3D porous Ni/NiOx as a bifunctional oxygen electrocatalyst derived from freeze-dried Ni(OH)2.

Bifunctional electrocatalytic properties of freeze-dried Ni/NiOx, freeze-dried NiO, and freeze-dried Ni(OH)2 are reported. Freeze-dried Ni(OH)2 was synthesized by the freeze-drying method. Freeze-dried Ni/NiOx and freeze-dried Ni were obtained from the thermal annealing of the material. Both Ni(OH)2 and Ni/NiOx could sustain with freestanding freeze-dried 3D structures without any carbon support. Freeze-dried Ni/NiOx exhibited excellent bifunctional electrocatalytic properties with the ORR performance at 0.62 V (half-wave potential) and OER at 1.47 V (η = 10 mA cm-2). Using freeze-dried metal hydroxides can be considered useful in a wide range of carbon-free applications and can improve the electrocatalytic performance. The bifunctional catalytic activities were calculated to be 0.86, 0.98 and 1.14 V for freeze-dried Ni/NiOx, freeze-dried NiO and freeze-dried Ni(OH)2, respectively. The stacking of 2D sheets into 3D mass seemed to play a vital role behind this excellent bifunctionality of freeze-dried Ni/NiOx. The material reveals possible applications in Zn-air batteries. Besides, the strategy developed herein could be justified to obtain other transition metal-oriented bifunctional electrocatalysts as alternatives to Pt- and Ir/Ru-based expensive benchmark catalysts.

Branched Alkylamine-Reduced Graphene Oxide Hybrids as a Dual Proton-Electron Conductor and Organic-Only Water-Splitting Photocatalyst.

We report multifunctionalities including the solid electrolytic property, electron conductivity (EnC), and photocatalytic water splitting (PWS) ability of organic-only hybrids obtained by intercalating short and branched-chain alkylamines including methylamine (MA), butylamine (BA), pentylamine (PA), and isomethylbytylamine (IMBA) in reduced graphene oxide (rGO). The alkylamine-rGO hybrids were synthesized by a facile solid-state reduction process. Within the series, IMBA-rGO exhibited high proton conductivity (PrC), EnC, and optimized PWS capacity. The PrC of IMBA-rGO was from 10-4 to 10-3 S cm-1, which is only half an order less than that for pristine GO. The EnC was 1.25 µA/V. Though the PWS performances of MA-rGO, BA-rGO, and PA-rGO were comparatively lower, IMBA-rGO could generate about 1.5 times H2 compared with that for R-TiO2. The IR spectra indicate the association of IMBA and GO by chemical bonds. The Raman spectra show the transformation of GO's nonconductive sp3 carbon sites into electron-conductive sp2 carbon centers. The thermogravimetric analysis show improved water adsorbing capacity of IMBA-rGO, which resulted in higher PrC. Doping of the nitrogen atom at the graphitic sp2 system was confirmed from the presence of pyrrolic N in X-ray photoelectron spectroscopy spectra. The resultant N-type semiconducting behavior is majorly responsible for the PWS process. The powder X-ray diffraction analysis indicates a more flexible interlayer space in IMBA-rGO, which facilitates both the reformation of hydrogen bonds during proton conduction and water dynamics during photocatalysis. The material indicates the possibility of devising graphene-based organic-only multifunctional hybrids.

Microwave-assisted catalytic conversion of glucose to 5-hydroxymethylfurfural using "three dimensional" graphene oxide hybrid catalysts.

Hybrids of reduced graphene oxide (rGO) and metal/metal oxide (Pt, NiO/Ni(OH)2, CoO, Fe3O4) nano particle were prepared by reduction of graphene oxide (GO) and metal ion (Pt2+, Ni2+, Co2+, Fe2+) hybrids. The M-rGO hybrids (M = Pt, Ni-, Co and Fe) were justified for the transformation of glucose to 5-hydroxymethylfurfural (5-HMF). High glucose → 5-HMF conversion was yielded depending on the nature of the M-rGO catalyst. The Ni-rGO showed the highest 5-HMF yield. The conversion reaction tuned to the optimized state under a microwave-assisted reaction accomplished by using Ni-rGO. In such case, the conversion rate was 99% with a 5-HMF yield of 75%. In order to improve both the conversion and yield, NiGO-FD was prepared by a freeze-dry method. The NiGO-FD remarkably showed the highest conversion of 99% and 5-HMF yield of 95%. Beside the biomass transformation process, the physico-chemical strategy employed herein for multiplying the catalytic efficiency might be justified for catalyzing similar reactions.

Correction: Microwave-assisted catalytic conversion of glucose to 5-hydroxymethylfurfural using "three dimensional" graphene oxide hybrid catalysts.

[This corrects the article DOI: 10.1039/D0RA01009J.].

Modulating the Work Function of Graphene by Pulsed Plasma Aided Controlled Chlorination.

Chlorine on graphene (G) matrices was doped by pulsed plasma stimulation on graphite electrode submerged in organochlorine solvents (CH2Cl2, CHCl3, CCl4). The study of work function by Kelvin probe force microscopy (KPFM) measurement clearly indicates that Cl-doped G behave like semiconductor and GG@CHCl3 exhibits the lowest value for the work function. We propose that this report not only represents a new route for tuning the semiconductivity of G but also indicates that doping level of halogen on G based carbon framework can be controlled by pulsed plasma treatment of carbon materials on various organohalogen derivatives.

Super Dielectric Materials of Two-Dimensional TiO2 or Ca2Nb3O10 Nanosheet Hybrids with Reduced Graphene Oxide.

High dielectric constants (εr) were observed in two-dimensional composites obtained from stacking of reduced graphene oxide (RGO) with Ca2Nb3O10 and with TiO2 nanosheets. The relative dielectric permittivity values of the composites were found to be higher than 105, an amazingly high value compared to that of similar GO composites and other common dielectric materials. As a consequence, we considered application of the hybrids as super dielectric materials in high capacitance supercapacitors. The route to high capacitance involves the variation of oxygen vacancies within the surface and in the closest bulk interior of the hybrids. The effective charges generated throughout the metal oxide and carbon-oxygen polar bonding systems within the graphene skeleton appear to highly influence dielectric polarization. Moreover, the replenishment of oxygen vacancies at the RGO and metal oxide interface also contributes to polarizability.

Development of an All Solid State Battery Incorporating Graphene Oxide as Proton Conductor.

Graphene oxide (GO) shows high proton conductivity (≈10-4 Scm-1), excellent mechanical stability, and electrical insulation property, which makes it an ideal candidate for use as a proton conducting solid state electrolyte. The prospects of using GO as single phase solid electrolyte in an all solid battery is presented herein. A battery with the cell configuration: Zn + ZnSO4•7H2O + graphite (anode) || GO (electrolyte) || MnO2 + graphite (cathode) is fabricated. Cyclic voltammetry confirms its rechargeable nature. The respective discharge capacity and power density of the cell are 360 µAh and 19.5 mW kg-1 at a constant current drain of 3 µA under the experimental conditions employed. GO based proton conductors are cleaner and cheaper than other solid electrolytes. The current study strongly suggests that GO can be used as a practical and beneficial component in solid state battery applications with low energy feedback.

Superionic Conductivity in Hybrid of 3-Hydroxypropanesulfonic Acid and Graphene Oxide.

Insertion of 3-hydroxypropanesulfonicacid (HPS) in the graphene oxide (GO) interlayer results in high proton conductivity (10-2 -10-1  S cm-1 ), owing to an improvement in oxygen content, interlayer distance and water absorbing capacity. This result indicates that hydroxyalkylsulfonicacids can be perfect guest molecules for improving the proton conductivity of carbon materials.

Thermally Stable Super Ionic Conductor from Carbon Sphere Oxide.

A highly stable proton conductor has been developed from carbon sphere oxide (CSO). Carbon sphere (CS) generated from sucrose was oxidized successfully to CSO using Hummers' graphite oxidation technique. At room temperature and 90 % relative humidity, the proton conductivity of thin layer CSO on microsized comb electrode was found to be 8.7×10(-3)  S cm(-1) , which is higher than that for a similar graphene oxide (GO) sample (3.4×10(-3)  S cm(-1) ). The activation energy (Ea ) of 0.258 eV suggests that the proton is conducted through the Grotthuss mechanism. The carboxyl functional groups on the CSO surface are primarily responsible for transporting protons. In contrast to conventional carbon-based proton conductors, in which the functional groups decompose around 80 °C, CSO has a stable morphology and functional groups with reproducible proton conductivity up to 400 °C. Even once annealed at different temperatures at high relative humidity, the proton conductivity of CSO remains almost unchanged, whereas significant change is seen with a similar GO sample. After annealing at 100 and 200 °C, the respective proton conductivity of CSO was almost the same, and was about ∼50 % of the proton conductivity at room temperature. Carbon-based solid electrolyte with such high thermal stability and reproducible proton conductivity is desired for practical applications. We expect that a CSO-based proton conductor would be applicable for fuel cells and sensing devices operating under high temperatures.

Optimization of proton conductivity in graphene oxide by filling sulfate ions.

Graphene oxide (GO) walled channels filled by sulfate ions exhibit an optimized proton conductivity, which is higher than the proton conductivity of all other forms of GO. The sulphate ion increases the water absorbing capacity and hydrogen bond reformation process in GO.

Proton conductivities of graphene oxide nanosheets: single, multilayer, and modified nanosheets.

Proton conductivities of layered solid electrolytes can be improved by minimizing strain along the conduction path. It is shown that the conductivities (σ) of multilayer graphene oxide (GO) films (assembled by the drop-cast method) are larger than those of single-layer GO (prepared by either the drop-cast or the Langmuir-Blodgett (LB) method). At 60% relative humidity (RH), the σ value increases from 1×10(-6) S cm(-1) in single-layer GO to 1×10(-4) and 4×10(-4) S cm(-1) for 60 and 200 nm thick multilayer films, respectively. A sudden decrease in conductivity was observed for with ethylenediamine (EDA) modified GO (enGO), which is due to the blocking of epoxy groups. This experiment confirmed that the epoxide groups are the major contributor to the efficient proton transport. Because of a gradual improvement of the conduction path and an increase in the water content, σ values increase with the thickness of the multilayer films. The reported methods might be applicable to the optimization of the proton conductivity in other layered solid electrolytes.

Graphene oxide nanosheet with high proton conductivity.

We measured the proton conductivity of bulk graphite oxide (GO'), a graphene oxide/proton hybrid (GO-H), and a graphene oxide (GO) nanosheet for the first time. GO is a well-known electronic insulator, but for proton conduction we observed the reverse trend, as it exhibited superionic conductivity. The hydrophilic sites present in GO as -O-, -OH, and -COOH functional groups attract the protons, which propagate through hydrogen-bonding networks along the adsorbed water film. The proton conductivities of GO' and GO-H at 100% humidity were ∼10(-4) and ∼10(-5) S cm(-1), respectively, whereas that for GO was amazingly high, nearly 10(-2) S cm(-1). This finding indicates the possibility of GO-based perfect two-dimensional proton-conductive materials for applications in fuel cells, sensors, and so on.