Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

Enhanced reversible hydrogen storage properties of wrinkled graphene microflowers confined LiBH_(4) system with high volumetric hydrogen storage capacity

LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.

Electrodeposition of chitosan/graphene oxide conduit to enhance peripheral nerve regeneration

Currently available commercial nerve guidance conduits have been applied in the repair of peripheral nerve defects.However,a conduit exhibiting good biocompatibility remains to be developed.In this work,a series of chitosan/graphene oxide(GO)films with concentrations of GO varying from 0-1 wt%(collectively referred to as CHGF-n)were prepared by an electrodeposition technique.The effects of CHGF-n on proliferation and adhesion abilities of Schwann cells were evaluated.The results showed that Schwann cells exhibited elongated spindle shapes and upregulated expression of nerve regeneration-related factors such as Krox20(a key myelination factor),Zeb2(essential for Schwann cell differentiation,myelination,and nerve repair),and transforming growth factorβ(a cytokine with regenerative functions).In addition,a nerve guidance conduit with a GO content of 0.25%(CHGFC-0.25)was implanted to repair a 10-mm sciatic nerve defect in rats.The results indicated improvements in sciatic functional index,electrophysiology,and sciatic nerve and gastrocnemius muscle histology compared with the CHGFC-0 group,and similar outcomes to the autograft group.In conclusion,we provide a candidate method for the repair of peripheral nerve defects using free-standing chitosan/GO nerve conduits produced by electrodeposition.

Poly(ionic liquid)-crosslinked graphene oxide/carbon nanotube membranes as efficient solar steam generators

Graphene oxide(GO)is regarded as a promising candidate to construct solar absorbers for addressing freshwater crisis,but the easy delamination of GO in water poses a critical challenge for practical solar desalination.Herein,we improve the stability of GO membranes by a self-crosslinking poly(ionic liquid)(PIL)in a mild condition,which crosslinks neighbouring GO nanosheets without blemishing the hydrophilic structure of GO.By further adding carbon nanotubes(CNTs),the sandwiched GO/CNT@PIL(GCP)membrane displays a good stability in pH=1 or 13 solution even for 270 days.The molecular dynamics simulation results indicate that the generation of water nanofluidics in nanochannels of GO nanosheets remarkably reduces the water evaporation enthalpy in GCP membrane,compared to bulk water.Consequently,the GCP membrane exhibits a high evaporation rate(1.87 kg m^(-2)h^(-1))and displays stable evaporation rates for 14 h under 1 kW m^(-2)irradiation.The GCP membrane additionally works very well when using different water sources(e.g.,dye-polluted water)or even strong acidic solution(pH=1)or basic solution(pH=13).More importantly,through bundling pluralities of GCP membrane,an efficient solar desalination device is developed to produce drinkable water from seawater.The average daily drinkable water amount in sunny day is 10.1 kg m^(-2),which meets with the daily drinkable water needs of five adults.The high evaporation rate,long-time durability and good scalability make the GCP membrane an outstanding candidate for practical solar seawater desalination.

Graphene Quantum Dot‑Mediated Atom‑Layer Semiconductor Electrocatalyst for Hydrogen Evolution

The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide(2H-MoS_(2))presents a significant hurdle in realizing its full potential applications.Here,we utilize theoretical calculations to predict possible functionalized graphene quantum dots(GQDs),which can enhance HER activity of bulk MoS_(2).Subsequently,we design a functionalized GQD-induced in-situ bottom-up strategy to fabricate near atom-layer 2H-MoS_(2) nanosheets mediated with GQDs(ALQD)by modulating the concentration of electron withdrawing/donating functional groups.Experimental results reveal that the introduction of a series of functionalized GQDs during the synthesis of ALQD plays a crucial role.Notably,the higher the concentration and strength of electron-withdrawing functional groups on GQDs,the thinner and more active the resulting ALQD are.Remarkably,the synthesized near atom-layer ALQD-SO_(3)demonstrate significantly improved HER performance.Our GQD-induced strategy provides a simple and efficient approach for expanding the catalytic application of MoS_(2).Furthermore,it holds substantial potential for developing nanosheets in other transition-metal dichalcogenide materials.

Porous heterostructure of graphene/hexagonal boron nitride as an efficient electrocatalyst for hydrogen peroxide generation

Compared with the traditional heteroatom doping,employing heterostructure is a new modulating approach for carbon-based electrocatalysts.Herein,a facile ball milling-assisted route is proposed to synthesize porous carbon materials composed of abundant graphene/hexagonal boron nitride(G/h-BN)heterostructures.Metal Ni powder and nanoscale h-BN sheets are used as a catalytic substrate/hard template and“nucleation seed”for the formation of the heterostructure,respectively.As-prepared G/h-BN heterostructures exhibit enhanced electrocatalytic activity toward H_(2)O_(2) generation with 86%-95%selectivity at the range of 0.45-0.75 V versus reversible hydrogen electrode(RHE)and a positive onset potential of 0.79 versus RHE(defined at a ring current density of 0.3 mA cm^(-2))in the alkaline solution.In a flow cell,G/h-BN heterostructured electrocatalyst has a H_(2)O_(2) production rate of up to 762 mmol g_(catalyst)^(-1) h^(-1) and Faradaic efficiency of over 75%during 12 h testing,superior to the reported carbon-based electrocatalysts.The density functional theory simulation suggests that the B atoms at the interface of the G/h-BN heterostructure are the key active sites.This research provides a new route to activate carbon catalysts toward highly active and selective O_(2)-to-H_(2)O_(2) conversion.

Reduced graphene oxide-embedded nerve conduits loaded with bone marrow mesenchymal stem cell-derived extracellular vesicles promote peripheral nerve regeneration

We previously combined reduced graphene oxide(rGO)with gelatin-methacryloyl(GelMA)and polycaprolactone(PCL)to create an rGO-GelMA-PCL nerve conduit and found that the conductivity and biocompatibility were improved.However,the rGO-GelMA-PCL nerve conduits differed greatly from autologous nerve transplants in their ability to promote the regeneration of injured peripheral nerves and axonal sprouting.Extracellular vesicles derived from bone marrow mesenchymal stem cells(BMSCs)can be loaded into rGO-GelMA-PCL nerve conduits for repair of rat sciatic nerve injury because they can promote angiogenesis at the injured site.In this study,12 weeks after surgery,sciatic nerve function was measured by electrophysiology and sciatic nerve function index,and myelin sheath and axon regeneration were observed by electron microscopy,immunohistochemistry,and immunofluorescence.The regeneration of microvessel was observed by immunofluorescence.Our results showed that rGO-GelMA-PCL nerve conduits loaded with BMSC-derived extracellular vesicles were superior to rGO-GelMA-PCL conduits alone in their ability to increase the number of newly formed vessels and axonal sprouts at the injury site as well as the recovery of neurological function.These findings indicate that rGO-GelMA-PCL nerve conduits loaded with BMSC-derived extracellular vesicles can promote peripheral nerve regeneration and neurological function recovery,and provide a new direction for the curation of peripheral nerve defect in the clinic.

基于midas Gen的单层球形网壳结构分析及应用研究

基于midas Gen软件模型,在不同应力比下对实体工程金属网壳模型进行分析,获得了工程实体金属网壳模型静力荷载下铸钢铰支座反力、罕遇地震时铸钢铰支座反力、静力荷载销轴反力、罕遇地震销轴反力分布情况。将设计模型得到的实体工程金属网壳荷载–位移曲线与有关设计模型网壳荷载–位移曲线进行对比,通过实体工程金属网壳模型设计实例,分析了不同应力下的杆件位移情况,从而证明了实体工程金属网壳模型设计的准确性及合理性。

Phosphorus and nitrogen co-doped graphene for catalytic dehydrochlorination of 1,2-dichloroethane

A phosphorus and nitrogen co-doped graphene(PNG)was developed via a two-step pyrolysis approach through the intermedium of g-C_(3)N_(4) template and glyphosate as the phosphorus source,and was used for the catalytic dehydrochlorination of 1,2-dichloroethane(EDC)to vinyl chloride monomer(VCM)production.The characterization results indicate that a volcano relationship of surface area and surface properties with the usage of phosphorus precursor was observed,and the sample of PNG-900-6 possesses not only the thin film structure with enhanced surface area but also the smaller grain size of PNG attachments.Accordingly,such PNGs show a great improvement of catalytic performance in the dehydrochlorination of EDC,and the PNG-900-6 catalyst behaves the best with a 4-times higher activity than that on the nitrogen doped graphene(NG).It was also proved that the synergetic effect of the unique P-C coordination on the graphene to generate more quaternary nitrogen species was crucial in determining the catalytic performance of EDC conversion.Our results demonstrate that the phosphorus and nitrogen co-doped graphene offers many advantages in physical structure and chemical property,and are also great potential on the catalytic application in the dehydrochlorination of 1,2-dichloroethane.

Emergence of correlations in twisted monolayer-trilayer graphene heterostructures

Twisted bilayer graphene heterostructures have recently emerged as a well-established platform for studying strongly correlated phases,such as correlated insulating,superconducting,and topological states.Extending this notion to twisted multilayer graphene heterostructures has exhibited more diverse correlated phases,as some fundamental properties related to symmetry and band structures are correspondingly modified.Here,we report the observations of correlated states in twisted monolayer-trilayer(Bernal stacked)graphene heterostructures.Correlated phases at integer fillings of the moire unit cell are revealed at a high displacement field and stabilized with a moderate magnetic field on the electron-doping side at a twist angle of 1.45°,where the lift of degeneracy at the integer fillings is observed in the Landau fan diagram.Our results demonstrate the effectiveness of moire engineering in an extended structure and provide insights into electric-field tunable correlated phases.

Spatial-five coordination promotes the high efficiency of CoN_(4) moiety in graphene-based bilayer for oxygen reduction electrocatalysis: A density functional theory study

The searching of highly efficient catalysts for oxygen reduction reaction(ORR) has attracted particular attention. In this work, we construct the graphene-based bilayers BG/X that consists by the CoN_(4) embedded graphene as the upper layer and the X modified graphene as the bottom layer(X = Si, P, S). The interfacial bonding between CoN_(4) site and the X dopant is spontaneously formed due to the strong pd hybridization, which changes the Co ligand from the planar-four N_(4) coordination into spatial-five N_(4)+X one. The additive glue atom weakens too strong adsorptions of the ORR intermediates on CoN_(4) site and thereby improves the ORR activities in comparison with the monolayer counterpart. From the free energy profiles, the overpotentials η are 0.47, 0.49 and 0.45 V for BG/Si_(a), BG/P_(a) and BG/S_(a), respectively,being comparable to that of state-of-the-art Pt material. Besides, the kinetic barriers for the bilayers are less than 0.75 eV, an indicative of the room temperature activity. Furthermore, the combination of thermodynamic and kinetic analysis ensures the preference of 4e^(-)-OOH associative mechanism over 2e^(-)-H_(2)O_(2) mechanism, being beneficial for membrane stability against the H_(2)O_(2) corrosion. Therefore,the graphene-based bilayers deliver the high efficiencies for oxygen reduction electrocatalysis.Therefore, the interfacial bonding in the graphene-based bilayers provides an interesting strategy to suppress the poisoning phenomenon for the material design from atom scale.

Greatly enhanced corrosion/wear resistances of epoxy coating for Mg alloy through a synergistic effect between functionalized graphene and insulated blocking layer

The poor corrosion and wear resistances of Mg alloys seriously limit their potential applications in various industries.The conventional epoxy coating easily forms many intrinsic defects during the solidification process,which cannot provide sufficient protection.In the current study,we design a double-layer epoxy composite coating on Mg alloy with enhanced anti-corrosion/wear properties,via the spin-assisted assembly technique.The outer layer is functionalized graphene(FG)in waterborne epoxy resin(WEP)and the inner layer is Ce-based conversion(Ce)film.The FG sheets can be homogeneously dispersed within the epoxy matrix to fill the intrinsic defects and improve the barrier capability.The Ce film connects the outer layer with the substrate,showing the transition effect.The corrosion rate of Ce/WEP/FG composite coating is 2131 times lower than that of bare Mg alloy,and the wear rate is decreased by~90%.The improved corrosion resistance is attributed to the labyrinth effect(hindering the penetration of corrosive medium)and the obstruction of galvanic coupling behavior.The synergistic effect derived from the FG sheet and blocking layer exhibits great potential in realizing the improvement of multi-functional integration,which will open up a new avenue for the development of novel composite protection coatings of Mg alloys.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

Radiative Blood-Based Hybrid Copper-Graphene Nanoliquid Flows along a Source-Heated Leaning Cylinder

Variant graphene,graphene oxides(GO),and graphene nanoplatelets(GNP)dispersed in blood-based copper(Cu)nanoliquids over a leaning permeable cylinder are the focus of this study.These forms of graphene are highly beneficial in the biological and medical fields for cancer therapy,anti-infection measures,and drug delivery.The non-Newtonian Sutterby(blood-based)hybrid nanoliquid flows are generalized within the context of the Tiwari-Das model to simulate the effects of radiation and heating sources.The governing partial differential equations are reformulated into a nonlinear set of ordinary differential equations using similar transformational expressions.These equations are then transformed into boundary value problems through a shooting technique,followed by the implementation of the bvp4c tool in MATLAB.The influences of various parameters on the model’s nondimensional velocity and temperature profiles,reduced skin friction,and reduced Nusselt number are presented for detailed discussions.The results indicated that Cu-GNP/blood and Cu-GO/blood hybrid nanofluids exhibit the lowest and highest velocity distributions,respectively,for increased nanoparticles volume fraction,curvature parameter,Sutterby fluid parameter,Hartmann number,and wall permeability parameter.Conversely,opposite trends are observed for the temperature distribution for all considered parameters,except the mixed convection parameter.Increases in the reduced skin friction magnitude and the reduced Nusselt number with higher values of graphene/GO/GNP nanoparticle volume fraction are also reported.Finally,GNP is identified as the superior heat conductor,with an average increase of approximately 5%and a peak of 7.8%in the reduced Nusselt number compared to graphene and GO nanoparticles in the Cu/blood nanofluids.

Aggregation-regulated bioreduction process of graphene oxide by Shewanella bacteria

The bioreduction of graphene oxide(GO)using environmentally functional bacteria such as Shewanella represents a green approach to produce reduced graphene oxide(rGO).This process differs from the chemical reduction that involves instantaneous molecular reactions.In bioreduction,the contact of bacterial cells and GO is considered the rate-limiting step.To reveal how the bacteria-GO integration regulates rGO production,the comparative experiments of GO and three Shewanella strains were carried out.Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,Raman spectroscopy,and atomic force microscopy were used to characterize the reduction degree and the aggregation degree.The results showed that a spontaneous aggregation of GO and Shewanella into the condensed entity occurred within 36 h.A positive linear correlation was established,linking three indexes of the aggregation potential,the bacterial reduction ability,and the reduction degree(ID/IG)comprehensively.

A study of highly activated hydrogen evolution reaction performance in acidic media by 2D heterostructure of N and S doped graphene on MoO_(x)

Herein,a layer of molybdenum oxide(MoO_(x)),a transition metal oxide(TMO),which has outstanding catalytic properties in combination with a carbonbased thin film,is modified to improve the hydrogen production performance and protect the MoO_(x)in acidic media.A thin film of graphene is transferred onto the MoO_(x)layer,after which the graphene structure is doped with N and S atoms at room temperature using a plasma doping method to modify the electronic structure and intrinsic properties of the material.The oxygen functional groups in graphene increase the interfacial interactions and electrical contacts between graphene and MoO_(x).The appearance of surface defects such as oxygen vacancies can result in vacancies in MoO_(x).This improves the electrical conductivity and electrochemically accessible surface area.Increasing the number of defects in graphene by adding dopants can significantly affect the chemical reaction at the interfaces and improve the electrochemical performance.These defects in graphene play a crucial role in the adsorption of H^(+)ions on the graphene surface and their transport to the MoO_(x)layer underneath.This enables MoO_(x)to participate in the reaction with the doped graphene.N^(‐)and S^(‐)doped graphene(NSGr)on MoO_(x)is active in acidic media and performs well in terms of hydrogen production.The initial overpotential value of 359 mV for the current density of−10 mA/cm^(2)is lowered to 228 mV after activation.

Valley-dependent transport in a mescoscopic twisted bilayer graphene device

We study the valley-dependent electron transport in a four-terminal mesoscopic device of the two monolayer graphene nanoribbons vertically stacked together, where the intersection forms a bilayer graphene lattice with a controllable twist angle. Using a tight-binding lattice model, we show that the longitudinal and transverse conductances exhibit significant valley polarization in the low energy regime for small twist angles. As the twist angle increases, the valley polarization shifts to the high energy regime. This arises from the regrouping effect of the electron band in the twisted bilayer graphene region. But for relatively large twist angles, no significant valley polarization is observed. These results are consistent with the spectral densities of the twisted bilayer graphene.

对二维Graphene/VS_(2)/BN范德华多层异质结构作为LIBs的阳极材料的相关研究

通过范德华尔斯作用将单层石墨烯(Graphene)、单层二硫化钒(VS2)和单层氮化硼(BN)构建成Graphene/VS2/BN范德华三层异质结构,并将其与不同数量的锂结合,研究了其作为锂离子电池(Li-Ion Batterys,LIBs)中阳极电极材料的可行性.Graphene/VS_(2)/BN范德华三层异质结构具有-0.33 e V/A2的形成能,具有较强的稳定性,理论上可实现合成.同时,计算了Graphene/VS_(2)/BN范德华异质结构的平面内刚度,得出的杨氏模量(Y)为886.88 N/m,高于单层VS_(2)的Y(82.5 N/m),具有较好的力学性能.Graphene/VS_(2)/BN范德华三层异质结构表面和界面上吸附Li的吸附能(-5~-2 e V)远大于相应单层的吸附能,表明其对Li具有较好的吸附性能.Li在Graphene/VS_(2)/BN范德华三层异质结构的不同表面和界面处迁移时的扩散势垒非常小(0.3~0.6 e V),对电池速率性能极为有利.Graphene/VS_(2)/BN范德华三层异质结构在LIBs的阳极电极材料方面的应用具有广泛的前景.

Improving the operational stability of perovskite solar cells with cesium-doped graphene oxide interlayer

Perovskite solar cells(PSCs)have made great advances in terms of power conversion efficiency(PCE),yet their subpar stability continues to hinder their commercialization.The interface between the perovskite layer and the charge-carrier transporting layers plays a crucial role in undermining the stability of PSCs.In this work,we propose a strategy to stabilize high-performance PSCs with PCE over 23%by introducing a cesium-doped graphene oxide(GO-Cs)as an interlayer between the perovskite and hole-transporting material.The GO-Cs treated PSCs exhibit excellent operational stability with a projected T80(the time where the device PCE reduces to 80%of its initial value)of 2143 h of operation at the maximum powering point under one sun illumination.

La内嵌graphene/MoS_(2)层的储氢性能研究

运用密度泛函理论研究了La内嵌graphene/MoS_(2)层的储氢性能.由于La的内嵌graphene/MoS_(2)异质结的层间距被拉大.详细研究了氢气分子在La内嵌的graphene/MoS_(2)结构上的吸附行为.结果表明,一个La原子最多可以吸附六个氢气分子,采用GGA/PBE泛函计算得到氢气分子的平均吸附能为0.198 eV.合适的吸附能使得设计材料能够在温和条件下实现可逆存储.重要的是,La原子能够分散地内嵌在graphene/MoS_(2)异质结中,这将为氢气分子提供更多吸附位.研究表明理论上预测La内嵌graphene/MoS_(2)材料是一种潜在的储氢材料.