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1.
Simple, yet versatile, methods to functionalize graphene flakes with metal (oxide) nanoparticles are in demand, particularly for the development of advanced catalysts. Herein, based on light‐induced electrochemistry, a laser‐assisted, continuous, solution route for the simultaneous reduction and modification of graphene oxide with catalytic nanoparticles is reported. Electrochemical graphene oxide (EGO) is used as starting material and electron–hole pair source due to its low degree of oxidation, which imparts structural integrity and an ability to withstand photodegradation. Simply illuminating a solution stream containing EGO and metal salt (e.g., H2PtCl6 or RuCl3) with a 248 nm wavelength laser produces reduced EGO (rEGO, oxygen content 4.0 at%) flakes, decorated with Pt (≈2.0 nm) or RuO2 (≈2.8 nm) nanoparticles. The RuO2–rEGO flakes exhibit superior catalytic activity for the oxygen evolution reaction, requiring a small overpotential of 225 mV to reach a current density of 10 mA cm?2. The Pt–rEGO flakes (10.2 wt% of Pt) show enhanced mass activity for the hydrogen evolution reaction, and similar performance for oxygen reduction reaction compared to a commercial 20 wt% Pt/C catalyst. This simple production method is also used to deposit PtPd alloy and MnOx nanoparticles on rEGO, demonstrating its versatility in synthesizing functional nanoparticle‐modified graphene materials.  相似文献   

2.
To the photocatalytic H2 evolution, the exposure of a reduction surface over a catalyst plays an important role for the reduction of hydrogen protons. Here, this study demonstrates the design of a noble‐metal‐free spatially separated photocatalytic system exposed with reduction surfaces (MnOx @CdS/CoP) for highly solar‐light‐driven H2 evolution activity. CoP and MnOx nanoparticles are employed as the electron and hole collectors, which are selectively anchored on the outer and inner surface of CdS shells, respectively. Under solar light irradiation, the photogenerated holes and electrons can directionally move to the MnOx and CoP, respectively, leading to the exposure of a reduction surface. As a result, the H2 evolution increases from 32.0 to 238.4 µmol h?1, which is even higher than the activity of platinum‐loaded photocatalyst (MnOx @CdS/Pt). Compared to the pure CdS with serious photocorrosion, the MnOx @CdS/CoP maintains a changeless activity for the H2 evolution and rhodamine B degradation, even after four cycles. The research provides a new strategy for the preparation of spatially separated photocatalysts with a selective reduction surface.  相似文献   

3.
Tungsten oxide nanostructures functionalized with gold or platinum NPs are synthesized and integrated, using a single‐step method via aerosol‐assisted chemical vapour deposition, onto micro‐electromechanical system (MEMS)‐based gas‐sensor platforms. This co‐deposition method is demonstrated to be an effective route to incorporate metal nanoparticles (NP) or combinations of metal NPs into nanostructured materials, resulting in an attractive way of tuning functionality in metal oxides (MOX). The results show variations in electronic and sensing properties of tungsten oxide according to the metal NPs introduced, which are used to discriminate effectively analytes (C2H5OH, H2, and CO) that are present in proton‐exchange fuel cells. Improved sensing characteristics, in particular to H2, are observed at 250 °C with Pt‐functionalized tungsten oxide films, whereas non‐functionalized tungsten oxide films show responses to low concentrations of CO at low temperatures. Differences in the sensing characteristics of these films are attributed to the different reactivities of metal NPs (Au and Pt), and to the degree of electronic interaction at the MOX/metal NP interface. The method presented in this work has advantages over other methods of integrating nanomaterials and devices, of having fewer processing steps, relatively low processing temperature, and no requirement for substrate pre‐treatment.  相似文献   

4.
Flexible energy storage devices are critical components for emerging flexible and wearable electronics. Improving the electrochemical performance of flexible energy storage devices depends largely on development of novel electrode architectures and new systems. Here, a new class of flexible energy storage device called flexible sodium‐ion pseudocapacitors is developed based on 3D‐flexible Na2Ti3O7 nanosheet arrays/carbon textiles (NTO/CT) as anode and flexible reduced graphene oxide film (GFs) as cathode without metal current collectors or conducting additives. The NTO/CT anode with advanced electrode architectures is fabricated by directly growing Na2Ti3O7 nanosheet arrays on carbon textiles with robust adhesion through a simple hydrothermal process. The flexible GF//NTO/CT configuration achieves a high energy density of 55 Wh kg?1 and high power density of 3000 W kg?1. Taking the fully packaged flexible sodium‐ion pseudocapacitors into consideration, the maximum practical volumetric energy density and power density reach up to 1.3 mWh cm?3 and 70 mW cm?3, respectively. In addition, the flexible GF//NTO/CT device demonstrates a stable electrochemical performances with almost 100% capacitance retention under harsh mechanical deformation.  相似文献   

5.
A foldable array of patterned graphene/ZnO nanoparticle UV sensor and asymmetric micro‐supercapacitors (AMSCs) integrated on a paper substrate with patterned liquid metal interconnections is reported. The resistor type UV sensor based on graphene/ZnO nanoparticles is patterned to be driven by the stored energy of the integrated AMSCs. The AMSC consists of MnO2 nanoball deposited multiwalled carbon nanotubes (MWNTs) and V2O5 wrapped MWNTs as positive and negative electrodes, respectively. As an electrolyte, propylene carbonate‐poly(methyl methacrylate)‐LiClO4, an organic solvent‐based gel, is used. The UV sensor and AMSCs can be easily integrated on a liquid metal, Galinstan, patterned, waterproof mineral paper and show a mechanically stable UV sensing, regardless of repetitive folding cycles. This work demonstrates a novel foldable nanomaterial based sensor system driven by integrated energy storage devices, applicable to future wearable and portable electronics.  相似文献   

6.
One of the formidable challenges facing aprotic lithium‐oxygen (Li‐O2) batteries is the high charge overpotential, which induces the formation of byproducts, loss in efficiency, and poor cycling performance. Herein, the synthesis of the ultrasmall Pt‐coated hollow graphene nanocages as cathode in Li‐O2 batteries is reported. The charge voltage plateau can reduce to 3.2 V at the current density of 100 mA g?1, even maintain below 3.5 V when the current density increased to 500 mA g?1. The unique hollow graphene nanocages matrix can not only provide numerous nanoscale tri‐phase regions as active sites for efficient oxygen reduction, but also offer sufficient amount of mesoscale pores for rapid oxygen diffusion. Furthermore, with strong atomic‐level oxygen absorption into its subsurface, ultrasmall Pt catalytically serves as the nucleation site for Li2O2 growth. The Li2O2 is subsequently induced into a favorable form with small size and amorphous state, decomposed more easily during recharge. Meanwhile, the conductive hollow graphene substrate can enhance the catalytic activity of noble metal Pt catalysts due to the graphene‐metal interfacial interaction. Benefiting from the above synergistic effects between the hollow graphene nanocages and the nanosized Pt catalysts, the ultrasmall Pt‐decorated graphene nanocage cathode exhibits enhanced electrochemical performances.  相似文献   

7.
Hybrid metal–organic frameworks (MOFs) demonstrate great promise as ideal electrode materials for energy‐related applications. Herein, a well‐organized interleaved composite of graphene‐like nanosheets embedded with MnO2 nanoparticles (MnO2@C‐NS) using a manganese‐based MOF and employed as a promising anode material for Li‐ion hybrid capacitor (LIHC) is engineered. This unique hybrid architecture shows intriguing electrochemical properties including high reversible specific capacity 1054 mAh g?1 (close to the theoretical capacity of MnO2, 1232 mAh g?1) at 0.1 A g?1 with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance may be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO2 nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel LIHC is assembled using a MnO2@C‐NS anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium‐based MOFs) cathode materials. The LIHC full‐cell delivers an ultrahigh specific energy of 166 Wh kg?1 at 550 W kg?1 and maintained to 49.2 Wh kg?1 even at high specific power of 3.5 kW kg?1 as well as long cycling stability (91% over 5000 cycles). This work opens new opportunities for designing advanced MOF derived electrodes for next‐generation energy storage devices.  相似文献   

8.
Three kinds of Mn3O4 nanoparticles with different shapes (spheres, cubes, and ellipsoids) are selectively grown on nitrogen‐doped graphene sheets through a two‐step liquid‐phase procedure. These non‐precious hybrid materials display an excellent ORR activity and good durability. The mesoporous microstructure, nitrogen doping, and strong bonding between metal species and doped graphene are found to facilitate the ORR catalytic process. Among these three kinds of Mn3O4 particles, the ellipsoidal particles on nitrogen‐doped graphene exhibit the highest ORR activity with a more positive onset‐potential of –0.13 V (close to that of Pt/C, –0.09 V) and a higher kinetic limiting current density (JK) of 11.69 mA cm–2 at –0.60 V. It is found that the ORR performance of hybrid materials can be correlated to the shape of Mn3O4 nanocrystals, and specifically to the exposed crystalline facets associated with a given shape. The shape dependence of Mn3O4 nanoparticles integrated with nitrogen‐doped graphene on the ORR performance, reported here for the first time, may advance the development of fuel cells and metal‐air batteries.  相似文献   

9.
Nanoscale coordination polymers (NCPs) self‐assembled from metal ions and organic bridging ligands exhibit many unique features promising for applications in nanomedicine. In this work, manganese dioxide (MnO2) nanoparticles stabilized by bovine serum albumin are encapsulated by NCP‐shells constructed based on high‐Z element hafnium (Hf) ions and c,c,t‐(diamminedichlorodisuccinato)Pt(IV) (DSP), a cisplatin prodrug. After further modification with polyethylene glycol (PEG), the formed BM@NCP(DSP)‐PEG can simultaneously serve as a radio‐sensitizer owing to the strong X‐ray attenuation capability of Hf to enhance radiotherapy, as well as a chemotherapeutic agent resulting from the reduction‐induced release of cisplatin. Meanwhile, the in situ generated oxygen resulting from MnO2‐triggered decomposition of tumor endogenous H2O2 will be greatly helpful for overcoming hypoxia‐associated radio‐resistance. Upon intravenous injection, BM@NCP(DSP)‐PEG shows efficient tumor homing as well as rapid renal excretion, as illustrated by magnetic resonance imaging and confirmed by biodistribution measurement. Notably, an excellent in vivo tumor growth inhibition effect is observed with BM@NCP(DSP)‐PEG nanoparticles after the combined chemoradiotherapy treatment. Therefore, the NCP‐based composite nanoparticles with inherent biodegradability and no appreciable in vivo toxicity may be a unique type of multifunctional nanoplatform responsive to different parameters in the tumor microenvironment, promising for cancer theranostics with great efficacy.  相似文献   

10.
Graphene sheets have been demonstrated to be the building blocks for various assembly structures, which eventually determine the macroscopic properties of graphene materials. As a new assembly structure, transparent macroporous graphene thin films (MGTFs) are not readily prepared due to the restacking tendency of graphene sheets during processing. Here, an ice crystal‐induced phase separation process is proposed for preparation of transparent MGTFs. The ice crystal‐induced phase separation process exhibits several unique features, including efficient prevention of graphene oxide restacking, easy control on the transparency of the MGTFs, and wide applicability to substrates. It is shown that the MGTFs can be used as porous scaffold with high conductivity for electrochemical deposition of various semiconductors and rare metal nanoparticles such as CdSe, ZnO, and Pt, as well as successive deposition of different materials. Notably, the macroporous structures bestow the MGTFs and the nanoparticle‐decorated MGTFs (i.e., Pt@MGTF and CdSe@MGTF) enhanced performance as electrode for oxygen reduction reaction and photoelectrochemical H2 generation.  相似文献   

11.
Asymmetric supercapacitors have attracted tremendous attention in energy storage devices since they have an enhanced energy density in comparison with symmetric supercapacitor devices. Furthermore, the development of diverse and flexible electronic devices requires the asymmetric supercapacitor devices to be flexible and in various configurations. However, it is still a challenge to develop a universal strategy to obtain both capacitive and Faradic electrodes with various architectures. Herein, a spontaneously reducing/assembling strategy in an alkaline condition is developed to fabricate large‐area reduced graphene oxide (RGO) and RGO–metal oxide/hydroxide composite films or microsized structures. As a proof of concept, the large‐area pure RGO and RGO/Mn3O4 composite films with porous structure and superior mechanical property are achieved by such strategy. These RGO‐based films can directly serve as the anodes and cathodes of the flexible asymmetric film supercapacitors. Furthermore, the interdigital RGO and RGO/Mn3O4 patterns are also obtained via a selectively reducing/assembling process to achieve the asymmetric microsized supercapacitors. These asymmetric supercapacitors with different configurations possess good electrochemical performance and excellent flexibility. Therefore, such reducing and assembling strategy provides a route to achieve large‐area RGO‐based films and microsized structures for the applications in the various fields such as energy storage and photocatalysis.  相似文献   

12.
A molten lithium infusion strategy has been proposed to prepare stable Li‐metal anodes to overcome the serious issues associated with dendrite formation and infinite volume change during cycling of lithium‐metal batteries. Stable host materials with superior wettability of molten Li are the prerequisite. Here, it is demonstrated that a series of strong oxidizing metal oxides, including MnO2, Co3O4, and SnO2, show superior lithiophilicity due to their high chemical reactivity with Li. Composite lithium‐metal anodes fabricated via melt infusion of lithium into graphene foams decorated by these metal oxide nanoflake arrays successfully control the formation and growth of Li dendrites and alleviate volume change during cycling. A resulting Li‐Mn/graphene composite anode demonstrates a super‐long and stable lifetime for repeated Li plating/stripping of 800 cycles at 1 mA cm?2 without voltage fluctuation, which is eight times longer than the normal lifespan of a bare Li foil under the same conditions. Furthermore, excellent rate capability and cyclability are realized in full‐cell batteries with Li‐Mn/graphene composite anodes and LiCoO2 cathodes. These results show a major advancement in developing a stable Li anode for lithium‐metal batteries.  相似文献   

13.
Hypoxia not only promotes tumor metastasis but also strengthens tumor resistance to therapies that demand the involvement of oxygen, such as radiation therapy and photodynamic therapy (PDT). Herein, taking advantage of the high reactivity of manganese dioxide (MnO2) nanoparticles toward endogenous hydrogen peroxide (H2O2) within the tumor microenvironment to generate O2, multifunctional chlorine e6 (Ce6) loaded MnO2 nanoparticles with surface polyethylene glycol (PEG) modification (Ce6@MnO2‐PEG) are formulated to achieve enhanced tumor‐specific PDT. In vitro studies under an oxygen‐deficient atmosphere uncover that Ce6@MnO2‐PEG nanoparticles could effectively enhance the efficacy of light‐induced PDT due to the increased intracellular O2 level benefited from the reaction between MnO2 and H2O2, the latter of which is produced by cancer cells under the hypoxic condition. Owing to the efficient tumor homing of Ce6@MnO2‐PEG nanoparticles upon intravenous injection as revealed by T1‐weighted magnetic resonance imaging, the intratumoral hypoxia is alleviated to a great extent. Thus, in vivo PDT with Ce6@MnO2‐PEG nanoparticles even at a largely reduced dose offers remarkably improved therapeutic efficacy in inhibiting tumor growth compared to free Ce6. The results highlight the promise of modulating unfavorable tumor microenvironment with nanotechnology to overcome current limitations of cancer therapies.  相似文献   

14.
Hybrid metal oxide nano‐ and microstructures exhibit novel properties, which make them promising candidates for a wide range of applications, including gas sensing. In this work, the characteristics of the hybrid ZnO‐Bi2O3 and ZnO‐Zn2SnO4 tetrapod (T) networks are investigated in detail. The gas sensing studies reveal improved performance of the hybrid networks compared to pure ZnO‐T networks. For the ZnO‐T‐Bi2O3 networks, an enhancement in H2 gas response is obtained, although the observed p‐type sensing behavior is attributed to the formed junctions between the arms of ZnO‐T covered with Bi2O3 and the modulation of the regions where holes accumulate under exposure to H2 gas. In ZnO‐T‐Zn2SnO4 networks, a change in selectivity to CO gas with high response is noted. The devices based on individual ZnO‐T‐Bi2O3 and ZnO‐T‐Zn2SnO4 structures showed an enhanced H2 gas response, which is explained on the basis of interactions (electronic sensitization) between the ZnO‐T arm and Bi2O3 shell layer and single Schottky contact structure, respectively. Density functional theory‐based calculations provide mechanistic insights into the interaction of H2 and CO gas molecules with Bi‐ and Sn‐doped ZnO(0001) surfaces, revealing changes in the Fermi energies, as well as charge transfer between the molecules and surface species, which facilitate gas sensing.  相似文献   

15.
Transition‐metal oxides show genuine potential in replacing state‐of‐the‐art carbonaceous anode materials in lithium‐ or sodium‐ion batteries because of their much higher theoretical capacity. However, they usually undergo massive volume change, which leads to numerous problems in both material and electrode levels, such as material pulverization, instable solid‐electrolyte interphase, and electrode failure. Here, it is demonstrated that lithium‐ion breathable hybrid electrodes with 3D architecture tackle all these problems, using a typical conversion‐type transition‐metal oxide, Fe3O4, of which nanoparticles are anchored onto 3D current collectors of Ni nanotube arrays (NTAs) and encapsulated by δ‐MnO2 layers (Ni/Fe3O4@MnO2). The δ‐MnO2 layers reversibly switch lithium insertion/extraction of internal Fe3O4 nanoparticles and protect them against pulverizing and detaching from NTA current collectors, securing exceptional integrity retention and efficient ion/electron transport. The Ni/Fe3O4@MnO2 electrodes exhibit superior cyclability and high‐capacity lithium storage (retaining ≈1450 mAh g?1, ≈96% of initial value at 1 C rate after 1000 cycles).  相似文献   

16.
Novel composites composed of α‐Fe2O3 tetrakaidecahedrons and graphene oxide have been easily fabricated and demonstrated to be efficient photoelectrodes for photoelectrochemical water splitting reaction with superior photocurrent response. α‐Fe2O3 tetrakaidecahedrons are facilely synthesized in a green manner without any organic additives and then modified with graphene oxide. The morphological and structural properties of α‐Fe2O3/graphene composite are intensively investigated by several means, such as X‐ray diffraction, field‐emission scanning electron microscope, transmission electron microscope, X‐ray photoelectron spectroscopy, Fourier Transform infrared spectroscopy, and Raman spectroscopy. The tetrakaidecahedronal hematite particles have been indicated to be successfully coupled with graphene oxide. Systematical photoelectrochemical and impedance spectroscopy measurements have been carried out to investigate the favorable performance of α‐Fe2O3/graphene composites, which are found to be effective photoanodes with rapid, steady, and reproducible feature. The coupling of graphene with α‐Fe2O3 particles has greatly enhanced the photoelectrochemical performance, resulting in higher photocurrent and lower onset potential than that of pure α‐Fe2O3. This investigation has provided a feasible method to synthesize α‐Fe2O3 tetrakaidecahedron and fabricate an efficient α‐Fe2O3/graphene photoelectrode for photoelectrochemical water oxidation, suggesting a promising route to design noble metal free semiconductor/graphene photocatalysts.  相似文献   

17.
Ultrathin MnO2/graphene oxide/carbon nanotube (G/M@CNT) interlayers are developed as efficient polysulfide‐trapping shields for high‐performance Li–S batteries. A simple layer‐by‐layer procedure is used to construct a sandwiched vein–membrane interlayer of thickness 2 µm and areal density 0.104 mg cm?2 by loading MnO2 nanoparticles and graphene oxide (GO) sheets on superaligned carbon nanotube films. The G/M@CNT interlayer provides a physical shield against both polysulfide shuttling and chemical adsorption of polysulfides by MnO2 nanoparticles and GO sheets. The synergetic effect of the G/M@CNT interlayer enables the production of Li–S cells with high sulfur loadings (60–80 wt%), a low capacity decay rate (?0.029% per cycle over 2500 cycles at 1 C), high rate performance (747 mA h g?1 at a charge rate of 10 C), and a low self‐discharge rate with high capacity retention (93.0% after 20 d rest). Electrochemical impedance spectroscopy, cyclic voltammetry, and scanning electron microscopy observations of the Li anodes after cycling confirm the polysulfide‐trapping ability of the G/M@CNT interlayer and show its potential in developing high‐performance Li–S batteries.  相似文献   

18.
Manganese dioxide (MnO2) nanoparticles (NPs) were discovered in previous work to be effective in improving tumor oxygenation (hypoxia) and reducing H2O2 and acidity in the tumor microenvironment (TME) via local injection. To develop MnO2 formulations useful for clinical application, hybrid NPs are designed with tailored hydrophobicity and structure suitable for intravenous injection, with good blood circulation, biocompatibility, high tumor accumulation, and programmable oxygen generation rate. Two different hybrid NPs are constructed by embedding polyelectrolyte‐MnO2 (PMD) in hydrophilic terpolymer/protein‐MnO2 (TMD) or hydrophobic polymer/lipid‐MnO2 (LMD) matrices. The in vitro reactivity of the MnO2 toward H2O2 is controlled by matrix material and NP structure and dependent on pH with up to two‐fold higher O2 generation rate at acidic (tumor) pH than at systemic pH. The hybrid NPs are found to be safe to cells in vitro and organs in vivo and effectively decrease tumor hypoxia and hypoxia‐inducible‐factor‐1alpha through local or systemic administration. Fast acting TMD reduces tumor hypoxia by 70% in 0.5 h by local injection. Slow acting LMD exhibits superior tumor accumulation and retention through the systemic administration and decreased hypoxia by 45%. These findings encourage a broader use of hybrid MD NPs to overcome TME factors for cancer treatment.  相似文献   

19.
2D nanoscale oxides have attracted a large amount of research interest due to their unique properties. Here, a facile synthetic approach to prepare graphene‐mimicking, porous 2D Co3O4 nanofoils using graphene oxide (GO) as a sacrificial template is reported. The thermal instability of graphene, as well as the catalytic ability of Co3O4 particles to degrade carbon backbones, allow the fabrication of porous 2D Co3O4 nanofoils without the loss of the 2D nature of GO. Based on these results, a graphene mimicking as a route for large‐area 2D transition metal oxides for applications in electrochemical energy storage devices is proposed. As a proof of concept, it is demonstrated that graphene‐like, porous 2D Co3O4 nanofoils exhibit a high reversible capacity (1279.2 mAh g?1), even after 50 cycles. This capacity is far beyond the theoretical capacity of Co3O4 based on the conversion mechanism from Co3O4 to Li2O and metallic Co.  相似文献   

20.
Improving the antibacterial activity of H2O2 and reducing its usage are requirements for wound disinfection. Nanomaterials with intrinsic peroxidase‐like properties are developed to enhance the antibacterial performance of H2O2 and avoid the toxicity seen with high H2O2 levels. Here, Pd–Pt core–frame nanodendrites consist of a dense array of platinum (Pt) branches on a Pd core are synthesized, and subsequently converted to Pt hollow nanodendrites by selective removal of the Pd cores by wet etching. The fabricated Pt hollow nanodendrites exert striking peroxidase‐like activity due to the maximized utilization efficiency of the Pt atoms and the presence of high‐index facets on their surfaces. By catalyzing the decomposition of H2O2 into more toxic hydroxyl radicals (?OH), Pt hollow nanodendrites exhibit excellent bactericidal activity against both Gram‐negative and Gram‐positive bacteria with the assistance of low concentrations of H2O2. Furthermore, Pt hollow nanodendrites accelerate wound healing in the presence of low doses of H2O2. In addition, no obvious adverse effects are observed at the given dose of nanodendrites. These findings can be used to guide the design of noble metal‐based nanomaterials as potential enzyme‐mimetic systems and advance the development of nanoenzymes to potentiate the antibacterial activity of H2O2.  相似文献   

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