New Insights in the Natural Organic Matter Fouling Mechanism of Polyamide and Nanocomposite Multiwalled Carbon Nanotubes-Polyamide Membranes.

Polyamide (PA) membranes comprise most of the reverse osmosis membranes currently used for desalination and water purification. However, their fouling mechanisms with natural organic matter (NOM) is still not completely understood. In this work, we studied three different types of PA membranes: a laboratory made PA, a commercial PA, and a multiwalled carbon nanotube (CNT-PA nanocomposite membrane during cross-flow measurements by NaCl solutions including NOM, humic acid (HA), or alginate, respectively). Molecular dynamic simulations were also used to understand the fouling process of NOM down to its molecular scale. Low molecular weight humic acid binds to the surface cavities on the PA structures that leads to irreversible adsorption induced by the high surface roughness. In addition, the larger alginate molecules show a different mechanism, due to their larger size and their ability to change shape from the globule type to the uncoiled state. Specifically, alginate molecules either bind through Ca2+ bridges or they uncoil and spread on the surface. This work shows that carbon nanotubes can help to decrease roughness and polymer mobility on the surfaces of the membranes at the molecular scale, which represents a novel method to design antifouling membranes.

Ultrasensitive gas detection of large-area boron-doped graphene.

Heteroatom doping is an efficient way to modify the chemical and electronic properties of graphene. In particular, boron doping is expected to induce a p-type (boron)-conducting behavior to pristine (nondoped) graphene, which could lead to diverse applications. However, the experimental progress on atomic scale visualization and sensing properties of large-area boron-doped graphene (BG) sheets is still very scarce. This work describes the controlled growth of centimeter size, high-crystallinity BG sheets. Scanning tunneling microscopy and spectroscopy are used to visualize the atomic structure and the local density of states around boron dopants. It is confirmed that BG behaves as a p-type conductor and a unique croissant-like feature is frequently observed within the BG lattice, which is caused by the presence of boron-carbon trimers embedded within the hexagonal lattice. More interestingly, it is demonstrated for the first time that BG exhibits unique sensing capabilities when detecting toxic gases, such as NO2 and NH3, being able to detect extremely low concentrations (e.g., parts per trillion, parts per billion). This work envisions that other attractive applications could now be explored based on as-synthesized BG.

Rice husk-derived graphene with nano-sized domains and clean edges.

A new synthetic method is demonstrated for transforming rice husks into bulk amounts of graphene through its calcination and chemical activation. The bulk sample consists of crystalline nano-sized graphene and corrugated individual graphene sheets; the material generally contains one, two, or a few layers, and corrugated graphene domains are typically observed in monolayers containing topological defects within the hexagonal lattice and edges. Both types of graphenes exhibit atomically smooth surfaces and edges.

Three-dimensional nitrogen-doped multiwall carbon nanotube sponges with tunable properties.

A three-dimensional (3D) nitrogen-doped multiwall carbon nanotube (N-MWCNT) sponge possessing junctions induced by both nitrogen and sulfur was synthesized by chemical vapor deposition (CVD). The formation of "elbow" junctions as well as "welded" junctions, which are attributed to the synergistic effect of the nitrogen dopant and the sulfur promoter, plays a critically important role in the formation of 3D nanotube sponges. To the best of our knowledge, this is the first report showing the synthesis of macroscale 3D N-MWCNT sponges. Most importantly, the diameter of N-MWCNT can be simply controlled by varying the concentration of sulfur, which in turn controls both the sponge's mechanical and its electrical properties. It was experimentally shown that, with increasing diameter of N-MWCNT, the elastic modulus of the sponge increased while the electrical conductivity decreased. The mechanical behaviors of the sponges have also been quantitatively analyzed by employing strain energy function modeling.

Electrochemical Deposition of Polypyrrole in the Presence of Silanes as Adhesion Promoters.

Polypyrrole adhesion to indium-tin oxide electrodes was improved by adding pre-hydrolyzed alkoxysilanes to the electrodeposition media. The pyrrole oxidation and film growth rates were studied by potentiostatic polymerization in acidic media. The morphology and thickness of the films were studied by contact profilometry and surface-scanning electron microscopy. The bulk and surface semiquantitative chemical composition was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Finally, the adhesion was studied by scotch-tape adhesion test, where both alkoxysilanes showed a significant improvement in adhesion. We proposed a hypothesis for the improvement in adhesion, that involves the formation of siloxane material as well as in situ surface modification of the transparent metal oxide electrode.

Nanocomposite desalination membranes made of aromatic polyamide with cellulose nanofibers: synthesis, performance, and water diffusion study.

Reverse osmosis membranes of aromatic polyamide (PA) reinforced with a crystalline cellulose nanofiber (CNF) were synthesized and their desalination performance was studied. Comparison with plain PA membranes shows that the addition of CNF reduced the matrix mobility resulting in a molecularly stiffer membrane because of the attractive forces between the surface of the CNFs and the PA matrix. Fourier transform-infrared spectroscopy and X-ray photoelectron spectroscopy results showed complex formation between the carboxy groups of the CNF surface and the m- phenylenediamine monomer in the CNF-PA composite. Molecular dynamics simulations showed that the CNF-PA had higher hydrophilicity which was key for the higher water permeability of the synthesized nanocomposite membrane. The CNF-PA reverse osmosis nanocomposite membranes also showed enhanced antifouling performance and improved chlorine resistance. Therefore, CNF shows great potential as a nanoreinforcing material towards the preparation of nanocomposite aromatic PA membranes with longer operation lifetime due to its antifouling and chlorine resistance properties.

Single-atom doping of MoS2 with manganese enables ultrasensitive detection of dopamine: Experimental and computational approach.

Two-dimensional transition metal dichalcogenides (TMDs) emerged as a promising platform to construct sensitive biosensors. We report an ultrasensitive electrochemical dopamine sensor based on manganese-doped MoS2 synthesized via a scalable two-step approach (with Mn ~2.15 atomic %). Selective dopamine detection is achieved with a detection limit of 50 pM in buffer solution, 5 nM in 10% serum, and 50 nM in artificial sweat. Density functional theory calculations and scanning transmission electron microscopy show that two types of Mn defects are dominant: Mn on top of a Mo atom (MntopMo) and Mn substituting a Mo atom (MnMo). At low dopamine concentrations, physisorption on MnMo dominates. At higher concentrations, dopamine chemisorbs on MntopMo, which is consistent with calculations of the dopamine binding energy (2.91 eV for MntopMo versus 0.65 eV for MnMo). Our results demonstrate that metal-doped layered materials, such as TMDs, constitute an emergent platform to construct ultrasensitive and tunable biosensors.

Enhanced desalination performance in compacted carbon-based reverse osmosis membranes.

Reverse osmosis membranes typically suffer compaction during the initial stabilization stage due to the applied hydraulic pressure, altering the desalination performance. The elucidation of the underlying transformations during compaction is key for further development of new membranes and its deployment in real-world scenarios. Hydraulic compaction of amorphous carbon (a-C) based membranes under cross-flow operation for water purification and desalination has been observed experimentally, and analysed employing molecular dynamics simulations. The previous outstanding separation performance for carbon membranes, especially for the nitrogen-containing (a-C:N) type, has been studied during compaction using lab-scale cross-flow desalination membrane systems. Our results indicate that the high-water pressure induces an overall reduction in the interstitial spaces within the a-C structure. Remarkably, the compacted a-C:N membrane exhibits improved performance in salt rejection and water permeability, compared to the a-C based membrane. Our analysis shows that performance improvement can be related to the higher mechanical stability of the carbon structure due to the presence of nitrogen sites, which also promote water diffusion and permeability. These results show that a-C:N based membranes are a feasible alternative to conventional polymeric membranes.

Flash reduction and patterning of graphite oxide and its polymer composite.

Graphite oxide (GO) is a promising precursor for the bulk production of graphene-based materials due to its relatively low cost of synthesis. The superior solvent processability of GO makes it particularly attractive for making composites by premixing with other materials. Typically, the reduction of GO has relied on either chemical agents or high temperature treatment. Here we report a room temperature, chemical-free flash reduction process where a photographic camera flash instantaneously triggers the deoxygenation reaction of GO by photothermal heating. Flash irradiation also rapidly creates a fused polymer composite from a random mixture of GO and polymer particles. Using a photomask, conducting patterns such as interdigitated electrode arrays can be readily made on flexible substrates.

Defect Engineering and Surface Functionalization of Nanocarbons for Metal-Free Catalysis.

With the advent of carbon nanotechnology, which initiated significant research efforts more than two decades ago, novel materials for energy harvesting and storage have emerged at an amazing pace. Nevertheless, some fundamental applications are still dominated by traditional materials, and it is especially evident in the case of catalysis, and environmental-related electrochemical reactions, where precious metals such as Pt and Ir are widely used. Several strategies are being explored for achieving competitive and feasible metal-free carbon nanomaterials, among which doping and defect engineering approaches within nanocarbons are recurrent and promising. Here, the most recent efforts regarding the control of doping and defects in carbon nanostructures for catalysis, and in particular for energy-related applications, are addressed. Finally, an overview of alternative proposals that can make a difference when enabling carbon nanomaterials as efficient and emerging catalysts is presented.

Removal of Tetracycline Pollutants by Adsorption and Magnetic Separation Using Reduced Graphene Oxide Decorated with α-Fe2O3 Nanoparticles.

Nanocomposites of reduced graphene oxide (RGO) with ferromagnetic α-Fe2O3 nanoparticles have been prepared in-situ by thermal treatment. The structure and morphology of the hybrid material were studied by X-ray photoelectron spectroscopy, Raman, X-ray diffraction, and transmission electron microscopy. The results show a hybrid material highly modified with α-Fe2O3 nanoparticles distributed on the graphene surface. The adsorption kinetics show the presence of α-Fe2O3 nanoparticles on the RGO surface, and the amount of remaining functional groups dominated by ionization and dispersion. The adsorption kinetics of this adsorbent was characterized and found to fit the pseudo-second-order model. The α-Fe2O3 nanoparticles on RGO modify the electrostatic interaction of RGO layers and tetracycline, and adsorption properties decreased in the hybrid material. Adsorption isotherms fit with the Langmuir model very well, and the maximum capacity adsorption was 44.23 mg/g for RGO and 18.47 mg/g for the hybrid material. Magnetic characterization of the hybrid material shows ferromagnetic behavior due to the nanosize of α-Fe2O3 with a saturation magnetization, Ms = 7.15 Am²/kg, a remanence Mr = 2.29 Am²/kg, and a coercive field, Hc = 0.02 T.

Enhanced Antifouling Feed Spacer Made from a Carbon Nanotube-Polypropylene Nanocomposite.

Spacers are widely used in membrane technologies to reduce fouling and concentration polarization. Fouling can start from the spacer surface and grow, thereby reducing flux, selectivity, and operation lifetime. Fluorescein isothiocyanate labeled bovine serum albumin was used for fouling studies and observed during cross-flow filtration operation for up to 144 h. Here, we mixed carbon nanotubes (CNTs) and polypropylene (PP) to make a spacer with better antifouling than plain PP spacers. The fouling process was observed by scanning electron microscopy and monitored in situ by fluorescence microscopy. Molecular dynamics simulations show that bovine serum albumin has a lower interaction energy with the nanocomposite CNTs/PP spacer than with the plain PP. The findings are relevant for the development of spacers to improve the operation lifetime of membranes in filtration technologies.

Effective Antiscaling Performance of Reverse-Osmosis Membranes Made of Carbon Nanotubes and Polyamide Nanocomposites.

The antiscaling properties of multiwalled carbon nanotube (MWCNT)-polyamide (PA) nanocomposite reverse-osmosis (RO) desalination membranes (MWCNT-PA membranes) were studied. An aqueous solution of calcium chloride (CaCl2) and sodium bicarbonate (NaHCO3) was used to precipitate in situ calcium carbonate (CaCO3) to emulate scaling. The MWCNT contents of the studied nanocomposite membranes prepared by interfacial polymerization ranged from 0 wt % (plain PA) to 25 wt %. The inorganic antiscaling performances were compared for the MWCNT-PA membranes to laboratory-made plain and commercial PA-based RO membranes. The scaling process on the membrane surface was monitored by fluorescence microscopy after labeling the scale with a fluorescent dye. The deposited scale on the MWCNT-PA membrane was less abundant and more easily detached by the shear stress under cross-flow compared to other membranes. Molecular dynamics simulations revealed that the attraction of Ca2+ ions was hindered by the interfacial water layer formed on the surface of the MWCNT-PA membrane. Together, our findings revealed that the observed outstanding antiscaling performance of MWCNT-PA membranes results from (i) a smooth surface morphology, (ii) a low surface charge, and (iii) the formation of an interfacial water layer. The MWCNT-PA membranes described herein are advantageous for water treatment.

Effective NaCl and dye rejection of hybrid graphene oxide/graphene layered membranes.

Carbon nanomaterials are robust and possess fascinating properties useful for separation technology applications, but their scalability and high salt rejection when in a strong cross flow for long periods of time remain challenging. Here, we present a graphene-based membrane that is prepared using a simple and environmentally friendly method by spray coating an aqueous dispersion of graphene oxide/few-layered graphene/deoxycholate. The membranes were robust enough to withstand strong cross-flow shear for a prolonged period (120 h) while maintaining NaCl rejection near 85% and 96% for an anionic dye. Experimental results and molecular dynamic simulations revealed that the presence of deoxycholate enhances NaCl rejection in these graphene-based membranes. In addition, these novel hybrid-layered membranes exhibit better chlorine resistance than pure graphene oxide membranes. The desalination performance and aggressive shear and chlorine resistance of these scalable graphene-based membranes are promising for use in practical water separation applications.

Antiorganic Fouling and Low-Protein Adhesion on Reverse-Osmosis Membranes Made of Carbon Nanotubes and Polyamide Nanocomposite.

We demonstrate efficient antifouling and low protein adhesion of multiwalled carbon nanotubes-polyamide nanocomposite (MWCNT-PA) reverse-osmosis (RO) membranes by combining experimental and theoretical studies using molecular dynamics (MD) simulations. Fluorescein isothiocyanate (FITC)-labeled bovine serum albumin (FITC-BSA) was used for the fouling studies. The fouling was observed in real time by using a crossflow system coupled to a fluorescence microscope. Notably, it was observed that BSA anchoring on the smooth MWCNT-PA membrane was considerably weaker than that of other commercial/laboratory-made plain PA membranes. The permeate flux reduction of the MWCNT-PA nanocomposite membranes by the addition of FITC-BSA was 15% of its original value, whereas those of laboratory-made plain PA and commercial membranes were much larger at 34%-50%. Computational MD simulations indicated that the presence of MWCNT in PA results in weaker interactions between the membrane surface and BSA molecule due to the formation of (i) a stiffer PA structure resulting in lower conformity of the molecular structure against BSA, (ii) a smoother surface morphology, and (iii) an increased hydrophilicity involving the formation of an interfacial water layer. These results are important for the design and development of promising antiorganic fouling RO membranes for water treatment.

Fullerene and nanotube growth: new insights using first principles and molecular dynamics.

Shortly after the discovery of fullerenes, many researchers pointed out that carbon nanotubes could be considered as elongated fullerenes. However, the detailed formation mechanism for both structures has been a topic of debate for several years, and consequently it has been difficult to draw a clear connection between the two systems. While the synthesis conditions appear to be different for both fullerenes and nanotubes, here, we demonstrate that it is highly likely that, at an initial growth stage, single-walled carbon nanotubes begin to grow from a hemisphere-like fullerene cap. More importantly, by analysing the minimum-energy path, it is shown that the insertion of C2 fragments drives the transformation of this fullerene cap into an elongated structure that leads to the formation of very short carbon nanotubes.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.

Strengthened PAN-based carbon fibers obtained by slow heating rate carbonization.

Large efforts have been made over the last 40 years to increase the mechanical strength of polyacrylonitrile (PAN)-based carbon fibers (CFs) using a variety of chemical or physical protocols. In this paper, we report a new method to increase CFs mechanical strength using a slow heating rate during the carbonization process. This new approach increases both the carbon sp(3) bonding and the number of nitrogen atoms with quaternary bonding in the hexagonal carbon network. Theoretical calculations support a crosslinking model promoted by the interstitial carbon atoms located in the graphitic interlayer spaces. The improvement in mechanical performance by a controlled crosslinking between the carbon hexagonal layers of the PAN based CFs is a new concept that can contribute further in the tailoring of CFs performance based on the understanding of their microstructure down to the atomic scale.

Molecular Dynamics Study of Carbon Nanotubes/Polyamide Reverse Osmosis Membranes: Polymerization, Structure, and Hydration.

Carbon nanotubes/polyamide (PA) nanocomposite thin films have become very attractive as reverse osmosis (RO) membranes. In this work, we used molecular dynamics to simulate the influence of single walled carbon nanotubes (SWCNTs) in the polyamide molecular structure as a model case of a carbon nanotubes/polyamide nanocomposite RO membrane. It was found that the addition of SWCNTs decreases the pore size of the composite membrane and increases the Na and Cl ion rejection. Analysis of the radial distribution function of water confined in the pores of the membranes shows that SWCNT+PA nanocomposite membranes also exhibit smaller clusters of water molecules within the membrane, thus suggesting a dense membrane structure (SWCNT+PA composite membranes were 3.9% denser than bare PA). The results provide new insights into the fabrication of novel membranes reinforced with tubular structures for enhanced desalination performance.

Encapsulation and immobilization of papain in electrospun nanofibrous membranes of PVA cross-linked with glutaraldehyde vapor.

In this paper, papain enzyme (E.C. 3.4.22.2, 1.6 U/mg) was successfully immobilized in poly(vinyl alcohol) (PVA) nanofibers prepared by electrospinning. The morphology of the electrospun nanofibers was characterized by scanning electron microscopy (SEM) and the diameter distribution was in the range of 80 to 170 nm. The presence of the enzyme within the PVA nanofibers was confirmed by infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDXS) analyses. The maximum catalytic activity was reached when the enzyme loading was 13%. The immobilization of papain in the nanofiber membrane was achieved by chemical crosslinking with a glutaraldehyde vapor treatment (GAvt). The catalytic activity of the immobilized papain was 88% with respect to the free enzyme. The crosslinking time by GAvt to immobilize the enzyme onto the nanofiber mat was 24h, and the enzyme retained its catalytic activity after six cycles. The crosslinked samples maintained 40% of their initial activity after being stored for 14 days. PVA electrospun nanofibers are excellent matrices for the immobilization of enzymes due to their high surface area and their nanoporous structure.