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At least 289 records · Page 16

Magnetically Recoverable and Reusable Titanium Dioxide Nanocomposite for Water Disinfection

A bifunctional magnetic Fe3O4@SiO2@TiO2 or MS-TiO2 antimicrobial nanocomposite was prepared based on simple sol-gel methods with common equipment and chemicals. Reaction pH was found to influence the TiO2 upload in the nanocomposite. The alkaline condition produced the greatest TiO2 upload, while the acidic condition the least. Annealing at 300 °C turned the as-synthesized amorphous TiO2 into one with high content of anatase, the most photoactive form of TiO2. Irradiated by 365 nm UV light, a sample of 30 mg/mL of annealed nanocomposite containing 12.6 wt.% Ti was shown to be able to completely eradicate 104 CFU/mL of the laboratory-grown E. coli within 25 min, 25 min faster than the control when the 365 nm UV light was employed alone. The nanocomposite demonstrated consistent antimicrobial performance over repeated uses and was easily recoverable magnetically due to its high magnetization value (33 emu/g). Additionally, it was shown to reduce the bacterial count in a real surface water sample containing 500–5000 CFU/mL of different microbes by 62 ± 3% within 30 min. The irradiating 365 nm UV light alone was found to have generated little biocidal effect on this surface water sample. The nanocomposite is promising to serve as an effective, safe, and eco-friendly antimicrobial agent, especially for surface water disinfection.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Giant Domain Wall Conductivity in Self‐Assembled BiFeO 3 Nanocrystals

Abstract Ever‐increasing demand on electronic devices with ultrahigh‐density non‐volatile data storage has attracted great interest in novel ferroelectric memories based on conductive ferroelectric domain walls. Embedded in an insulating material, ferroelectric domain walls have the capability of being (re)created, displaced, erased, and altered in their spatial configurations and electronic characteristics. However, the domain wall conductivities are in most cases not yet sufficiently high to ensure the current density required to drive read‐out circuits operating at high speeds. In this work, a giant domain wall current (>10 µA) of a single charged domain wall is obtained through conductive atomic force microscopy with a bias field of 4 V. This is achieved in self‐assembled BiFeO 3 nanocrystals grown by sol‐gel method on Nb‐doped SrTiO 3 substrates. Local configurations of domains and domain wall types are studied using vector piezoresponse force microscopy and high‐resolution transmission electronic microscopy. The enhancement of the wall current is shown to be due to the formation of conducting pathways of charged defects accumulated along domain walls and traversing the nanocrystals. The diverse domain walls can be manipulated by electric field in a perpendicular architecture. The perpendicular array structure of BiFeO 3 nanocrystals should have great potentials for developing perpendicular nanoelectronic prototypes.

Liu, Lisha↗

Lithium Iron Aluminum Nickelate, LiNi x Fe y Al z O 2 —New Sustainable Cathodes for Next–Generation Cobalt–Free Li–Ion Batteries

In recent years, cobalt has become a critical constraint on the supply chain of the Li-ion battery industry. Here, with the ever-increasing projections for electric vehicles, the dependency of current Li-ion batteries on the ever-fluctuating cobalt prices poses serious environmental and sustainability issues. To address these challenges, a new class of cobalt-free materials with general formula of LiNi x Fe y Al z O 2 ( x + y + z = 1), termed as the lithium iron aluminum nickelate (NFA) class of cathodes, is introduced. These cobalt-free materials are synthesized using the sol–gel process to explore their compositional landscape by varying aluminum and iron. These NFA variants are characterized using electron microscopy, neutron and X-ray diffraction, and Mössbauer and X-ray photoelectron spectroscopy to investigate their morphological, physical, and crystal-structure properties. Operando experiments by X-ray diffraction, Mössbauer spectroscopy, and galvanostatic intermittent titration have been also used to study the crystallographic transitions, electrochemical activity, and Li-ion diffusivity upon lithium removal and uptake in the NFA cathodes. NFA compositions yield specific capacities of ≈200 mAh g -1 , demonstrating reasonable rate capability and cycling stability with ≈80% capacity retention after 100 charge/discharge cycles. While this is an early stage of research, the potential that these cathodes could have as viable candidates in next-generation cobalt-free lithium-ion batteries is highlighted here.

25 ENERGY STORAGE↗

Long–Cycling Sulfide–Based All–Solid–State Batteries Enabled by Electrochemo–Mechanically Stable Electrodes

Anode significantly determines the energy density of all-solid-state Lithium batteries (ASLBs). Silicon (Si) and Lithium (Li) metal are two of the most attractive anodes because of their ultrahigh theoretical capacities. However, most investigations focus on Li metal; the great potential of Si is underrated. This study investigates Si anode's stability, processability, and cost in ASLBs and compares them with Li metal. Moreover, the single-crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 is stabilized with a lithium silicate (Li 2 SiO x ) through a scalable sol-gel method. ASLBs with a cell-level energy density of 285 Wh kg -1 are obtained through sandwiching Si anode, thin sulfide solid-state electrolyte membrane, and interface stabilized LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The full cell delivered a high capacity of 145 mAh g -1 at C/3 and maintained stability for 1000 cycles. This work inspires commercializing the ASLBs on a large scale with exciting manufacturing lines for large-scale, safe, and economical energy storage.

25 ENERGY STORAGE↗

Disordered Rocksalts as High‐Energy and Earth‐Abundant Li‐Ion Cathodes

To address the growing demand for energy and support the shift toward transportation electrification and intermittent renewable energy, there is an urgent need for low‐cost, energy‐dense electrical storage. Research on Li‐ion electrode materials has predominantly focused on ordered materials with well‐defined lithium diffusion channels, limiting cathode design to resource‐constrained Ni‐ and Co‐based oxides and lower‐energy polyanion compounds. Recently, disordered rocksalts with lithium excess (DRX) have demonstrated high capacity and energy density when lithium excess and/or local ordering allow statistical percolation of lithium sites through the structure. This cation disorder can be induced by high temperature synthesis or mechanochemical synthesis methods for a broad range of compositions. DRX oxides and oxyfluorides containing Earth‐abundant transition metals have been prepared using various synthesis routes, including solid‐state, molten‐salt, and sol‐gel reactions. This review outlines DRX design principles and explains the effect of synthesis conditions on cation disorder and short‐range cation ordering (SRO), which determines the cycling stability and rate capability. In addition, strategies to enhance Li transport and capacity retention with Mn‐rich DRX possessing partial spinel‐like ordering are discussed. Finally, the review considers the optimization of carbon and electrolyte in DRX materials and addresses key challenges and opportunities for commercializing DRX cathodes.

Li-ion batteries↗

Refractive Index and Abbe Number Tuning via 3D Printable Optical Quality Silica–Titania–Germania Glasses

The development of optical quality GeO 2 –TiO 2 –SiO 2 glasses compatible with direct ink writing (DIW) 3D printing is reported in this study. Colloidal GeO 2 and TiO 2 –SiO 2 core–shell feedstocks are prepared by a sol–gel method and converted to printable inks for DIW. Printed inks are subsequently densified to glass using heat treatment at temperatures up to 1100 °C in air. A series of print‐compatible glass compositions are prepared, yielding transparent glass with the highest refractive index n = 1.576. Herein, it is shown that more TiO 2 can be incorporated into the glass without haziness or scattering through the addition of GeO 2 . The mechanisms for this are discussed, and it is shown that crystallization persists in these glasses despite the lack of visible light scattering. Finally, the combination of both TiO 2 and GeO 2 into a ternary glass also is used to independently tune the dispersion properties of the glass, as demonstrated by measured refractive indices and Abbe numbers, which has potential implications for 3D‐printed optics.

36 MATERIALS SCIENCE↗

Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation

Abstract Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol‐gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource‐H 2 separation processes.

Cao, Yuhe↗

Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation

Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol-gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource-H 2 separation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and activity of supported bimetallic NiPd nanoparticles: influence of preparation method on CO 2 reduction

Here, bimetallic Ni-Pd and monometallic reference catalysts were prepared by decomposing organometallic precursors, Ni(cod) 2 and Pd 2 (dba) 3 , leading to nanoparticles with sizes ranging from 3 to 6 nm. Two different synthesis procedures were followed: i) solution synthesis using capping ligand (hexadecylamine) followed by impregnation of pre-formed nanoparticles on SiO 2 , called Sol-immobilization (SI); and 2) direct precursor decomposition onto SiO 2 , without stabilizer, called Direct Decomposition (DD). Samples prepared by SI procedure are alloyed bimetallic nanoparticles, whereas samples obtained by DD one show phase segregation. Interestingly, DD samples show better activity for CO 2 hydrogenation into CO (reverse water-gas shift reaction - RWGS) than SI ones. The best compromise between activity for CO 2 activation (at lower temperature) and CO selectivity was achieved with Ni DD and NiPd DD catalysts. Moreover, the addition of palladium increased the concentration of surface undercoordinated sites, which chemisorb CO weakly, thus improving activity and selectivity, in opposition to other samples that chemisorb CO strongly, in multiband configuration. In the presence of Pd, different decomposition rates drive the formation of smaller and more active Ni clusters. The knowledge acquired here on the influence of synthesis conditions on the catalytic properties of Ni-Pd catalysts should guide us to better catalysts for CO 2 transformations into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temperature-dependent Battery Performance of a Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT Cathode and In-situ Heat Generation on Cycling

Excellent structural stability, high operating voltage, and high capacity have made Na 3 V 2 (PO 4 ) 2 F 3 a promising cathode material for sodium-ion batteries. However, high-temperature battery performances and heat generation measurements have not been systematically reported yet. Carbon-coated Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT (multi-walled carbon nanotube) samples are fabricated by a hydrothermal-assisted sol-gel method and the electrochemical performances are evaluated at three different temperatures (25, 45, and 55 °C). Furthermore, the well-crystallized Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples exhibit good cycling stability at both low and high temperatures; they deliver an initial discharge capacity of 120–125 mAhg -1 at a 1 C rate with a retention of 53 % capacity after 1,400 cycles with 99 % columbic efficiency. The half-cell delivers a capacity of 100 mAhg -1 even at a high rate of 10 C at room temperature. Furthermore, the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples show good long-term durability; the capacity loss is an average of 0.05 % per cycle at a 1 C rate at 55 °C. Additionally, ionic diffusivity and charge transfer resistance are evaluated as functions of state of charge, and they explain the high electrochemical performance of the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples. In-situ heat generation measurements reveal reversible results upon cycling owing to the high structural stability of the material. Excellent electrochemical performances are also demonstrated in the full-cell configuration with hard carbon as well as antimony Sb/C anodes.

25 ENERGY STORAGE↗

UEDGE modeling of plasma detachment of CFETR with ITER ‐like divertor geometry by external impurity seeding

Abstract Efficient handling of high heat flux on the plasma‐facing components, particularly the divertor targets, poses a significant challenge for the Chinese Fusion Engineering Testing Reactor (CFETR) with fusion power of Gigawatt. This work investigates the divertor plasma detachment of CFETR with a standard ITER‐like divertor geometry by neon (Ne) or argon (Ar) impurity seeding using UEDGE code. The cross‐field drifts terms are switched off, and fluid neutral models and a “fixed‐fraction” impurity model are applied to enable efficient simulations for the study of CFETR detachment. In order to reduce the heat load on the divertor targets below the acceptable level (<10 MW/m 2 ), the impurity fraction ( f ), pumping speed ( S ), and upstream density are varied to identify the suitable operations window during Ne seeding. The effects of Ne and Ar impurities on the plasma detachment are compared. It is found that with the power across the core‐edge interface P SOL = 200 MW and separatrix density of 2.8 10 19 , Ne impurity fraction ≥1.7%, and Ar impurity fraction ≥0.24% can achieve the partial detachment. Achieving similar total radiation power (˜148 MW), the Ne fraction is 2.3% and the Ar fraction is 0.24%. Moreover, the simulation results indicate that Ar exhibits better power radiation efficiency and core compatibility compared with Ne.

Zhang, M. Z.↗

Rheological and Structural Properties of k‐Carrageenan/Xanthan Gum Gummies Architected With a New Natural Additive

ABSTRACT Biohybrids (BHs)based on bentonite and anthocyanins can be produced as alternatives to synthetic colorants. However, no information is available on the interaction of biohybrid with food system. This research studies the rheological properties of gummies containing k‐carrageenan and xanthan gum incorporated with a BH. The incorporation of BH (≤ 2% w/w) increased the flow consistency index and shear thinning effect in melted gummies at 85°C. During cooling from 90°C to 25°C, the presence of BH altered the sol–gel transition temperature typical in carrageenan systems, probably by the formation of carrageenan complexes. At 25°C, all gummies had a solid‐like response with elastic modulus ( G ') higher than viscous modulus ( G "). G ' values increased linearly with BH concentration, and the linear viscoelastic region and breaking strain decreased with BH concentration, indicating that this natural additive acted as a reinforcing material.

Valencia, German Ayala [Department of Chemical and↗

Ionic Liquid–Directed Nanoporous TiNb 2 O 7 Anodes with Superior Performance for Fast–Rechargeable Lithium–Ion Batteries

Nanoporous TiNb 2 O 7 (NPTNO) material is synthesized by a sol–gel method with an ionic liquid (IL) as the nanoporous structure directing template. NPTNO exhibits a high reversible capacity of 210 mAh g –1 even at the charging rate of 50 C and an excellent cyclability of half-cell capacity retention of 74% for 1000 cycles at 5 C and LiNi 0.5 Mn 1.5 O 4 -coupled full-cell capacity retentions of 81% and 87% for 1000 cycles at 1 C and 2 C, respectively. The studies of the 1000 cycled NPTNO electrode illustrate that the IL-directed mesoporous structure can enhance the cyclability of NPTNO cells due to the alleviation of repetitive mechanical stress and volume fluctuation induced by the repetitive Li + insertion-extraction processes. The measured Li + diffusion coefficients from the galvanostatic intermittent titration technique suggest that the IL-templating strategy indeed ensures the fast rechargeability of NPTNO cells based on the fast Li + diffusion kinetics. Benefitting from the nanoporous structure, NPTNO with unhindered Li + diffusion pathways achieves a superior rate capability in the titanium-based oxide materials and the best full-cell cyclability in the TNO materials. Furthermore, the templating potential of IL is demonstrated, and the superb electrochemical performance establishes the IL-directed NPTNO as a promising anode candidate for fast-rechargeable LIBs.

25 ENERGY STORAGE↗

Microwave‐Assisted Synthesis of SrTiO 3 Nanocuboids without TiCl 4

Strontium titanate (STO) nanocuboids are a novel support for Pt nanoparticle catalysts (Pt/STO). The first of many steps in commercializing Pt/STO will be developing a scalable, environmentally sustainable, and cost‐effective STO nanocuboid synthesis. Herein, Sr–Ti–OH mixtures are synthesized from various Sr 2+ and Ti 4+ reagents and treated by convection‐ and microwave‐assisted heating to obtain STO nanoparticles. These experiments clarify how phase composition of the prehydrothermal Sr–Ti–OH mixture and choice of heating method affect final nanoparticle morphology. In Sr–Ti–OH mixtures synthesized with TiCl 4 , STO is the most stable phase and precipitates prior to heating, while titania sol–gels are the most stable phase when other Ti 4+ sources are used. STO nanocrystals always form when Sr–Ti–OH mixtures are treated by convection heating, though nanocuboids are only observed if STO precipitates from the Sr–Ti–OH mixture. Microwave‐assisted hydrothermal treatment more rapidly heats the precursor solution, and thus, STO nanocuboids can form from a variety of Sr–Ti–OH mixtures regardless of mixture composition. Two microwave syntheses of STO nanocuboids are reported: one which uses TiCl 4 as a Ti 4+ source, and another that uses titanium(IV) bis(ammonium lactato) dihydroxide ([NH 4 CH 3 CH(O)CO 2 ] 2 Ti(OH) 2 ), a water‐stable Ti 4+ complex.

Peczak, Ian L.↗

Efficient and selective dual-pathway polyolefin hydro-conversion over unexpectedly bifunctional M/TiO 2 -anatase catalysts

The huge scale of plastic waste generation and its environmental consequences drive the demands for catalytic plastic upcycling processes. Here, we report efficient polypropylene (PP) hydro-conversion over Ru and Ni supported on a sol-gel anatase TiO 2 (TiO 2 -A-SG). A small number of Brønsted acid sites on TiO 2 -A-SG enables hydrocracking, improving efficiency, steering the selectivity towards high-valued C 4-20 , and allowing more isomerization, compared to Ru-based monofunctional hydrogenolysis catalysts. The relative contribution of hydrocracking increases with lower hydrogen partial pressure, more branched substrates, and lower Ru loading. Ni/TiO 2 -A-SG exhibits superior hydrocracking activity and selectivity to Ni on conventional Brønsted-acidic supports, particularly zeolites. Further, mechanistic studies shows fast isomerization and sequential ß-scissions caused by strong polymer-catalyst interaction and fast cracking with abundant 3 C. This favors C 4-12 formation and prevents secondary reactions. This work demonstrated a novel, highly efficient noble-metal-free catalyst for plastic waste upcycling, while advancing the mechanistic understanding of polyolefin hydro-conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A methodology for selection of solid desiccants in energy recovery ventilators

Controlling indoor humidity levels is essential for maintaining acceptable indoor air quality in buildings. The use of energy recovery ventilators (ERVs) is an energy-efficient way to regulate indoor air humidity. Fixed-bed regenerators and rotary wheels are widely used ERVs because of their high sensible and latent effectiveness. These ERVs are made of desiccant-coated substrates, which enable them to transfer moisture between the supply and exhaust air streams. However, the moisture transfer ability of ERVs depends on the physiochemical and sorption properties of desiccants. Extensive, full-scale experiments are required to determine the best desiccant material for these systems. This paper presents a simplified method of selecting suitable desiccant materials for ERVs. The methodology involves important characterization methods, literature correlations for performance prediction, and cost-effective testing methods prior to full-scale testing, and full-scale test methods are discussed in detail. Furthermore, the performance of a few newly derived materials is evaluated and compared with that of conventional desiccants such as silica gel and molecular sieves. The highest latent effectiveness was obtained for composite of super absorbent polymer (SAP) with potassium formate (SAP-HCO2K-50 %), all-polymer porous solid desiccant (APPSD) and metal organic framework (MOF)–MIL–101 (Cr), followed by activated carbon fibre felt (ACFF) Silica sol-LiCl30, SAP, silica gel, MOF–303, and molecular sieve. Researchers and manufacturers would benefit from the proposed methodology and presented data in developing new desiccant materials for ERV applications.

Energy recovery↗

Photocatalytic degradation of orange II dye via high pore volume polymorph zirconium-doped titania under visible light irradiation

A series of mixed-phase Zr-doped TiO 2 was utilized for the photocatalytic degradation of orange II dye. These materials were synthesized through a sol–gel technique by varying the amounts of zirconium in the photocatalysts. These materials were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray fluorescence (XRF), Raman spectroscopy, thermogravimetry analysis (TGA), and X-ray photoelectron spectroscopy (XPS) among others. XRF and XPS data showed that the elemental composition of the photocatalysts consists of zirconium, titanium, and oxygen. In addition, XRD and Raman spectroscopy confirmed the existence of anatase and rutile phases of TiO 2 . The TGA analyses showed that the undoped TiO 2 was the most stable, with no significant weight loss during the heating range. Furthermore, the materials can effectively degrade orange II dye solution up to 7 cycles through asymmetric cleavage of the azo bond.

36 MATERIALS SCIENCE↗