Ultrasmall NiS_(2)Nanocrystals Embedded in Ordered Macroporous Graphenic Carbon Matrix for Efficiently Pseudocapacitive Sodium Storage

Sodium-ion hybrid capacitor(SIHC)is one of the most promising alternatives for large-scale energy storage due to its high energy and power densities,natural abundance,and low cost.However,overcoming the imbalance between slow Na^(+)reaction kinetics of battery-type anodes and rapid ion adsorption/desorption of capacitive cathodes is a significant challenge.Here,we propose the high-rate-performance NiS_(2)@OMGC anode material composed of monodispersed NiS_(2) nanocrystals(8.8±1.7 nm in size)and N,S-co-doped graphenic carbon(GC).The NiS_(2)@OMGC material has a three-dimensionally ordered macroporous(3DOM)morphology,and numerous NiS_(2) nanocrystals are uniformly embedded in GC,forming a core-shell structure in the local area.Ultrafine NiS_(2) nanocrystals and their nano-microstructure demonstrate high pseudocapacitive Na-storage capability and thus excellent rate performance(355.7 mAh/g at 20.0 A/g).A SIHC device fabricated using NiS_(2)@OMGC and commercial activated carbon(AC)cathode exhibits ultrahigh energy densities(197.4 Wh/kg at 398.8 W/kg)and power densities(43.9 kW/kg at 41.3 Wh/kg),together with a long life span.This outcome exemplifies the rational architecture and composition design of this type of anode material.This strategy can be extended to the design and synthesis of a wide range of high-performance electrode materials for energy storage applications.

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.

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.

Valley filtering and valley-polarized collective modes in bulk graphene monolayers

The presence of two sublattices in hexagonal graphene brings two energetically degenerate extremes in the conduction and valence bands, which are identified by the valley quantum number. Recently, this valley degree of freedom has been suggested to encode and process information, which develops a new carbon-based electronics named graphene valleytronics. In this topical review, we present and discuss valley-related transport properties in bulk graphene monolayers,which are due to strain-induced pseudomagnetic fields and associated vector potential, sublattice-stagger potential, and the valley-Zeeman effect. These valley-related interactions can be utilized to obtain valley filtering, valley spatial separation, valley-resolved guiding modes, and valley-polarized collective modes such as edge or surface plasmons. The present challenges and the perspectives on graphene valleytronics are also provided in this review.

A green cross-linking method for the preparation of renewable threedimensional graphene sponges for efficient adsorption of Congo red dye

Graphene-based materials possess significant potential for the treatment of dye wastewater due to their exceptional adsorption properties toward stubborn pollutants.However,their utilization is hindered by high preparation costs,low yields,environmental pollution during synthesis,and challenges in regenerating the adsorbent.This study proposes a novel approach to address these limitations by developing nitrogen-doped three-dimensional(3D)polyvinyl alcohol(PVA)crosslinked graphene sponges(N-PGA)using a cross-linking method with ammonium carbonate.This method offers a relatively mild,environmentally friendly approach.Ammonium carbonate serves as both a reducing and modifying agent,facilitating the formation of the intrinsic structure of N-PGA and acting as a nitrogen source.Meanwhile,PVA is utilized as the cross-linking agent.The results demonstrate that N-PGA exhibits a favorable internal 3D hierarchical porous structure and possesses robust mechanical properties.The measured specific surface area(BET)of N-PGA was as high as406.538 m^(2)·g^(-1),which was favorable for its efficient adsorption of Congo red(CR)dye molecules.At an initial concentration of 50 mg·L^(-1),N-PGA achieved an impressive removal rate of 89.6%and an adsorption capacity of 112 mg·g^(-1)for CR dye.Furthermore,it retained 79%of its initial adsorption capacity after 10 cycles,demonstrating excellent regeneration performance.In summary,the synthesized N-PGA displays remarkable efficacy in the adsorption of CR dye in wastewater,opening up new possibilities for utilizing 3D porous graphene nanomaterials as efficient adsorbents in wastewater treatment.

Density functional theory study of B- and Si-doped carbons and their adsorption interactions with sulfur compounds

Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

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.

Carbon nanocages bridged with graphene enable fast kinetics for dual-carbon lithium-ion capacitors

Lithium-ion capacitors(LICs) combining the advantages of lithium-ion batteries and supercapacitors are considered a promising nextgeneration energy storage device. However, the sluggish kinetics of battery-type anode cannot match the capacitor-type cathode, restricting the development of LICs. Herein, hierarchical carbon framework(HCF) anode material composed of 0D carbon nanocage bridged with 2D graphene network are developed via a template-confined synthesis process. The HCF with nanocage structure reduces the Li^(+) transport path and benefits the rapid Li^(+) migration, while 2D graphene network can promote the electron interconnecting of carbon nanocages. In addition, the doped N atoms in HCF facilitate to the adsorption of ions and enhance the pseudo contribution, thus accelerate the kinetics of the anode. The HCF anode delivers high specific capacity, remarkable rate capability. The LIC pouch-cell based on HCF anode and active HCF(a-HCF) cathode can provide a high energy density of 162 Wh kg^(-1) and a superior power density of 15.8 kW kg^(-1), as well as a long cycling life exceeding 15,000cycles. This study demonstrates that the well-defined design of hierarchical carbon framework by incorporating 0D carbon nanocages and 2D graphene network is an effective strategy to promote LIC anode kinetics and hence boost the LIC electrochemical performance.

Highly Thermoconductive,Strong Graphene‑Based Composite Films by Eliminating Nanosheets Wrinkles

Graphene-based thermally conductive composites have been proposed as effective thermal management materials for cooling high-power electronic devices.However,when flexible graphene nanosheets are assembled into macroscopic thermally conductive composites,capillary forces induce shrinkage of graphene nanosheets to form wrinkles during solution-based spontaneous drying,which greatly reduces the thermal conductivity of the composites.Herein,graphene nanosheets/aramid nanofiber(GNS/ANF)composite films with high thermal conductivity were prepared by in-plane stretching of GNS/ANF composite hydrogel networks with hydrogen bonds andπ-πinteractions.The in-plane mechanical stretching eliminates graphene nanosheets wrinkles by suppressing inward shrinkage due to capillary forces during drying and achieves a high in-plane orientation of graphene nanosheets,thereby creating a fast in-plane heat transfer channel.The composite films(GNS/ANF-60 wt%)with eliminated graphene nanosheets wrinkles showed a significant increase in thermal conductivity(146 W m^(−1)K^(−1))and tensile strength(207 MPa).The combination of these excellent properties enables the GNS/ANF composite films to be effectively used for cooling flexible LED chips and smartphones,showing promising applications in the thermal management of high-power electronic devices.

Graphene-calcium carbonate coating to improve the degradation resistance and mechanical integrity of a biodegradable implant

Biodegradable implants are critical for regenerative orthopaedic procedures,but they may suffer from too fast corrosion in human-body environment.This necessitates the synthesis of a suitable coating that may improve the corrosion resistance of these implants without compromising their mechanical integrity.In this study,an AZ91 magnesium alloy,as a representative for a biodegradable Mg implant material,was modified with a thin reduced graphene oxide(RGO)-calcium carbonate(CaCO_(3))composite coating.Detailed analytical and in-vitro electrochemical characterization reveals that this coating significantly improves the corrosion resistance and mechanical integrity,and thus has the potential to greatly extend the related application field.

Supposition of graphene stacks to estimate the contact resistance and conductivity of nanocomposites

In this study,the effects of stacked nanosheets and the surrounding interphase zone on the resistance of the contact region between nanosheets and the tunneling conductivity of samples are evaluated with developed equations superior to those previously reported.The contact resistance and nanocomposite conductivity are modeled by several influencing factors,including stack properties,interphase depth,tunneling size,and contact diameter.The developed model's accuracy is verified through numerous experimental measurements.To further validate the models and establish correlations between parameters,the effects of all the variables on contact resistance and nanocomposite conductivity are analyzed.Notably,the contact resistance is primarily dependent on the polymer tunnel resistivity,contact area,and tunneling size.The dimensions of the graphene nanosheets significantly influence the conductivity,which ranges from 0 S/m to90 S/m.An increased number of nanosheets in stacks and a larger gap between them enhance the nanocomposite's conductivity.Furthermore,the thicker interphase and smaller tunneling size can lead to higher sample conductivity due to their optimistic effects on the percolation threshold and network efficacy.

2D black arsenic phosphorous

Since the successful exfoliation of graphene in 2014,twodimensional(2D)materials have explosively increased in the past few years[1].2D pnictogen materials with intriguing properties beyond graphene are gradually coming into eyesight,such as black phosphorous(BP)[2],arsenene[3],antimonene[4],bismuthine[5],etc.BP is a star material in 2D materials.

Bending results of graphene origami reinforced doubly curved shell

The present work investigates higher order stress,strain and deformation analyses of a shear deformable doubly curved shell manufactures by a Copper(Cu)core reinforced with graphene origami auxetic metamaterial subjected to mechanical and thermal loads.The effective material properties of the graphene origami auxetic reinforced Cu matrix are developed using micromechanical models cooperate both material properties of graphene and Cu in terms of temperature,volume fraction and folding degree.The principle of virtual work is used to derive governing equations with accounting thermal loading.The numerical results are analytically obtained using Navier's technique to investigate impact of significant parameters such as thermal loading,graphene amount,folding degree and directional coordinate on the stress,strain and deformation responses of the structure.The graphene origami materials may be used in aerospace vehicles and structures and defence technology because of their low weight and high stiffness.A verification study is presented for approving the formulation,solution methodology and numerical results.

Graphene effectively activating "dead" water molecules between manganese dioxide layers in potassium-ion battery

Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies.

Actively tuning anisotropic light-matter interaction in biaxial hyperbolic materialα-MoO_(3) using phase change material VO_(2) and graphene

Anisotropic hyperbolic phonon polaritons(PhPs)in natural biaxial hyperbolic materialα-MoO_(3) has opened up new avenues for mid-infrared nanophotonics,while active tunability ofα-MoO_(3) PhPs is still an urgent problem necessarily to be solved.In this study,we present a theoretical demonstration of actively tuningα-MoO_(3) PhPs using phase change material VO_(2) and graphene.It is observed thatα-MoO_(3) PhPs are greatly dependent on the propagation plane angle of PhPs.The insulator-to-metal phase transition of VO_(2) has a significant effect on the hybridization PhPs of theα-MoO_(3)/VO_(2) structure and allows to obtain actively tunableα-MoO_(3) PhPs,which is especially obvious when the propagation plane angle of PhPs is 900.Moreover,when graphene surface plasmon sources are placed at the top or bottom ofα-MoO_(3) inα-MoO_(3)/VO_(2)structure,tunable coupled hyperbolic plasmon-phonon polaritons inside its Reststrahlen bands(RB s)and surface plasmonphonon polaritons outside its RBs can be achieved.In addition,the above-mentionedα-MoO_(3)-based structures also lead to actively tunable anisotropic spontaneous emission(SE)enhancement.This study may be beneficial for realization of active tunability of both PhPs and SE ofα-MoO_(3),and facilitate a deeper understanding of the mechanisms of anisotropic light-matter interaction inα-MoO_(3) using functional materials.

Progress on the application of graphene-based composites toward energetic materials:A review

Carbon material is an important additive in energetic materials.Graphene is a monolayer carbon material in which carbon atoms are arranged in two-dimensional honeycomb structure,who has special optical,electrical,and mechanical properties.Recently,the application of graphene-based composites in energetic materials has received extensive attention.This review mainly summarizes the applications of graphene and graphene-based nanomaterials in energetic materials.The effects of these materials on the thermal stability,sensitivity,mechanical property,ignition and combustion of energetic materials were discussed.Furthermore,the progress of functionalized modification of graphene has been summarized,including covalent bonding modification and doping modification.These studies show that graphenebased materials exhibit excellent performances and might emerge as promising candidate for energetic materials.

Construction of core@double-shell structured energetic composites with simultaneously enhanced thermal stability and safety performance

The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane(CL-20).Herein,a kind of novel core@double-shell CL-20 based energetic composites were fabricated to address the above issues.The coordination complexes which consist of natural polyphenol tannic acid(TA) and Fe~Ⅲ were chosen to construct the inner shell,while the graphene sheets were used to build the outer shell.The resulting CL-20/TA-Fe~Ⅲ/graphene composites exhibited simultaneously improved thermal stability and safety performance with only 1 wt% double-shell content,which should be ascribed to the intense physical encapsulation effect from inner shell combined with the desensitization effect of carbon nano-materials from outer shell.The phase transition(ε to γ) temperature increased from 173.70 ℃ of pure CL-20 to 191.87℃ of CL-20/TA-Fe~Ⅲ/graphene composites.Meanwhile,the characteristic drop height(H_(50)) dramatically increased from 14.7 cm of pure CL-20 to112.8 cm of CL-20/TA-Fe~Ⅲ/graphene composites,indicating much superior safety performance after the construction of the double-shell structure.In general,this work has provided an effective and versatile strategy to conquer the thermal stability and safety issues of CL-20 and contributes to the future application of high energy density energetic materials.

Mussel-inspired Methacrylic Gelatin-dopamine/Ag Nanoparticles/Graphene Oxide Hydrogels with Improved Adhesive and Antibacterial Properties for Applications as Wound Dressings

A novel strategy was developed to prepare the methacrylic gelatin-dopamine(GelMA-DA)/Ag nanoparticles(NPs)/graphene oxide(GO) composite hydrogels with good biocompatibility,mechanical properties,and antibacterial activity.Mussel-inspired DA was utilized to modify the GelMA molecules,which imparts good adhesive performance to the hydrogels.GO,interfacial enhancer,not only improves mechanical properties of the hydrogels,but also provides anchor sites for loading Ag NPs through numerous oxygencontaining functional groups on the surface.The experimental results show that the GelMA/Ag NPs/GO hydrogels have good biocompatibility,and exhibit a swelling rate of 202±16%,the lap shear strength of 147±17 kPa,and compressive modulus of 136±53 kPa,in the case of the Ag NPs/GO content of 2 mg/mL.Antibacterial activity of the hydrogels against both gram-negative and gram-positive bacteria is dependent on the Ag NPs/GO content derived from the release of Ag^(+).Furthermore,the GelMA/Ag NPs/GO hydrogels possess good adhesive ability,which is resistant to highly twisted state when stuck on the surface of pigskin.These results demonstrate promising potential of the GelMA-DA/Ag NPs/GO hydrogels as wound dressings for biomedical applications in clinical and emergent treatment.

Spin-polarized pairing induced by the magnetic field in the Bernal bilayer graphene

Recent experimental findings have demonstrated the occurrence of superconductivity in Bernal bilayer graphene when induced by a magnetic field.In this study,we conduct a theoretical investigation of the potential pairing symmetry within this superconducting system.By developing a theoretical model,we primarily calculate the free energy of the system with p+ip-wave parallel spin pairing,p+ip-wave anti-parallel spin pairing and d+i d-wave pairing symmetry.Our results confirm that the magnetic field is indeed essential for generating the superconductivity.We discover that the p+ip-wave parallel spin pairing leads to a lower free energy for the system.The numerical calculations of the energy band structure,zero-energy spectral function and density of states for each of the three pairing symmetries under consideration show a strong consistency with the free energy results.