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1.
Hollow nanoparticles with large specific surface area and high atom utilization are promising catalysts for the hydrogen evolution reaction (HER). We describe herein the design and synthesis of a series of ultra-small hollow ternary alloy nanostructures using a simple one-pot strategy. The same technique was demonstrated for hollow PtNiCu nanoparticles, hollow PtCoCu nanoparticles and hollow CuNiCo nanoparticles. During synthesis, the displacement reaction and oxidative etching played important roles in the formation of hollow structures. Moreover, our hollow PtNiCu and PtCoCu nanoparticles were single crystalline, with an average diameter of 5 nm. Impressively, ultra-small hollow PtNiCu nanoparticles, containing only 10% Pt, exhibited greater electrocatalytic HER activity and stability than a commercial Pt/C catalyst. The overpotential of hollow PtNiCu nanoparticles at 10 mA cm−2 was 28 mV versus reversible hydrogen electrode (RHE). The mass activity was 4.54 A mgPt−1 at −70 mV versus RHE, which is 5.62-fold greater than that of a commercial Pt/C system (0.81 A mgPt−1). Through analyses of bonding and antibonding orbital filling, density functional theory calculations demonstrated that the bonding strength of different metals to the hydrogen intermediate (H*) was in the order of Pt > Co > Ni > Cu. The excellent HER performance of our hollow PtNiCu nanoparticles derives from moderately synergistic interactions between the three metals and H*. This work demonstrates a new strategy for the design of low-cost and high-activity HER catalysts.  相似文献   

2.
The functionalization of otherwise unreactive C–H bonds adds a new dimension to synthetic chemistry, yielding useful molecules for a range of applications. Arylation has emerged as an increasingly viable strategy for functionalization of heteroarenes which constitute an important class of structural moieties for organic materials. However, direct bisarylation of heteroarenes to enable aryl-heteroaryl-aryl bond formation remains a formidable challenge, due to the strong coordination between heteroatom of N or S and transitional metals. Here we report Pd interstitial nanocatalysts supported on ordered mesoporous carbon as catalysts for a direct and highly efficient bisarylation method for five-membered heteroarenes that allows for green and mild reaction conditions. Notably, in the absence of any base, ligands and phase transfer agents, high activity (turn-over frequency, TOF, up to 107 h−1) and selectivity (>99%) for the 2,5-bisarylation of five-membered heteroarenes are achieved in water. A combination of characterization reveals that the remarkable catalytic reactivity here is attributable to the parallel adsorption of heteroarene over Pd clusters, which breaks the barrier to electron transfer in traditional homogenous catalysis and creates dual electrophilic sites for aryl radicals and adsorbate at C2 and C5 positions. The d-band filling at Pd sites shows a linear relationship with activation entropy and catalytic activity. The ordered mesopores facilitate the absence of a mass transfer effect. These findings suggest alternative synthesis pathways for the design, synthesis and understanding of a large number of organic chemicals by ordered mesoporous carbon supported palladium catalysts.  相似文献   

3.
Blood analysis plays a major role in medical and science applications and white blood cells (WBCs) are an important target of analysis. We proposed an integrated microfluidic chip for direct and rapid trapping WBCs from whole blood. The microfluidic chip consists of two basic functional units: a winding channel to mix and arrays of two-layer trapping structures to trap WBCs. Red blood cells (RBCs) were eliminated through moving the winding channel and then WBCs were trapped by the arrays of trapping structures. We fabricated the PDMS (polydimethylsiloxane) chip using soft lithography and determined the critical flow velocities of tartrazine and brilliant blue water mixing and whole blood and red blood cell lysis buffer mixing in the winding channel. They are 0.25 μl/min and 0.05 μl/min, respectively. The critical flow velocity of the whole blood and red blood cell lysis buffer is lower due to larger volume of the RBCs and higher kinematic viscosity of the whole blood. The time taken for complete lysis of whole blood was about 85 s under the flow velocity 0.05 μl/min. The RBCs were lysed completely by mixing and the WBCs were trapped by the trapping structures. The chip trapped about 2.0 × 103 from 3.3 × 103 WBCs.  相似文献   

4.
Development of novel catalysts for nitrogen reduction at ambient pressures and temperatures with ultrahigh ammonia (NH3) yield and selectivity is challenging. In this work, an atomic catalyst with separated Pd atoms on graphdiyne (Pd-GDY) was synthesized, which shows fascinating electrocatalytic properties for nitrogen reduction. The catalyst has the highest average NH3 yield of 4.45 ± 0.30 mgNH3 mgPd−1 h−1, almost tens of orders larger than for previously reported catalysts, and 100% reaction selectivity in neutral media. Pd-GDY exhibits almost no decreases in NH3 yield and Faradaic efficiency. Density functional theory calculations show that the reaction pathway prefers to perform at the (Pd, C1, C2) active area because of the strongly coupled (Pd, C1, C2), which elevates the selectivity via enhanced electron transfer. By adjusting the p–d coupling accurately, reduction of self-activated nitrogen is promoted by anchoring atom selection, and side effects are minimized.  相似文献   

5.
Applying metal organic frameworks (MOFs) in electrochemical systems is a currently emerging field owing to the rich metal nodes and highly specific surface area of MOFs. However, the problems for MOFs that need to be solved urgently are poor electrical conductivity and low ion transport. Here we present a facile in situ growth method for the rational synthesis of MOFs@hollow mesoporous carbon spheres (HMCS) yolk–shell-structured hybrid material for the first time. The size of the encapsulated Zeolitic Imidazolate Framework-67 (ZIF-67) is well controlled to 100 nm due to the spatial confinement effect of HMCS, and the electrical conductivity of ZIF-67 is also increased significantly. The ZIF@HMCS-25% hybrid material obtained exhibits a highly efficient oxygen reduction reaction activity with 0.823 V (vs. reversible hydrogen electrode) half-wave potential and an even higher kinetic current density (JK = 13.8 mA cm−2) than commercial Pt/C. ZIF@HMCS-25% also displays excellent oxygen evolution reaction performance and the overpotential of ZIF@HMCS-25% at 10 mA cm−2 is 407 mV. In addition, ZIF@HMCS-25% is further employed as an air electrode for a rechargeable Zn–air battery, exhibiting a high power density (120.2 mW cm−2 at 171.4 mA cm−2) and long-term charge/discharge stability (80 h at 5 mA cm−2). This MOFs@HMCS yolk–shell design provides a versatile method for the application of MOFs as electrocatalysts directly.  相似文献   

6.
Contact interface properties are important in determining the performances of devices that are based on atomically thin two-dimensional (2D) materials, especially for those with short channels. Understanding the contact interface is therefore important to design better devices. Herein, we use scanning transmission electron microscopy, electron energy loss spectroscopy, and first-principles calculations to reveal the electronic structures within the metallic (1T′)-semiconducting (2H) MoTe2 coplanar phase boundary across a wide spectral range and correlate its properties to atomic structures. We find that the 2H-MoTe2 excitonic peaks cross the phase boundary into the 1T′ phase within a range of approximately 150 nm. The 1T′-MoTe2 crystal field can penetrate the boundary and extend into the 2H phase by approximately two unit-cells. The plasmonic oscillations exhibit strong angle dependence, that is a red-shift of π+σ (approximately 0.3–1.2 eV) occurs within 4 nm at 1T′/2H-MoTe2 boundaries with large tilt angles, but there is no shift at zero-tilted boundaries. These atomic-scale measurements reveal the structure–property relationships of the 1T′/2H-MoTe2 boundary, providing useful information for phase boundary engineering and device development based on 2D materials.  相似文献   

7.
Homogeneous molecular catalysts and heterogeneous catalysts possess complementary strengths, and are of great importance in laboratory/commercial procedures. While various porous hosts, such as polymers, carbons, silica, metal oxides and zeolites, have been used in an attempt to heterogenize homogeneous catalysts, realizing the integration of both functions at the expense of discounting their respective advantages, it remains a significant challenge to truly combine their intrinsic strengths in a single catalyst without compromise. Here, we describe a general template-assisted approach to incorporating soluble molecular catalysts into the hollow porous capsule, which prevents their leaching due to the absence of large intergranular space. In the resultant yolk (soluble)–shell (crystalline) capsules, the soluble yolks can perform their intrinsic activity in a mimetic homogeneous environment, and the crystalline porous shells endow the former with selective permeability, substrate enrichment, size-selective and heterogeneous cascade catalysis, beyond the integration of the respective advantages of homogeneous and heterogeneous catalysts.  相似文献   

8.
We report a 3D microfluidic device with 32 detection channels and 64 sheath flow channels and embedded microball lens array for high throughput multicolor fluorescence detection. A throughput of 358 400 cells/s has been accomplished. This device is realized by utilizing solid immersion micro ball lens arrays for high sensitivity and parallel fluorescence detection. High refractive index micro ball lenses (n = 2.1) are embedded underneath PDMS channels close to cell detection zones in channels. This design permits patterning high N.A. micro ball lenses in a compact fashion for parallel fluorescence detection on a small footprint device. This device also utilizes 3D microfluidic fabrication to address fluid routing issues in two-dimensional parallel sheath focusing and allows simultaneous pumping of 32 sample channels and 64 sheath flow channels with only two inlets.  相似文献   

9.
Tuning the surface-embellishing ligands of metal nanoparticles (NPs) is a powerful strategy to modulate their morphology and surface electronic and functional features, impacting their catalytic activity and selectivity. In this work, we report the design and synthesis of a polytriazolium organic cage PIC-T, capable of stabilizing PdNPs within its discrete cavity. The obtained material (denoted Pd@PCC-T) is highly durable and monodispersed with narrow particle-size distribution of 2.06 ± 0.02 nm, exhibiting excellent catalytic performance and recyclability in the Sonogashira coupling and tandem reaction to synthesize benzofuran derivatives. Further investigation indicates that the modulation of N-heterocyclic carbene sites embedded in the organic cage has an impact on NPs’ catalytic efficiency, thus providing a novel methodology to design superior NP catalysts.  相似文献   

10.
Some aqueous reactions in biological or chemical fields are accomplished at a high temperature. When the reaction temperature is higher than 100 °C, an autoclave reactor is usually required to elevate the boiling point of the water by creating a high-pressure environment in a closed system. This work presented an alternative continuous flowing microfluidic solution for aqueous reaction with a reaction temperature higher than 100 °C. The pressure regulating function was successfully fulfilled by a small microchannel based on a delicate hydrodynamic design. Combined with micro heater and temperature sensor that integrated in a single chip by utilizing silicon-based microfabrication techniques, this pressure regulating microchannel generated a high-pressure/high-temperature environment in the upstream reaction zone when the reagents continuously flow through the chip. As a preliminary demonstration, thermal digestion of aqueous total phosphorus sample was achieved in this continuous flowing micro-reactor at a working pressure of 990 kPa (under the working flow rate of 20 nl/s) along with a reaction temperature of 145 °C. This continuous flowing microfluidic solution for high-temperature reaction may find applications in various micro total analysis systems.  相似文献   

11.
We report on low-cost fabrication and high-energy density of full-cell lithium-ion battery (LIB) models. Super-hierarchical electrode architectures of Li2SiO3/TiO2@nano-carbon anode (LSO.TO@nano-C) and high-voltage olivine LiMnPO4@nano-carbon cathode (LMPO@nano-C) are designed for half- and full-system LIB-CR2032 coin cell models. On the basis of primary architecture-power-driven LIB geometrics, the structure keys including three-dimensional (3D) modeling superhierarchy, multiscale micro/nano architectures and anisotropic surface heterogeneity affect the buildup design of anode/cathode LIB electrodes. Such hierarchical electrode surface topologies enable continuous in-/out-flow rates and fast transport pathways of Li+-ions during charge/discharge cycles. The stacked layer configurations of pouch LIB-types lead to excellent charge/discharge rate, and energy density of 237.6 Wh kg−1. As the most promising LIB-configurations, the high specific energy density of hierarchical pouch battery systems may improve energy storage for long-driving range of electric vehicles. Indeed, the anisotropic alignments of hierarchical electrode architectures in the large-scale LIBs provide proof of excellent capacity storage and outstanding durability and cyclability. The full-system LIB-CR2032 coin cell models maintain high specific capacity of ∼89.8% within a long-term life period of 2000 cycles, and average Coulombic efficiency of 99.8% at 1C rate for future configuration of LIB manufacturing and commercialization challenges.  相似文献   

12.
Hydrogel optical light-guides have received substantial interest for applications such as deep-tissue biosensors, optogenetic stimulation and photomedicine due to their biocompatibility, (micro)structure control and tissue-like Young''s modulus. However, despite recent developments, large-scale fabrication with a continuous synthetic methodology, which could produce core-sheath hydrogel fibers with the desired optical and mechanical properties suitable for deep-tissue applications, has yet to be achieved. In this study, we report a versatile concept of integrated light-triggered dynamic wet spinning capable of continuously producing core-sheath hydrogel optical fibers with tunable fiber diameters, and mechanical and optical propagation properties. Furthermore, this concept also exhibited versatility for various kinds of core-sheath functional fibers. The wet spinning synthetic procedure and fabrication process were optimized with the rational design of the core/sheath material interface compatibility [core = poly(ethylene glycol diacrylate-co-acrylamide); sheath = Ca-alginate], optical transparency, refractive index and spinning solution viscosity. The resulting hydrogel optical fibers exhibited desirable low optical attenuation (0.18 ± 0.01 dB cm−1 with 650 nm laser light), excellent biocompatibility and tissue-like Young''s modulus (<2.60 MPa). The optical waveguide hydrogel fibers were successfully employed for deep-tissue cancer therapy and brain optogenetic stimulation, confirming that they could serve as an efficient versatile tool for diverse deep-tissue therapy and brain optogenetic applications.  相似文献   

13.
Despite extensive research and several stunning breakthroughs in the synthesis of interlocked molecular species, [3]catenanes, Borromean rings and ring-in-ring complexes are exceedingly rare and their targeted synthesis remains a formidable challenge. Herein, a series of Cp*Rh-based homogeneous and heterogeneous interlocked structures have been prepared by coordination-driven self-assembly, not only including metalla[2]catenanes and molecular Borromean rings, but also linear metalla[3]catenanes and ring-in-ring complexes. The interlocked structures are all based on bithiophenyl groups. The bithiophenyl groups effectively enhance the strength of the inter-ring interactions and play a crucial role in the formation of these interlocked structures. By taking advantage of the strong interaction between π-donor (D) and π-acceptor (A) groups, the electron-deficient methylviologen cation was introduced into a cationic metallarectangle based on bithiophenyl groups. Taking inspiration from these results, a cationic metallarectangle based on A units was threaded into a metallarectangle based on D units, leading to a heterogeneous D–A ring-in-ring structure.  相似文献   

14.
Most metal–organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to alkaline aqueous solutions, thus precluding their use as potential electrode materials for electrochemical energy storage devices. Here, we present the design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co3O4 nanocube@Co-MOF (Co3O4@Co-MOF), via a controllable and facile one-pot hydrothermal method under highly alkaline conditions. The obtained composite possesses exceptional alkaline stability, retaining its original structure in 3.0 M KOH for at least 15 days. Benefitting from the exceptional alkaline stability, unique structure, and larger surface area, the Co3O4@Co-MOF composite shows a specific capacitance as high as 1020 F g−1 at 0.5 A  g−1 and a high cycling stability with only 3.3% decay after 5000 cycles at 5 A g−1. The as-constructed solid-state flexible device exhibits a maximum energy density of 21.6 mWh cm−3.  相似文献   

15.
Microfluidic paper-based analytical devices (μPADs) are a promising solution for a wide range of point-of-care applications. The feasibility of inducing ion concentration polarization (ICP) on μPADs has thus far attracted little attention. Accordingly, this study commences by demonstrating the ICP phenomenon in a μPAD with a Nafion ion-selective membrane. We are the first to measure the current-voltage curve on a Nafion-coated μPAD in order to indicate that the ion depletion occurs and the ICP is triggered when the current reaches the limiting current. The ICP effect is then exploited to preconcentrate fluorescein on μPADs incorporating straight and convergent channels. By an optimal geometric design, it is shown that the convergent channel results in a greater preconcentration effect than the straight channel. Specifically, a 20-fold enhancement in the sample concentration is achieved after 130 s given an initial concentration of 10?5 M and an external potential of 50 V. By contrast, the straight channel yields only a 10-fold improvement in the concentration after 180 s. Further, the practical feasibility of the proposed convergent-channel μPAD is demonstrated using fluorescein isothiocyanate labeled bovine serum albumin. The experimental results show that a 15-fold enhancement of the initial sample concentration (10?5 M) is obtained after 120 s given an external potential of 50 V.  相似文献   

16.
We present an immunoaggregation assay chip for multiplexed biomarkers detection. This chip is based on immunoaggregation of antibody functionalized microparticles (Ab-MPs) to quantify concentrations of multiple biomarkers simultaneously. A mixture of multiple types of Ab-MPs probes with different sizes and magnetic properties, which were functionalized by different antibodies, was used for the multiplexed assay. The interactions between biomarkers and their specific Ab-MPs probes caused the immunoaggregation of Ab-MPs. A two-stage micro resistive pulse sensor was used to differentiate and count the Ab-MP aggregates triggered by different biomarkers via size and magnetic property for multiplexed detection. The volume fraction of each type of Ab-MP aggregates indicates the concentration of the corresponding target biomarker. In our study, we demonstrated multiplexed detection of two model biomarkers (human ferritin and mouse anti-rabbit IgG) in 10% fetal bovine serum, using anti-ferritin Ab and anti-mouse IgG Ab functionalized MPs. We found that the volume fraction of Ab-MP aggregates increased with the increased biomarker concentrations. The detection ranges from 5.2 ng/ml to 208 ng/ml and 3.1 ng/ml to 5.12 × 104 ng/ml were achieved for human ferritin and mouse anti-rabbit IgG. This bioassay chip is able to quantitatively detect multiple biomarkers in a single test without fluorescence or enzymatic labeling process and hence is promising to serve as a useful tool for rapid detection of multiple biomarkers in biomedical research and clinical applications.  相似文献   

17.
In this study, a multiple sample dispenser for precisely metered fixed volumes was successfully designed, fabricated, and fully characterized on a plastic centrifugal lab-on-a-disk (LOD) for parallel biochemical single-end-point assays. The dispenser, namely, a centrifugal multiplexing fixed-volume dispenser (C-MUFID) was designed with microfluidic structures based on the theoretical modeling about a centrifugal circumferential filling flow. The designed LODs were fabricated with a polystyrene substrate through micromachining and they were thermally bonded with a flat substrate. Furthermore, six parallel metering and dispensing assays were conducted at the same fixed-volume (1.27 μl) with a relative variation of ±0.02 μl. Moreover, the samples were metered and dispensed at different sub-volumes. To visualize the metering and dispensing performances, the C-MUFID was integrated with a serpentine micromixer during parallel centrifugal mixing tests. Parallel biochemical single-end-point assays were successfully conducted on the developed LOD using a standard serum with albumin, glucose, and total protein reagents. The developed LOD could be widely applied to various biochemical single-end-point assays which require different volume ratios of the sample and reagent by controlling the design of the C-MUFID. The proposed LOD is feasible for point-of-care diagnostics because of its mass-producible structures, reliable metering/dispensing performance, and parallel biochemical single-end-point assays, which can identify numerous biochemical.  相似文献   

18.
Lithium metal is one of the most promising anode materials for high-energy-density Li batteries. However, low stability caused by dendrite growth and volume change during cycling hinders its practical application. Herein, we report an ingenious design of bio-inspired low-tortuosity carbon with tunable vertical micro-channels to be used as a host to incorporate nanosized Sn/Ni alloy nucleation sites, which can guide Li metal''s plating/stripping and meanwhile accommodate the volume change. The pore sizes of the vertical channels of the carbon host can be regulated to investigate the structure–performance correlation. After compositing Li, the bio-inspired carbon host with the smallest pore size (∼14 μm) of vertical channels exhibits the lowest overpotential (∼18 mV at 1 mA cm−2), most stable tripping/plating voltage profiles, and best cycling stability (up to 500 cycles) in symmetrical cells. Notably, the carbon/Li composite anode is more rewarding than Li foil when coupled with LiFePO4 in full cells, exhibiting a much lower polarization effect, better rate capability and higher capacity retention (90.6% after 120 cycles). This novel bio-inspired design of a low-tortuosity carbon host with nanoalloy coatings may open a new avenue for fabricating advanced Li-metal batteries with high performance.  相似文献   

19.
A rapid and simple technique is proposed for methanol concentration detection using a PMMA (Polymethyl-Methacrylate) microfluidic chip patterned using a commercially available CO2 laser scriber. In the proposed device, methanol and methanol oxidase (MOX) are injected into a three-dimensional circular chamber and are mixed via a vortex stirring effect. The mixture is heated to prompt the formation of formaldehyde and is flowed into a rectangular chamber, to which fuchsin-sulphurous acid is then added. Finally, the microchip is transferred to a UV spectrophotometer for methanol detection purposes. The experimental results show that a correlation coefficient of R2 = 0.9940 is obtained when plotting the optical density against the methanol concentration for samples and an accuracy as high as 93.1% are compared with the determined by the high quality gas chromatography with concentrations in the range of 2 ∼ 100 ppm. The methanol concentrations of four commercial red wines are successfully detected using the developed device. Overall, the results show that the proposed device provides a rapid and accurate means of detecting the methanol concentration for a variety of applications in the alcoholic beverage inspection and control field.  相似文献   

20.
A new microchannel with a series of symmetric sharp corner structures is reported for passive size-dependent particle separation. Micro particles of different sizes can be completely separated based on the combination of the inertial lift force and the centrifugal force induced by the sharp corner structures in the microchannel. At appropriate flow rate and Reynolds number, the centrifugal force effect on large particles, induced by the sharp corner structures, is stronger than that on small particles; hence after passing a series of symmetric sharp corner structures, large particles are focused to the center of the microchannel, while small particles are focused at two particle streams near the two side walls of the microchannel. Particles of different sizes can then be completely separated. Particle separation with this device was demonstrated using 7.32 μm and 15.5 μm micro particles. Experiments show that in comparison with the prior multi-orifice flow fractionation microchannel and multistage-multiorifice flow fractionation microchannel, this device can completely separate two-size particles with narrower particle stream band and larger separation distance between particle streams. In addition, it requires no sheath flow and complex multi-stage separation structures, avoiding the dilution of analyte sample and complex operations. The device has potentials to be used for continuous, complete particle separation in a variety of lab-on-a-chip and biomedical applications.  相似文献   

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