 and B2O3, mediated by a molten chloride salt (NaCl, KCl, or MgCl2). The effects of salt type, initial batch composition, and firing temperature/time on the phase formation and overall reaction extent were examined. Based on the results and equilibrium thermodynamic calculations, the mechanisms underpinning the reaction/synthesis processes were clarified. Given their evaporation losses at test temperatures, appropriately excessive amounts of Al and B2O3 are needed to complete the synthesis reaction. Following this, phase-pure Al2O3-TiB2 composite powders composed of 0.3-0.6 µm Al2O3 and 30-60 nm TiB2 particles were successfully fabricated in NaCl after 5 h at 1050 °C. By increasing the firing temperature to 1150 °C, the time required to complete the synthesis reaction could be reduced to 4 h, although the sizes of Al2O3 and TiB2 particles in the resultant phase pure composite powder increased slightly to 1-2 µm and 100-200 nm, respectively.

Ultrathin mesoporous graphitic carbon nitride nanosheets with functional cyano group decoration and nitrogen-vacancy defects for an efficient selective CO2 photoreduction.

Graphitic carbon nitrides have CO2 photoreduction ability, but their activities are limited by the low potential and mobility of photogenerated carriers. Herein, ultrathin mesoporous graphitic carbon nitride nanosheets (CNNS) synchronously decorated with functional cyano groups and nitrogen vacancies were prepared by a facile molten salt route. The CNNS presented unprecedentedly excellent gas-phase CO2 photoreduction performance under visible light irradiation without any co-catalyst or a sacrificial agent, and have a CH4-yielding rate of 23.0 µmol g-1 h-1 and a selectivity of 97.9%. This boosted performance can be attributed to the synergistic effect of cyano group decoration, abundant nitrogen vacancies and extremely high surface area, which improve electron storage, charge carrier mobility, CO2 affinity, and optimize the energy band structure. This work demonstrates that a structural optimization combined with defect design of carbon nitride framework is a powerful approach to improve the photocatalytic activity, providing an accessible way to design highly efficient carbon-based photocatalysts.

Recent Advances in Metal-Organic Frameworks Derived Nanocomposites for Photocatalytic Applications in Energy and Environment.

Solar energy is a key sustainable energy resource, and materials with optimal properties are essential for efficient solar energy-driven applications in photocatalysis. Metal-organic frameworks (MOFs) are excellent platforms to generate different nanocomposites comprising metals, oxides, chalcogenides, phosphides, or carbides embedded in porous carbon matrix. These MOF derived nanocomposites offer symbiosis of properties like high crystallinities, inherited morphologies, controllable dimensions, and tunable textural properties. Particularly, adjustable energy band positions achieved by in situ tailored self/external doping and controllable surface functionalities make these nanocomposites promising photocatalysts. Despite some progress in this field, fundamental questions remain to be addressed to further understand the relationship between the structures, properties, and photocatalytic performance of nanocomposites. In this review, different synthesis approaches including self-template and external-template methods to produce MOF derived nanocomposites with various dimensions (0D, 1D, 2D, or 3D), morphologies, chemical compositions, energy bandgaps, and surface functionalities are comprehensively summarized and analyzed. The state-of-the-art progress in the applications of MOF derived nanocomposites in photocatalytic water splitting for H2 generation, photodegradation of organic pollutants, and photocatalytic CO2 reduction are systemically reviewed. The relationships between the nanocomposite properties and their photocatalytic performance are highlighted, and the perspectives of MOF derived nanocomposites for photocatalytic applications are also discussed.

Enhanced Diffusion Kinetics of Li Ions in Double-Shell Hollow Carbon Fibers.

The rational design and preparation of hierarchical hollow structures have promising potential in electrochemical energy storage systems. In this paper, double-shell hollow carbon fibers (DSHCFs) with tunable thickness and shell spacing are prepared using hollow electrospun polystyrene fibers as the hard template and in situ coated polypyrrole as the carbon source. The as-prepared DSHCFs with an optimized structure exhibit a submicrometer shell spacing and a nanoscaled shell thickness, which guarantees sufficient contact area with the electrolyte and provides abundant electrochemical active sites for Li+ storage. Owing to the unique structural advantages, a DSHCF-based anode shows favorable transport kinetics for both Li+ ions and electrons during the lithiation/delithiation process, and a high reversible capacity of 348 mAh g-1 at 5.0 A g-1 is well maintained even after 500 cycles with no obvious capacity attenuation. Particular emphasis is given to kinetic Li+ storage mechanisms in DSHCFs that are discussed in detail, providing a new avenue for developing high-performance carbon materials for the practical application of energy storage devices.

Joule-heatable bird-nest-bioinspired/carbon nanotubes-modified sepiolite porous ceramics: An efficient, sturdy, and continuous strategy for oil recovery.

Oil-spill accident is a severe globally concerned environmental issue. In this work, a Joule-heatable bird-nest-bioinspired/carbon nanotubes-modified sepiolite porous ceramic (JBN/CM-SC) was developed, using inexpensive sepiolite porous ceramics as the substrate and carbon nanotubes (CNTs) derived from waste plastics as the modifier. The former exhibited outstanding mechanical property (1.7 MPa of compressive strength), gas permeability (9.1 × 10-11 m2), thermal conductivity (0.215 W·m-1·K-1) and thermal/chemical stability. As expected, the deposited CNTs not only conferred a hydrophobic surface, but also resulted in a Joule-heating ability of intrinsically non-conductive ceramics. As-prepared JBN/CM-SC demonstrated a separation rate as high as 120-200 kg·s-1·m-2 for oil recovery and a high selectivity of over 95%. The Joule heat generated by the heated JBN/CM-SC could in-situ reduce the oil-viscosity, remarkably increasing the oil-diffusion. The separation rate was enhanced by ~12 times with respect to that of the non-heated counterpart. In addition, the idea of modular design was proposed. By simply combining JBN/CM-SC components with pipes and a pump, a continuous in-situ collection of oil from an oil/water mixture was realized, providing an efficient, sturdy, and continuous approach to recover the spilled oil in an oil-spill accident.

Ultra-porous Co foam supported FeCoP electrode for high efficiency hydrogen evolution reaction.

Development an alternative approach to efficiently and economically produce hydrogen from water to replace non-renewable fossil fuels is one of the great challenges in the energy field. In this paper, a Co foam (CF) with 90% porosity and pore size of a few tens of micrometers was prepared, on which FeCoP nanoflowers were in-situ formed. Such a combination was used as a new electrocatalyst/self-supporting electrode for high efficiency hydrogen evolution reaction. Thanks to the larger surface area (and thus many more active sites), and quicker mass transfer through the porous structure, the CF supported FeCoP electrode exhibited much better hydrogen evolution reaction (HER) performance than the commercial Ni foam supported counterpart prepared under identical conditions. In the case of the former, only -44 mV overpotential was required to achieve a geometric current density of -10 mA cm-2, and the electrode showed a high stability at a current density < -500 mA cm-2. The electrode developed in this work could be potentially used as a novel electrode for future large-scale production of hydrogen. In addition, the novel strategy reported here could be similarly used to develop many other types of self-supporting electrodes with further improved HER performance.

Preparation and Photocatalytic Performance for Degradation of Rhodamine B of AgPt/Bi4Ti3O12 Composites.

Loading a noble metal on Bi4Ti3O12 could enable the formation of the Schottky barrier at the interface between the former and the latter, which causes electrons to be trapped and inhibits the recombination of photoelectrons and photoholes. In this paper, AgPt/Bi4Ti3O12 composite photocatalysts were prepared using the photoreduction method, and the effects of the type and content of noble metal on the photocatalytic performance of the catalysts were investigated. The photocatalytic degradation of rhodamine B (RhB) showed that the loading of AgPt bimetallic nanoparticles significantly improved the catalytic performance of Bi4Ti3O12. When 0.10 wt% noble metal was loaded, the degradation rate for RhB of Ag0.7Pt0.3/Bi4Ti3O12 was 0.027 min-1, which was respectively about 2, 1.7 and 3.7 times as that of Ag/Bi4Ti3O12, Pt/Bi3Ti4O12 and Bi4Ti3O12. The reasons may be attributed as follows: (i) the utilization of visible light was enhanced due to the surface plasmon resonance effect of Ag and Pt in the visible region; (ii) Ag nanoparticles mainly acted as electron acceptors to restrain the recombination of photogenerated electron-hole pairs under visible light irradiation; and (iii) Pt nanoparticles acted as electron cocatalysts to further suppress the recombination of photogenerated electron-hole pairs. The photocatalytic performance of Ag0.7Pt0.3/Bi4Ti3O12 was superior to that of Ag/Bi4Ti3O12 and Pt/Bi3Ti4O12 owing to the synergistic effect between Ag and Pt nanoparticles.

Molten salt synthesis of carbon-doped boron nitride nanosheets with enhanced adsorption performance.

Owing to their large specific areas, high thermal stability and chemical inertness, two-dimensional boron carbon nitride nanosheets (BCNNs) have captured much attention in recent years in the field of adsorption of pollutants. The formation of BCNNs via incorporating carbon into boron nitride (BN) can effectively improve the photoelectric and adsorption properties of the latter. In this work, carbon-doped BN (BCN) nanosheets were prepared at 1100 °C via a molten salt route using boric acid, melamine and glucose as the main starting materials. The effects of molten salt type and carbon doping level on the formation of BCN were investigated, and their isothermal adsorption properties in a methylene blue (MB) aqueous solution were evaluated based on the Langmuir and Freundlich models. The results indicated that using molten LiCl-KCl as a liquid medium was more favorable than NaCl-KCl to the formation of BCNNs. As-prepared BC0.4N sample possessed a sheet-like structure of about 10 nm thick and a specific surface area as high as 484 m2 g-1. Moreover, the adsorption test of MB demonstrated a high adsorption capacity of 249.04 mg g-1, which was about 14 times higher than that in the case of the pristine BN, and the kinetic rate constant value in the case of using BC0.4N is about ten times as high as that of BN following a pseudo-second-order model, suggesting that the as-formed BC0.4N nanosheets could be potentially used as a value-added effective adsorbent for future wastewater remediation.

Catalytic Preparation of Carbon Nanotubes from Waste Polyethylene Using FeNi Bimetallic Nanocatalyst.

In this work, carbon nanotubes (CNTs) were synthesized by catalytic pyrolysis from waste polyethylene in Ar using an in-situ catalyst derived from ferric nitrate and nickel nitrate precursors. The influence factors (such as temperature, catalyst content and Fe/Ni molar ratio) on the formation of CNTs were investigated. The results showed that with the temperature increasing from 773 to 1073 K, the carbon yield gradually increased whereas the aspect (length-diameter) ratio of CNTs initially increased and then decreased. The optimal growth temperature of CNTs was 973 K. With increasing the Fe/Ni molar ratio in an FeNi bimetallic catalyst, the yield of CNTs gradually increased, whereas their aspect ratio first increased and then decreased. The optimal usage of the catalyst precursor (Fe/Ni molar ratio was 5:5) was 0.50 wt% with respect to the mass of polyethylene. In this case, the yield of CNTs reached as high as 20 wt%, and their diameter and length were respectively 20-30 nm, and a few tens of micrometers. The simple low-cost method developed in this work could be used to address the environmental concerns about plastic waste, and synthesize high value-added CNTs for a range of future applications.