Defect-Healed Carbon Nanomembranes for Enhanced Salt Separation: Scalable Synthesis and Performance.

Carbon nanomembranes (CNMs), with a high density of subnanometer channels, enable superior salt separation performance compared to conventional membranes. However, defects that occur during the synthesis and transfer processes impede their technical realization on a macroscopic scale. Here, we introduce a practical and scalable interfacial polymerization method to effectively heal defects while preserving the subnanometer pores within CNMs. The defect-healed freestanding CNMs show an exceptional performance in forward osmosis (FO), achieving a water flux of 105 L m-2 h-1 and a specific reverse salt flux of 0.1 g L-1 when measured with 1 M NaCl as draw solution. This water flux is 10 times higher than that of commercially available FO membranes, and the reverse salt flux is 70% lower. Through successful implementation of the defect-healing method and support optimization, we demonstrate the synthesis of fully functional, centimeter-scale CNM-based composite membranes showing high water permeance and a high salt rejection. Our defect-healing method presents a promising pathway to overcome limitations in CNM synthesis, advancing their potential for practical salt separation applications.

Protein Nanopore Membranes Prepared by a Simple Langmuir-Schaefer Approach.

Filtration through membranes with nanopores is typically associated with high transmembrane pressures and high energy consumption. This problem can be addressed by reducing the respective membrane thickness. Here, a simple procedure is described to prepare ultrathin membranes based on protein nanopores, which exhibit excellent water permeance, two orders of magnitude superior to comparable, industrially applied membranes. Furthermore, incorporation of either closed or open protein nanopores allows tailoring the membrane's ion permeability. To form such membranes, the transmembrane protein ferric hydroxamate uptake protein component A (FhuA) or its open-pore variant are assembled at the air-water interface of a Langmuir trough, compressed to a dense film, crosslinked by glutaraldehyde, and transferred to various support materials. This approach allows to prepare monolayer or multilayer membranes with a very high density of protein nanopores. Freestanding membranes covering holes up to 5 µm in diameter are visualized by atomic force microscopy (AFM), helium ion microscopy, and transmission electron microscopy. AFM PeakForce quantitative nanomechanical property mapping (PeakForce QNM)  demonstrates remarkable mechanical stability and elastic properties of freestanding monolayer membranes with a thickness of only 5 nm. The new protein membrane can pave the way to energy-efficient nanofiltration.

Scanning transmission helium ion microscopy on carbon nanomembranes.

A dark-field scanning transmission ion microscopy detector was designed for the helium ion microscope. The detection principle is based on a secondary electron conversion holder with an exchangeable aperture strip allowing its acceptance angle to be tuned from 3 to 98 mrad. The contrast mechanism and performance were investigated using freestanding nanometer-thin carbon membranes. The results demonstrate that the detector can be optimized either for most efficient signal collection or for maximum image contrast. The designed setup allows for the imaging of thin low-density materials that otherwise provide little signal or contrast and for a clear end-point detection in the fabrication of nanopores. In addition, the detector is able to determine the thickness of membranes with sub-nanometer precision by quantitatively evaluating the image signal and comparing the results with Monte Carlo simulations. The thickness determined by the dark-field transmission detector is compared to X-ray photoelectron spectroscopy and energy-filtered transmission electron microscopy measurements.

Mechanics of free-standing inorganic and molecular 2D materials.

The discovery of graphene has triggered a great interest in inorganic as well as molecular two-dimensional (2D) materials. In this review, we summarize recent progress in the mechanical characterization of free-standing 2D materials, such as graphene, hexagonal boron nitride (hBN), transition metal-dichalcogenides, MXenes, black phosphor, carbon nanomembranes (CNMs), 2D polymers, 2D metal organic frameworks (MOFs) and covalent organic frameworks (COFs). Elastic, fracture, bending and interfacial properties of these materials have been determined using a variety of experimental techniques including atomic force microscopy based nanoindentation, in situ tensile/fracture testing, bulge testing, Raman spectroscopy, Brillouin light scattering and buckling-based metrology. Additionally, we address recent advances of 2D materials in a variety of mechanical applications, including resonators, microphones and nanoelectromechanical sensors. With the emphasis on progress and challenges in the mechanical characterization of inorganic and molecular 2D materials, we expect a continuous growth of interest and more systematic experimental work on the mechanics of such ultrathin nanomaterials.

Combined nanofiltration and advanced oxidation processes with bifunctional carbon nanomembranes.

Wastewater reclamation is becoming a top global interest as population growth and rapid industrialization pose a major challenge that requires development of sustainable cost-effective technologies and strategies for wastewater treatment. Carbon nanomembranes (CNMs)-synthetic 2D carbon sheets-can be tailored chemically with specific surface functions and/or physically with nanopores of well-defined size as a strategy for multifunctional membrane design. Here, we explore a bifunctional design for combined secondary wastewater effluent treatment with dual action of membrane separation and advanced oxidation processes (AOP), exploiting dissolved oxygen. The bifunctional membrane consists of a CNM layer on top of a commercial ultrafiltration membrane (Microlon™) and a spray-coated reduced graphene oxide (rGO) thin film as the bottom layer. The CNM/support/rGO membrane was characterized by helium ion and atomic force microscopy, FTIR, XPS with a four-point conductivity probe, cyclic voltammetry, galvanostatic measurements, and impedance spectroscopy. Combined treatment of water by nanofiltration and AOP was demonstrated, employing a unique three electrode-dead end filtration setup that enables concurrent application of potential and pressure on the integrated membrane. For the model organic compound methylene blue, oxidation (by the Fenton reaction) was evaluated using UV-vis (610 nm). The rejection rate and permeability provided by the CNM layer were evaluated by dissolving polyethylene glycol (400 and 1000 Da) in the feed solution and applying pressure up to 1.5 bar. This demonstration of combined membrane separation and AOP using an integrated membrane opens up a new strategy for wastewater treatment.

Thiol Redox Regulation of Plant ß-Carbonic Anhydrase.

ß-carbonic anhydrases (ßCA) accelerate the equilibrium formation between CO2 and carbonate. Two plant ßCA isoforms are targeted to the chloroplast and represent abundant proteins in the range of >1% of chloroplast protein. While their function in gas exchange and photosynthesis is well-characterized in carbon concentrating mechanisms of cyanobacteria and plants with C4-photosynthesis, their function in plants with C3-photosynthesis is less clear. The presence of conserved and surface-exposed cysteinyl residues in the ßCA-structure urged to the question whether ßCA is subject to redox regulation. Activity measurements revealed reductive activation of ßCA1, whereas oxidized ßCA1 was inactive. Mutation of cysteinyl residues decreased ßCA1 activity, in particular C280S, C167S, C230S, and C257S. High concentrations of dithiothreitol or low amounts of reduced thioredoxins (TRXs) activated oxidized ßCA1. TRX-y1 and TRX-y2 most efficiently activated ßCA1, followed by TRX-f1 and f2 and NADPH-dependent TRX reductase C (NTRC). High light irradiation did not enhance ßCA activity in wildtype Arabidopsis, but surprisingly in ßca1 knockout plants, indicating light-dependent regulation. The results assign a role of ßCA within the thiol redox regulatory network of the chloroplast.

Selective Diffusion of CO2 and H2O through Carbon Nanomembranes in Aqueous Solution as Studied with Radioactive Tracers.

Nanometer-thin carbon nanomembranes (CNMs) are promising candidates for efficient separation processes due to their thinness and intrinsic well-defined pore structure. This work used radioactive tracer molecules to characterize diffusion of [3H]H2O, [14C]NaHCO3, and [32P]H3PO4 through a p-[1,1',4',1″]-terphenyl-4-thiol (TPT) CNM in aqueous solution. The experimental setup consisted of two microcompartments separated by a CNM-covered micropore. Tracers were added to one compartment and their time-dependent increase in the other compartment was monitored. Occurring concentration polarization and outgassing effects were fully considered using a newly developed mathematical model. Our findings are consistent with previous gas/vapor permeation measurements. The high sensitivity toward a small molecule flow rate enables quantification of diffusion through micron-sized CNMs in aqueous solution. Furthermore, the results allow unambiguous distinction between intact and defective membranes. Even for extremely small membrane areas, this method allows detailed insight into the transmembrane transport properties, which is crucial for the design of 2D-separation membranes.

Ultrahigh Ionic Exclusion through Carbon Nanomembranes.

The collective "single-file" motion of water molecules through natural and artificial nanoconduits inspires the development of high-performance membranes for water separation. However, a material that contains a large number of pores combining rapid water flow with superior ion rejection is still highly desirable. Here, a 1.2 nm thick carbon nanomembrane (CNM) made from cross-linking of terphenylthiol (TPT) self-assembled monolayers is reported to possess these properties. Utilizing their extremely high pore density of 1 sub-nm channel nm-2 , TPT CNMs let water molecules rapidly pass, while the translocation of ions, including protons, is efficiently hindered. Their membrane resistance reaches ≈104 Ω cm2 in 1 m Cl- solutions, comparable to lipid bilayers of a cell membrane. Consequently, a single CNM channel yields an ≈108 higher resistance than pores in lipid membrane channels and carbon nanotubes. The ultrahigh ionic exclusion by CNMs is likely dominated by a steric hindrance mechanism, coupled with electrostatic repulsion and entrance effects. The operation of TPT CNM membrane composites in forward osmosis is also demonstrated. These observations highlight the potential of utilizing CNMs for water purification and opens up a simple avenue to creating 2D membranes through molecular self-assembly for highly selective and fast separations.

Size limits of magnetic-domain engineering in continuous in-plane exchange-bias prototype films.

Background: The application of superparamagnetic particles as biomolecular transporters in microfluidic systems for lab-on-a-chip applications crucially depends on the ability to control their motion. One approach for magnetic-particle motion control is the superposition of static magnetic stray field landscapes (MFLs) with dynamically varying external fields. These MFLs may emerge from magnetic domains engineered both in shape and in their local anisotropies. Motion control of smaller beads does necessarily need smaller magnetic patterns, i.e., MFLs varying on smaller lateral scales. The achievable size limit of engineered magnetic domains depends on the magnetic patterning method and on the magnetic anisotropies of the material system. Smallest patterns are expected to be in the range of the domain wall width of the particular material system. To explore these limits a patterning technology is needed with a spatial resolution significantly smaller than the domain wall width. Results: We demonstrate the application of a helium ion microscope with a beam diameter of 8 nm as a mask-less method for local domain patterning of magnetic thin-film systems. For a prototypical in-plane exchange-bias system the domain wall width has been investigated as a function of the angle between unidirectional anisotropy and domain wall. By shrinking the domain size of periodic domain stripes, we analyzed the influence of domain wall overlap on the domain stability. Finally, by changing the geometry of artificial two-dimensional domains, the influence of domain wall overlap and domain wall geometry on the ultimate domain size in the chosen system was analyzed. Conclusion: The application of a helium ion microscope for magnetic patterning has been shown. It allowed for exploring the fundamental limits of domain engineering in an in-plane exchange-bias thin film as a prototypical system. For two-dimensional domains the limit depends on the domain geometry. The relative orientation between domain wall and anisotropy axes is a crucial parameter and therefore influences the achievable minimum domain size dramatically.

Volume phase transition kinetics of smart N-n-propylacrylamide microgels studied by time-resolved pressure jump small angle neutron scattering.

The use of smart colloidal microgels for advanced applications critically depends on their response kinetics. We use pressure jump small angle neutron scattering with supreme time resolution to study the rapid volume phase transition kinetics of such microgels. Utilizing the pressure induced microphase separation inside the microgels we were able to resolve their collapse and swelling kinetics. While the collapse occurs on a time scale of 10 ms, the particle swelling turned out to be much faster. Photon correlation spectroscopy and static small angle neutron scattering unambiguously show, that the much slower collapse can be associated with the complex particle architecture exhibiting a loosely-crosslinked outer region and a denser inner core region. These insights into the kinetics of stimuli-responsive materials are of high relevance for their applications as nano-actuators, sensors or drug carriers. Moreover, the used refined pressure jump small angle neutron scattering technique is of broad interest for soft matter studies.

High-Q, low-mode-volume and multiresonant plasmonic nanoslit cavities fabricated by helium ion milling.

Helium ion milling of chemically-synthesized micron-sized gold flakes is performed to fabricate ultra-narrow nanoslit cavities with a varying length and width down to 5 nm. Their plasmon resonances are characterized by one-photon photoluminescence spectroscopy. The combination of fabrication based on single-crystalline gold and resonant modes with low radiative losses leads to remarkably high quality factors of up to 24. Multiple Fabry-Pérot-type resonances in the visible/near infrared spectral range are observed due to the achieved narrow slit widths and the resulting short effective wavelengths of nanoslit plasmons. These features make nanoslit cavities attractive for a range of applications such as surface-enhanced spectroscopy, ultrafast nano-optics and strong light-matter coupling.

Large-Area All-Carbon Nanocapacitors from Graphene and Carbon Nanomembranes.

We report on the fabrication of large-area all-carbon capacitors (ACCs) composed of multilayer stacks of carbon nanomembranes as dielectrics sandwiched between two carbon-based conducting electrodes. Carbon nanomembranes (CNMs) are prepared from aromatic self-assembled monolayers of phenylthiol homologues via electron irradiation. Two types of carbon-based electrode materials, (1) trilayer graphene made by chemical vapor deposition and mechanical stacking and (2) pyrolyzed graphitic carbon made by pyrolysis of cross-linked aromatic molecules, have been employed for this study. The capacitor area is defined by the width of electrode ribbons, and the separation between two electrodes is tuned by the number of CNM layers. Working ACCs with an area of up to 1200 µm2 were successfully fabricated by a combination of bottom-up molecular self-assembly and top-down lithographic approaches. Then ACCs were characterized by Raman spectroscopy, helium ion microscopy, and impedance spectroscopy. A dielectric constant of 3.5 and an average capacitance density of 0.3 µF/cm2 were derived from the obtained capacitances. A dielectric strength of 3.2 MV/cm was determined for CNMs embedded in graphene electrodes with the interfacial capacitance being taken into account. These results show the potential of carbon nanomembranes to be used as dielectric components in next-generation environment-friendly carbon-based energy storage devices.

Rapid Water Permeation Through Carbon Nanomembranes with Sub-Nanometer Channels.

The provision of clean water is a global challenge, and membrane filtration is a key technology to address it. Conventional filtration membranes are constrained by a trade-off between permeance and selectivity. Recently, some nanostructured membranes demonstrated the ability to overcome this limitation by utilizing well-defined carbon nanoconduits that allow a coordinated passage of water molecules. The fabrication of these materials is still very challenging, but their performance inspires research toward nanofabricated membranes. This study reports on molecularly thin membranes with sub-nanometer channels that combine high water selectivity with an exceptionally high permeance. Carbon nanomembranes (CNMs) of ∼1.2 nm thickness are fabricated from terphenylthiol (TPT) monolayers. Scanning probe microscopy and transport measurements reveal that TPT CNMs consist of a dense network of sub-nanometer channels that efficiently block the passage of most gases and liquids. However, water passes through with an extremely high permeance of ∼1.1 × 10-4 mol·m-2·s-1·Pa-1, as does helium, but with a ∼ 2500 times lower flux. Assuming all channels in a TPT CNM are active in mass transport, we find a single-channel permeation of ∼66 water molecules·s-1·Pa-1. This suggests that water molecules translocate fast and cooperatively through the sub-nanometer channels, similar to carbon nanotubes and membrane proteins (aquaporins). CNMs are thus scalable two-dimensional sieves that can be utilized toward energy-efficient water purification.

Surface-Enhanced Raman Spectroscopy of Carbon Nanomembranes from Aromatic Self-Assembled Monolayers.

Surface-enhanced Raman scattering spectroscopy (SERS) was employed to investigate the formation of self-assembled monolayers (SAMs) of biphenylthiol, 4'-nitro-1,1'-biphenyl-4-thiol, and p-terphenylthiol on Au surfaces and their structural transformations into carbon nanomembranes (CNMs) induced by electron irradiation. The high sensitivity of SERS allows us to identify two types of Raman scattering in electron-irradiated SAMs: (1) Raman-active sites exhibit similar bands as those of pristine SAMs in the fingerprint spectral region, but with indications of an amorphization process and (2) Raman-inactive sites show almost no Raman-scattering signals, except a very weak and broad D band, indicating a lack of structural order but for the presence of graphitic domains. Statistical analysis showed that the ratio of the number of Raman-active sites to the total number of measurement sites decreases exponentially with increasing the electron irradiation dose. The maximum degree of cross-linking ranged from 97 to 99% for the three SAMs. Proof-of-concept experiments were conducted to demonstrate potential applications of Raman-inactive CNMs as a supporting membrane for Raman analysis.

Modification of the saturation magnetization of exchange bias thin film systems upon light-ion bombardment.

The magnetic modification of exchange bias materials by 'ion bombardment induced magnetic patterning' has been established more than a decade ago. To understand these experimental findings several theoretical models were introduced. Few investigations, however, did focus on magnetic property modifications caused by effects of ion bombardment in the ferromagnetic layer. In the present study, the structural changes occurring under ion bombardment were investigated by Monte-Carlo simulations and in experiments. A strong reduction of the saturation magnetization scaling linearly with increasing ion doses is observed and our findings suggest that it is correlated to the swelling of the layer material based on helium implantation and vacancy creation.

Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II) oxalate precursor layers.

Copper(II) oxalate grown on carboxy-terminated self-assembled monolayers (SAM) using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II) acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II) oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS). Helium ion microscopy (HIM) reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS) confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor.

Helium Ion Microscopy Visualizes Lipid Nanodomains in Mammalian Cells.

Cell membranes are composed of 2D bilayers of amphipathic lipids, which allow a lateral movement of the respective membrane components. These components are arranged in an inhomogeneous manner as transient micro- and nanodomains, which are believed to be crucially involved in the regulation of signal transduction pathways in mammalian cells. Because of their small size (diameter 10-200 nm), membrane nanodomains cannot be directly imaged using conventional light microscopy. Here, direct visualization of cell membrane nanodomains by helium ion microscopy (HIM) is presented. It is shown that HIM is capable to image biological specimens without any conductive coating and that HIM images clearly allow the identification of nanodomains in the ultrastructure of membranes with 1.5 nm resolution. The shape of these nanodomains is preserved by fixation of the surrounding unsaturated fatty acids while saturated fatty acids inside the nanodomains are selectively removed. Atomic force microscopy, fluorescence microscopy, 3D structured illumination microscopy, and direct stochastic optical reconstruction microscopy provide additional evidence that the structures in the HIM images of cell membranes originate from membrane nanodomains. The nanodomains observed by HIM have an average diameter of 20 nm and are densely arranged with a minimal nearest neighbor distance of ≈ 15 nm.

Imaging of carbon nanomembranes with helium ion microscopy.

Carbon nanomembranes (CNMs) prepared from aromatic self-assembled monolayers constitute a recently developed class of 2D materials. They are made by a combination of self-assembly, radiation-induced cross-linking and the detachment of the cross-linked SAM from its substrate. CNMs can be deposited on arbitrary substrates, including holey and perforated ones, as well as on metallic (transmission electron microscopy) grids. Therewith, freestanding membranes with a thickness of 1 nm and macroscopic lateral dimensions can be prepared. Although free-standing CNMs cannot be imaged by light microscopy, charged particle techniques can visualize them. However, CNMs are electrically insulating, which makes them sensitive to charging. We demonstrate that the helium ion microscope (HIM) is a good candidate for imaging freestanding CNMs due to its efficient charge compensation tool. Scanning with a beam of helium ions while recording the emitted secondary electrons generates the HIM images. The advantages of HIM are high resolution, high surface sensitivity and large depth of field. The effects of sample charging, imaging of multilayer CNMs as well as imaging artefacts are discussed.

Controlled translocation of DNA through nanopores in carbon nano-, silicon-nitride- and lipid-coated membranes.

We investigated experimentally and theoretically the translocation forces when a charged polymer is threaded through a solid-state nanopore and found distinct dependencies on the nanopore diameter as well as on the nano membrane material chemistry. For this purpose we utilized dedicated optical tweezers force mechanics capable of probing the insertion of negatively charged double-stranded DNA inside a helium-ion drilled nanopore. We found that both the diameter of the nanopore and the membrane material itself have significant influences on the electroosmotic flow through the nanopore and thus on the threading force. Compared to a bare silicon-nitride membrane, the threading of DNA through only 3 nm thin carbon nano membranes as well as lipid bilayer-coated nanopores increased the threading force by 15% or 85%, respectively. This finding was quantitatively described by our recently developed theoretical model that also incorporates hydrodynamic slip effects on the translocating DNA molecule and the force dependence on the membrane thickness. The additional measurements presented in this paper further support our model.

Preparation of conductive gold nanowires in confined environment of gold-filled polymer nanotubes.

Continuous conductive gold nanofibers are prepared via the "tubes by fiber templates" process. First, poly(l-lactide) (PLLA)-stabilized gold nanoparticles (AuNP) with over 60 wt% gold are synthesized and characterized, including gel permeation chromatography coupled with a diode array detector. Subsequent electrospinning of these AuNP with template PLLA results in composite nanofibers featuring a high gold content of 57 wt%. Highly homogeneous gold nanowires are obtained after chemical vapor deposition of 345 nm of poly(p-xylylene) (PPX) onto the composite fibers followed by pyrolysis of the polymers at 1050 °C. The corresponding heat-induced transition from continuous gold-loaded polymer tubes to smooth gold nanofibers is studied by transmission electron microscopy and helium ion microscopy using both secondary electrons and Rutherford backscattered ions.