Three-dimensional Graphene Research Articles

Synthesis and characterization of three-dimensional graphene oxide-chitosan/ glutaraldehyde nanocomposites: Towards adsorption of crocin from saffron

Despite the unique properties of graphene oxide (GO) as a green adsorbent, its low structural stability presents a drawback. This study aimed to modify the properties of GO through its functionalization with chitosan (CH), cross-linked with glutaraldehyde (GLU), and synthesized via the freeze-drying method (GO-CH/GLU). Microscopic analysis illustrated that covering the GO sheets with CH and nanoparticles (NPs) resulted in a 15.8 % increase in d-spacing and a 600 % increase in sheet thickness. The GO-CH/GLU composite was utilized for the separation/purification of crocin from saffron extract under varying pH (5–9), temperature (298–318 K), stirring rate (100–300 rpm), and crocin concentration (25–200 mg/mL). The Freundlich isotherm and pseudo-second-order kinetic models provided a good fit for crocin adsorption. Thermodynamic analysis revealed that the process was endothermic, spontaneous, and physical. Optimal adsorption conditions in batch mode were pH 7, a stirring rate of 300 rpm, a temperature of 318 K, and a crocin concentration of 100 mg/mL. These conditions were applied in a continuous system, resulting in a crocin separation efficiency of 94.17 % at 180 mL/h. Additionally, HPLC data indicated that the purity of separated crocin exceeded 90 %. So, the GO-CH/GLU composite is a promising and economical adsorbent for the food industry.

Iron phosphide nanoparticles anchored on 3D nitrogen-doped graphene as an efficient electrocatalysts for hydrogen evolution reaction in alkaline media

Electrocatalysts play a crucial role in hydrogen evolution reaction (HER), facilitating a clean and sustainable generation of hydrogen energy. To promote the HER process, it is imperative to employ highly efficient, stable, and cost-effective electrocatalysts. This research focuses on the design of iron phosphide nanoparticles anchored onto a porous three-dimensional nitrogen-doped graphene (FeP@3DNG). The porous framework of 3DNG serves a multifaceted purpose: it prevents the aggregation of FeP nanoparticles during phosphidation, safeguards the FeP electrocatalyst from oxidation during the HER, and simultaneously enhances electrical conductivity and stability. Notably, the FeP@3DNG nanocomposite demonstrated the efficient activity and highest HER activity with an overpotential of 76 mV to achieve 10 mA cm−2 and a small Tafel slope of 40.2 mV dec−1 as well as good long-term durability for 20 h in 1.0 M KOH solution. The high performance of the FeP@3DNG nanocomposite can be primarily corresponded to the synergistic effects of the highly active of FeP nanoparticles and advantages of porous three-dimensional graphene with excellent electrocatalytic activity, high specific surface area, and chemical stability, thus, resulting in the improvement the overall electrocatalytic activity.

Implementation of a simple functionalisation of graphene (Gii-Sens) in the determination of a suitable linker for use in biocatalytic devices

We adapted a single-step method to functionalise three-dimensional graphene foam (Gii-Sens) electrodes with a 1-pyrenebutyric acid N-hydroxysuccinimide ester (Pyr-NHS). The physical and chemical properties of these functionalised electrodes were subsequently probed via Raman spectroscopy, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. Combined with data acquired from cyclic voltammetry and electrical impedance spectroscopy, we confirmed the presence of Pyr-NHS on the surface of the graphene foam in sufficient quantity for it to serve as a suitable linker for the immobilisation of the enzyme glucose dehydrogenase (GDH) on the electrode. Evidence of this immobilisation was provided through electrochemical characterisation, before demonstrating an active enzyme response from GDH via the mediated oxidation of glucose at the electrode surface. A proportional relationship between the concentration of glucose and the peak anodic current from the redox mediator p-aminophenol led to the determination of a high sensitivity of 22.7µA/mM/cm2 and a limit of detection of 5.25 µM. Such a result confirms the viability of these functionalised graphene foam electrodes as a metal-free high-performing anode within miniaturised, glucose-based biocatalytic devices, including enzymatic biofuel cells and biosensors.

Influence of defocusing of UV pulse laser radiation on LIG synthesis on Polyetheretherketone

Laser-induced graphene (LIG) technology, a technique for preparing three-dimensional porous graphene by laser direct writing on carbon precursors under ambient condition, has been widely used due to its low cost and high efficiency. However, there is still a lack of research on the influence of the defocusing on LIG synthesis. In this paper, LIG is prepared by UV laser on Polyetheretherketone (PEEK) film, and a finite element simulation of this process is established to infer the temperature field. The influence of the defocusing on the structure, morphology, specific surface area SSA, and electrical properties of PEEK-LIG is investigated while maintaining the same energy radiated per unit area. The results show that the defocusing changes the structure and morphology of PEEK-LIG by affecting the temperature field distribution in both the surface and thickness directions, which affects the properties of LIG, where the surface area ratio Sdr does not depend on the defocusing amount monotonically. As the UV laser nears the beam waist at the threshold of LIG formation, Sdr has its maximum value and improves its electrical conductivity.

Preparation of an imidazolium-based poly(ionic liquid) functionalized magnetic three-dimensional graphene oxide for magnetic solid phase extraction of pyrethroids from tea samples

In this work, an imidazolium-based poly(ionic liquid) (poly(1-dodecyl-3-vinyl-imidazolium bromide) functionalized magnetic three-dimensional graphene oxide (Fe3O4@3D-GO@poly(ImC12+Br−)) was synthesized via a vacuum freezing-drying method and used as a magnetic solid phase extraction (MSPE) adsorbent for the efficient extraction of pyrethroid pesticides from tea samples. The prepared Fe3O4@3D-GO@poly(ImC12+Br−) was confirmed by scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FT-IR), vibrating sample magnetometer (VSM) and X-ray photoelectron spectrogram (XPS). Due to its large specific surface area and the ability to offer multiple intermolecular interactions, including π-π stacking, hydrophobic and hydrogen bond interactions, the prepared Fe3O4@3D-GO@poly(ImC12+Br−) showed high extraction efficiency for pyrethroids. The experimental parameters were optimized by a combination of single-factor method and Box-Behnken design to improve the extraction efficiency. Under the optimum conditions, coupled with high performance liquid chromatography (HPLC), a sensitive analytical method was developed for the determination of pyrethroids, and the proposed method showed wide linear ranges (1.00–100 μg L−1) with correlation coefficients (R) ranging from 0.9980 to 0.9994, low limits of detection (0.100 μg L−1) and good repeatability with intra-day relative standard deviations (RSDs) in the range of 2.90–5.53 % and inter-day RSDs in the range of 1.83–7.76 %. Moreover, the developed method was successfully applied to the determination of pyrethroids in tea samples and satisfactory recoveries ranging from 82.37 % to 114.34 % were obtained. The results showed that the developed Fe3O4@3D-GO@poly(ImC12+Br−) was an ideal, effective and selective material for the extraction and enrichment of pyrethroids from tea samples.

Overcoming strength-ductility trade-off in bimodal metal matrix composite with 3D graphene-strengthened hetero-interface

Strength-ductility synergy has long been a challenge in the development of advanced metallic materials. In this study, we fabricated a novel bimodal-structured nickel matrix composite, which features in-situ synthesized three-dimensional graphene networks (3DGN) strengthening the hetero-interfaces between coarse-grained and fine-grained zones (CGZ and FGZ). Compared to the bimodal matrix, this 3DGN-reinforced composite exhibits remarkable enhancements of 30 % in yield strength, 40 % in ultimate tensile strength, and 40 % in uniform elongation, respectively, representing the highest comprehensive performance among nickel matrix composites and pure nickel obtained through cold rolling, severe plastic deformation, and dynamic plastic deformation as reported in the previous literature. The superior strength-ductility combination originates from the incorporation of 3DGN, which enables multiple strengthening and toughening mechanisms. Specially, the strength and strain hardening capability have been enhanced through improved dislocation storage capacity, a stronger hetero-deformation induced (HDI) hardening effect, and the activation of numerous stacking fault ribbons. Moreover, high-density dispersed microcracks in the FGZ relieve strain/stress concentrations while being constrained within the CGZ, further enhancing tensile ductility. This study provides new insights into addressing the inherent strength-ductility paradox in metal matrix composites.

A high-power hybrid carbon nanotube/three-dimensional reduced graphene oxide glucose/O2 enzymatic biofuel cell

Long-lasting, high-performance enzymatic biofuel cells (EBFCs) are among the most promising candidates for renewable and green power generation. There are two main drawbacks to EBFCs: 1) short enzyme lifetime due to the enzyme's (protein) denaturation; and 2) low electron transfer efficiency as the enzyme's active site is deeply buried inside the non-conductive protein structure of the enzyme. In this study, a hybrid of carbon nanotubes (CNT) and three-dimensional graphene (3DG) was used to immobilize the glucose oxidase (GOx) on the surface of a glassy carbon electrode (GCE) to fabricate a modified bioanode in a glucose/O2 EBFC. This facile and low-cost CNT/3DG hybrid is a solution to the problems of instability, short lifespan, and poor electron transport in EBFCs. The exceptional electrocatalytic activity of the porous CNT/3DG hybrid is demonstrated by its effective immobilization of GOx and ability to collect energy from glucose oxidation by direct electron transfer (DET) while preserving the structure of the enzyme. The CNT acts like a tiny electrical wire that reaches and harvests the electron directly from the flavin adenine dinucleotide (FAD) (the redox center of GOx) and transfers it to the electrode surface, thus enhancing the performance of the EBFC. The immobilized GOx lifetime was increased to 210 days with a maximum power density of 253.36 µWcm-2 at 0.65 V. These results demonstrate the attractive capability of the CNT/3DG hybrid in the development of efficient biofuel cells and biosensors that employ enzymes in their structures.

Laser micro/nano structuring of three-dimensional porous gradient graphene: Advanced heater for antibacterial surfaces and ion-selective electrode for sweat sensing

The development of three-dimensional (3D) gradient porous graphene (GPG) patterns, leveraging the remarkable properties and unique structure of graphene, has garnered considerable attention owing to their excellent electrochemical and electrothermal performances. Among the numerous graphene synthesis methods, laser-induced graphene (LIG) stands out as an eco-friendly and practical approach for creating patterned graphene structures on commercial films, with synthetic details varying depending on the application. Unlike conventional LIG with uniform geometric characteristics, we developed an innovative approach for circular line-scribed ultraviolet (UV)-LIG patterning; these approaches utilize a high overlapping factor and low power to achieve uneven graphitization. A comprehensive analysis of the 3D GPG was conducted via specific surface area measurements, contact angle analyses, sheet resistance measurements, X-ray photoelectron spectroscopy, and Raman spectroscopy. These 3D GPG structures exhibit large surface areas, low sheet resistance, and superior ion transport, thus improving heater and ion-selective electrode (ISE) performances. The fabricated 3D GPG heaters were successfully applied to antibacterial surfaces, and the ISEs were applied in a sweat sensor was demonstrated owing to the remarkable combination of high surface area, low electrical resistance, and unique 3D porous structure.

Synthesis of a MOF derived porous graphene and pyrolytic carbon supported zinc stannate nanohybrid electrode with enhanced lithium-ion storage performances

Compositing nano-sized zinc stannate (Zn2SnO4) with supportive carbon skeleton usually brings in improved lithium-ion storage performances. One of the most challenging tasks is to effectively stabilize Zn2SnO4 nanocrystals via simplified preparation routes from eco-friendly raw materials. In this work, the water-soluble natural molecule gallic acid (GA) is directly employed to coordinate with Zn2+/Sn2+ ions, and the corresponding metal-organic framework (MOF) precursor samples of pure Zn-GA MOF and bimetallic ZnSn-GA MOF can be synthesized. The Zn-GA MOF and ZnSn-GA MOF precursors are further converted to a three-dimensional (3D) porous graphene sample (ZMG) and a pyrolytic carbon domain supported Zn2SnO4 nanocomposite (Zn2SnO4@C), respectively, by taking the advantages of the unique micro-structures and compositions of MOF materials. By rationally mixing the ZMG and Zn2SnO4@C in electrode fabrication, the finally obtained Zn2SnO4@C/ZMG nanohybrid electrode exhibits a high reversible capacity of 1117 mAh·g−1 after 500 cycles at a current density of 1000 mA g−1 in half-cells as well as inspiring full-cell performance. The favorable synergistic effect in lithium-ion storage for the Zn2SnO4@C/ZMG electrode has been investigated. The MOF derived samples and involved sustainable synthesis protocols can be further developed for wider applications.

Ultrafast reaction kinetic of polyaniline in flexible hydrogel electrodes facilitated by graphene ribbons

Abstract By loading energy storage active materials on hydrogel which is inherently flexible, the flexibility of electrode materials can be simply realized, thereby achieving the flexibility of energy storage devices. However, the polymer network that constructs the three-dimensional skeleton of the hydrogel is not conductive, which inhibits the redox ability of the active material. If a high speed conductive structure can be added to the colloidal phase, the performance of the flexible electrode material can be greatly improved. Here, we introduce redox graphene ribbons into the polyvinyl alcohol hydrogel loaded with polyaniline. The in situ three-dimensional conductive graphene network greatly enhanced the conductivity of the hydrogel electrode, thus increasing the specific capacitance to as high as 1117 F g−1 at 2 mg cm−2 mass loading, with a retention ratio of 66.96% from 0.5 A g−1 to 20 A g−1. These highlighted properties enable the PRP hydrogel as an electrode for flexible supercapacitors, which provides a promising possibility for the practical application of wearable electronics.

Removal of malachite green in wastewater and its mechanism by three-dimensional graphene oxide-based aerogels

Malachite green (MG) is a significant water pollutant due to its widespread use and harmful properties, making its effective removal crucial. Graphene oxide (GO) has emerged as a promising material for dye adsorption. Doping GO into cellulose aerogels enhances mechanical properties and prevents GO dissolution. Many reports claim the advantages of GO in adsorption, but challenges remain in understanding and optimizing the adsorption of MG in three-dimensional cellulosic GO (CLGO) aerogels. In this study, three-dimensional CLGO aerogels were prepared using the freeze-drying method. They achieved an MG maximum adsorption capacity of 33.98 mg g−1, and the adsorbent still had 97.04 % adsorption capacity at the seventh adsorption–desorption cycle. The photothermal properties of the CLGO aerogels were also studied, contributing to the development of the zero-liquid discharge (ZLD) post-processing concept. Molecular force field simulations indicated that π-π interaction is the primary force between MG and CLGO aerogels in the absorption process. We believe our research will guide the future optimization of MG specialized absorbent.

Rapid and efficient adsorption of p-nitrophenol over biomass-derived vertically aligned graphene nanosheets fabricated by hydrothermal/molten salt-assisted pyrolysis method

Vertical graphene (VG) is an emerging three-dimensional graphene with unique structure and properties, which is expected to possess outstanding adsorption performance. Nevertheless, the utilization of VG as an adsorbent has not been investigated, and its conventional preparation methods are complex and expensive. Herein, we utilize a facile hydrothermal/ molten K2CO3-assisted pyrolysis method for preparing VG from cost-effective and renewable fir bark. The optimized VG-1.0 achieved a high adsorption capacity (556 mg/g) for p-nitrophenol (PNP) within 10 min, far superior to commercial activated carbon (360 mg/g) and previously reported graphene-based materials. Its excellent performance can be ascribed to high specific surface area (1423 m2/g), open & vertical channels, rich oxygen-containing groups and high graphitization degree, providing sufficient adsorption sites and unhindered mass transfer pathways. VG-1.0 was easily regenerated by rinsing with NaOH solution and showed good reusability, maintaining > 80 % of its original adsorption capacity after 5 cycles of reuse. The adsorption isotherm and kinetic data of PNP over VG were fitted well with Freundlich/Temkin model and pseudo-second-order kinetic model, respectively. Various characterizations and density functional theory (DFT) simulations have confirmed that the adsorption of PNP on VG is a spontaneous and endothermic process, involving pore filling and surface adsorption such as hydrogen bonding and π-π interactions.

Graphene Incorporated Sugar Derived Carbon Aerogel for Pyridine Adsorption and Oil-Water Separation.

Herein, we have synthesized a three-dimensional and hydrophobic graphene incorporated carbon aerogel (G-SCA) derived from sugar. G-SCA is being used as a multifunctional sorbent material for removing various advanced water-soluble and insoluble pollutants. Initially, G-SCA is being explored for the adsorption of nitroarenes (nitrophenols, 3-nitroaniline), an insecticide (Phoskill), an antibiotic (ciprofloxacin), and a pharmaceutical drug precursor (pyridine). Later, the same G-SCA is also explored in the absorption of various protic and aprotic organic solvents, and oils (including crude oil, waste cooking oil, and waste engine oil), with excellent recyclability checked up to 10 cycles. Moreover, oil-water separation experiments are also being done in various industrial wastewater and seawater samples to support the real-life accessibility of the present approach. Large-scale applicability of G-SCA is also checked by performing crude oil-seawater separation experiments using a laboratory-scale prototype demonstrating the successful continuous recovery of crude oil.

Boosting bioelectricity generation in bioelectrochemical systems with nitrogen-doped three-dimensional graphene aerogel anode

Bioelectricity generation by electrochemically active bacteria has become particularly appealing due to its vast potential in energy production, pollution treatment, and biosynthesis. However, developing high-performance anodes for bioelectricity generation remains a significant challenge. In this study, a highly efficient three-dimensional nitrogen-doped macroporous graphene aerogel anode with a nitrogen content of approximately 4.38 ± 0.50 at% was fabricated using hydrothermal method. The anode was successfully implemented in bioelectrochemical systems inoculated with Shewanella oneidensis MR-1, resulting in a significantly higher anodic current density (1.0 A/m2) compared to the control one. This enhancement was attributed to the greater biocapacity and improved extracellular electron transfer efficiency of the anode. Additionally, the N-doped aerogel anode demonstrated excellent performance in mixed-culture inoculated bioelectrochemical systems, achieving a high power density of 4.2 ± 0.2 W/m², one of the highest reported for three-dimensional carbon-based bioelectrochemical systems to date. Such improvements are likely due to the good biocompatibility of the N-doped aerogel anode, increased extracellular electron transfer efficiency at the bacteria/anode interface, and selectively enrichment of electroactive Geobacter soli within the NGA anode. Furthermore, based on gene-level Picrust2 prediction results, N-doping significantly upregulated the conductive pili-related genes of Geobacter in the three-dimensional anode, increasing the physical connection channels of bacteria, and thus strengthening the extracellular electron transfer process in Geobacter.

Study on the synthesis mechanism of new α-FeOOH@3DGF material and its lithium storage performance

A new self-supporting material contained nanorods α-FeOOH and three-dimensional skeleton graphene foam (3D Graphene Foam, 3DGF) was prepared by hydrothermal method. The growth mechanism and phase change rules of nanorods α-FeOOH@3DGF were studied to obtain the electrochemical lithium storage performance. The results showed that growth mechanism of nanorods α-FeOOH was accompanied by the consumption of nanoparticles β-FeOOH. If the hydrothermal time reached to 12 h, the nanoparticle β-FeOOH phase completely disappeared with only rod-shaped α-FeOOH@3DGF single phase obtained. Rod-shaped α-FeOOH@3DGF was used as anode material of lithium-ion batteries and the reversible specific capacity remained at about 305 mAh·g−1 after charging and discharging 250 times at 500 mA·g−1, with significantly cycling stability compared with that of the monomaterial α-FeOOH.

Syntheses of Heteroatom-Substituted and Three-Dimensional Nanocarbon Materials on Surfaces

I will present our recent studies on on-surface chemistry with high-resolution scanning probe microscopy operating at low temperature under ultra-high vacuum. We synthesized three-dimensional organometallic compound and graphene nanoribbon by coupling hexabromo substituted-propellane molecules on Au(111) and Ag(111).[1] In the structure, the C-Br bonds distant from the surface remained intact even after the reaction. The radical species were formed by tip-induced debromination and were also stabilized by either tip-manipulated Br atom or fullerene molecule. We also demonstrate systematic tip-induced isomerization via embedding a text of “NIMS” by following binary and ternary ascii cords, in which two chiral dehydroazulene and diradical units were used.[2] Among the three states, the diradical unit showed the spin coupling of 90 meV. For heteroatom substitution, we developed an on-surface reaction, which can synthesize graphene nanoribbon and covalent organic frameworks with silabenzene units by coupling Si atom and Br-substituted molecule.[3] The heavier congeners of cyclic aromatic compounds have been studied as an elusive target product for organic synthesis due to their high reactivity at ambient temperature and difficult isolation. Thus, this result shows the advantage of on-surface synthesis.Reference[1] S. Kawai, et al Sci. Adv. 6, eaay8913 (2020).[2] S. Kawai, et al Nat. Commun. 14, 7741 (2023).[3] K. Sun et al, Nat. Chem. 15, 136 (2023).

(Invited) Electron Transport in Nanocarbon Networks for Energy Conversion and Storage Applications

Carbon nanostructures have attracted great attention in recent years as novel electrode materials in batteries with increased capacity and conductivity as well as enhanced material stability. In these nanostructures, nanocarbons such as carbon nanotubes and graphene nanoplatelets are interconnected to construct their three-dimensional networks around the host materials for Li deposition. This work focuses on the study of electron transport phenomena in these nanocarbon networks with two model material systems: (1) single-walled carbon nanotube (SWCNT) networks co-embedded with silica microparticles (Fig. (a)), and (2) free-standing three-dimensional graphene (3DG) structures with polymeric surface modifications (Fig. (b)). We characterize the materials for electrical conductivity and thermopower with varying material contents in the composites to reveal several key factors determining their energy-dependent carrier transport characteristics. It is found that in these three-dimensional nanocarbon networks, carrier tunneling at the junctions between nanocarbons along with the network morphology predominantly determines the transport properties. Simultaneous increase in electrical conductivity and thermopower is achieved for SWCNT networks co-embedded with silica microparticles by increasing silica content up to 40 w.t.% at a fixed CNT content. The enhanced electron transport is attributed to the reduced junction distances due to the intimate network formation on the surface of silica particles with a polymer binder. Our transport theory based on the Landauer formalism for junction tunneling reveals that the junction modification with polymer can alter the potential barrier heights for both electrons and holes at the junction to significantly change the transport properties of the composite. Doping of nanocarbons is also investigated for their impacts on the junction transport and the geometric factor of the networks. Finally, we also investigate the use of these carbon nanostructures in solid-state thermoelectric (TE) energy harvesters and ionic TE capacitors to harvest thermal energy from temperature gradients and fluctuations. Figure 1

Melamine foam scaffolded 3D porous polyaniline/reduced graphene oxide composite electrode for flexible supercapacitor

Graphene composite foam with enhanced mechanical and electrochemical properties holds great promise for flexible supercapacitors. This work developed a cost-effective method for massive production of three-dimensional (3D) porous graphene composite using melamine foam (MF) as a flexible scaffold. The MF was coated reduced graphene oxide (RGO) to form an interconnected conductive layer by dip-coating and vapor reduction, and loaded with polyaniline (PANI) by in-situ polymerization. The resulted PANI/RGO/MF, as self-supporting electrode, exhibits extraordinary mechanical flexibility and a high specific capacitance of 806.2 mF cm−2 at 0.5 mA cm−2. Furthermore, the assembled solid-state supercapacitor exhibits an outstanding capacity of 299.1 mF cm−2 at 0.5 mA cm−2, a high energy density of 26.6 μWh cm−2 at 200 μW cm−2, nearly 100 % capacitance retention at 0°–180°, and good cycling stability. This study provides a scalable strategy for fabricating graphene composite foam suitable for flexible energy storage application.

Engineering strong spin-frustration at the surface of three-dimensional graphene

Engineering strong spin-frustration at the surface of three-dimensional graphene

Construction of electron-interactive CoMoO4 @ CoP core–shell structure on boron-doped graphene aerogel as strongly interface coupled hybrid electrodes for high flexible supercapacitor

Exploring high energy density, lightweight and self-supporting flexible electrodes is essentially significant to flexible energy storage equipment. Herein, boron-doped three-dimensional porous graphene aerogel (BGA) is engineered and novel flake-like CoP encapsulating flower-like CoMoO4 core–shell structure is arranged on it (CoMoO4@CoP/BGA) utilizing a combination of solvothermal, freeze-drying and vapor deposition techniques. Boron-doped graphene aerogel as flexible self-supporting positrode creates a unique three-dimensional porous interface with a larger specific surface area, which is conducive to exposing more active sites and avoids the additional process of adding binders and conductive agents. The heterointerface engineering of CoP epitaxial growth on CoMoO4 can efficiently enhance electrolyte ions adsorption ability and fast reaction kinetics. As expected, the fabricated CoMoO4@CoP/BGA demonstrates a better specific capacitance of 3056.4F/g than that of CoMoO4/BGA (1582.4F/g) and pure CoMoO4 (669.2F/g), apart from retains the remarkable cyclic stability of 88.4 % after 10,000 cycles. Furthermore, a hybrid supercapacitor composed of CoMoO4@CoP/BGA and BGA can provide a high energy density of 50.2 Wh kg−1 at 800.0 W kg−1, and retains good capacitance retention of 95.6 % after 10,000 cycles, which can be attributed to the large specific surface of B doping 3D porous graphene aerogel and the rich strong coupling interface synergy between CoP and CoMoO4. More importantly, this work provides important guidance for the design of heterojunction electrodes based on heteroatom doped graphene aerogel and phosphides @ oxide based flexible energy storage devices.