High performance organic devices including polymer solar cells (PSCs) and light emitting diodes (PLEDs) were successfully demonstrated with the presence of highly ordered nanoimprinted Au nanodisks (Au NDs) in their solution-processed active/emissive layers, respectively. PSCs and PLEDs were fabricated using a low bandgap polymer and acceptor, nitrogen doped multiwalled carbon nanotubes poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]-thiophenediyl] (n-MWCNTs:PTB7), and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) and (4,4-N,N-dicarbazole) biphenyl (CBP) doped with tris(2-phenylpyridine) iridium(iii) (Ir(ppy)3) as active/emissive layers, respectively. We synthesized nitrogen doped graphene and used it as anodic buffer layer in both devices. The localized surface plasmon resonance (LSPR) effect from Au NDs clearly contributed to the increase in light absorption/emission in the active layers from electromagnetic field enhancement, which originated from the excited LSPR in PSCs and PLEDs. In addition to the high density of LSPR and strong exciton-SP coupling, the electroluminescent (EL) enhancement is ascribed to enhanced spontaneous emission rates. This is due to the plasmonic near-field effect induced by Au NDs. The PSCs and PLEDs exhibited 14.98% (8.08% to 9.29%) under one sun of simulated air mass 1.5 global (AM1.5G) illumination (100 mW cm(-2)) and 19.18% (8.24 to 9.82 lm W(-1)) enhancement in the power conversion efficiencies (PCEs) compared to the control devices without Au NDs.
Successful application of a magnetophoretic separation technique for harvesting biological cells often relies on the need to tag the cells with magnetic nanoparticles. This study investigates the underlying principle behind the attachment of iron oxide nanoparticles (IONPs) onto microalgal cells, Chlorella sp. and Nannochloropsis sp., in both freshwater and seawater, by taking into account the contributions of various colloidal forces involved. The complex interplay between van der Waals (vdW), electrostatic (ES) and Lewis acid-base interactions (AB) in dictating IONP attachment was studied under the framework of extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) analysis. Our results showed that ES interaction plays an important role in determining the net interaction between the Chlorella sp. cells and IONPs in freshwater, while the AB and vdW interactions play a more dominant role in dictating the net particle-to-cell interaction in high ionic strength media (≥100 mM NaCl), such as seawater. XDLVO predicted effective attachment between cells and surface functionalized IONPs (SF-IONPs) with an estimated secondary minimum of -3.12 kT in freshwater. This prediction is in accordance with the experimental observation in which 98.89% of cells can be magnetophoretically separated from freshwater with SF-IONPs. We have observed successful magnetophoretic separation of microalgal cells from freshwater and/or seawater for all the cases as long as XDLVO analysis predicts particle attachment. For both the conditions, no pH adjustment is required for particle-to-cell attachment.
Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are thoroughly examined, with additional insights related to the charge transfer events for each strategy of the modified-TiO2 composites. Finally, we offer a summary and some invigorating perspectives on the major challenges and new research directions for future exploitation in this emerging frontier, which we hope will advance us to rationally harness the outstanding structural and electronic properties of {001} facets for various environmental and energy-related applications.
An integrated cohesive band structure of carbon nanotubes (CNTs) applicable to all chirality directions (n, m), starting from the Dirac cone of a graphene nanolayer in k-space, is demarcated, in direct contrast to dissimilar chiral and achiral versions in the published literature. The electron wave state of a CNT is quantized into one-dimensional (1-D) nanostructure with a wrapping mode, satisfying the boundary conditions from one Dirac K-point to an equivalent neighboring one with an identical phase and returning to the same K point. The repetitive rotation for an identical configuration with added band index (n-m)mod3, yields one metallic (M) with zero bandgap corresponding to (n-m)mod3 = 0, semiconducting state SC1 with (n-m)mod3 = 1 and SC2 with (n-m)mod3 = 2. The band gap and effective mass of SC2 state are twice as large as those of SC1 state. A broad-spectrum expression signifying the linear dependence of the effective mass on the bandgap is obtained. Both the Fermi energy and the intrinsic velocity limiting the current to the saturation level is calculated as a function of the carrier concentration. Limitations of the parabolic approximation are pointed out. Several new features of the band structure are acquired in a seamlessly unified mode for all CNTs, making it suitable for all-encompassing applications. Applications of the theory to high-field transport are advocated with an example of a metallic CNT, in agreement with experimental observations. The mechanism behind the breakdown of the linear current-voltage relation of Ohm's law and the associated surge in resistance are explained on the basis of the nonequilibrium Arora's distribution function (NEADF). These results are important for the performance evaluation and characterization of a variety of applications on CNT in modern nanoscale circuits and devices.
Solution processed zirconium acetylacetonate (Zr(acac)) is successfully employed as an electron extraction layer, replacing conventional titanium oxide, in planar CH3NH3PbI3 perovskite solar cells. The as-prepared Zr(acac) film possesses high transparency, high conductivity, a smooth morphology, high wettability, compatibility with PbI2 DMF solution, and an energy level matching that of CH3NH3PbI3 perovskite material. An average power conversion efficiency of about 11.93%, along with a high fill factor of 74.36%, an open circuit voltage of 1.03 V, and a short-circuit current density of 15.58 mA cm(-2) is achieved. The overall performance of the devices is slight better than that of cells using ruthenium acetylacetonate (Ru(acac)). The differences between solar cells with different electron extraction layers in charge recombination, charge transport and transfer and lifetime are further explored and it is demonstrate that Zr(acac) is a more effective and promising electron extraction layer. This work provides a simple, and cost effective route for the preparation of an effective hole extraction layer.
Organo-metal halide perovskite field-effect transistors present serious challenges in terms of device stability and hysteresis in the current-voltage characteristics. Migration of ions located at grain boundaries and surface defects in the perovskite film are the main reasons for instability and hysteresis issues. Here, we introduce a perovskite grain molecular cross-linking approach combined with amine-based surface passivation to address these issues. Molecular cross-linking was achieved through hydrogen bond interactions between perovskite halogens and dangling bonds present at grain boundaries and a hydrophobic cross-linker, namely diethyl-(12-phosphonododecyl)phosphonate, added to the precursor solution. With our approach, we obtained smooth and compact perovskite layers composed of tightly bound grains hence significantly suppressing the generation and migration of ions. Moreover, we achieved efficient surface passivation of the perovskite films upon surface treatment with an amine-bearing polymer, namely polyethylenimine ethoxylated. With our synergistic grain and surface passivation approach, we were able to demonstrate the first perovskite transistor with a complete lack of hysteresis and unprecedented stability upon continuous operation under ambient conditions. Added to the merits are its ambipolar transport of opposite carriers with balanced hole and electron mobilities of 4.02 and 3.35 cm2 V-1 s-1, respectively, its high Ion/Ioff ratio >104 and the lowest sub-threshold swing of 267 mV dec-1 reported to date for any perovskite transistor. These remarkable achievements obtained through a cost-effective molecular cross-linking of grains combined with amine-based surface passivation of the perovskite films open a new era and pave the way for the practical application of perovskite transistors in low-cost electronic circuits.
We report the self-assembly of an extensive inter-ligand hydrogen-bonding network of octylphosphonates on the surface of cesium lead bromide nanocrystals (CsPbBr3 NCs). The post-synthetic addition of octylphosphonic acid to oleic acid/oleylamine-capped CsPbBr3 NCs promoted the attachment of octylphosphonate to the NC surface, while the remaining oleylammonium ligands maintained the high dispersability of the NCs in non-polar solvent. Through powerful 2D solid-state 31P-1H NMR, we demonstrated that an ethyl acetate/acetonitrile purification regime was crucial for initiating the self-assembly of extensive octylphosphonate chains. Octylphosphonate ligands were found to preferentially bind in a monodentate mode through P-O-, leaving polar P[double bond, length as m-dash]O and P-OH groups free to form inter-ligand hydrogen bonds. The octylphosphonate ligand network strongly passivated the nanocrystal surface, yielding a fully-purified CsPbBr3 NC ink with PLQY of 62%, over 3 times higher than untreated NCs. We translated this to LED devices, achieving maximum external quantum efficiency and luminance of 7.74% and 1022 cd m-2 with OPA treatment, as opposed to 3.59% and 229 cd m-2 for untreated CsPbBr3 NCs. This represents one of the highest efficiency LEDs obtained for all-inorganic CsPbBr3 NCs, accomplished through simple, effective passivation and purification processes. The robust binding of octylphosphonates to the perovskite lattice, and specifically their ability to interlink through hydrogen bonding, offers a promising passivation approach which could potentially be beneficial across a breadth of halide perovskite optoelectronic applications.
Metal-free carbonaceous nanomaterials have witnessed a renaissance of interest due to the surge in the realm of nanotechnology. Among myriads of carbon-based nanostructures with versatile dimensionality, one-dimensional (1D) carbon nanotubes (CNTs) and zero-dimensional (0D) carbon dots (CDs) have grown into a research frontier in the past few decades. With extraordinary mechanical, thermal, electrical and optical properties, CNTs are utilized in transparent displays, quantum wires, field emission transistors, aerospace materials, etc. Although CNTs possess diverse characteristics, their most attractive property is their unique photoluminescence. On the other hand, another growing family of carbonaceous nanomaterials, which is CDs, has drawn much research attention due to its cost-effectiveness, low toxicity, environmental friendliness, fluorescence, luminescence and simplicity to be synthesized and functionalized with surface passivation. Benefiting from these unprecedented properties, CDs have been widely employed in biosensing, bioimaging, nanomedicine, and catalysis. Herein, we have systematically presented the fascinating properties, preparation methods and multitudinous applications of CNTs and CDs (including graphene quantum dots). We will discuss how CNTs and CDs have emerged as auspicious nanomaterials for potential applications, especially in electronics, sensors, bioimaging, wearable devices, batteries, supercapacitors, catalysis and light-emitting diodes (LEDs). Last but not least, this review is concluded with a summary, outlook and invigorating perspectives for future research horizons in this emerging platform of carbonaceous nanomaterials.
As an indispensable energy source, ammonia plays an essential role in agriculture and various industries. Given that the current ammonia production is still dominated by the energy-intensive and high carbon footprint Haber-Bosch process, photocatalytic nitrogen fixation represents a low-energy consuming and sustainable approach to generate ammonia. Heterostructured photocatalysts are hybrid materials composed of semiconductor materials containing interfaces that make full use of the unique superiorities of the constituents and synergistic effects between them. These promising photocatalysts have superior performances and substantial potential in photocatalytic reduction of nitrogen. In this review, a wide spectrum of recently developed heterostructured photocatalysts for nitrogen fixation to ammonia are evaluated. The fundamentals of solar-to-ammonia conversion, basic principles of various heterojunction photocatalysts and modification strategies are systematically reviewed. Finally, a brief summary and perspectives on the ongoing challenges and directions for future development of nitrogen photofixation catalysts are also provided.
Neurodegenerative disorder is an illness involving neural dysfunction/death attributed to complex pathological processes, which eventually lead to the mortality of the host. It is generally recognized through features such as mitochondrial dysfunction, protein aggregation, oxidative stress, metal ions dyshomeostasis, membrane potential change, neuroinflammation and neurotransmitter impairment. The aforementioned neuronal dysregulations result in the formation of a complex neurodegenerative microenvironment (NME), and may interact with each other, hindering the performance of therapeutics for neurodegenerative disease (ND). Recently, smart nanoassemblies prepared from functional nanoparticles, which possess the ability to interfere with different NME factors, have shown great promise to enhance the diagnostic and therapeutic efficacy of NDs. Herein, this review highlights the recent advances of stimuli-responsive nanoassemblies that can effectively combat the NME for the management of ND. The first section outlined the NME properties and their interrelations that are exploitable for nanoscale targeting. The discussion is then extended to the controlled assembly of functional nanoparticles for the construction of stimuli-responsive nanoassemblies. Further, the applications of stimuli-responsive nanoassemblies for the enhanced diagnosis and therapy of ND are introduced. Finally, perspectives on the future development of NME-tailored nanomedicines are given.
"Giant" core/shell quantum dots (g-QDs) are promising candidates for emerging optoelectronic technologies thanks to their facile structure/composition-tunable optoelectronic properties and outstanding photo-physical/chemical stability. Here, we synthesized a new type of CuInTeSe (CITS)/CdS g-QDs and regulated their optoelectronic properties by controlling the shell thickness. Through increasing the shell thickness, as-prepared g-QDs exhibited tunable red-shifted emission (from 900 to 1200 nm) and prolonged photoluminescence (PL) lifetimes (up to ∼14.0 μs), indicating a formed band structure showing efficient charge separation and transfer, which is further testified by theoretical calculations and ultrafast time-resolved transient absorption (TA) spectroscopy. These CITS/CdS g-QDs with various shell thicknesses can be employed to fabricate photoelectrochemical (PEC) cells, exhibiting improved photoresponse and stability as compared to the bare CITS QD-based devices. The results indicate that the rational design and engineering of g-QDs is very promising for future QD-based optoelectronic technologies.
This investigation has characterised the structure and surface chemistry of CsPbBr3 nanocrystals with controlled diameters between 6.4 to 12.8 nm. The nanocrystals were investigated via a thorough 133Cs solid state NMR and nuclear relaxation study, identifying and mapping radially-increasing nanoscale disorder. This work has formalised 133Cs NMR as a highly sensitive probe of nanocrystal size, which can conveniently analyse nanocrystals in solid forms, as they would be utilised in optoelectronic devices. A combined multinuclear solid state NMR and XPS approach, including 133Cs-1H heteronuclear correlation 2D (HETCOR) NMR, was utilised to study the nanocrystal surface and ligands, demonstrating that the surface is Cs-Br rich with vacancies passivated by didodecyldimethylammonium bromide (DDAB) ligands. Furthermore, it is shown that a negligible amount of phosphonate ligands remain on the powder nanocrystal surface, despite the key role of octylphosphonic acid (OPA) in controlling the colloidal nanocrystal growth. The CsPbBr3 NCs were shown to be structurally stable under ambient conditions for up to 6 months, albeit with some particle agglomeration.
The design of DNA nanotubes is a promising and hot research branch in structural DNA nanotechnology, which is rapidly developing as a versatile method for achieving subtle nanometer scale materials and molecular diagnostic/curative devices. Multifarious methods have been proposed to achieve varied DNA nanotubes, such as using square tiles and single-stranded tiles, but it is still a challenge to develop a bottom-up assembly way to build DNA nanotubes with different diameters and patterns using certain universal DNA nanostructures. This work addresses the challenge by assembling three types of spatial DNA nanotubes with different diameters and patterns from the so-called "basic bricks", i.e., hierarchical DNA sub-tiles. A high processing rate and throughput synthesis of DNA nanotubes are observed and analyzed by atomic force microscopy. Experimental observations and data analysis suggests the stability and controllability of DNA nanotubes assembled by hierarchical DNA sub-tiles.
We exploit the possibility of enhancing the molecular transport of liquids through graphene films using amplitude modulated surface acoustic waves (SAWs) to demonstrate effective and efficient nanoparticle filtration. The use of the SAW, which is an extremely efficient means for driving microfluidic transport, overcomes the need for the large mechanical pumps required to circumvent the large pressure drops encountered in conventional membranes for nanoparticle filtration. 100% filtration efficiency was obtained for micron-dimension particulates, decreasing to only 95% for the filtration of particles of tens of nanometers in dimension, which is comparable to that achieved with other methods. To circumvent clogging of the film, which is typical with all membrane filters, a backwash operation to flush the nanoparticles is incorporated simply by reversing the SAW-induced flow such that 98% recovery of the initial filtration rate is recovered. Given these efficiencies, together with the low cost and compact size of the chipscale SAW devices, we envisage the possibility of scaling out the process by operating a large number of devices in parallel to achieve typical industrial-scale throughputs with potential benefits in terms of substantially lower capital, operating and maintenance costs.
The search for effective and non-invasive delivery modules to transport therapeutic molecules across skin has led to the discovery of a number of nanocarriers (viz.: liposomes, ethosomes, dendrimers, etc.) in the last few decades. However, available literature suggests that these delivery modules face several issues including poor stability, low encapsulation efficiency, and scale-up hurdles. Recently, carbon nanotubes (CNTs) emerged as a versatile tool to deliver therapeutics across skin. Superior stability, high loading capacity, well-developed synthesis protocol as well as ease of scale-up are some of the reason for growing interest in CNTs. CNTs have a unique physical architecture and a large surface area with unique surface chemistry that can be tailored for vivid biomedical applications. CNTs have been thus largely engaged in the development of transdermal systems such as tuneable hydrogels, programmable nonporous membranes, electroresponsive skin modalities, protein channel mimetic platforms, reverse iontophoresis, microneedles, and dermal buckypapers. In addition, CNTs were also employed in the development of RNA interference (RNAi) based therapeutics for correcting defective dermal genes. This review expounds the state-of-art synthesis methodologies, skin penetration mechanism, drug liberation profile, loading potential, characterization techniques, and transdermal applications along with a summary on patent/regulatory status and future scope of CNT based skin therapeutics.
Lithium-sulfur (Li-S) batteries have attracted great attention owing to their excellent electrochemical properties, such as the high discharge voltage of 2.3 V, specific capacity of 1675 mA h g(-1) and energy density of 2600 Wh kg(-1). The widely used slurry made electrodes of Li-S batteries are plagued by the serious shuttle effect and insulating nature of sulfur. Herein, a reduced graphene oxide coated porous carbon nanofiber flexible paper (rGO@S-PCNP) was fabricated and directly used as an additive-free cathode for Li-S batteries. The results show that the rGO@S-PCNP is certified to be effective at relieving the shuttle effect and improving the conductivity, thus achieving high electrochemical performance. The rGO@S-PCNP composite with a sulfur content of 58.4 wt% delivers a high discharge capacity of 623.7 mA h g(-1) after 200 cycles at 0.1 C (1 C = 1675 mA g(-1)) with the average Coulombic efficiency of 97.1%. The excellent cyclability and high Coulombic efficiency indicate that the as-prepared rGO@S-PCNP composite paper can be a promising cathode for lithium-sulfur batteries, and is envisioned to have great potential in high energy density flexible power devices. This facile strategy brings great significance for large-scale industrial fabrication of flexible lithium-sulfur batteries.
A novel polyoxometalate-based electrode was developed by incorporating phosphotungstic acid (PWA) in nylon-6,6 nanofiber, followed by carbonization. The developed PWA-carbon nanofiber (PWA-CNF) showed the characteristics of the dual-scale porosity of micro- and mesoporous substrate with surface area of around 684 m2 g-1. The compound exhibited excellent stability in vanadium electrolyte and battery cycling. Evaluation of electrocatalytic properties toward V2+/V3+ and VO2+/VO2+ redox couples indicated promising advantages in electron transfer kinetics and increasing energy efficiency, particularly for the VO2+/VO2+ couple. Moreover, the developed electrode exhibited substantially improved energy efficiency (14% higher than that of pristine carbon felt) in the single cell vanadium redox flow battery. This outstanding performance was attributed to high surface area and abundant oxygen-containing linkages in the developed electrode.
12 years after the introduction of DNA-templated silver nanoclusters (DNA-AgNCs), exciting progress has been made and yet we are still in the midst of trying to fully understand this nanomaterial. The prominent excellence of DNA-AgNCs is undoubtedly its modulatable emission property, of which how variation in DNA templates causes emission tuning remains elusive. Based on the up-to-date DNA-AgNCs, we aim to establish the correlation between the structure/sequence of DNA templates and emission behaviour of AgNCs. Herein, we systematically present a wide-range of DNA-AgNCs based on the structural complexity of the DNA templates, including single-stranded DNA (ssDNA), double-stranded DNA (dsDNA), triple-stranded DNA (tsDNA) and DNA nanostructures. For each DNA category, we discuss the emission property, quantum yield and synthesis condition of the respective AgNCs, before cross-comparing the impact of different DNA scaffolds on the properties of AgNCs. A future outlook for this area is given as a conclusion. By putting the information together, this review may shed new light on understanding DNA-AgNCs while we are expecting continuous breakthroughs in this field.
Cellulose nanocrystals, a class of fascinating bio-based nanoscale materials, have received a tremendous amount of interest both in industry and academia owing to its unique structural features and impressive physicochemical properties such as biocompatibility, biodegradability, renewability, low density, adaptable surface chemistry, optical transparency, and improved mechanical properties. This nanomaterial is a promising candidate for applications in fields such as biomedical, pharmaceuticals, electronics, barrier films, nanocomposites, membranes, supercapacitors, etc. New resources, new extraction procedures, and new treatments are currently under development to satisfy the increasing demand of manufacturing new types of cellulose nanocrystals-based materials on an industrial scale. Therefore, this review addresses the recent progress in the production methodologies of cellulose nanocrystals, covering principal cellulose resources and the main processes used for its isolation. A critical and analytical examination of the shortcomings of various approaches employed so far is made. Additionally, structural organization of cellulose and nomenclature of cellulose nanomaterials have also been discussed for beginners in this field.