Metal oxide mesocrystals are the alignment of metal oxide nanoparticles building blocks into the ordered superstructure,which have potentially tunable optical,electronic,and electrical properties suitable for practica...Metal oxide mesocrystals are the alignment of metal oxide nanoparticles building blocks into the ordered superstructure,which have potentially tunable optical,electronic,and electrical properties suitable for practical applications.Herein,we report an effective method for synthesizing mesocrystal zinc oxide nanorods(ZnONRs).The crystal,surface,and internal structures of the zinc oxide mesocrystals were fully characterized.Mesocrystal zinc oxide nanorods/reduced graphene oxide(ZnONRs/rGO)nanocomposite superstructure were synthesized also using the hydrothermal method.The crystal,surface,chemical,and internal structures of the ZnONRs/rGO nanocomposite superstructure were also fully characterized.The optical absorption coefficient,bandgap energy,band structure,and electrical conductivity of the ZnONRs/rGO nanocomposite superstructure were investigated to understand its optoelectronic and electrical properties.Finally,the photoconductivity of the ZnONRs/rGO nanocomposite superstructure was explored to find the possibilities of using this nanocomposite superstructure for ultraviolet(UV)photodetection applications.Finally,we concluded that the ZnONRs/rGO nanocomposite superstructure has high UV sensitivity and is suitable for UV detector applications.展开更多
Over the span of years, improvements over various synthesis methods of graphene are constantly pursued to provide safer and more effective alternatives. Though the extraction of graphene through Hummers method is one ...Over the span of years, improvements over various synthesis methods of graphene are constantly pursued to provide safer and more effective alternatives. Though the extraction of graphene through Hummers method is one of the oldest techniques yet it is one of the most suitable methods for the formation of bulk graphene. Graphene can be obtained in the form of reduced Graphite oxide, sometimes also referred as Graphene oxide. The effectiveness of this oxidation process can be evaluated by the magnitude of carbon/oxygen ratio of the obtained graphene. Here, graphene oxide (GO) was prepared by oxidizing the purified natural flake graphite (NFG) by a modified Hummers method. The attempts have been made to synthesize GO having few layers by using a modified Hummers method where the amount of NaNO3 has been decreased, and the amount of KMnO4 is increased. The reaction has been performed in a 9:1 (by volume) mixture of H2SO4/H3PO4. This modification is successful in increasing the reaction yield and reducing the toxic gas evolution while using a varied proportion of KMnO4 and H2SO4 as those required by Hummers method. A new component of K2S2O8 has been introduced to the reaction system to maintain the pH value. Reduced graphene oxide (rGO) was thereafter extracted by thermal modification of GO. Here, GO has been used as a precursor for graphene synthesis by thermal reduction processes. The results of FTIR and Raman spectroscopy analysis show that the NFG when oxidized by strong oxidants like KMnO4 and NaNO3, introduced oxygen atoms into the graphite layers and formed bonds like C=O, C-H, COOH and C-O-C with the carbon atoms in the graphite layers. The structure and morphology of both GO and rGO were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy, Raman spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis and differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).展开更多
Graphene oxide(GO)with excellent dispersion ability can assist the dispersion of single-walled carbon nanotube(SWCNT)and promote the formation of uniform and stable GO/SWCNT coating liquid.The highly conductive polyet...Graphene oxide(GO)with excellent dispersion ability can assist the dispersion of single-walled carbon nanotube(SWCNT)and promote the formation of uniform and stable GO/SWCNT coating liquid.The highly conductive polyethylene terephthalate/reduced graphene oxide/SWCNT(PET/rGO/SWCNT)electromagnetic shielding composite fabric was successfully prepared by anchoring rGO/SWCNT on PET fabric via dip-coating piror to low-temperature thermal reduction.The results showed that the carboxyl groups and hydroxyl groups formed of hydrophilic-treated PET were conducive to the formation of hydrogen bonds with that of GO,which enhanced the interaction between PET fabric and GO/SWCNT coating;the loading of GO/SWCNT increased with the number of dip-coating,the unit area loading of rGO/SWCNT in the final composite fabric was 2.7 mg/cm^(2) after 10 dip-coating cycles and thermal reduction;the PET/rGO/SWCNT composite fabric had a continuous and dense conductive network,with a conductivity of up to 41.6 S/m and the average electromagnetic interference shielding effectiveness in X-band was 22 dB;the flexible PET/rGO/SWCNT composite fabric was not only easy to process,but also exhibited excellent conductivity and shielding efficiency,showing great potential in the application of electromagnetic shielding fabrics.展开更多
We report a simple and green approach to synthesize reduced graphene oxide （RGO） nanosheets at room temperature based on Zn reduction of exfoliated GO. The evolution of GO to RGO has been characterized by X-ray diff...We report a simple and green approach to synthesize reduced graphene oxide （RGO） nanosheets at room temperature based on Zn reduction of exfoliated GO. The evolution of GO to RGO has been characterized by X-ray diffraction, UV-Vis absorption spectroscopy and Raman spectroscopy. The results of X-ray photoelectron spectroscopy reveal that the atomic ratio of carbon to oxygen in the RGO can be tuned from 1.67 to 13.7 through controlling the reduction time. Moreover, the conductivity of the RGO is measured to be 26.9±2.2 kS/m, much larger than those previously obtained by chemical reduction through other reducing agents. More importantly, the resistance of the RGO film with 20 nm thickhess can be as low as 2 kΩ/square, while a high transparency over 70% within a broad spectral range from 0.45 pm to 1.50 p.m can be retained. The proposed method is low-cost, eco-friendly and highly-eiffcient, the as-prepared thinner RGO films are useful in a variety of potential application fields such as optoelectronics, photovoltaics and electrochemistry by serving as an ultralight, flexible and transparent electrode material.展开更多
Gamma-ray irradiation technique is an effective method for preparing graphene aerogel(GA).The effective reduction and self-assembly of graphene oxide(GO) sheets into 3D porous GA in ethylenediamine(EDA) aqueous soluti...Gamma-ray irradiation technique is an effective method for preparing graphene aerogel(GA).The effective reduction and self-assembly of graphene oxide(GO) sheets into 3D porous GA in ethylenediamine(EDA) aqueous solution under the protection of nitrogen have been achieved via γ-ray irradiation.The reduction degree and self-assembly process,which can be controlled by varying EDA dose and irradiation dose,are investigated by X-ray photoelectron spectroscopy,Fourier transform infrared spectroscopy,X-ray diffractometer,and thermogravimetric analysis.A reduction mechanism is proposed for interactions among EDA molecules,active radicals from the radiolysis of water,and oxygen-containing groups on GO sheets.展开更多
In this paper,the factors influencing the local thermal reduction of graphene oxide (GO) sheets are investigated.The lateral force microscopy and scanning polarization force microscopy verify that the heated tips of a...In this paper,the factors influencing the local thermal reduction of graphene oxide (GO) sheets are investigated.The lateral force microscopy and scanning polarization force microscopy verify that the heated tips of atomic force microscope (AFM) can thermally reduce the GO into electrical conductive nanostructures.The tip temperature,heating time,and loading force applied by the AFM tip are found to have important effects on the thermal reduction of GO,while the environmental humidity is negligible.展开更多
The modified Hummers method was employed to generate graphene oxide,and Ag /reduced graphene oxide (RGO) nanocomposites were synthesized at different temperatures by using sodium citrate as the reductant. Scanning ele...The modified Hummers method was employed to generate graphene oxide,and Ag /reduced graphene oxide (RGO) nanocomposites were synthesized at different temperatures by using sodium citrate as the reductant. Scanning electron microscopy (SEM),transmission electron microscopy (TEM),X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were employed to characterize the reaction products. The results indicate that RGO has been synthesized successfully,and Ag particles are distributed evenly on the surface of RGO.The RGO prepared at a reaction temperature of 120℃ shows the best surface-enhanced Raman scattering (SERS) activity.The Ag /RGO nanocomposites modified by 10^- 5 mol /L 4-aminothiophenol (PATP) successfully detect a 10^- 5 mol /L 2,4,6-trinitrotoluene (TNT) alcohol solution.展开更多
The thermostability, structure, oxidized functional group and hydrophilic of the different reduction temperature of graphene oxide were investigated by TG-DTA, XRD, FTIR, Raman and Water contact angle analysis. There ...The thermostability, structure, oxidized functional group and hydrophilic of the different reduction temperature of graphene oxide were investigated by TG-DTA, XRD, FTIR, Raman and Water contact angle analysis. There are three stages in the process. The first stage, under 150℃, desorption of adsorbed water on the graphene oxide, hydrophilic is best. The second stage, at 150–300℃, thermal decomposition of partial oxide functional group, graphene oxide was partly thermal reduction, hydrophilic diminishing. The third stage, at 300–550℃, temperature of 300–450℃ when oxidized functional group of graphene oxide is further decomposition, hydrophilic further reduced, temperature of 450–550℃, the carbon skeleton of graphene oxide decomposition. The thermal reduction process of graphene oxide only removed the oxidized functional group their structural deficiencies have not been restored, but due to thermal reduction process and build new structure defect.展开更多
Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which...Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp^2 domains have smaller sizes and larger quantity. The content of sp^2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.展开更多
Monolayer ultra-large graphene oxide （UL-GO） sheets with diameter up to about 100 μm were synthesized based on a chemical method. Transparent conductive films were produced using the UL-GO sheets that were deposite...Monolayer ultra-large graphene oxide （UL-GO） sheets with diameter up to about 100 μm were synthesized based on a chemical method. Transparent conductive films were produced using the UL-GO sheets that were deposited layer-by-layer on a substrate by the Langmuir-Blodgett （L-B） assembly technique. The films produced from UL-GO sheets with a close-packed flat structure exhibit exceptionally high electrical conductivity and transparency after thermal reduction. A remarkable sheet resistance of 605 -/sq at 86% transparency is obtained, which outperforms the graphene films grown on a Ni substrate by chemical vapor deposition. The technique used to produce transparent conductive films is facile, inexpensive and tunable for mass production.展开更多
Ultrathin flat metalenses have emerged as promising alternatives to conventional diffractive lenses,offering new possibilities for myriads of miniaturization and interfacial applications.Graphene-based materials can a...Ultrathin flat metalenses have emerged as promising alternatives to conventional diffractive lenses,offering new possibilities for myriads of miniaturization and interfacial applications.Graphene-based materials can achieve both phase and amplitude modulations simultaneously at a single position due to the modification of the complex refractive index and thickness by laser conversion from graphene oxide into graphene like materials.In this work,we develop graphene oxide metalenses to precisely control phase and amplitude modulations and to achieve a holistic and systematic lens design based on a graphene-based material system.We experimentally validate our strategies via demonstrations of two graphene oxide metalenses:one with an ultra-long(~16λ)optical needle,and the other with axial multifocal spots,at the wavelength of 632.8 nm with a 200 nm thin film.Our proposed graphene oxide metalenses unfold unprecedented opportunities for accurately designing graphene-based ultrathin integratable devices for broad applications.展开更多
In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridiniu...In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin) intercalated into the layer of graphene oxide(GO) by the cooperative effects of electrostatic and π-π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2 D MtTMPyP/rGO_n were fabricated. The as-prepared 2 D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction(ORR) in an alkaline medium. The MtTMPyP/rGO_n hybrids, especially CoTMPyP/rGO_5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries.展开更多
The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for th...The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for the development of direct methanol fuel cells(DMFCs). In this work, we develop a cyanogel-reduction method to synthesize reduced graphene oxide(rGO) supported highly dispersed PdNi alloy nanocrystals(PdNi/rGO) with high alloying degree and tunable Pd/Ni ratio. The large specific surface area and the d-band center downshift of Pd result in excellent activity of Pd4 Ni1/rGO nanohybrids for the ORR. The modification of Pd electronic structure can facilitate the adsorption of CH3 OH on Pd surface and the highly oxophilic property of Ni can eliminate/mitigate the COadsintermediates poisoning, which make PdNi/r GO nanohybrids possess superior MOR activity. In addition, rGO improve the stability of PdNi alloy nanocrystals for the ORR and MOR. Due to high activity and stability for the ORR and MOR, PdNi/rGO nanohybrids are promising to be an available bifunctional electrocatalyst in DMFCs.展开更多
Nitrogen(N_(2))fixation at ambient condition by electrochemical N_(2)reduction reaction(NRR)is energy-efficient and eco-friendly as compared to the traditional Harber–Bosch process,but it is extremely challenging.Dev...Nitrogen(N_(2))fixation at ambient condition by electrochemical N_(2)reduction reaction(NRR)is energy-efficient and eco-friendly as compared to the traditional Harber–Bosch process,but it is extremely challenging.Development and design of high-performance NRR electrocatalysts are indispensable to achieve the goal.In this work,a strongly coupled hybrid of nano-Fe3O4 with reduced graphene oxide(rGO)is synthesized via an in situ redox hydrothermal approach,and the synthesized Fe_(3)O_(4)@r GO hybrid has excellent activity,selectivity,and stability as an NRR catalyst.The NH_(3) yield rate of 28.01μg h^(-1)mg^(-1)at-0.3 V and the Faradaic efficiency(FE)of 19.12%at-0.1 V are obtained in 0.1 M Na_(2)SO_(4) solutions at ambient conditions.The superior NRR performance is attributed to the chemical coupling effect between r GO and nano-Fe_(3)O_(4) particles,which leads to the enhancement of the binding affinity to N_(2) molecules,improvement of the conductivity,and lowering the free energy of reaction for the limiting reaction step.This work provides a facile route in fabricating hybrid NRR catalysts with superior performance and shed lights on the reaction mechanism with theoretical mechanistic calculations.展开更多
A novel ternary nanocomposite, Pd nanoparticles（NPs）/polyoxometalates（POMs）/reduced graphene oxide（rGO）, was prepared by a green, mild, electrochemical-reductionassisted assembly. It is worth noting that the Keg...A novel ternary nanocomposite, Pd nanoparticles（NPs）/polyoxometalates（POMs）/reduced graphene oxide（rGO）, was prepared by a green, mild, electrochemical-reductionassisted assembly. It is worth noting that the Keggin-type POM acts as an electrocatalyst as well as a bridging molecule. During the reduction process, POMs transfer the electrons from the electrode to GO, leading to a deep reduction of GO and the content of oxygen-containing groups is decreased to around 6.1%. Meanwhile, the strong adsorption effect between the POM clusters and rGO nanosheets induces the spontaneous assembly of POM on r GO in a uniformly dispersed state, forming a nanocomposite. The ternary Pd NPs/POMs/rGO nanocomposite exhibits higher electrocatalytic activities, better electrochemical stability, and higher resistance to CO poisoning than the Pd/C catalyst towards the formic acid oxidation（FAOR）. Especially, the Pd/PW（12）/rGO exhibits the best electrocatalytic performance among three Pd/POMs/rGO composites（POMs = PW（12）, SiW（12）, PMo（12））.展开更多
Graphene oxide(GO)is a kind of water soluble two-dimensional materials containing a large amount of oxygen-containing groups which infuse GO with water solubility,biocompatibility and functionality,etc.But GO can be e...Graphene oxide(GO)is a kind of water soluble two-dimensional materials containing a large amount of oxygen-containing groups which infuse GO with water solubility,biocompatibility and functionality,etc.But GO can be easily reduced by losing oxygen-containing groups under some circumstances such as irradiation of-ray or ultraviolet(UV).In this work,we found that acetone can significantly slow down the reduction process of GO under the irradiation of either-ray or UV,which was supported by analysis results with UV-visible(UV-Vis)absorption spectra,X-ray photoelectron spectroscopy,etc.Acetone can capture and remove strongly reducible hydrated electrons generated under-irradiation.GO reduction by UV also involves electron transfer process which can be affected by the presence of acetone.Hence,acetone can be used to stabilize,adjust the radiation reduction process of GO.This would be interesting not only in radiation and radiation protection,but also in understanding the redox properties of GO.展开更多
Unique MoS_(2)‐SnS_(2)heterogeneous nanoplates have successfully in‐situ grown on poly(3‐(1‐vinylimidazolium‐3‐yl)propane‐1‐sulfonate)functionalized polypyrrole/graphene oxide(PVIPS/PPy/GO).PVIPS can attract h...Unique MoS_(2)‐SnS_(2)heterogeneous nanoplates have successfully in‐situ grown on poly(3‐(1‐vinylimidazolium‐3‐yl)propane‐1‐sulfonate)functionalized polypyrrole/graphene oxide(PVIPS/PPy/GO).PVIPS can attract heptamolybdate ion(Mo7O246−)and Sn^(4+)as the precursors by the ion‐exchange,resulting in the simultaneous growth of 1T’‐MoS2 and the berndtite‐2T‐type hexagonal SnS_(2)by the interfacial induced effect of PVIPS.The obtained MoS_(2)‐SnS_(2)/PVIPS/PPy/GO can serve as electrocatalysts,exhibiting good NRR performance by the synergistic effect.The semi‐conducting SnS_(2)would limit the surface electron accessibility for suppressing HER process of 1T’‐MoS_(2),while metallic 1T’‐MoS_(2)might efficiently improve the NRR electroactivity of SnS_(2)by the creation of Mo‐Sn‐Sn trimer catalytic sites.Otherwise,the irreversible crystal phase transition has taken place during the NRR process.Partial 1T’‐MoS_(2)and SnS_(2)have electrochemically reacted with N_(2),and irreversibly converted into Mo^(2)N and SnxNz due to the formation of Mo−N and Sn−N bonding,meanwhile,partial SnS_(2) has been irreversibly evolved into SnS due to the reduction by the power source in the electrochemical system.It would put forward a new design idea for optimizing the preparation method and electrocatalytic activity of transition metal dichalcogenides.展开更多
文摘Metal oxide mesocrystals are the alignment of metal oxide nanoparticles building blocks into the ordered superstructure,which have potentially tunable optical,electronic,and electrical properties suitable for practical applications.Herein,we report an effective method for synthesizing mesocrystal zinc oxide nanorods(ZnONRs).The crystal,surface,and internal structures of the zinc oxide mesocrystals were fully characterized.Mesocrystal zinc oxide nanorods/reduced graphene oxide(ZnONRs/rGO)nanocomposite superstructure were synthesized also using the hydrothermal method.The crystal,surface,chemical,and internal structures of the ZnONRs/rGO nanocomposite superstructure were also fully characterized.The optical absorption coefficient,bandgap energy,band structure,and electrical conductivity of the ZnONRs/rGO nanocomposite superstructure were investigated to understand its optoelectronic and electrical properties.Finally,the photoconductivity of the ZnONRs/rGO nanocomposite superstructure was explored to find the possibilities of using this nanocomposite superstructure for ultraviolet(UV)photodetection applications.Finally,we concluded that the ZnONRs/rGO nanocomposite superstructure has high UV sensitivity and is suitable for UV detector applications.
文摘Over the span of years, improvements over various synthesis methods of graphene are constantly pursued to provide safer and more effective alternatives. Though the extraction of graphene through Hummers method is one of the oldest techniques yet it is one of the most suitable methods for the formation of bulk graphene. Graphene can be obtained in the form of reduced Graphite oxide, sometimes also referred as Graphene oxide. The effectiveness of this oxidation process can be evaluated by the magnitude of carbon/oxygen ratio of the obtained graphene. Here, graphene oxide (GO) was prepared by oxidizing the purified natural flake graphite (NFG) by a modified Hummers method. The attempts have been made to synthesize GO having few layers by using a modified Hummers method where the amount of NaNO3 has been decreased, and the amount of KMnO4 is increased. The reaction has been performed in a 9:1 (by volume) mixture of H2SO4/H3PO4. This modification is successful in increasing the reaction yield and reducing the toxic gas evolution while using a varied proportion of KMnO4 and H2SO4 as those required by Hummers method. A new component of K2S2O8 has been introduced to the reaction system to maintain the pH value. Reduced graphene oxide (rGO) was thereafter extracted by thermal modification of GO. Here, GO has been used as a precursor for graphene synthesis by thermal reduction processes. The results of FTIR and Raman spectroscopy analysis show that the NFG when oxidized by strong oxidants like KMnO4 and NaNO3, introduced oxygen atoms into the graphite layers and formed bonds like C=O, C-H, COOH and C-O-C with the carbon atoms in the graphite layers. The structure and morphology of both GO and rGO were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy, Raman spectroscopy, Brunauer-Emmett-Teller (BET) surface area analysis and differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).
文摘Graphene oxide(GO)with excellent dispersion ability can assist the dispersion of single-walled carbon nanotube(SWCNT)and promote the formation of uniform and stable GO/SWCNT coating liquid.The highly conductive polyethylene terephthalate/reduced graphene oxide/SWCNT(PET/rGO/SWCNT)electromagnetic shielding composite fabric was successfully prepared by anchoring rGO/SWCNT on PET fabric via dip-coating piror to low-temperature thermal reduction.The results showed that the carboxyl groups and hydroxyl groups formed of hydrophilic-treated PET were conducive to the formation of hydrogen bonds with that of GO,which enhanced the interaction between PET fabric and GO/SWCNT coating;the loading of GO/SWCNT increased with the number of dip-coating,the unit area loading of rGO/SWCNT in the final composite fabric was 2.7 mg/cm^(2) after 10 dip-coating cycles and thermal reduction;the PET/rGO/SWCNT composite fabric had a continuous and dense conductive network,with a conductivity of up to 41.6 S/m and the average electromagnetic interference shielding effectiveness in X-band was 22 dB;the flexible PET/rGO/SWCNT composite fabric was not only easy to process,but also exhibited excellent conductivity and shielding efficiency,showing great potential in the application of electromagnetic shielding fabrics.
基金V. ACKNOWLEDGMENTS This work is supported by the Ministry of Science and Technologyh of China （No.2011CB921403）, the National Natural Science Foundation of China （No.10874165, No.90921013, No.11074231, and No.11004179） and Chinese Academy of Sciences .
文摘We report a simple and green approach to synthesize reduced graphene oxide （RGO） nanosheets at room temperature based on Zn reduction of exfoliated GO. The evolution of GO to RGO has been characterized by X-ray diffraction, UV-Vis absorption spectroscopy and Raman spectroscopy. The results of X-ray photoelectron spectroscopy reveal that the atomic ratio of carbon to oxygen in the RGO can be tuned from 1.67 to 13.7 through controlling the reduction time. Moreover, the conductivity of the RGO is measured to be 26.9±2.2 kS/m, much larger than those previously obtained by chemical reduction through other reducing agents. More importantly, the resistance of the RGO film with 20 nm thickhess can be as low as 2 kΩ/square, while a high transparency over 70% within a broad spectral range from 0.45 pm to 1.50 p.m can be retained. The proposed method is low-cost, eco-friendly and highly-eiffcient, the as-prepared thinner RGO films are useful in a variety of potential application fields such as optoelectronics, photovoltaics and electrochemistry by serving as an ultralight, flexible and transparent electrode material.
基金supported by the National Natural Science Foundation of China(No.11505270)Shanghai Municipal Commission for Science and Technology(No.15ZR1448300)
文摘Gamma-ray irradiation technique is an effective method for preparing graphene aerogel(GA).The effective reduction and self-assembly of graphene oxide(GO) sheets into 3D porous GA in ethylenediamine(EDA) aqueous solution under the protection of nitrogen have been achieved via γ-ray irradiation.The reduction degree and self-assembly process,which can be controlled by varying EDA dose and irradiation dose,are investigated by X-ray photoelectron spectroscopy,Fourier transform infrared spectroscopy,X-ray diffractometer,and thermogravimetric analysis.A reduction mechanism is proposed for interactions among EDA molecules,active radicals from the radiolysis of water,and oxygen-containing groups on GO sheets.
基金supported by National Basic Research Program of China (No. 2007CB936000)Chinese Academy of Sciences (No. KJCX2-EW-N03)National Science Foundation of China (No. 10975175,90923002,and 90923041)
文摘In this paper,the factors influencing the local thermal reduction of graphene oxide (GO) sheets are investigated.The lateral force microscopy and scanning polarization force microscopy verify that the heated tips of atomic force microscope (AFM) can thermally reduce the GO into electrical conductive nanostructures.The tip temperature,heating time,and loading force applied by the AFM tip are found to have important effects on the thermal reduction of GO,while the environmental humidity is negligible.
基金Beijing Higher Education Young Elite Teacher Project(YETP0499)
文摘The modified Hummers method was employed to generate graphene oxide,and Ag /reduced graphene oxide (RGO) nanocomposites were synthesized at different temperatures by using sodium citrate as the reductant. Scanning electron microscopy (SEM),transmission electron microscopy (TEM),X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were employed to characterize the reaction products. The results indicate that RGO has been synthesized successfully,and Ag particles are distributed evenly on the surface of RGO.The RGO prepared at a reaction temperature of 120℃ shows the best surface-enhanced Raman scattering (SERS) activity.The Ag /RGO nanocomposites modified by 10^- 5 mol /L 4-aminothiophenol (PATP) successfully detect a 10^- 5 mol /L 2,4,6-trinitrotoluene (TNT) alcohol solution.
文摘The thermostability, structure, oxidized functional group and hydrophilic of the different reduction temperature of graphene oxide were investigated by TG-DTA, XRD, FTIR, Raman and Water contact angle analysis. There are three stages in the process. The first stage, under 150℃, desorption of adsorbed water on the graphene oxide, hydrophilic is best. The second stage, at 150–300℃, thermal decomposition of partial oxide functional group, graphene oxide was partly thermal reduction, hydrophilic diminishing. The third stage, at 300–550℃, temperature of 300–450℃ when oxidized functional group of graphene oxide is further decomposition, hydrophilic further reduced, temperature of 450–550℃, the carbon skeleton of graphene oxide decomposition. The thermal reduction process of graphene oxide only removed the oxidized functional group their structural deficiencies have not been restored, but due to thermal reduction process and build new structure defect.
基金Project(51274248)supported by the National Natural Science Foundation of ChinaProjects(2015DFR50580,2013DFA31440)supported by the International Scientific and Technological Cooperation Program of China
文摘Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp^2 domains have smaller sizes and larger quantity. The content of sp^2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.
基金Project (51102170) supported by the National Natural Science Foundation of ChinaProject (2010CB234609) supported by the National Basic Research Program of China
文摘Monolayer ultra-large graphene oxide （UL-GO） sheets with diameter up to about 100 μm were synthesized based on a chemical method. Transparent conductive films were produced using the UL-GO sheets that were deposited layer-by-layer on a substrate by the Langmuir-Blodgett （L-B） assembly technique. The films produced from UL-GO sheets with a close-packed flat structure exhibit exceptionally high electrical conductivity and transparency after thermal reduction. A remarkable sheet resistance of 605 -/sq at 86% transparency is obtained, which outperforms the graphene films grown on a Ni substrate by chemical vapor deposition. The technique used to produce transparent conductive films is facile, inexpensive and tunable for mass production.
基金Hongtao Wang acknowledges the support from National Key Research and Development Program of China(2017YFB0403602)China Scholarship Council.Baohua Jia acknowledges the support from the Australian Research Council through the Discovery Projects(DP150102972,DP190103186)+5 种基金the Industrial Transformation Training Centres scheme(Grant No.IC180100005)support from Defence Science Institute(DSI)and Defence Science and Technology Group(DSTG).C.W.Q.acknowledges the support from the National Research Foundation,Prime Minister’s Office,Singapore,under its Competitive Research Programme(CRP award NRF CRP22-2019-0006)Advanced Research and Technology Innovation Centre(ARTIC)under the grant(R-261-518-004-720)A STAR under Advanced Manufacturing and Engineering(AME)Individual Research Grant(IRG A2083c0060)Tian Lan acknowledges National Key Basic Research Program 973 Project(2013CB329202)National Major Scientific Instruments and Equipments Development Project supported by National Natural Science Foundation of China(No.61827814).
文摘Ultrathin flat metalenses have emerged as promising alternatives to conventional diffractive lenses,offering new possibilities for myriads of miniaturization and interfacial applications.Graphene-based materials can achieve both phase and amplitude modulations simultaneously at a single position due to the modification of the complex refractive index and thickness by laser conversion from graphene oxide into graphene like materials.In this work,we develop graphene oxide metalenses to precisely control phase and amplitude modulations and to achieve a holistic and systematic lens design based on a graphene-based material system.We experimentally validate our strategies via demonstrations of two graphene oxide metalenses:one with an ultra-long(~16λ)optical needle,and the other with axial multifocal spots,at the wavelength of 632.8 nm with a 200 nm thin film.Our proposed graphene oxide metalenses unfold unprecedented opportunities for accurately designing graphene-based ultrathin integratable devices for broad applications.
基金supported by Natural Science Fund of Jiangsu Province (BK20141247, BK20140447)Exceptional Talent Project in Jiangsu Province (2015-XCL-035)+3 种基金University Science Research Project of Jiangsu Province (13KJB430005, 11KJA430008)funded by the Priority Academic Program development of Jiangsu Higher Education InstitutionsJiangsu Province universities' "blue and green blue project"financial support from the ARC (CE140100012, FT130100380, and DP170102267)
文摘In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin) intercalated into the layer of graphene oxide(GO) by the cooperative effects of electrostatic and π-π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2 D MtTMPyP/rGO_n were fabricated. The as-prepared 2 D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction(ORR) in an alkaline medium. The MtTMPyP/rGO_n hybrids, especially CoTMPyP/rGO_5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries.
基金the National Natural Science Foundation of China (21473111)the Fundamental Research Funds for the Central Universities (GK201701007)
文摘The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for the development of direct methanol fuel cells(DMFCs). In this work, we develop a cyanogel-reduction method to synthesize reduced graphene oxide(rGO) supported highly dispersed PdNi alloy nanocrystals(PdNi/rGO) with high alloying degree and tunable Pd/Ni ratio. The large specific surface area and the d-band center downshift of Pd result in excellent activity of Pd4 Ni1/rGO nanohybrids for the ORR. The modification of Pd electronic structure can facilitate the adsorption of CH3 OH on Pd surface and the highly oxophilic property of Ni can eliminate/mitigate the COadsintermediates poisoning, which make PdNi/r GO nanohybrids possess superior MOR activity. In addition, rGO improve the stability of PdNi alloy nanocrystals for the ORR and MOR. Due to high activity and stability for the ORR and MOR, PdNi/rGO nanohybrids are promising to be an available bifunctional electrocatalyst in DMFCs.
基金Sichuan Science and Technology Program(2018GZ0459)Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(XHT2020-003)the Fundamental Research Funds for the Central Universities(WUT:2020Ⅲ029)
文摘Nitrogen(N_(2))fixation at ambient condition by electrochemical N_(2)reduction reaction(NRR)is energy-efficient and eco-friendly as compared to the traditional Harber–Bosch process,but it is extremely challenging.Development and design of high-performance NRR electrocatalysts are indispensable to achieve the goal.In this work,a strongly coupled hybrid of nano-Fe3O4 with reduced graphene oxide(rGO)is synthesized via an in situ redox hydrothermal approach,and the synthesized Fe_(3)O_(4)@r GO hybrid has excellent activity,selectivity,and stability as an NRR catalyst.The NH_(3) yield rate of 28.01μg h^(-1)mg^(-1)at-0.3 V and the Faradaic efficiency(FE)of 19.12%at-0.1 V are obtained in 0.1 M Na_(2)SO_(4) solutions at ambient conditions.The superior NRR performance is attributed to the chemical coupling effect between r GO and nano-Fe_(3)O_(4) particles,which leads to the enhancement of the binding affinity to N_(2) molecules,improvement of the conductivity,and lowering the free energy of reaction for the limiting reaction step.This work provides a facile route in fabricating hybrid NRR catalysts with superior performance and shed lights on the reaction mechanism with theoretical mechanistic calculations.
基金financially supported by the National Natural Science Foundation of China(No.21571034)the Natural Science Foundation of Fujian Province(No.2014J01033)a Key Item of Education Department of Fujian Province(No.JA13085)
文摘A novel ternary nanocomposite, Pd nanoparticles（NPs）/polyoxometalates（POMs）/reduced graphene oxide（rGO）, was prepared by a green, mild, electrochemical-reductionassisted assembly. It is worth noting that the Keggin-type POM acts as an electrocatalyst as well as a bridging molecule. During the reduction process, POMs transfer the electrons from the electrode to GO, leading to a deep reduction of GO and the content of oxygen-containing groups is decreased to around 6.1%. Meanwhile, the strong adsorption effect between the POM clusters and rGO nanosheets induces the spontaneous assembly of POM on r GO in a uniformly dispersed state, forming a nanocomposite. The ternary Pd NPs/POMs/rGO nanocomposite exhibits higher electrocatalytic activities, better electrochemical stability, and higher resistance to CO poisoning than the Pd/C catalyst towards the formic acid oxidation（FAOR）. Especially, the Pd/PW（12）/rGO exhibits the best electrocatalytic performance among three Pd/POMs/rGO composites（POMs = PW（12）, SiW（12）, PMo（12））.
基金supported by the National Natural Science Foundation of China (No.51673181)
文摘Graphene oxide(GO)is a kind of water soluble two-dimensional materials containing a large amount of oxygen-containing groups which infuse GO with water solubility,biocompatibility and functionality,etc.But GO can be easily reduced by losing oxygen-containing groups under some circumstances such as irradiation of-ray or ultraviolet(UV).In this work,we found that acetone can significantly slow down the reduction process of GO under the irradiation of either-ray or UV,which was supported by analysis results with UV-visible(UV-Vis)absorption spectra,X-ray photoelectron spectroscopy,etc.Acetone can capture and remove strongly reducible hydrated electrons generated under-irradiation.GO reduction by UV also involves electron transfer process which can be affected by the presence of acetone.Hence,acetone can be used to stabilize,adjust the radiation reduction process of GO.This would be interesting not only in radiation and radiation protection,but also in understanding the redox properties of GO.
文摘Unique MoS_(2)‐SnS_(2)heterogeneous nanoplates have successfully in‐situ grown on poly(3‐(1‐vinylimidazolium‐3‐yl)propane‐1‐sulfonate)functionalized polypyrrole/graphene oxide(PVIPS/PPy/GO).PVIPS can attract heptamolybdate ion(Mo7O246−)and Sn^(4+)as the precursors by the ion‐exchange,resulting in the simultaneous growth of 1T’‐MoS2 and the berndtite‐2T‐type hexagonal SnS_(2)by the interfacial induced effect of PVIPS.The obtained MoS_(2)‐SnS_(2)/PVIPS/PPy/GO can serve as electrocatalysts,exhibiting good NRR performance by the synergistic effect.The semi‐conducting SnS_(2)would limit the surface electron accessibility for suppressing HER process of 1T’‐MoS_(2),while metallic 1T’‐MoS_(2)might efficiently improve the NRR electroactivity of SnS_(2)by the creation of Mo‐Sn‐Sn trimer catalytic sites.Otherwise,the irreversible crystal phase transition has taken place during the NRR process.Partial 1T’‐MoS_(2)and SnS_(2)have electrochemically reacted with N_(2),and irreversibly converted into Mo^(2)N and SnxNz due to the formation of Mo−N and Sn−N bonding,meanwhile,partial SnS_(2) has been irreversibly evolved into SnS due to the reduction by the power source in the electrochemical system.It would put forward a new design idea for optimizing the preparation method and electrocatalytic activity of transition metal dichalcogenides.
