IrCo nanocacti on CoxSy nanocages as a highly efficient and robust electrocatalyst for the oxygen evolution reaction in acidic media.

Developing highly efficient Ir-based electrocatalysts for the oxygen evolution reaction (OER) has been an important agenda in spearheading the water splitting technology. In this study, the synthesis of IrCo nanocacti on CoxSy nanocages (ICS NCs) is demonstrated by utilizing CoO@CoxSy nanoparticles as reactive nanotemplates. In addition to the high catalytic activities with a low overpotential of 281 mV at 10 mA cm-2 and an outstanding mass activity of 1285 mA mgIr-1 at 1.53 V, the ICS NCs endure a prolonged OER test for over 100 h, greatly outperforming other previously reported Ir-based electrocatalysts. This work suggests that the unique hetero-nanostructure of IrCo/CoxSy induces in situ S doping during electrochemical oxidation and the beneficial effect of S doping on the enhanced stability of ICS NCs for the OER.

Pt2+-Exchanged ZIF-8 nanocube as a solid-state precursor for L10-PtZn intermetallic nanoparticles embedded in a hollow carbon nanocage.

Nanoparticles with an atomically ordered alloy phase have received enormous attention for application as catalysts in fuel cells because of their unique electronic properties resulting from unusually strong d-orbital interactions between two metal components. However, the synthesis of intermetallic nanoparticles requires a high reaction temperature, thus necessitating the protection of nanoparticles with inorganic layers to prevent aggregation of nanoparticles during synthesis. The protective layer needs to be removed later for application as a catalyst, which is a cumbersome process. Herein, a novel synthetic strategy is reported for the preparation of L10-PtZn intermetallic nanoparticles by utilizing Pt2+-exchanged ZIF-8 nanocubes as a solid-state precursor. The Pt2+-exchanged ZIF-8 phase plays a dual role as a metal ion source for L10-PtZn nanoparticles and as a carbonaceous matrix that restrains the aggregation of nanoparticles during thermal treatment. The L10-PtZn nanoparticles embedded in a hollow carbon nanocage obtained from one-step annealing of Pt2+-exchanged ZIF-8 showed better electrocatalytic activity and durability toward methanol oxidation under acidic electrolyte conditions than those obtained from commercial Pt/C catalysts.

Janus to Core-Shell to Janus: Facile Cation Movement in Cu2-xS/Ag2S Hexagonal Nanoplates Induced by Surface Strain Control.

Nanocrystals with multiple compositions and heterointerfaces have received great attention due to promising multifunctional and synergistic physicochemical properties. In particular, heterointerfaces have been at the focal point of nanocatalyst research because the strain caused by lattice mismatches between different phases is the dominant determinant of surface energy and catalytic activity. The ensemble effects of different material phases have also contributed to the interest in heterointerfaced multicomponent materials. Until now, heterointerfaces have largely been regarded as static, and the dynamic movement of components within the multicomponent material phases has received little attention, although the dynamic movement of individual components within multicomponent materials can revise the interpretation of the catalytic behaviors of these materials and lead to fascinating opportunities for nanostructure synthesis. In this study, we demonstrate unprecedented cation migrations within a sulfide matrix induced by surface strain modulation initiated by cation exchange. Specifically, Cu and Ag cations in the sulfide matrix were initially segregated to form a Janus structure. This Janus configuration was then transformed into a core-shell Cu2-xS@Ag2S structure via surface Pt doping. When the surface strain was relieved by a reduced Pt concentration at the nanoparticle surface, the core-shell transitioned back into a Janus structure. We expect that the facile composition fluctuations in multiphasic nanostructures will expand synthetic methodologies for the design and synthesis of intricate nanostructures with useful physicochemical properties.

Gold Nanotetrapods with Unique Topological Structure and Ultranarrow Plasmonic Band as Multifunctional Therapeutic Agents.

Owing to their excellent surface plasmonic properties, Au nanobranches have drawn increasing attention in various bioapplications, such as contrast agents for photoacoustic imaging, nanomedicines for photothermal therapy, and carriers for drug delivery. The monodispersity and plasmonic bandwidth of Au nanobranches are of great importance for the efficacy of those bioapplications. However, it is still a challenge to accurately synthesize size- and shape-controlled Au nanobranches. Here we report a facile seed-mediated growth method to synthesize monodisperse Au nanotetrapods (NTPs) with tunable and ultranarrow plasmonic bands. The NTPs have a novel D2d symmetry with four arms elongated in four ⟨110⟩ directions. The growth mechanism of NTPs relies on the delicate kinetic control of deposition and diffusion rates of adatoms. Upon laser irradiation, the PEGylated NTPs possess remarkable photothermal conversion efficiencies and photoacoustic imaging properties. The NTPs can be applied as a multifunctional theranostic agent for both photoacoustic imaging and image-guided photothermal therapy.

Topotactic Transformations in an Icosahedral Nanocrystal to Form Efficient Water-Splitting Catalysts.

Designing high-performance, precious-metal-based, and economic electrocatalysts remains an important challenge in proton exchange membrane (PEM) electrolyzers. Here, a highly active and durable bifunctional electrocatalyst for PEM electrolyzers based on a rattle-like catalyst comprising a Ni/Ru-doped Pt core and a Pt/Ni-doped RuO2 frame shell, which is topotactically transformed from an icosahedral Pt/Ni/Ru nanocrystal, is reported. The RuO2 -based frame shell with its highly reactive surfaces leads to a very high activity for the oxygen evolution reaction (OER) in acidic media, reaching a current density of 10 mA cm-2 at an overpotential of 239 mV, which surpasses those of previously reported catalysts. The Pt dopant in the RuO2 shell enables a sustained OER activity even after a 2000 cycles of an accelerated durability test. The Pt-based core catalyzes the hydrogen evolution reaction with an excellent mass activity. A two-electrode cell employing Pt/RuO2 as the electrode catalyst demonstrates very high activity and durability, outperforming the previously reported cell performances.

RuOx-decorated multimetallic hetero-nanocages as highly efficient electrocatalysts toward the methanol oxidation reaction.

Direct methanol fuel cell technology awaits the development of highly efficient and robust nanocatalysts driving the methanol oxidation reaction (MOR) in a CO poisoning-free fashion. Thus far, various Pt-based alloy nanoparticles have been studied as electrocatalysts toward the MOR, and it has been found that the introduction of dopants such as Ru and Cu to Pt has been particularly successful in mitigating the CO poisoning problem. Herein, we report a facile synthesis of Ru-branched RuPtCu nanocages that involves in situ formation of Ru-doped PtCu nanoparticles and subsequent outgrowth of Ru branches by insertion of additional Ru precursors. We show that the electrocatalytic activity and stability of Ru branched RuPtCu ternary nanocages toward the MOR are greatly improved compared to those of PtCu/C and RuPtCu/C counterparts and state-of-the-art PtRu/C and Pt/C catalysts, mainly due to the synergy between the CO-tolerant RuOx phase and the highly open and robust RuPtCu nanoframe.

Janus Nanoparticle Structural Motif Control via Asymmetric Cation Exchange in Edge-Protected Cu1.81S@Ir xS y Hexagonal Nanoplates.

Post-synthetic transformation of nanoparticles has received great attention, because this approach can provide an unusual route to elaborately composition-controlled nanostructures while maintaining the overall structure of the template. In principle, anisotropic heteronanoparticles of semiconductor materials can be synthesized via localized, that is, single site, cation exchange in symmetric nanoparticles. However, the differentiation of multiple identical cation exchange sites in symmetric nanoparticles can be difficult to achieve, especially for semiconductor systems with very fast cation exchange kinetics. We posited that single-site cation exchange in semiconductor nanoparticles might be realized by imposing a significant kinetic hurdle to the cation exchange reaction. The different atomic arrangements of the core and crown in core-crown structures might further differentiate the surface energies of originally identical cation exchange sites, leading to different reactivities of these sites. The first cation exchange site would be highly reactive due to the presence of a formed interface, thereby continuing to act as a site for cation exchange propagation. Herein, we present the proof-of-concept synthesis of Janus nanoparticles by using edge-protected Cu1.81S@Ir xS y hexagonal nanoplates. The Janus nanoparticles comprising {Au2S-Cu1.81S}@Ir xS y or {PdS-Cu1.81S}@Ir xS y exhibited dissimilar structural motifs due to the disparate cation exchange directions. This synthetic methodology exploiting cation exchange of surface-passivated semiconductor nanoparticles could fabricate the numerous symmetry-controlled Janus heterostructures.

A facet-controlled Rh3Pb2S2 nanocage as an efficient and robust electrocatalyst toward the hydrogen evolution reaction.

Highly active and durable electrocatalysts for the hydrogen evolution reaction (HER) may play a pivotal role in commercial success of electrolytic water splitting technology. Among various material classes, binary metal sulphides show a great promise as HER catalysts because of their tunable energy levels conducive to a high catalytic activity and high robustness under harsh operating conditions. On the other hand, facet-controlled nanoparticles with controlled surface energies have gained great recent popularity as active and selective catalysts. However, binary metal sulphide nanoparticles with well-defined facets and high surface areas are very rare. Herein we report the synthesis of a facet-controlled hollow Rh3Pb2S2 nanocage as a new catalytic material and its excellent activity (overpotential: 87.3 mV at 10 mA cm-2) and robustness toward HER under harsh acidic conditions.

Dendrite-Embedded Platinum-Nickel Multiframes as Highly Active and Durable Electrocatalyst toward the Oxygen Reduction Reaction.

Pt-based nanoframe catalysts have been explored extensively due to their superior activity toward the oxygen reduction reaction (ORR). Herein, we report the synthesis of Pt-Ni multiframes, which exhibit the unique structure of tightly fused multiple nanoframes and reinforced by an embedded dendrite. Rapid reduction and deposition of Ni atoms on Pt-Ni nanodendrites induce the alloying/dealloying of Pt and Ni in the overall nanostructures. After chemical etching of Ni, the newly formed dendrite-embedded Pt-Ni multiframes show an electrochemically active surface area (ECSA) of 73.4 m2 gPt-1 and a mass ORR activity of 1.51 A mgPt-1 at 0.93 V, which is 30-fold higher than that of the state-of-the-art Pt/C catalyst. We suggest that high ECSA and ORR performances of dendrite-embedded Pt-Ni multiframes/C can be attributed to the porous nanostructure and numerous active sites exposed on surface grain boundaries and high-indexed facets.

NiOOH Exfoliation-Free Nickel Octahedra as Highly Active and Durable Electrocatalysts Toward the Oxygen Evolution Reaction in an Alkaline Electrolyte.

A layered ß-NiOOH crystal with undercoordinated facets is an active and economically viable nonnoble catalyst for the oxygen evolution reaction (OER) in alkaline electrolytes. However, it is extremely difficult to enclose the ß-NiOOH crystal with undercoordinated facets because of its inevitable crystal transformation to γ-NiOOH, resulting in the exfoliation of the catalytic surfaces. Herein, we demonstrate {111}-faceted Ni octahedra as the parent substrates whose surfaces are easily transformed to catalytically active ß-NiOOH during the alkaline OER. Electron microscopic measurements demonstrate that the horizontally stacked ß-NiOOH on the surfaces of Ni octahedra has resistance to further oxidation to γ-NiOOH. By contrast, significant crystal transformation and thus the exfoliation of the γ-NiOOH sheets can be observed on the surfaces of Ni cubes and rhombic dodecahedra (RDs). Electrocatalytic measurements show that the ß-NiOOH formed on Ni octahedra exhibits highly enhanced OER durability compared to the Ni cubes, Ni RDs, and the state-of-the-art Ir/C catalysts.

Highly robust, uniform and ultra-sensitive surface-enhanced Raman scattering substrates for microRNA detection fabricated by using silver nanostructures grown in gold nanobowls.

Highly sensitive and reproducible surface enhanced Raman spectroscopy (SERS) requires not only a nanometer-level structural control, but also superb uniformity across the SERS substrate for practical imaging and sensing applications. However, in the past, increased reproducibility of the SERS signal was incompatible with increased SERS sensitivity. This work presents multiple silver nanocrystals inside periodically arrayed gold nanobowls (SGBs) via an electrochemical reaction at an overpotential of -3.0 V (vs. Ag/AgCl). The gaps between the silver nanocrystals serve as hot spots for SERS enhancement, and the evenly distributed gold nanobowls lead to a high device-to-device signal uniformity. The SGBs on the large sample surface exhibit an excellent SERS enhancement factor of up to 4.80 × 109, with excellent signal uniformity (RSD < 8.0 ± 2.5%). Furthermore, the SGBs can detect specific microRNA (miR-34a), which plays a widely acknowledged role as biomarkers in diagnosis and treatment of diseases. Although the small size and low abundance of miR-34a in total RNA samples hinder their detection, by utilizing the advantages of SGBs in SERS sensing, reliable and direct detection of human gastric cancer cells has been successfully accomplished.

Ni@Ru and NiCo@Ru Core-Shell Hexagonal Nanosandwiches with a Compositionally Tunable Core and a Regioselectively Grown Shell.

The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core-shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one-step synthetic route is reported to prepare hexagonal nanosandwich-shaped Ni@Ru core-shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core-shell nanoparticles with tunable core compositions (Ni3 Cox @Ru HNS). Core-shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO2 black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru4+ ) species, which can be modulated by the core compositions.

Synthesis of compositionally tunable, hollow mixed metal sulphide CoxNiySz octahedral nanocages and their composition-dependent electrocatalytic activities for oxygen evolution reaction.

Hollow nanostructures such as nanocages and nanoframes can serve as advanced catalysts with their enlarged active surface areas, and hence they have been of widespread interest. Despite the recent progress in the synthesis of this class of nanomaterials, hollow nanostructures with tunable compositions and controlled morphologies have rarely been reported. Here, we report a facile synthetic route to a series of compositionally tunable, hollow mixed metal sulphide (CoxNiySz) octahedral nanocages. The sulfidation of CoO octahedral nanoparticles generates CoO@CoxSy core-shell octahedra, and the in situ etching of the CoO core and annealing yield Co9S8 (pentlandite) octahedral nanocages (ONC). The addition of a Ni precursor during the etching/annealing process of CoO@CoxSy core-shell octahedra progressively yields hollow ONC structures of Co9-xNixS8, Ni9S8, Ni9S8/ß-NiS, and Ni3S2/ß-NiS via cation exchange reactions. Mixed cobalt/nickel sulphide, Co9-xNixS8 ONC, shows superior oxygen evolution reaction activity to monometallic sulphide ONC structures, demonstrating the synergy between different metal species.

Rational design of Pt-Ni-Co ternary alloy nanoframe crystals as highly efficient catalysts toward the alkaline hydrogen evolution reaction.

The rational design of highly efficient electrocatalysts for the hydrogen evolution reaction (HER) is of prime importance for establishing renewable and sustainable energy systems. The alkaline HER is particularly challenging as it involves a two-step reaction of water dissociation and hydrogen recombination, for which platinum-based binary catalysts have shown promising activity. In this work, we synthesized high performance platinum-nickel-cobalt alloy nanocatalysts for the alkaline HER through a simple synthetic route. This ternary nanostructure with a Cartesian-coordinate-like hexapod shape could be prepared by a one-step formation of core-dual shell Pt@Ni@Co nanostructures followed by a selective removal of the Ni@Co shell. The cobalt precursor brings about a significant impact on the control of size and shape of the nanostructure. The PtNiCo nanohexapods showed a superior alkaline HER activity to Pt/C and binary PtNi hexapods, with 10 times greater specific activity than Pt/C. In addition, the PtNiCo nanohexapods demonstrated excellent activity and durability for the oxygen reduction reaction in acidic media.

An ultrasensitive and incubation-free electrochemical immunosensor using a gold-nanocatalyst label mediating outer-sphere-reaction-philic and inner-sphere-reaction-philic species.

This communication reports a new nanocatalytic scheme based on the facts that the redox reaction between a highly outer-sphere-reaction-philic (OSR-philic) species and a highly inner-sphere-reaction-philic (ISR-philic) species is slow and that an OSR- and ISR-philic Au-nanocatalyst label can mediate the two different types of redox species. This scheme allows highly sensitive and incubation free detection of creatine kinase-MB.

Skeletal octahedral nanoframe with Cartesian coordinates via geometrically precise nanoscale phase segregation in a Pt@Ni core-shell nanocrystal.

Catalytic properties of nanoparticles can be significantly enhanced by controlling nanoscale alloying and its structure. In this work, by using a facet-controlled Pt@Ni core-shell octahedron nanoparticle, we show that the nanoscale phase segregation can have directionality and be geometrically controlled to produce a Ni octahedron that is penetrated by Pt atoms along three orthogonal Cartesian axes and is coated by Pt atoms along its edges. This peculiar anisotropic diffusion of Pt core atoms along the ⟨100⟩ vertex, and then toward the ⟨110⟩ edges, is explained via the minimum strain energy for Ni-Ni pair interactions. The selective removal of the Ni-rich phase by etching then results in structurally fortified Pt-rich skeletal PtNi alloy framework nanostructures. Electrochemical evaluation of this hollow nanoframe suggests that the oxygen reduction reaction (ORR) activity is greatly improved compared to conventional Pt catalysts.

Telephone follow-up care for disabled patients discharged after receiving dental treatment under outpatient general anesthesia.

BACKGROUND: Patients were subjected to post-discharge follow-up (by telephone) in order to investigate the potential complications of outpatient general anesthesia or deep sedation that could develop in disabled dental patients discharged from the hospital. The ultimate aim of this study was to establish an appropriate response measure for such complications. METHODS: The caregivers of 79 disabled patients who underwent dental procedures under general anesthesia at our outpatient clinic were interviewed over telephone. Necessary care instructions were provided during the phone calls when required. The patient satisfaction level regarding the telephonic follow-up care was surveyed by additional telephone calls. RESULTS: Most of the patients did not suffer any serious complications; however, some reported fever and bleeding. The data obtained in this study can be utilized towards the development of caregiver education pertaining to the ambulatory general anesthesia of dental patients with disabilities. CONCLUSIONS: Additionally, we hope that the findings of this study will help minimize the effects of complications experienced by disabled dental patients undergoing ambulatory general anesthesia, as well as increase the overall patient satisfaction level.

One pot synthesis of nanoscale phase-segregated PdPt nanoarchitectures via unusual Pt-doping induced structural reorganization of a Pd nanosheet into a PdPt nanotent.

Pt-doping of an ultrathin Pd nanosheet results in the unprecedented structural rearrangement of a Pd nanosheet into a PdPt nanotent structure, in which a tripod stands on a triangular nanosheet. Further growth of Pt phase on this nanotent structure is dependent on the presence of surface-stabilizing CO molecules, leading to the formation of two distinct nanoscale phase segregated structures with respective structural features of a popped out Pt facet and an overgrown Pt layer.

A highly crystalline manganese-doped iron oxide nanocontainer with predesigned void volume and shape for theranostic applications.

Hollow Mn-doped iron oxide nanocontainers, formed by a novel one-pot synthetic process, fulfill the dual requirements of delivering an effective dose of an anticancer drug to tumor tissue and enabling image-contrast monitoring of the nanocontainer fate through T2 -weighted magnetic resonance imaging, thereby determining the optimal balance between diagnostic and therapeutic moieties in an all-in-one theranostic nanoplatform.