Synthesis of cerium, zirconium, and copper doped zinc oxide nanoparticles as potential biomaterials for tissue engineering applications.

A novel eco-friendly high throughput continuous hydrothermal flow system was used to synthesise phase pure ZnO and doped ZnO in order to explore their properties for tissue engineering applications. Cerium, zirconium, and copper were introduced as dopants during flow synthesis of ZnO nanoparticles, Zirconium doped ZnO were successfully synthesised, however secondary phases of CeO and CuO were detected in X-ray diffraction (XRD). The nanoparticles were characterised using X-ray diffraction, Brunauer-Emmett-Teller (BET), Dynamic Light scattering Measurements, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and RAMAN spectroscopy was used to evaluate physical, chemical, and structural properties. The change in BET surface area was also significant, the surface area increased from 11.35 (ZnO_2) to 26.18 (ZrZnO_5). However. In case of CeZnO_5 and CuZnO_5 was not significant 13.68 (CeZnO_5) and 12.16 (CuZnO_5) respectively. Cell metabolic activity analysis using osteoblast-like cells (MG63) and human embryonic derived mesenchymal stem cells (hES-MP) demonstrated that doped ZnO nanoparticles supported higher cell metabolic activity compared to cells grown in standard media with no nanoparticles added, or pure zinc oxide nanoparticles. The ZrZnO_5 demonstrated the highest cell metabolic activity and non-cytotoxicity over the duration of 28 days as compared to un doped or Ce or Cu incorporated nanoparticles. The current data suggests that Zirconium doping positively enhances the properties of ZnO nanoparticles by increasing the surface area and cell proliferation. Therefore, are potential additives within biomaterials or for tissue engineering applications.

Palladium Encapsulated by an Oxygen-Saturated TiO2 Overlayer for Low-Temperature SO2 -Tolerant Catalysis during CO Oxidation.

The development of oxidation catalysts that are resistant to sulfur poisoning is crucial for extending the lifespan of catalysts in real-working conditions. Herein, we describe the design and synthesis of oxide-metal interaction (OMI) catalyst under oxidative atmospheres. By using organic coated TiO2 , an oxide/metal inverse catalyst with non-classical oxygen-saturated TiO2 overlayers were obtained at relatively low temperature. These catalysts were found to incorporate ultra-small Pd metal and support particles with exceptional reactivity and stability for CO oxidation (under 21 vol % O2 and 10 vol % H2 O). In particular, the core (Pd)-shell (TiO2 ) structured OMI catalyst exhibited excellent resistance to SO2 poisoning, yielding robust CO oxidation performance at 120 °C for 240 h (at 100 ppm SO2 and 10 vol % H2 O). The stability of this new OMI catalyst was explained through density functional theory (DFT) calculations that interfacial oxygen atoms at Pd-O-Ti sites (of oxygen-saturated overlayers) serve as non-metal active sites for low-temperature CO oxidation, and change the SO2 adsorption from metal(d)-to-SO2 (π*) back-bonding to much weaker σ(Ti-S) bonding.

Tuneable magnetic nanocomposites for remote self-healing.

When polymer composites containing magnetic nanoparticles (MNPs) are exposed to an alternating magnetic field, heat is generated to melt the surrounding polymer locally, partially filling voids across any cracks or deformities. Such materials are of interest for structural applications; however, structural polymers with high melting temperatures pose the challenge of generating high localised temperatures enabling self-healing. A method to prepare a multiferroic-Polyamide 6 (PA6) nanocomposite with tuneable magnetocaloric properties is reported. Tunability arises from varying the MNP material (and any coating, its dispersion, and agglomerate sizes in the nanocomposite). The superparamagnetic MNPs (SMNPs) and iron oxide MNPs with and without surface functionalization were dispersed into PA6 through in situ polymerization, and their magnetic properties were compared. Furthermore, computer simulations were used to quantify the dispersion state of MNPs and assess the influence of the interaction radius on the magnetic response of the self-healable magnetic nanoparticle polymer (SHMNP) composite. It was shown that maintaining the low interaction radius through the dispersion of the low coercivity MNPs could allow tuning of the bulk magnetocaloric properties of the resulting mesostructures. An in-situ polymerization method improved the dispersion and reduced the maximum interaction radius value from ca. 806 to 371 nm and increased the magnetic response for the silica-coated SMNP composite. This sample displayed ca. three orders of magnitude enhancement for magnetic saturation compared to the unfunctionalized Fe3O4 MNP composite.

Cycling Rate-Induced Spatially-Resolved Heterogeneities in Commercial Cylindrical Li-Ion Batteries.

Synchrotron high-energy X-ray diffraction computed tomography has been employed to investigate, for the first time, commercial cylindrical Li-ion batteries electrochemically cycled over the two cycling rates of C/2 and C/20. This technique yields maps of the crystalline components and chemical species as a cross-section of the cell with high spatiotemporal resolution (550 × 550 images with 20 × 20 × 3 µm3 voxel size in ca. 1 h). The recently developed Direct Least-Squares Reconstruction algorithm is used to overcome the well-known parallax problem and led to accurate lattice parameter maps for the device cathode. Chemical heterogeneities are revealed at both electrodes and are attributed to uneven Li and current distributions in the cells. It is shown that this technique has the potential to become an invaluable diagnostic tool for real-world commercial batteries and for their characterization under operating conditions, leading to unique insights into "real" battery degradation mechanisms as they occur.

Control of crystal size tailors the electrochemical performance of α-V2O5 as a Mg2+ intercalation host.

α-V2O5 has been extensively explored as a Mg2+ intercalation host with potential as a battery cathode, offering high theoretical capacities and potentials vs. Mg2+/Mg. However, large voltage hysteresis is observed with Mg insertion and extraction, introducing significant and unacceptable round-trip energy losses with cycling. Conventional interpretations suggest that bulk ion transport of Mg2+ within the cathode particles is the major source of this hysteresis. Herein, we demonstrate that nanosizing α-V2O5 gives a measurable reduction to voltage hysteresis on the first cycle that substantially raises energy efficiency, indicating that mechanical formatting of the α-V2O5 particles contributes to hysteresis. However, no measurable improvement in hysteresis is found in the nanosized α-V2O5 in latter cycles despite the much shorter diffusion lengths, suggesting that other factors aside from Mg transport, such as Mg transfer between the electrolyte and electrode, contribute to this hysteresis. This observation is in sharp contrast to the conventional interpretation of Mg electrochemistry. Therefore, this study uncovers critical fundamental underpinning limiting factors in Mg battery electrochemistry, and constitutes a pivotal step towards a high-voltage, high-capacity electrode material suitable for Mg batteries with high energy density.

Enhanced charge storage of nanometric ζ-V2O5 in Mg electrolytes.

V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g-1) compared to bulk ζ-V2O5 (70 mA h g-1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases.

High Throughput Synthesis and Screening of Oxygen Reduction Catalysts in the MTiO3 (M = Ca, Sr, Ba) Perovskite Phase Diagram.

A library of 66 perovskite BaxSryCazTiO3 (x + y + z = 1) samples (ca. three grams per sample) was made in ca. 14 h using a high-throughput continuous hydrothermal flow synthesis system. The as-synthesized samples were collected from the outlet of the process and then cleaned and freeze-dried before being evaluated individually as oxygen reduction catalysts using a rotating disk electrode testing technique. To establish any correlations between physical and electrochemical characterization data, the as-synthesized samples were investigated using analytical methods including BET surface area, powder X-ray diffraction (PXRD) and in selected cases, transmission electron microscopy (TEM). The aforementioned approach was validated as being able to quickly identify oxygen reduction catalysts from new libraries of electrocatalysts.

Probing Mg Intercalation in the Tetragonal Tungsten Bronze Framework V4Nb18O55.

While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg2+ insertion and extraction at high voltages; this is thought to be due to poor Mg2+ diffusion kinetics within the oxide structural framework. Herein, the authors provide conclusive evidence of electrochemical insertion of Mg2+ into the tetragonal tungsten bronze V4Nb18O55, with a maximum reversible electrochemical capacity of 75 mA h g-1, which corresponds to a magnesiated composition of Mg4V4Nb18O55. Experimental electrochemical magnesiation/demagnesiation revealed a large voltage hysteresis with charge/discharge (1.12 V vs Mg/Mg2+); when magnesiation is limited to a composition of Mg2V4Nb18O55, this hysteresis can be reduced to only 0.5 V. Hybrid-exchange density functional theory (DFT) calculations suggest that a limited number of Mg sites are accessible via low-energy diffusion pathways, but that larger kinetic barriers need to be overcome to access the entire structure. The reversible Mg2+ intercalation involved concurrent V and Nb redox activity and changes in crystal structure, as confirmed by an array of complementary methods, including powder X-ray diffraction, X-ray absorption spectroscopy, and energy-dispersive X-ray spectroscopy. Consequently, it can be concluded that the tetragonal tungsten bronzes show promise as intercalation electrode materials for Mg batteries.

Aerosol-assisted route to low-E transparent conductive gallium-doped zinc oxide coatings from pre-organized and halogen-free precursor.

Thermal control in low-emission windows is achieved by the application of glazings, which are simultaneously optically transparent in the visible and reflective in the near-infrared (IR). This phenomenon is characteristic of coatings with wide optical band gaps that have high enough charge carrier concentrations for the material to interact with electromagnetic radiation in the IR region. While conventional low-E coatings are composed of sandwiched structures of oxides and thin Ag films or of fluorinated SnO2 coatings, ZnO-based glazing offers an environmentally stable and economical alternative with competitive optoelectronic properties. In this work, gallium-doped zinc oxide (GZO) coatings with properties for low-E coatings that exceed industrial standards (T visible > 82%; R 2500 nm > 90%; λ (plasma) = 1290 nm; ρ = 4.7 × 10-4 Ω cm; R sh = 9.4 Ω·â–¡-1) are deposited through a sustainable and environmentally friendly halogen-free deposition route from [Ga(acac)3] and a pre-organized zinc oxide precursor [EtZnOiPr]4 (1) via single-pot aerosol-assisted chemical vapor deposition. GZO films are highly (002)-textured, smooth and compact without need of epitaxial growth. The method herein describes the synthesis of coatings with opto-electronic properties commonly achievable only through high-vacuum methods, and provides an alternative to the use of pyrophoric ZnEt2 and halogenated SnO2 coatings currently used in low-emission glazing and photovoltaic technology.

Enhancing bifunctional catalytic activity of cobalt-nickel sulfide spinel nanocatalysts through transition metal doping and its application in secondary zinc-air batteries.

Developing large-scale and high-performance OER (oxygen evolution reaction) and ORR (oxygen reduction reaction) catalysts have been a challenge for commercializing secondary zinc-air batteries. In this work, transition metal-doped cobalt-nickel sulfide spinels are directly produced via a continuous hydrothermal flow synthesis (CHFS) approach. The nanosized cobalt-nickel sulfides are doped with Ag, Fe, Mn, Cr, V, and Ti and evaluated as bifunctional OER and ORR catalyst for Zn-air battery application. Among the doped spinel catalysts, Mn-doped cobalt-nickel sulfides (Ni1.29Co1.49Mn0.22S4) exhibit the most promising OER and ORR performance, showing an ORR onset potential of 0.9 V vs. RHE and an OER overpotential of 348 mV measured at 10 mA cm-2, which is attributed to their high surface area, electronic structure of the dopant species, and the synergistic coupling of the dopant species with the active host cations. The dopant ions primarily alter the host cation composition, with the Mn(iii) cation linked to the introduction of active sites by its favourable electronic structure. A power density of 75 mW cm-2 is achieved at a current density of 140 mA cm-2 for the zinc-air battery using the manganese-doped catalyst, a 12% improvement over the undoped cobalt-nickel sulfide and superior to that of the battery with a commercial RuO2 catalyst.

Tailoring the electrochemical activity of magnesium chromium oxide towards Mg batteries through control of size and crystal structure.

Chromium oxides with the spinel structure have been predicted to be promising high voltage cathode materials in magnesium batteries. Perennial challenges involving the mobility of Mg2+ and reaction kinetics can be circumvented by nano-sizing the materials in order to reduce diffusion distances, and by using elevated temperatures to overcome activation energy barriers. Herein, ordered 7 nm crystals of spinel-type MgCr2O4 were synthesized by a conventional batch hydrothermal method. In comparison, the relatively underexplored Continuous Hydrothermal Flow Synthesis (CHFS) method was used to make highly defective sub-5 nm MgCr2O4 crystals. When these materials were made into electrodes, they were shown to possess markedly different electrochemical behavior in a Mg2+ ionic liquid electrolyte, at moderate temperature (110 °C). The anodic activity of the ordered nanocrystals was attributed to surface reactions, most likely involving the electrolyte. In contrast, evidence was gathered regarding the reversible bulk deintercalation of Mg2+ from the nanocrystals made by CHFS. This work highlights the impact on electrochemical behavior of a precise control of size and crystal structure of MgCr2O4. It advances the understanding and design of new cathode materials for Mg-based batteries.

Mechanistic insights of Li+ diffusion within doped LiFePO4 from Muon Spectroscopy.

The Li+ ion diffusion characteristics of V- and Nb-doped LiFePO4 were examined with respect to undoped LiFePO4 using muon spectroscopy (µSR) as a local probe. As little difference in diffusion coefficient between the pure and doped samples was observed, offering DLi values in the range 1.8-2.3 × 10-10 cm2 s-1, this implied the improvement in electrochemical performance observed within doped LiFePO4 was not a result of increased local Li+ diffusion. This unexpected observation was made possible with the µSR technique, which can measure Li+ self-diffusion within LiFePO4, and therefore negated the effect of the LiFePO4 two-phase delithiation mechanism, which has previously prevented accurate Li+ diffusion comparison between the doped and undoped materials. Therefore, the authors suggest that µSR is an excellent technique for analysing materials on a local scale to elucidate the effects of dopants on solid-state diffusion behaviour.

Continuous Hydrothermal Synthesis of Inorganic Nanoparticles: Applications and Future Directions.

Nanomaterials are at the leading edge of the emerging field of nanotechnology. Their unique and tunable size-dependent properties (in the range 1-100 nm) make these materials indispensable in many modern technological applications. In this Review, we summarize the state-of-art in the manufacture and applications of inorganic nanoparticles made using continuous hydrothermal flow synthesis (CHFS) processes. First, we introduce ideal requirements of any flow process for nanoceramics production, outline different approaches to CHFS, and introduce the pertinent properties of supercritical water and issues around mixing in flow, to generate nanoparticles. This Review then gives comprehensive coverage of the current application space for CHFS-made nanomaterials including optical, healthcare, electronics (including sensors, information, and communication technologies), catalysis, devices (including energy harvesting/conversion/fuels), and energy storage applications. Thereafter, topics of precursor chemistry and products, as well as materials or structures, are discussed (surface-functionalized hybrids, nanocomposites, nanograined coatings and monoliths, and metal-organic frameworks). Later, this Review focuses on some of the key apparatus innovations in the field, such as in situ flow/rapid heating systems (to investigate kinetics and mechanisms), approaches to high throughput flow syntheses (for nanomaterials discovery), as well as recent developments in scale-up of hydrothermal flow processes. Finally, this Review covers environmental considerations, future directions and capabilities, along with the conclusions and outlook.

Nano-sized Mo- and Nb-doped TiO2 as anode materials for high energy and high power hybrid Li-ion capacitors.

Nano-sized Mo-doped titania (Mo0.1Ti0.9O2) and Nb-doped titania (Nb0.25Ti0.75O2) were directly synthesized via a continuous hydrothermal flow synthesis process. Materials characterization was conducted using physical techniques such as transmission electron microscopy, powder x-ray diffraction, x-ray photoelectron spectroscopy, Brunauer-Emmett-Teller specific surface area measurements and energy dispersive x-ray spectroscopy. Hybrid Li-ion supercapacitors were made with either a Mo-doped or Nb-doped TiO2 negative electrode material and an activated carbon (AC) positive electrode. Cells were evaluated using electrochemical testing (cyclic voltammetry, constant charge discharge cycling). The hybrid Li-ion capacitors showed good energy densities at moderate power densities. When cycled in the potential window 0.5-3.0 V, the Mo0.1Ti0.9O2/AC hybrid supercapacitor showed the highest energy densities of 51 Wh kg-1 at a power of 180 W kg-1 with energy densities rapidly declining with increasing applied specific current. In comparison, the Nb0.25Ti0.75O2/AC hybrid supercapacitor maintained its energy density of 45 Wh kg-1 at 180 W kg-1 better, showing 36 Wh g-1 at 3200 W kg-1, which is a very promising mix of high energy and power densities. Reducing the voltage window to the range 1.0-3.0 V led to an increase in power density, with the Mo0.1Ti0.9O2/AC hybrid supercapacitor giving energy densities of 12 Wh kg-1 and 2.5 Wh kg-1 at power densities of 6700 W kg-1 and 14 000 W kg-1, respectively.

High-Throughput Continuous Hydrothermal Synthesis of Transparent Conducting Aluminum and Gallium Co-doped Zinc Oxides.

High-throughput continuous hydrothermal flow synthesis was used to generate a library of aluminum and gallium-codoped zinc oxide nanoparticles of specific atomic ratios. Resistivities of the materials were determined by Hall Effect measurements on heat-treated pressed discs and the results collated into a conductivity-composition map. Optimal resistivities of ∼9 × 10-3 Ω cm were reproducibly achieved for several samples, for example, codoped ZnO with 2 at% Ga and 1 at% Al. The optimum sample on balance of performance and cost was deemed to be ZnO codoped with 3 at% Al and 1 at% Ga.

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode.

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(i) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO2 saturated KHCO3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO2. On cycling to negative potentials, larger reduction currents were observed in the presence of CO2; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO2 CuO underwent reduction to Cu2O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

S, N-Co-Doped Graphene-Nickel Cobalt Sulfide Aerogel: Improved Energy Storage and Electrocatalytic Performance.

Metal sulfides are commonly used in energy storage and electrocatalysts due to their redox centers and active sites. Most literature reports show that their performance decreases significantly caused by oxidation in alkaline electrolyte during electrochemical testing. Herein, S and N co-doped graphene-based nickel cobalt sulfide aerogels are synthesized for use as rechargeable alkaline battery electrodes and oxygen reduction reaction (ORR) catalysts. Notably, this system shows improved cyclability due to the stabilization effect of the S and N co-doped graphene aerogel (SNGA). This reduces the rate of oxidation and the decay of electronic conductivity of the metal sulfides materials in alkaline electrolyte, i.e., the capacity decrease of CoNi2S4/SNGA is 4.2% for 10 000 cycles in a three-electrode test; the current retention of 88.6% for Co-S/SNGA after 12 000 s current-time chronoamperometric response in the ORR test is higher than corresponding Co-S nanoparticles and Co-S/non-doped graphene aerogels. Importantly, the results here confirm that the Ni-Co-S ternary materials behave as an electrode for rechargeable alkaline batteries rather than supercapacitors electrodes in three-electrode test as commonly described and accepted in the literature. Furthermore, formulas to evaluate the performance of hybrid battery devices are specified.

Exploring 3D microstructural evolution in Li-Sulfur battery electrodes using in-situ X-ray tomography.

Lithium sulfur (Li-S) batteries offer higher theoretical specific capacity, lower cost and enhanced safety compared to current Li-ion battery technology. However, the multiple reactions and phase changes in the sulfur conversion cathode result in highly complex phenomena that significantly impact cycling life. For the first time to the authors' knowledge, a multi-scale 3D in-situ tomography approach is used to characterize morphological parameters and track microstructural evolution of the sulfur cathode across multiple charge cycles. Here we show the uneven distribution of the sulfur phase fraction within the electrode thickness as a function of charge cycles, suggesting significant mass transport limitations within thick-film sulfur cathodes. Furthermore, we report a shift towards larger particle sizes and a decrease in volume specific surface area with cycling, suggesting sulfur agglomeration. Finally, we demonstrate the nano-scopic length-scale required for the features of the carbon binder domain to become discernible, confirming the need for future work on in-situ nano-tomography. We anticipate that X-ray tomography will be a powerful tool for optimization of electrode structures for Li-S batteries.

Mapping Structure-Composition-Property Relationships in V- and Fe-Doped LiMnPO4 Cathodes for Lithium-Ion Batteries.

A series of LiMn1-x-yFexVyPO4 (LMFVP) nanomaterials have been synthesized using a pilot-scale continuous hydrothermal synthesis process (CHFS) and evaluated as high voltage cathodes in Li-ion batteries at a production rate of 0.25 kg h-1. The rapid synthesis and screening approach has allowed the specific capacity of the high Mn content olivines to be optimized, particularly at high discharge rates. Consistent and gradual changes in the structure and performance are observed across the compositional region under investigation; the doping of Fe at 20 at% (with respect to Mn) into lithium manganese phosphate, rather than V or indeed codoping of Fe and V, gives the best balance of high capacity and high rate performance.

Comparison of three-dimensional analysis and stereological techniques for quantifying lithium-ion battery electrode microstructures.

Lithium-ion battery performance is intrinsically linked to electrode microstructure. Quantitative measurement of key structural parameters of lithium-ion battery electrode microstructures will enable optimization as well as motivate systematic numerical studies for the improvement of battery performance. With the rapid development of 3-D imaging techniques, quantitative assessment of 3-D microstructures from 2-D image sections by stereological methods appears outmoded; however, in spite of the proliferation of tomographic imaging techniques, it remains significantly easier to obtain two-dimensional (2-D) data sets. In this study, stereological prediction and three-dimensional (3-D) analysis techniques for quantitative assessment of key geometric parameters for characterizing battery electrode microstructures are examined and compared. Lithium-ion battery electrodes were imaged using synchrotron-based X-ray tomographic microscopy. For each electrode sample investigated, stereological analysis was performed on reconstructed 2-D image sections generated from tomographic imaging, whereas direct 3-D analysis was performed on reconstructed image volumes. The analysis showed that geometric parameter estimation using 2-D image sections is bound to be associated with ambiguity and that volume-based 3-D characterization of nonconvex, irregular and interconnected particles can be used to more accurately quantify spatially-dependent parameters, such as tortuosity and pore-phase connectivity.