Graphene Oxide Based Transparent Resins For Accurate 3D Printing of Conductive Materials

Digital Light Processing (DLP) allows the fast realization of 3D objects with high spatial resolution. However, DLP is limited to transparent resins, and therefore not well suited for printing electrically conductive materials. Manufacturing conductive materials will significantly broaden the spectrum of applications of the DLP technology. But conductive metals or carbon-based fillers absorb and scatter light; inhibiting thereby photopolymerization, and lowering resolution. In this study, UV transparent liquid crystal graphene oxide (GO) is used as precursor for generating in situ conductive particles. The GO materials are added to a photopolymerizable resin via an original solvent exchange process. By contrast to earlier contributions, the absence of drying during the all process allows the GO material to be transferred as monolayers to limit UV scattering. The absence of UV scattering and absorption allows for fast and high-resolution 3D printing. The chosen resin sustain high temperature to enable an in situ efficient thermal reduction of GO into reduced graphene oxide (rGO) that is electrically conductive. The rGO particles form percolated networks with conductivities up to 1.2 × 10⁻² S m⁻¹. The present method appears therefore as a way to reconcile the DLP technology with the manufacturing of 3D electrically conductive objects.     

Self‐Healing Graphene Oxide Based Functional Architectures Triggered by Moisture

Self‐healing materials are capable of spontaneously repairing themselves at damaging sites without additional adhesives. They are important functional materials with wide applications in actuators, shape memorizing materials, smart coatings, and medical treatments, etc. Herein, this study reports the self‐healing of graphene oxide (GO) functional architectures and devices with the assistance of moisture. These GO architectures can completely restore their mechanical‐performance (e.g., compressibility, flexibility, and strength) after healing their broken sites using a little amount of water moisture. On the basis of this effective moisture‐triggered self‐healing process, this study develops GO smart actuators (e.g., bendable actuator, biomimetic walker, rotatable fiber motor) and sensors with self‐healing ability. This work provides a new pathway for the development of self‐healing materials for their applications in multidimensional spaces and functional devices.     

Direct 3D Printing of Ultralight Graphene Oxide Aerogel Microlattices

Graphene aerogel microlattices (GAMs) hold great prospects for many multifunctional applications due to their low density, high porosity, designed lattice structures, good elasticity, and tunable electrical conductivity. Previous 3D printing approaches to fabricate GAMs require either high content of additives or complex processes, limiting their wide applications. Here, a facile ion‐induced gelation method is demonstrated to directly print GAMs from graphene oxide (GO) based ink. With trace addition of Ca²⁺ ions as gelators, aqueous GO sol converts to printable gel ink. Self‐standing 3D structures with programmable microlattices are directly printed just in air at room temperature. The rich hierarchical pores and high electrical conductivity of GAMs bring admirable capacitive performance for supercapacitors. The gravimetric capacitance (C_s) of GAMs is 213 F g^?1 at 0.5 A g^?1 and 183 F g^?1 at 100 A g^?1, and retains over 90% after 50 000 cycles. The facile, direct 3D printing of neat graphene oxide can promote wide applications of GAMs from energy storage to tissue engineering scaffolds.     

Graphene Oxide/Hexylamine Superlattice Field-Effect Biochemical Sensors

The bulky assembly of 2D materials is highly desired for macroscopic applications, but it is still challenging to access the exceptional properties of 2D materials owing to their spontaneous aggregation. Here, to facilitate the access of the field-effect sensing abilities of semiconducting 2D materials in bulk quantities, 3D hybrid superlattices of alternating graphene oxide (GO) and hexylamine molecular layers are constructed. Strikingly, the fabricated flexible GO/hexylamine superlattice exhibits a “V”-shaped ambipolar field-effect transfer characteristic under electrolyte gating, with exceptional sensing ability to pH value and DNA molecules in buffer solutions. In contrast, GO paper prepared by annealing the hybrid superlattices exhibits neither field-effect nor sensing responses to various analytes, highlighting the essential role that hexylamine plays in modulating the GO/hexylamine superlattice to enable a wider interlayer spacing for biomolecules transportation in the internal graphene layer. These achievements, along with stable electrical and sensing performance under mechanical stress of the 3D hybrid superlattices, highlight the unique potential of flexible graphene 3D hybrid superlattices for biochemical applications by overcoming multilayer aggregation.     

Facile Synthesis of Graphene Quantum Dots from 3D Graphene and their Application for Fe3+ Sensing

Owing to their small size, biocompatibility, unique and tunable photoluminescence, and physicochemical properties, graphene quantum dots (GQDs) are an emerging class of zero‐dimensional materials promising a wide spectrum of novel applications in bio‐imaging, optical, and electrochemical sensors, energy devices, and so forth. Their widespread use, however, is largely limited by the current lack of high yield synthesis methods of high‐quality GQDs. In this contribution, a facile method to electrochemically exfoliate GQDs from three‐dimensional graphene grown by chemical vapor deposition (CVD) is reported. Furthermore, the use of such GQDs for sensitive and specific detection of ferric ions is demonstrated.     

In Situ Co-transformation of Reduced Graphene Oxide Embedded in Laser-Induced Graphene and Full-Range On-Body Strain Sensor

On-body strain information provides various indicators such as heart rate, physiological pulse, voice waveform, respiratory rate, and body motion status. Recent advances in wearable strain sensors using nanomaterials have significantly enhanced sensor performance with regard to sensitivity, detectable range, and response time. However, it is still challenging to obtain all types of body strain information, from small vibrations to joint movements, using one type of sensor. Herein, a full-range on-body strain (FROS) sensor covering ultrasmall-to-large strains such as vocal vibration and joint movement is reported. To achieve an ultrawide detectable range, reduced graphene oxide (rGO)-embedded laser-induced graphene (LIG) is synthesized by laser engraving on a graphene oxide (GO)-embedded polyimide (PI) complex film. An rGO-LIG homostructure based on sp²-carbons is photothermally reconstructed from the GO-PI heterostructure in a complex film by in situ co-transformation and then transferred to an elastomer substrate. The fabricated FROS sensor successfully performs on-body strain monitoring of various indicators, such as physiological pulse, vocal sound waveform, and body movement, as well as American sign language translation. Furthermore, it is believed that this rGO-LIG homostructure-based material synthesized by in situ co-transformation can potentially provide novel functionalities in fields such as wearable electronics, humanoid, soft robotics, and intelligent prosthetics.     

High Performance Three‐Dimensional Chemical Sensor Platform Using Reduced Graphene Oxide Formed on High Aspect‐Ratio Micro‐Pillars

The sensing performance of chemical sensors can be achieved not only by modification or hybridization of sensing materials but also through new design in device geometry. The performance of a chemical sensing device can be enhenced from a simple three‐dimensional (3D) chemiresistor‐based gas sensor platform with an increased surface area by forming networked, self‐assembled reduced graphene oxide (R‐GO) nanosheets on 3D SU8 micro‐pillar arrays. The 3D R‐GO sensor is highly responsive to low concentration of ammonia (NH₃) and nitrogen dioxide (NO₂) diluted in dry air at room temperature. Compared to the two‐dimensional planar R‐GO sensor structure, as the result of the increase in sensing area and interaction cross‐section of R‐GO on the same device area, the 3D R‐GO gas sensors show improved sensing performance with faster response (about 2%/s exposure), higher sensitivity, and even a possibly lower limit of detection towards NH₃ at room temperature.     

Free‐Standing Functionalized Graphene Oxide Solid Electrolytes in Electrochemical Gas Sensors

A free‐standing sulfonic acid functionalized graphene oxide (fSGO)‐based electrolyte film is prepared and used in an electrochemical gas sensor, an alcohol fuel cell sensor (AFCS), for the detection of alcohol. The fSGO electrolyte film‐based AFCS detects ethanol vapor with excellent response, linearity, and sensitivity, since it possesses a high proton conductivity (58 mS cm^?1 at 55 °C). An ethanol detection limit level as low as 25 ppm is achieved and high selectivity for ethanol over acetone is demonstrated. These results do not only show the promising potential of fSGO films in an electrochemical gas sensors, specifically a portable breathalyzer, but also open an alternative pathway to investigate the application of graphene derivatives in the field of gas sensors.     

Facile Synthesis of 3D Graphene Flowers for Ultrasensitive and Highly Reversible Gas Sensing

Fabrication of nanostructured graphene (Gr) for gas sensing applications has become increasingly attractive. For the first time, 3D graphene flowers (GF) cluster patterns are grown directly on an Ni foam substrate by inexpensive homebuilt microwave plasma‐enhanced chemical vapor deposition (MPCVD) using the gas mixture H₂/C₂H₄O₂@Ar as a precursor. The interim morphologies of the synthesized GF are investigated and the growth mechanism of the GF film is proposed. The GF are decomposed to few‐layer Gr sheets by ultrasonication in ethanol. For the first time, MPCVD‐synthesized Gr is exploited to fabricate a gas sensor that exhibits an ultrahigh sensitivity of 133.2 ppm^?1 to NO₂. Outstanding sensor responses of 1411% and 101% to 10 ppm and 200 ppb NO₂, respectively, are achieved. Furthermore, a low theoretical detection limit of 785 ppt NO₂ is achieved. An ultrafast (within 2 s) recovery is observed at room temperature, and an imbedded microheater is employed to improve the selectivity of NO₂ detection relative to humidity. This work represents a simple, clean, and efficient route to synthesize large‐area cauliflower Gr for gas detection with high performance, including ultrahigh sensitivity, good selectivity, fast recovery, and reversibility.     

Ultrafast Fabrication of Covalently Cross‐linked Multifunctional Graphene Oxide Monoliths

Stable graphene oxide monoliths (GOMs) have been fabricated by exploiting epoxy groups on the surface of graphene oxide (GO) in a ring opening reaction with amine groups of poly(oxypropylene) diamines (D₄₀₀). This method can rapidly form covalently bonded GOM with D₄₀₀ within 60 s. FTIR and XPS analyses confirm the formation of covalent C‐N bonds. Investigation of the GOM formation mechanism reveals that the interaction of GO with a diamine cross‐linker can result in 3 different GO assemblies depending on the ratio of D₄₀₀ to GO, which have been proven both by experiment and molecular dynamics calculations. Moreover, XRD results indicate that the interspacial distance between GO sheets can be tuned by varying the diamine chain length and concentration. We demonstrate that the resulting GOM can be moulded into various shapes and behaves like an elastic hydrogel. The fabricated GOM is non‐cyctotoxic to L929 cell lines indicating a potential for biomedical applications. It could also be readily converted to graphene monolith upon thermal treatment. This new rapid and facile method to prepare covalently cross‐linked GOM may open the door to the synthesis and application of next generation multifunctional 3D graphene structures.     

空间整形飞秒激光图案化加工氧化石墨烯

氧化石墨烯(GO)是结构中含有部分含氧官能团的石墨烯衍生物,通过加热、化学反应和激光诱导等方法,该材料可以被还原。激光辐照可以诱导一定区域内的GO发生还原反应,具有灵活、区域选择性良好、无需特殊环境等优点。提出了一种基于空间整形的飞秒激光图案化加工GO的方法,即空间整形激光辐照法,分别采用空间整形激光辐照法和激光逐点扫描法在GO上加工图案,并对加工结果进行表征和对比,分析了辐照时间、激光通量等参数对加工结果的影响。结果表明空间整形激光辐照法可以图案化加工GO并使加工区域的GO被还原,从而提高图案化加工效率,且该方法具有良好的可重复性和图案灵活性,在制备GO基底的微电路、微器件方面具有应用潜力。     

3D Bicontinuous Nanoporous Reduced Graphene Oxide for Highly Sensitive Photodetectors

Reduced graphene oxide (RGO) is an important graphene derivative for applications in photonics and optoelectronics because of the band gap created by chemical oxidation. However, most RGO materials made by chemically exfoliated graphite oxide are 2D flakes. Their optoelectronic performance deteriorates significantly as a result of weak light‐matter interaction and poor electrical contact between stacking flakes. Here we report a bicontinuous 3D nanoporous RGO (3D np‐RGO) with high optoelectronic performance for highly sensitive photodetectors. 3D np‐RGO demonstrates a over 40 times higher light absorption than monolayer graphene materials and at least two orders of magnitude higher electron mobility than conventional RGO from discrete RGO flakes. The np‐RGO with an optimal reduction state shows ultrahigh photoresponse of 3.10 3 10⁴ A W^?1 at room temperature, approximately four orders of magnitude higher than graphene and other graphene derivatives at similar levels of light intensity radiations, and the excellent external quantum efficiency of 1.04 3 10⁷% better than commercial silicon photodetector. The ultrahigh capability of conversing photons to photocurrent originates from strongly enhanced light absorption, facilitated photocarrier transport, and tunable oxygenous defects and reduction states in the 3D interconnected bicontinuous RGO network.     

A Flexible Reduced Graphene Oxide Field‐Effect Transistor for Ultrasensitive Strain Sensing

A new kind of flexible strain sensor based on a reduced graphene oxide field‐effect transistor (rGO FET) with ultrasensitivity, stability, and repeatability for the detection of tensile and compressive strains is demonstrated. The novelty of the rGO FET strain sensor is the incorporation of a rGO channel as a sensing layer in which the electrical resistance can be greatly modified upon application of an extremely low level of strain resulting in an intrinsically amplified sensing signal. The rGO FET device is ultrasensitive to extremely low strain levels, as low as 0.02%. Due to weak coupling between adjacent nanosheets, therefore, upon applying small levels of strain into the rGO thin film, a modulation of the internanosheet resistance (R_inter) is expected, inducing a large change in the transconductance of the rGO FET. Using a simple printing and self‐assembly process, the facile fabrication of an rGO FET array over a large area is also demonstrated. In addition, the device can detect small and rapid physical movements of the human body.     

Thermally Conductive Reduced Graphene Oxide Thin Films for Extreme Temperature Sensors

Reduced graphene oxide (RGO) films are promising in applications ranging from electronics to flexible sensors. Though high electrical and thermal conductivities have been reported for RGO films, existing thermal conductivity data for RGO films show large variations from 30 to 2600 W m^?1 K^?1. Further, there is a lack of data at low temperatures (<300 K), which is critical for the understanding of thermal transport mechanisms. In this work, a temperature‐dependent study of thermal (10–300 K) and electrical (10–3000 K) transport in annealed RGO films indicates the potential application of RGO films for sensing temperatures across an extremely wide range. The room‐temperature thermal conductivity increases significantly from 46.1 to 118.7 W m^?1 K^?1 with increasing annealing temperature from 1000 to 3000 K with a corresponding increase in the electrical conductivity from 5.2 to 1481.0 S cm^?1. In addition, films reduced at 3000 K are promising for sensing extreme temperatures as demonstrated through the measured electrical resistivity from 10 to 3000 K. Sensors based on RGO films are advantageous over conventional temperature sensors due to the wide temperature range and flexibility. Thus, this material is useful in many applications including flexible electronics and thermal management systems.     

Hierarchical Composite Electrodes of Nickel Oxide Nanoflake 3D Graphene for High‐Performance Pseudocapacitors

NiO nanoflakes are created with a simple hydrothermal method on 3D (three‐dimensional) graphene scaffolds grown on Ni foams by microwave plasma enhanced chemical vapor deposition (MPCVD). Such as‐grown NiO‐3D graphene hierarchical composites are then applied as monolithic electrodes for a pseudo‐supercapacitor application without needing binders or metal‐based current collectors. Electrochemical measurements impart that the hierarchical NiO‐3D graphene composite delivers a high specific capacitance of ≈1829 F g^?1 at a current density of 3 A g^?1 (the theoretical capacitance of NiO is 2584 F g^?1). Furthermore, a full‐cell is realized with an energy density of 138 Wh kg^?1 at a power density of 5.25 kW kg^?1, which is much superior to commercial ones as well as reported devices in asymmetric capacitors of NiO. More attractively, this asymmetric supercapacitor exhibits capacitance retention of 85% after 5000 cycles relative to the initial value of the 1^st cycle.     

Ultraprecise 3D Printed Graphene Aerogel Microlattices on Tape for Micro Sensors and E-Skin

3D printed graphene aerogels hold promise for flexible sensing fields due to their flexibility, low density, conductivity, and piezo-resistivity. However, low printing accuracy/fidelity and stochastic porous networks have hindered both sensing performance and device miniaturization. Here, printable graphene oxide (GO) inks are formulated through modulating oxygen functional groups, which allows printing of self-standing 3D graphene oxide aerogel microlattice (GOAL) with an ultra-high printing resolution of 70 µm. The reduced GOAL (RGOAL) is then stuck onto the adhesive tape as a facile and large-scale strategy to adapt their functionalities into target applications. Benefiting from the printing resolution of 70 µm, RGOAL tape shows better performance and data readability when used as micro sensors and robot e-skin. By adjusting the molecular structure of GO, the research realizes regulation of rheological properties of GO hydrogel and the 3D printing of lightweight and ultra-precision RGOAL, improves the sensing accuracy of graphene aerogel electronic devices and realizes the device miniaturization, expanding the application of graphene aerogel devices to a broader field such as micro robots, which is beyond the reach of previous reports.     

3D Graphene Films Enable Simultaneously High Sensitivity and Large Stretchability for Strain Sensors

Integration of 2D membranes into 3D macroscopic structures is essential to overcome the intrinsically low stretchability of graphene for the applications in flexible and wearable electronics. Herein, the synthesis of 3D graphene films (3D‐GFs) using chemical vapor deposition (CVD) is reported, in which a porous copper foil (PCF) is chosen as a template in the atmospheric‐pressure CVD preparation. When the 3D‐GF prepared at 1000 °C (noted as 3D‐GF‐1000) is transferred onto a polydimethylsiloxane (PDMS) membrane, the obtained 3D‐GF‐1000/PDMS hybrid film shows an electrical conductivity of 11.6 S cm^?1 with good flexibility, indicated by small relative resistance changes (ΔR/R₀) of 2.67 and 0.36 under a tensile strain of 50% and a bending radius of 1.6 mm, respectively. When the CVD temperature is reduced to 900 °C (generating a sample noted as 3D‐GF‐900), the 3D‐GF‐900/PDMS hybrid film exhibits an excellent strain‐sensing performance with a workable strain range of up to 187% and simultaneously a gauge factor of up to ≈1500. The 3D‐GF‐900/PDMS also shows a remarkable durability in resistance in repeated 5000 stretching‐releasing cycles. Kinetics studies show that the response of ΔR/R₀ upon strain is related to the graphitization and conductivity of 3D‐GF which are sensitive to the CVD preparation temperature.     

Remarkable Antibacterial Activity of Reduced Graphene Oxide Functionalized by Copper Ions

Despite long-term efforts for exploring antibacterial agents or drugs, potentiating antibacterial activity and meanwhile minimizing toxicity to the environment remains a challenge. Here, it is experimentally shown that the functionality of reduced graphene oxide (rGO) through copper ions displays selective antibacterial activity that is significantly stronger than that of rGO itself and no toxicity to mammalian cells. Remarkably, this antibacterial activity is two-orders-of-magnitude greater than the activity of its surrounding copper ions. It is demonstrated that rGO is functionalized through the cation–π interaction to massively adsorb copper ions to form a rGO–copper composite and result in an extremely low concentration level of surrounding copper ions (less than ≈0.5 µm ). These copper ions on rGO are positively charged and strongly interact with negatively charged bacterial cells to selectively achieve antibacterial activity, while rGO exhibits the functionality to not only actuate rapid delivery of copper ions and massive assembly onto bacterial cells but also result in the valence shift in the copper ions from Cu²⁺ into Cu⁺, which greatly enhances the antibacterial activity. Notably, this rGO functionality through cation–π interaction with copper ions can similarly achieve algaecidal activity but does not exert cytotoxicity against neutrally charged mammalian cells.