Trophic transfer of nanomaterials and their effects on high-trophic-level predators.

Nanotechnology offers great opportunities for numerous sectors in society. One important challenge in sustainable nanotechnology is the potential of trophic transfer of nanomaterials (NMs), which may lead to unintentional impacts on environmental and human health. Here, we highlight the key advances that have been made in recent 15 years with respect to trophic transfer of heterogeneous NMs, including metal-based NMs, carbon-based NMs and nanoplastics, across various aquatic and terrestrial food chains. Particle number-based trophic transfer factors (TTFs), rather than the variable mass-based TTFs, capture the particle-specific transfer, for which NMs exhibit dynamic and complex biotransformation (e.g., dissolution, sulfidation, reduction, and corona formation). Trophic transfer of NMs has toxicological significance to predators at molecular (e.g., increased oxidative stress and modified metabolites), physiological (e.g., feeding inhibition) and population (e.g., reproduction inhibition) levels. However, linking NM exposure and toxicity remains a challenge, partly due to the dynamic biotransformation along the food chain. Although NMs have been used to increase crop yield in agriculture, they can exert detrimental impacts on crop yield and modify crop quality, depending on NMs type, exposure dose, and crop species, with unknown consequences to human health via crop consumption. Given this information, we describe the challenges and opportunities in understanding the significance of NMs trophic transfer to develop more sustainable, effective and safer nanotechnology.

Trophic transfer of silver nanoparticles shifts metabolism in snails and reduces food safety.

Food security and sustainable development of agriculture has been a key challenge for decades. To support this, nanotechnology in the agricultural sectors increases productivity and food security, while leaving complex environmental negative impacts including pollution of the human food chains by nanoparticles. Here we model the effects of silver nanoparticles (Ag-NPs) in a food chain consisting of soil-grown lettuce Lactuca sativa and snail Achatina fulica. Soil-grown lettuce were exposed to sulfurized Ag-NPs via root or metallic Ag-NPs via leaves before fed to snails. We discover an important biomagnification of silver in snails sourced from plant root uptake, with trophic transfer factors of 2.0-5.9 in soft tissues. NPs shifts from original size (55-68 nm) toward much smaller size (17-26 nm) in snails. Trophic transfer of Ag-NPs reprograms the global metabolic profile by down-regulating or up-regulating metabolites for up to 0.25- or 4.20- fold, respectively, relative to the control. These metabolites control osmoregulation, phospholipid, energy, and amino acid metabolism in snails, reflecting molecular pathways of biomagnification and pontential adverse biological effects on lower trophic levels. Consumption of these Ag-NP contaminated snails causes non-carcinogenic effects on human health. Global public health risks decrease by 72% under foliar Ag-NP application in agriculture or through a reduction in the consumption of snails sourced from root application. The latter strategy is at the expense of domestic economic losses in food security of $177.3 and $58.3 million annually for countries such as Nigeria and Cameroon. Foliar Ag-NP application in nano-agriculture has lower hazard quotient risks on public health than root application to ensure global food safety, as brought forward by the United Nations Sustainable Development Goals.

Threats to Terrestrial Plants from Emerging Nanoplastics.

Nanoplastics are ubiquitous in ecosystems and impact planetary health. However, our current understanding on the impacts of nanoplastics upon terrestrial plants is fragmented. The lack of systematic approaches to evaluating these impacts limits our ability to generalize from existing studies and perpetuates regulatory barriers. Here, we undertook a meta-analysis to quantify the overall strength of nanoplastic impacts upon terrestrial plants and developed a machine learning approach to predict adverse impacts and identify contributing features. We show that adverse impacts are primarily associated with toxicity metrics, followed by plant species, nanoplastic mass concentration and size, and exposure time and medium. These results highlight that the threats of nanoplastics depend on a diversity of reactions across molecular to ecosystem scales. These reactions are rooted in both the spatial and functional complexities of nanoplastics and, as such, are specific to both the plastic characteristics and environmental conditions. These findings demonstrate the utility of interrogating the diversity of toxicity data in the literature to update both risk assessments and evidence-based policy actions.

Effect of metal cations on antimicrobial activity and compartmentalization of silver in Shewanella oneidensis MR-1 upon exposure to silver ions.

Silver is an antimicrobial agent that is used extensively in consumer products, such as fabrics and humidifiers. Silver ion (Ag+) uptake in bacteria represents a crucial phase of antimicrobial activity. However, the uptake mechanism of Ag+ in bacteria remains largely unknown. The genus Shewanella drives many geochemical processes of nutrients and pollutants in soils. In the present study, Ag+ uptake by Shewanella oneidensis MR-1 was first investigated in a laboratory in defined anaerobic, oligotrophic, and inorganic media with or without cations (potassium ions [K+], magnesium ions [Mg2+], and zinc ions [Zn2+]). Our results revealed variations in antimicrobial activity of Ag+ in the presence of Mg2+ and Zn2+. First, Mg2+ significantly decreased antimicrobial activity of Ag+ in S. oneidensis MR-1 by inhibiting cellular Ag+ uptake when compared with K+. The results were consistent with that of Co2+ (Mg2+ channel blocker) decreased Ag+ uptake by S. oneidensis MR-1. Moreover, Mg2+ promoted riboflavin secretion and facilitated the formation of metallic Ag nanoparticles on bacterial surfaces, which was beneficial for extracellular electron transfer and consequently reduced antibacterial activity of Ag+. Second, Zn2+ increased the antimicrobial activity of Ag+ in S. oneidensis MR-1, although the effect on Ag+ uptake was minimal. A synergistic interaction between Zn2+ and Ag+ led to an increase in dead cells and decreased ferrihydrite reduction capacity. The findings suggest that Mg2+ could reduce the environmental risk of Ag+ to soil bacteria, while Zn2+ should be of particular concern due to its synergistic antimicrobial effect on bacteria.

Atomically Dispersed Manganese on Biochar Derived from a Hyperaccumulator for Photocatalysis in Organic Pollution Remediation.

Phytoremediation is a potentially cost-effective and environmentally friendly remediation method for environmental pollution. However, the safe treatment and resource utilization of harvested biomass has become a limitation in practical applications. To address this, a novel manganese-carbon-based single-atom catalyst (SAC) method has been developed based on the pyrolysis of a manganese hyperaccumulator, Phytolacca americana. In this method, manganese atoms are dispersed atomically in the carbon matrix and coordinate with N atoms to form a Mn-N4 structure. The SAC developed exhibited a high photooxidation efficiency and excellent stability during the degradation of a common organic pollutant, rhodamine B. The Mn-N4 site was the active center in the transformation of photoelectrons via the transfer of photoelectrons between adsorbed O2 and Mn to produce reactive oxygen species, identified by in situ X-ray absorption fine structure spectroscopy and density functional theory calculations. This work demonstrates an approach that increases potential utilization of biomass during phytoremediation and provides a promising design strategy to synthesize cost-effective SACs for environmental applications.

Greater Bioaccessibility of Silver Nanoparticles in Earthworm than in Soils.

The buildup of silver nanoparticles (AgNPs) in soil has raised mounting concerns on their impact on human health. Human are exposed to AgNPs in soils via hand-to-mouth activities (direct exposure) and food consumption (indirect exposure). However, the bioaccessibility of AgNPs under these exposure scenarios remains largely unknown. We used a physiologically based extraction test (PBET) to assess Ag bioaccessibility in AgNP-containing soils and in earthworms (Pheretima guillemi) cultured in these soils. Silver bioaccessibility was 1.2 - 8.4% and 8.1 - 78.7% upon direct exposure and indirect exposure, respectively. These results indicated greater Ag bioaccessibility in earthworms than in soils. Moreover, particle size decreased upon direct exposure, but remained constant upon indirect exposure in wetland soil, as revealed by single particle inductively coupled plasma-mass spectrometry (spICP-MS) analysis. Our results highlight the importance of indirect exposure to NPs.

Oxidative dissolution of Sb2O3 mediated by surface Mn redox cycling in oxic aquatic systems.

Antimony trioxide (Sb2O3) is one of the primary forms of Sb in the environment, and its dissolution significantly impacts the migration and bioavailability of Sb. However, the dissolution of Sb2O3 coupled with abiotic redox of Mn processes is unclear. Here, we investigated the kinetics of Sb2O3 dissolution in the presence of the ubiquitous Mn(II) by kinetic experiments, spectroscopies, density functional theory calculations and the chemical kinetic modeling. The oxidative dissolution of Sb2O3 was catalyzed by Mn(II) through the in-situ generated amorphous Mn oxides (MnOx) under oxic conditions, during which the generation of Mn(III) is a critical step in Sb(V) release. The released Sb(V) was partially retained on MnOx through bidentate-binuclear (corner-sharing) complexes as revealed by extended X-ray absorption fine structure analysis. The coexistent morphological forms of Sb2O3, i.e., senarmontite and valentinite exhibited distinct dissolution patterns. Valentinite showed higher activity in catalyzing Mn(II) oxidation and faster oxidative dissolution than senarmontite, due to its higher surface energy and lower conduction band minimum of its exposed facets. These abiotic processes can extrapolate to other metal(loid)s (hydr)oxides, further supplying for the comprehensive understanding of the redox transformation of Mn.

Metabolic response of earthworms (Pheretima guillemi) to silver nanoparticles in sludge-amended soil.

Silver nanoparticles (AgNPs) can enter soils via the application of sludge and pose risks to soil invertebrates. However, current knowledge regarding the toxicity of AgNPs at environmentally relevant concentration is insufficient, especially at the molecular level. Therefore, we examined the effects of low-level AgNPs (7.2 mg kg-1, dry weight) on the bioaccumulation, pathology and metabolism of earthworms (Pheretima guillemi). After exposure for 28 d, earthworms were dissected into digestive system and the rest of the body to explore the response of different body parts to AgNPs. Ag concentration in the digestive system of exposed group (2.5 mg kg-1, dry weight) was significantly higher than that of the control group (0.5 mg kg-1, dry weight). AgNPs exposure had no significant effects on the survival and growth, but induced intestinal damage and metabolic interference to earthworms relative to the control. Metabolomics analysis showed that AgNPs exposure disturbed the glycerophospholipid metabolism, glutathione metabolism and energy metabolism in the digestive system and the energy metabolism in the rest of the body. AgNPs exposure also induced lipid peroxidation in the digestive system. The different metabolic responses between two body parts highlighted the importance of the uptake routes of Ag. These results provide a biochemical insight for the risk assessment of low-level AgNPs in terrestrial environment.

Extraction and Quantification of Nanoparticulate Mercury in Natural Soils.

Nanoparticulate mercury (Hg-NPs) are ubiquitous in nature. However, the lack of data on their concentration in soils impedes reliable risk assessments. This is due to the analytical difficulties resulting from low ambient Hg concentrations and background interferences of heterogeneous soil components. Here, coupled to single particle inductively coupled plasma-mass spectrometry (spICP-MS), a standardized protocol was developed for extraction and quantification of Hg-NPs in natural soils with a wide range of properties. High particle number-, particle mass-, and total mass-based recoveries were obtained for spiked HgS-NPs (74-120%). Indigenous Hg-NPs across soils were within 107-1011 NPs g-1, corresponding to 3-40% of total Hg on a mass basis. Metacinnabar was the primary Hg species in extracted samples from the Wanshan mercury mining site, as characterized by X-ray absorption spectroscopy and transmission electron microscopy. In agreement with the spICP-MS analysis, electron microscopy revealed comparable size distribution for nanoparticles larger than 27 nm. These indigenous Hg-NPs contributed to 5-65% of the measured methylmercury in soils. This work paves the way for experimental determinations of indigenous Hg-NPs in natural soils, which is critical to understand the biogeochemical cycling of mercury and thereby the methylation processes governing the public exposure to methylmercury.

Key knowledge gaps for One Health approach to mitigate nanoplastic risks.

There are increasing concerns over the threat of nanoplastics to environmental and human health. However, multidisciplinary barriers persist between the communities assessing the risks to environmental and human health. As a result, the hazards and risks of nanoplastics remain uncertain. Here, we identify key knowledge gaps by evaluating the exposure of nanoplastics in the environment, assessing their bio-nano interactions, and examining their potential risks to humans and the environment. We suggest considering nanoplastics a complex and dynamic mixture of polymers, additives, and contaminants, with interconnected risks to environmental and human health. We call for comprehensive integration of One Health approach to produce robust multidisciplinary evidence to nanoplastics threats at the planetary level. Although there are many challenges, this holistic approach incorporates the relevance of environmental exposure and multi-sectoral responses, which provide the opportunity to identify the risk mitigation strategies of nanoplastics to build resilient health systems.

UV-Irradiation Facilitating Pb Release from Recycled PVC Microplastics.

Microplastics (MPs) are ubiquitously in ecosystem and have evoked wide attention. The potential risk of MPs to the ecosystems is associated with MPs and the additives such as Pb, which serves as a traditional stabilizer. However, the release of Pb from MPs remains largely unknown. In this study, we evaluated the release of Pb from recycled polyvinyl chloride (PVC) under UV-irradiation. The release process was dominated by two processes: H+ facilitated dissolution of Pb, and light-induced hydroxyl radical (·OH) caused C-H bond cleavage from PVC with the generation of alkyl radical. The effects of pH and coexisting low molecular weight organic acids (LMWOAs) were also evaluated. Lower pH speeds up the Pb release from MPs. The LMWOAs act as a filter of UV to restrain the Pb release. Overall, this study shows the release of Pb from recycled PVC MPs and indicates the potential risk of Pb to the environment.

Identification and Speciation of Nanoscale Silver in Complex Solid Matrices by Sequential Extraction Coupled with Inductively Coupled Plasma Optical Emission Spectrometry.

Nanoscale silver (n-Ag) including silver nanoparticles (Ag-NPs), silver chloride nanoparticles (AgCl-NPs), and silver sulfide nanoparticles (Ag2S-NPs) and their corresponding ionic counterpart, namely, dissolved Ag, may coexist in soils. X-ray absorption near edge spectroscopy (XANES) is used to elucidate the speciation of n-Ag in soils, whereas it possesses drawbacks like high costs, rare availability of the instrument, and providing semiquantitative data. We developed a new method for the identification and speciation of n-Ag in soils and sediments based on a sequential extraction technique coupled with inductively coupled plasma optical emission spectrometry. Extraction conditions were first evaluated, establishing the optimal extraction procedure; Ag-NPs, AgCl-NPs, and dissolved Ag in soil were simultaneously extracted by using an aqueous solution of 10 mM tetrasodium pyrophosphate, followed by selective isolation and quantification via AgCl-NPs dissolution (4.45 M aqueous ammonia), centrifugation (Ag-NPs), and detection. The Ag2S-NPs remaining in the soil were then extracted with Na2S solution at pH 7.0 through selective complexation. Optimal recoveries of Ag-NPs, AgCl-NPs, Ag2S-NPs, and dissolved Ag were 99.1 ± 2.4%, 112.0 ± 3.4%, 96.4 ± 4.0%, and 112.2 ± 4.1%, respectively. The method was validated to investigate the speciation of n-Ag in soils and sediments, exhibiting the distribution of Ag-NPs, AgCl-NPs, Ag2S-NPs, and dissolved Ag in each sample, wherein Ag2S-NPs, the major species of n-Ag, accounted for 35.42-68.87% of the total Ag. The results of n-Ag speciation in soil are comparable to those obtained through the linear combination fitting of XANES. This method thus is a powerful, yet convenient, substitute for XANES to understand the speciation of n-Ag in complex solid matrices.

Effects of landfill refuse on the reductive dechlorination of pentachlorophenol and speciation transformation of heavy metals.

Landfill refuse is a mixture of inorganic minerals and organic matter that is capable of undergoing complexation and redox reactions due to its active functional groups. Organic matter often combines with minerals in landfill refuse and it remains unclear whether this combination involves electron transfer. Therefore, the effects of landfill refuse composition on reductive dechlorination and speciation transformation of heavy metals were investigated in this study. Results show that landfill refuse comprises protein- and humic-like substances, aliphatic structures, and a large number of hydroxyl, carboxyl, quinoid and other active functional group. The electron donating capacity (0.09-0.26 µmol/g(C)) of landfill refuse was found to be higher than its electron accepting capacity (0.03-0.23 µmol/g(C)), indicating that electron donating groups (hydroxyl) were the main redox-active moieties, facilitating the reductive dechlorination of pentachlorophenol (PCP) by microorganism. Fe2O3, FeO and SiO2 were the main inorganic minerals affecting PCP dechlorination. The speciation distribution of heavy metals in landfill refuse was determined by the BCR sequential extraction method. Results showed that Zn and Ni have high potential migration capacity, poor stability and the highest bioavailability, while Cr, Cu and Pb are relatively stable and have weak migration potential. The oxygen- and nitrogen-containing functional groups, aliphatic structures and aromatic carbon in landfill refuse can promote the transformation of Ni and Cr from an unstable to stable state. Protein-like substances exhibit a strong Cu binding ability, allowing Cu to combine with organic matter more easily than other assessed heavy metals. Both Fe2O3 and FeO affected the stability of Cu. FeO promoted the stabilization of Zn, whereas Fe2O3 and SiO2 promoted Cu instability. These results could provide some references for the treatment of organic chlorides and the stabilization of heavy metals in landfill refuse in China.

Mercury methylation from mercury selenide particles in soils.

Selenium-inhibited monomethylmercury (MeHg) production is an attractive strategy for mitigating the risks of MeHg exposure. However, it is poorly understood the methylation potential of mercury selenide (HgSe) particles during their aging in soils and sediments. Net MeHg production in three floodplain soils amended with different geochemical species of mercury selenides, i.e., dissolved inorganic mercury freshly mixed with selenite (Hg(II)+Se(IV)), HgSe nanoparticles (45.2 ± 0.5 nm) and microparticles (> 1 µm) is examined. Among mercury types, the methylation from nanoparticulate HgSe was similar to (0.05 - 0.5 % vs. 0.1 - 0.4 %, yellow brown soil) or 12.9 - 21.0 times lower (0.02 - 0.1 vs. 0.6 - 1.5 %, black soil) than that from Hg(II)+Se(IV); however, net MeHg production from HgSe nanoparticles (0.02 - 0.5 %) was 1.9 - 15.5 times greater than HgSe microparticles (< 0.05 %) in all soils. Furthermore, net MeHg production from nanoparticulate HgSe varied significantly among soil types, attributable to differences in soil organic matter contents (2.4-5.8%) and microbial methylator community among soils. These results address the importance of geochemical intermediates of mercury selenide precipitation reactions and soil properties in MeHg production, and develop Se-based remediation strategy to minimize negative effects of MeHg on environmental and human health.

Copper(I) Promotes Silver Sulfide Dissolution and Increases Silver Phytoavailability.

Metal sulfides, including acanthite (Ag2S), are persistent in the environment. In colloidal form, however, they can serve as a "Trojan horse", facilitating the mobility of trace metal contaminants. The natural processes that lead to the in situ dissolution of colloidal metal sulfides in soil are largely unknown. In this study, the dissolution of colloidal Ag2S in topsoil and Ag phytoavailability to wheat were examined in Ag2S-Cu(II)-thiosulfate systems. Cu(II) and thiosulfate strongly increased silver release (up to 83% of total Ag) from Ag2S in the dark. Electron paramagnetic resonance, X-ray photoelectron spectroscopy, and Cu K-edge X-ray absorption spectroscopy identified Cu(I) as the driving force of Ag2S dissolution. Density functional theory calculations further demonstrated the ability of Cu(I) to substitute for surface Ag on Ag2S in an energetically favorable manner. However, excess Cu(II) could enhance the formation of precipitates containing Cu(I), Ag, and S. Our results indicate that at ambient temperature and in the dark, Cu(I) can promote the dissolution of Ag2S and act as a precipitating agent. These findings reveal previously unrecognized biogeochemical processes of colloidal Ag2S and their importance in determining the fate of metal sulfides in the environment and probably also in vivo.

Uptake kinetics of silver nanoparticles by plant: relative importance of particles and dissolved ions.

Quantifying the relative bioavailability of particles versus ions is a key step toward understanding the mechanisms of bioaccumulation and toxicity of silver nanoparticles (AgNPs). Here we investigated AgNP uptake kinetics by wheat Triticum aestivum L. at different ages (i.e. 15- and 30-day after germination) in hydroponics. The concentration-dependent accumulation of AgNPs under the experimental conditions, in which AgNP dissolution in bulk suspension and at the biological interface was ruled out, confirmed the direct uptake of particles. This was further validated by the detection of Ag-containing particles within plants by single particle inductively coupled plasma mass spectrometry. Plants differentiated particles and dissolved ions, with uptake rate constants of particles and dissolved ions 4.3 ± 0.6 to 5.2 ± 0.6 and 288.6 ± 13.4 to 450.6 ± 63.4 L kg-1 h-1, respectively. Plant age appeared to have a negligible influence on uptake rate constant ratio of particles to ions. As a result, the relative contribution of particulate uptake to overall AgNP accumulation varied as a function of AgNP dissolution in nature. Particulate uptake was dominant when the dissolution was less than 1.2%. These findings help clearing up the inconsistency of uptake mechanisms of AgNPs in literature and could be used to predict their environmental impact and significance.

Contrasting effects of iron plaque on the bioavailability of metallic and sulfidized silver nanoparticles to rice.

Interaction between silver nanoparticles (AgNPs) and iron plaque, which forms at the root surface of wetland plants under waterlogging conditions, is a critical process that controls the bioavailability of AgNPs. In this study, we comparatively evaluated how and to what extent iron plaque affected silver uptake sourced from metallic (Ag0NPs) and sulfidized (Ag2S-NPs) silver nanoparticles under hydroponic conditions. After the formation of iron plaque at the root surface upon exposure to Fe2+ at 0-100 µg mL-1, rice (Oryza sativa L.) seedlings were transferred to AgNP suspensions. Silver uptake depended on the amount of iron plaque and AgNP species (Ag0NPs vs. Ag2S-NPs): Ag2S-NP exposure had lower or comparable Ag uptake to that of Ag0NP exposure at low levels of Fe2+ (0-80 µg mL-1), but significantly higher Ag uptake at 100 µg Fe2+ mL-1. Such contrasting effects of iron plaque on the bioavailability of Ag0NPs and Ag2S-NPs were attributed to their influences on AgNP dissolution. However, the translocation factors (TFs) and particle size distribution of NPs in planta (as determined by single-particle inductively coupled plasma-mass spectrometry analysis) were not affected by the amount of iron plaque. These results reveal contrasting effects of iron plaque on the bioavailability of Ag0NPs and Ag2S-NPs, and raise concerns about the exposure of wetland plants to Ag2S-NPs in Fe-rich environments, where high Fe levels may facilitate Ag2S-NP bioavailability.

Copper pre-exposure reduces AgNP bioavailability to wheat.

Heavy metals in contaminated sites can affect plant responses to emerging contaminates such as engineered silver nanoparticles (AgNPs), but the underlying mechanisms are poorly understood. After 4-day exposure to 0-2.5 mg Cu L-1 hydroponically, Cu concentrations in roots of wheat seedlings (Triticum aestivum L.) increased from 20 ± 3 to 325 ± 58 mg kg-1. Meanwhile, the cell death in root tips, as measured by the uptake of Evans blue stain, increased 1.8-2.8 times in response to Cu exposure. Total thiol contents in roots (including glutathione, cysteine and phytochelatins), as measured by high performance liquid chromatography, increased 1.4 times upon low Cu exposure but decreased 2.2 times upon high Cu exposure. After those wheats were exposed to 10 mg L-1 AgNPs for 8 h, the Ag influx rates decreased 1.3-3.9 times in Cu pre-exposed plants. Together, the cell death in root tips and thiol levels in roots could explain the decreased Ag influx rates of Cu pre-exposed plants. These findings indicate that the bioavailability of AgNPs without consideration of pre-existing metals could be over-estimated.

Environmental and human health risks from metal exposures nearby a Pb-Zn-Ag mine, China.

Metal contamination in mining areas, where mining and farming coexist, is of great concern worldwide. Nevertheless, a disconnection exists between those risks to environmental and human health. In this study, an integrated approach was used to connect the environmental and human health risks from metal exposures nearby a Pb-Zn-Ag mine. The field survey showed metal contamination in soils and crop plants as well as variation in soil microbial community in mining region relative to the reference site. Together with non-carcinogenic and carcinogenic risk assessment with a probabilistic approach, Cd and Cr were identified as the priority contaminants. Further, consumption of contaminated food crops was a significant pathway of human exposure. Especially, children were susceptible to metal contamination with non-carcinogenic hazard index (0.45 for soil ingestion and 1.19 for dietary intake) and carcinogenic risk index (3.47 × 10-4 for soil ingestion and 5.10 × 10-3 for dietary intake) at the 50th percentile. These findings facilitate the priority actions on mitigation strategies to minimize the environmental and health risks. Also, the potential environmental and human health consequences due to uncontrolled mining in this region serve as a case study for other regions involved in mining activities.

Synergistic effect of supercritical CO2 and organic solvent on exfoliation of graphene: experiment and atomistic simulation studies.

In this work, experiments and molecular dynamics (MD) simulations are carried out to explore the synergistic effect of supercritical CO2 (scCO2) and organic solvent on intercalation and exfoliation of graphene. Experimental characterizations via transmission electron microscopy, atomic force microscopy and Raman spectroscopy indicate that by combining scCO2 and organic solvent (N-methylpyrrolidone, NMP), few-layer graphene is successfully exfoliated from graphite, among which over 30% is 1-4 layers, and 55% is 5-8 layers. Systematic experiments have shown that compared with pure scCO2 or NMP, the mixed scCO2 and NMP can significantly increase the amount of graphene and the rate of few-layer graphene, and the optimum volume fraction of NMP is 25%. Parallel MD simulations indicate that the scCO2 molecules first diffuse into the interlayer of graphite, and then the larger NMP molecules insert as wedges and further expand interlayer spacing, promoting intercalation and exfoliation. The iteration of scCO2 diffusion and the NMP wedge can generate positive feedback to improve the exfoliation productivity and efficiency. This work explores the synergistic effect of scCO2 and NMP on the exfoliation of graphene, which may provide useful insights for exfoliation of other two dimensional materials.