Development of photo-anodes based on strontium doped zinc oxide-reduced graphene oxide nanocomposites for improving performance of dye-sensitized solar cells

The goal of this study was to create highly efficient dye-sensitized solar cells (DSSCs) using strontium doped zinc oxide-reduced graphene oxide (Sr-doped ZnO/rGO) nanocomposites. As photo-anodes of DSSCs, ZnO, ZnO/rGO (with weight percent rGO in composites: 0, 0.01, 0.1, 0.5, and 1 wt%) and Sr-doped ZnO/rGO (with Zn_1-xSr_xO nanoparticle stoichiometry: x = 0, 0.02, 0.04, 0.06 and 0.08) nanocomposites were designed and characterized. AFM, FESEM, XRD, EDS, XPS, PL, and FTIR analyses were used to investigate the morphology and structure properties of prepared nanocomposites. UV–vis spectroscopy and photo-electrochemical measurements were used to investigate the efficiency of prepared photo-anodes. The efficiency (η) and short-circuit photocurrent density (JSC) of DSSCs based on Zn_0.92Sr_0.08O/rGO nanocomposite were 7.98 % and 18.4 mA cm⁻², respectively. The results showed that doping Sr on ZnO/rGO nanocomposites resulted in a wide bandgap energy and increased the values of η, J_SC, IPCE, and photo-anode electron transportability. These findings suggest that Sr-doped ZnO/rGO nanocomposites can provide a novel approach for increasing photo-electrochemical activity in ZnO-based DSSCs.     

Improved Photocatalytic Activity Using Ternary Au-ZnO/rGO Nanocomposite

In the present study, ternary Au-ZnO/rGO nanocomposite was prepared using a modified polyol protocol. The ternary structure was attained by deposition of both gold nanoparticles (AuNPs) and ZnO NPs on the rGO surface. No surfactants or ligands are used in this chemical process. On the other hand, 1,3-propanediol was used as solvent, reducing agent and surfactant to ensure the formation of NPs and inhibit particles accumulation. The XRD data confirm the successful formation of the three materials and the high crystallinity of the as-prepared sample. Moreover, the XPS measurements confirmed the high purity of the nanocomposite. TEM images show the formation of ternary Au/ZnO/rGO nanostructure. However, Au and ZnO NPs exhibited spherical shape with an average size of 20 nm and homogeneously distribution onto the rGO surface. The ternary Au-ZnO/rGO nanocomposite exhibited optical response in both UV and visible region due to the plasmonic properties of AuNPs. The BET data revealed an increase of the surface area of Au-ZnO/rGO nanocomposite compared to bare ZnO and hybrid Au-ZnO NPs which render it a promising system for high photocatalytic activity. The preliminary photodegradation measurements against MB molecules prove the high performance of the ternary Au-ZnO/rGO nanocomposite to decompose pollutant molecules compared to bare ZnO. The observed photocatalytic activity enhancement could be attributed to the apport given by both plasmonic properties of AuNPs and the high surface area of rGO.

     

Nanocrystalline transition metal oxides and their composites with reduced graphene oxide and carbon nanotubes for photocatalytic applications

Transition metal oxide nanoparticles (CuO, ZnO & Fe₂O₃) and mixed metal oxides CuO. ZnO.Fe₂O₃ were fabricated by facile co-precipitation approach for photocatalytic treatment of organic dyes. The structural features, phase purity, crystallite size and morphology of individual and mixed metal oxides were analysed by X-rays diffraction patterns (XRD) and scanning electron microscopic (SEM) analysis. Electrical behaviour of CuO, ZnO, Fe₂O₃ and mixed metal oxides CuO. ZnO.Fe₂O₃ was explored by current-voltage (I-V) measurements. Functional groups present in the synthesized metal oxides were investigated by Fourier transform infrared spectroscopy (FTIR) which ensures the existence of M-O functional groups in the samples. The optical bandgap analysis was carried out by UV–visible spectroscopic technique which revealed that the blend of three different transition metal oxides reduced the bandgap energy of mixed metal oxides. The reason behind this reduced bandgap energy is formation of new electronic state which arises due to the metal-oxygen interactions. Moreover, the nanocomposites of CuO.ZnO.Fe₂O₃ with reduced graphene oxide (rGO) and carbon nanotubes (CNTs) were prepared to study the effect of the carbonaceous materials on the rate of photodegradation. These carbonaceous nanomaterials have plethora properties which can bring advancement in sector of photocatalytic treatment of wastewater. The photocatalytic experiments were performed using methylene blue (MB) as standard dye for comparative study of metal oxides and their composites with rGO and CNTs. The percentage degradation of methylene blue (MB) by nanocomposite CuO.ZnO.Fe₂O₃/rGO is 87% which is prominent among all samples. This result ascribed the photocatalytic aspects of reduced graphene oxide along with mixed metal oxides.     

Tailoring the properties of cerium doped zinc oxide/reduced graphene oxide composite: Characterization,photoluminescence study,antibacterial activity

Ce doped ZnO/rGO composite materials were prepared by a one-pot hydrothermal process without any surfactant. The size, crystallography and morphology of the composite were investigated in detail by X- ray diffraction (XRD) studies, Raman spectroscopy, scanning electron microscopic (SEM), transmission electron microscopic (TEM) studies, UV–Vis spectroscopic analysis and X-ray photoelectron spectroscopic (XPS) analysis. The XRD pattern substantiates the formation of Ce doped ZnO/rGO composite revealing the wurtzite structure of ZnO. The SEM micrograph illustrates flower-like morphology for ZnO/rGO composite which coalesced further after cerium incorporation. Additionally, TEM image illustrated that ZnO hexagons were disoriented from its flower structure in Ce/ZnO/rGO composite. The XPS spectra further reaffirm the formation of cerium doped ZnO/rGO composite. The photoluminescence (PL) spectra confirms that emission occurs in the UV and visible region and several active sub-levels were observed in visible region on deconvolution, due to the incorporation of cerium. Antibacterial activity towards B. subtills and V. harveyi affirmed that the incorporation of Ce in ZnO/rGO composite leads to an improved antibacterial activity.     

Enhanced optical properties of ZnS–rGO nanocomposites for ultraviolet detection applications

In this research, fabrication and characterization of ultraviolet (UV) detectors based on zinc sulfide–reduced graphene oxide (rGO) nanocomposite with the focus on the wurtzite structure of zinc sulfide was carried out. The nanoparticles of ZnS were synthesized using chemical deposition method and annealed at 500?°C under flow of argon. X-ray diffraction pattern showed that ZnS with the wurtzite phase was formed at 500?°C. Here, rGO as a unique material with similar properties to graphene such as high electron transport was used in order to improve the optical properties of ZnS. For this purpose, rGO was added to ZnS with three different weight percentages of 5, 10 and 15. Scanning electron microscopy showed that ZnS nanoparticles were well placed in rGO sheets. The UV–visible spectra of the synthesized composites showed that with increasing rGO in composite, light absorption is increased. Photoluminescence (PL) spectra also showed that with increasing the percentage of rGO the generation of electron-hole in composite was increased and PL peak was enhanced. The effect of elevated generation of electron-hole pairs was apparent in optoelectrical properties of fabricated UV detectors based on the sample with higher concentration of rGO in composite. For this sample, the response time was decreased to 310 ms, and the sensitivity to UV irradiation was increased by 7.7 times.     

Stabilizing nanocrystalline Cu2O with ZnO/rGO: Engineered photoelectrodes enables efficient water splitting

The engineered photoelectrodes have received significant attention in the photoelectrochemical (PEC) applications. Herein, we prepared a highly effective photoelectrode based on Cu₂O decorated with ZnO and rGO for efficient PEC water splitting. Firstly, different thickness Cu₂O is sputtered on the FTO substrate (FC). The PEC performance of the FC photoelectrode further improved by depositing the ZnO and rGO protection layers (FCZG). The fabricated photoelectrodes are systematically investigated for their morphological and crystal structure by AFM, FESEM, TEM, XPS, XRD, and RAMAN, UVDRS, and PL analysis. The FCZG hybrid photoelectrode exhibit a photocurrent density of 4.94 mA cm^?2 at 0 V vs. reversible hydrogen electrode (RHE), which is 1.5 times higher than the unmodified photoelectrodes. The improved PEC performance of the FCZG hybrid photoelectrode is due to the high surface roughness, larger electrochemical active surface area, and less radiative recombination rate of the photogenerated charge carriers.     

Unusual functionalization of reduced graphene oxide for excellent chemical surface-enhanced Raman scattering by coupling with ZnO

A low-cost noble metal-free substrate comprised of annealed graphene oxide (GO)/ZnO composites is prepared to demonstrate an efficient chemical surface-enhanced Raman scattering effect. A high enhancement factor of about 10⁴, better than those reported for reduced GO (rGO)/Au and GO/Ag composites, is mainly attributed to the unusually abundant oxygen-containing groups generated on surface of rGO by coupling with ZnO nanoparticles at moderate temperature. High-resolution transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy are employed to examine the evolution of ZnO as well as reduction and functionalization of GO after different heat treatments.     

Synthesis of manganese (IV) oxide at activated carbon on reduced graphene oxide sheets via laser irradiation technique for organic binder-free electrodes in flexible supercapacitors

We report a novel, green, scalable technique to synthesize binder-free, high-purity conductive composite comprising activated carbon (AC), manganese dioxide nanorods (MnO₂), and reduced graphene oxide sheets (rGO) for flexible supercapacitors with outstanding electrochemical performance. UV pulsed laser irradiation of GO-based composite dispersion (AC/GO or MnO₂@AC/GO) in ethanol aqueous medium was used to induce a photocatalytic reduction of GO and simultaneous anchor AC particles or AC loaded MnO₂ nanorods (MnO₂@AC) on the reduced GO sheets (rGO) at room temperature and atmospheric pressure. rGO sheets serve as a large surface area, conductive binder to enhance the ion adsorption, electrical conductivity, and mechanical flexibility of supercapacitor electrodes. This laser-induced photocatalytic reduction method was used to prepare two different rGO-based colloidal composites AC/rGO (CG) and MnO₂@AC/rGO (MCG). The prepared rGO-based colloidal composites were used to fabricate symmetric supercapacitors (CG//CG and MCG//MCG) and asymmetric supercapacitors (MCG//CG) in which MCG is the positive electrode and CG is the negative one. All prepared rGO-based supercapacitors demonstrated significant improvement in their electrochemical performance compared with rGO-free AC based supercapacitors. The enhancement in the electrochemical properties of rGO-based supercapacitors could be attributed to the intrinsic characteristics of rGO, such as high surface area, excellent electrical conductivity, and super mechanical flexibility. Our approach is a one-step, scalable, cost-effective synthesis technique to produce all binder-free AC/rGO based composites for flexible energy-storage devices.     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Controllable synthesis of FeSe2/rGO porous composites towards an excellent electromagnetic wave absorption with broadened bandwidth

Due to the escalating demand for electronic dependability and defense security, there has been a surge in research into broadband and lightweight microwave absorbers. Porous composites that are lightweight and plentiful in interfaces have the potential to be high-performance absorbers due to their ability to attenuate waves in a balanced manner and match impedance. “Using a solvothermal technique we generated FeSe₂/rGO composites with a porous topology. By varying the weight of rGO, the electromagnetic properties of FeSe₂/rGO composites may be finely tuned. Impedance matching and attenuation capability are both improved as a direct result of the porous structure and the appropriate electromagnetic parameters. FeSe₂/rGO composites benefit from the tunable composition, porous structure, and strong synergistic effect between FeSe₂ and rGO sheets and display outstanding microwave absorption performance with an ultrabroad bandwidth approaching 5.2 GHz with a thin thickness of 1.6 mm which covers 75% of the studied frequency range. At the same thickness, a significant reflection loss of ?43.7 dB is attained. This work not only enables the tuning of electromagnetic parameters but also expands the use of high-performance microwave absorption devices. Remarkable microwave absorption ability, of the porous composites FeSe₂/rGO can be utilized as a high-performance microwave absorber.”     

掺杂石墨烯的ZnO复合材料研究进展

ZnO是一种低成本且应用广泛的材料,石墨烯具有较大的比表面积以及优良的吸附、光电等特性,易于与ZnO结合,可提高ZnO的性能。掺杂石墨烯的ZnO基材料在气体检测、抗菌表面涂层、发光二极管、透明导电电极和光催化等方面都有着应用性。本文概述了近几年来石墨烯掺杂ZnO材料作为导电薄膜、传感器、光催化剂等在光电子、生物医疗、环保等不同领域内的研究与发展,提出了目前该复合材料在制备工艺复杂与可控性差,实际应用与理论有较大差距等问题,并对未来的研究趋势进行了预测和展望。     

Microwave assisted synthesis of rGO/ZnO composites for non-enzymatic glucose sensing and supercapacitor applications

Zinc oxide (ZnO) and Graphene Oxide (GO) are known to show good electrochemical properties. In this paper, rGO/ZnO nanocomposites have been synthesised using a simple microwave assisted method. The nanocomposites are characterized using XRD, Raman, SEM and TEM. XRD reveals the wurtzite structure of ZnO and TEM shows the heterogeneous nucleation of ZnO nanocrystals anchored onto graphene sheets. The electrochemical properties of the rGO/ZnO nanocomposite enhanced significantly for applications in glucose sensors and supercapacitors. The non-enzymatic glucose sensor of this nanocomposite tested using cyclic voltammetry (CV) and chronoamperometry, exhibits high sensitivity (39.78 mA cm⁻² mM⁻¹) and a lower detection limit of 0.2 nM. The supercapacitor electrode of rGO/ZnO nanocomposite exhibits a significant increase in specific capacitance.     

Multifunctional ZnO/Fe-O and graphene oxide nanocomposites: Enhancement of optical and magnetic properties

ZnO is a semiconductor with a great interest, but it has several deficiencies which limit its use in technologic applications. One important limitation is having the band gap in the UV which reduces its use in optical devices. To solve this problem, in this work, composites based in ZnO with goethite and graphene oxide (GO) by sol-gel are prepared. The obtained samples (powders and thin films) were characterized microstructurally (DTA, XRD, micro-Raman, FE-SEM), optically (transmittance and photoluminescence) and magnetically (SQUID). The ZnO band gap of multifunctional composites shows a red-shift towards visible range (E_g ∼3.01 eV) with high transmittance ∼85% (thickness of 362 nm) over the visible wavelength range. A long-range magnetic order at room temperature appears in these nanocomposites (Ms = 1.60·10⁻² emu/g). The combination of both dopants allows modifying the functional properties of ZnO, opening a great field of applications in ZnO composites, such as spintronic and optoelectronic devices.     

Effects of SiC on the microstructures and mechanical properties of B4C–SiC–rGO composites prepared using spark plasma sintering

In this study, B₄C–SiC–rGO composites with different SiC contents were prepared by spark plasma sintering at 1800 °C for 5 min under a uniaxial pressure of 50 MPa. The effects of SiC on the microstructures and mechanical properties of the B₄C–SiC–rGO composites were investigated. The optimal values for flexural strength (545.25 ± 23 MPa) and fracture toughness (5.72 ± 0.13 MPa·m^1/2) were obtained simultaneously when 15 wt.% SiC was added to 5 wt.%–GO reinforced B₄C composites (BS15G5). It was found that SiC and rGO inhibited the grain growth of B₄C and improved the mechanical properties of the B₄C–SiC–rGO composites. The clear and narrow grain boundaries of rGO–B₄C and rGO–SiC, as well as the semi-coherent B₄C–SiC interface, indicated strong interface compatibility. The twin structures of SiC and B₄C observed in the composites improved their fracture toughness. Crack deflection and crack bridging caused by the SiC grains as well as rGO bridging and rGO pull-out were observed on the crack propagation path.     

Sintering effect on microstructural evolution and mechanical properties of spark plasma sintered Ti matrix composites reinforced by reduced graphene oxides

Ti matrix composites reinforced with 0.6?wt% reduced graphene oxide (rGO) sheets were fabricated using spark plasma sintering (SPS) technology at different sintering temperatures from 800?°C to 1100?°C. Effects of SPS sintering temperature on microstructural evolution and mechanical properties of rGO/Ti composites were studied. Results showed that with an increase in the sintering temperature, the relative density and densification of the composites were improved. The Ti grains were apparently refined owing to the presence of rGO. The optimum sintering temperature was found to be 1000?°C with a duration of 5?min under a pressure of 45?MPa in vacuum, and the structure of rGO was retained. At the same time, the reaction between Ti matrix and rGO at such high sintering temperatures resulted in uniform distribution of micro/nano TiC particle inside the rGO/Ti composites. The sintered rGO/Ti composites exhibited the best mechanical properties at the sintering temperature of 1000?°C, obtaining the values of micro-hardness, ultimate tensile strength, 0.2% yield strength of 224 HV, 535?MPa and 446?MPa, respectively. These are much higher than the composites sintered at the temperature of 900?°C. The fracture mode of the composites was found to change from a predominate trans-granular mode at low sintering temperatures to a ductile fracture mode with quasi-cleavage at higher temperatures, which is consistent with the theoretical calculations.     

聚偏氟乙烯/石墨烯复合材料的制备及性能研究

用溶液共混法制备出聚偏氟乙烯/氧化石墨烯复合材料(PVDF/GO),经高温热压将GO还原得到聚偏氟乙烯/还原氧化石墨烯复合材料(PVDF/rGO)。研究了填料种类及含量对复合材料电学性能、热稳定性和力学性能的影响。结果表明：随GO和rGO的添加,两种复合材料的介电常数(ε _r)均变大、介电损耗(tanδ)变化不大;低含量下GO和rGO均能提高PVDF的热稳定性,但rGO对PVDF性能的改善效果更好;随填料含量从0增加到8%(质量),100 Hz下PVDF/rGO复合材料的ε _r从3.60增加到38.30,PVDF/rGO[4%(质量)]复合材料失重率为5%的分解温度较纯PVDF提高了6.44℃。rGO增强了PVDF的刚性,PVDF/rGO复合材料的拉伸强度先增大后减小,杨氏模量逐渐增大,当rGO含量为4%(质量)时拉伸强度最大,拉伸强度和弹性模量分别较纯PVDF提高了35.30%、22.58%。但GO和rGO都降低了复合材料的击穿场强。     

Characterization of the fracture behavior and viscoelastic properties of epoxy-polyamide coating reinforced with nanometer and micrometer sized ZnO particles

The mechanical and viscoelastic properties of an epoxy-polyamide coating containing nano and micro sized ZnO particles were studied. The nanocomposites were prepared at different loadings of the nano sized ZnO particles. The composites were also prepared using micro sized ZnO particles at different lambdas (lambda (λ) = PVC/CPVC). The optical properties of each nanocomposite were studied by UV–vis technique. Dynamic mechanical thermal analysis (DMTA) and micro-Vickers were used to investigate the mechanical properties of the composites. The viscoelastic properties of the composites were studied by a tensile test. The fracture morphologies of the composites were studied by a scanning electron microscope (SEM). An increase in Tg together with a decrease in cross-linking density of the composites was obtained when the coating was reinforced with the micro sized ZnO particles. On the other hand, the Tg and cross-linking density of the composites were decreased using nano sized ZnO particles. It was also found that, the Young's modulus and the fracture energy of the coating were decreased using micro and nano sized ZnO particles. The greater toughness as well as fracture energy of the composite was obtained when it was reinforced with the nano sized ZnO particles. The curing behavior of the epoxy coating was affected in the presence of the micro and nano sized ZnO particles.     

石墨烯/玻璃块体复合材料的制备及性能

本文报道了还原氧化石墨烯/钠钙硅(rGO/SLS)玻璃块体复合材料的热压制备和力学性能。首先以3-氨基丙基三乙氧基硅烷为表面活性剂修饰玻璃粉微粒;然后在水溶液中带负电的氧化石墨烯(GO)纳米片通过静电自组装与被氨基修饰过带正电的玻璃颗粒相结合生成复合颗粒。通过高温真空热压烧结,GO被还原成rGO,从而原位生成rGO/SLS玻璃块状复合材料。结果表明,rGO均匀分布在玻璃基质中,并明显增强了复合材料的机械性能。rGO/SLS玻璃块体复合材料中rGO的含量为0.5%(质量分数)时,复合材料的弯曲强度比纯的SLS玻璃提高了约一倍。     

Effects of treatment temperature on the reduction of GO under alkaline solution during the preparation of graphene/geopolymer composites

Homogeneously dispersed reduced-graphene-oxide (rGO) reinforced geopolymer composites were successfully prepared through in-situ reduction of graphene oxide (GO) under alkaline geopolymeric condition. The effects of treatment temperatures on the reduction of GO under the alkaline solution during the rGO/geopolymer preparation process were characterized systematically. The results showed that GO could be in situ reduced under alkaline geopolymer solution at various temperatures (25–80 °C) for 3 h. The reduction degree of rGO was improved with increasing the reaction temperature. The rGO was well dispersed, and the rGO/geopolymer composites showed amorphous structure.     

Preparation and characterization of reduced graphene oxide-reinforced boron carbide ceramics by self-assembly polymerization and spark plasma sintering

A self-assembly polymerization process was used to prepare graphene oxide/boron carbide (GO/B₄C) composite powders, spark plasma sintering (SPS) was used to fabricate reduced graphene oxide/boron carbide (rGO/B₄C) composites at 1800 °C and 30 MPa with a soaking time of 5 min. The effects of rGO addition on mechanical properties of the composites, such as Vickers hardness, flexural strength and fracture toughness, were investigated. The results showed that GO/B₄C composite powders were successfully self-assembled and a network structure was formed at high GO contents. The flexural strength and fracture toughness of rGO/B₄C composites were 643.64 MPa and 5.56 MPa m^1/2, respectively, at 1 and 2.5 wt.% rGO content, corresponding to an increase of 99.11% and 71.6% when compared to B₄C ceramics. Uniformly dispersed rGO in rGO/B₄C composites played an important role in improving their strength and toughness. The toughening mechanisms of rGO/B₄C composites were explained by graphene pull-out, crack deflection and bridging.