Enhanced visible-light photocatalytic degradation and disinfection performance of oxidized nanoporous g-C3N4 via decoration with graphene oxide quantum dots

Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.

High-Performance Photo-Modulated Thin-Film Transistor Based on Quantum dots/Reduced Graphene Oxide Fragment-Decorated ZnO Nanowires

In this paper, a photo-modulated transistor based on the thin-film transistor structure was fabricated on the flexible substrate by spin-coating and magnetron sputtering. A novel hybrid material that composed of Cd Se quantum dots and reduced graphene oxide(RGO) fragment-decorated ZnO nanowires was synthesized to overcome the narrow optical sensitive waveband and enhance the photo-responsivity. Due to the enrichment of the interface and heterostructure by RGO fragments being utilized, the photo-responsivity of the transistor was improved to 2000 AW^(-1) and the photo-sensitive wavelength was extended from ultraviolet to visible. In addition, a positive back-gate voltage was employed to reduce the Schottky barrier width of RGO fragments and ZnO nanowires. As a result, the amount of carriers was increased by 10 folds via the modulation of back-gate voltage. With these inherent properties, such as integrated circuit capability and wide optical sensitive waveband, the transistor will manifest great potential in the future applications in photodetectors.

Photocatalytic degradation of Brilliant Green dye using CdSe quantum dots hybridized with graphene oxide under sunlight irradiation

CdSe quantum dots(QDs)hybridized with graphene oxide(GO)are synthesized by a facile chemical precipitation method.The absorption of the CdSe/GO nanocomposite is increased with a significantblue shift with respect to CdSe QDs.The specific surface area of the CdSe/GO nanocomposite is10.4m2/g,which is higher than that of CdSe QDs(5m2/g).The PL intensity of the CdSe/GO nanocomposite is lower than that of the CdSe QDs owing to the inhibition of the recombination of electron‐hole pairs in the composite.In Raman analysis,the two bands of the CdSe/GO nanocomposite are shifted to higher wavenumbers with respect to graphene oxide,which is attributed to electron injection that is induced by CdSe QDs into graphene oxide.Using the Brilliant Green dye,the photocatalytic reduction efficiency of CdSe QDs and the CdSe/GO nanocomposite under sunlight irradiation for90min are approximately81.9%and95.5%,respectively.The calculated photodegradation rate constants for CdSe QDs and the CdSe/GO nanocomposite are0.0190min–1and0.0345min–1,respectively.The enhanced photocatalytic activity of the CdSe/GO nanocomposite can be attributed to the high specific surface area and the reduction of electron‐hole pair recombination because of the introduction of graphene oxide.

Decrease of back recombination rate in CdS quantum dots sensitized solar cells using reduced graphene oxide

The photovoltaic performance of CdS quantum dots sensitized solar cells （QDSSCs） using the 0.2 wt% of reduced graphene oxide and TiO2 nanoparticles （RGO＋TiO2 nanocomposite） photoanode is investigated. CdS QDs are adsorbed onto RGO＋TiO2 nanocomposite films by the successive ionic layer adsorption and reaction （SILAR） technique for several cycles. The current density-voltage （J-V） characteristic curves of the assembled QDSSCs are measured at AM1.5 simulated sunlight. The optimal photovoltaic performance for CdS QDSSC was achieved for six SILAR cycles. Solar cells based on the RGO＋TiO2 nanocomposite photoanode achieve a 33% increase in conversion efficiency （η） compared with those based on plain TiO2 nanoparticle （NP） photoanodes. The electron back recombination rates decrease significantly for CdS QDSSCs based on RGO＋TiO2 nanocomposite photoanodes. The lifetime constant （τ） for CdS QDSSC based on the RGO＋TiO2 nanocomposite photoanode is at least one order of magnitude larger than that based on the bare TiO2NPs photoanode.

Surface-Modified Graphene Oxide/Lead Sulfide Hybrid Film-Forming Ink for High-Efficiency Bulk Nano-Heterojunction Colloidal Quantum Dot Solar Cells

Solution-processed colloidal quantum dot solar cells(CQDSCs) is a promising candidate for new generation solar cells.To obtain stable and high performance lead sulfide(PbS)-based CQDSCs,high carrier mobility and low non-radiative recombination center density in the PbS CQDs active layer are required.In order to effectively improve the carrier mobility in PbS CQDs layer of CQDSCs,butylamine(BTA)-modified graphene oxide(BTA@GO) is first utilized in PbS-PbX2(X=I-,Br-) CQDs ink to deposit the active layer of CQDSCs through one-step spin-coating method.Such surface treatment of GO dramatically upholds the intrinsic superior hole transfer peculiarity of GO and attenuates the hydrophilicity of GO in order to allow for its good dispersibility in ink solvent.The introduction of B TA@GO in CQDs layer can build up a bulk nano-heterojunction architecture,which provides a smooth charge carrier transport channel in turn improves the carrier mobility and conductivity,extends the carriers lifetime and reduces the trap density of PbS-PbX2 CQDs film.Finally,the BTA@GO/PbS-PbX2 hybrid CQDs film-based relatively large-area(0.35 cm2) CQDSCs shows a champion power conversion efficiency of 11.7% which is increased by 23.1% compared with the control device.

Synergistically coupling of graphene quantum dots with Zn-intercalated MnO2 cathode for high-performance aqueous Zn-ion batteries

Cost-effective,safe,and highly performing energy storage devices require rechargeable batteries,and among various options,aqueous zinc-ion batteries(ZIBs)have shown high promise in this regard.As a cathode material for the aqueous ZIBs,manganese dioxide(MnO_(2))has been found to be promising,but certain drawbacks of this cathode material are slow charge-transfer capability and poor cycling performance.Herein,a novel design of graphene quantum dots(GQDs)integrated with Zn-intercalated MnO_(2)nanosheets is put forward to construct a 3D nanoflower-like GQDs@ZnxMnO_(2)composite cathode for aqueous ZIBs.The synergistic coupling of GQDs modification with Zn intercalation provides abundant active sites and conductive medium to facilitate the ion/electron transmission,as well as ensure the GQDs@ZnxMnO_(2)composite cathode with enhanced charge-transfer capability and high electrochemical reversibility,which are elucidated by experiment results and in-situ Raman investigation.These impressive properties endow the GQDs@ZnxMnO_(2)composite cathode with superior aqueous Zn^(2+) storage capacity(~403.6 mAh·g^(−1)),excellent electrochemical kinetics,and good structural stability.For actual applications,the fabricated aqueous ZIBs can deliver a substantial energy density(226.8 W·h·kg^(−1)),a remarkable power density(650 W·kg^(−1)),and long-term cycle performance,further stimulating their potential application as efficient electrochemical storage devices for various energy-related fields.

Graphene quantum dots doped poly(vinyl alcohol)hybrid membranes for desalination via pervaporation

Pervaporation desalination by highly hydrophilic materials such as poly(vinyl alcohol)(PVA)based separation membrane is a burgeoning technology of late years.However,the improvement of membrane flux in pervaporation desalination has been a difficult task.Here,a novel hybrid membrane with doped graphene oxide quantum dots(GOQDs)which is rich in hydrophilic groups and small size into the matrix of PVA was prepared to improve the membrane flux.The membranes structures were described by field emission scanning electron microscopy(FESEM),atomic force microscopy(AFM),Fourier transform infrared(FT-IR),differential scanning calorimetry(DSC),thermogravimetric analysis(TGA)and X-ray diffraction(XRD).And more,Water contact angle,swelling degree,and pervaporation properties were carried out to explore the effect of GOQDs in PVA matrix.In addition,GOQDs content in the hybrid membrane,NaCl concentration,and feed temperature were investigated accordingly.Moreover,the hydrogen bonds between PVA chains were weakened by the interaction between GOQDs and PVA chains.Significantly,the hybrid membrane with optimized doped GOQDs content,200 mg·L^(-1),displays a high membrane flux of 17.09 kg·m^(-2)·h^(-1)and the salt rejection is consistently greater than 99.6%.

Synthesis, properties, and applications of graphene oxide/reduced graphene oxide and their nanocomposites

Thanks to their remarkable mechanical, electrical, thermal, and barrier properties, graphene-based nanocomposites have been a hot area of research in the past decade. Because of their simple top-down synthesis, graphene oxide (GO) and reduced graphene oxide (rGO) have opened new possibilities for gas barrier, membrane separation, and stimuli-response characteristics in nanocomposites. Herein, we review the synthesis techniques most commonly used to produce these graphene derivatives, discuss how synthesis affects their key material properties, and highlight some examples of nanocomposites with unique and impressive properties. We specifically highlight their performances in separation applications, stimuli-responsive materials, anti-corrosion coatings, and energy storage. Finally, we discuss the outlook and remaining challenges in the field of practical industrial-scale production and use of graphene-derivative-based polymer nanocomposites.

A Graphene Oxide-based Immuno-biosensor for Vibrio parahaemolyticus Detection

Vibrio parahaemolyticus is the leading causal agent of human acute gas- troenteritis. Real-time accurate detection means is the key to prevention and control of its spread. This study provided a novel detection strategy for realizing rapid and specific determination of V. parahaemolyticus by labeling its monoclonal antibody （Ab） with quantum dots （QDs）. The results showed that the fluorescence of these QDs-Ab bioconjugates was quenched by graphene oxide （GO） to produce a bacteri- um capture probe. And the optimal quenched concentration of GO was 60 ng/ml. When the bacterium capture probe was exposed to the target, green color fluores- cence was turned on by releasing the QDs-Ab due to the antibody antigen combi- nation. The detection limit of V. parahaemolyticus was 104 CFU/ml based on 3 times signal-to-noise ratio. The specificity of the FRET sensor towards V. para- haemolyticus was examined by comparing with controls such as V. splendidus, V. alginolyticus, Edwardsiella tarda and Aeromonas hydrophila with the same condition. The controls couldn＇t cause obvious fluorescence alteration, while the target resulted in significant fluorescence enhancement. This strategy could be further used as a universal method for any bacterial determination by changing the conjugated antibod- ies in early disease diagnosis. Therefore, the sensor has good potential to expand its application to the early diagnosis and determination of bacteria.

Graphene oxide quantum dots embedded polysulfone membranes with enhanced hydrophilicity,permeability and antifouling performance

Graphene oxide(GO) has been demonstrated to be an effective hydrophilic nanofiller to modify the polymeric membranes when forming a mixed matrix structure. GO quantum dots(QDs) are promising candidates to fully exert the rich oxygen containing functional groups due to their unique size induced edge effects. In this work, GO QDs modified polysulfone(PSF) ultrafiltration(UF) membranes were prepared by phase inversion method with various GO QDs loadings(0.1–0.5 wt.%). A proper amount of GO QDs addition led to a more porous and hydrophilic membrane structure. With 0.3 wt.% GO QDs, the membranes showed a60% increase in permeability(130.54 vs. 82.52 LMH bar^-1).The pristine PSF membranes had a complete cutoff of bovine serum albumin molecules and it was well maintained with GO QDs incorporated. The membranes with 0.5 wt.% GO QDs exhibited the highest flux recovery ratio of 89.7% and the lowest irreversible fouling of 10.3%(54.5% and 33.3% for the pristine PSF membranes). Our results proved that GO QDs can function as effective nanofillers to enhance the hydrophilicity, permeability and antifouling performance of PSF UF membranes.

Enhanced charge extraction for all-inorganic perovskite solar cells by graphene oxide quantum dots modified TiO_(2)layer

All-inorganic cesium lead bromide(CsPbBr_(3))perovskite solar cells have been attracting growing interest due to superior performance stability and low cost.However,low light absorbance and large charge recombination at TiO_(2)/CsPbBr_(3)interface or within CsPbBr_(3)film still prevent further performance improvement.Herein,we report devices with high power conversion efficiency(9.16%)by introducing graphene oxide quantum dots(GOQDs)between TiO_(2)and perovskite layers.The recombination of interfacial radiation can be effectively restrained due to enhanced charge transfer capability.GOQDs with C-rich active sites can involve in crystallization and fill within the CsPbBr_(3)perovskite film as functional semiconductor additives.This work provides a promising strategy to optimize the crystallization process and boost charge extraction at the surface/interface optoelectronic properties of perovskites for high efficient and low-cost solar cells.

Properties of fluorescence based on the immobilization of graphene oxide quantum dots in nanostructured porous silicon films

The fluorescence of graphene oxide quantum dots （GOQDs） that are infiltrated into porous silicon （PSi） is investigated. By dropping activated GOQDs solution onto silanized PSi samples, GOQDs are successfully in- filtrated into a PSi device. The results indicate that the intensity of the fluorescence of the GOQD-inflltrated multilayer with a high reflection band located at its fluorescence spectra scope is approximately double that of the single layer sample. This indicates that the multilayer GOQD-infiltrated PSi substrate is a suitable material for the preparation of sensitive photoluminescence biosensors.

基于ZnO/Graphene纳米复合材料紫外光探测器的制备与实现

利用化学气相沉积法制备氧化锌(ZnO)纳米线,通过微加工工艺获得了基于ZnO纳米线与ZnO石墨烯量子点纳米复合材料的紫外光探测器。ZnO石墨烯纳米复合材料的结构和表面形貌通过X射线电子衍射和扫描电镜来表征,结果表明,ZnO纳米线的直径约为33nm,与石墨烯量子点很好地复合在了一起。利用紫外可见吸收谱对样品的光吸收进行了记录,实验表明,基于ZnO复合石墨烯量子点纳米复合材料的紫外探测器在UV照射下显示出良好的光响应行为,该类型基于ZnO复合石墨烯量子点探测器可能在ZnO紫外探测的应用方面具有潜在的意义。

GO-induced effective interconnection layer for all solution-processed tandem quantum dot light-emitting diodes

Compared to conventional quantum dot light-emitting diodes,tandem quantum dot light-emitting diodes(TQLEDs)possess higher device efficiency and more applications in the field of flat panel display and solid-state lighting in the future.The TQLED is a multilayer structure device which connects two or more light-emitting units by using an interconnection layer(ICL),which plays an extremely important role in the TQLED.Therefore,realizing an effective ICL is the key to obtain high-efficiency TQLEDs.In this work,the p-type materials polys(3,4-ethylenedioxythiophene),poly(styrenesulfonate)(PEDOT:PSS)and the n-type material zinc magnesium oxide(ZnMgO),were used,and an effective hybrid ICL,the PEDOT:PSS-GO/ZnMgO,was obtained by doping graphene oxide(GO)into PEDOT:PSS.The effect of GO additive on the ICL was systematically investigated.It exhibits that the GO additive brought the fine charge carrier generation and injection capacity simultaneously.Thus,the all solutionprocessed red TQLEDs were prepared and characterized for the first time.The maximum luminance of 40877 cd/m^(2) and the highest current efficiency of 19.6 cd/A were achieved,respectively,showing a 21%growth and a 51%increase when compared with those of the reference device without GO.The encouraging results suggest that our investigation paves the way for efficient all solution-processed TQLEDs.

Enhanced permeability and biofouling mitigation of forward osmosis membranes via grafting graphene quantum dots

In this paper,graphene oxide quantum dots with amino groups(NH_(2)-GOQDs)were tailored to the surface of a thin-film composite(TFC)membrane surface for optimizing forward osmosis(FO)membrane performance using the amide coupling reaction.The results jointly demonstrated hydrophilicity and surface roughness of the membrane enhanced after grafting NH_(2)-GOQDs,leading to the optimized affinity and the contact area between the membrane and water molecules.Therefore,grafting of the membrane with a concentration of 100 ppm(TFC-100)exhibited excellent permeability performance(58.32 L·m^(–2)·h^(–1))compared with TFC membrane(16.94 L·m^(–2)·h^(–1)).In the evaluation of static antibacterial properties of membranes,TFC-100 membrane destroyed the cell morphology of Escherichia coli(E.coli)and reduced the degree of bacterial adsorption.In the dynamic biofouling experiment,TFC-100 membrane showed a lower flux decline than TFC membrane.After the physical cleaning,the flux of TFC-100 membrane could recover to 96%of the initial flux,which was notably better than that of TFC membrane(63%).Additionally,the extended Derjaguin–Landau–Verwey–Overbeek analysis of the affinity between pollutants and membrane surface verified that NH_(2)-GOQDs alleviates E.coli contamination of membrane.This work highlights the potential applications of NH_(2)-GOQDs for optimizing permeability and biofouling mitigation of FO membranes.

Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

Graphene oxide（GO）, as an important derivative of graphene, could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface, which endows graphene high reactivity with other molecules. In our previous work, we demonstrated that GO sheets were cut into small pieces（graphene quantum dots, GQDs） by oxidative free radicals（hydroxyl radical HO＂ or oxygen radical [0]） under UV irradiation. It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly. However, researches on details about reactions of GO with free radicals have not been reported thus far. In this work, the effects of different factors on the photo-Fenton reaction of GO were studied. It is demonstrated that the reaction rate is closely related to the concentration of free radicals. It is speculated that through the optimization of reaction conditions, the reaction of graphene with free radicals could carry out efficiently for further applications.

氧化石墨烯量子点对鸡卵清蛋白递送-免疫增强佐剂效力评估

利用改进的Hummers法氧化鳞片石墨,获得富含羟基和羧基的氧化石墨烯量子点(GOQDs)。通过透射电子显微镜、X射线衍射、红外光谱及拉曼光谱测试表征其理化性质。此外,利用鸡卵清蛋白(OVA)作为模式抗原,构筑GOQDs/OVA纳米疫苗并评估其载量、安全性、免疫效力等。结果显示,GOQDs/OVA纳米疫苗直径在5 nm左右,具有高度的水分散性和稳定性。其对OVA的最大负载量约为500 mg·g^(-1),在pH=5.5和7.4环境下24 h的释放率分别为74.65%和56.93%,表现出pH刺激响应释放性能。当GOQDs浓度在500μg·mL^(-1)以下时,不会引起溶血、细胞损伤、重要组织发生病变等现象。免疫后,与OVA单独免疫对照组相比,GOQDs/OVA纳米疫苗可以诱导产生高水平的免疫球蛋白G(IgG)、免疫球蛋白G1(IgG1)及免疫球蛋白G2a(IgG2a)抗体,提高白细胞介素(IL)-1β、IL-2、IL-4和IL-6、肿瘤坏死因子-α(TNF-α)和γ干扰素(IFN-γ)的分泌,同时促进脾中辅助性(CD4+)和细胞毒性(CD8+)T淋巴细胞百分比的增加。

荧光氧化石墨烯量子点的光化学法制备及其细胞毒性研究

氧化石墨烯量子点(GOQDs)凭借其细胞毒性低、荧光稳定性好、水分散性高、生物相容性好等优点而备受青睐。本实验以氧化石墨烯(GO)为碳源,H_(2)O_(2)作为氧化剂,采用一步原位光化学法在30 min内快速得到GOQDs,提出了一种高效、绿色制备GOQDs的方法。采用TEM、XPS、UV-Vis等对GOQDs的结构、形貌等进行表征。结果表明,当光照反应时间为0.5 h,H_(2)O_(2)加入量为18 mL条件下,得到产率高,粒径分布在4-8 nm之间均匀的GOQDs。研究表明,不同浓度GOQDs溶液培养的生物细胞存活率均维持在70%以上。这说明GOQDs作为一种毒性小、生物相容性很好的新型纳米材料可能取代常规的荧光纳米材料,在致病菌检测、组织细胞荧光标记、细胞成像、药物检测等方面有望得到应用。

氮掺杂石墨烯/黑磷量子点纳米复合材料的低温光催化法制备及其储锂性能

纳米黑磷/石墨烯复合材料在锂离子电池领域具有很好的应用前景,但以纳米黑磷为原料制备纳米黑磷/石墨烯复合材料的过程中往往伴随纳米黑磷的氧化,一定程度上影响了制得的纳米黑磷/石墨烯复合材料性能。本研究以纳米黑磷为磷源,价廉易得的氧化石墨烯为碳源,在氨气气氛下,采用低温光催化法制得了氮掺杂石墨烯/黑磷量子点(N-rGO/BPQDs)复合材料,FTIR、Raman、XPS、SEM等表征结果表明采用上述方法制备的纳米黑磷基材料中纳米黑磷的氧化程度低。恒流充放电测试结果表明N-rGO/BPQDs复合材料在0.1A/g电流密度下的初始可逆比容量为620mA·h/g,循环100次后仍保持450mA·h/g的可逆比容量,高于石墨负极材料的理论比容量(372mA·h/g)。

基于中空复合纳米粒子的超声溶栓体系构建及效果验证

目的 评价超声辅助微泡溶栓联合声动力疗法的中空复合纳米粒子的生物安全性及体外溶栓效果,评估其治疗静脉血栓栓塞症的潜在应用价值。方法 制备氮掺杂石墨烯量子点(NGQD)和一氧化氮供体N,N’-二仲丁基-N,N’-二亚硝基-1,4-苯二胺(BNN6),BNN6负载于NGQD上,将二者复合体载入利用盐模板法制备的中空介孔二氧化硅(HMSN)中,形成纳米溶栓体系BNM;通过电镜和纳米粒度仪观察BNM的形貌、尺寸等特征;通过细胞毒性实验、活-死细胞染色及溶血实验评价纳米溶栓体系BNM的生物安全性;通过体外溶栓和纤维蛋白凝块降解评价纳米材料的体外溶栓效果。结果 与对照组相比,不同浓度的BNM对HUVECs和RAW264.7细胞的活性无影响,中低浓度BNM的溶血率未超过纳米材料溶血安全限,3个浓度的BNM对红细胞和血小板的形貌未产生明显影响,不引起血小板活化;与对照组相比,超声辅助BNM组的溶栓率随BNM浓度增加而提高,纤维蛋白网络出现空洞,荧光面积比降低。结论 本研究制备的纳米溶栓系统具有很好的生物相容性和血液安全性,可以响应超声进行溶栓,表现出优良的溶栓性能,为临床应用提供了新策略。