RESUMEN

The development of advanced functional nanomaterials for solid-phase microextraction (SPME) remains an imperative aspect of sample pretreatment. Herein, we introduce a novel SPME fiber consisting of graphene fibers modified with ordered mesoporous carbon nanotubes arrays (CNTAs) tailored for the determination of benzene series in oilfield wastewater, which is synthesized by an ionic liquid-assisted wet spinning process of graphene nanosheets, followed by a precisely controlled growth of metal-organic framework and subsequent pyrolysis treatment. The resulting robust microfiber structure resembles a "hairbrush" configuration, with a crumpled graphene fiber "stem" and high-order mesoporous CNTAs "hairs". This unique architecture significantly enhances the SPME capacity, as validated by gas chromatography-mass spectrometry. The hairbrush-like nanocarbon assembled microfibers possess structural characteristics, a high specific surface area, and numerous binding sites, offering efficient enrichment of benzene series compounds in oilfield wastewater, including benzene, ethylbenzene, m-xylene, p-xylene, and toluene. Our analysis demonstrates that these microfibers exhibit broad linear ranges (0.2-600 µg L-1), low detection limits (0.005-0.03 mg L-1), and excellent repeatability (3.2-5.5% for one fiber, 2.1-6.7% for fiber-to-fiber) for detection. When compared to commercial alternatives, these hairbrush-like nanocarbon-assembled microfibers exhibit significantly enhanced extraction efficiency for benzene series compounds.

RESUMEN

Efficient separation, enrichment, and detection of bacteria in diverse media are pivotal for identifying bacterial diseases and their transmission pathways. However, conventional bacterial detection methods that split the separation and detection steps are plagued by prolonged processing times. Herein, a multistage annular functionalized carbon nanotube array device designed for the seamless integration of complex biological sample separation and multimarker detection is introduced. This device resorts to the supersmooth fluidity of the liquid sample in the carbon nanotubes interstice through rotation assistance, achieving the ability to quickly separate impurities and capture biomarkers (1 mL sample cost time of 2.5 s). Fluid dynamics simulations show that the reduction of near-surface hydrodynamic resistance drives the capture of bacteria and related biomarkers on the functionalized surface of carbon nanotube in sufficient time. When further assembled as an even detection device, it exhibited fast detection (<30 min), robust linear correlation (101-107 colony-forming units [CFU] mL-1, R2 = 0.997), ultrasensitivity (limit of detection = 1.7 CFU mL-1), and multitarget detection (Staphylococcus aureus, extracellular vesicles, and enterotoxin proteins). Collectively, the material and system offer an expanded platform for real-time diagnostics, enabling integrated rapid separation and detection of various disease biomarkers.

Asunto(s)

RESUMEN

In the era of big data, the growing demand for data transmission capacity requires the communication band to expand from the traditional optical communication windows (∼1.3-1.6 µm) to the 2 µm band (1.8-2.1 µm). However, the largest bandwidth (∼30 GHz) of the current high-speed photodetectors for the 2 µm window is considerably less than the developed 1.55 µm band photodetectors based on III-V materials or germanium (>100 GHz). Here, we demonstrate a high-performance carbon nanotube (CNT) photodetector that can operate in both the 2 and 1.55 µm wavelength bands based on high-density CNT arrays on a quartz substrate. The CNT photodetector exhibits a high responsivity of 0.62 A/W and a large 3 dB bandwidth of 40 GHz (setup-limited) at 2 µm. The bandwidth is larger than that of existing photodetectors working in this wavelength range. Moreover, the CNT photodetector operating at 1.55 µm exhibits a setup-limited 3 dB bandwidth over 67 GHz at zero bias. Our work indicates that CNT photodetectors with high performance and low cost have great potential for future high-speed optical communication at both the 2 and 1.55 µm bands.

RESUMEN

The controllability of the microstructure of a compressed hierarchical building block is essential for optimizing a variety of performance parameters, such as thermal management. However, owing to the strong orientation effect during compression molding, optimizing the alignment of materials perpendicular to the direction of pressure is challenging. Herein, to illustrate the effect of the ordered microstructure on heat dissipation, thermally conductive carbon-based materials are fabricated by tailoring dense, orientation-tunable, and interleaved structures. Vertically aligned carbon nanotube arrays (VACNTs) interconnected with graphene films (GF) are prepared as a 3D core-ordered material to fabricate compressed building blocks of O-VA-GF and S-VA-GF. Leveraging the densified interleaved structure offered by VACNTs, the hierarchical O-VA-GF achieves excellent through-plane (41.7 W m-1 K-1 ) and in-plane (397.9 W m-1 K-1 ) thermal conductivities, outperforming similar composites of S-VA-GF (through-plane: 10.3 W m-1 K-1 and in-plane: 240.9 W m-1 K-1 ) with horizontally collapsed carbon nanotubes. As heat dissipation plates, these orderly assembled composites yield a 144% and 44% enhancement in the cooling coefficient compared with conventional Si3 N4 for cooling high-power light-emitting diode chips.

RESUMEN

Arrays of aligned carbon nanotubes (CNTs) are anisotropic nanomaterials possessing a high length-to-diameter aspect ratio, channels passing through the array, and mechanical strength along with flexibility. The arrays are produced in one step using aerosol-assisted catalytic chemical vapor deposition (CCVD), where a mixture of carbon and metal sources is fed into the hot zone of the reactor. Metal nanoparticles catalyze the growth of CNTs and, during synthesis, are partially captured into the internal cavity of CNTs. In this work, we considered various stages of multi-walled CNT (MWCNT) growth on silicon substrates from a ferrocene-toluene mixture and estimated the amount of iron in the array. The study showed that although the mixture of precursors supplies evenly to the reactor, the iron content in the upper part of the array is lower and increases toward the substrate. The size of carbon-encapsulated iron-based nanoparticles is 20-30 nm, and, according to X-ray diffraction data, most of them are iron carbide Fe3C. The reasons for the gradient distribution of iron nanoparticles in MWCNT arrays were considered, and the possibilities of controlling their distribution were evaluated.

RESUMEN

Recently, aluminum-air batteries have attracted great interest owing to their high output energy density, low cost, and feasibility to store and transport Al metal. However, the commercial application is still hindered by the lack of a high-performance air cathode, where the oxygen reduction reaction (ORR) happens, requiring fast charge transfer and mass transport at the catalyst-electrolyte-air interface. Herein, we report an aerophilic air cathode featuring both high intrinsic catalytic activity and large three-phase interface to facilitate air transport, which is prepared by growing cobalt-embedded and nitrogen-doped carbon nanotube (CoNCNT) arrays on carbon fiber paper and then modifying surface wettability with polytetrafluoroethylene solution. The optimized air electrode during the ORR shows a high onset potential of 0.95 V and fast current increase of 342.96 mA cm-2 V-1, which is comparable to the commercial 20 wt % Pt/C, and has even better stability under the same conditions. Moreover, the aluminum-air battery with the aerophilic air electrode is superior to the battery with a commercial Pt/C electrode or aerophobic electrode in terms of maximum power density and long discharging durability. Bubble behavior measurement shows that aerobic wettability plays an important role in gas transport, thus controlling ORR efficiency of the air electrode. The concept of the gas-wettable electrode proves to be effective in the enhancement of oxygen reduction kinetics and would be also adapted in other gas-involved electrodes for energy-related applications.

RESUMEN

W atoms/clusters are employed to in situ assist the development of layered vertically aligned carbon nanotube arrays (VACNTs) through hot-filament-assisted chemical vapor deposition (HFCVD) with liquid binary Fe3O4/AlOx catalysts. The hot W filament was utilized to in situ evaporate atomic W and form W clusters on Fe catalysts, which have a strong impact on the growth of layered VACNT arrays. The migration and Ostwald ripening of Fe catalysts are found to be suppressed immediately with more W clusters deposition during CNT growth. Through controlling the deposition of W clusters, the electrochemical energy storage performance of as-prepared layered VACNT arrays is also tunable as electrodes of ion-based supercapacitors. The layered VACNT arrays can achieve a high capacity of 83.1 mF cm-2 and possess desirable rate performance due to the suitable hot filament condition (55 W for 90 s). This work provides a new perspective to in-depth understand the behavior of W filament during HFCVD and the significant role of the in situ generated W clusters on the growth of CNTs by maintaining the catalytic activity and structure of catalysts.

RESUMEN

In-situ growth of high-density single-walled carbon nanotube (SWNT) arrays with homogeneity is highly desirable for integrated circuits. However, disastrous migration and aggregation of catalyst nanoparticles on substrate has greatly limited the area of as-grown SWNT arrays. Herein, we develop a magnesium-assisted catalyst anchoring strategy to restrain catalyst nanoparticles sintering on substrate. Magnesium modification ameliorates sapphire surface by high temperature solid reaction and thus provides a stronger metal-support interaction (SMSI). Hereby, we realize the direct growth of high-density SWNT arrays that fully cover an entire 10×10 mm2 substrate with the local highest density of ≈110 tubes µm-1 using iron as catalyst. This strategy was also proven universal when employing solid carbide catalysts.

RESUMEN

Vertically aligned carbon nanotube (CNT) arrays show potential for the development of planar low-voltage emission cathodes. The characteristics of cathodes can be improved by modifying their surface, e.g., by hydrogen plasma treatment, as was performed in this work. The surface of multi-walled CNT arrays grown on silicon substrates from toluene and ferrocene using catalytic chemical vapor deposition was treated in a high-pressure (~104 Pa) microwave reactor. The structure, composition, and current-voltage characteristics of the arrays were studied before and after hydrogen plasma treatment at various power values and durations. CNT tips were destroyed and catalytic iron was released from the CNT channels. The etching rate was influenced by iron particles that formed on the array surface. The lower emission threshold in the plasma-treated arrays than in the initial sample is explained by the amplification factor of the local electric field increasing due to graphene structures of unfolded nanotube layers that formed at the CNT tips.

RESUMEN

In this work, bipolar electrochemistry is used to perform wireless indirect electrodeposition of two different polymer coatings on both sides of carbon nanotube arrays. Using a thermoresponsive hydrogel on one side and an inert insoluble polymer on the other side, it is possible to generate, in a single step, a nanoporous reservoir with Janus character closed on one side by a thermoresponsive membrane. The thermoresponsive polymer, poly(N-isopropylacrylamide) (pNIPAM), is generated by the local reduction of persulfate ions, which initiates radical polymerization of NIPAM. Electrophoretic paint (EP) is chosen as an inert polymer. It is deposited by precipitation because of a local decrease in pH during water oxidation. Both polymers can be deposited simultaneously on opposite sides of the bipolar electrode during the application of the electric field, yielding a double-modified Janus object. Moreover, the length and thickness of the polymer layers can be controlled by varying the electric field and the deposition time. This concept is applied to vertically aligned carbon nanotube arrays (VACNTs), trapped inside an anodic aluminum oxide membrane, which can further be used as a smart reservoir for chemical storage and release. A fluorescent dye is loaded in the VACNTs and its release is studied as a function of temperature. Low temperature, when the hydrogel layer is in the swollen state, allows diffusion of the molecule. Dye release occurs on the hydrogel-modified side of the VACNTs. At high temperatures, when the hydrogel layer is in the collapsed state, dye release is blocked because of the impermeability of the pNIPAM layer. This concept paves the way toward the design of advanced devices in the fields of drug storage and directed delivery.

RESUMEN

Boosting electrochemical sodium storage properties is achieved by utilizing functionalized N-doped carbon nanotube arrays (NCNAs) as anode materials. The NCNA anodes are first fabricated by self-polymerization of dopamine on cobalt hydroxide nanorod arrays as the template. The NCNAs with diameters of 100-120 nm are grown vertically to Ni foam, forming self-supported nanotube arrays. Such a structure has attractive advantages including large porosity and surface area, good electrical conductivity and mechanical strength. Consequently, the NCNAs are demonstrated to achieve excellent sodium storage performances with high capacity (335 mA h g-1 at 100 mA g-1), good rate capability (140 mA h g-1 at 2 A g-1), and superior capacity retention of 90.9% after 500 cycles. Especially, high performance is verified in the assembled full cells by using an NCNA anode and Na3V2(PO4)3/C cathode. The developed synthetic strategy provides an effective approach for the fabrication of advanced heteroatom-doped carbon-based electrodes for electrochemical energy storage.

RESUMEN

Vertically aligned carbon nanotube arrays (VACNTs) show a great potential for various applications, such as thermal interface materials (TIMs). Besides the thermally oxidized SiO2, atomic layer deposition (ALD) was also used to synthesize oxide buffer layers before the deposition of the catalyst, such as Al2O3, TiO2, and ZnO. The growth of VACNTs was found to be largely dependent on different oxide buffer layers, which generally prevented the diffusion of the catalyst into the substrate. Among them, the thickest and densest VACNTs could be achieved on Al2O3, and carbon nanotubes were mostly triple-walled. Besides, the deposition temperature was critical to the growth of VACNTs on Al2O3, and their growth rate obviously reduced above 650 °C, which might be related to the Ostwald ripening of the catalyst nanoparticles or subsurface diffusion of the catalyst. Furthermore, the VACNTs/graphene composite film was prepared as the thermal interface material. The VACNTs and graphene were proved to be the effective vertical and transverse heat transfer pathways in it, respectively.

RESUMEN

Vertically aligned carbon nanotube (CNT) arrays are promising candidates for advanced thermal interface materials (TIMs) since they possess high mechanical compliance and high intrinsic thermal conductivity. Some of the previous works indicate that the CNT arrays in direct dry contact with the target surface possess low contact thermal conductance, which is the dominant thermal resistance. Using a phase sensitive transient thermo-reflectance (PSTTR) technique, we measure the thermal conductance between CNT arrays and copper (Cu) surfaces under different pressures. The experiments demonstrated that the contact force is one of the crucial factors for optimizing the thermal performance of CNT array-based TIMs. The experimental results suggest that the Cu-CNT arrays' contact thermal conductance has a strong dependence on the surface deformation and has an order of magnitude rise as the contact pressure increases from 0.05 to 0.15 MPa. However, further increase of the contact pressure beyond 0.15 MPa has little effect on the contact thermal resistance. This work could provide guidelines to determine the minimum requirement of packaging pressure on CNT TIMs.

RESUMEN

A three-dimensional hierarchical nanohybrid based on Cu-Au bimetallic nanocrystals integrated carbon nanotube arrays vertically grown on carbon spheres was successfully developed as an active platform for sensing application. Such nanohybrid can provide abundant active sites and act as an exceptional platform for immobilizing highly dense and well-dispersed carcinoembryonic antibody (anti-CEA) to sensitively detect CEA, an emerging biomarker of various cancer diseases. Due to the unique nanoarchitecture with altered electronic structure of Cu-Au bimetallic catalyst and enhanced interactions between components, such nanohybrid based biosensor demonstrated excellent electrochemical performance towards CEA detection with great sensitivity, wide linear detection range (0.025-25 ng/mL), very low limit of detection (0.5 pg/mL), and good selectivity. The results imply that this sensor has great potential to offer essential information for cancer diagnosis and management with great clinical importance.

Asunto(s)

RESUMEN

The rapidly growing demand for in situ real-time monitoring of chemical information in vitro and in vivo has attracted tremendous research efforts into the design and construction of high-performance biosensor devices. Herein, we develop a new type of flexible nanohybrid microelectrode based on carbon fiber wrapped by gold nanoparticles decorated nitrogen-doped carbon nanotube arrays, and explore its practical application in in situ electrochemical detection of cancer biomarker H2O2 secreted from live cancer cells. Our results demonstrate that carbon fiber material with microscale size and fascinating mechanical properties can be used as a robust and flexible microelectrode substrate in the electrochemical biosensor system. And the highly ordered nitrogen-doped carbon nanotube arrays that grown on carbon fiber possess high surface area-to-volume ratio and abundant active sites, which facilitate the loading of high-density and uniformly dispersed gold nanoparticles on it. Benefited from the unique microstructure and excellent electrocatalytic properties of different components in the nanohybrid fiber microelectrode, an effective electrochemical sensing platform based on it has been built up for the sensitive and selective detection of H2O2, the detection limit is calculated to be 50nM when the signal-to-noise ratio is 3:1, and the linear dynamic range is up to 4.3mM, with a high sensitivity of 142µAcm-2mM-1. These good sensing performances, coupled with its intrinsic mechanical flexibility and biocompatibility, allow for its use in in situ real-time tracking H2O2 secreted from breast cancer cell lines MCF-7 and MBA-MD-231, and evaluating the sensitivity of different cancer cells to chemotherapy or radiotherapy treatments, which hold great promise for clinic application in cancer diagnose and management.

Asunto(s)

RESUMEN

The unique structure of a vertically aligned carbon nanotube (VACNT) array makes it behave most similarly to a blackbody. It is reported that the optical absorptivity of an extremely black VACNT array is about 0.98-0.99 over a large spectral range of 200 nm-200 µm, inspiring us to explore the performance of VACNT arrays in solar energy harvesting. In this work, we report the highly efficient steam generation simply by laminating a layer of VACNT array on the surface of water to harvest solar energy. It is found that under solar illumination the temperature of upper water can significantly increase with obvious water steam generated, indicating the efficient solar energy harvesting and local temperature rise by the thin layer of VACNTs. We found that the evaporation rate of water assisted by VACNT arrays is 10 times that of bare water, which is the highest ratio for solar-thermal-steam generation ever reported. Remarkably, the solar thermal conversion efficiency reached 90%. The excellent performance could be ascribed to the strong optical absorption and local temperature rise induced by the VACNT layer, as well as the ultrafast water transport through the VACNT layer due to the frictionless wall of CNTs. Based on the above, we further demonstrated the application of VACNT arrays in solar-driven desalination.

RESUMEN

We demonstrate the thermal conductivity enhancement of the vertically aligned carbon nanotube (CNT) arrays (from ∼15.5 to 29.5 W/mK, ∼90% increase) by encapsulating outer boron nitride nanotube (BNNT, 0.97 nm-thick with ∼3-4 walls). The heat transfer enhancement mechanism of the coaxial C@BNNT was further revealed by molecular dynamics simulations. Because of their highly coherent lattice structures, the outer BNNT serves as additional heat conducting path without impairing the thermal conductance of inner CNT. This work provides deep insights into tailoring the heat transfer of arbitrary CNT arrays and will enable their broader applications as thermal interface material.

RESUMEN

ABSTRACT: The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays (VACNTs) through single-step CVD growth is investigated. The evolution of the structures and defect concentration of the VACNTs are tracked by scanning electron microscopy (SEM) and Raman spectroscopy. During the growth, the catalyst particles are stayed constantly on the substrate. The precipitation of the second CNT layer happens at around 30 min as proved by SEM. During the growth of the first layer, catalyst nanoparticles are deactivated with the accumulation of amorphous carbon coatings on their surfaces, which leads to the termination of the growth of the first layer CNTs. Then, the catalyst particles are reactivated by the hydrogen in the gas flow, leading to the precipitation of the second CNT layer. The growth of the second CNT layer lifts the amorphous carbon coatings on catalyst particles and substrates. The release of mechanical energy by CNTs provides big enough energy to lift up amorphous carbon flakes on catalyst particles and substrates which finally stay at the interfaces of the two layers simulated by finite element analysis. This study sheds light on the termination mechanism of CNTs during CVD process. GRAPHICAL ABSTRACT: The mechanism for the formation of double-layer vertically aligned carbon nanotube arrays (VACNTs) through single-step CVD growth was investigated. The growth of the second CNT layer lifts the amorphous carbon coatings on catalyst particles and substrates.

RESUMEN

A micro-/nanostructured "superaerophilic" electrode constructed by direct growth of cobalt-incorporated and nitrogen-doped carbon-nanotube arrays with subsequent hydrophobic modification is demonstrated for a high-performance oxygen-reduction-reaction electrode, superior to the Pt/C-air electrode. This high performance is attributed to the simultaneously accelerated gas-diffusion and electron-transport processes induced by the unique structural advantages.

RESUMEN

Previous research demonstrated that arrays of vertically aligned carbon nanotubes (VACNTs) exhibit strong frictional properties. Experiments indicated a strong decrease of the friction coefficient from the first to the second sliding cycle in repetitive measurements on the same VACNT spot, but stable values in consecutive cycles. VACNTs form clusters under shear applied during friction tests, and self-organization stabilizes the mechanical properties of the arrays. With increasing load in the range between 300 µN and 4 mN applied normally to the array surface during friction tests the size of the clusters increases, while the coefficient of friction decreases. To better understand the experimentally obtained results, we formulated and numerically studied a minimalistic model, which reproduces the main features of the system with a minimum of adjustable parameters. We calculate the van der Waals forces between the spherical friction probe and bunches of the arrays using the well-known Morse potential function to predict the number of clusters, their size, instantaneous and mean friction forces and the behaviour of the VACNTs during consecutive sliding cycles and at different normal loads. The data obtained by the model calculations coincide very well with the experimental data and can help in adapting VACNT arrays for biomimetic applications.