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Showing papers in "ACS Nano in 2016"


Journal ArticleDOI
26 Jan 2016-ACS Nano
TL;DR: Carbon dots with tunable photoluminescence (PL) and a quantum yield of up to 35% in water were hydrothermally synthesized in one pot and separated via silica column chromatography, and these separated CDs emitted bright and stable luminescence in gradient colors under a single-wavelength UV light.
Abstract: Carbon dots (CDs) with tunable photoluminescence (PL) and a quantum yield of up to 35% in water were hydrothermally synthesized in one pot and separated via silica column chromatography. These separated CDs emitted bright and stable luminescence in gradient colors from blue to red under a single-wavelength UV light. They exhibited high optical uniformity; that is, every sample showed only one peak in the PL excitation spectrum, only one peak in the excitation-independent PL emission spectrum, and similar monoexponential fluorescence lifetimes. Although these samples had similar distributions of particle size and graphite structure in their carbon cores, the surface state gradually varied among the samples, especially the degree of oxidation. Therefore, the observed red shift in their emission peaks from 440 to 625 nm was ascribed to a gradual reduction in their band gaps with the increasing incorporation of oxygen species into their surface structures. These energy bands were found to depend on the surfac...

1,707 citations


Journal ArticleDOI
26 Jan 2016-ACS Nano
TL;DR: It is found that ligand binding to the NC surface is highly dynamic, and therefore, ligands are easily lost during the isolation and purification procedures, and when a small amount of both oleic acid and oleylamine is added, the NCs can be purified, maintaining optical, colloidal, and material integrity.
Abstract: Lead halide perovskite materials have attracted significant attention in the context of photovoltaics and other optoelectronic applications, and recently, research efforts have been directed to nanostructured lead halide perovskites. Collodial nanocrystals (NCs) of cesium lead halides (CsPbX3, X = Cl, Br, I) exhibit bright photoluminescence, with emission tunable over the entire visible spectral region. However, previous studies on CsPbX3 NCs did not address key aspects of their chemistry and photophysics such as surface chemistry and quantitative light absorption. Here, we elaborate on the synthesis of CsPbBr3 NCs and their surface chemistry. In addition, the intrinsic absorption coefficient was determined experimentally by combining elemental analysis with accurate optical absorption measurements. 1H solution nuclear magnetic resonance spectroscopy was used to characterize sample purity, elucidate the surface chemistry, and evaluate the influence of purification methods on the surface composition. We fi...

1,267 citations


Journal ArticleDOI
20 May 2016-ACS Nano
TL;DR: It is found that exposing PSCs to a temperature of 70 °C is enough to induce gold migration through the hole-transporting layer (HTL), spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions.
Abstract: Perovskite solar cells (PSCs) have now achieved efficiencies in excess of 22%, but very little is known about their long-term stability under thermal stress. So far, stability reports have hinted at the importance of substituting the organic components, but little attention has been given to the metal contact. We investigated the stability of state-of-the-art PSCs with efficiencies exceeding 20%. Remarkably, we found that exposing PSCs to a temperature of 70 °C is enough to induce gold migration through the hole-transporting layer (HTL), spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions. Importantly, we found that the main cause of irreversible degradation is not due to decomposition of the organic and hybrid perovskite layers. By introducing a Cr metal interlayer between the HTL and gold electrode, high-temperature-induced irreversible long-term losses are avoided. This key finding is essential in the quest for achieving...

914 citations


Journal ArticleDOI
Shibin Sun1, Dan Yuan1, Yuan Xu1, Aifei Wang1, Zhengtao Deng1 
19 Feb 2016-ACS Nano
TL;DR: This method provides a facile and versatile route to rationally control the shape of the CsPbX3 perovskites nanocrystals, which will create opportunities for applications such as displays, lasing, light-emitting diodes, solar concentrators, and photon detection.
Abstract: Colloidal nanocrystals of fully inorganic cesium lead halide (CsPbX3, X = Cl, Br, I, or combinations thereof) perovskites have attracted much attention for photonic and optoelectronic applications. Herein, we demonstrate a facile room-temperature (e.g., 25 °C), ligand-mediated reprecipitation strategy for systematically manipulating the shape of CsPbX3 colloidal nanocrystals, such as spherical quantum dots, nanocubes, nanorods, and nanoplatelets. The colloidal spherical quantum dots of CsPbX3 were synthesized with photoluminescence (PL) quantum yield values up to >80%, and the corresponding PL emission peaks covering the visible range from 380 to 693 nm. Besides spherical quantum dots, the shape of CsPbX3 nanocrystals could be engineered into nanocubes, one-dimensional nanorods, and two-dimensional few-unit-cell-thick nanoplatelets with well-defined morphology by choosing different organic acid and amine ligands via the reprecipitation process. The shape-dependent PL decay lifetimes have been determined t...

851 citations


Journal ArticleDOI
21 Jan 2016-ACS Nano
TL;DR: With the unique structural advantages for aligned energy levels, electron transfer, light harvesting, and the richly available reaction sites, the as-prepared monolayer of mesoporous g-C3N4 nanomesh exhibits a superior photocatalytic hydrogen evolution rate and an apparent quantum efficiency.
Abstract: Delamination of layer materials into two-dimensional single-atom sheets has induced exceptional physical properties, including large surface area, ultrahigh intrinsic carrier mobility, pronounced changes in the energy band structure, and other properties. Here, atomically thin mesoporous nanomesh of graphitic carbon nitride (g-C3N4) is fabricated by solvothermal exfoliation of mesoporous g-C3N4 bulk made from thermal polymerization of freeze-drying assembled Dicyandiamide nanostructure precursor. With the unique structural advantages for aligned energy levels, electron transfer, light harvesting, and the richly available reaction sites, the as-prepared monolayer of mesoporous g-C3N4 nanomesh exhibits a superior photocatalytic hydrogen evolution rate of 8510 μmol h(-1) g(-1) under λ > 420 nm and an apparent quantum efficiency of 5.1% at 420 nm, the highest of all the metal-free g-C3N4 nanosheets photocatalysts.

815 citations


Journal ArticleDOI
25 Oct 2016-ACS Nano
TL;DR: Improved extrinsic pseudocapacitive contribution is demonstrated as the origin of fast kinetics of an alloying-based SnS2 electrode and the S-edge effect on the fast Na+ migration and reversible and sensitive structure evolution during high-rate charge/discharge is verified.
Abstract: The abundant reserve and low cost of sodium have provoked tremendous evolution of Na-ion batteries (SIBs) in the past few years, but their performances are still limited by either the specific capacity or rate capability. Attempts to pursue high rate ability with maintained high capacity in a single electrode remains even more challenging. Here, an elaborate self-branched 2D SnS2 (B-SnS2) nanoarray electrode is designed by a facile hot bath method for Na storage. This interesting electrode exhibits areal reversible capacity of ca. 3.7 mAh cm–2 (900 mAh g–1) and rate capability of 1.6 mAh cm–2 (400 mAh g–1) at 40 mA cm–2 (10 A g–1). Improved extrinsic pseudocapacitive contribution is demonstrated as the origin of fast kinetics of an alloying-based SnS2 electrode. Sodiation dynamics analysis based on first-principles calculations, ex-situ HRTEM, in situ impedance, and in situ Raman technologies verify the S-edge effect on the fast Na+ migration and reversible and sensitive structure evolution during high-ra...

799 citations


Journal ArticleDOI
01 Mar 2016-ACS Nano
TL;DR: The antibacterial properties of single- and few-layer Ti3C2Tx MXene flakes in colloidal solution were investigated and showed a higher antibacterial efficiency toward both Gram-negative E. coli and Gram-positive B. subtilis compared with graphene oxide (GO), which has been widely reported as an antibacterial agent.
Abstract: MXenes are a family of atomically thin, two-dimensional (2D) transition metal carbides and carbonitrides with many attractive properties. Two-dimensional Ti3C2Tx (MXene) has been recently explored for applications in water desalination/purification membranes. A major success indicator for any water treatment membrane is the resistance to biofouling. To validate this and to understand better the health and environmental impacts of the new 2D carbides, we investigated the antibacterial properties of single- and few-layer Ti3C2Tx MXene flakes in colloidal solution. The antibacterial properties of Ti3C2Tx were tested against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis) by using bacterial growth curves based on optical densities (OD) and colonies growth on agar nutritive plates. Ti3C2Tx shows a higher antibacterial efficiency toward both Gram-negative E. coli and Gram-positive B. subtilis compared with graphene oxide (GO), which has been widely reported as an antibacterial agent. Concentratio...

785 citations


Journal ArticleDOI
29 Nov 2016-ACS Nano
TL;DR: Wound healing results indicate that the synergy antibacterial system could be conveniently used for wound disinfection in vivo.
Abstract: We have developed a biocompatible antibacterial system based on polyethylene glycol functionalized molybdenum disulfide nanoflowers (PEG-MoS2 NFs). The PEG-MoS2 NFs have high near-infrared (NIR) absorption and peroxidase-like activity, which can efficiently catalyze decomposition of low concentration of H2O2 to generate hydroxyl radicals (·OH). The conversion of H2O2 into ·OH can avoid the toxicity of high concentration of H2O2 and the ·OH has higher antibacterial activity, making resistant bacteria more vulnerable and wounds more easily cured. The PEG-MoS2 NFs combine the catalysis with NIR photothermal effect, providing a rapid and effective killing outcome in vitro for Gram-negative ampicillin resistant Escherichia coli (Ampr E. coli) and Gram-positive endospore-forming Bacillus subtilis (B. subtilis) as compared to catalytic treatment or photothermal therapy (PTT) alone. Wound healing results indicate that the synergy antibacterial system could be conveniently used for wound disinfection in vivo. Inte...

717 citations


Journal ArticleDOI
12 Sep 2016-ACS Nano
TL;DR: The atomic structure of freestanding monolayer Ti3C2Tx flakes prepared via the minimally intensive layer delamination method is determined and it is determined that the Ti vacancy concentration can be controlled by the etchant concentration during preparation.
Abstract: The 2D transition metal carbides or nitrides, or MXenes, are emerging as a group of materials showing great promise in lithium ion batteries and supercapacitors. Until now, characterization and properties of single-layer MXenes have been scarcely reported. Here, using scanning transmission electron microscopy, we determined the atomic structure of freestanding monolayer Ti3C2Tx flakes prepared via the minimally intensive layer delamination method and characterized different point defects that are prevalent in the monolayer flakes. We determine that the Ti vacancy concentration can be controlled by the etchant concentration during preparation. Density function theory-based calculations confirm the defect structures and predict that the defects can influence the surface morphology and termination groups, but do not strongly influence the metallic conductivity. Using devices fabricated from single- and few-layer Ti3C2Tx MXene flakes, the effect of the number of layers in the flake on conductivity has been de...

670 citations


Journal ArticleDOI
08 Aug 2016-ACS Nano
TL;DR: These studies have shed light on the influence of ligand chemistry on crystal growth and stabilization of the nanocrystals, which opens the door to functionalizable perovskite nanocrsytals through surface ligand manipulation.
Abstract: While convenient solution-based procedures have been realized for the synthesis of colloidal perovskite nanocrystals, the impact of surfactant ligands on the shape, size, and surface properties still remains poorly understood, which calls for a more detailed structure-morphology study. Herein we have systematically varied the hydrocarbon chain composition of carboxylic acids and amines to investigate the surface chemistry and the independent impact of acid and amine on the size and shape of perovskite nanocrystals. Solution phase studies on purified nanocrystal samples by (1)H NMR and IR spectroscopies have confirmed the presence of both carboxylate and alkylammonium ligands on surfaces, with the alkylammonium ligand being much more mobile and susceptible to detachment from the nanocrystal surfaces during polar solvent washes. Moreover, the chain length variation of carboxylic acids and amines, ranging from 18 carbons down to two carbons, has shown independent correlation to the size and shape of nanocrystals in addition to the temperature effect. We have additionally demonstrated that employing a more soluble cesium acetate precursor in place of the universally used Cs2CO3 results in enhanced processability without sacrificing optical properties, thus offering a more versatile recipe for perovskite nanocrystal synthesis that allows the use of organic acids and amines bearing chains shorter than eight carbon atoms. Overall our studies have shed light on the influence of ligand chemistry on crystal growth and stabilization of the nanocrystals, which opens the door to functionalizable perovskite nanocrsytals through surface ligand manipulation.

654 citations


Journal ArticleDOI
20 Jan 2016-ACS Nano
TL;DR: It is reported that iron oxide nanoparticles have the dual capacity to act as both magnetic and photothermal agents, and single-mode treatments (magnetic or laser hyperthermia) reduced tumor growth, while DUAL-mode treatment resulted in complete tumor regression.
Abstract: The pursuit of innovative, multifunctional, more efficient, and safer treatments is a major challenge in preclinical nanoparticle-mediated thermotherapeutic research. Here, we report that iron oxide nanoparticles have the dual capacity to act as both magnetic and photothermal agents. We further explore every key aspect of this magnetophotothermal approach, choosing iron oxide nanocubes for their high efficiency for the magnetic hyperthermia modality itself. In aqueous suspension, the nanocubes' exposure to both: an alternating magnetic field and near-infrared laser irradiation (808 nm), defined as the DUAL-mode, amplifies the heating effect 2- to 5-fold by comparison with magnetic stimulation alone, yielding unprecedented heating powers (specific loss powers) up to 5000 W/g. In cancer cells, the laser excitation restores the optimal efficiency of magnetic hyperthermia, otherwise inhibited by intracellular confinement, resulting in a remarkable heating efficiency in the DUAL-mode (up to 15-fold amplification), with respect to the magnetophotothermal mode. As a consequence, the dual action yielded complete apoptosis-mediated cell death. In solid tumors in vivo, single-mode treatments (magnetic or laser hyperthermia) reduced tumor growth, while DUAL-mode treatment resulted in complete tumor regression, mediated by heat-induced tumoral cell apoptosis and massive denaturation of the collagen fibers, and a long-lasting thermal efficiency over repeated treatments.

Journal ArticleDOI
14 Oct 2016-ACS Nano
TL;DR: It is demonstrated that nitrogen doping of few-layered graphene can increase the storage capacity of potassium from a theoretical maximum of 278 m Ah/g in graphite to over 350 mAh/g, competitive with anode capacity in commercial lithium ion batteries and the highest reported anodecapacity so far for potassium ion batteries.
Abstract: Potassium is an earth abundant alternative to lithium for rechargeable batteries, but a critical limitation in potassium ion battery anodes is the low capacity of KC8 graphite intercalation compounds in comparison to conventional LiC6. Here we demonstrate that nitrogen doping of few-layered graphene can increase the storage capacity of potassium from a theoretical maximum of 278 mAh/g in graphite to over 350 mAh/g, competitive with anode capacity in commercial lithium ion batteries and the highest reported anode capacity so far for potassium ion batteries. Control studies distinguish the importance of nitrogen dopant sites as opposed to sp3 carbon defect sites to achieve the improved performance, which also enables >6× increase in rate performance of doped vs undoped materials. Finally, in situ Raman spectroscopy studies elucidate the staging sequence for doped and undoped materials and demonstrate the mechanism of the observed capacity enhancement to be correlated with distributed storage at local nitrog...

Journal ArticleDOI
10 Nov 2016-ACS Nano
TL;DR: A cancer cell membrane-cloaked nanoparticle system as a theranostic nanoplatform with homologous properties of cancer cell membranes can serve as a bionic nanoplplatform for cancer-targeted imaging and phototherapy.
Abstract: An active cell membrane–camouflaged nanoparticle, owning to membrane antigens and membrane structure, can achieve special properties such as specific recognition, long blood circulation, and immune escaping. Herein, we reported a cancer cell membrane–cloaked nanoparticle system as a theranostic nanoplatform. The biomimetic nanoparticles (indocyanine green (ICG)-loaded and cancer cell membrane-coated nanoparticles, ICNPs) exhibit a core–shell nanostructure consisting of an ICG-polymeric core and cancer cell membrane shell. ICNPs demonstrated specific homologous targeting to cancer cells with good monodispersity, preferable photothermal response, and excellent fluorescence/photoacoustic (FL/PA) imaging properties. Benefited from the functionalization of the homologous binding adhesion molecules from cancer cell membranes, ICNPs significantly promoted cell endocytosis and homologous-targeting tumor accumulation in vivo. Moreover, ICNPs were also good at disguising as cells to decrease interception by the liv...

Journal ArticleDOI
05 Feb 2016-ACS Nano
TL;DR: Two-dimensional transition metal carbide materials called MXenes show potential application for energy storage due to their remarkable electrical conductivity and low Li(+) diffusion barrier, but their lower capacity limits their further application in lithium-ion batteries.
Abstract: Two-dimensional transition metal carbide materials called MXenes show potential application for energy storage due to their remarkable electrical conductivity and low Li+ diffusion barrier. However, the lower capacity of MXene anodes limits their further application in lithium-ion batteries. Herein, with inspiration from the unique metal ion uptake behavior of highly conductive Ti3C2 MXene, we overcome this impediment by fabricating Sn4+ ion decorated Ti3C2 nanocomposites (PVP-Sn(IV)@Ti3C2) via a facile polyvinylpyrrolidone (PVP)-assisted liquid-phase immersion process. An amorphous Sn(IV) nanocomplex, about 6–7 nm in lateral size, has been homogeneously anchored on the surface of alk-Ti3C2 matrix by ion-exchange and electrostatic interactions. In addition, XRD and TEM results demonstrate the successful insertion of Sn4+ into the interlamination of an alkalization-intercalated Ti3C2 (alk-Ti3C2) matrix. Due to the possible “pillar effect” of Sn between layers of alk-Ti3C2 and the synergistic effect between...

Journal ArticleDOI
26 Jan 2016-ACS Nano
TL;DR: First-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions are presented, including ab initio predictions of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies.
Abstract: The behavior of metals across a broad frequency range from microwave to ultraviolet frequencies is of interest in plasmonics, nanophotonics, and metamaterials. Depending on the frequency, losses of collective excitations in metals can be predominantly classical resistive effects or Landau damping. In this context, we present first-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions so generated. Specifically, we include ab initio predictions of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies. In the commonly used plasmonic materials, gold, silver, copper, and aluminum, we find that resistive losses compete with phonon-assisted carrier generation below the interband threshold, but hot carrier generation via direct transitions dominates above thre...

Journal ArticleDOI
14 Sep 2016-ACS Nano
TL;DR: The pomegranate-like N,P-doped Mo2C@C nanospheres exhibit extraordinary electrocatalytic activity for the hydrogen evolution reaction (HER) in terms of an extremely low overpotential of 47 mV at 10 mA cm(-2) in 1 M KOH, which is one of the best Mo-based HER catalysts.
Abstract: Well-defined pomegranate-like N,P-doped Mo2C@C nanospheres were prepared by simply using phosphomolybdic acid (PMo12) to initiate the polymerization of polypyrrole (PPy) and as a single source for Mo and P to produce N,P-doped Mo2C nanocrystals. The existence of PMo12 at the molecular scale in the polymer network allows the formation of pomegranate-like Mo2C@C nanospheres with a porous carbon shell as peel and Mo2C nanocrystals well-dispersed in the N-doped carbon matrix as seeds. This nanostructure provides several favorable features for hydrogen evolution application: (1) the conductive carbon shell and matrix effectively prevent the aggregation of Mo2C nanocrystals and facilitate electron transportation; (2) the uniform N,P-doping in the carbon shell/matrix and plenty of Mo2C nanocrystals provide abundant catalytically highly active sites; and (3) nanoporous structure allows the effective exposure of active sites and mass transfer. Moreover, the uniform distribution of P and Mo from the single source o...

Journal ArticleDOI
18 Apr 2016-ACS Nano
TL;DR: The possible killer application of a TENG for harvesting energy at low frequency from motions such as human motions for powering small electronics and possibly ocean waves for large-scale blue energy is verified.
Abstract: Electromagnetic generators (EMGs) and triboelectric nanogenerators (TENGs) are the two most powerful approaches for harvesting ambient mechanical energy, but the effectiveness of each depends on the triggering frequency. Here, after systematically comparing the performances of EMGs and TENGs under low-frequency motion ( 10–100 V) and independent of frequency so that most of the generated power can be effectively used to po...

Journal ArticleDOI
26 Feb 2016-ACS Nano
TL;DR: Electronic and photonic nanotechnologies that are integrated with textiles are discussed and their applications in displays, sensing, and drug release within the context of performance, durability, and connectivity are shown.
Abstract: Increasing customer demand for durable and functional apparel manufactured in a sustainable manner has created an opportunity for nanomaterials to be integrated into textile substrates. Nanomoieties can induce stain repellence, wrinkle-freeness, static elimination, and electrical conductivity to fibers without compromising their comfort and flexibility. Nanomaterials also offer a wider application potential to create connected garments that can sense and respond to external stimuli via electrical, color, or physiological signals. This review discusses electronic and photonic nanotechnologies that are integrated with textiles and shows their applications in displays, sensing, and drug release within the context of performance, durability, and connectivity. Risk factors including nanotoxicity, nanomaterial release during washing, and environmental impact of nanotextiles based on life cycle assessments have been evaluated. This review also provides an analysis of nanotechnology consolidation in the textiles ...

Journal ArticleDOI
01 Feb 2016-ACS Nano
TL;DR: Carbon paper/carbon tubes/cobalt-sulfide is introduced as an integrated three-dimensional array electrode for cost-effective and energy-efficient HER and OER in alkaline medium and displays superior performance compared to non-noble metal catalysts reported previously.
Abstract: The development of an efficient catalytic electrode toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of great significance for overall water splitting associated with the conversion and storage of clean and renewable energy. In this study, carbon paper/carbon tubes/cobalt-sulfide is introduced as an integrated three-dimensional (3D) array electrode for cost-effective and energy-efficient HER and OER in alkaline medium. Impressively, this electrode displays superior performance compared to non-noble metal catalysts reported previously, benefiting from the unique 3D array architecture with increased exposure and accessibility of active sites, improved vectorial electron transport capability, and enhanced release of gaseous products. Such an integrated and versatile electrode makes the overall water splitting proceed in a more direct and smooth manner, reducing the production cost of practical technological devices.

Journal ArticleDOI
22 Mar 2016-ACS Nano
TL;DR: The in vivo experiments demonstrated high tumor-inhibition efficacy and low side effects of the charge-convertible CDs, proving its capability as a smart drug nanocarrier with enhanced therapeutic effects, and a strategy to promote potential clinical application of CDs in the cancer treatment.
Abstract: Carbon dots (CDs) are remarkable nanocarriers due to their promising optical and biocompatible capabilities. However, their practical applicability in cancer therapeutics is limited by their insensitive surface properties to complicated tumor microenvironment in vivo. Herein, a tumor extracellular microenvironment-responsive drug nanocarrier based on cisplatin(IV) prodrug-loaded charge-convertible CDs (CDs–Pt(IV)@PEG-(PAH/DMMA)) was developed for imaging-guided drug delivery. An anionic polymer with dimethylmaleic acid (PEG-(PAH/DMMA)) on the fabricated CDs–Pt(IV)@PEG-(PAH/DMMA) could undergo intriguing charge conversion to a cationic polymer in mildly acidic tumor extracellular microenvironment (pH ∼ 6.8), leading to strong electrostatic repulsion and release of positive CDs–Pt(IV). Importantly, positively charged nanocarrier displays high affinity to negatively charged cancer cell membrane, which results in enhanced internalization and effective activation of cisplatin(IV) prodrug in the reductive cytos...

Journal ArticleDOI
19 Aug 2016-ACS Nano
TL;DR: In vitro study showed that PCCN could increase the intracellular O2 concentration and improve the reactive oxygen species generation in both hypoxic and normoxic environments upon light irradiation, and in vivo experiments indicated that P CCN had superior ability to overcome tumor hypoxia.
Abstract: Hypoxia, a typical feature of solid tumors, remarkably restricts the efficiency of photodynamic therapy (PDT). Here, a carbon nitride (C3N4)-based multifunctional nanocomposite (PCCN) for light-driven water splitting was used to solve this problem. Carbon dots were first doped with C3N4 to enhance its red region absorption because red light could be used to trigger the in vivo water splitting process. Then, a polymer containing a protoporphyrin photosensitizer, a polyethylene glycol segment, and a targeting Arg-Gly-Asp motif was synthesized and introduced to carbon-dot-doped C3N4 nanoparticles. In vitro study showed that PCCN, thus obtained, could increase the intracellular O2 concentration and improve the reactive oxygen species generation in both hypoxic and normoxic environments upon light irradiation. Cell viability assay demonstrated that PCCN fully reversed the hypoxia-triggered PDT resistance, presenting a satisfactory growth inhibition of cancer cells in an O2 concentration of 1%. In vivo experime...

Journal ArticleDOI
25 Jul 2016-ACS Nano
TL;DR: In this paper, a solution growth of single-crystal lead halide perovskite nanowires (NWs) is proposed for tunable light-emitting diodes (LEDs).
Abstract: Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic–inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry–Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420–710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing si...

Journal ArticleDOI
26 Jan 2016-ACS Nano
TL;DR: A superior lithium and sodium storage performance is derived from the well-designed hierarchical hollow ball-in-ball structure of NiO/Ni/Graphene composites, which not only mitigates the volume expansion of Ni O during the cycles but also provides a continuous highly conductive graphene matrix to facilitate the fast charge transfer and form a stable SEI layer.
Abstract: Ni-based metal organic frameworks (Ni-MOFs) with unique hierarchical hollow ball-in-ball nanostructure were synthesized by solvothermal reactions. After successive carbonization and oxidation treatments, hierarchical NiO/Ni nanocrystals covered with a graphene shell were obtained with the hollow ball-in-ball nanostructure intact. The resulting materials exhibited superior performance as the anode in lithium ion batteries (LIBs): they provide high reversible specific capacity (1144 mAh/g), excellent cyclability (nearly no capacity loss after 1000 cycles) and rate performance (805 mAh/g at 15 A/g). In addition, the hierarchical NiO/Ni/Graphene composites demonstrated promising performance as anode materials for sodium-ion batteries (SIBs). Such a superior lithium and sodium storage performance is derived from the well-designed hierarchical hollow ball-in-ball structure of NiO/Ni/Graphene composites, which not only mitigates the volume expansion of NiO during the cycles but also provides a continuous highly ...

Journal ArticleDOI
24 Feb 2016-ACS Nano
TL;DR: The HA-coated, mannan-conjugated MnO2 particle (Man-HA-MnO2) treatment significantly increased tumor oxygenation and down-regulated hypoxia-inducible factor-1 α (HIF-1α) and vascular endothelial growth factor (VEGF) in the tumor.
Abstract: Hypoxia promotes not only the invasiveness of tumor cells, but also chemoresistance in cancer. Tumor associated macrophages (TAMs) residing at the site of hypoxic region of tumors have been known to cooperate with tumor cells, and promote proliferation and chemoresistance. Therefore, there is an urgent need for new strategies to alleviate tumor hypoxia and enhance chemotherapy response in solid tumors. Herein, we have taken advantage of high accumulation of TAMs in hypoxic regions of tumor and high reactivity of manganese dioxide nanoparticles (MnO2 NPs) toward hydrogen peroxide (H2O2) for the simultaneous production of O2 and regulation of pH to effectively alleviate tumor hypoxia by targeted delivery of MnO2 NPs to the hypoxic area. Furthermore, we also utilized the ability of hyaluronic acid (HA) modification in reprogramming anti-inflammatory, pro-tumoral M2 TAMs to pro-inflammatory, antitumor M1 macrophages to further enhance the ability of MnO2 NPs to lessen tumor hypoxia and modulate chemoresistanc...

Journal ArticleDOI
29 Jul 2016-ACS Nano
TL;DR: A high-performance strain sensor with a fish-scale-like graphene-sensing layer that can be fabricated via stretching/releasing the composite films of reduced graphene oxide and elastic tape, making the process simple, cheap, energy-saving, and scalable.
Abstract: Strain sensors with large stretchability, broad sensing range, and high sensitivity are highly desirable because of their potential applications in electronic skins and health monitoring systems. In this paper, we report a high-performance strain sensor with a fish-scale-like graphene-sensing layer. This strain sensor can be fabricated via stretching/releasing the composite films of reduced graphene oxide and elastic tape, making the process simple, cheap, energy-saving, and scalable. It can be used to detect both stretching and bending deformations with a wide sensing range (up to 82% strain), high sensitivity (a gauge factor of 16.2 to 150), ultralow limit of detection ( 5000 cycles). Therefore, it is attractive and promising for practical applications, such as for the full-range detection of human motions.

Journal ArticleDOI
28 Nov 2016-ACS Nano
TL;DR: Electrochemical evaluation demonstrates that Mo2C/NCF exhibits excellent HER electrocatalytic performance with low onset overpotentials, small Tafel slopes, and excellent cycling stability in both acidic and alkaline solutions.
Abstract: The development of nonprecious metal based electrocatalysts for hydrogen evolution reaction (HER) has received increasing attention over recent years. Previous studies have established Mo2C as a promising candidate. Nevertheless, its preparation requires high reaction temperature, which more than often causes particle sintering and results in low surface areas. In this study, we show supporting Mo2C nanoparticles on the three-dimensional scaffold as a possible solution to this challenge and develop a facile two-step preparation method for ∼3 nm Mo2C nanoparticles uniformly dispersed on carbon microflowers (Mo2C/NCF) via the self-polymerization of dopamine. The resulting hybrid material possesses large surface areas and a fully open and accessible structure with hierarchical order at different levels. MoO42– was found to play an important role in inducing the formation of this morphology presumably via its strong chelating interaction with the catechol groups of dopamine. Our electrochemical evaluation dem...

Journal ArticleDOI
26 Jan 2016-ACS Nano
TL;DR: The flawless and surface-nanostructured NiOx film can make the interfacial recombination and monomolecular Shockley-Read-Hall recombination of PVSC reduce and improve the hole extraction and thus PVSC performances, which contributes to the evolution of flexible PVSCs with simple fabrication process and high device performances.
Abstract: Recently, researchers have focused on the design of highly efficient flexible perovskite solar cells (PVSCs), which enables the implementation of portable and roll-to-roll fabrication in large scale. While NiOx is a promising material for hole transport layer (HTL) candidate for fabricating efficient PVSCs on a rigid substrate, the reported NiOx HTLs are formed using different multistep treatments (such as 300–500 °C annealing, O2-plasma, UVO, etc.), which hinders the development of flexible PVSCs based on NiOx. Meanwhile, the features of nanostructured morphology and flawless film quality are very important for the film to function as highly effective HTL of PVSCs. However, it is difficult to have the two features coexist natively, particularly in a solution process that flawless film will usually come with smooth morphology. Here, we demonstrate the flawless and surface-nanostructured NiOx film from a simple and controllable room-temperature solution process for achieving high performance flexible PVSCs...

Journal ArticleDOI
08 Aug 2016-ACS Nano
TL;DR: The results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR.
Abstract: Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials—exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n−1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n–1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum y...

Journal ArticleDOI
26 Jan 2016-ACS Nano
TL;DR: In this work, a range of devices containing different cathode metal contacts in the configuration ITO/PEDOT:PSS/MAPbI3/PCBM/Metal are fully electrically characterized before and after degradation caused by steady illumination during 4 h that induces a dramatic reduction in power conversion efficiency.
Abstract: The stability of perovskite solar cells is one of the major challenges for this technology to reach commercialization, with water believed to be the major degradation source. In this work, a range of devices containing different cathode metal contacts in the configuration ITO/PEDOT:PSS/MAPbI3/PCBM/Metal are fully electrically characterized before and after degradation caused by steady illumination during 4 h that induces a dramatic reduction in power conversion efficiency from values of 12 to 1.8%. We show that a decrease in performance and generation of the S-shape is associated with chemical degradation of the metal contact. Alternatively, use of Cr2O3/Cr as the contact enhances the stability, but modification of the energetic profile during steady illumination takes place, significantly reducing the performance. Several techniques including capacitance–voltage, X-ray diffraction, and optical absorption results suggest that the properties of the bulk perovskite layer are little affected in the device de...

Journal ArticleDOI
08 Jul 2016-ACS Nano
TL;DR: This paper demonstrates a wearable electrochemical device for continuous monitoring of ionized calcium and pH of body fluids using a disposable and flexible array of Ca(2+) and pH sensors that interfaces with a flexible printed circuit board that enables real-time quantitative analysis of these sensing elements in body fluids.
Abstract: Homeostasis of ionized calcium in biofluids is critical for human biological functions and organ systems. Measurement of ionized calcium for clinical applications is not easily accessible due to its strict procedures and dependence on pH. pH balance in body fluids greatly affects metabolic reactions and biological transport systems. Here, we demonstrate a wearable electrochemical device for continuous monitoring of ionized calcium and pH of body fluids using a disposable and flexible array of Ca2+ and pH sensors that interfaces with a flexible printed circuit board. This platform enables real-time quantitative analysis of these sensing elements in body fluids such as sweat, urine, and tears. Accuracy of Ca2+ concentration and pH measured by the wearable sensors is validated through inductively coupled plasma-mass spectrometry technique and a commercial pH meter, respectively. Our results show that the wearable sensors have high repeatability and selectivity to the target ions. Real-time on-body assessment...