Silicon-based Nanomaterials Research Articles

Micro/nano additives in 3D printing concrete

3D concrete printing has attracted burgeoning interest in the construction industry for its ability to offer cost-effectiveness, architectural design flexibility, efficient use of energy and materials, as well as significant time savings in the construction process. However, conventional cement-geopolymer-based materials cannot be used directly for printing due to their lack of printability. This review explores the utilization of inorganic micro/nanomaterials to modify the rheological and mechanical performance of fresh-state and post-hardening cementitious composites, respectively, offering an in-depth analysis of the mechanisms underpinning their effects. This paper discusses a wide range of inorganic micro/nanomaterials, including carbon-based nanomaterials, silicon-based nanomaterials, metallic oxide nanomaterials, nano-calcium carbonate particles, and other micro/nano-materials. Those materials have been utilized in 3D printing concrete or show considerable potential for future applications in this field. Furthermore, this work provides insights into the multiple applications that arise from the synergistic combination of 3D printing construction techniques with the distinctive properties of different nanomaterials.

Application of porous carbon nanoelectrode materials for lithium-ion batteries

Abstract In order to achieve carbon neutrality and gradually improve the current global warming environmental situation, the world’s major research teams are committed to developing lithium-ion batteries with better performance, trying to use in various new energy facilities, such as electric vehicles, which can effectively reduce polluting gas emissions. Nowadays, many electrode materials that can improve the performance of lithium-ion batteries have been continuously emerging, such as carbon nanotubes and silicon-based nanomaterials. However, carbon nanotube electrode materials have the disadvantages of high irreversible capacity, voltage lag and high manufacturing cost, while silicon-based nanomaterials also have the drawbacks of volume expansion and poor electrical conductivity. Based on the mature research of carbon materials, extensive raw material sources and large reserves, completely non-toxic and low comprehensive cost, this research analyzes three new porous carbon nanoelectrode materials with high development potential, and shows their electrochemical performance advantages, such as high charge-discharge specific capacity, excellent rate performance, and low charge transfer impedance.

Applying different nanomaterials to improve the performance of lithium-ion batteries

Due to their superior qualities, lithium-ion batteries (LIBs) have lately taken the top spot among rechargeable secondary batteries. To achieve the increasing demand for electricity in the related industries, its improvement and development are in full swing, especially the nanomaterials have become an important direction of improvement because of their special structure matching with charging-discharging mechanisms. This paper focuses on the application of nanomaterials in the LIBs. It briefly introduces carbon-based and silicon-based nanomaterials, metal (alloy), metal oxide (sulfide), MOFs nanomaterials, and Mxenes in lithium-ion batteries and lithium-sulfur batteries by reviewing the pertinent literature from recent years. including the reasons for their application, the application mechanism and the effectiveness of their improvement. It has been discovered that nanoparticles have numerous and intricate uses in the LIBs. It is hoped that this study can provide new ideas for the structural design and functional modification of nanomaterials in battery applications in the future.

Application of silicon-based nanomaterials for improving the performance of battery

This research discussed the improvement of using silicon-based nanomaterial in batteries compared to graphite batteries because not only in electric vehicles, but also mobile phone users are requiring for longer battery life and faster charging speed and phones cannot increase into an unacceptable weight. This research first introduces how lithium-ion batteries work and analyses the failure of lithium metallic battery: high cost and low security because of dendrites growth. Secondly, this paper discussed how mobile phone manufacturers improved their batteries by using silicon: Honors silicon carbon battery and Xiaomis silicon-oxygen anode battery. Both have increased the energy density and charging speed and lighter the weight at the same time. In general, silicon can improve battery performance through its high capacity for lithium-ion, and silicon can easily be found in a natural environment which will lead to lower manufacturing costs. As a result, this research can provide a new design approach for the structural design and application performance of nanomaterials in the field of battery applications.

Recent advances on nanomaterial-based glutathione sensors.

Glutathione (GSH) is one of the most common thiol-containing molecules discovered in biological systems, and it plays an important role in many cellular functions, where changes in physiological glutathione levels contribute to the progress of a variety of diseases. Molecular imaging employing fluorescent probes is thought to be a sensitive technique for online fluorescence detection of GSH. Although various molecular probes for (intracellular) GSH sensing have been reported, some aspects remain unanswered, such as quantitative intracellular analysis, dynamic monitoring, and compatibility with biological environment. Some of these drawbacks can be overcome by sensors based on nanostructured materials, that have attracted considerable attention owing to their exceptional properties, including a large surface area, heightened electro-catalytic activity, and robust mechanical resilience, for which they have become integral components in the development of highly sensitive chemo- and biosensors. Additionally, engineered nanomaterials have demonstrated significant promise in enhancing the precision of disease diagnosis and refining treatment specificity. The aim of this review is to investigate recent advancements in fabricated nanomaterials tailored for detecting GSH. Specifically, it examines various material categories, encompassing carbon, polymeric, quantum dots (QDs), covalent organic frameworks (COFs), metal-organic frameworks (MOFs), metal-based, and silicon-based nanomaterials, applied in the fabrication of chemo- and biosensors. The fabrication of nano-biosensors, mechanisms, and methodologies employed for GSH detection utilizing these fabricated nanomaterials will also be elucidated. Remarkably, there is a noticeable absence of existing reviews specifically dedicated to the nanomaterials for GSH detection since they are not comprehensive in the case of nano-fabrication, mechanisms and methodologies of detection, as well as applications in various biological environments. This research gap presents an opportune moment to thoroughly assess the potential of nanomaterial-based approaches in advancing GSH detection methodologies.

Alleviating the volume expansion of silicon anodes by constructing a high-strength ordered multidimensional encapsulation structure.

The application of silicon-based nanomaterials in fast-charging scenarios is hindered by volume expansion during lithiation and side reactions induced by surface effects. Constructing a robust encapsulation structure with high mechanical strength and conductivity is pivotal for optimizing the electrochemical performance of nanostructured silicon anodes. Herein, we propose a multifaceted hierarchical encapsulation structure featuring excellent mechanical strength and high conductivity by sequentially incorporating SiO x , hard carbon, and closed-pore carbon layers around silicon quantum dots, thereby enabling stable cycling at high current densities. In this structure, the ultra-thin SiO x layer strengthens the Si-C interface, while the outermost carbon matrix with closed pores functions both as a conductive network and a barrier against electrolyte intrusion. Notably, the synthesized material exhibits a specific capacity of 1506 mA h g-1 with 90.17% retention after 300 cycles at 1.0 A g-1. After 500 cycles at 5.0 A g-1, it retains 640.4 mA h g-1, over 70% of its initial capacity.

Carbon-Based and Silicon-Based Nanomaterials for Enhanced Structural Adhesives

Various carbon-based (i.e., carbon nanofibres (CNF), cellulose nanocrystals and graphite nanoparticles) and silicon-based nanomaterials (i.e., silica and MMT clay nanoparticles) were incorporated into neat structural epoxy adhesive (NE) (Sikadur®-30) at 0.5, 1.0 and 1.5 wt.% by means of a simple and cost-effective mixing method to produce the nanomaterial-modified epoxy adhesives (NMEAs). The performance of the NMEAs in regard with the bond characteristics and strength of cement paste (CP)-adhesive joints was investigated through conducting lap-shear test. Results showed that loading epoxy with 0.5 and 1.0 wt.% of carbon-based nanofillers, except in the case of adding 1.0 wt.% CNF, contributed to a significant enhancement in the joints’ strength, but a strength reduction the of the joints, even below those of the NE-bonded joints, was observed upon a further loading (i.e., at 1.5 wt.%). While all the joints bonded with epoxy loaded with silicon-based nanofillers at all wt.% showed a strength increase over the unfilled epoxy. The joints’ strength was found to decrease with the wt.% of the nanofillers due to particles’ agglomerations. All joints failed in a mixed cohesive and adhesive mode.

Performance and modification of novel nanomaterials for the anode of lithium-ion batteries

Due to the burning of fossil energy which is a non-renewable nature resource, it has caused many environmental problems, then the world began to face energy shortage and environmental problems. In order to solve these two problems, people have started to develop new energy sources and vigorously research new methods for energys efficient storage and utilization. The Li-ion battery is a research priority because it has great properties such as high specific energy and environmental friendliness, but they still need further performance improvement before it can be put into use. In this paper, the lithium-ion batterys anode is selected as the research object to investigate the performance of carbon-based nanomaterials, silicon-based nanomaterials, and metal-based nanomaterials, and to study the actual performance and modification methods to analyze the application prospects of the materials. Improving the Li-ion battery cathode material performance can significantly improve the batterys capacity and performance stability, speed up the process of putting lithium-ion batteries into use, and improve people's ability to store and use energy to cope with the energy crisis.

Effect of incorporating carbon- and silicon-based nanomaterials on the physico-chemical properties of a structural epoxy adhesive

Various carbon-based (i.e. carbon nanofibres (CNF), cellulose nanocrystals and graphite nanopowder) and silicon-based nanomaterials (i.e. silica nanopowder and MMT nanoclay) were incorporated into neat structural epoxy (NE) adhesive (Sikadur®-30) at 0.5, 1.0 and 1.5% by weight and mixed using a simple and cost-effective approach to produce the nanomaterial-modified epoxy adhesives (NMEAs). The impact of incorporating these nanomaterials into the NE on its chemical composition was investigated using Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. X-ray diffraction (XRD) measurements were also used to identify the changes in the physical structure (i.e. the degree of crystallinity) that may occur in the NE with the addition of nanomaterials. Furthermore, the microstructure of the NE and NMEAs (in terms of the degree of dispersibility of the nanoparticles through the matrix) was investigated through scanning electron microscopy (SEM) analysis. A porosity analysis was also conducted across all samples. The results obtained from various tests were correlated to investigate the changes that occurred in the different properties of the matrix and the corresponding nanocomposites effectively and more critically. The SEM images showed some particle agglomeration, which increased with increasing wt%. An increase in the % porosity ratio of all nanocomposites over that of the NE was also observed, accompanied by a decrease in crystallinity compared to the NE. As per the FTIR spectroscopy, the chemical bonds in the NE and carbon-based NMEAs were observed to have different intensities, which were changed in the NMEAs, with the type and wt. % of the nanomaterials. No new bonds were formed by incorporating any of the nanomaterials (i.e. carbon- and silicon-based), except when adding 1.0 wt% CNF, where a bond at 1710 cm−1 was observed indicating a new CO stretching bond. As shown by Raman spectroscopy, all CNF and graphite NMEAs exhibited higher ID/IG values than those of the corresponding pristine materials.

Recent advances in silicon-based nanostructures for thermoelectric applications

In this work, implementations of silicon-based thermoelectric nanomaterials are reviewed. Approaches ranging from nanostructured bulk—i.e., macroscopic materials presenting nanoscale features—to more complex low-dimensional materials are covered. These implementations take advantage of different phonon scattering mechanisms and eventual modifications of the electronic band-structure for the enhancement of the thermoelectric figure of merit. This work is focused on the recent advances in silicon and silicon-based thermoelectric nanomaterials of the last decade—at both the theoretical and experimental level—with the spotlight on the most recent works. Different nanostructures and their fabrication methods are detailed, while the thermoelectric performances and the feasibility of their integration into functional micro-harvester generators are compared and discussed. This Research Update first covers the advances in nanostructured bulk, such as nanometric-sized polycrystals or defect-induced materials. Subsequently, it reviews low-dimensional materials, namely, thin films and nanowires. Later, other complex structures based on nanoporosity, superlattices, or core–shell schemes are detailed. Finally, it is devoted to present examples of the successful implementation of nanostructured silicon into functional thermoelectric devices.

Hydrogenated Amorphous Silicon-Based Nanomaterials as Alternative Electrodes to Graphite for Lithium-Ion Batteries.

Graphite is the material most used as an electrode in commercial lithium-ion batteries. On the other hand, it is a material with low energy capacity, and it is considered a raw critical material given its large volume of use. In the current energy context, we must promote the search for alternative materials based on elements that are abundant, sustainable and that have better performance for energy storage. We propose thin materials based on silicon, which has a storage capacity eleven times higher than graphite. Nevertheless, due to the high-volume expansion during lithiation, it tends to crack, limiting the life of the batteries. To solve this problem, hydrogenated amorphous silicon has been researched, in the form of thin film and nanostructures, since, due to its amorphous structure, porosity and high specific surface, it could better absorb changes in volume. These thin films were grown by plasma-enhanced chemical vapor deposition, and then the nanowires were obtained by chemical etching. The compositional variations of films deposited at different temperatures and the incorporation of dopants markedly influence the stability and longevity of batteries. With these optimized electrodes, we achieved batteries with an initial capacity of 3800 mAhg-1 and 82% capacity retention after 50 cycles.

Thermal Properties of Porous Silicon Nanomaterials.

The thermal properties, including the heat capacity, thermal conductivity, effusivity, diffusivity, and phonon density of states of silicon-based nanomaterials are analyzed using a molecular dynamics calculation. These quantities are calculated in more detail for bulk silicon, porous silicon, and a silicon aerocrystal (aerogel), including the passivation of the porous internal surfaces with hydrogen, hydroxide, and oxygen ions. It is found that the heat capacity of these materials increases monotonically by up to 30% with an increase in the area of the porous inner surface and upon its passivation with these ions. This phenomenon is explained by a shift of the phonon density of states of the materials under study to the low-frequency region. In addition, it is shown that the thermal conductivity of the investigated materials depends on the degree of their porosity and can be changed significantly upon the passivation of their inner surface with different ions. It is demonstrated that, in the various simulated types of porous silicon, the thermal conductivity changes by 1-2 orders of magnitude compared with the value for bulk silicon. At the same time, it is found that the nature of the passivation of the internal nanosilicon surfaces affects the thermal conductivity. For example, the passivation of the surfaces with hydrogen does not significantly change this parameter, whereas a passivation with oxygen ions reduces it by a factor of two on average, and passivation with hydroxyl ions increases the thermal conductivity by a factor of 2-3. Similar trends are observed for the thermal effusivities and diffusivities of all the types of nanoporous silicon under passivation, but, in that case, the changes are weaker (by a factor of 1.5-2). The ways of tuning the thermal properties of the new nanostructured materials are outlined, which is important for their application.

Ligand-Induced Ground- and Excited-State Chirality in Silicon Nanoparticles: Surface Interactions Matter.

Silicon-based light-emitting materials have emerged as a favorable substitute to various organic and inorganic systems due to silicon's high natural abundance, low toxicity, and excellent biocompatibility. However, efforts on the design of free-standing silicon nanoparticles with chiral non-racemic absorption and emission attributes are rather scare. Herein, we unravel the structural requirements for ligand-induced chirality in silicon-based nanomaterials by functionalizing with D- and L-isomers of a bifunctional ligand, namely, tryptophan. The structural aspects of these systems are established using high-resolution high-angle annular dark-field imaging in the scanning transmission electron microscopy mode, solid-state nuclear magnetic resonance, Fourier transform infrared, and X-ray photoelectron spectroscopy. Silicon nanoparticles capped with L- and D-isomers of tryptophan displayed positive and negative monosignated circular dichroic signals and circularly polarized luminescence indicating their ground- and excited-state chirality. Various studies supported by density functional theory calculations signify that the functionalization of indole ring nitrogen on the silicon surface plays a decisive role in modifying the chiroptical characteristics by generating emissive charge-transfer states. The chiroptical responses originate from the multipoint interactions of tryptophan with the nanoparticle surface through the indole nitrogen and -CO2- groups that can transmit an enantiomeric structural imprint on the silicon surface. However, chiroptical properties are not observed in phenylalanine- and alanine-capped silicon nanoparticles, which are devoid of Si-N bonds and chiral footprints. Thus, the ground- and excited-state chiroptics in tryptophan-capped silicon nanoparticles originates from the collective effect of ligand-bound emissive charge-transfer states and chiral footprints. Being the first report on the circularly polarized luminescence in silicon nanoparticles, this work will open newer possibilities in the field of chirality.

Thermostructural Characterization of Silicon Carbide Nanocomposite Materials via Molecular Dynamics Simulations

In this paper, we investigate the thermostructural properties of a type of silicon-based nanomaterials, which we refer to as SiC@Si nanocomposites, formed by SiC crystalline nanoparticles (with the cubic phase), embedded within an amorphous Si matrix. We have followed an in silico approach to characterize the mechanical and thermal behaviour of these materials, by calculating the elastic constants, uniaxial stress-strain curves, coefficients of thermal expansion, and specific heats, at different temperatures, using interatomic potential calculations. The results obtained from our simulations suggest that this type of material presents enhanced thermal resistance features, making it suitable to be used in devices subjected to big temperature changes, such as heat sinks in micro and nanoelectronics, solar energy harvesters at high temperatures, power electronics, or in other applications in which good thermomechanical properties are required.

Effect of Temperature on Silicon-Based and Silicon-Rich Anodes for Li-Ion Batteries

Several governments are committed to fight against climate change and, reducing the pollution derived from the utilization of fossil fuel powered cars is considered as a part of the solution. Therefore, environmentally friendly electric vehicles (EVs) keep on gaining importance [1], [2] . Nevertheless, in order to extend the autonomy range of EVs to that achieved by internal combustion cars, next-generation lithium-ion batteries (LIBs) with larger specific capacities and subsequent higher energy densities are required.Replacing graphite, the anode widely used in current LIBs, with other materials capable of providing much larger capacities, is a well-known strategy to boost the specific capacity of this technology [3], [4] . In this sense, silicon is one of the most promising materials, not only because it can deliver a capacity (~3579 mAh/g) approximately 10 times that of graphite (~370 mAh/g) [5], [6] , but also because it is an affordable substitute anode material for LIBs, since it is the second most abundant element in the earth’s crust [7] .Numerous scientific investigations have been carried out in silicon anodes for LIBs, however, a parameter that has not been assessed and would be crucial in its real performance in EVs is the effect that temperature would have over its cyclability. To determine such effect, we have conducted galvanostatic tests with silicon-based and silicon-rich anodes in half-cells at different temperatures. Besides, the absence or presence of fluoroethylene carbonate (FEC) as electrolyte additive has also been evaluated. The different capacities and cycle-lifes observed, along with the possible kinetic mechanisms behind them, will be here discussed. We gratefully acknowledge support from the U. S. Department of Energy (DOE), Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. The U.S. government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the government. [1] M. Armand and J-M. Tarascon. Nature 2008, 451, 652-657. Building better batteries. [2] C. C. Chan. EEE 1999 International Conference on Power Electronics and Drive Systems, PEDS’99, Hong Kong. The Past, Present and Future of Electric Vehicle Development. [3] W-J. Zhang, J. Power Sources 2011, 196 (1), 12-24. A review of the electrochemical performance of alloy anodes for lithium-ion batteries. [4] V. Etacheri, R. Marom, R. Elazari, G. Salitra and D. Aurbach. Energy Environm. Sci. 2011, 4, 3243-3262. Challenges in the development of advanced Li-ion batteries: a review. [5] X. Su, Q. Wu, J. Li, X. Xiao, A. Lott, W. Lu, B. W. Sheldon and J. Wu. Adv. Energy Mater. 2014, 4, 1300882. Silicon-Based Nanomaterials for Lithium-Ion Batteries: A Review. [6] H. Wu and Y. Cui. Nanotoday 2012, 7(5), 414-429. Designing nanostructured silicon anodes for high energy lithium ion batteries. [7] U. Kasavajjula, C. Wang and A. J. Appleby. Journal of Power Sources 2007, 163, 1003. Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells.

Hydrogen-bonded silicene nanosheets of engineered bandgap and selective degradability for photodynamic therapy

Silicon, a highly biocompatible and ubiquitous chemical element in living systems, exhibits great potentials in biomedical applications. However, the silicon-based nanomaterials such as silica and porous silicon have been largely limited to only serving as carriers for delivery systems, due to the lack of intrinsic functionalities of silicon. This work presents the facile construction of a two-dimensional (2D) hydrogen-bonded silicene (H-silicene) nanosystem which is highlighted with tunable bandgap and selective degradability for tumor-specific photodynamic therapy facilely by surface covalent modification of hydrogen atoms. Briefly, the H-silicene nanosheet material is selectively degradable in normal neutral tissues but rather stable in the mildly acidic tumor microenvironment (TME) for achieving efficient photodynamic therapy (PDT). Such a 2D hydrogen-bonded silicene nanosystem featuring the tunable bandgap and tumor-selective degradability provides a new paradigm for the application of multi-functional two-dimensional silicon-based biomaterials towards the diagnosis and treatments of cancer and other diseases.

Fluorescent Silicon-based Nanomaterials Imaging Technology in Diseases

Fluorescent Silicon-based Nanomaterials Imaging Technology in Diseases

Flash Solid-Solid Synthesis of Silicon Oxide Nanorods.

1D silicon-based nanomaterials, renowned for their unique chemical and physical properties, have enabled the development of numerous advanced materials and biomedical technologies. Their production often necessitates complex and expensive equipment, requires hazardous precursors and demanding experimental conditions, and involves lengthy processes. Herein, a flash solid-solid (FSS) process is presented for the synthesis of silicon oxide nanorods completed within seconds. The innovative features of this FSS process include its simplicity, speed, and exclusive use of solid precursors, comprising hydrogen-terminated silicon nanosheets and a metal nitrate catalyst. Advanced electron microscopy and X-ray spectroscopy analyses favor a solid-liquid-solid reaction pathway for the growth of the silicon oxide nanorods with vapor-liquid-solid characteristics.

Advances in Laser Ablation Synthesized Silicon-Based Nanomaterials for the Prevention of Bacterial Infection.

Nanomaterials have unique properties and characteristics derived from their shape and small size that are not present in bulk materials. If size and shape are decisive, the synthesis method used, which determines the above parameters, is equally important. Among the different nanomaterial’s synthesis methods, we can find chemical methods (microemulsion, sol-gel, hydrothermal treatments, etc.), physical methods (evaporation-condensation, laser treatment, etc.) and biosynthesis. Among all of them, the use of laser ablation that allows obtaining non-toxic nanomaterials (absence of foreign compounds) with a controlled 3D size, has emerged in recent years as a simple and versatile alternative for the synthesis of a wide variety of nanomaterials with numerous applications. This manuscript reviews the latest advances in the use of laser ablation for the synthesis of silicon-based nanomaterials, highlighting its usefulness in the prevention of bacterial infection.

Advances in chemiluminescence and electrogenerated chemiluminescence based on silicon nanomaterials.

Since 1950, when chemiluminescence (CL) of siloxane upon treatment with strong oxidants was discovered by Kurtz, many silicon-based nanomaterials with different elements, specific molecules, shapes and sizes have been developed as light emitters, energy acceptors, and catalyzers to provide valuable CL and electrogenerated CL (ECL) detection platforms in analytical chemistry fields. This review mainly focuses on the recent development of their mechanisms and sensing methodologies for small molecules, free radicals, ion, enzyme, protein, DNA, cancer cells, and metabolites based on specific reactions such as aptamer sensing and enzymatic reaction. Additionally, the future trend is discussed.