Hydrogen-Location-Sensitive Modulation of the Redox Reactivity for Oxygen-Deficient TiO2.

Hydrogenated black TiO2 is receiving ever-increasing attention, primarily due to its ability to capture low-energy photons in the solar spectrum and its highly efficient redox reactivity for solar-driven water splitting. However, in-depth physical insight into the redox reactivity is still missing. In this work, we conducted a density functional theory study with Hubbard U correction (DFT+U) based on the model obtained from spectroscopic and aberration-corrected scanning transmission electron microscopy (AC-STEM) characterizations to reveal the synergy among H heteroatoms located at different surface sites where the six-coordinated Ti (Ti6C) atom is converted from an inert trapping site to a site for the interchange of photoexcited electrons. This in-depth understanding may be applicable to the rational design of highly efficient solar-light-harvesting catalysts.

Synthesis of Mesoporous ZIF-8 Nanoribbons and their Conversion into Carbon Nanoribbons for High-Performance Supercapacitors.

ZIF-8 nanoribbons, with tunable morphology and pore structure, were synthesized by using the tri-block co-polymer Pluronic F127 as a soft template. The as-synthesized ZIF-8 nanoribbons were converted into carbon nanoribbons by thermal transformation with largely preserved morphology and porosity. The resulting carbon nanoribbons feature both micro- and meso-pores with high surface areas of over 1000 m2 g-1 . In addition, nitrogen-doping in the carbon nanoribbons was achieved, as confirmed by XPS and EELS measurements. The hybrid carbon nanoribbons provide pseudo-capacitance that promotes electrochemical performance, rendering a high specific capacitance of up to 297 F g-1 at a current density of 0.5 A g-1 in a three-electrode system. A long cycle life was also demonstrated by recording a 90.26 % preservation of capacitance after 10 000 cycles of charge-discharge at a current density of 4.0 A g-1 . Furthermore, a symmetrical supercapacitor is fabricated by employing the carbon nanoribbons, which shows good electrochemical performance with respect to energy, power and cycle life.

4D Additive-Subtractive Manufacturing of Shape Memory Ceramics.

The development of high-temperature structural materials, such as ceramics, is limited by their extremely high melting points and the difficulty in building complicated architectures. Four-dimensional (4D) printing helps enhance the geometrical flexibility of ceramics. However, ceramic 4D printing systems are limited by the separate processes for shape and material transformations, low accuracy of morphing systems, low resolution of ceramic structures, and their time-intensive nature. Here, a paradigm for a one-step shape/material transformation, high-2D/3D/4D-precision, high-efficiency, and scalable 4D additive-subtractive manufacturing of shape memory ceramics is developed. Original/reverse and global/local multimode shape memory capabilities are achieved using macroscale SiOC-based ceramic materials. The uniformly deposited Al2 O3 -rich layer on the printed SiOC-based ceramic lattice structures results in an unusually high flame ablation performance of the complex-shaped ceramics. The proposed framework is expected to broaden the applications of high-temperature structural materials in the aerospace, electronics, biomedical, and art fields.

Multi-heterostructured SnO2/SnSx embedded in carbon framework for high-performance sodium-ion storage.

Heterostructure materials, as newborn electrode materials for rechargeable batteries, are attracting increasing attention due to their robust architectures and superior electrochemical performances. It is widely believed that the inner electric field induced at the interface can improve the electric conductivity and ion diffusion kinetics, thus enhancing the long-term stability and high-rate performance of the batteries. Although much progress is made on heterostructure construction, the performance of the batteries is still far from satisfying the commercial applications. In this work, a new type of SnO2/SnSx (x = 1, 1.5) heterostructure embedded in carbon framework (C@SnO2/SnSx) is constructed via a facile sulfidation process. Compared to a single heterojunction, the multi-heterojunctions generated at SnO2/SnSx interface can induce an intensified built-in electric field, which promotes charge transportation and reaction kinetics of the electrode for Na-ions storage. Upon the sodiation process, the induced intensified electric field drives Na ions from Sn2S3 or SnO2 to SnS, while an inverse transportation of Na ions are accelerated upon the desodation process. As a result, C@SnO2/SnSx exhibits an outstanding reversible capacity of 510 mA h g-1 after 300 cycles at 200 mA g-1.

Forming a Highly Active, Homogeneously Alloyed AuPt Co-catalyst Decoration on TiO2 Nanotubes Directly During Anodic Growth.

Au and Pt do not form homogeneous bulk alloys as they are thermodynamically not miscible. However, we show that anodic TiO2 nanotubes (NTs) can in situ be uniformly decorated with homogeneous AuPt alloy nanoparticles (NPs) during their anodic growth. For this, a metallic Ti substrate containing low amounts of dissolved Au (0.1 atom %) and Pt (0.1 atom %) is used for anodizing. The matrix metal (Ti) is converted to oxide, whereas at the oxide/metal interface direct noble metal particle formation and alloying of Au and Pt takes place; continuously these particles are then picked up by the growing nanotube wall. In our experiments, the AuPt alloy NPs have an average size of 4.2 nm, and at the end of the anodic process, these are regularly dispersed over the TiO2 nanotubes. These alloyed AuPt particles act as excellent co-catalyst in photocatalytic H2 generation, with a H2 production rate of 12.04 µL h-1 under solar light. This represents a strongly enhanced activity as compared to TiO2 NTs decorated with monometallic particles of Au (7 µL h-1) or Pt (9.96 µL h-1).

In situ reduction of silver nanoparticles on hybrid polydopamine-copper phosphate nanoflowers with enhanced antimicrobial activity.

The development of novel antimicrobial materials with high antimicrobial activity and low environmental impact is of importance for global health, but has proven to be challenging. Herein we report a facile mineralization process to create a flower-like, porous antimicrobial agent, which is stable, selective, effective and environmentally benign. This new antimicrobial material is made of organic polydopamine (PD) and inorganic (copper phosphate) components, where the incorporation of PD on the hybrid architecture endows the direct in situ reduction of silver ions into silver nanoparticles (Ag NPs) without the need of external toxic reductants. The combination of Ag NPs and high surface area of the nanoflower results in high selectivity in the antimicrobial activity towards Gram-negative Escherichia coli (E. coli), while leaving co-cultured mammalian cells healthy and intact. Moreover, we show that the hybrid antimicrobial material is stable, and can be easily recovered after use, avoiding the persistent hazard to the environment. We envision that this novel antimicrobial agent may find useful applications for clinical studies and industrial products.

Mesoporous SnO2 Nanostructures of Ultrahigh Surface Areas by Novel Anodization.

Here we report a novel type of hierarchical mesoporous SnO2 nanostructures fabricated by a facile anodization method in a novel electrolyte system (an ethylene glycol solution of H2C2O4/NH4F) followed by thermal annealing at a low temperature. The SnO2 nanostructures thus obtained feature highly porous nanosheets with mesoporous pores well below 10 nm, enabling a remarkably high surface area of 202.8 m2/g which represents one of the highest values reported to date on SnO2 nanostructures. The formation of this novel type of SnO2 nanostructures is ascribed to an interesting self-assembly mechanism of the anodic tin oxalate, which was found to be heavily impacted by the anodization voltage and water content in the electrolyte. The electrochemical measurements of the mesoporous SnO2 nanostructures indicate their promising applications as lithium-ion battery and supercapacitor electrode materials.

Graphene-Nanowall-Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2+/VO2+ Couple for All Vanadium Redox Flow Battery.

3D graphene-nanowall-decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO2+/VO2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging-discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode.

P2-Type NaxCu0.15Ni0.20Mn0.65O2 Cathodes with High Voltage for High-Power and Long-Life Sodium-Ion Batteries.

Cu-Ni-Mn-based ternary P2-type NaxCu0.15Ni0.20Mn0.65O2 (x = 0.50, 0.67, and 0.75) cathodes for sodium-ion batteries (SIBs) are synthesized by a co-precipitation method. We find that Na content plays a key role on the structure, morphology, and the charge-discharge performances of these materials. For x = 0.67 and 0.75, superstructure from Na+-vacancy ordering is observed, while it is absent in the x = 0.50 sample. Despite the same synthesis conditions, materials with x = 0.67 and 0.75 show smaller particle sizes compared to that of the x = 0.50 sample. In addition, redox potentials of the materials differ significantly even though they have the same transition metal ratios. These differences are attributed to the changes in local structures of the as-prepared materials arising from the different amount of Na and possibly oxygen in the lattice. Materials with x = 0.67 and 0.75 show excellent rate performance and cycle stability when tested as cathode material of SIBs. Average discharge potential is as high as 3.41 V versus Na-Na+ with capacity of 87 mAh g-1 at 20 mA g-1. Excellent capacity and cycle stability are maintained even when they are tested with higher current rates. For instance, a capacity of 62.3 mAh g-1 is obtained from the x = 0.67 sample at 1000 mA g-1 after 1000 cycles between 3.0 and 4.2 V without any decrease in capacity.

Low-temperature fabrication of brown TiO2 with enhanced photocatalytic activities under visible light.

Here we report a facile one-step low-temperature solution-based method to treat native TiO2 with NaH. The NaH treatment effectively induces the Ti(iii) species and oxygen vacancies into the TiO2 host lattice, and enables the absorption edge of TiO2 to be conveniently adjusted from the UV region to the red end of the visible spectrum.

Uniformly dispersed and controllable ligand-free silver-nanoparticle-decorated TiO2 nanotube arrays with enhanced photoelectrochemical behaviors.

Homogeneously dispersed silver nanoparticles (AgNPs) were successfully decorated onto the surface of TiO2 nanotube arrays (TNTA) by means of an in situ photoreduction method. TNTA films as supports exhibit excellent properties to prevent agglomeration of AgNPs, and they also avoid using polymer ligands, which is deleterious to enhancing the properties of the fabricated NPs. The silver particle size and its content could be controlled just by changing the immersion time. Detailed SEM and TEM analyses combined with energy-dispersive X-ray spectroscopy analyses with different immersion times (5, 10, 30, 60 min) have revealed the variation tendency. The prepared Ag/TNTA composite films were also characterized by XRD, X-ray photoelectron spectroscopy, and high-resolution TEM. The UV/Vis diffuse reflectance spectra displayed a redshift of the absorption peak with the growth of AgNPs. The photocurrent response and the photoelectrocatalytic degradation of methyl orange (MO) were used to evaluate the photoelectrochemical properties of the fabricated samples. The results showed that the photocurrent response and photoelectrocatalytic activity largely depended on the loaded Ag particle size and content. TNTA films with a diameter of 17.92 nm and silver content of 1.15 at% showed the highest photocurrent response and degradation rate of MO. The enhanced properties could be attributed to the synergistic effect between AgNPs and TiO2. To make good use of this effect, particle size and silver content should be well controlled to develop the electron charge and discharge process during the photoelectrical process. Neither smaller nor larger AgNPs caused decreased photoelectrical properties.