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.
"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.
Liquid-exfoliated 2D transition metal disulfides (TMDs) are potential substitutes for poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as hole transport layers (HTLs) in Organic Solar Cells (OSCs). Herein, high-yield and high-quality WS2 flake layers are prepared by comprehensively controlling the initial concentration, sonication processing time and centrifugal speed. The WS2 layers deposited on in situ transparent indium tin oxide (ITO) without plasma treatment show higher uniformity and conductivity than that formed on ITO after plasma treatment. With a significant increase in the short-circuit current density (JSC), the power conversion efficiency (PCE) of PM6:Y6-based non-fullerene OSCs using optimized WS2 as the HTL is higher than that using PEDOT:PSS as the HTL(15.75% vs. 15.31%). Combining the morphology characteristics with carrier recombination characteristics, the higher quality of the ITO/WS2 composite substrate leads to better charge transport and a lower bimolecular recombination rate in OSCs, thereby improving the device performance.
Due to the complexity of surgery for large-area bone injuries, implanting a large volume of materials into the injury site remains a big challenge in orthopedics. To solve this difficulty, in this study, a series of biomimetic hydroxyapatite/shape-memory composite scaffolds were designed and synthesized with programmable pore structures, based on poly(ε-caprolactone) (PCL), polytetrahydrofuran (PTMG) and the osteoconductive hydroxyapatite (HA). The obtained scaffolds presented various pore structures, high connectivity, tunable mechanical properties, and excellent shape memory performance. Moreover, the mineralization activity of the developed scaffolds could enhance the formation of hydroxyapatite and they showed good biocompatibility in vitro. The in vivo experiments show that scaffolds could promote the formation of new bone in critical size cranial defects. The programmable porous scaffold biomaterials exhibited potential application promise in bone regeneration.
In recent assassinations reported in London and Malaysia, nerve agents were used to cause death, by skin poisoning. Skin decontamination is the ultimate and most important defense against nerve agent poisoning, because no effective antidote currently exists. However, almost no existing material can achieve effective and rapid decontamination without irritating the skin. This study links proteins that exhibit no decontamination ability with polymers to form a nanocomposite. This creates a nanospace on the surface of the protein that attracts and traps organic molecules, effectively adsorbing the nerve agent Soman within several seconds, without irritating the skin. Analysis of the different components of proteins and polymers reveals that the decontamination efficiency is considerably affected by the thickness of the coated polymer. Moreover, the thickness of the layer is predominantly determined by the size and species of the core and the crosslinking method. Further in vivo experiments on rats poisoned with Soman verify the efficiency and safety of the nanocomposite. These results could be used to design and synthesize more multi-functional and effective decontamination materials.
Heterojunction photocatalysts have shown their immense capability in enhancing photogenerated charge carrier separation. Yet, the intrinsic scarcity of active sites in semiconductor components of heterojunction photocatalysts limits their potential for photocatalysis being used in practical applications. Herein, we employ a non-noble metal cocatalyst (i.e., NiS) for modulating a S-scheme heterojunction photocatalyst consisting of Cd3(C3N3S3)2 (CdCNS) and CdS. It is revealed that the formation of the CdCNS/CdS S-scheme heterojunction can enable optimal photogenerated charge carrier utilization efficiency and optimized redox capability. More importantly, the meticulous loading of NiS can play multiple roles in enhancing the photocatalytic performance of the CdCNS/CdS photocatalyst, including endowing it with abundant surface-active sites and acting as a photogenerated electron acceptor. As a result, the optimized NiS-loaded CdCNS/CdS attains an excellent hydrogen production rate of 38.17 mmol g-1 h-1, to reach a quantum efficiency of 29.02% at 420 nm. The results reported in this work provide an interesting insight into the important roles of surface-active site modulation in optimizing photocatalytic performances.
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.
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.
Oxide perovskites (OPs) have emerged as promising photocatalysts for numerous applications, such as energy conversion, renewable fuels, and environmental remediation. Although OPs are gaining traction, their efficacies are still hindered by low charge carrier mobility and poor stability. This study investigated the function of polymers actively participating in OP structures to improve the overall characteristics. An overview of the polymer-enhanced perovskite oxide photocatalyst (PEPOP) field was effectively reviewed. These PEPOPs were demonstrated in photovoltaics, pollutant degradation, and gas conversion and reduction. Nonetheless, additional research is needed to explore the potential of PEPOPs to establish their efficacy in photocatalytic applications. The technological improvements of PEPOPs were hindered by significant challenges related to stability and sensitivity. The urgency of this review was apparent due to the fast-paced nature of research in the field of photocatalysis. Recent breakthroughs and emerging applications highlight the need for a comprehensive overview of PEPOPs and their enhanced catalytic capabilities. Consequently, a broad outlook was provided for the current state of PEPOP-related studies, highlighting the potential of these materials for future applications.
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.
The electro/photocatalytic CO2 reduction reaction (CO2RR) is a long-term avenue toward synthesizing renewable fuels and value-added chemicals, as well as addressing the global energy crisis and environmental challenges. As a result, current research studies have focused on investigating new materials and implementing numerous fabrication approaches to increase the catalytic performances of electro/photocatalysts toward the CO2RR. MXenes, also known as 2D transition metal carbides, nitrides, and carbonitrides, are intriguing materials with outstanding traits. Since their discovery in 2011, there has been a flurry of interest in MXenes in electrocatalysis and photocatalysis, owing to their several benefits, including high mechanical strength, tunable structure, surface functionality, high specific surface area, and remarkable electrical conductivity. Herein, this review serves as a milestone for the most recent development of MXene-based catalysts for the electrocatalytic and photocatalytic CO2RR. The overall structure of MXenes is described, followed by a summary of several synthesis pathways classified as top-down and bottom-up approaches, including HF-etching, in situ HF-formation, electrochemical etching, and halogen etching. Additionally, the state-of-the-art development in the field of both the electrocatalytic and photocatalytic CO2RR is systematically reviewed. Surface termination modulation and heterostructure engineering of MXene-based electro/photocatalysts, and insights into the reaction mechanism for the comprehension of the structure-performance relationship from the CO2RR via density functional theory (DFT) have been underlined toward activity enhancement. Finally, imperative issues together with future perspectives associated with MXene-based electro/photocatalysts are proposed.
Developing a meta-structure with near-unity absorbance in the visible and infrared spectra for solar energy harvesting, photodetection, thermal imaging, photo-trapping, and optical communications is a long-term research challenge. This research presents a four-layered (insulator-metal-insulator-metal) meta-structure unit cell that showed a peak absorbance of 99.99% at 288-300 nm and the average absorbance of 99.18% over the 250-2000 nm wavelength range in TE and TM modes, respectively. The symmetric pattern of the resonator layer shows polarization insensitivity with an average absorption of 99.18% in both TE and TM modes. Furthermore, the proposed design shows a wide incident angle stability up to ≤60 degrees in both TE and TM modes. The proposed structure also exhibits negative index properties at 288-300 nm and 1000-2000 nm, respectively. The negative index properties of the proposed design generate an anti-parallel surface current flow in the ground and resonator layers, which induces magnetic and electric field resonance and increases absorption. The performance of the proposed design is further validated by the interference theory model and a zero value for the polarization conversion ratio (PCR). The electric field E, magnetic field H, and current distribution are analyzed to explain the absorption mechanism of the proposed meta-structure unit cell. It also exhibits the highest photo-thermal conversion efficiency of 99.11%, demonstrating the viability of the proposed design as a solar absorber. The proposed design promises potentially valuable applications such as solar energy harvesting, photodetection, thermal imaging, photo-trapping, and optical communications because of its decent performance.
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.
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.
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.
Quasi-homogeneous ligand-protected gold nanoclusters (Au NCs) with atomic precision and well-defined structure offer great opportunity for exploring the catalytic nature of nanogold catalysts at a molecular level. Herein, using real-time electrospray ionization mass spectrometry (ESI-MS), we have successfully identified the desorption and re-adsorption of p-mercaptobenzoic acid (p-MBA) ligands from Au25(p-MBA)18 NC catalysts during the hydrogenation of 4-nitrophenol in solution. This ligand dynamic (desorption and re-adsorption) would initiate structural transformation of Au25(p-MBA)18 NC catalysts during the reaction, forming a mixture of smaller Au NCs (Au23(p-MBA)16 as the major species) at the beginning of catalytic reaction, which could further be transformed into larger Au NCs (Au26(p-MBA)19 as the major species). The adsorption of hydrides (from NaBH4) is identified as the determining factor that could induce the ligand dynamic and structural transformation of NC catalysts. This study provides fundamental insights into the catalytic nature of Au NCs, including catalytic mechanism, active species and stability of Au NC catalysts during a catalytic reaction.
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.
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.
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.