The conductive polyurethane/polypyrrole/graphene (CPU/PPy/Gr) particle electrode was prepared by an in-situ oxidative polymerization method and used as particle electrodes to degrade levofloxacin (LEV) in a three-dimensional electrode reactor. The prepared CPU/PPy/Gr electrode was characterized systematically and the effects of initial pH, initial LEV concentration, aeration volume, voltage, and electrolyte concentration on the degradation efficiency were investigated. Results showed that more than 90% LEV was degraded and the energy consumption was 20.12 kWh/g LEV under conditions of pH 7, 6 V voltage, 2.0 L/min aeration volume, 20 mg/L initial LEV concentration, and 7 mM concentration of electrolyte (Na₂SO₄). A possible electrochemical oxidation pathway of LEV by the CPU/PPy/Gr electrode was proposed. In addition, the biotoxicity of LEV and its oxidation products was calculated using ECOSAR (Ecological Structure Activity Relationships) program in EPISuite. Toxicity evaluation using luminescent bacteria showed that the toxicities of some intermediates were higher than the parent compound. But the toxicity of degradation processes for LEV was effective decreasing. A possible reactive mechanism in the three-dimensional reactor was also recommended. In brief, the prepared CPU/PPy/Gr particle electrode constitutes an insight into the promising practical application in the wastewater treatment.

In this work, the electrochemical degradation of antibiotic ceftazidime has been studied using a novel rare earth metal Ce and carbon nanotubes codoped PbO₂ electrode. A competitively high oxygen evolution potential (2.4 V) and enhanced catalytic surface area were obtained, evidence by LSV and CV electrochemical characterization. The G/CNT-Ce/PbO₂–Ce electrode possessed a more compact structure and a smaller grain size than the other PbO₂ and Ce–PbO₂ electrodes, exhibiting a prolonged service lifetime, evidence by accelerated lifespan test and recycling degradation experiment. As electrolysis time reached 120 min, the removal efficiency of ceftazidime and TOC arrived at 100.0% and 54.2% respectively in 0.05 M Na₂SO₄ solution containing 50 mg⋅L⁻¹ ceftazidime. The effect of applied current density, pH value, initial ceftazidime concentration and chloride contents on the degradation performance were systematically evaluated. The results demonstrated that electrochemical oxidation of ceftazidime over the G/CNT-Ce/PbO₂–Ce electrode was highly effective, and the mineralization rate was greatly improved, compared with pristine PbO₂ electrode. Considering the toxicity was increased after 30 min electrolysis, the intermediates were quantitatively investigated through HPLC-MS, GC-MS and IC technology. According to the identified products, a reaction mechanism has been proposed and pyridine and aminothiazole were detected with concentration from approximately 1 to 3 mg⋅L⁻¹, which were regarded as toxic byproducts during electrooxidation. Further electrocatalyzing by ring cleavage reaction and complete mineralization to CO₂, NO₃⁻ and NH₄⁺ was proposed, which demonstrated the G/CNT-Ce/PbO₂–Ce electrode exhibited high efficiency for ceftazidime removal in mild conditions.

Immobilization of enzymes on carriers have been pursued to make the enzyme stable, reusable and obtaining even better enzyme activity. Due to the highly stable two-dimensional layer structure, large surface area and pore volume, graphene materials were seemed as ideal carrier for enzyme immobilization. In this paper, pristine few layer graphene (FLG) was applied to interact with laccase to synthesize laccase-graphene composite and the results of AFM, FT-IR and adsorption isotherm suggested that laccase was loaded on the FLG with a very high loading dosage (221.1 mg g⁻¹). Based on the measured interaction force and binding type between laccase and graphene, we proposed that the great enzyme loading on FLG is likely due to the non-covalent π-π stacking in addition to the large surface area of FLG. The composite has better stability to the variance of pH and storage temperature than free laccase. The synthesized composite can effectively transform beta-blocker labetalol with an enhanced efficiency, though the possible reaction pathways kept not changing. We further performed molecular simulation study on the crystal structure variation of laccase binding on FLG and proposed that catalytic activity enhancement may be attributed to the more exposure extent of the catalytic center of laccase. In addition, the laccase-graphene composite can be reused more than ten times in catalyzing the labetalol removal.

Graphene with atomic layer of sp²-hybridized carbon atoms in a hexagonal structure has attracted multidisciplinary attention since its discovery. Due to the inherent advantages of large specific surface area and abundant functional groups, its derivative graphene oxide (GO) nanomaterials have achieved large-scale development in effective pollution treatment. In the past few years, novel GO-based nanomaterials through coupling with other nanomaterials have been synthesized with significant process and applied for efficient elimination of different kinds of pollutants. This paper aims to summarize recent research results on the excellent removal ability of GO-based nanomaterials for various heavy metal ions in aqueous solutions. The synthesis, adsorption process characteristics and interaction mechanism of the adsorbent are emphasized and discussed. The effects of various environmental conditions are outlined. At last, a brief summary, perspective and outlook are presented. This review is intended to provide some thrilling information for the design and manufacture of GO-based nanomaterials for the elimination of heavy metal ions from wastewater in environmental pollution management.

The increasing production and use of graphene-based nanomaterials (e.g., graphene oxide (GO) and reduced graphene oxide (RGO)) will lead to their environmental release. To date, transport of RGOs in saturated porous media is poorly understood. Here, we examined the transport behaviors of three RGO materials obtained by reducing a GO product with commonly used reducing agents – N₂H₄, NaBH₄ and L-ascorbic acid (referred to as N₂H₄-RGO, NaBH₄-RGO and VC-RGO, respectively). When the dominant background cation was Na⁺, K⁺ or Mg²⁺, the mobility of the RGOs and GO in saturated quartz sand correlated well with their surface C/O ratio. Interestingly, the lower mobility of the more reduced materials (the ones with higher C/O values) was not only the results of their less negative surface charges and larger particle sizes, but also the outcome of their greater hydrophobicity, in line with the calculated extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) profiles. Counterintuitively, when the background cation was Ca²⁺, the least reduced material among the three RGOs, VC-RGO, exhibited the lowest mobility. Analysis of electrophoretic and aggregation properties, as well as pH-effect experiments, indicated that the surprisingly low mobility of VC-RGO was attributable to the strong cation-bridging effect (primarily Ca²⁺-bridging between RGO and quartz sand) associated with this material, as VC-RGO contained the highest amount of surface carboxyl group (a strong metal-binding moiety). Notably, enhanced attachment (due to increased hydrophobic effect and cation-bridging) and particle aggregation appeared to work synergistically to increase RGO retention, as the attachment of large RGO aggregates significantly enhanced particle straining by narrowing the flow path. These observations reveal a largely overlooked link between the mobility of graphene-based materials and their key physicochemical properties.

Graphene family nanomaterials (GFNs) have attracted significant attention due to their unique characteristics and applications in the fields of biomedicine and nanotechnology. However, previous studies highlighted the in vitro and in vivo toxicity of GFNs with size and oxidation state differences are still elusive. Therefore, we prepared graphene (G) and graphene oxide (GO) of three different sizes (S-small, M-medium, and L-large), and characterized them using multiple surface-sensitive analytical techniques. In vitro assays using HEK 293T cells revealed that the small and large sizes of G and GO significantly reduced the cell viability and increased DNA damage, accompanying with activated reactive oxygen species (ROS) generation and induced various expressions of associated critical genetic markers. Moreover, the bacterial assays highlighted that G and GO caused strong acute toxicity on Tox2 bacteria. Effects of G were higher than GO and showed size dependent effect: L > M > S, while the medium size of GO induced mild genetic toxicity on RecA bacteria. In vivo assays revealed that exposure to G and GO caused the developmental toxicity, induced ROS generation, and activated related pathways (specifically GO) in zebrafish. Taken together, G showed stronger ability to decrease the survival rate and induce the acute toxicity, while GO showed obvious toxicity in terms of DNA damages, ROS generation, and abnormal gene expressions. Our findings highlighted that G and GO differentially induced toxicity based on their varying physical characteristics, especially sizes and oxidation state, and exposure concentrations and sensitivity of the employed in vitro and in vivo models. In short, this study provided deep insights on the negative effects of GFNs exposure.

The cleaning-up of viscous oil spilled in ocean is a global challenge, especially in Bohai, due to its slow current movement and poor self-purification capacity. Frequent oil-spill accidents not only cause severe and long-term damages to marine ecosystems, but also lead to a great loss of valuable resources. To eliminate the environmental pollution of oil spills, an efficient and environment-friendly oil-recovery approach is necessary. In this study,¹expanded graphite (EG) modified by CTAB-KBr/H₃PO₄ was synthesized via composite intercalation agents of CTAB-KBr and natural flake graphite, followed by the activation of phosphoric acid at low temperature. The resultant modified expanded graphite (M-EG) obtained an interconnected and continuous open microstructure with lower polarity surface, more and larger pores, and increased surface hydrophobicity. Due to these characteristics, M-EG exhibited a superior adsorption capacity towards marine oil. The saturated adsorption capacities of M-EG were as large as 7.44 g/g for engine oil, 6.12 g/g for crude oil, 5.34 g/g for diesel oil and 4.10 g/g for gasoline oil in 120min, exceeding the capacity of pristine EG. Furthermore, M-EG maintained good removal efficiency under different adsorption conditions, such as temperature, oil types, and sodium salt concentration. In addition, oils sorbed into M-EG could be recovered either by a simple compression or filtration-drying treatment with a recovery ratio of 58–83%. However, filtration-drying treatment shows better performance in preserving microstructures of M-EG, which ensures the adsorbents can be recycled several times. High removal capability, fast adsorption efficiency, excellent stability and good recycling performance make M-EG an ideal candidate for treating marine oil pollution in practical application.

To further assess the human being's exposure to polycyclic aromatic hydrocarbons (PAHs) through the dietary pathway, understanding the partitioning of these chemicals co-existed with nanomaterials in edible vegetable systems deserves specific consideration. In this study, the fiber-optic fluorimetry was applied to in situ examine the effects of graphene (GNS) and graphene oxide (GO) nanosheets on the quantification and depuration of three-ringed phenanthrene (Phe) and four-ringed fluoranthene (Fla) adsorbed individually onto the living spinach (Spinacia oleracea L.) surfaces. When the GNS and GO dosages separately increased to the maximum values: a respective red-shift of 4–5 nm and blue-shift of 2–3 nm occurred for the optimal detection emission wavelengths (λem) of the two PAHs, indicating that individual GNS and GO resulted in different changes to the epicuticular wax (ECW) polarity; GNS-inducing fluorescence quenching for the PAHs was about two times greater than GO, owing to the stronger π-π interactions between PAH molecules and GNS relative to GO; the volatilization coefficients (kC1) were reduced by 31.1% versus 26.7% for Phe, and 51.6% versus 34.4% for Fla, mainly via providing an additional adsorbent and promoting the accessibility of the leaf cuticle; respective photolysis coefficients (kP2) of Phe and Fla decreased by 42.9% and 50.0% with GNS, primarily owing to the enhancement of the ECW light-adsorption capacity, but increased by 33.3% and 40.0% with GO due to its photocatalytic activities; overall, total depuration coefficients (kT1, kT2) of the two PAHs decreased by 11.1–55.6%. These findings demonstrate that GNS and GO significantly alter the depuration behavior of PAHs in vegetable systems, potentially posing a threat to the safety of edible vegetables.

Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.

Crumpled graphene oxide nanosheets have drawn large attentions due to its compressibility and self-avoiding stacking as flat graphene sheets trend to aggregate and restack. Up to now, most of the synthesis approaches were relied on external substrates, such as elastic substrates or ultrasonic atomizer, and the crumpled structures were obtained in a solid state directly. Here we report a facile method to produce crumpled dispersive nanosheets in solution through general base-washing treatment by taking advantage of the amphipathy of GO nanosheets. With the dissociation of oxygen-functional groups on nanosheets in alkaline environment, highly water-soluble oxidative debris (OD) would fall off from the nanosheets due to the increase of electrostatic repulsions, and resulted in the crumple of the flat sheets, while the covalent oxygen-functional groups on the nanosheets were reserved. As a result, the nanosheets remained dispersible in solution, and could be used directly for surface modifications. Pt nanoparticles could be directly deposited onto both sides of the sheets through common nucleation and growth from precursor ions process. Compared with flat graphene-based hybrid, the catalytic performance of crumpled-graphene-Pt (CG-Pt) is more excellent and attractive, and corresponding apparent kinetic rate constant (kₐₚₚ) of CG-Pt toward 4-nitrophenol reduction is enhanced by 2.7–4.6-fold. This study provides a new and facile way to fabricate crumpled nanosheets and demonstrates to be easy modified for various purpose.