3D microprinting of inorganic porous materials by chemical linking-induced solidification of nanocrystals.

Three-dimensional (3D) microprinting is considered a next-generation manufacturing process for the production of microscale components; however, the narrow range of suitable materials, which include mainly polymers, is a critical issue that limits the application of this process to functional inorganic materials. Herein, we develop a generalised microscale 3D printing method for the production of purely inorganic nanocrystal-based porous materials. Our process is designed to solidify all-inorganic nanocrystals via immediate dispersibility control and surface linking-induced interconnection in the nonsolvent linker bath and thereby creates multibranched gel networks. The process works with various inorganic materials, including metals, semiconductors, magnets, oxides, and multi-materials, not requiring organic binders or stereolithographic equipment. Filaments with a diameter of sub-10 µm are printed into designed complex 3D microarchitectures, which exhibit full nanocrystal functionality and high specific surface areas as well as hierarchical porous structures. This approach provides the platform technology for designing functional inorganics-based porous materials.

Multifunctional Macroassembled Graphene Nanofilms with High Crystallinity.

A "cooling-contraction" method to separate large-area (up to 4.2 cm in lateral size) graphene oxide (GO)-assembled films (of nanoscale thickness) from substrates is reported. Heat treatment at 3000 °C of such free-standing macroscale films yields highly crystalline "macroassembled graphene nanofilms" (nMAGs) with 16-48 nm thickness. These nMAGs present tensile strength of 5.5-11.3 GPa (with ≈3 µm gauge length), electrical conductivity of 1.8-2.1 MS m-1 , thermal conductivity of 2027-2820 W m-1 K-1 , and carrier relaxation time up to ≈23 ps. As a demonstration application, an nMAG-based sound-generator shows a 30 µs response and sound pressure level of 89 dB at 1 W cm-2 . A THz metasurface fabricated from nMAG has a light response of 8.2% for 0.159 W mm-2 and can detect down to 0.01 ppm of glucose. The approach provides a straightforward way to form highly crystallized graphene nanofilms from low-cost GO sheets.

A general approach to composites containing nonmetallic fillers and liquid gallium.

We report a versatile method to make liquid metal composites by vigorously mixing gallium (Ga) with non-metallic particles of graphene oxide (G-O), graphite, diamond, and silicon carbide that display either paste or putty-like behavior depending on the volume fraction. Unlike Ga, the putty-like mixtures can be kneaded and rolled on any surface without leaving residue. By changing temperature, these materials can be stiffened, softened, and, for the G-O-containing composite, even made porous. The gallium putty (GalP) containing reduced G-O (rG-O) has excellent electromagnetic interference shielding effectiveness. GalP with diamond filler has excellent thermal conductivity and heat transfer superior to a commercial liquid metal-based thermal paste. Composites can also be formed from eutectic alloys of Ga including Ga-In (EGaIn), Ga-Sn (EGaSn), and Ga-In-Sn (EGaInSn or Galinstan). The versatility of our approach allows a variety of fillers to be incorporated in liquid metals, potentially allowing filler-specific "fit for purpose" materials.

Gram-scale synthesis of alkoxide-derived nitrogen-doped carbon foam as a support for Fe-N-C electrocatalysts.

Non-platinum group metal (non-PGM) catalysts for the oxygen reduction reaction (ORR) are set to reduce the cost of polymer electrolyte membrane fuel cells (PEFCs) by replacing platinum at the cathode. We previously developed unique nitrogen-doped carbon foams by template-free pyrolysis of alkoxide powders synthesized using a high temperature and high pressure solvothermal reaction. These were shown to be effective ORR electrocatalysts in alkaline media. Here, we present a new optimised synthesis protocol which is carried out at ambient temperature and pressure, enabling us to safely increase the batch size to 2 g, increase the yield by 60%, increase the specific surface area to 1866 m2 g-1, and control the nitrogen content (between 1.0 and 5.2 at%). These optimized nitrogen-doped carbon foams are then utilized as effective supports for Fe-N-C catalysts for the ORR in acid media, whilst multiphysics modelling is used to gain insight into the electrochemical performance. This work highlights the importance of the properties of the carbon support in the design of Pt-free electrocatalysts.

Ultrastiff, Strong, and Highly Thermally Conductive Crystalline Graphitic Films with Mixed Stacking Order.

A macroscopic film (2.5 cm × 2.5 cm) made by layer-by-layer assembly of 100 single-layer polycrystalline graphene films is reported. The graphene layers are transferred and stacked one by one using a wet process that leads to layer defects and interstitial contamination. Heat-treatment of the sample up to 2800 °C results in the removal of interstitial contaminants and the healing of graphene layer defects. The resulting stacked graphene sample is a freestanding film with near-perfect in-plane crystallinity but a mixed stacking order through the thickness, which separates it from all existing carbon materials. Macroscale tensile tests yields maximum values of 62 GPa for the Young's modulus and 0.70 GPa for the fracture strength, significantly higher than has been reported for any other macroscale carbon films; microscale tensile tests yield maximum values of 290 GPa for the Young's modulus and 5.8 GPa for the fracture strength. The measured in-plane thermal conductivity is exceptionally high, 2292 ± 159 W m-1 K-1 while in-plane electrical conductivity is 2.2 × 105 S m-1 . The high performance of these films is attributed to the combination of the high in-plane crystalline order and unique stacking configuration through the thickness.

Efficient Metal-Free Electrocatalysts from N-Doped Carbon Nanomaterials: Mono-Doping and Co-Doping.

N-doped carbon nanomaterials have rapidly grown as the most important metal-free catalysts in a wide range of chemical and electrochemical reactions. This current report summarizes the latest advances in N-doped carbon electrocatalysts prepared by N mono-doping and co-doping with other heteroatoms. The structure-performance relationship of these materials is subsequently rationalized and perspectives on developing more efficient and sustainable electrocatalysts from carbon nanomaterials are also suggested.

Colossal grain growth yields single-crystal metal foils by contact-free annealing.

Single-crystal metals have distinctive properties owing to the absence of grain boundaries and strong anisotropy. Commercial single-crystal metals are usually synthesized by bulk crystal growth or by deposition of thin films onto substrates, and they are expensive and small. We prepared extremely large single-crystal metal foils by "contact-free annealing" from commercial polycrystalline foils. The colossal grain growth (up to 32 square centimeters) is achieved by minimizing contact stresses, resulting in a preferred in-plane and out-of-plane crystal orientation, and is driven by surface energy minimization during the rotation of the crystal lattice followed by "consumption" of neighboring grains. Industrial-scale production of single-crystal metal foils is possible as a result of this discovery.

Folding Large Graphene-on-Polymer Films Yields Laminated Composites with Enhanced Mechanical Performance.

A folding technique is reported to incorporate large-area monolayer graphene films in polymer composites for mechanical reinforcement. Compared with the classic stacking method, the folding strategy results in further stiffening, strengthening, and toughening of the composite. By using a water-air-interface-facilitated procedure, an A5-size 400 nm thin polycarbonate (PC) film is folded in half 10 times to a ≈0.4 mm thick material (1024 layers). A large PC/graphene film is also folded by the same process, resulting in a composite with graphene distributed uniformly. A three-point bending test is performed to study the mechanical performance of the composites. With a low volume fraction of graphene (0.085%), the Young's modulus, strength, and toughness modulus are enhanced in the folded composite by an average of 73.5%, 73.2%, and 59.1%, respectively, versus the pristine stacked polymer films, or 40.2%, 38.5%, and 37.3% versus the folded polymer film, proving a remarkable mechanical reinforcement from the combined folding and reinforcement of graphene. These results are rationalized with combined theoretical and computational analyses, which also allow the synergistic behavior between the reinforcement and folding to be quantified. The folding approach could be extended/applied to other 2D nanomaterials to design and make macroscale laminated composites with enhanced mechanical properties.

Controlled Folding of Single Crystal Graphene.

Folded graphene in which two layers are stacked with a twist angle between them has been predicted to exhibit unique electronic, thermal, and magnetic properties. We report the folding of a single crystal monolayer graphene film grown on a Cu(111) substrate by using a tailored substrate having a hydrophobic region and a hydrophilic region. Controlled film delamination from the hydrophilic region was used to prepare macroscopic folded graphene with good uniformity on the millimeter scale. This process was used to create many folded sheets each with a defined twist angle between the two sheets. By identifying the original lattice orientation of the monolayer graphene on Cu foil, or establishing the relation between the fold angle and twist angle, this folding technique allows for the preparation of twisted bilayer graphene films with defined stacking orientations and may also be extended to create folded structures of other two-dimensional nanomaterials.

Graphene Coatings as Barrier Layers to Prevent the Water-Induced Corrosion of Silicate Glass.

Corrosion-protective coatings for silicate glass based on the transfer of one or two layers of graphene grown on copper by chemical vapor deposition have been demonstrated. The effectiveness of graphene to act as a glass corrosion inhibitor was evaluated by water immersion testing. After 120 days of immersion in water, bare glass samples had a significant increase in surface roughness and defects, which resulted in a marked reduction in fracture strength. In contrast, the single- and double-layer graphene-coated glasses experienced negligible changes in both fracture strength and surface roughness. The anticorrosion mechanism was also studied.

Graphitized silicon carbide microbeams: wafer-level, self-aligned graphene on silicon wafers.

Currently proven methods that are used to obtain devices with high-quality graphene on silicon wafers involve the transfer of graphene flakes from a growth substrate, resulting in fundamental limitations for large-scale device fabrication. Moreover, the complex three-dimensional structures of interest for microelectromechanical and nanoelectromechanical systems are hardly compatible with such transfer processes. Here, we introduce a methodology for obtaining thousands of microbeams, made of graphitized silicon carbide on silicon, through a site-selective and wafer-scale approach. A Ni-Cu alloy catalyst mediates a self-aligned graphitization on prepatterned SiC microstructures at a temperature that is compatible with silicon technologies. The graphene nanocoating leads to a dramatically enhanced electrical conductivity, which elevates this approach to an ideal method for the replacement of conductive metal films in silicon carbide-based MEMS and NEMS devices.

Selective, cytotoxic organoruthenium(II) full-sandwich complexes: a structural, computational and in vitro biological study.

A structurally diverse range of lipophilic, cationic η(6)-arene η(5)-cyclopentadienyl (η(5)-Cp*) full-sandwich complexes of ruthenium(II) have been prepared and structurally characterized by Fourier-transform IR and NMR spectroscopy, electrospray mass spectrometry, and elemental microanalyses. Computational experiments incorporating the Hartree-Fock theory and the second-order Møller-Plesset perturbation theory predict each complex to possess a uniform δ+ electrostatic potential, with the cationic charge of the [RuCp*](+) moiety completely delocalizing throughout the molecular structure of each metallocene. In vitro cytotoxicity studies demonstrate these delocalized lipophilic cations to be potent growth inhibitors of eleven unique tumorigenic cell lines, while exhibiting significantly lower levels of toxicity towards both a normal human fibroblast and a mouse macrophage cell line. Single-crystal X-ray structural determinations are additionally reported for five complexes, [Ru(η(6)-C(6)H(5)(CH(2))(2)CH(3))(η(5)-C(5)(CH(3))(5))]BPh(4), [Ru(η(6)-C(6)H(5)CO(2)CH(2)CH(3))(η(5)-C(5)(CH(3))(5))]BF(4), [Ru(η(6)-C(10)H(8))(η(5)-(5) (CH(3))(5))]BPh(4), [Ru(η(6)-C(14)H(10))(η(5)-C(5)(CH(3))(5))]BPh(4), and [Ru(η(6)-C(16)H(10))(η(5)-C(5)(CH(3))(5))]BPh(4).

Different approaches for evaluating exponentially weighted nonequilibrium relations.

The Kawasaki identity (KI) and the Jarzynski equality (JE) are important nonequilibrium relations. Both of these relations take the form of an ensemble average of an exponential function and can exhibit convergence problems when the average of the exponent differs greatly from the log of the average of the exponential function. In this work, we re-express these relations so that only selected regions need to be evaluated in an attempt to avoid these convergence issues. In the context of measuring free energies, we compare our method to the JE and the literature standard approach, the maximum likelihood estimator (MLE), and show that in a system with asymmetric work distributions it can perform as well as the MLE. For the KI, we derive an analog to the MLE to compare with our relation and show that these two new relations improve on the KI and are complimentary to each other.