Triphenylamine-functionalized graphene decorated with Pt nanoparticles and its application in photocatalytic hydrogen production

A new type of graphene-based nanohybrid was prepared from graphene nanosheets and 4-(diphenylamino)benzaldehyde (TPA-CHO) through 1,3-dipolar cycloaddition. The nanohybrid was modified by platinum nanoparticles via photodeposition. The nanohybrid and its Pt modified nanocomposite were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Ultraviolet–visible absorption (UV–vis), Fourier transform infrared (FTIR), and Raman spectra confirmed that triphenylamine moiety grafted on the graphene surface. The results of fluorescence quenching and photocurrent enhancement of the triphenylamine-functionalized graphene revealed that photoinduced electron transfer from triphenylamine moiety to the graphene sheet. The investigation of using the Pt modified graphene-based nanocomposite as a photocatalyst for H₂ evolution showed that under UV–vis light irradiation, the average H₂ evolution rate and the quantum efficiency is 2.3 μmol h⁻¹ and 0.45% mol E⁻¹, respectively. This work demonstrated a potential application of an organic sensitizer covalently functionalized graphene as a novel photocatalyst in the field of solar energy conversion.     

Carbon nanodots prepared from NaOH-boiled graphene and its usage as a support of PdO for ethanol oxidation reaction

For the first time, carbon nanodots were prepared from NaOH-boiled graphene. And, a novel catalyst that contained PdO and carbon nanodots (denoted as PdO/CND) was fabricated in this work. In this work, 0.5 M and 1.5 M NaOH solutions were respectively employed with an intention to study the influence of NaOH concentration on the electrocatalytic activity of the obtained catalysts for ethanol oxidation reaction (EOR). The obtained samples were thoroughly characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and fourier transform infrared spectrometry (FTIR). The results indicated that the intensities of the diffraction peaks for graphene were significantly promoted with increasing the NaOH concentration and carbon nanodots with an average particle size less than 4 nm were fabricated by this developed boiling–grinding–ultrasonication (BGU) method. The electrocatalytic performances of the obtained PdO/CND catalysts for EOR were investigated using cyclic voltammetry (CV) and chronoamperometry (CA). And the consequences strongly demonstrated that PdO/CND prepared from 0.5 M NaOH-boiled graphene showed the best electrocatalytic activity towards EOR among all the prepared catalysts. Developing a very facile method for producing carbon nanodots as well as a novel composite catalyst that contained PdO and carbon nanodots for EOR was the main contribution of this work.     

Fabrication of Pt nanoparticles on ethylene diamine functionalized graphene for formic acid electrooxidation

A novel and simple synthesis method of preparing ethylene diamine (ED) functionalized graphene (ED-Gh) decorated with Pt nanoparticle has been reported. Morphology, microstructure of the resulted material was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (Raman), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Electrochemical studies toward formic acid electrooxidation were investigated by cyclic voltammetry (CV) and chronoamperometry (CA). These results showed that Pt nanoparticle with the crystallite size of about 5 nm was highly dispersed on ED-Gh and the catalyst exhibited good electrocatalytic activity and long-term stability. Therefore, ED-Gh can be a potential support for Pt in direct formic acid fuel cells.     

Polypyrrole/carbon aerogel composite materials for supercapacitor

Polypyrrole (PPy)/carbon aerogel (CA) composite materials with different PPy contents are prepared by chemical oxidation polymerization through ultrasound irradiation and are used as active electrode material for supercapacitor. The morphology of PPy/CA composite is examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that PPy is deposited onto the surface of CA. As evidenced by cyclic voltammetry, galvanostatic charge/discharge test and EIS measurements, PPy/CA composites show superior capacitive performances to CA, moreover, the results based on cyclic voltammograms show that the composite material has a high specific capacitance of 433 F g⁻¹, while the capacitance of CA electrode is only 174 F g⁻¹. Although the supercapacitor used PPy/CA as active electrode material has an initial capacitance loss due to the instability of PPy, the specific capacitance after 500 cycles stabilizes nearly at a fixed value.     

Study on the hydrogen storage properties of the dual active metals Ni and Al doped graphene composites

The graphene nanosheets are synthesized by modified Hummer's method, based on which the dual active metals Ni and Al doped graphene composites are prepared through in-suit reaction and self-assembly with high-temperature reduction process. The molecular structure, morphology and specific surface area of graphene nanosheets are characterized systematically. The phase composition, surface morphology and hydrogen storage properties of dual active metals Ni and Al doped graphene composites are further investigated by X-ray diffraction, scanning electron microscopy and gas reaction controller. Results show that the graphene nanosheets have typical graphene feature, whose transparent graphene edges can be observed clearly, and the specific surface area is as high as 604.2 m² g⁻¹. The Ni and Al doped graphene composites are composed with Ni, Al and C phases, which have high hydrogen storage capacity and excellent hydriding/dehydriding stabilities. The maximum hydrogen storage uptake of such composites is up to 5.7 wt% at 473 K, and the dehydriding efficiency is high as 96%∼97% at the dehydriding temperature of 380 K. The hydrogen adsorption and desorption rate control step of the Ni and Al doped graphene composites is complied to the nucleation and two-dimensional growth mechanism.     

The effect of annealing on the properties of diamond-like carbon protective antireflection coatings

In addition to its similarity to genuine diamond film, diamond-like carbon (DLC) film has many advantages, including its wide band gap and variable refractive index. Therefore, as one of the diverse applications, DLC film can be utilized as a protective coating for IR windows and an anti-reflective coating for solar cells. For this study, DLC films were prepared by the radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD) method on silicon substrates using methane (CH₄) and hydrogen (H₂) gas. We examined the effects of the post-annealing temperature and the annealing ambient on structural, electrical and optical properties of DLC films. The films were annealed at temperatures ranging from 300 to 900 °C in steps of 200 °C using rapid thermal annealing equipment in nitrogen ambients. The thickness of the film was observed by scanning electron microscopy (SEM) and surface profile analysis. The variation of structure according to the annealing treatment was examined using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). The reflectance of DLC thin film was investigated by UV–vis spectrometry and its electrical properties were investigated using a four point probe and I–V meter. The carrier lifetime of the film was also checked.     

Platinum–Iron nanoparticles supported on reduced graphene oxide as an improved catalyst for methanol electro oxidation

Platinum–Iron nanoparticles supported on reduced graphene oxide powder are synthesized by chemical reduction method as an anode catalyst for the methanol electro oxidation. The characterization of the catalyst has been investigated using physical and electrochemical methods. Prepared catalyst was characterized by scanning electron microscopy (SEM), TEM (Transmission electron microscopy), FT-IR (Fourier-transform infrared spectroscopy), Raman spectroscopy and, X-ray diffraction (XRD) and energy dispersive analysis of X-ray (EDX). Pt and Pt-Fe nanoparticles are uniformly dispersed on the surface of reduced graphene oxide (rGO) powder nanocomposite support. The catalytic properties of the catalyst for methanol electro-oxidation were thoroughly studied by electrochemical methods that involved in the cyclic voltammetry, linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The Pt-Fe/rGo exhibits high electrocatalytic activity, catalyst tolerance for the CO poisoning and catalyst durability for electro-oxidation of methanol compared to the Pt/rGo and commercial Pt/C catalyst. Therefore, the Pt-Fe/rGo catalyst is a good choice for application in direct methanol fuel cells.     

Bridging TiO2 nanoparticles using graphene for use in dye‐sensitized solar cells

The use of graphene to bridge TiO₂ particles in the photoanode of dye‐sensitized solar cell for reduced electrical resistance has been investigated. The difficulty in dispersing graphene in TiO₂ paste was overcome by first dispersing graphene oxide (GO) into the TiO₂ paste. The GO was then reduced to graphene after the sintering of TiO₂. This is shown through transmission electron microscopy and X‐ray photoelectron spectroscopy analysis. Cell performance was evaluated using a solar simulator, incident photon to electron conversion efficiency, intensity modulated photocurrent/photovoltage spectroscopy under blue light, and electrochemical impedance spectroscopy. Depending on the amount of graphene in the photoanode, the cell performance was enhanced to different degrees. A maximum increase of 11.4% in the cell efficiency has been obtained. In particular, the inclusion of graphene has reduced the electron diffusion time by as much as 23.4%, i.e. from 4.74 to 3.63 ms and increased the electron lifetime by as much as 42.3%, i.e. from 19.58 to 27.85 ms. Copyright © 2014 John Wiley & Sons, Ltd.     

Bottom-up construction of three-dimensional porous MXene/nitrogen-doped graphene architectures as efficient hydrogen evolution electrocatalysts

The exploration of highly-active non-platinum electrocatalysts with low-cost has been regarded as a crucial way to alleviate the major bottleneck in electrocatalytic hydrogen evolution reaction (HER) technology. Herein, we demonstrate the bottom-up construction of three-dimensional (3D) hybrid architectures built from Ti₃C₂T_x MXene and nitrogen-doped graphene nanosheets (MX/NG) through a facile and cost-effective co-assembly approach. The as-derived MX/NG architectures are endowed with a number of distinctive structural advantages, such as large specific surface areas, 3D cross-linked porous frameworks, ultrathin walls, optimized electronic structures, and good electron conductivity. As a result, exceptional HER performances with a relatively low onset potential, a small Tafel slope, and reliable long-term stability are achieved on the optimized MX/NG electrode, markedly outperforming those of bare Ti₃C₂T_x and NG electrodes.     

活性碳纤维作还原剂降低NO实验研究

利用程序升温反应装置（TPR），在微型反应器中对国产各种活性碳纤维（ACF）进行了脱除NO的效果对比实验，定量测定了在不同温度下ACF与NO的反应产物，并通过程序升温脱附（TPD）、热重（TG）及扫描电镜（SEM）的研究，初步探讨了ACF宏观反应机理，并考察了所选ACF基不同气氛下的变化规律。实验结果表明，聚丙烯腈基ACF脱除NO性能最佳。     

Fabrication of cost-effective non-noble metal supported on conducting polymer composite such as copper/polypyrrole graphene oxide (Cu2O/PPy–GO) as an anode catalyst for methanol oxidation in DMFC

Cost-effective non-noble metal catalysts are of key significance to the successful use of direct methanol fuel cells (DMFCs) for electricity generation. Herein, cuprous oxide nanoparticles (Cu₂O NPs) supported graphene oxide (GO), polypyrrole (PPy) and polypyrrole–graphene oxide (PPy–GO) matrices were prepared using borohydride reduction method. The prepared catalysts were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–Vis spectra, Zeta potential and transmission electron microscopy (TEM). The elemental analysis of the composites was done by energy dispersive X-ray spectroscopy (EDX). Cu₂O NPs were homogeneously dispersed and strongly anchored on the PPy grafted GO matrix and this was examined through morphological analysis. The Cu₂O/PPy–GO (80:10:10) NPs exhibited noticeable improvement in electrochemical performance in comparison to pure graphene oxide (GO) and pure PPy supported Cu₂O NPs catalyst and revealed the peak current density of 300 μA cm^?2 at +0.68 V. The Cu₂O/PPy–GO system demonstrated higher current density and also exhibited greater stability in comparison to the commercial Pt–Ru/C catalyst as characterized by chronoamperometry (CA) analysis. This prospective nano-catalyst showed higher I_F/I_B ratio (26%, 8.6% and 19%) compared to the corresponding catalyst systems of Cu₂O/GO, Cu₂O/PPy and Pt–Ru/C. In direct methanol fuel cell (DMFC), the efficiency of Cu₂O/PPy–GO nano-catalyst system as an anode catalyst for methanol oxidation reaction (MOR) was investigated and the result revealed a maximum current density of 155 mA cm^?2 at +0.2 V and power density of 31 mW cm^?2. Hence, Cu₂O/PPy–GO NPs are a cost-effective alternative for Pt–Ru/C system to execute practical application in DMFC.     

Flexible TCO-free counter electrode for dye-sensitized solar cells using graphene nanosheets from a Ti–Ti(III) acid solution

A rapid and simple route to synthesize highly conductive graphene-based nanosheets for use as a flexible counter electrode in dye-sensitized solar cells is presented. The flexible counter electrode is free of transparent conductive oxide layer, i.e., TCO-free. A clean graphene with high quality is obtained by the chemical reduction of graphene oxide (GO) using titanium metallic powders in a hydrochloric acid solution. The Ti⁺³ ions that dissociated from metallic Ti particles in a hydrochloric acid solution result in a clean graphene material with no formation of TiO₂ nanoparticles, which are always present on graphene when only Ti⁺³ ions are used for the reduction, i.e., an anatase TiO₂ nanoparticle by-product will be always left on the graphene product when not using metallic Ti particles. The chemical reaction mechanisms for these differences are revealed in this report. The reduced materials are characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, thermo-gravimetric analysis, Fourier transform infrared spectrometry, UV–vis spectroscopy and X-ray photoelectron spectroscopy. The four-point probe method is also employed to characterize the surface conductivity of the graphene films. This high quality graphene film exhibits comparable or better performance than those obtained using conventional sputtered Pt counter electrode when used as a flexible counter electrode of dye-sensitized solar cells.     

Dye-sensitized solar cells using graphene-based carbon nano composite as counter electrode

We demonstrated a counter electrode in dye-sensitized solar cells (DSSCs) using the graphene-based multi-walled carbon nanotubes (GMWNTs) structure. Graphene layers were prepared by drop casting on a SiO₂/Si substrate and multi-walled carbon nanotubes (MWNTs) were synthesized on graphene layers using iron catalyst by chemical vapor deposition. The structural properties of GMWNTs were investigated by transmission electron microscope and field-emission scanning electron microscopy. The GMWNTs sheets were lifted off from the Si substrate by buffered oxide etching and were transplanted on fluorine-doped tin oxide glass by Van der Waals force as a counter electrode. From the electrochemical impedance spectroscopy and energy conversion efficiencies, electrochemical properties of GMWNTs were comparable with those of MWNTs counter electrode. The results suggested that GMWNTs were one of the candidates for a counter electrode for dye-sensitized solar cells.     

Pd/Cu bimetallic nanoparticles supported on graphene nanosheets: Facile synthesis and application as novel electrocatalyst for ethanol oxidation in alkaline media

Well distributed Pd/Cu bimetallic nanoparticles supported on graphene nanosheets as novel electrocatalyst has been prepared via a facile synthetic method: started with an electroless deposition route to anchor Cu nanoseeds on graphene nanosheets, followed by a latter displacement reaction to achieve Pd/Cu overlaying nanostructure. The loading density and morphology of bimetallic nanoparticles on graphene are varied by adjusting the initial amount of Cu precursor and reducing agent proportionally. Scanning transmission electron microscopy (STEM) images combining energy dispersive X-ray spectroscopy (EDX) mapping results confirm the existance and distribution of Pd and Cu in the bimetallic nanoparticles, while transmission electron microscopy (TEM) reveals the nanoparticle size and overlaying nanostructure. Cyclic voltammograms tests for the hybrid electrocatalysts in 1.0 M KOH solution show a gradual increase of electrochemically active surface area (EASA) against the increment of nanoparticle loading. Meanwhile, a significantly enhanced tolerance to poisoning of electrocatalyst is observed by cyclic voltammograms curves for ethanol electrooxidation in alkaline media with high I_f/I_b ratios compared to previous research. The large enhancement on I_f/I_b ratios of the hybrid electrocatalysts can be ascribed to the well distributed overlaying bimetallic nanostructure supported on graphene nanosheets. The facilely prepared Pd/Cu/graphene hybrid materials demonstrate vastly superior electrocatalytic properties compared to the commercial Pd/C catalyst, indicating a great potential in fuel cells application.     

Polyol synthesis of reduced graphene oxide supported platinum electrocatalysts for fuel cells: Effect of Pt precursor,support oxidation level and pH

In this work, a comprehensive study on the polyol synthesis of platinum supported on reduced graphene oxide (Pt/rGO) catalysts, including both ex-situ and in-situ characterizations of the prepared Pt/rGO catalysts, was performed. The polyol synthesis was studied considering the influence of the platinum precursor, oxidation level of graphite oxide and pH of reaction medium. The as-prepared catalysts were analyzed using thermo-gravimetric (TG) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and cyclic voltammetry (CV). The best results in terms of platinum particle size and distribution were obtained when the synthesis was performed in acidic medium, using chloroplatinic acid as precursor and using graphene oxide with high oxidation level. The most promising graphene-supported catalyst was used to prepare a polymer electrolyte membrane fuel cell electrode. The membrane electrode assembly (MEA) prepared with graphene-based electrode was compared with a MEA prepared with catalyst based on commercial platinum supported in carbon black (Pt/C). Single cell characterization included polarization curves and in-situ electrochemical impedance spectroscopy (EIS). The graphene-based electrode presented promising albeit unstable electrochemical performance due to water management issues. Additionally, EIS measurements revealed that the MEA made with Pt/rGO catalyst presented a lower mass transport resistance than the commercial Pt/C.     

Electrospun capric acid/polyethylene terephthalate composite nanofibres for storage and retrieval of thermal energy

Abstract

Composite nanofibres based on capric acid (CA) and polyethylene terephthalate (PET) with different mass ratios of CA/PET ranging from 0·5∶1, 1∶1, 1·5∶1, 2∶1 to 2·5∶1 were fabricated by electrospinning as innovative form-stable phase change materials for storage and retrieval of thermal energy. The morphological structures, thermal energy storage properties and thermal stability of electrospun CA/PET composite nanofibres were characterised by field emission scanning electron microscopy (FE-SEM), transmission electronic microscopy (TEM), differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA) respectively. The FE-SEM images revealed that the electrospun CA/PET composite nanofibres had a cylindrical morphology with average fibre diameters in the range of about 145–192 nm. Additionally, the FE-SEM and TEM images indicated that the CA distributed on the surface and within the core of the composite nanofibres. The results acquired from DSC analyses indicated that the mass ratio of CA versus PET played an important role on the enthalpy values of melting and crystallisation of the composite nanofibres, while it had no appreciable effect on the temperatures of phase transitions. Moreover, the results of DSC thermal cycling suggested that the thermal energy storage properties of the CA in the composite nanofibres had hardly been influenced during thermal cycling, indicating that the electrospun CA/PET composite nanofibres had good thermal reliability. The TGA results showed that both the onset thermal degradation temperature and the charred residue at 700°C of the composite nanofibres were lower than those of pure PET nanofibres as a result of the thermal instability of the CA molecular chains.     

Pool Boiling Enhancement through Graphene and Graphene Oxide Coatings

ABSTRACT

Boiling has served as an effective means to dissipate large quantities of heat over small areas. Graphene, a two-dimensional material, has garnered significant attention of researchers due to its excellent thermal properties. In this study, copper test chips are dip coated with a solution consisting of graphene oxide and graphene and its pool boiling performance with distilled water at atmospheric pressure was investigated. The surfaces were characterized using X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy which confirmed the presence of graphene and graphene oxide. The contact angles measured on the coated surfaces indicated hydrophobic wetting behavior. Four heat transfer surfaces were prepared with dip coating durations of 120 s, 300 s, 600 s, and 1200 s, respectively. A Critical Heat Flux (CHF) of 182 W/cm² and a heat transfer coefficient (HTC) of 96 kW/m²°C was obtained with the shortest coating duration which translated to an enhancement of 42% in CHF and 47% in HTC when compared to a plain uncoated surface under similar conditions. Contact angle changes were not seen to be responsible, although roughness was seen as an influencing factor contributing to the enhancement. Further studies are needed to explain the enhancement mechanism.     

Preparation of new self-humidifying composite membrane by incorporating graphene and phosphotungstic acid into sulfonated poly(ether ether ketone) film

In this work, a combination of constituent materials capable of improving the moisture retention and proton conductivity (PC) was incorporated into sulfonated poly (ether ether ketone) (SPEEK) membranes in order to prepare new, self-humidifying composite membranes (SHMs) for proton exchange membrane fuel cells. The property-improving components were incorporated into the cast SPEEK film in an appropriate microstructural architecture to prepare the SHMs with increased water retention and PC. SHMs were therefore prepared with the inclusion of carboxyl-functionalized graphene (G(c)) and phosphotungstic acid (PWA) with varying proportions into the SPEEK film. The structure of the SPEEK/G(c)/PWA composite membranes was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The physicochemical properties of the composite membranes, such as ion exchange capacity, water uptake, thermal stability and PC, were investigated. This work provides confirmation that self-humidifying properties are improved at temperature above 60 °C through a combinational inclusion of G(c) and PWA within SPEEK and the new self-humidifying membranes have potential for use in medium temperature direct methanol fuel cells.     

Graphene decorated Pd-Ag nanoparticles for H2 sensing

Hydrogen sensor based on graphene nano-composite with Pd-Ag nanoparticles was fabricated by MEMS process. Structural and morphological properties of the sensing film were studied by an energy dispersive spectroscopy (EDS) and field emission scanning electron microscopy (FESEM), respectively. The H₂ sensing properties of as-formed sensor were investigated by measuring the resistance changes at different H₂ concentrations. The maximum gas response was 16.2% at 1000 ppm of H₂ gas. The gas sensitivity of the as-formed H₂ sensor showed linear behavior with the hydrogen concentration. Experimental results showed that the coupling of graphene with Pd/Ag alloy enhanced significantly hydrogen sensing performance.     

Electrocatalytic hydrogen production on GCE/RGO/Au hybrid electrode

We have prepared a nanocomposite hybrid film to produce a collaborative network of gold (Au) nanoparticles that are highly dispersed on reduced graphene oxide (RGO) sheets, and tested it for electrocatalytic hydrogen production. The RGO/Au nanocomposite film synthesized on glassy carbon electrode (GCE) allows significant improvements to the electron-transfer process. The Au nanoparticles decorated on the surface of graphene increases the electron density, which synergistically promote the adsorption of hydrogen atoms on the graphene sheets and consequently enhance the hydrogen evolution reaction (HER) activity. The surface properties of the composite was characterized by field-emission scanning electron microscopy (FE-SEM) and the electrocatalytical performances evaluated as-prepared electrocatalyst toward (HER) by linear sweep voltammetry (LSV), Tafel polarization curves and electrochemical impedance spectroscopy (EIS) analyses. The GCE/RGO/Au nanohybrid electrode exhibited good catalytic activity for HER with an onset potential of ?0.3 V and a Tafel slope of 136 mV dec^?1, achieving a current density of 10 mA cm^?2 at an overpotential of ?0.43 V.