Heterogeneous single-cluster catalysts(Mn_(3),Fe_(3),Co_(3),and Mo_(3))supported on nitrogen-doped graphene for robust electrochemical nitrogen reduction

Electrochemical nitrogen reduction reaction(NRR)is one of the most promising alternatives to the traditional Haber-Bosch process.Designing efficient electrocatalysts is still challenging.Inspired by the recent experimental and theoretical advances on single-cluster catalysts(SCCs),we systematically investigated the catalytic performance of various triple-transition-metal-atom clusters anchored on nitrogen-doped graphene for NRR through density functional theory(DFT)calculation.Among them,Mn_(3)-N4,Fe_(3)-N4,Co_(3)-N4,and Mo_(3)-N4 were screened out as electrocatalysis systems composed of non-noble metal with high activity,selectivity,stability,and feasibility.Particularly,the Co_(3)-N4 possesses the highest activity with a limiting potential of-0.41 V through the enzymatic mechanism.The outstanding performance of Co_(3)-N4 can be attributed to the unique electronic structure leading to strong π backdonation,which is crucial in effective N_(2) activation.This work not only predicts four efficient non-noble metal electrocatalysts for NRR,but also suggest the SCCs can serve as potential candidates for other important electrochemical reactions.

Zeolitic imidazolate framework-67 derived Al-Co-S hierarchical sheets bridged by nitrogen-doped graphene:Incorporation of PANI derived carbon nanorods for solid-state asymmetric supercapacitors

Metal sulfides have been widely enticed as battery-type electrodes in supercapacitor devices because of their maximal theoretical capacitance.Nevertheless,their lower conductivity and ion transport kinetics can largely restrict their rate performance,hence the practical usage in fields of demanding high power devices.Therefore,the design of new electrodes with higher energy and power densities remains a highly challenging task.To the best of our knowledge,a novel hierarchical composite of Al-CoS_(2) on nitrogendoped graphene(NG)is prepared based on a zeolite imidazole framework using a simple and scalable hydrothermal process.In this hybrid,ultrathin Al-CoS_(2) nanosheet arrays are vertically orientated on the NG framework to limit self-aggregation,hence increasing the electrical property and cycle stability of composite.It is investigated that the Al/Co feeding ratio plays a crucial role in controlling the obtained hierarchical structure of Al-Co-S sheets and their electrode performance.Also,Al^(3+) can influence remarkably the morphology and electrochemical property of the resultant graphene composite.An effective synergism is noticed between the redox Al-CoS_(2) and NG resulting in fast electron transfer and chargingdischarging processes.Surprisingly,when the as-developed composite is utilized as a positive electrode at an applied current density of 1 A/g,a specific capacitance of 1915.8 F/g is attained with ultra-long cycle stability(96%,10,000 cycles)and an excellent retention rate(~89%).As a consequence,when a solid-state asymmetric supercapacitor(ASC)device is made by combining an Al-CoS_(2) @NG hybrid with a negative electrode made of polyaniline(PANI)derived carbon nanorods(PCNRs),it demonstrates remarkable specific capacitance(188 F/g),energy density(66.9 Wh/kg),and cyclic stability of 92%after 10,000 cycles.This may open the pathway for the application of the next-generation supercapacitors in the future.

Novel Formaldehyde Sensor based on Hydrogen Peroxide/Melamine Modulated Photoluminescence of Nitrogen-doped Graphene Quantum Dots

A modulated photoluminescence nanosensor was developed for the quantitative detection of formaldehyde with nitrogen-doped graphene quantum dots and melamine. The sensing system was based on the different activated effects of melamine and hydrogen peroxide on the photoluminescence intensity of nitrogendoped graphene quantum dots. Under the optimal conditions, the modulated photoluminescence sensing system can be used to detect formaldehyde with a good linear relationship between the nitrogen-doped graphene quantum dots photoluminescence difference and the concentration of formaldehyde. The novel sensing system provided new directions for the detection of formaldehyde with high selectivity and quick response.

Nitrogen-doped TiO_(2)/Graphene Composites Synthesized via the Vapour-thermal Method

TiO_(2)/graphene composite was synthesized in the vapor environment of isopropanol.In order to improve the properties of composite,N-doped of TiO_(2)/graphene with different N/Ti molar ratio was prepared in the vapor environment of deionized water and used urea as the source of nitrogen.The N-doped occupies in the interstitial sites of TiO_(2) lattice,substitutes for O element in TiO_(2) and for C element in graphene,and simultaneously changes the chemical states of Ti and O elements in TiO_(2).N-doped changes the morphology of TiO_(2) from nano-sheets to nanoparticles,accompanying with the decrease in specific surface area of the composites,first increases the particle size of TiO_(2) and then decreases,and alters the vibration modes of Ti-OTi.The composite with RN/Ti=2 exhibits the enhanced photocatalytic degradation performance to methylene blue,and the degradation rate increases from 7.7×10^(−2) min^(−1) for the undoped composite to 9.6×10^(−2) min^(−1).

C-Nanostructures Cluster Models in Organic Solvents： Fullerenes, Tubes, Buds and Graphenes

The existence of nanographene in cluster form is discussed in organic solvents. Theories are developed based on the columnlet, bundlet and droplet models describing the size-distribution functions. Phenomena present a unified explanation in the columnlet model in which free energy of Cgraphene involved in cluster is combined from a volume part proportional to the number of molecules n in cluster and a constant. The columnlet model enables describing distribution function of Cgraphene clusters by size. From purely geometrical considerations the columnlet （Cgraphene）, bundlet （single-wall carbon nanotube）, CNT （carbon nanotube）, SWNT （single-wall C-nanotube）, and carbon nanobud, CNB （carbon nanobud）） and droplet （fullerene） models predict dissimilar behaviours. The interaction-energy parameters of Cgraphene are taken from C60. An CNB behaviour or further is expected. The decay of solubility with rising temperature is smaller for Cgraphene than for SWNT and CNB and, furthermore, than for C60, in agreement with lesser numbers of units in Cgraphene clusters. The discrepancy between the experimental data of the heat of solution of fullerenes, CNTs, CNBs and graphenes is ascribed to the sharp concentration dependence of the heat of solution. The diffusion coefficient drops with temperature result greater for Cgraphene than CNB and SWNT than C60 corresponding to lesser number of units in clusters. The aggregates near （C60）13, SWNT/CNB7 and （Cgraphene）3 could be representative of the droplet, bundlet and columnlet models.

Modified Nitrogen-Doped Graphene Electrocatalyst for Oxygen Reduction Reaction in Alkaline Fuel Cells

We report modified nitrogen-doped graphene （CN） as electrocatalyst for ORR （oxygen reduction reaction） in alkaline medium. CN was synthesized by a novel procedure based on graphite oxide thermally treated with cyanamide suitable for facile N-doping and large-scale production, whereas cyanamide was used as N-precursor. The structure of the material was characterized by TEM （transmission electron microscopy）, SEM （scanning electron microscopy）, Raman spectroscopy and XPS （X-ray photoelectron spectroscopy）. Structural and electrochemical properties of CN were compared with those of non-modified graphene （TRGO （thermally reduced graphite oxide））. The electrochemical characterization of TRGO and CN in alkaline solution demonstrates enhanced electrocatalytic ORR activity and improved long-term stability for N-doped CN. Voltammetric studies confirmed that, oxygen reduction on CN rather follows four-electron pathway. Compared with commercial 20% PtC catalyst, CN is characterized by exceptional methanol crossover resistance and superb long-term operation stability. Owing to these factors, nitrogen-doped graphene has a great potential to be used as metal-free electrocatalyst in cathodes of alkaline fuel cells.

Morphological features and nanostructures generated during SiC graphitization process

Surface morphological features and nanostructures generated during SiC graphitization process can significantly affect fabrication of high-quality epitaxial graphene on semiconductor substrates.In this work,we investigate the surface morphologies and atomic structures during graphitization process of 4H-SiC(0001) using scanning tunneling microscopy.Our high-magnified scanning-tunneling-microscope images exhibit the appearance and gradual developments of SiC(1 × 1)nanostructures after 1100℃ cleaning treatments,irregularly distributed among carbon nanocaps and(√3×√3) reconstruction domains.A model for the formation and growth progression of SiC(1 × 1) nanostructures has been proposed.When post-annealing temperature reaches 1300 ℃,the nanoholes and nanoislands can be observed on the surface,and multilayer graphene is often detected lying on the top surface of those nanoislands.These results provide profound insights into the complex evolution process of surface morphology during SiC thermal decomposition and will shed light on fabrication of SiC nanostructures and graphene nanoflakes.

Honeycomb-like MoCo alloy on 3D nitrogen-doped porous graphene for efficient hydrogen evolution reaction

An efficient electrocatalyst is indispensable to significantly reduce energy consumption and accelerate the conversion efficiency of water splitting.In this work,the honeycomb-like porous MoCo alloy on nitrogen-doped three-dimensional(3D)porous graphene substrate(Mo_(0.3)Co_(0.7)@NPG)has been synthesized from the annealing of layered double hydroxide(MoCo-LDH@NPG).Especially,the Mo_(0.3)Co_(0.7)@NPG exhibits low hydrogen evolution overpotential of 75 mV(10 mA·cm^(-2))and a Tafel slope of 69.9 mV·dec^(-1),which can be attributed to highly conductive NPG substrate,the unique nanostructure and the synergistic effect of Mo and Co.Moreover,the Mo_(0.3)Co_(0.7)@NPG can maintain the original morphology and high catalytic activity after 50-h stability test.This work proposes a general strategy to synthesize a multi-element alloy on conductive substrates with high porosity for electrocatalytic reaction.

Uncovering the magnetic response of open-shell graphene nanostructures on metallic surfaces at different doping levels

Open-shell graphene nanostructures(GNs)are promising candidates for future spintronics and quantum technologies.Recent progress based on on-surface synthetic approach has successfully created such GNs on metallic surfaces.Meanwhile,the doping effect of metallic surfaces is inevitably present and can significantly tune their electronic and magnetic properties.Here,we investigate the zigzag end states of open-shell 7-armchair graphene nanoribbons(7-AGNRs)on Au(111),Au(100)and Ag(111)surfaces.Combined with the manipulation of a scanning tunneling microscope,we demonstrate that the end states can be tuned from empty states to singly occupied states and to doubly occupied states by substrate doping.Furthermore,the singly occupied states can be finely tuned,with the occupancy number of the states and related magnetic behaviors uncovered by experiments at different temperatures and magnetic fields.Our results provide a comprehensive study of the magnetic response of open-shell GNs on metallic surfaces at different doping levels.

Optical bistability and multistability via double dark resonance in graphene nanostructure

Electrons in graphene nanoribbons can lead to exceptionally strong optical responses in the infrared and terahertz regions owing to their unusual dispersion relation.Therefore,on the basis of quantum optics and solid-material scientific principles,we show that optical bistability and multistability can be generated in graphene nanostructure under strong magnetic field.We also show that by adjusting the intensity and detuning of infrared laser field,the threshold intensity and hysteresis loop can be manipulated efficiently.The effects of the electronic cooperation parameter which are directly proportional to the electronic number density and the length of the graphene sample are discussed.Our proposed model may be useful for the nextgeneration all-optical systems and information processing based on nano scale devices.

Enhanced Kerr nonlinearity in a quantized four-level graphene nanostructure

In this paper, a new model is proposed for manipulating the Kerr nonlinearity of right-hand circular probe light in a monolayer of graphene nanostructure. By using the density matrix equations and quantum optical approach, the third-order susceptibility of probe light is explored numerically. It is realized that the enhanced Kerr nonlinearity with zero linear absorption can be provided by selecting the appropriate quantities of controllable parameters, such as Rabi frequency and elliptical parameter of elliptical polarized coupling field. Our results may be useful applications in future all-optical system devices in nanostructures.

Microspheres of graphene oxide coupled to N-doped Bi_2O_2CO_3 for visible light photocatalysis

Hierarchical microspheres of a graphene oxide（GO） coupled to N‐doped（BiO）2CO3 composite（N‐BOC‐GO） was synthesized by a simple hydrothermal approach. The N‐BOC‐GO composite gave enhancement in photocatalytic activity compared to the pure BOC and N‐BOC samples. With 1.0wt% GO, 62% NO removal was obtained with N‐BOC‐GO. The factors enhancing the photocatalytic performance were the high electron‐withdrawing ability and high conductivity of GO and improved visible light‐harvesting ability of N‐BOC‐GO with a 3D hierarchical architecture due to the surface scattering and reflecting（SSR） effect. An effective charge transfer from N‐BOC to GO was demonstrated by the much weakened photoluminescene intensity of the N‐BOC‐GO composite. This work highlights the potential application of GO‐based photocatalysts in air purification.

Octopus-like DNA nanostructure coupled with graphene oxide enhanced fluorescence anisotropy for hepatitis B virus DNA detection

Fluorescence Anisotropy(FA)is an effective biochemical detection method based on molecular rotations.Graphene oxide(GO)has been extensively used as an FA amplifier.However,the enhancement of FA by GO alone is limited and the strong scattering of GO will easily make the measurement of FA inaccurate.In order to address these problems,an octopus-like DNA nanostructure(ODN)was designed and coupled with GO to enhance the FA together in this work.By mimicking the multi-clawed structure of the octopus,the ODN can be adsorbed on GO tightly,which not only could improve the sensitivity because of the double FA enhancement abilities of GO and ODN,but also could improve the specificity due to the decrease of the nonspecific interaction in complex samples.Furthermore,ODN could maintain a certain distance between the fluorophore and GO to reduce the fluorescence quenching efficiency of GO,which could improve the accuracy.This method has been applied for the detection of hepatitis B virus DNA(HBV-DNA)in a range of 1-50 nmol/L and the limit of detection(LOD)was 330 pmol/L.In addition,the proposed method has been successfully utilized to detect HBV-DNA in human serum,indicating that this method has a great practical application prospect.

Kinetic study of methane hydrate formation in the presence of carbon nanostructures

The effect of synthesized nanostructures,including graphene oxide,chemically reduced graphene oxide with sodium dodecyl sulfate(SDS),chemically reduced graphene oxide with polyvinylpyrrolidone,and multi-walled carbon nanotubes,on the kinetics of methane hydrate formation was investigated in this work.The experiments were carried out at a pressure of 4.5 MPa and a temperature of 0 ℃ in a batch reactor.By adding nanostructures,the induction time decreases,and the shortest induction time appeares at certain concentrations of reduced graphene oxide with SDS and graphene oxide,that is,at a concentration of 360 ppm for reduced graphene oxide with SDS and 180 ppm for graphene oxide,with a 98% decrease in induction time compared to that in pure water.Moreover,utilization of carbon nanostructures increases the amount and the rate of methane consumed during the hydrate formation process.Utilization of multi-walled carbon nanotubes with a concentration of 90 ppm showes the highest amount of methane consumption.The amount of methane consumption increases by 173% in comparison with that in pure water.The addition of carbon nanostructures does not change the storage capacity of methane hydrate in the hydrate formation process,while the percentage of water conversion to hydrate in the presence of carbon nanotubes increases considerably,the greatest value of which occurres at a 90 ppm concentration of carbon nanotubes,that is,a 253% increase in the presence of carbon nanotubes compared to that of pure water.

One-Pot Microwave-Assisted Synthesis of Graphene/Layered Double Hydroxide(LDH) Nanohybrids

A facile and rapid method to synthesize graphene/layered double hydroxide(LDH)nanohybrids by a microwave technique is demonstrated.The synthesis procedure involves hydrothermal crystallization of Zn–Al LDH at the same time in situ reduction of graphene oxide(GO)to graphene.The microstructure,composition,and morphology of the resulting graphene/LDH nanohybrids were characterized.The results confirmed the formation of nanohybrids and the reduction of graphene oxide.The growth mechanism of LDH and in situ reduction of GO were discussed.The LDH sheet growth was found to prevent the scrolling of graphene layers in resulting hybrids.The electrochemical properties exhibit superior performance for graphene/Zn–Al LDH hybrids over pristine graphene.The present approach may open a strategy in hybridizing graphene with multimetallic nano-oxides and hydroxides using microwave method.

Self-assembly of nitrogen-doped TiO_(2) with exposed {001} facets on a graphene scaffold as photo-active hybrid nanostructures for reduction of carbon dioxide to methane

Tailored synthesis of well-defined anatase TiO_(2)-based crystals with exposed{001}facets has stimulated incessant research interest worldwide due to their scientific and technological importance.Herein,anatase nitrogen-doped TiO_(2)(N-TiO_(2))nanoparticles with exposed{001}facets deposited on the graphene(GR)sheets(N-TiO_(2)-001/GR)were synthesized for the first time via a one-step solvothermal synthetic route using NH4F as the morphology-controlling agent.The experimental results exemplified that GR was uniformly covered with anatase N-TiO_(2) nanoparticles(10-17 nm),exposing the{001}facets.The percentage of exposed{001}facets in the N-TiO_(2)-001/GR nanocomposites was calculated to be ca.35%.Also,a red shift in the absorption edge and a strong absorption in the visible light range were observed due to the formation of Ti-O-C bonds,resulting in the successful narrowing of the band gap from 3.23 to 2.9 eV.The photocatalytic activities of the as-prepared photocatalysts were evaluated for CO_(2) reduction to produce CH,in the presence of water vapor under ambient temperature and atmospheric pressure using a low-power 15 W energy-saving daylight lamp as the visible light source--in contrast to the most commonly employed high-power xenon lamps--which rendered the process economically and practically feasible.Among all the studied photocatalysts,the N-TiO_(2)-001/GR nanocomposites exhibited the greatest CH4 yield of 3.70 p-mol'gcatalyst 1,approxi-mately 11-fold higher activity than the TiO_(2)-001.The enhancement of photocatalyfic performance was ascribed to the effective charge anti-recombination of graphene,high absorption of visible light region relative to the{101}facets.and high catalytic activity of{001}facets.

Electron-Induced Perpendicular Graphene Sheets Embedded Porous Carbon Film for Flexible Touch Sensors

Graphene-based materials on wearable electronics and bendable displays have received considerable attention for the mechanical flexibility,superior electrical conductivity,and high surface area,which are proved to be one of the most promising candidates of stretching and wearable sensors.However,polarized electric charges need to overcome the barrier of graphene sheets to cross over flakes to penetrate into the electrode,as the graphene planes are usually parallel to the electrode surface.By introducing electron-induced perpendicular graphene(EIPG)electrodes incorporated with a stretchable dielectric layer,a flexible and stretchable touch sensor with"in-sheet-chargestransportation"is developed to lower the resistance of carrier movement.The electrode was fabricated with porous nanostructured architecture design to enable wider variety of dielectric constants of only 50-μm-thick Ecoflex layer,leading to fast response time of only 66 ms,as well as high sensitivities of 0.13 kPa-1 below 0.1 kPa and 4.41 MPa-1 above 10 kPa,respectively.Moreover,the capacitance-decrease phenomenon of capacitive sensor is explored to exhibit an object recognition function in one pixel without any other integrated sensor.This not only suggests promising applications of the EIPG electrode in flexible touch sensors but also provides a strategy for internet of things security functions.

Core-shell particles of C-doped CdS and graphene: A noble metal-free approach for efficient photocatalytic H_(2) generation

To achieve efficient photocatalytic H_(2) generation from water using earth-abundant and cost-effective materials,a simple synthesis method for carbon-doped CdS particles wrapped with graphene(C-doped CdS@G)is reported.The doping effect and the application of graphene as cocatalyst for CdS is studied for photocatalytic H_(2) generation.The most active sample consists of CdS and graphene(CdS-0.15G)exhibits promising photocatalytic activity,producing 3.12 mmol g^-(1) h^-(1) of H_(2) under simulated solar light which is^4.6 times superior than pure CdS nanoparticles giving an apparent quantum efficiency(AQY)of 11.7%.The enhanced photocatalytic activity for H_(2) generation is associated to the narrowing of the bandgap,enhanced light absorption,fast interfacial charge transfer,and higher carrier density(N_(D))in C-doped CdS@G samples.This is achieved by C doping in CdS nanoparticles and the formation of a graphene shell over the C-doped CdS nanoparticles.After stability test,the spent catalysts sample was also characterized to investigate the nanostructure.

Nanoscale strain engineering of graphene and graphene-based devices

Structural distortions in nano-materials can induce dramatic changes in their electronic properties. This situation is well manifested in graphene, a two-dimensional honeycomb structure of carbon atoms with only one atomic layer thickness. In particular, strained graphene can result in both charging effects and pseudo-magnetic fields, so that controlled strain on a perfect graphene lattice can be tailored to yield desirable electronic properties. Here, we describe the theoretical foundation for strain-engineering of the electronic properties of graphene, and then provide experimental evidence for strain-induced pseudo-magnetic fields and charging effects in monolayer graphene. We further demonstrate the feasibility of nano-scale strain engineering for graphene-based devices by means of theoretical simulations and nano-fabrication technology.

Effective exposure of nitrogen heteroatoms in 3D porous graphene framework for oxygen reduction reaction and lithium–sulfur batteries

The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.