Highly Aligned Graphene Aerogels for Multifunctional Composites

Stemming from the unique in-plane honeycomb lattice structure and the sp^(2)hybridized carbon atoms bonded by exceptionally strong carbon–carbon bonds,graphene exhibits remarkable anisotropic electrical,mechanical,and thermal properties.To maximize the utilization of graphene’s in-plane properties,pre-constructed and aligned structures,such as oriented aerogels,films,and fibers,have been designed.The unique combination of aligned structure,high surface area,excellent electrical conductivity,mechanical stability,thermal conductivity,and porous nature of highly aligned graphene aerogels allows for tailored and enhanced performance in specific directions,enabling advancements in diverse fields.This review provides a comprehensive overview of recent advances in highly aligned graphene aerogels and their composites.It highlights the fabrication methods of aligned graphene aerogels and the optimization of alignment which can be estimated both qualitatively and quantitatively.The oriented scaffolds endow graphene aerogels and their composites with anisotropic properties,showing enhanced electrical,mechanical,and thermal properties along the alignment at the sacrifice of the perpendicular direction.This review showcases remarkable properties and applications of aligned graphene aerogels and their composites,such as their suitability for electronics,environmental applications,thermal management,and energy storage.Challenges and potential opportunities are proposed to offer new insights into prospects of this material.

Fabrication of super-elastic graphene aerogels by ambient pressure drying and application to adsorption of oils

Three-dimensional graphene-based aerogels have promising applications in oil adsorption and environmental restoration.However,current research of graphene-based aerogels is often hindered by high preparation cost,poor mechanical properties and low recycling efficiency.Here,superelastic graphene aerogel(SGA)was prepared through one-step freezing and twice hydrothermal reduction followed by drying under ambient pressure.The simple atmospheric drying provides a possibility for large-scale preparation of high performance graphene-based aerogels.The prepared SGA not only has the ability of highly repeatable compression rebound,but also exhibits excellent oil adsorption performance.And the overall performance of SGA is better than most of graphenebased aerogels prepared by freeze drying.After the SGA was cyclically compressed with 70%strain for 300 times,it can return to the original shape and height substantially.SGA retained about 90%of the initial adsorption capacity after 50 cycles of adsorption and compression regeneration for cyclohexane.

Hyperelastic Graphene Aerogels Reinforced by In‑suit Welding Polyimide Nano Fiber with Leaf Skeleton Structure and Adjustable Thermal Conductivity for Morphology and Temperature Sensing

Graphene-aerogel-based flexible sensors have heat tolerances and electric-resistance sensitivities superior to those of polymer-based sensors.However,graphene sheets are prone to slips under repeated compression due to inadequate chemical con-nections.In addition,the heat-transfer performance of existing compression strain sensors under stress is unclear and lacks research,making it difficult to perform real-temperature detections.To address these issues,a hyperelastic polyimide fiber/graphene aerogel(PINF/GA)with a three-dimensional interconnected structure was fabricated by simple one-pot compound-ing and in-situ welding methods.The welding of fiber lap joints promotes in-suit formation of three-dimensional crosslinked networks of polyimide fibers,which can effectively avoid slidings between fibers to form reinforced ribs,preventing graphene from damage during compression.In particular,the inner core of the fiber maintains its macromolecular chain structure and toughness during welding.Thus,PINF/GA has good structural stabilities under a large strain compression(99%).Moreover,the thermal and electrical conductivities of PINF/GA could not only change with various stresses and strains but also keep the change steady at specific stresses and strains,with its thermal-conductivity change ratio reaching up to 9.8.Hyperelastic PINF/GA,with dynamically stable thermal and electrical conductivity,as well as high heat tolerance,shows broad applica-tion prospects as sensors in detecting the shapes and temperatures of unknown objects in extreme environments.

Investigation of Projectile Impact Behaviors of Graphene Aerogel Using Molecular Dynamics Simulations

Graphene aerogel(GA),as a novel solid material,has shown great potential in engineering applications due to its unique mechanical properties.In this study,the mechanical performance of GA under high-velocity projectile impacts is thoroughly investigated using full-atomic molecular dynamics(MD)simulations.The study results show that the porous structure and density are key factors determining the mechanical response of GA under impact loading.Specifically,the impact-induced penetration of the projectile leads to the collapse of the pore structure,causing stretching and subsequent rupture of covalent bonds in graphene sheets.Moreover,the effects of temperature on the mechanical performance of GA have been proven to be minimal,thereby highlighting the mechanical stability of GA over a wide range of temperatures.Finally,the energy absorption density(EAD)and energy absorption efficiency(EAE)metrics are adopted to assess the energy absorption capacity of GA during projectile penetration.The research findings of this work demonstrate the significant potential of GA for energy absorption applications.

Fiber-reinforced Three-dimensional Graphene Aerogels for Electrically Conductive Epoxy Composites with Enhanced Mechanical Properties

To enhance the mechanical properties of three-dimensional graphene aerogels with aramid fibers, graphene/organic fiber aerogels are prepared by chemical reduction of graphene oxide in the presence of organic fibers of poly（p-phenylene terephthalamide） （PPTA） and followed by freeze-drying. Thermal annealing of the composite aerogels at 1300℃ is adopted not only to restore the conductivity of the reduced graphene oxide component but also to convert the insulating PPTA organic fibers to conductive carbon fibers by the carbonization. The resultant graphene/carbon fiber aerogels （GCFAs） exhibit high electrical conductivities and enhanced compressive properties, which are highly efficient in improving both mechanical and electrical performances of epoxy composites. Compared to those of neat epoxy, the compressive modulus, compressive strength and energy absorption of the electrically conductive GCFA/epoxy composite are significantly increased by 60%, 59% and 131%, respectively.

Facile Synthesis of Nitrogen-Doped Graphene Aerogels for Electrode Materials in Supercapacitors

Three-dimensional porous nitrogen-doped graphene aerogels （NGAs） were synthesized by using graphene oxide （GO） and chitosan （CS） via a self-assembly process by one-pot hydrothermal method. The morphology and struc- ture of the as-prepared materials were characterized by means of scanning electron microscopy, transmission elec- tron microscopy, X-ray diffraction, XPS spectroscopy, Raman spectroscopy, nitrogen adsorption/desorption meas- urement and Fourier transform infrared spectroscopy. The electrochemical performance of NGAs was studied by cyclic voltammetry, galvanostatic charge/discharge and impedance spectroscopy measurements. The microstructure, surface area and capacitance of NGAs could be facilely controlled by adding different amounts of chitosan. The prepared NGA-4 showed a specific capacitance of 148.0 F/g at the discharge current density of 0.5 A/g and also re- tained 95.3% of the initial capacitance after 5000 cycles at the scan rate of 10 mV/s. It provided a possible way to obtain graphene based materials with high surface area and capacitance.

Facile synthesis of nitrogen-doped graphene aerogels functionalized with chitosan for supercapacitors with excellent electrochemical performance

Three-dimensional porous nitrogen-doped graphene aerogels（NGAs） were synthesized by using graphene oxide（GO） and chitosan via a self-assembly process by a rapid method.The morphology and structure of the as-prepared aerogels were characterized.The results showed that NGAs possesed the hierarchical pores with the wide size distribution ranging from mesopores to macropores.The NGAs carbonized at different temperature all showed excellent electrochemical performance in 6 mol/L KOH electrolyte and the electrochemical performance of the NGA-900 was the best.When working as a supercapacitor electrode,NGA-900 exhibited a high specific capacitance（244.4 F/g at a current density of 0.2 A/g）,superior rate capability（51.0% capacity retention） and excellent cycling life（96.2% capacitance retained after 5000 cycles）.

Weakly hydrophobic nanoconfinement by graphene aerogels greatly enhances the reactivity and ambient stability of reactivity of MIL-101-Fe in Fenton-like reaction

In the pursuit of heterogeneous catalysts with high reactivity,metal organic framework(MOF)nanomaterials have received tremendous attentions.However,many MOF catalysts especially Fe-based MOFs need to be utilized immediately after synthesis or being activated using high temperature,because of the easy loss of reactivity in humid environments resulting from the occupation of active Fe sites by water molecules.Here,we describe an inspiring strategy of growing MIL-101-Fe nanoparticles inside the three-dimensional confined space of graphene aerogel(GA),generating shapeable GA/MIL-101-Fe nanocomposite convenient for practical use.Compared to MIL-101-Fe,GA/MIL-101-Fe as catalyst demonstrates much higher reactivity in Fenton-like reaction,attributing to smaller MIL-101-Fe particle size,presence of active Fe(II)sites,and abundant defects in GA.Strikingly,the weakly hydrophobic nature of the composite greatly inhibits the loss of catalytic reactivity after being stored in humid air and accelerates the recovery of reactivity in mild temperature,by resisting the entrance of water molecules and helping to exclude water molecules.This work demonstrates that a delicate design of nanocomposite structure could not only improve the reactivity of the catalytic component,but also overcome its intrinsic drawback by taking advantage of the properties of host.We hope this functional nanoconfinement strategy could be extended to more scenarios in other fields.

A Prussian blue route to nitrogen-doped graphene aerogels as efficient electrocatalysts for oxygen reduction with enhanced active site accessibility

Developing high-performance nonprecious-metal electrocatalysts for the oxygen reduction reaction （ORR） is crucial for a variety of renewable energy conversion and storage systems. Toward that end, rational catalyst design principles that lead to highly active catalytic centers and enhanced active site accessibility are undoubtedly of paramount importance. Here, we used Prussian blue nano- particles to anchor Fe/Fe3C species to nitrogen-doped reduced graphene oxide aerogels as ORR catalysts. The strong interaction between nanosized Fe3C and the graphitic carbon shell led to synergistic effects in the ORR, and the protection of the carbon shell guaranteed stability of the catalyst. As a result, the aerogel electrocatalyst displayed outstanding activity in the ORR on par with the state-of-the-art Pt/C catalyst at the same mass loading in alkaline media, good performance in acidic media, and excellent stability and crossover tolerance that rivaled that of the best nonprecious-metal ORR electrocatalysts reported to date.

Reduced graphene oxide aerogel decorated with Mo_(2)C nanoparticles toward multifunctional properties of hydrophobicity,thermal insulation and microwave absorption

Reduced graphene oxide(rGO)aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials(EWAMs)due to their intrinsic conductive networks and intricate interior microstructure,as well as good compatibility with other electromagnetic(EM)components.Herein,we realized the decoration of rGO aerogel with Mo_(2)C nanoparticles by sequential hydrothermal assembly,freeze-drying,and high-temperature pyrolysis.Results show that Mo_(2)C nanoparticle loading can be easily controlled by the ammonium molybdate to glucose molar ratio.The hydrophobicity and thermal insulation of the rGO aerogel are effectively improved upon the introduction of Mo_(2)C nanoparticles,and more importantly,these nanoparticles regulate the EM properties of the rGO aerogel to a large extent.Although more Mo_(2)C nanoparticles may decrease the overall attenuation ability of the rGO aerogel,they bring much better impedance matching.At a molar ratio of 1:1,a desirable balance between attenuation ability and impedance matching is observed.In this context,the Mo_(2)C/r GO aerogel displays strong reflection loss and broad response bandwidth,even with a small applied thickness(1.7 mm)and low filler loading(9.0wt%).The positive effects of Mo_(2)C nanoparticles on multifunctional properties may render Mo_(2)C/r GO aerogels promising candidates for high-performance EWAMs under harsh conditions.

Three-Dimensional N-Doped Carbon Nanotube/Graphene Composite Aerogel Anode to Develop High-Power Microbial Fuel Cell

Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings that limit the output of MFCs,such as high intrinsic resistance,poor electrolyte wettability,and low microbial load capacity.Here,a three-dimensional(3D)nitrogen-doped multiwalled carbon nanotube/graphene(N-MWCNT/GA)composite aerogel is synthesized as the anode for MFCs.Comparing nitrogen-doped GA,MWCNT/GA,and N-MWCNT/GA,the macroporous hydrophilic N-MWCNT/GA electrode with an average pore size of 4.24μm enables high-density loading of the microbes and facilitates extracellular electron transfer with low intrinsic resistance.Consequently,the hydrophilic surface of N-MWCNT can generate high charge mobility,enabling a high-power output performance of the MFC.In consequence,the MFC system based on N-MWCNT/GA anode exhibits a peak power density and output voltage of 2977.8 mW m^(−2)and 0.654 V,which are 1.83 times and 16.3%higher than those obtained with MWCNT/GA,respectively.These results demonstrate that 3D N-MWCNT/GA anodes can be developed for high-power MFCs in different environments by optimizing their chemical and microstructures.

Spider Web‑Inspired Graphene Skeleton‑Based High Thermal Conductivity Phase Change Nanocomposites for Battery Thermal Management

Phase change materials(PCMs)can be used for efficient thermal energy harvesting,which has great potential for cost-effective thermal management and energy storage.However,the low intrinsic thermal conductivity of polymeric PCMs is a bottleneck for fast and efficient heat harvesting.Simultaneously,it is also a challenge to achieve a high thermal conductivity for phase change nanocomposites at low filler loading.Although constructing a three-dimensional(3D)thermally conductive network within PCMs can address these problems,the anisotropy of the 3D framework usually leads to poor thermal conductivity in the direction perpendicular to the alignment of fillers.Inspired by the interlaced structure of spider webs in nature,this study reports a new strategy for fabricating highly thermally conductive phase change composites(sw-GS/PW)with a 3D spider web(sw)-like structured graphene skeleton(GS)by hydrothermal reaction,radial freeze-casting and vacuum impregnation in paraffin wax(PW).The results show that the sw-GS hardly affected the phase transformation behavior of PW at low loading.Especially,sw-GS/PW exhibits both high cross-plane and in-plane thermal conductivity enhancements of~1260%and~840%,respectively,at an ultra-low filler loading of 2.25 vol.%.The thermal infrared results also demonstrate that sw-GS/PW possessed promising applications in battery thermal management.

In-situ assembly of TiO2 with high exposure of(001)facets on three-dimensional porous graphene aerogel for lithium-sulfur battery

Resulting from the development of electric vehicles,high energy-density Li-S batteries have recently attracted ever-increasing attentions worldwide.However,continuous dissolution of cathodic sulfur and followed shuttle effect of polysulfides lead to very limited service lifetime for currently-applied Li-S batteries.Herein,a 3 D porous graphene aerogel(GA)decorated with high exposure of anatase TiO2(001)nanoplatelets is proposed as robust host to immobilize cathodic sulfur.Compared with commonly used TiO2(101)nanoparticles,the Ti O2(001)nanoplatelets have highly matched lattices with graphene(002)nanosheets,thus facilitating the electronic transfer.The in-site assembled TiO2@GA host exhibits superior sulfur-immobilized capability,which cannot only entrap sulfur by physical confinement,but also capture dissoluble sulfurous species by chemical bonding.The fabricated S@TiO2@GA cathode shows excellent electrochemical performance with high discharge capacity,superior rate capability,and durable cycling stability as well,supposed to be a promising cathode for high-performance Li-S battery applications.

PdNi/N-doped graphene aerogel with over wide potential activity for formic acid electrooxidation

Anti-CO poisoning ability is significant in formic acid oxidation in the fuel cell technique.Herein,Pd Ni alloy supported on N-doped graphene aerogel(Pd Ni/GA-N)was found to have catalytic ability toward formic acid electrooxidation over a wide potential range because of the improved anti-CO poisoning ability.This catalyst was fabricated by simple freeze-drying of mixture solution of graphene aerogel,polyvinylpyrrolidone,Pd^(2+)and Ni^(2+)and the subsequent thermal annealing reduction approach in the N2/H2 atmosphere.Pd-Ni alloy particles anchored over the folding N-doped graphene surface with a porous hierarchical architecture structure in the 3 D directions.It showed the catalytic performance of its maximum mass activity of 836 m A mg^(-1)in a broad potential range(0.2-0.6 V)for formic acid oxidation.The CO stripping experiment demonstrated its largely improved anti-CO poisoning ability with the peak potential of 0.67 V,approximately 60 and 40 m V less compared to those of Pd/GA-N and Pd/C samples.The high anti-CO poisoning ability and strong electronic effect resulting from the interaction between the3 D GA-N support and the Pd-Ni alloy makes it a promising catalyst for application in direct formic acid fuel cells.

Adsorptive Behavior of Methyl Blue on Graphene Aerogel:A Mechanism Study

Graphene aerogel was synthesized and used for the removal of methyl blue from aqueous solutions.The effect of solution pH,temperature and adsorption time on the adsorption performance of the graphene aerogel was studied systematically.In addition,investigations were also performed to determine the nature of adsorption.The experimental results show that graphene aerogel is a highly efficient adsorbent for the treatment of methyl blue in aqueous solutions.In addition,the adsorption of methyl blue proceeds through a single layer physical adsorption on the graphene aerogel.The findings herein are useful for the future development of adsorbent for in water.

Nitrogen and sulfur co-doped graphene aerogel with hierarchically porous structure for high-performance supercapacitors

Supercapacitors with unique performance have been widely utilized in many fields. Herein, we report a nitrogen and sulfur co-doped graphene aerogel(N/S-GA-2) prepared using a low toxic precursor for high-performance supercapacitors. The as-obtained material possesses a hierarchically porous structure and a large number of electrochemical active sites. At a current density of 1 Ag^-1, the specific capacitance of the N/S-GA-2 for supercapacitors with the ionic liquid as the electrolyte is 169.4 Fg^-1, and the corresponding energy density is 84.5 Wh kg^-1.At a power density of 8.9 k W kg^-1, the energy density can reach up to 75.7 Wh kg^-1, showing that the N/S-GA-2 has an excellent electrochemical performance. Consequently, the N/S-GA-2 can be used as a promising candidate of electrode materials for supercapacitors with high power density and high energy density.

Porous monoliths of 3D graphene for electric double-layer supercapacitors

For delivering the nanoscaled extraordinary characteristics in macroscopical bulk,it is essential to integrate two-dimensional nanosheets into threedimensional(3D)porous monoliths,alternatively called as 3D architectures,3D networks,or aerogels.The intersupported structure of porous monolithic 3D graphene(3DG)can prevent aggregation or restacking of graphene individuals,and the interconnected sp^(2) network of 3DG not only can provide the highway for the transport of electron/phonon but also can present continual cavities/channels for mass transfer.This review summarizes the synthesis methodology of 3DG porous monoliths and highlights the application for electric double-layer capacitors.Present challenges and future prospects about the manufacture and application of 3DG are also discussed.

Monodisperse polar NiCo_(2)O_(4) nanoparticles decorated porous graphene aerogel for high-performance lithium sulfur battery

Lithium sulfur battery(LSB)is a promising energy storage system to meet the increasing energy demands for electric vehicles and smart grid,while its wide commercialization is severely inhibited by the"shuttle effect"of polysulfides,low utilization of sulfur cathode,and safety of lithium anode.To overcome these issues,herein,monodisperse polar NiCo_(2)O_(4)nanoparticles decorated porous graphene aerogel composite(NCO-GA)is proposed.The aerogel composite demonstrates high conductivity,hierarchical porous structure,high chemisorption capacity and excellent electrocatalytic ability,which effectively inhibits the"shuttle effect",promotes the ion/electron transport and increases the reaction kinetics.The NCO-GA/S cathode exhibits high discharge specific capacity(1214.1 mAh g^(-1)at 0.1 C),outstanding rate capability(435.7 mAh g^(-1)at 5 C)and remarkable cycle stability(decay of 0.031%/cycle over 1000 cycles).Quantitative analyses show that the physical adsorption provided by GA mainly contributes to the capacity of NCO-GA/S at low rate,while the chemical adsorption provided by polar NiCo_(2)O_(4)contributes mainly to the capacity of NCO-GA/S with the increase of current density and cycling.This work provides a new strategy for the design of GA-based composite with synergistic adsorption and electrocatalytic activity for the potential applications in LSB and related energy fields.

Phosphorous-doped carbon nanotube/reduced graphene oxide aerogel cathode enabled by pseudocapacitance for high energy and power zinc-ion hybrid capacitors

The design and development of energy storage device with high energy/power density has become a research hotspot.Zinc-ion hybrid capacitors(ZHCs)are considered as one of the most promising candidates.However,the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material.In this study,a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide(P-CNT/rGO)aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design.The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera,expanded interlayer spacing,and enhanced pseudocapacitance behavior,thus leading to significantly enhanced specific capacitance and superb ions transport performance.The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life.In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs.Furthermore,the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations.This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.

Facile g-ray irradiation synthesis of Pt/GA nanocomposite for catalytic reduction of 4-nitrophenol

Up to now,facile and pollution-free routes for catalyst preparation are in high demand.In this study,a green and cost-effective strategy was successfully developed to construct platinum/graphene aerogel(Pt/GA)nanocomposites by the co-reduction of graphene oxides(GO)and chloroplatinic acid(H_(2)PtCl6$6H_(2)O)with the assists of g-ray irradiation in the absence of any other reductants.Characterization studies indicated that the energy of g-ray irradiation and the hole scavenger isopropanol(IPA)played a vital role in forming small Pt nanoparticles with uniform size of~3 nm on the surface of graphene aerogel(GA).Furthermore,Pt/GA synthesized with a mass ratio of 2:1(Pt/GA-2)exhibited a lowest activation energy value and outstanding catalytic properties for the reduction of 4-nitrophenol(4-NP).The excellent catalytic and cycling performance suggest that Pt/GA-2 catalyst has a promising prospect for the reduction of nitroaromatic compounds in wastewater treatment and other industrial applications.