A Review on Low-Dimensional Nanomaterials: Nanofabrication, Characterization and Applications.

The development of modern cutting-edge technology relies heavily on the huge success and advancement of nanotechnology, in which nanomaterials and nanostructures provide the indispensable material cornerstone. Owing to their nanoscale dimensions with possible quantum limit, nanomaterials and nanostructures possess a high surface-to-volume ratio, rich surface/interface effects, and distinct physical and chemical properties compared with their bulk counterparts, leading to the remarkably expanded horizons of their applications. Depending on their degree of spatial quantization, low-dimensional nanomaterials are generally categorized into nanoparticles (0D); nanorods, nanowires, and nanobelts (1D); and atomically thin layered materials (2D). This review article provides a comprehensive guide to low-dimensional nanomaterials and nanostructures. It begins with the classification of nanomaterials, followed by an inclusive account of nanofabrication and characterization. Both top-down and bottom-up fabrication approaches are discussed in detail. Next, various significant applications of low-dimensional nanomaterials are discussed, such as photonics, sensors, catalysis, energy storage, diverse coatings, and various bioapplications. This article would serve as a quick and facile guide for scientists and engineers working in the field of nanotechnology and nanomaterials.

Rational design of hetero-dimensional C-ZnO/MoS2 nanocomposite anchored on 3D mesoporous carbon framework towards synergistically enhanced stability and efficient visible-light-driven photocatalytic activity.

For efficient solar energy harvesting, various engineering strategies to strengthen visible-light responsivity of ZnO photocatalyst is under intensive investigation. In this work, a new ternary C-ZnO/MoS2/mesoporous carbon nanocomposite was successfully prepared by a two-step solution-processed synthesis protocol. The ternary composite exhibits a well-interconnected 3D mesoporous microstructure assembled by carbon nanosheets, which is loaded with quasi 0D ZnO nanoparticles and 2D MoS2 nanosheets. The carbonaceous nanocomposites show enhanced visible-light-driven photocatalytic performance and high photo-corrosion resistance. The incorporation of carbon in the hybrid design has manifold benefits that drastically promotes the photoactivity and photostability. The significant enhancement in photodegradation activity of the hybrid catalysts can be ascribed to a few positive synergistic effects, such as increased surface area and active reaction sites, boosted surface charge utilization efficiency, and band-gap lowering. The high porosity of the distinct microstructure raises the dye adsorption within the material. Tailored interface/surface properties enable more effective mass transport and higher separation efficiency of photo-generated carriers. The modulated electronic structure leads to the narrowing of the ZnO optical bandgap. Meanwhile, coupling with carbon prevents ZnO from photo-corrosion. Our approach highlights the roles of carbon as structure directing and stabilizing agents as well as heteroatom in defect engineering for wide band-gap oxide materials. The rational material design of multivariate mixed-dimensional architecture also provides guiding insight for the advancement of heterogeneous photocatalyst materials with superior performance and durability. The presented engineering strategy would be a promising method for the preparation of nanomaterials supported on 3D carbon network with high porosity and visible-light-driven photocatalytic performance.

2D CTAB-MoSe2 Nanosheets and 0D MoSe2 Quantum Dots: Facile Top-Down Preparations and Their Peroxidase-Like Catalytic Activity for Colorimetric Detection of Hydrogen Peroxide.

We report the facile and economic preparation of two-dimensional (2D) and 0D MoSe2 nanostructures based on systematic and non-toxic top-down strategies. We demonstrate the intrinsic peroxidase-like activity of these MoSe2 nanostructures. The catalytic processes begin with facilitated decomposition of H2O2 by using MoSe2 nanostructures as peroxidase mimetics. In turn, a large amount of generated radicals oxidizes 3,3,5,5-tetramethylbenzidine (TMB) to produce a visible color reaction. The enzymatic kinetics of our MoSe2 nanostructures complies with typical Michaelis-Menten theory. Catalytic kinetics study reveals a ping-pong mechanism. Moreover, the primary radical responsible for the oxidation of TMB was identified to be È®2- by active species-trapping experiments. Based on the peroxidase mimicking property, we developed a new colorimetric method for H2O2 detection by using 2D and 0D MoSe2 nanostructures. It is shown that the colorimetric sensing capability of our MoSe2 catalysts is comparable to other 2D materials-based colorimetric platforms. For instance, the linear range of H2O2 detection is between 10 and 250 µM by using 2D functionalized MoSe2 nanosheets as an artificial enzyme. Our work develops a systematic approach to use 2D materials to construct novel enzyme-free mimetic for a visual assay of H2O2, which has promising prospects in medical diagnosis and food security monitoring.

Facile Bottom-up Preparation of WS2-Based Water-Soluble Quantum Dots as Luminescent Probes for Hydrogen Peroxide and Glucose.

Photoluminescent zero-dimensional (0D) quantum dots (QDs) derived from transition metal dichalcogenides, particularly molybdenum disulfide, are presently in the spotlight for their advantageous characteristics for optoelectronics, imaging, and sensors. Nevertheless, up to now, little work has been done to synthesize and explore photoluminescent 0D WS2 QDs, especially by a bottom-up strategy without using usual toxic organic solvents. In this work, we report a facile bottom-up strategy to synthesize high-quality water-soluble tungsten disulfide (WS2) QDs through hydrothermal reaction by using sodium tungstate dihydrate and L-cysteine as W and S sources. Besides, hybrid carbon quantum dots/WS2 QDs were further prepared based on this method. Physicochemical and structural analysis of QD hybrid indicated that the graphitic carbon quantum dots with diameters about 5 nm were held onto WS2 QDs via electrostatic attraction forces. The resultant QDs show good water solubility and stable photoluminescence (PL). The excitation-dependent PL can be attributed to the polydispersity of the synthesized QDs. We found that the PL was stable under continuous irradiation of UV light but can be quenched in the presence of hydrogen peroxide (H2O2). The obtained WS2-based QDs were thus adopted as an electrodeless luminescent probe for H2O2 and for enzymatic sensing of glucose. The hybrid QDs were shown to have a more sensitive LOD in the case of glucose sensing. The Raman study implied that H2O2 causes the partial oxidation of QDs, which may lead to oxidation-induced quenching. Overall, the presented strategy provides a general guideline for facile and low-cost synthesis of other water-soluble layered material QDs and relevant hybrids in large quantity. These WS2-based high-quality water-soluble QDs should be promising for a wide range of applications in optoelectronics, environmental monitoring, medical imaging, and photocatalysis.

Facile and Cost-Efficient Synthesis of Quasi-0D/2D ZnO/MoS2 Nanocomposites for Highly Enhanced Visible-Light-Driven Photocatalytic Degradation of Organic Pollutants and Antibiotics.

Nanoscale transition-metal dichalcogenide materials showed promising potential for visible-light responsive photocatalysis. Here, we report our investigations on the synthesis of heterodimensional nanostructures of two-dimensional (2D) ultrathin MoS2 nanosheets interspersed with ZnO nanoparticles by using a facile two-step method consisting of sonication-aided exfoliation technique followed by a wet chemical process. The photocatalytic activity of the nanocomposites was examined by studying the degradation of different organic dye pollutants and tetracycline, a common antibiotic, under visible-light irradiation. It is found that within 30 min more than 90 % of the model organic dye was photodegraded by the optimized quasi-0D/2D hybrid nanomaterial. The reaction rate of pollutant degradation is about five and eight times higher than those of the pristine MoS2 naonosheets and P25 photocatalysts, respectively. The outstanding photocatalytic activity of the heterodimensional hybrids can be attributed to a few beneficial features from the synergetic effects. Most importantly, the intimate junction between ZnO and MoS2 facilitates the separation of photogenerated carriers, leading to the enhancement of photocatalytic efficiency. A tentative photocatalytic degradation mechanism was proposed and tested. Overall, the present work provides valuable insights for the exploration of cost-effective nanoscale heterodimensional hybrids constructed from atomically thin layered materials.

Comparative Photothermal Performance among Various Sub-Stoichiometric 2D Oxygen-Deficient Molybdenum Oxide Nanoflakes and In†Vivo Toxicity.

The present study deals with photothermal therapy of solid tumors using different forms of oxygen-deficient sub-stoichiometric two-dimensional (2D) molybdenum oxide nanoflakes (α-MoO3-x ). Upon exfoliation of molybdenum oxide power using fine gridding followed by ultrasonication, bluish green molybdenum oxide (BG α-MoO3 ) was obtained. Oxygen vacancies in BG were generated upon irradiation with an intense xenon lamp. Irradiating the BG for 3 and 5 h, deep blue (B) and olive green (G) oxygen-deficient nanoflakes were obtained respectively. All exhibited high NIR absorption, making these nanomaterials suitable for photothermal therapy. All three forms were functionalized with polypyrrole (PPy@BG, PPy@B, PPy@G) to boost the photothermal stability and transduction efficiency. After functionalization and irradiation with 808 nm laser, the enhancement of temperature for BG, B, G was 50, 65, 52 °C respectively and the corresponding photothermal transduction efficiencies (PTE) were 29.32, 44.42 and 42.00 %. Each of the nanoflakes were found to be highly biocompatible and photostable both in vitro and in vivo. There was substantial decrease in the size of tumors after seven days of treatment on tumor-bearing experimental mice models.

Two dimensional α-MoO3-x nanoflakes as bare eye probe for hydrogen peroxide in biological fluids.

We report a rapid and facile method for detection of hydrogen peroxide (H2O2) in biological fluids using sub-stoichiometric two-dimensional (2D) molybdenum trioxide (α-MoO3-x) nanoflakes. The two-dimensional nanoflakes, initially blue in color, is oxidized after interaction with hydrogen peroxide thereby changing its oxidation state to form α-MoO3. The change in oxidation state of nanoflakes transforms from blue to a visually distinct hazy blue color with change in absorption spectrum. The phenomenal property is explored here in sensing up to 34 nM as limit of detection. The efficacy of the detection system was analyzed by "zone of inhibition" based agar diffusion assay with different concentrations of H2O2. The current approach is highly accurate, effective and reproducible for quantification of physiological concentration of H2O2 in biological fluid such as human urine.

Glucose oxidase assisted visual detection of glucose using oxygen deficient α-MoO3-x nanoflakes.

An optical method is described for the quantitation of glucose by using oxygen-deficient α-MoO3-x nanoflakes. It is based on the use of glucose oxidase (GOx) which produces hydrogen peroxide on oxidation of glucose. Hydrogen peroxide then oxidizes the α-MoO3-x nanoflakes, and this results in a visible color change from blue to colorless. The color change can be measured photometrically at 740 nm. The method has a 68 nM detection limit. Graphical Abstract Mechanism of glucose detection using blue colored oxygen deficient 2D α-MoO3-x nanoflakes. Hydrogen peroxide (H2O2) is formed as a by-product in the conversion of glucose to glucono-1,5-lactone by glucose oxidase (GOx). In the presence of H2O2, the oxygen vacancies in α-MoO3-x nanoflakes are filled up, and this leads to the loss of blue color of the nanoflakes because they are converted back to colorless bulk α-MoO3.

Full Solution-Processed Synthesis and Mechanisms of a Recyclable and Bifunctional Au/ZnO Plasmonic Platform for Enhanced UV/Vis Photocatalysis and Optical Properties.

The synthesis of noble metal/semiconductor hybrid nanostructures for enhanced catalytic or superior optical properties has attracted a lot of attention in recent years. In this study, a facile and all-solution-processed synthetic route was employed to demonstrate an Au/ZnO platform with plasmonic-enhanced UV/Vis catalytic properties while retaining strengthened luminescent properties. The visible-light response of photocatalysis is supported by localized surface plasmon resonance (LSPR) excitations while the enhanced performance under UV is aided by charge separation and strong absorption. The enhancement in optical properties is mainly due to local field enhancement effect and coupling between exciton and LSPR. Luminescent characteristics are investigated and discussed in detail. Recyclability tests showed that the Au/ZnO substrate is reusable by cleaning and has a long shelf life. Our result suggests that plasmonic enhancement of photocatalytic performance is not necessarily a trade-off for enhanced near-band-edge emission in Au/ZnO. This approach may give rise to a new class of versatile platforms for use in novel multifunctional and integrated devices.

Enhanced Photocatalytic Performance of ZnO Nanorods Coupled by Two-Dimensional α-MoO3 Nanoflakes under UV and Visible Light Irradiation.

We exploit the utilization of two-dimensional (2D) molybdenum oxide nanoflakes as a co-catalyst for ZnO nanorods (NRs) to enhance their photocatalytic performance. The 2D nanoflakes of orthorhombic α-MoO3 were synthesized through a sonication-aided exfoliation technique. The 2D MoO3 nanoflakes can be further converted to substoichiometric quasi-metallic MoO3-x by using UV irradiation. Subsequently, 1D-2D MoO3 /ZnO NR and MoO3-x /ZnO NR composite photocatalysts have been successfully synthesized. The photocatalytic performances of the novel nanosystems in the decomposition of methylene blue are studied by using UV- and visible-illumination setup. The incorporated 2D nanoflakes show a positive influence on the photocatalytic activity of the ZnO. The obtained rate constant values follow the order of pristine ZnO NR

Annealing effects on the optical and morphological properties of ZnO nanorods on AZO substrate by using aqueous solution method at low temperature.

Vertically aligned ZnO nanorods (NRs) on aluminum-doped zinc oxide (AZO) substrates were fabricated by a single-step aqueous solution method at low temperature. In order to optimize optical quality, the effects of annealing on optical and structural properties were investigated by scanning electron microscopy, X-ray diffraction, photoluminescence (PL), and Raman spectroscopy. We found that the annealing temperature strongly affects both the near-band-edge (NBE) and visible (defect-related) emissions. The best characteristics have been obtained by employing annealing at 400°C in air for 2 h, bringing about a sharp and intense NBE emission. The defect-related recombinations were also suppressed effectively. However, the enhancement decreases with higher annealing temperature and prolonged annealing. PL study indicates that the NBE emission is dominated by radiative recombination associated with hydrogen donors. Thus, the enhancement of NBE is due to the activation of radiative recombinations associated with hydrogen donors. On the other hand, the reduction of visible emission is mainly attributed to the annihilation of OH groups. Our results provide insight to comprehend annealing effects and an effective way to improve optical properties of low-temperature-grown ZnO NRs for future facile device applications.

Fabrication and photoresponse of ZnO nanowires/CuO coaxial heterojunction.

The fabrication and properties of n-ZnO nanowires/p-CuO coaxial heterojunction (CH) with a photoresist (PR) blocking layer are reported. In our study, c-plane wurtzite ZnO nanowires were grown by aqueous chemical method, and monoclinic CuO (111) was then coated on the ZnO nanowires by electrochemical deposition to form CH. To improve the device performance, a PR layer was inserted between the ZnO buffer layer and the CuO film to serve as a blocking layer to block the leakage current. Structural investigations of the CH indicate that the sample has good crystalline quality. It was found that our refined structure possesses a better rectifying ratio and smaller reverse leakage current. As there is a large on/off ratio between light on and off and the major light response is centered at around 424 nm, the experimental results suggest that the PR-inserted ZnO/CuO CH can be used as a good narrow-band blue light detector.

Room-temperature violet luminescence and ultraviolet photodetection of Sb-doped ZnO/Al-doped ZnO homojunction array.

A Sb-doped ZnO microrod array was fabricated on an Al-doped ZnO thin film by electrodeposition. Strong violet luminescence, originated from free electron-to-acceptor level transitions, was identified by temperature-dependent photoluminescence measurements. This acceptor-related transition was attributed to substitution of Sb dopants for Zn sites, instead of O sites, to form a complex with two Zn vacancies (VZn), the SbZn-2VZn complex. This SbZn-2VZn complex has a lower formation energy and acts as a shallow acceptor which can induce the observed strong violet luminescence. The photoresponsivity of our ZnO p-n homojunction device under a negative bias demonstrated a nearly 40-fold current gain, illustrating that our device is potentially an excellent candidate for photodetector applications in the ultraviolet wavelength region.