Graphene Oxide Dots Research Articles

Co-catalyst design to control charge transfer and product composition for photocatalytic H2 production and biomass reforming

Pt co-catalyst results in strong H2 evolution and piece-by-piece peeling of xylose; Ag co-catalyst results in cleavage of C2–C3 bond.

Elucidating the mechanism of photocatalytic reduction of bicarbonate (aqueous CO2) into formate and other organics

The photocatalytic reduction of CO2 under solar irradiation is an ideal approach to mitigating global warming, and reducing aqueous forms of CO2 that interact strongly with a catalyst (e.g., HCO3−) is a promising strategy to expedite such reductions. This study uses Pt-deposited graphene oxide dots as a model photocatalyst to elucidate the mechanism of HCO3− reduction. The photocatalyst steadily catalyzes the reduction of an HCO3− solution (at pH = 9) containing an electron donor under 1-sun illumination over a period of 60 h to produce H2 and organic compounds (formate, methanol, and acetate). H2 is derived from solution-contained H2O, which undergoes photocatalytic cleavage to produce •H atoms. Isotopic analysis reveals that all of the organics formed via interactions between HCO3− and •H. This study proposes mechanistic steps, which are governed by the reacting behavior of the •H, to correlate the electron transfer steps and product formation of this photocatalysis. This photocatalysis achieves overall apparent quantum efficiency of 27% in the formation of reaction products under monochromatic irradiation at 420 nm. This study demonstrates the effectiveness of aqueous-phase photocatalysis in converting aqueous CO2 into valuable chemicals and the importance of H2O-derived •H in governing the product selectivity and formation kinetics.

Concise nanotherapeutic modality for cancer involving graphene oxide dots in conjunction with ascorbic acid.

Cancer cells tend to have higher intracellular reactive oxygen species (ROS) levels and are more vulnerable to ROS-generating therapies such as ascorbic acid (H2Asc) therapy, whose potency has been explored by several clinical trials. However, its efficiency is restricted by the requirement of pharmacologically high local H2Asc concentrations. Here, we show that nitrogen-doped graphene oxide dots (NGODs), which are highly crystalline and biocompatible, can serve as a catalytic medium for improving H2Asc cancer therapy at orally achievable physiological H2Asc concentrations. NGODs catalyze H2Asc oxidation for H2O2 and dehydroascorbic acid generation to disrupt cancer cells by consuming intracellular glutathione (GSH) and inducing ROS damage. This is the first study to demonstrate the direct consumption of GSH using a carbon-based nano-catalyst (NGODs), which further expedites tumor killing. In addition, as in our previous study, NGODs can also serve as a highly efficient photosensitizer for photodynamic therapy. Under illumination, NGODs produce a considerable amount of H2O2 in the presence of physiological levels of H2Asc as a hole scavenger and further enhance the therapeutic efficiency. Thus, a concise nanotherapeutic modality could be achieved through the conjunction of multifunctional NGODs and H2Asc to selectively eliminate deep-seated and superficial tumors simultaneously (under 65% of normal cell viability, it kills almost all cancer cells). Note that this level of therapeutic versatility generally requires multiple components and complex manufacturing processes that run into difficulties with FDA regulations and clinical applications. In this study, the concise NGOD-H2Asc nanotherapeutic modality has demonstrated its great potential in cancer therapy.

Integration of Nitrogen-Doped Graphene Oxide Dots with Au Nanoparticles for Enhanced Electrocatalytic Hydrogen Evolution

Integration of Nitrogen-Doped Graphene Oxide Dots with Au Nanoparticles for Enhanced Electrocatalytic Hydrogen Evolution

Modification of structure and optical properties of graphene oxide dots, prepared by laser ablation method

Modification of structure, optical and luminescent properties of graphene oxide (GO) by laser ablation at 532 nm during various times was studied. It was shown that after 30 minutes of laser ablation, the average lateral size of GO sheets decreases from 272±120 nm to 62±29 nm. Studies of structural properties by Raman and FTIR spectroscopy and microscopy indicate the reduction and graphitization of GO at laser irradiation times greater than 20 minutes, which leads to an increase in the average crystallite size of sp2 carbon domains and a decrease in the number of GO layers in the resulting particles. The optical density of the resulting GO solutions and the intensity of their fluorescence are also time dependent. After ablation, the GO fluorescence intensity increased by 10, 25, and 36% for 10, 20 and 30 minutes, respectively. In the long-lived luminescence spectrum of GO, a broad emission band was recorded after ablation, whereas for GO before ablation long-lived luminescence was not exhibited.

Biocompatible hole scavenger-assisted graphene oxide dots for photodynamic cancer therapy.

Photodynamic therapy (PDT) receives scholarly attention for its low invasiveness and mild adverse effects. Among the reactive oxygen species for PDT, H2O2 is advantageous for achieving long life and low cytotoxicity. Nitrogen-doped graphene oxide dots (NGODs), which are small (∼4.4 nm) and highly biocompatible, can serve as a photosensitizer for PDT. The charge transfer in NGODs is efficient because the NGOD structure is highly crystalline and its carbon-π orbitals are extensively conjugated with nitrogen-nonbonding orbitals. In the presence of ascorbic acid (AA), to scavenge photogenerated holes, NGODs effectively produce H2O2 under white-light irradiation and their H2O2 rate is proportional to the AA concentration. This AA-supplemented PDT effectively kills lung, head and neck, colon, and oral cancer cells and it is highly safe for normal cells. During PDT, the NGODs are uptaken into the cell body and they produce concentrated H2O2 and subsequently induce both the apoptosis and necrosis pathways for cell death. The unique structure of NGODs confines the transfer of the photogenerated electrons for H2O2 production. This study demonstrates the high potential for efficacious and accurate deployment of the proposed NGOD-AA combination in PDT.

Z-scheme photocatalyst based on porphyrin derivative decorated few-layer BiVO4 nanosheets for efficient visible-light-driven overall water splitting

It is highly desirable to simulate natural photosynthesis by using sunlight to drive the overall water splitting without using external bias and sacrificial agent. Herein, few-layer monoclinic BiVO4 nanosheets (BVNS) with a thickness of (∼)4.3 nm, exposed (010) facets and abundant oxygen vacancies are fabricated using graphene oxide dots as templating reagent. After decorating with asymmetric chromium porphyrin derivative bearing one benzoic acid and three phenyls as meso-position substituents (chromium-5-(4-carboxyphenyl)-10,15,20-triphenylporphrin, CrmTPP) and PtOx cocatalyst, the obtained two-dimensional (2D) hybrid nanocomposite (BVNS/CrmTPP/Pt) with an optimal component ratio delivers a robust overall water splitting performance with a relatively high apparent quantum yield (8.67%) at 400 nm monochromatic light. The ultrathin structure and widely distributed oxygen vacancies on the exposed (010) facets of BVNS not only endow strong and intimate contact with the decorated CrmTPP molecules to promote a two-step excitation Z-scheme charge transfer mechanism for preserving the high redox ability of the photogenerated charge carriers, but also alleviate their recombination, and thus causing the robust overall water splitting performance of the 2D hybrid nanocomposites. The present results provide a novel strategy to construct highly efficient artificial photosynthetic system for overall water splitting.

Nitrogen-Doped Graphene Oxide Dots-Based "Turn-OFF" H2O2, Au(III), and "Turn-OFF-ON" Hg(II) Sensors as Logic Gates and Molecular Keypad Locks.

Fluorescent nitrogen-doped graphene oxide dots (NGODs) have been demonstrated as an on–off nanosensor for the detection of Hg2+, Au3+, and H2O2. As compared to l-cystine, where the luminescence signal recovery results from the detachment of Hg2+ from the NGODs, signal recovery through l-ascorbic acid (turn-off–on model) has been attributed to the reduction of Hg2+ to Hg0. The sustainable recovery of the photoluminescence signal is demonstrated using common citrus fruits containing vitamin C (l-AA), suggesting a promising practical usage of this sensing system. Additionally, the sensitivity of NGOD- and AA-originated signal recovery from the Hg(II)–NGODs mixture has been successfully tested in Hg2+ ion-spiked tap water from three different places. Mimic devices were executed and verified on the basis of characteristic spectral changes, and the possible utility of this system in electronic security and memory element devices has also been demonstrated. Considering an easy synthesis process and excellent performance of NGODs, this investigation opens up new opportunities for preparing high-quality fluorescent NGODs to meet the requirements of many applications.

Synthesis of graphene oxide dots coated biomatrices and its application for the removal of multiple pollutants present in wastewater

Synthesis of a suitable adsorbent with multiple pollutants removal capacity could be a perfect solution to all water related pollution. This article presents a promising case, where graphene oxide dots (GOD) had been used to coat two different biomatrices and used to remove pollutants like dyes, fluoride, biomolecules and bacteria. The results indicated that after GOD coating the dyes and fluoride removal efficiency for both the biomatrices enhanced around 2–3 times than their untreated counterparts. Also protein removal efficiency of jute enhanced from 10% to around 70% after GOD coating. Similarly, bacteria removal efficiency of both the jute and chitin biomatrices enhanced more than 75%. Also, it was noticed that the preparation of GOD coated biomatrices were cost-effective and technically sound than the GO and GOD based alternatives. However, further study in detail is essential to establish the usability of the materials in multiple pollutants removal from water in large scale.

Nanostructured Graphene Oxide Dots: Synthesis, Characterization, Photoinduced Electron Transfer Studies, and Detection of Explosives/Biomolecules.

Herein, we report the preparation of graphene oxide dots (GO dots) by fine-tuning the carbonization degree of citric acid. The structure of GO dots was characterized by absorption spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, as well as high-resolution scanning electron microscopy and transmission electron microscopy analyses. The typical particle size of the GO dots was 42 nm. The fluorescent characteristics of the GO dots were analyzed by fluorescence spectroscopy. Once excited at 360 nm, the GO dots were fluorescent in the range of 450–550 nm, which was dependent on the excitation wavelength. Further, GO dots were effectively utilized for multifarious applications such as photoinduced electron transfer and detection of explosives and biomolecules. The emission property of GO dots was competently quenched by viologens, picric acid (PA), and bilirubin (BR). The mechanism of quenching by viologens and explosives/biomolecules was found to be due to photoinduced electron transfer and the internal filter effect, respectively. Intriguingly, the detection minimum of PA is in the nanomolar level. Toward commercialization, the economic test strips have also been introduced for the identification of PA. Furthermore, the GO dots have been applied as an efficient luminescent bioprobe for a selective and perceptive finding of BR.

Nano-Graphene Oxide Functionalized Bioactive Poly(lactic acid) and Poly(ε-caprolactone) Nanofibrous Scaffolds.

A versatile and convenient way to produce bioactive poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) electrospun nanofibrous scaffolds is described. PLA and PCL are extensively used as biocompatible scaffold materials for tissue engineering. Here, biobased nano graphene oxide dots (nGO) are incorporated in PLA or PCL electrospun scaffolds during the electrospinning process aiming to enhance the mechanical properties and endorse osteo-bioactivity. nGO was found to tightly attach to the fibers through secondary interactions. It also improved the electrospinnability and fiber quality. The prepared nanofibrous scaffolds exhibited enhanced mechanical properties, increased hydrophilicity, good cytocompatibility and osteo-bioactivity. Therefore, immense potential for bone tissue engineering applications is anticipated.

Roles of nitrogen functionalities in enhancing the excitation-independent green-color photoluminescence of graphene oxide dots.

Fluorescent graphene oxide dots (GODs) are environmentally friendly and biocompatible materials for photoluminescence (PL) applications. In this study, we employed annealing and hydrothermal ammonia treatments at 500 and 140 °C, respectively, to introduce nitrogen functionalities into GODs for enhancing their green-color PL emissions. The hydrothermal treatment preferentially produces pyridinic and amino groups, whereas the annealing treatment produces pyrrolic and amide groups. The hydrothermally treated GODs (A-GODs) present a high conjugation of the nonbonding electrons of nitrogen in pyridinic and amino groups with the aromatic π orbital. This conjugation introduces a nitrogen nonbonding (nN 2p) state 0.3 eV above the oxygen nonbonding state (nO 2p state; the valence band maximum of the GODs). The GODs exhibit excitation-independent green-PL emissions at 530 nm with a maximum quantum yield (QY) of 12% at 470 nm excitation, whereas the A-GODs exhibit a maximum QY of 63%. The transformation of the solvent relaxation-governed π* → nO 2p transition in the GODs to the direct π* → nN 2p transition in the A-GODs possibly accounts for the substantial QY enhancement in the PL emissions. This study elucidates the role of nitrogen functionalities in the PL emissions of graphitic materials and proposes a strategy for designing the electronic structure to promote the PL performance.

Architecting Nitrogen Functionalities on Graphene Oxide Photocatalysts for Boosting Hydrogen Production in Water Decomposition Process

This study elucidates how nitrogen functionalities influence the transition and transfer of photogenerated electrons in graphene‐based materials. Graphene oxide dots (GODs) and Nitrogen‐doped GODs (NGODs) are synthesized by thermally treating graphene oxide (GO) sheets in argon and ammonia, respectively, and then ultrasonically exfoliating the sheets in nitric acid. The nitrogen functionalities of NGODs are mainly quaternary/pyridinic/pyrrolic, and the nitrogen atoms in these functionalities are planar to the GO sheets and repair the vacancy defects on the sheets. Hydrothermal treatment of NGODs in ammonia yields ammonia‐treated NGODs (A‐NGODs), with some pyridinic/pyrrolic groups being converted to amino/amide groups. The nitrogen atoms in the amino/amide groups are not planar to the GO sheets and are prone to donate their lone pair electrons to resonantly conjugate with the aromatic π electrons. The promoted conjugation facilitates the relaxation of photogenerated electrons to the triplet states and prolongs the electron lifetime. When deposited with Pt as the co‐catalyst, the samples catalyze H2 production from an aqueous triethanolamine solution under 420 nm monochromatic irradiation at quantum yields of 7.3% (GODs), 9.7% (NGODs), and 21% (A‐NGODs). The high activity of A‐NGODs demonstrates that architecting nitrogen functionalities effectively mediate charge motion in carbon‐based materials for application to photoenergy conversion.

Incorporating nitrogen-doped graphene oxide dots with graphene oxide sheets for stable and effective hydrogen production through photocatalytic water decomposition

This study proposes incorporating nitrogen-doped graphene oxide dots (NGODs) with graphene oxide (GO) sheets to form a stable and effective NGOD:GO composite for photocatalytic H2 production through water splitting under visible light illumination. Although Pt-deposited NGOD catalysts were active in the photocatalytic H2 production reaction, they were only moderately stable. Introducing GO sheets in light-absorbing NGODs effectively mediated the transfer of photogenerated electrons from the NGODs to the GO sheets. This vectorial electron transfer, confirmed by a photoluminescence spectroscopy analysis, led to the relocation of the reaction sites from the NGODs to the GO sheets, protecting the NGODs from attack by reaction intermediates. Moreover, the GO sheets acted as an electron sink, facilitating charge separation in the NGODs. When 3wt% Pt was deposited on the developed NGOD:GO catalyst, the catalyst steadily catalyzed H2 production from a 10vol% aqueous solution of triethanolamine under visible light illumination for 96h, unlike a NGOD catalyst that exhibited an activity decay of 50% within 96h. The apparent quantum yield of H2 under 420-nm light irradiation was 16.0%, demonstrating the high activity of the NGOD:GO catalyst.

Synthesis of graphene oxide dots for excitation-wavelength independent photoluminescence at high quantum yields

Nitrogen-doped graphene oxide dots exhibit excitation-wavelength independent photoluminescence at 530 nm and 50% quantum yield. The dots show excellent white light emission by combining green emissions with violet light used for excitation.

Graphene-coated Rayleigh SAW Resonators for NO2 Detection

This paper describes the development of a novel low-cost Rayleigh Surface Acoustic Wave Resonator (SAWR) device coated with a graphene layer that is capable of detecting PPM levels of NO2 in air. The sensor comprises two 262 MHz ST-cut quartz based Rayleigh SAWRs arranged in a dual oscillator configuration; where one resonator is coated with gas-sensitive graphene, and the other left uncoated to act as a reference. An array of NMP-dispersed exfoliated reduced graphene oxide dots was deposited in the active area inside the SAWR IDTs by a non-contacting, micro ink-jet printing system. An automated Mass Flow Controller system has been developed that delivers gases to the SAWR sensors with circuitry for excitation, amplification, buffering and signal read-out. This SAW-based graphene sensor has sensitivity to NO2 of ca. 25 Hz/ppm and could be implemented in a low-power low-cost gas sensor.