Search

Metal borides, a class of materials intensively used in industry as superconductors, magnetic materials, or hot cathodes, remain largely unexplored at the nanoscale mainly due to the difficulty in synthesizing single-phase nanocrystals. Recent works have shown that synthetic methods at lower temperatures (xB) could be a potential catalyst for a broad range of applications (hydrogenations, electrochemical hydrogen, and oxygen evolution reactions) under challenging conditions (such as high pH or high temperatures). Here, we report a novel solid-state method to synthesize NixB nanopowders (with a diameter of approximately 45 nm) and their conversion into colloidal suspensions (inks) through treatment of the nanocrystal surface. For the solid-state synthesis, we used commercially available salts and explored the reaction between the Ni and B sources while varying the synthetic parameters under mild and solvent-free reaction conditions. We show that pure phase Ni3B and Ni2B NCs can be obtained with high yield in the pure phase using as precursors NiCl2 and Ni, respectively. Through extensive mechanistic studies, we show that Ni nanoclusters (1-2 nm) are an intermediate in the boriding process, while the metal co-reactant lowers the decomposition temperature of NaBH4 (used as a reducing agent and B source). Size control can instead be exerted through reaction mediators, as seen from the differential nucleation and growth of Ni (clusters) or NixB NCs when employing L- (amine, phosphine) and X-type (carboxylate) mediators. Applying surface engineering methods to our NixB NCs, we stabilized them with inorganic (NOBF4) or organic (borane tert-butyl amine, oleylamine) ligands in the appropriate solvent (DMSO, hexane). With this method, we produce stable inks for further solution processing applications. Our results provide tools for further development of catalysts based on NixB NCs and pave the way for synthesizing other metal boride colloidal nanostructures.

Keratin is an important byproduct of the animal industry, but almost all of it ends up in landfills due to a lack of efficient recycling methods. To make better use of keratin-based natural resources, the current extraction and processing strategies need to be improved or replaced by more sustainable and cost-effective processes. Here, we developed a simple and environmentally benign method to process extracted keratin, using HCl to induce the formation of a coacervate, a separate aqueous phase with a very high protein concentration. Remarkably, this pH-induced coacervation did not result in the denaturation of keratin, and we could even observe an increase in the amount of ordered secondary structures. The low-pH coacervates could be extruded and wet-spun into high-performance keratin fibers, without requiring heating or any organic solvents. The secondary structure of keratin was largely conserved in these regenerated fibers, which exhibited excellent mechanical performance. The process developed in this study represents a simple and environmentally friendly strategy to upcycle waste keratin into high-performance materials.

Administration of temperature-responsive drug carriers that release anticancer drugs at high temperatures can benefit hyperthermia therapies because of the synergistic effect of anticancer drug molecules and high temperature on killing the cancer cells. In this study, we design and characterize a new temperature-responsive nanocarrier based on a naturally occurring and biocompatible clay mineral, halloysite nanotubes. Poly(N-isopropylacrylamide) brushes were grown on the surface of halloysite nanotubes using a combination of mussel-inspired dopamine polymerization and surface-initiated atom transfer radical polymerization. The chemical structure of the hybrid materials was investigated using X-ray photoelectron spectroscopy, thermogravimetric analysis and energy-dispersive X-ray spectroscopy. The hybrid material was shown to have a phase transition temperature of about 32 °C, corresponding to a 40 nm thick polymer layer surrounding the nanotubes. Cell studies suggested that grafting of poly(N-isopropylacrylamide) brushes on the polydopamine-modified halloysite nanotubes suppresses the cytotoxicity caused by the polydopamine interlayer and drug release studies on nanotubes loaded with doxorubicin showed that thanks to the poly(N-isopropylacrylamide) brushes a temperature-dependent drug release is observed. Finally, a fluorescent dye molecule was covalently attached to the polymer-grafted nanotubes and stimulated emission depletion nanoscopy was used to confirm the internalization of the nanotubes in HeLa cells.

Germanane, a two-dimensional Ge lattice in which each atom is hydrogen-terminated in the z-direction, possesses a remarkable combination of electronic and optical properties that are attractive for applications ranging from chemical sensing to electrocatalysis and photocatalysis. In this work, we studied germanane (GeH) and the novel butyl-functionalized germanane (GeBuxH(1−x)) as photocatalysts for water purification under visible light irradiation and utilizing challenging conditions in terms of photocatalyst loading (1 mg per g of aqueous solution containing 200 ppm of pollutant). The synthesized GeH and GeBuxH(1−x) have significantly higher specific surface area (121 m2 g−1 and 76 m2 g−1, respectively) than other germanane derivatives reported to date and display optical band gaps suitable for visible light absorption (1.40 eV and 1.55 eV, respectively). In terms of photocatalytic performance, GeH displayed the best activity in the degradation of rhodamine B (61% removal after 3 h under visible radiation), while GeBuxH(1−x) proved to be the best photocatalyst for the degradation of phenol (33% removal after 3 h under visible radiation). In both cases, the activity under visible radiation surpassed that of P25 TiO2 and could be enhanced significantly by sonication in water before interaction with the pollutants. Recycling tests showed that GeH could be reused with no or negligible loss of photocatalytic activity, whereas GeBuxH(1−x) showed a minor decrease in activity upon reuse.

Ibuprofen is a non-steroidal, anti-inflammatory drug that is widely prescribed for its analgesic, antipyretic, and anti-inflammatory actions to treat pain, symptoms of rheumatoid arthritis and fever, but it is also known to cause stomach-related side effects. The development of efficient drug delivery systems for this compound to prevent these side effects is hampered by its poor water solubility. In this work, we show that graphite oxide and its derivatives have great potential as effective drug delivery systems not only to overcome side effects but also to increase the short biological half-life of ibuprofen. We studied the adsorption capacity of graphite oxide and carboxylated and sulfonated graphene oxide for this drug and its release in simulated gastric and intestinal fluid. The obtained compounds were characterized by X-ray diffraction, thermogravimetric analysis and Fourier transform infrared spectroscopy. DFT calculations were conducted to elucidate the Ibuprofen/host interactions, to establish which properties of these carbon nanomaterials control the loading and release, as well as to provide a better understanding of the orientation of the drug molecules on the single-layer GO.

In this work, we investigate the use of aqueous deep eutectic solvents (DESs) consisting of different hydrogen bond acceptors (choline chloride, ammonium salts or betaine) and hydrogen bond donors (amines, sugars and alcohols), as co-solvents in biocatalytic reactions catalyzed by a nano-biocatalyst with β-glucosidase (BGL) activity. For this purpose, β-glucosidase from Thermotoga maritima was immobilized on the surface of green zinc oxide-iron oxide nanoparticles (BGL@ZnOFe) derived from an aqueous olive leaf extract. The covalent bonding of β-glucosidase on the surface of nanoparticles was demonstrated by X-ray photoelectron spectroscopy. The effect of a wide range of DES solutions on the biocatalytic features of BGL@ZnOFe was thoroughly investigated. The concentration of DES as well as the specific combination of hydrogen bond acceptors and hydrogen bond donors had a significant impact on the hydrolytic activity of immobilized β-glucosidase. Most choline chloride and betaine-based DESs enhanced the enzymatic activity and thermal stability of BGL@ZnOFe up to 50%. The enzymatic activity of the nano-biocatalyst towards the hydrolysis of bioactive phenolic compounds depends on the nature of the DES used. Choline chloride:butylene glycol-based medium had beneficial effect on a transglycosylation reaction, such as the synthesis of salidroside, increasing the total turnover number of the biocatalytic process by 55%. This work indicates that the use of several choline chloride and betaine-based DESs can be successfully employed as green co-solvents in various hydrolytic and synthetic biocatalytic processes.

The development of stimuli-responsive drug nanocarriers is an increasingly important area in nanomedicine because efficient delivery of toxic drugs to targeted tissues minimizes side effects. The specific objective of this study was to synthesize and characterize a novel pH-responsive drug carrier based on halloysite nanotubes for the controlled release of the anticancer drug doxorubicin. Poly(N,N-dimethylaminoethyl methacrylate) brushes were grafted from the surface of halloysite nanotubes using the combination of mussel-inspired polydopamine surface modification and activators regenerated by electron transfer in atom transfer radical polymerization. The chemical structure and morphology of the modified halloysite nanotubes were investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermal gravimetric analysis as well as scanning and transmission electron microscopies. Dynamic light scattering and zeta potential analysis were carried out to evaluate the pH-responsivity of the functionalized halloysite nanotubes. The results of the drug loading and release study of pristine and functionalized halloysite nanotubes showed that grafting of poly(N,N-dimethylaminoethyl methacrylate) brushes on the polydopamine-modified halloysite nanotubes surface leads to a drastic increase in doxorubicin loading capacity and a highly pH-sensitive release behaviour. Less than 10 % of the loaded doxorubicin was released from poly (N,N-dimethylaminoethyl methacrylate)-grafted halloysite nanotubes at pH 7.4 after 24 h; in contrast, at pH 5.5 there was a continuous release of doxorubicin totalling 13 % in the first 30 min, i.e. lower than for the pristine halloysite nanotubes (32 %), but reaching 48 % after 24 h. Poly (N,N-dimethylaminoethyl methacrylate)-grafted halloysite nanotubes can hence be considered as a potential candidate for delivering highly toxic drug molecules to the acidic target sites.

This study reports on the ultralubricity of a high-temperature resilient nanocomposite WS2/a-C tribocoating. The coefficient of friction of this coating remains at around 0.02 independently of a thermal treatment up to ∼500 °C, as confirmed by high-temperature tribotests. Moreover, the coating annealed at 450 °C keeps exhibiting a similar ultralubricity when cooled back down to room temperature and tested there, implying a tribological self-adaptation over a broad temperature range. High-resolution TEM observations of the tribofilms on the wear track unveil that WS2 nanoplatelets form dynamically via atomic rearrangement and extend via unfaulting geometrical defects (bound by partial climb dislocations). The (002) basal planes of the WS2 nanoplatelets, reoriented parallel to the tribo-sliding direction, contribute to a sustainable ultralubricity. The declining triboperformance beyond 500 °C is associated with sulfur loss rather than the transformation of WS2 into inferior WO3 via oxidation as suggested earlier. This self-adaptive WS2/a-C tribocoating holds promise for a constant ultralubrication with excellent thermal performance.

Germanane (GeH), a graphane analogue, has attracted significant interest because of its optoelectronic properties; however, the environmental and biological effects of GeH have scarcely been investigated so far. Here we report a facile approach based on the Langmuir-Schaefer deposition to produce homogeneous and dense GeH monolayer films on various substrates. In view of possible applications and to extend the use of GeH to unexplored fields, we investigated its antibacterial activity for the first time and found that this promising 2D structure exhibits remarkable antibacterial activity against both Gram-negative and Gram-positive bacterial strains.

The contamination of aqueous environments by aromatic pollutants has become a global issue. Chloridazon, a herbicide considered as harmless to the ecosystem, has been widely used in recent decades and has accumulated, together with its degradation products desphenyl-chloridazon and methyl-desphenyl-chloridazon, to a non-negligible level in surface water and groundwater. To respond to the consequent necessity for remediation, in this work, we study the adsorption of chloridazon and its metabolites by graphene oxide and elucidate the underlying mechanism by X-ray photoelectron spectroscopy. We find a high adsorption capacity of 67 g kg-1for chloridazon and establish that bonding of chloridazon to graphene oxide is mainly due to hydrophobic interaction and hydrogen bonding. These findings demonstrate the potential of graphene-based materials for the remediation of chloridazon and its metabolites from aqueous environments.

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells., Germanane was synthesized by topotatic deintercalation of β‐CaGe2 in aqueous HF solution at room temperature under stirring for 2‐3 minutes. In order to remove the residual CaF2 the material was treated with a saturated aqueous solution of EDTA.

Incorporation of isolated metal centers into well-organized nanostructures is a promising route in the development of the next generation of chemical, magnetic and electronic devices. In this work, a layer-by-layer protocol to grow highly ordered thin films of metal-decorated organic-inorganic cage-like polyhedral oligomeric silsesquioxane (POSS) is introduced. The key strategy is to use metal ions (Cu2+ or Fe3+) as linker for the amino-functionalized cage-like POSS, which are self-assembled between arachidic acid layers during Langmuir–Schaefer deposition. The Langmuir–Schaefer films are examined by X-ray photoelectron spectroscopy, X-ray diffraction, grazing incidence wide-angle X-ray scattering and extended X-ray absorption fine structure in order to understand how the coordination of metal ions influences the structure in the course of the layer-by-layer formation of the films.

To explore the role of Li in establishing room-temperature ferromagnetism in SnO2, the structural, electronic and magnetic properties of Li-doped SnO(2)compounds were studied for different size regimes, from nanoparticles to bulk crystals. Li-doped nanoparticles show ferromagnetic ordering plus a paramagnetic contribution for particle sizes in the range of 16-51 nm, while pure SnO(2)and Li-doped compounds below and above this particular size range are diamagnetic. The magnetic moment is larger for compositions where the Li substitutes for Sn than for compositions where Li prevalently occupies interstitial sites. The observed ferromagnetic ordering in Li-doped SnO(2)nanoparticles is mainly due to the holes created when Li substitutes at a Sn site. Conversely, Li acts as an electron donor and electrons from Li may combine with holes to decrease ferromagnetism when lithium mainly occupies interstitial sites in the SnO(2)lattice.

The transition away from fossil fuel and ultimately to a carbon-neutral energy sector requires new storage materials for hydrogen and methane as well as new solutions for carbon capture and storage. Among the investigated adsorbents, activated carbons are considered especially promising because they have a high specific surface area, are lightweight, thermally and chemically stable, and easy to produce. Moreover, their porosity can be tuned and they can be produced from inexpensive and environmentally friendly raw materials. This study reports on the development and characterization of activated carbons synthesized starting from amorphous cellulose with and without the inclusion of copper nanoparticles. The aim was to investigate how the presence of different concentrations of metal nanoparticles affects porosity and gas storage properties. Therefore, the research work focused on synthesis and characterization of physical and chemical properties of pristine and metal-doped activated carbons materials and on further investigation to analyze their hydrogen, methane and carbon dioxide adsorption capacity. For an optimized Cu content the microporosity is improved, resulting in a specific surface area increase of 25%, which leads to a H2 uptake (at 77 K) higher than the theoretical value predicted by the Chahine Rule. For CH4, the storage capacity is improved by the addition of Cu but less importantly because the size of the molecule hampers easy access of the smaller pores. For CO2 a 26% increase in adsorption capacity compared to pure activated carbon was achieved, which translated with an absolute value of over 48 wt% at 298 K and 15 bar of pressure.

Lead halide perovskite nanocrystals are highly attractive for next-generation optoelectronics because they are easy to synthesize and offer great compositional and morphological tunability. However, the replacement of lead by tin for sustainability reasons is hampered by the unstable nature of Sn2+ oxidation state and by an insufficient understanding of the chemical processes involved in the synthesis. Here we demonstrate an optimized synthetic route to obtain stable, tunable, and monodisperse CsSnI3 nanocrystals, exhibiting well defined excitonic peaks. Similar to lead halide perovskites, we prepare these nanocrystals by combining a precursor mixture of SnI2 , oleylamine and oleic acid, with a Cs-oleate precursor. Among the products, nanocrystals with 10 nm lateral size in the γ-orthorhombic phase prove to be the most stable. To achieve such stability, an excess of precursor SnI2 as well as sub-stoichiometric Sn:ligand ratios are key. Structural, compositional and optical investigations complemented by first-principle DFT calculations confirm that nanocrystal nucleation and growth follow the formation of (R-NH3 + )2 SnI4 nanosheets with R = C18 H35 . Under specific synthetic conditions, stable mixtures of 3D nanocrystals CsSnI3 and 2D nanosheets (Ruddlesden-Popper (R-NH3 + )2 Csn-1 Snn I3n+1 with n>1) are obtained. These results set a path to exploiting the high potential of Sn halide perovskite nanocrystals for opto-electronic applications. This article is protected by copyright. All rights reserved.

In the present work we report for the first time the carbonization of biomass waste, such as stale bread and spent coffee, in piranha solution (H2SO4-H2O2) at ambient conditions. Carbonization is fast and exothermic, resulting in the formation of carbon nanosheets at decent yields of 25–35%, depending on the starting material. The structure and morphology of the nanosheets were verified by X-ray diffraction, Raman, X-ray photoelectron and microscopy techniques. Interestingly, the obtained carbon spontaneously ignites upon contact with fuming nitric acid HNO3 at ambient conditions, thus offering a rare example of hypergolicity involving carbon as the solid fuel (i.e., hypergolic carbon). Based on the relatively large interlayer spacing of the as-produced carbons, a simple structural model is proposed for the observed hypergolicity, wherein HNO3 molecules fit in the gallery space of carbon, thus exposing its basal plane and defect sites to a spontaneous reaction with the strong oxidizing agent. This finding may pave the way towards new type hypergolic propellants based on carbon, the latter exclusively obtained by the carbonization of biomass waste in piranha solution.

Perovskite oxides with dispersed nanoparticles on their surface are considered instrumental in energy conversion and catalytic processes. Redox exsolution is an alternative method to the conventional deposition techniques for directly growing well-dispersed and anchored nanoarchitectures from the oxide support through thermochemical or electrochemical reduction. Herein, we show a new method for such nanoparticle nucleation through the exposure of the host perovskite to plasma. The applicability of this new method was demonstrated by performing catalytic tests for CO2 hydrogenation over Ni exsolved nanoparticles prepared by either plasma or conventional H2 reduction. Compared to the conventional thermochemical H2 reduction, there were plasma conditions that led to the exsolution of more than ten times higher Ni amount from a lanthanum titanate perovskite, which is similar to the reported values of the electrochemical method. Unlike the electrochemical method, however, plasma does not require the integration of the material in an electrochemical cell, and is thus applicable to a wide range of microstructures and physical forms. Additionally, when N2 plasma was employed, the nitrogen species stripped out oxygen from the perovskite lattice, generating a key chemical intermediate, such as NO, rendering this technology even more appealing., Funding: SynCat@DIFFER NWO-731.016.301, Electricity to Chemistry

Soft matter containing Ti3C2Tx MXenes exhibits promising potential in electromechanical sensor development. Current systems suffer from a decrease in sensibility up to complete breakdown due to small structural defects that will be generated during their longtime practical service. Various non-covalent hydrogel systems, based on hydrogen bonding and ionic coupling, have been employed to improve their durability related to their repairability. However, Ti3C2Tx MXenes are not stable in those networks, since they will be irreversibly oxidized in high humidity environment during practical application. Here, we report the use of a novel dynamic covalent bond based network – a MXene acrylate vitrimer network (MAVIN) with a low glass transition temperature, which can not only be repaired fast with high efficiency but also protects the MXenes in sensor applications from oxidation under working conditions. In addition, owing to the strong microwave absorptivity of Ti3C2Tx and of the flexible dynamic covalent bond network, a damaged MAVIN sensor can be repaired by microwave radiation with a high healing efficiency of 92.4% within 1 minute, which is as good as the best healing efficiency reported in literature so far but 30 times faster. With stability at a voltage of 3 V and fast healing demonstrated, MAVIN promises potential usage in reliable and sustainable strain sensors.

[EN] This work reports initial results on the effect of low concentrations (ppm level) of a stabilizing agent (2,6-di-tert-butyl-4-methylphenol, BHT) present in an off-the-shelf solvent on the catalyst performance for the hydrogenolysis of γ-butyrolactone over Cu-ZnO-based catalysts. Tetrahydrofuran (THF) was employed as an alternative solvent in the hydrogenolysis of γ-butyrolactone. It was found that the Cu-ZnO catalyst performance using a reference solvent (1,4-dioxane) was good, meaning that the equilibrium conversion was achieved in 240 min, while a zero conversion was found when employing tetrahydrofuran. The deactivation was studied in more detail, arriving at the preliminary conclusion that one phenomenon seems to play a role: the poisoning effect of a solvent additive present at the ppm level (BHT) that appears to inhibit the reaction completely over a Cu-ZnO catalyst. The BHT effect was also visible over a commercial Cu-ZnO-MgO-AlOcatalyst but less severe than that over the Cu-ZnO catalyst. Hence, the commercial catalyst is more tolerant to the solvent additive, probably due to the higher surface area. The study illustrates the importance of solvent choice and purification for applications such as three-phase-catalyzed reactions to achieve optimal performance., European Commission (HPMF-CT-2002-01873), and was benefited from financial support by the Advanced Materials research program of the Zernike National Research Centre under the Bonus Incentive Scheme of the Dutch Ministry for Education, Culture and Science. Additional joint financial support from Comunidad de Madrid (Spain) and ERDF (European Regional Development Fund), Grant Number S2018/EMT-4344 (BIOTRES-CM) is acknowledged. Profs. Em. J. A. Moulijn and F. Kapteijn are thanked for hosting and supporting this project (binary catalyst study) in their lab.

The authors regret that in Fig. 1b some data points of s/w ratio were not correctly aligned with the x-axis of target-to-substrate distance. The corrected Fig. 1b is shown below. [Figure presented] The authors would like to apologise for any inconvenience caused.

A better understanding of the effects of carbonaceous particulates in air pollution on human health and on the transmission of viruses requires studies with artificially produced aerosols that mimic the real ones. To produce such aerosols, methods to precisely tailor the morphology as well as the physical and chemical properties of carbon-based nanomaterials are crucial. Here we describe a facile and flexible approach to produce carbon-based nanoparticles with tailored N content by spark discharge utilizing graphite rods. Carbon-based nanoparticles with different nanotexture and N doping could be obtained by simply changing dilution gas (nitrogen, argon) and dilution gas purity (99 and 99.999%). The effect of the discharge frequency (50, 300 Hz) was also explored. The carbon-based nanoparticles were characterized by Fourier transform infrared and X-ray photoelectron spectroscopy, thermogravimetric analysis, and transmission electron microscopy. We find that the nanotexture is strictly linked to the chemical reactivity and to the surface chemistry. The use of N2 as dilution gas allowed for the incorporation of significant amounts of nitrogen (5–7 wt.%) in the carbonaceous particle network mainly as pyrrolic N, graphitic N and N-oxide functional groups.

Chloridazon has been a widely used herbicide during the past decades, especially in sugar-beet cultivation. UV-induced degradation of chloridazon leads to the formation of desphenyl counterparts, i.e. desphenyl-chloridazon and methyl-desphenyl-chloridazon. Even if accumulation of these residues in natural waters is far from alarming, a low-cost effective and environmentally friendly adsorbent, capable of binding chloridazon and its degradation products is desirable to reduce their concentration in water even further below legal limits. Here we show that pillared smectite clay, prepared by cation exchange of sodium with copper complexed, cage-shaped polyhedral oligomeric silsesquioxane (Cu2+@POSS) could be a promising candidate for this purpose. X-ray diffraction and high resolution transmission electron microscopy evidenced a homogeneous layered structure where the interlayer spacing is enlarged by 7.1 ± 0.2 Å (the diameter of Cu2+@POSS) with respect to the pristine clay. Exposure of this pillared smectite clay to chloridazon and its metabolites in water showed that Cu2+@POSS intercalation significantly improved its adsorption capacity. In addition, after several thermal regeneration cycles, Cu2+@POSS_SWy-2 still exhibited excellent adsorption properties. These findings demonstrate that smectite clay pillared with copper complexed polyhedral oligosilsesquioxane is a promising environmentally friendly and relatively low cost material for herbicide waste remediation.

Organic-inorganic hybrid materials have shown a remarkable and rapid development during the past decade because they can be tailored to obtain new device concepts with controlled physical properties. Here, we report on the electronic and magnetic properties of multilayer organic-inorganic hybrid films. Electrical transport properties arising from the pi electrons in the organic layer are characteristic of a metallic state at high temperature and evolve into a state described by two-dimensional variable range hopping when temperature decreases below 150 K. The intrinsic electronic behavior of the hybrid films was further studied via the optical properties in the IR range. The optical response confirms the metallic character of the hybrid films. In the second part, the magnetic properties are discussed. A long-range ferromagnetic order with an ordering temperature of similar to 1 K is revealed in the Gd-based hybrid film. The Cu-based hybrid film, however, shows more extended ferromagnetic exchange interactions than the Gd-based hybrid LB film.

This paper describes an experimental approach to eliminating the loss of reversibility that surface-bound spiropyrans exhibit when switched with light. Although such fatigue can be controlled in other contexts, on surfaces, the photochromic compounds are held in close proximity to each other and relatively few molecules modulate the properties of a device, leading to a loss of functionality after only a few switching cycles. The switching process was characterized by photoelectron spectroscopy and differences in tunneling currents in the spiropyran and merocyanine forms using eutectic Ga-In. Self-assembled monolayers comprising only the photochromic compounds degraded rapidly, while mixed monolayers with hexanethiol showed different behaviors depending on the relative humidity. Under dry conditions, no chemical degradation was observed and the switching process was reversible over at least 100 cycles. Under humid conditions, no degradation occurred, but the switching process became irreversible. The absence of degradation observed in mixed monolayers is ascribed to the lack of solvation, which increases the barrier to a key bond rotation past the available thermal energy. These results highlight important differences in the contexts in which photochromic compounds are utilized and demonstrate that they can be leveraged to extract device-relevant functionality from surface-bound switches by suppressing fatigue and irreversibility.

WSxC(H) coatings were deposited on single crystal silicon(100) wafers by magnetron co-sputtering and reactive sputtering at various target-substrate distances. Upon increasing the distance, the stoichiometric S/W ratio increases from 0.51 to 1.89. Also, the porosity of coatings gradually augments and a columnar microstructure tends to form. Preferential sulfur resputtering rather than contaminations primarily accounts for the low S/W ratio. TEM reveals randomly oriented WS2(002) platelets in the WSxC coatings when deposited at a large distance, which is supported by XRD. The composite coatings exhibit a decreasing hardness and elastic modulus with increasing target-substrate distance. The triboperformance is strongly affected by the coating composition, the target-substrate distance and the testing environment. Cross-sectional TEM of formed tribofilms reveals an obvious reorientation of WS2(002) basal planes parallel to the plane of sliding, leading to an ultralow friction.

Similar to carbon, germanium exists in various structures such as three-dimensional crystalline germanium and germanene, a two-dimensional germanium atomic layer. Regarding the electronic properties, they are either semiconductors or Dirac semimetals. Here, we report a highly conductive metallic state in thermally annealed germanane (hydrogen-terminated germanene, GeH), which shows a resistivity of similar to 10(-7) Omega.m that is orders of magnitude lower than any other allotrope of germanium. By comparing the resistivity, Raman spectra, and thickness change measured by AFM, we suggest the highly conductive metallic state is associated with the dehydrogenation during heating, which likely transforms germanane thin flakes to multilayer germanene. In addition, weak antilocalization is observed, serving as solid evidence for strong spin-orbit interaction (SOI) in germanane/germanene. Our study opens a possible new route to investigate the electrical transport properties of germanane/germanene, and the large SOI might provide the essential ingredients to access their topological states predicted theoretically.

This study reports on the ultralubricity of a high-temperature resilient nanocomposite WS2/a-C tribocoating. The coefficient of friction of this coating remains at around 0.02 independently of a thermal treatment up to ∼500 °C, as confirmed by high-temperature tribotests. Moreover, the coating annealed at 450 °C keeps exhibiting a similar ultralubricity when cooled back down to room temperature and tested there, implying a tribological self-adaptation over a broad temperature range. High-resolution TEM observations of the tribofilms on the wear track unveil that WS2 nanoplatelets form dynamically via atomic rearrangement and extend via unfaulting geometrical defects (bound by partial climb dislocations). The (002) basal planes of the WS2 nanoplatelets, reoriented parallel to the tribo-sliding direction, contribute to a sustainable ultralubricity. The declining triboperformance beyond 500 °C is associated with sulfur loss rather than the transformation of WS2 into inferior WO3 via oxidation as suggested earlier. This self-adaptive WS2/a-C tribocoating holds promise for a constant ultralubrication with excellent thermal performance.

Poly(3,4-ethylenedioxy thiophene):poly(styrenesulfonate) (PEDOT:PSS) exhibits valuable characteristics concerning stability, green-processing, flexibility, high electrical conductivity, and ease of property modulation, qualifying it as one of the most promising p-type organic conductors for thermoelectric (TE) applications. While blending with inorganic counterparts is considered a good strategy to further improve polymeric TE properties, only a few attempts succeed so far due to inhomogeneous embedding and the non-ideal organic-inorganic contact. Here a new strategy to include nanoparticles (NPs) without any ligand termination inside PEDOT:PSS thin films is proposed. Spark discharge-generated tin oxide NPs (SnOx-NPs) are "gently" and homogenously deposited through low-energy diffusion mode. Strong interaction between naked SnOx-NPs and PSS chains occurs in the topmost layer, causing a structural reorganization towards an improved PEDOT chains crystalline packing at the bottom, providing a positive contribution to the electrical conductivity. Meanwhile, dedoping and energy filtering effect introduced by the SnOx-NPs cause dramatic Seebeck coefficient enhancement. The optimized power factor of 116 mu Wm(-1) K-2 achieved is more than six times higher than the value found for the film without NPs. This easy and efficient strategy promises well for future mass production of flexible TE devices and the mechanism revealed may inspire future research on TEs and flexible electronics.

In the race for viable solutions that could slow down carbon emissions and help in meeting the climate change targets a lot of effort is being made towards the development of suitable CO