Macroporous Directed and Interconnected Carbon Architectures Endow Amorphous Silicon Nanodots as Low‑Strain and Fast‑Charging Anode for Lithium‑Ion Batteries

Fabricating low-strain and fast-charging silicon-carbon composite anodes is highly desired but remains a huge challenge for lithium-ion batteries.Herein,we report a unique silicon-carbon composite fabricated by uniformly dis-persing amorphous Si nanodots(SiNDs)in carbon nanospheres(SiNDs/C)that are welded on the wall of the macroporous carbon framework(MPCF)by vertical graphene(VG),labeled as MPCF@VG@SiNDs/C.The high dispersity and amor-phous features of ultrasmall SiNDs(~0.7 nm),the flexible and directed electron/Li+transport channels of VG,and the MPCF impart the MPCF@VG@SiNDs/C more lithium storage sites,rapid Li+transport path,and unique low-strain property during Li+storage.Consequently,the MPCF@VG@SiNDs/C exhibits high cycle stability(1301.4 mAh g^(-1) at 1 A g^(-1) after 1000 cycles without apparent decay)and high rate capacity(910.3 mAh g^(-1),20 A g^(-1))in half cells based on industrial electrode standards.The assembled pouch full cell delivers a high energy density(1694.0 Wh L^(-1);602.8 Wh kg^(-1))and an excellent fast-charging capability(498.5 Wh kg^(-1),charging for 16.8 min at 3 C).This study opens new possibilities for preparing advanced silicon-carbon com-posite anodes for practical applications.

Microfluidic-oriented synthesis of enriched iridium nanodots/carbon architecture for robust electrocatalytic nitrogen fixation

Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.

Super-strong and Intrinsically Fluorescent Silkworm Silk from Carbon Nanodots Feeding

Fluorescent silk is fundamentally important for the development of future tissue engineering scaffolds.Despite great progress in the preparation of a variety of colored silks,fluorescent silk with enhanced mechanical properties has yet to be explored.In this study,we report on the fabrication of intrinsically super-strong fluorescent silk by feeding Bombyx mori silkworm carbon nanodots(CNDs).The CNDs were incorporated into silk fibroin,hindering the conformation transformation,confining crystallization,and inducing orientation of mesophase.The resultant silk exhibited super-strong mechanical properties with breaking strength of 521.9±82.7 MPa and breaking elongation of 19.2±4.3%,improvements of 55.1%and 53.6%,respectively,in comparison with regular silk.The CNDs-reinforced silk displayed intrinsic blue fluorescence when exposed to 405 nm laser and exhibited no cytotoxic effect on cells,suggesting that multi-functional silks would be potentially useful in bioimaging and other applications.

Facile fabrication of MoP nanodots embedded in porous carbon as excellent anode material for potassium-ion batteries

Molybdenum phosphide(MoP),owing to its abundant reserve and high theoretical capacity,is regarded as a promising anode material for potassium-ion batteries.However,it still suffers from the problems of acute volume expansion and weak diffusion kinetics.This study reports a simple method to synthesize a composite of molybdenum phosphide and porous carbon(MoP@PC)through simple mixing and annealing treatment.In the MoP@PC,lots of MoP nanodots with an average diameter of about 4 nm uniformly embedded in the petal-like porous carbon.The MoP@PC shows reversible capacities of 330 mAh g^(-1) at100 mA g^(-1) after 100 cycles,and ultra-long cycling stability with a capacity of 240 mAh g^(-1) after 1000 cycles at 1 A g^(-1) and 161 mAh g^(-1) after 1000 cycles at 5 A g^(-1).The structure of MoP@PC after charging-discharging cycles is also investigated by high resolution transmission electron microscope(HRTEM)and the result shows that MoP can still maintain the nanodot morphology without any agglomeration after 1000 cycles at 5 A g^(-1).The storage mechanism of potassium ions was studied as well,which reveals that MoP and potassium ion have a conversion reaction.

Prompt Electrodeposition of Ni Nanodots on Ni Foam to Construct a High-Performance Water-Splitting Electrode:Efficient, Scalable,and Recyclable

In past decades,Ni-based catalytic materials and electrodes have been intensively explored as low-cost hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts for water splitting.With increasing demands for Ni worldwide,simplifying the fabrication process,increasing Ni recycling,and reducing waste are tangible sustainability goals.Here,binder-free,heteroatom-free,and recyclable Ni-based bifunctional catalytic electrodes were fabricated via a one-step quick electrodeposition method.Typically,active Ni nanodot(NiND)clusters are electrodeposited on Ni foam(NF)in Ni(NO3)2 acetonitrile solution.After drying in air,NiO/NiND composites are obtained,leading to a binder-free and heteroatom-free NiO/NiNDs@NF catalytic electrode.The electrode shows high efficiency and long-term stability for catalyzing hydrogen and oxygen evolution reactions at low overpotentials(10ηHER= 119 mV and 50ηOER=360 mV)and can promote water catalysis at 1.70 V@ 10mA cm-2.More importantly,the recovery of raw materials(NF and Ni(NO3)2)is quite easy because of the solubility of NiO/NiNDs composites in acid solution for recycling the electrodes.Additionally,a large-sized(S^70 cm2)NiO/NiNDs@NF catalytic electrode with high durability has also been constructed.This method provides a simple and fast technology to construct high-performance,low-cost,and environmentally friendly Ni-based bifunctional electrocatalytic electrodes for water splitting.

Modulating charge separation and transfer kinetics in carbon nanodots for photoredox catalysis

Artificial photosynthesis has gained increasing interest as a promising solution to the worldwide energy and environmental issues. A crucial requirement for realizing a sustainable system for artificial photosynthesis is to explore low cost, highly-efficient and stable photoactive materials. Carbon nanodots(CNDs) have attracted considerable attention owing to their low cost, tunable chemistry and unique light-harvesting capability. Previous review articles have highlighted the photocatalytic and photoelectrocatalytic applications of CNDs and CNDs-based composite photocatalysts. However, the control of the separation and transfer processes of photogenerated electron/hole pairs in CNDs has not been reviewed.This review summarizes the recent progress in the design of CNDs as new light-harvesting materials and highlights their applications in photocatalytic hydrogen production, CO2 photoreduction and environmental remediation. Strategies that have been employed to modulate the separation and transfer kinetics of photogenerated charge carriers in CNDs are discussed in detail. The challenges and new directions in this emerging area of research are also proposed.

Ultrafine VN nanodots induced generation of abundant cobalt single-atom active sites on nitrogen-doped carbon nanotube for efficient hydrogen evolution

Development of highly active and stable non-noble electrocatalysts with well-defined nanostructures is crucial for efficient hydrogen evolution reaction(HER). Herein, a novel three-dimensional(3D) selfsupported electrode consists of vanadium nitride(VN) nanodots and Co nanoparticles co-embedded and highly active single Co atoms anchored in N-doped carbon nanotubes supported on carbon cloth(VN-Co@CoSAs-NCNTs/CC) is fabricated via a one-step in situ nanoconfined pyrolysis strategy, which shows remarkable enhanced HER electrocatalytic activity in acidic medium. During pyrolysis, the formed VN nanodots induce the generation of atomic Co Nxsites in NCNTs, contributing to superior electrocatalytic activity. Experimental and density functional theory(DFT) calculation results reveal that the electrode has multiple accessible active sites, fast reaction kinetics, low charge/mass transfer resistances,high conductivity, as well as downshifted d-band center with a thermodynamically favorable hydrogen adsorption free energy(△G_(H·)), all of which greatly boost the HER performance. As a result, the VNCo@CoSAs-NCNTs/CC electrode displays superb catalytic performance toward HER with a low overpotential of 29 mV at 10 mA cm^(-2) in acidic medium, which could maintain for at least 60 h of stable performance. This work opens a facile avenue to explore low-cost, high performance, but inexpensive metals/nitrogen-doped carbon composite electrocatalysts for HER.

Controllable preparation of tungsten/tungsten carbide nanowires or nanodots in nanostructured carbon with hollow macroporous core/mesoporous shell

Large scale tungsten nanowires and tungsten nanodots are prepared in a controllable way. The preparation is based on mechanisms of chemical vapor transportation and phase transformation during the reduction of ammonium metatungstate(AMT) in H_2. The AMT is first encapsulated into the hollow core of nanostructured carbon with hollow macroporous core/mesoporous shell(NC-HMC/MS) and forms nanorods, which are the precursors of both tungsten nanowires and tungsten nanodots. Just by controlling H_2 flow rate and heating rate in the reduction process, the AMT nanorods could turn into nanowires(under low rate condition) or nanodots(under high rate condition). Besides, via heat treatment at 1200?C, the as-obtained nano-sized tungsten could convert into W_2C nanorods or WC nanodots respectively. Furthermore, the diameter of the as-obtained tungsten or tungsten carbide is confined within 50 nm by the NC-HMC/MS, and no agglomeration appears in the obtained nanomaterials.

Carbon-nanodot-coverage-dependent photocatalytic performance of carbon nanodot/TiO2 nanocomposites under visible light

Carbon nanodots(CDs) with visible absorption band and TiO_2 are integrated to enhance the photosensitivity of TiO_2.The CD/TiO_2 nanocomposites show obvious CD-coverage-dependent photocatalytic performance. The CD/TiO_2 nanocomposites with moderate CD coverge exhibit the highest photocatalytic activity after being irradiated with visible light, which is more excellent than that of TiO_2. Too little CD coverage could result in poor visible light absorption, which limits the photocatalytic performance of CD/TiO_2 nanocomposites. While, too much CD coverage weakens the photocatalytic activity of CD/TiO_2 nanocomposites by restraining the extraction of conduction band electrons within TiO_2 to generate active oxygen radicals and the electron transfer(ET) process from CDs to TiO_2. These results indicate that rational regulation of CD coverage and the realization of efficient ET process are important means to optimize the photocatalytic performance of CD/TiO_2 nanocomposites.

A Glucose-Responsive Enzymatic Electrode on Carbon Nanodots for Glucose Biosensor and Glucose/Air Biofuel Cell

In this study, an enzymatic electrode for glucose biosensing and bioanode of glucose/air biofuel cell has been fabricated by immobilizing poly (methylene green) (polyMG) for electrocatalytic NADH oxidation and NAD+-dependent glucose dehydrogenase (GDH) for oxidizing glucose on carbon nanodots (CNDs). The polyMG-CNDscomposites obtained by electro-polymerization of dye MG molecules adsorbed on CNDs display excellent electrocatalytic activity toward NADH electro-oxidation at a low overpotential of ca. -0.10 V (vs. Ag/AgCl) and the integrated enzymatic electrode shows fast response to glucose electrooxidation. Using the fabricated GDH-based enzymatic electrode, a glucose biosensor was constructed and exhibits a wide linear dynamic range from 0 to 8 mM, a low detection limit of 0.02 μM (S/N = 3), and fast response time (ca. 4 s) under the optimized conditions. The developed glucose biosensor was used to detect glucose content in human blood with satisfactory results. The fabricated GDH-based enzymatic electrode was also employed as bioanode to assembly a glucose/air biofuel cell with the laccase-CNDs/GC as the biocathode. The maximum power density delivered by the assembled glucose/air biofuel cell reaches 3.1 μW·cm-2 at a cell voltage of 0.22 V in real sample fruit juice. The present study demonstrates that potential applications of GDH-based CNDs electrode in analytical and biomedical measurements.

Nanodot array deposition via single shot laser interference pattern using laser-induced forward transfer

Laser-induced forward transfer(LIFT)is a direct-writing technique capable of depositing a single dot smaller than the laser wavelength at small shot energy through the laser-induced dot transfer(LIDT)technique.To deposit a single nanodot in a single shot of laser irradiation,a liquid nanodrop is transferred from donor to receiver and finally solidified via a solid–liquid–solid(SLS)process.In conventional LIDT experiments,multi-shots with step scanning have been used to form array structures.However,interference laser processing can achieve an arrayed process and generate a periodic structure in a single shot.In this study,a femtosecond laser interference pattern was first applied to LIDT,and an array of nanodots was successfully deposited in a single shot,producing the following unit structures:a single dot,adjoining dots,and stacking dots.The diameter of the smallest nanodot was 355 nm,and the narrowest gap between two adjoining nanodots was 17.2 nm.The LIDT technique produces high-purity,catalyst-free that do not require post-cleaning or alignment processes.Given these significant advantages,LIDT can expand the usability of nanodots in a wide range of fields.

Shape-induced phase transition of vortex domain structures in ferroelectric nanodots and their controllability by electrical and mechanical loads

Shape-induced phase transition of vortex domain structures(VDSs)in BaTiO_3(BT)nanodots under open circuit boundary condition have been investigated using an effective Hamiltonian method.Our calculation indicates the tetragonal VDS missing in cubic BT nanodots can be induced by varying the shape of a nanodot from cube to platelet.Interestingly,a novel VDS is found in BT nanoplatelets in our simulations.Further investigation shows that it is a result of compromise between the ground state and the symmetry of the shape of the nanodot.Furthermore,based on the novel VDS,routes of controlling VDSs governed by homogeneous electric field and uniform stress are discussed.In particular,our results show the possibility of designing multi-states devices based on a single VDS.

Nanodots and microwires of ZrO_2 grown on LaAlO_3 by photo-assisted metal–organic chemical vapor deposition

ZrO_2 nanodots are successfully prepared on LaAlO_3(LAO)(100) substrates by photo-assisted metal-organic chemical vapor deposition(MOCVD). It is indicated that the sizes and densities of ZrO_2 nanodots are controllable by modulating the growth temperature, oxygen partial pressure, and growth time. Meanwhile, the microwires are observed on the surfaces of substrates. It is found that there is an obvious competitive relationship between the nanodots and the microwires. In a growth temperature range from 500℃ to 660℃, the microwires turn longest and widest at 600℃, but in contrast, the nanodots grow into the smallest diameter at 600℃. This phenomenon could be illustrated by the energy barrier, decomposition rate of Zr(tmhd)_4, and mobility of atoms. In addition, growth time or oxygen partial pressure also affects the competitive relationship between the nanodots and the microwires. With increasing oxygen partial pressure from 451 Pa to 75_2 Pa,the microwires gradually grow larger while the nanodots become smaller. To further achieve the controllable growth, the coarsening effect of ZrO_2 is modified by varying the growth time, and the experimental results show that the coarsening effect of microwires is higher than that of nanodots by increasing the growth time to quickly minimize ZrO_2 energy density.

Density behaviors of Ge nanodots self-assembled by ion beam sputtering deposition

Self-assembled Ge nanodots with areal number density up to 2.33×1010 cm-2 and aspect ratio larger than 0.12 are prepared by ion beam sputtering deposition. The dot density, a function of deposition rate and Ge coverage, is observed to be limited mainly by the transformation from two-dimensional precursors to three-dimensional islands, and to be associated with the adatom behaviors of attachment and detachment from the islands. An unusual increasing temperature dependence of nanodot density is also revealed when a high ion energy is employed in sputtering deposition, and is shown to be related to the breaking down of the superstrained wetting layer. This result is attributed to the interaction between energetic atoms and the growth surface, which mediates the island nucleation.

Large scale and controllable preparation of W2C nanorods or WC nanodots with peroxidase-like catalytic activity

W_2C nanorods or WC nanodots are prepared via an easy,shape-controllable and large-scale preparation technique.Results reveal that each of the W_2C nanorods and WC nanodots has a peroxidase-like activity.Besides,the peroxidase-like activity of W_2C is the first time to be demonstrated.The catalytic efficiency of W_2C nanorods is much higher than that of WC nanodots and chemical condition range of W_2C can be wider than that of WC,which indicates that W_2C is likely to be used as artificial mimetic peroxidase or in-situ amplified colorimetric immunoassay.

Rational design multi-color-emissive chemiluminescent carbon nanodots in a single solvothermal reaction

Recently,the chemiluminescence(CL)induced by carbon nanodots(CDs)has intrigued researchers’extensive interests in various applications due to its special light emission principle.However,the difficulty of synthesizing chemiluminescent CDs with full-spectrum emission severely hinders the further regulation of the CL emission mechanism.Herein,the multi-color-emissive chemiluminescent CDs are rational designed and further synthesized by regulating the sp2-hybrid core and sp3-hybrid surface from the citrate-ammonia molecular in a single solvothermal reaction.More experimental characterizations and density functional theory calculations reveal that the higher temperature can promote the crosslinking polymerization/carbonization of carbon core and the higher protonation of solvent can determine the core size of final CDs,resulting in the variant CL emission from molecular-,crosslinking-and core-states.Thus,the CL emission of the CDs can be further synthesized by tuning the luminescence chromophores in the formation process via regulating the temperature and solvent,enabling the applications of the CL CDs in illumination and information encryption.This study paves a new technology to understand the luminescence of CDs and affords an industry translational potential over traditional chemiluminescent molecular.

Passively-targeted mitochondrial tungsten-based nanodots for efficient acute kidney injury treatment

Acute kidney injury(AKI)can lead to loss of kidney function and a substantial increase in mortality.The burst of reactive oxygen species(ROS)plays a key role in the pathological progression of AKI.Mitochondrial-targeted antioxidant therapy is very promising because mitochondria are the main source of ROS in AKI.Antioxidant nanodrugs with actively targeted mitochondria have achieved encouraging success in many oxidative stress-induced diseases.However,most strategies to actively target mitochondria make the size of nanodrugs too large to pass through the glomerular system to reach the renal tubules,the main damage site of AKI.Here,an ultra-small Tungsten-based nanodots(TWNDs)with strong ROS scavenging can be very effective for treatment of AKI.TWNDs can reach the tubular site after crossing the glomerular barrier,and enter the mitochondria of the renal tubule without resorting to complex active targeting strategies.To our knowledge,this is the first time that ultra-small negatively charged nanodots can be used to passively target mitochondrial therapy for AKI.Through in-depth study of the therapeutic mechanism,such passive mitochondria-targeted TWNDs are highly effective in protecting mitochondria by reducing mitochondrial ROS and increasing mitophagy.In addition,TWNDs can also reduce the infiltration of inflammatory cells.This work provides a new way to passively target mitochondria for AKI,and give inspiration for the treatment of many major diseases closely related to mitochondria,such as myocardial infarction and cerebral infarction.

Microfluidic platform serves as controllable fabrication of binary Mo/Ir nanodots/carbon hetero-material for efficient electrocatalytic nitrogen reduction

Electrocatalytic nitrogen reduction reaction(NRR)is regarded as a potential routine to achieve environment-friendly ammonia production,because of its abundant nitrogen resources,clean energy utilization and flexible operation.However,it is hindered by low activity and selectivity,in which con-dition well-designed catalysts are urgently in need.In this work,a binary Mo/Ir nanodots/carbon(Mo/Ir/C)hetero-material is efficiently constructed via microfluidic strategy,of which the nanodots are ho-mogeneously distributed on the carbon skeleton and the average size is approximately 1 nm.Excellent performance for NRR is obtained in 1 mol L^(-1) KOH,of which the optimized ammonia yield and faradic efficiency are 7.27μg h^(-1) cm^(-2) and 2.31%respectively.Moreover,the optimized ammonia yield of 6.20μg h-1 cm-2 and faradic efficiency of 10.59%are also obtained in 0.005 mol L^(-1) H_(2)SO_(4).This work achieves the continuous-flow synthesis and controllable adjustment of hetero-materials for favorable morphologies,which provides an innovative pathway for catalyst design and further promotes the development of ammonia production field.

Analysis of multi-center topological domain states in BiFeO_(3)nanodot arrays

High-density ferroelectric BiFeO_(3)(BFO)nanodot arrays were developed through template-assisted tailoring of epitaxial thin films.By combining piezoresponse force microscopy(PFM)and Kelvin probe force microscopy(KPFM)imaging techniques,we found that oxygen vacancies in nanodot arrays can be transported in the presence of an electric field.Besides triple-center domains,quadruple-center domains with different vertical polarizations were also identified.This was confirmed by combining the measurements of the domain switching and polarization vector distribution.The competition between the accumulation of mobile charges,such as oxygen vacancies,on the interface and the geometric constraints of nanodots led to the formation of these topological domain states.These abnormal multi-center topological defect states pave the way for improving the storage density of ferroelectric memory devices.

Rational design and synergistic effect of ultrafine Ag nanodots decorated fish-scale-like Zn nanoleaves for highly selective electrochemical CO_(2)reduction

The electrocatalytic CO_(2)reduction reaction(CO_(2)RR)is regarded as a promising route for renewable energy conversion and storage,but its development is limited by the high overpotential and low stability and selectivity of electrocatalysts.Moreover,it is complicated to accurately adjust the nanostructure of electrocatalysts,which impacts repeatability.Herein,we propose the rational design and controlled preparation of ultrafine Ag nanodots decorated fish-scale-like Zn nanoleaves(Ag-NDs/Zn-NLs)for highly selective electrocatalytic CO_(2)reduction.The Ag-NDs/Zn-NLs can be in-situ grown on copper foil with simple electrodeposition and replacement reactions.Benefiting from the coordination and synergistic effect of Zn and Ag species,the reconstruction of Zn surface and the agglomeration of Ag-NDs are efficiently prevented,bringing high activity and durable electrocatalytic stability for CO_(2)-to-CO conversion.The Faradaic efficiency for CO production reaches 85.2%at a moderate applied potential of-1.0 V vs.reversible hydrogen electrode(RHE).This study provides a promising approach for controlling the catalytic activity and selectivity of CO_(2)RR through the structural adjustment and decoration of transition metal based nanocatalysts.