Hydrogen, the smallest and the lightest atomic element, is reversibly incorporated into interstitial sites in vanadium dioxide (VO2), a correlated oxide with a 3d(1) electronic configuration, and induces electronic phase modulation. It is widely reported that low hydrogen concentrations stabilize the metallic phase, but the understanding of hydrogen in the high doping regime is limited. Here, we demonstrate that as many as two hydrogen atoms can be incorporated into each VO2 unit cell, and that hydrogen is reversibly absorbed into, and released from, VO2 without destroying its lattice framework. This hydrogenation process allows us to elucidate electronic phase modulation of vanadium oxyhydride, demonstrating two-step insulator (VO2)-metal (HxVO2)-insulator (HVO2) phase modulation during inter-integer d-band filling. Our finding suggests the possibility of reversible and dynamic control of topotactic phase modulation in VO2 and opens up the potential application in proton-based Mottronics and novel hydrogen storage.
There has been a tremendous amount of research in the past decade to optimize the mechanical properties and degradation behavior of the biodegradable Mg alloy for orthopedic implant. Despite the feasibility of degrading implant, the lack of fundamental understanding about biocompatibility and underlying bone formation mechanism is currently limiting the use in clinical applications. Herein, we report the result of long-term clinical study and systematic investigation of bone formation mechanism of the biodegradable Mg-5wt%Ca-1wt%Zn alloy implant through simultaneous observation of changes in element composition and crystallinity within degrading interface at hierarchical levels. Controlled degradation of Mg-5wt%Ca-1wt%Zn alloy results in the formation of biomimicking calcification matrix at the degrading interface to initiate the bone formation process. This process facilitates early bone healing and allows the complete replacement of biodegradable Mg implant by the new bone within 1 y of implantation, as demonstrated in 53 cases of successful long-term clinical study.biodegradable implant | bone formation | clinical application T he century-old concept of the fixation device that holds the fractured bones in place to allow repair through the natural bone remodeling process is still being practiced today without alteration (1-5). The recent rapid growth of the elderly demographic of physically active adults has tremendously intensified the occurrence of bone trauma cases, highlighting once again the major drawbacks of current surgical approaches and osteosynthesis systems, such as inevitable secondary surgery to remove the inert fixation devices after complete bone healing and inflammatory response due to the release of metal ions. In the past decade, countless studies have been performed to control and optimize the mechanical and corrosion properties of magnesium-based alloys (6-9), which, thanks to their degradation in the physiological environment, could overcome the limitations of inert implant materials and shift the paradigm of conventional bone fixation devices toward new horizons. Driven by these new possibilities, important findings regarding, among others, the degradation mechanism of Mg-based alloys (10, 11), the formation of corrosion protective layers by degradation products (12, 13), and the osteogenetic properties of Mg ions (14, 15) have been reported in the literature. However, such findings are based on the observation of degradation products and of bone healing at the macroscale level. Due to lack of fundamental understanding on biocompatibility and underlying bone formation mechanism of the degradation product, there is so far only one known case of statistically insignificant clinical study result (16) with a short-term follow-up. In our previous study, we reported successful development and long-term in vivo study of uniformly slowly degrading Mg-5wt%Ca-1wt%Zn alloy system (SI Appendix, Figs. S1 and S2) featuring adequate mechanical strength [ultimate tensile strength (UTS) ∼250 MPa] (17) a...
The application of nanoparticles for drug or gene delivery promises benefits in the form of single‐cell‐specific therapeutic and diagnostic capabilities. Many methods of cell transfection rely on unspecific means to increase the transport of genetic material into cells. Targeted transport is in principle possible with magnetically propelled micromotors, which allow responsive nanoscale actuation and delivery. However, many commonly used magnetic materials (e.g., Ni and Co) are not biocompatible, possess weak magnetic remanence (Fe3O4), or cannot be implemented in nanofabrication schemes (NdFeB). Here, it is demonstrated that co‐depositing iron (Fe) and platinum (Pt) followed by one single annealing step, without the need for solution processing, yields ferromagnetic FePt nanomotors that are noncytotoxic, biocompatible, and possess a remanence and magnetization that rival those of permanent NdFeB micromagnets. Active cell targeting and magnetic transfection of lung carcinoma cells are demonstrated using gradient‐free rotating millitesla fields to drive the FePt nanopropellers. The carcinoma cells express enhanced green fluorescent protein after internalization and cell viability is unaffected by the presence of the FePt nanopropellers. The results establish FePt, prepared in the L10 phase, as a promising magnetic material for biomedical applications with superior magnetic performance, especially for micro‐ and nanodevices.
Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.
Variables affecting the passivation capability of Cu(Mg) alloy films, which were sputter deposited from a Cu (4.5 atom %) target, have been investigated. As-deposited Cu(Mg)/SiO 2 /Si multilayer samples were annealed for 30 min in various oxygen ambients at pressures ranging from 10 mTorr to 30 Torr and at various temperatures in the 200-800ЊC range. The results show that the passivation capability of a Cu(Mg) alloy film is a function of annealing temperature, O 2 pressure, and Mg content in the film. Increasing the annealing temperature favors formation of a dense MgO layer on the surface. Decreasing the O 2 pressure enhances the preferential oxidation of Mg over Cu. Furthermore, increasing the Mg content in the Cu(Mg) film promotes formation of a dense MgO layer. Vacuum preannealing before taking the as-deposited samples to O 2 annealings was found to be very effective in segregating Mg to the surface, facilitating the passivation capability of the Cu(Mg) alloy film even when the Mg content is low. In the current study, self-aligned MgO layers with low resistivity and an effective passivation capability over the Cu surface have been obtained by manipulating these factors when Cu(Mg) thin films are annealed.
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