Surface-Modified Graphene Oxide/Lead Sulfide Hybrid Film-Forming Ink for High-Efficiency Bulk Nano-Heterojunction Colloidal Quantum Dot Solar Cells

Solution-processed colloidal quantum dot solar cells(CQDSCs) is a promising candidate for new generation solar cells.To obtain stable and high performance lead sulfide(PbS)-based CQDSCs,high carrier mobility and low non-radiative recombination center density in the PbS CQDs active layer are required.In order to effectively improve the carrier mobility in PbS CQDs layer of CQDSCs,butylamine(BTA)-modified graphene oxide(BTA@GO) is first utilized in PbS-PbX2(X=I-,Br-) CQDs ink to deposit the active layer of CQDSCs through one-step spin-coating method.Such surface treatment of GO dramatically upholds the intrinsic superior hole transfer peculiarity of GO and attenuates the hydrophilicity of GO in order to allow for its good dispersibility in ink solvent.The introduction of B TA@GO in CQDs layer can build up a bulk nano-heterojunction architecture,which provides a smooth charge carrier transport channel in turn improves the carrier mobility and conductivity,extends the carriers lifetime and reduces the trap density of PbS-PbX2 CQDs film.Finally,the BTA@GO/PbS-PbX2 hybrid CQDs film-based relatively large-area(0.35 cm2) CQDSCs shows a champion power conversion efficiency of 11.7% which is increased by 23.1% compared with the control device.

Sensitive Voltammetric Determination of Mitoxantrone by Using CS-Dispersed Graphene Modified Glassy Carbon Electrodes

A novel CS-dispersed graphene modified glassy carbon electrode was fabricated. Study electrochemical characteristics of mitoxantrone in the CS-dispersed graphene modified electrode by cyclic voltammetry and other methods, by selecting and optimizing the various parameters to create a new electrochemical method for the determination of mitoxantrone. The linear range of the oxidation peak current is from 6×10–10 to 1 ×10–6 mol/l in this method, after 2.5 mins open-circuit accumulation, the limit of detection is 2×10–10 mol/l. After 10 parallel determinations, the relative standard deviation was 3.7% that the concentration of mitoxantrone was 1×10–8 mol/l. The modified electrode has been successfully applied for the assay of mitoxantrone in human urine samples.

Highly dispersed Pd nanoparticles on chemically modified graphene with aminophenyl groups for formic acid oxidation

A novel electrode material based on chemically modified graphene （CMG） with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine. Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction. The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts.

Study on the Hydration and Physical Properties of Cement by M18 Polycarboxylate Superplasticizer Modified Graphene Oxide

Graphene oxide(GO)as a new nano-enhancer in cement-based materials has gained wide attention.However,GO is easy to aggregate in alkaline cement mortar with poor dispersibility.This hinders its application in practical infrastructure construction.In this work,GO-M18 polycarboxylate compound superplasticizer(GM)were obtained by compounding the M18 polycarboxylate superplasticizer with GO solution at different mass ratios.The dispersion of GM in alkaline solution was systematically studied.The phases and functional groups of GM were characterized by XRD and FTIR.The effects of GM on the cement mortar hydration and the formation of microstructure were investigated by measuring the heat of hydration,MIP,TG/DSC,and SEM.The results show that the long-chain structure of the M18 polycarboxylate superplasticizer can increase the interlayer spacing of GO and weaken the force between GO sheets.The modified GO can be uniformly dispersed in the cement slurry.GM can accelerate the early hydration process of cement,which can increase the content of Ca(OH)2 and decrease the grain size.It can optimize the pore size distribution of cement-based materials,increase the density of harmless and less harmful pores,thereby improving mechanical properties.Such methods can transform traditional cement-based materials into stronger,more durable composites,which prolong the life of cement-based materials and reduce the amount of cement used for later maintenance.This provides an idea for achieving sustainability goals in civil engineering.

Structural and Optical Properties of Graphene Oxide Prepared by Modified Hummers’Method

Graphene oxide was synthesized from graphite flakes using modified Hummers’method.The interlayer spacings of graphite,graphite oxide and graphene oxide were measured using X-ray diffraction technique.The C/O atomic ratios of graphite oxide and graphene oxide were calculated from XPS measurements.The transformation of graphite to graphite oxide and finally to graphene oxide was clearly observed from the micro-Raman spectroscopy data and was confirmed from the FESEM micrographs.UV-VIS-NIR spectrophotometer was used to study the absorbance of graphene oxide and reduced graphene oxide samples.Finally,the chemically reduced graphene oxide was heat-treated in air to obtain chemically modified graphene.

Controllable Nucleation of Nanobubbles at a Modified Graphene Surface

The properties of nanoscale gas bubbles at the solid/water interface have been investigated for more than 20 years. However, the stability of nanobubbles remains far from being understood. How to control the formation of nanobubbles is the key issue for understanding their long lifetime. In this work, using molecular dynamics simulations we modify the substrate （graphene） with charge dipoles in which the local properties of the surface could be changed. Nanobubbles could be stabilized on the local hydrophobic area and modified area with the hydrophilic boundary where gas nuclei are deposited beforehand. Those results provide two methods to control the nucleation of gas nanobubbles and fix them on a target area.

Ion and water transport in charge-modified graphene nanopores

Porous graphene has a high mechanical strength and an atomic-layer thickness that makes it a promising material for material separation and biomolecule sensing. Electrostatic interactions between charges in aqueous solutions are a type of strong long-range interaction that may greatly influence fluid transport through nanopores. In this study, molecular dynamic simulations were conducted to investigate ion and water transport through 1.05-nm diameter monolayer graphene nanopores, with their edges charge-modified. Our results indicated that these nanopores are selective to counterions when they are charged. As the charge amount increases, the total ionic currents show an increase-decrease profile while the coion currents monotonically decrease. The co-ion rejection can reach 76.5% and 90.2% when the nanopores are negatively and positively charged, respectively. The Cl-ion current increases and reaches a plateau, and the Na＋current decreases as the charge amount increases in systems in which Na＋ions act as counterions. In addition, charge modification can enhance water transport through nanopores. This is mainly due to the ion selectivity of the nanopores. Notably, positive charges on the pore edges facilitate water transport much more strongly than negative charges.

Graphene/Rh(111) Structure Studied Using In-Situ Scanning Tunneling Microscopy

Scanning tunnel microscopy （STM） is performed to verify if an Rh ＇nails＇ structure is formed accompanying the graphene growing during chemical vapor deposition. A structure of a graphene island in an Rh vacancy island is used as the start. While the graphene island is removed by oxygenation, the variations of the Rh vacancy island are imaged with an in-situ high-temperature STM. By fitting with our model and calculations, we conclude that the best fit is obtained for 0% Rh, i.e., for the complete absence of nails below graphene on Rh（111）. That is, when graphene is formed on Rh（111）, the substrate remains fiat and does not develop a SUPPorting nail structure.

Fe3C-N-doped carbon modified separator for high performance lithium-sulfur batteries

A new Fe3C-N-doped reduced graphene oxide(Fe3C-N-rGO)prepared by a facile method is used as a separator for high performance lithium-sulfur(Li-S)batteries.The Fe3C-N-rGO is coated on the surface of commercial polypropylene separator(Celgard 2400)close to the sulfur cathode.The special nanotubes are in-situ catalyzed by Fe3C nanoparticles.They could entrap lithium polysulfides(Li PSs)to restrain the shuttle effect and reduce the loss of active material.The battery with the modified separator and sulfur cathode shows an excellent cycle performance.It has a high rate performance,580.5 mAh/g at the high current rate of 4 C relative to 1075 mAh/g at 0.1 C.It also has an initial discharge capacity of 774.8 m Ah/g measured at 0.5 C and remains 721.8 mAh/g after 100 cycles with a high capacity retention of 93.2%.The outstanding performances are notable in recently reports with modified separator.

A 3D graphene/polyimide fiber framework with improved thermal conductivity and mechanical performance

The integration of electronic components and the popularity of flexible devices have come up with higher expectations for the heat dissipation capability and comprehensive mechanical performance of thermal management materials.In this work,after the modification of polyimide(PI)fibers through oxidation and amination,the obtained PDA@OPI fibers(polydopamine(PDA)-modified pre-oxidized PI fibers)with abundant amino groups were mixed into graphene oxide(GO)to form uniform GO-PDA@OPI composites.Followed by evaporation,carbonization,graphitization and mechanical compaction,the G-gPDA@OPI films with a stable three-dimensional(3D)long-range interconnected covalent structure were built.In particular,due to the rich covalent bonds between GO layers and PDI@OPI fibers,the enhanced synergistic graphitization promotes an ordered graphitized structure with less interlayer distance between adjacent graphene sheets in composite film.As a result,the optimized G-gPDA@OPI film displays an improved tensile strength of 78.5 MPa,tensile strain of 19.4%and thermal conductivity of 1028 W/(m·K).Simultaneously,it also shows superior flexibility and high resilience.This work provides an easily-controlled and relatively low-cost route for fabricating multifunctional graphene heat dissipation films.

Preparation and capacitance properties of Ni foam@graphene@Co_(3)O_(4)composite electrode materials

Graphene under high temperature was prepared and loaded on Ni foam.Then,cobalt tetroxide precursor was grown on Ni foam in situ by the hydrothermal method.Finally,the sample was burned at high temperature to obtain Co_(3)O_(4)+graphene@Ni.The hydrothermal method used in this paper is easy to operate,with low-risk factors and environmental protection.The prepared Co_(3)O_(4)+graphene@Ni electrode exhibits superior electrochemical performance than Co_(3)O_(4)@Ni electrode.At a current density of 1 A/g,the specific capacitance of the Co_(3)O_(4)+graphene@Ni electrode calculated by a charge-discharge test is 935 F/g,which is much larger than that of Co_(3)O_(4)@Ni electrode of 340 F/g.

Molecular insights on Ca^(2+)/Na+separation via graphene-based nanopores:The role of electrostatic interactions to ionic dehydration

Ca^(2+)/Na+separation is a common problem in industrial applications,biological and medical fields.However,Ca^(2+)and Na+have similar ionic radii and hydration radii,thus Ca^(2+)/Na+separation is challenging.Inspired by biological channels,group modification is one of the effective methods to improve the separation performance.In this work,molecular dynamics simulations were performed to investigate the effects of different functional groups(COO,NH3+)on the separation performance of Ca^(2+)and Na+through graphene nanopores under an electric field.The pristine graphene nanopore was used for comparison.Results showed that three types of nanopores preferred Ca^(2+)to Na+,and Ca^(2+)/Na+selectivity followed the order of GE-COO(4.06)>GE(1.85)>GE-NH3+(1.63).Detailed analysis of ionic hydration microstructure shows that different nanopores result in different hydration factors for the second hydration layer of Ca^(2+)and the first layer of Na+.Such different hydration factors corresponding to the dehydration ability can effectively evaluate the separation performance.In addition,the breaking of hydrogen bonds between water molecules due to electrostatic effects can directly affect the dehydration ability.Therefore,the electrostatic effect generated by group modification will affect the ionic hydration microstructure,thus reflecting the differences in dehydration ability.This in turn affects the permeable and separation performance of cations.The results of this work provide perceptive guidelines for the application of graphene-based membranes in ion separation.

In situ polymerization preparation and mechanical properties of nanocomposites based on PA10T/10I-block-PEG copolymer and graphene oxide

Poly(decamethylene terephthalamide/decamethylene isophthalamide)-block-polyvinyl alcoho)(PA10 T/10 IPEG) copolymer/graphene oxide(GO) composites were prepared via in-situ melt polymerization and two different nano-filler addition approaches were compared. The relationship between the micro-structure and performance of the elastomer composites prepared by one-step and two-step methods was explored. The results show that the two-step method significantly promoted the dispersion of the GO in a polymer matrix, and facilitated the grafting of more hard molecular chains. Thus, the elastic modulus and tensile strength of the nanocomposite have been significantly improved by the presence of GO. This was because of the strong interaction between the functional groups on the surface of the GO and the hard molecular chains. This would be also be favorable to load transfer across the interface. Additionally, the elongation at the break of composites increased by 10% with the addition of a small amount of GO(0.2% wt). This is because hard domains tend to be enriched on the surface of GO in composites and act as a lubricating layer at the interface between the GO and matrix, leading to increased deformation ability. This work provides an effective strategy to prepare elastomer composites with high strength and toughness.

Graphene as adsorbent for highly efficient extraction of modified nucleosides in urine prior to liquid chromatography-tandem mass spectrometry analysis

RNA modifications have been involved in numerous biological processes, and aberrations of these modifications are tightly associated with various diseases including cancer. Herein, we developed graphenebased solid-phase extraction and robust ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) combined with stable isotope-dilution for simultaneous enrichment and accurate determination of 17 modified nucleosides in human urine. We found graphene could effectively adsorb various modified nucleosides in human urine samples. With this method, we identified and quantified these modified nucleosides in urine samples collected from lung cancer patients and healthy controls.We revealed that the levels of 12 modified nucleosides were all diminished in urine from lung cancer patients, compared with healthy controls. It is worth noting that we demonstrated, for the first time, the presence of 5,2-O-dimethyluridine(m~5U_m) in human urine. Together, we established a robust analytical method for simultaneous determinations of 17 modified nucleosides in human urine, and our results revealed a close correlation between the concentrations of urinary modified nucleosides and the occurrence of lung cancer, implying the potential applications of these modified nucleosides as noninvasive biomarkers for the early detection of lung cancer. Moreover, this study will stimulate future investigations on the regulatory roles of RNA modifications in the initiation and progression of lung cancer.

Modification of separators with neodymium oxide/graphene composite to enhance lithium-sulfur battery performance

Lithium-sulfur(Li-S) batteries have generated significant attention due to their high theoretical specific capacity and energy density among a host of energy storage power devices.Nevertheless,the lithium polysulfide dissolution shuttle that occurs within Li-S batteries will lead to capacity deterioration and inadequate cycling stability.In the paper,we proposed a measure to deal with the above problems by modifying the separator with Nd_(2)O_(3)/graphene composite in Li-S batteries.Graphene's special chemical properties and structural qualities make it an excellent choice for Li-S batteries.Meanwhile,Nd_(2)O_(3) has a strong binding affinity with lithium polysulfide due to its low electronegativity,which exhibits Lewis' s acidity and forms strong interactions with lithium polysulfide,which is strongly Lewis basic.By utilizing these advantageous properties,Li-S batteries assembling Nd_(2)O_(3)-decorated reduced graphite oxide modified polypropylene separators(Nd_(2)O_(3)/RGO/PP) demonstrate outstanding electrochemical performance,including a mere 0.0525% capacity attenuation rate under 2C during 1000 cycles and with exceptional rate performance of 614 mAh/g even at 3C.This study presents valuable knowledge for effectively modifying separators using rare earth oxides to incorporate graphene,ultimately promoting the practical application of Li-S batteries.

Modified graphene as novel lubricating additive with high dispersion stability in oil

Graphene is a promising material as a lubricant additive for reducing friction and wear.Here,a dispersing method which combines chemical modification of graphene by octadecylamine and dicyclohexylcarbodiimide with a kind of effective dispersant has been successfully developed to achieve the remarkable dispersion stability of graphene in base oil.The stable dispersion time of modified graphene(0.5 wt%)with dispersant(1 wt%)in PAO-6 could be up to about 120 days,which was the longest time reported so far.At the same time,the lubricant exhibits a significant improvement of tribological performance for a steel ball to plate tribo-system with a normal load of 2 N.The coefficient of friction between sliding surfaces was~0.10 and the depth of wear track on plate was~21 nm,which decreased by about 44%and 90%when compared to pure PAO-6,respectively.Furthermore,the analysis of the lubricating mechanisms in regard to the sliding-induced formation of nanostructured tribo-film has been contacted by using Raman spectra and TEM.

Formation of uniform reduced graphene oxide films on modified PET substrates using drop-casting method

In this work,uniform reduced graphene oxide（RGO） films were formed on poly-（ethylene terephthalate）（PET） substrates using a simple drop-casting method.We investigated four types of substrates：unmodified PET,polydopamine-coated PET.carboxyl-group-modified PET,and alkyl-group-modified PET.Upon water evaporation,the surface of the polydopamine-modified PET substrates can interact with the reduced graphene oxide sheets to form flattened and continuous RGO films,which exhibit a sheet resistance of 21.75 kΩ/sq at 82% transmittance.The result indicates that the properties of the surface groups determined whether uniform and flattened RGO films could be formed on the substrates.Hence,we proposed a simple and effective way to produce transparent and conductive films in which the catechol unit exhibits a great effect on the deposition of uniform RGO films on PET substrates.

A novel ZnO/reduced graphene oxide and Prussian blue modified carbon paste electrode for the sensitive determination of Rutin

A carbon paste modified sensor based on a novel composite of zinc oxide nanoparticles deposited on reduced graphene oxide(ZnO-rGrO) and Prussian blue(PB) was drop-cast(ZnO-rGrO-PB/MCPE) for the sensitive estimation of Rutin(Rtn) at pH 7.0.The high surface area of ZnO-rGrO and electrocatalytic property of PB promotes the oxidation of Rtn. Field emission scanning electron microscope(FE-SEM) and energy-dispersive X-ray spectroscopy(EDX) techniques were employed to confirm the deposition of ZnO-rGrO and PB on carbon paste electrode(CPE). The ability of ZnO-rGrO-PB/MCPE in charge transfer at the interface was investigated using electrochemical impedance spectroscopy(EIS). The heterogeneous rate constant(ks) and the charge transfer coefficient(α) have been calculated as 6.08 s^(-1) and 0.74 respectively. This sensor showed a wide linear response for Rtn from 7.0×10^(-8)to 7.0×10^(-6) M and 7.0×10^(-6) to 1.0×10^(-4) M with a limit of detection(2.05±0.04)×10^(-8) M(S/N=3). The application of ZnO-rGrO-PB/MCPE was found in the analysis of Rtn in fruit juice samples using standard addition method. This sensor showed good reproducibility, stability, selectivity and sensitivity.

Electrochemical Study and Application on Shikonin at Poly（diallyldimethylammonium chloride） Functionalized Graphene Sheets Modified Glass Carbon Electrode

The electrochemical behaviors of shikonin at a poly（diallyldimethylammonium chloride） functionalized graphene sheets modified glass carbon electrode（PDDA-GS/GCE） have been investigated. Shikonin could exhibit a pair of well-defined redox peaks at the PDDA-GS/GCE located at 0.681 V（Epa） and 0.662 V（Epc）[vs. saturated calo- mel electrode（SCE）] in 0.1 mol/L phosphate buffer solution（pH=2.0） with a peak-to-peak separation of about 20 mV, revealing a fast electron-transfer process. Moreover, the current response was remarkably increased at PDDA- GS/GCE compared with that at the bare GCE. The electrochemical behaviors of shikonin at the modified electrode were investigated. And the results indicate that the reaction involves the transfer of two electrons, accompanied by two protons and the electrochemical process is a diffusional-controlled electrode process. The electrochemical para- meters of shikonin at the modified electrode, the electron-transfer coefficient（a）, the electron-transfer number（n） and the electrode reaction rate constant（ks） were calculated to be as 0.53, 2.18 and 3.6 s^-1, respectively. Under the optimal conditions, the peak current of differential pulse voltammetry（DPV） increased linearly with the shikonin concentra- tion in a range from 9A72×10^-8 mol/L to 3,789×10^-6 mol/L with a detection limit of 3,157× 10^-8 mol/L. The linear regression equation was Ip=O.7366c＋0.7855（R=0.9978; lp： 10-7 A, c： 10-8 mol/L）. In addition, the modified glass carbon electrode also exhibited good stability, selectivity and acceptable reproducibility that could be used for the sensitive, simple and rapid determination of shikonin in real samples. Therefore, the present work offers a new way to broaden the analytical application of graphene in pharmaceutical analysis.

A novel 2D graphene oxide modified α-AgVO_(3) nanorods: Design, fabrication, and enhanced visible-light photocatalytic performance

Silver vanadates are promising visible-light-responded photocatalysts with suitable bandgap for solar absorption.However,the easy recombination of photogenerated carriers limits their performance.To overcome this obstacle,a novel 2D graphene oxide(GO)modifiedα-AgVO_(3) nanorods(GO/α-AgVO_(3) )photocatalyst was designed herein to improve the separation of photocarriers.The GO/α-AgVO_(3) was fabricated through a facile in-situ coprecipitation method at room temperature.It was found that the as-prepared 0.5 wt%GO/α-AgVO_(3) exhibited the most excellent performance for rhodamine B(RhB)decomposition,with an apparent reaction rate constant 18 times higher than that of pureα-AgVO_(3) under visible-light irradiation.In light of the first-principles calculations and the hetero junction analysis,the mechanism underpinned the enhanced photocatalytic performance was proposed.The enhanced photocatalytic performance was ascribed to the appropriate bandgap ofα-AgVO_(3) nanorods for visible-light response and efficient separation of photocarriers through GO nanosheets.This work demonstrates the feasibility of overcoming the easy recombination of photogenerated carriers and provides a valuable GO/α-AgVO_(3) photocatalyst for pollutant degradation.