Kinetic Modulation of Carbon Nanotube Growth in Direct Spinning for High-Strength Carbon Nanotube Fibers.

With impressive individual properties, carbon nanotubes (CNTs) show great potential in constructing high-performance fibers. However, the tensile strength of as-prepared carbon nanotube fibers (CNTFs) by floating catalyst chemical vapor deposition (FCCVD) is plagued by the weak intertube interaction between the essential CNTs. Here, we developed a chlorine (Cl)/water (H2O)-assisted length furtherance FCCVD (CALF-FCCVD) method to modulate the intertube interaction of CNTs and enhance the mechanical strength of macroscopic fibers. The CNTs acquired by the CALF-FCCVD method show an improvement of 731% in length compared to that by the conventional iron-based FCCVD system. Moreover, CNTFs prepared by CALF-FCCVD spinning exhibit a high tensile strength of 5.27 ± 0.27 GPa (4.62 ± 0.24 N/tex) and reach up to 5.61 GPa (4.92 N/tex), which outperforms most previously reported results. Experimental measurements and density functional theory calculations show that Cl and H2O play a crucial role in the furtherance of CNT growth. Cl released from the decomposition of methylene dichloride greatly accelerates the growth of the CNTs; H2O can remove amorphous carbon on the floating catalysts to extend their lifetime, which further modulates the growth kinetics and improves the purity of the as-prepared fibers. Our design of the CALF-FCCVD platform offers a powerful way to tune CNT growth kinetics in direct spinning toward high-strength CNTFs.

Electronegativity Force Field for Prediction of Elastic Moduli.

Macroscopic elastic moduli (i.e., bulk modulus and shear modulus) of covalent crystals are mainly determined by microscopic structures and stiffnesses. Herein, the microscopic bond and angle force constants of covalent crystals were parameterized from their atomic electronegativities, which is named the electronegativity force field (EFF). Based on this force field, the elastic moduli of covalent crystals can be directly obtained by molecular mechanics calculations. The calculated moduli for various covalent crystals are generally consistent with first-principles calculations, while the computational cost is reduced by several orders of magnitude, indicating the accuracy and efficiency of the EFF. Finally, we found 25 ultrahigh-modulus crystals with a bulk modulus greater than 350 GPa, which demonstrates that this force field can be used for screening of ultrahigh-modulus materials from numerous crystal candidates.

Anisotropic Fracture of Graphene Revealed by Surface Steps on Graphite.

The anisotropic fracture toughness G(θ) is an intrinsic feature of graphene and is fundamental for fabrication, functioning, and robustness of graphene-based devices. However, existing results show significant discrepancies on the anisotropic factor, i.e., the ratio between zigzag (ZZ) and armchair (AC) directions, G_{ZZ}/G_{AC}, both qualitatively and quantitatively. Here, we investigate the anisotropic fracture of graphene by atomic steps on cleaved graphite surfaces. Depending on the relation between the peeling direction and local lattice orientation, two categories of steps with different structures and behaviors are observed. In one category are straight steps well aligned with local ZZ directions, while in the other are steps consisting of nanoscale ZZ and AC segments. Combined with an analysis on fracture mechanics, the microscale morphology of steps and statistics of their directions provides a measurement on the anisotropic factor of G_{ZZ}/G_{AC}=0.971, suggesting that the ZZ direction has a slightly lower fracture toughness. The results provide an experimental benchmark for the widely scattered existing results, and offer constraints on future models of graphene fracture.

Controlled fabrication of gold nanotip arrays by nanomolding-necking technology.

The fabrication of nanotips has been driven by the increasing industrial demands in developing high-performance multifunctional nanodevices. In this work, we proposed a controlled, rapid as well as low cost nanomolding-necking technology to fabricate gold nanotips arrays. The geometries of gold nanotips having cone angle range of ∼28-77° and curvature radii of <5 nm can be prepared by tailoring the diameters of raw nanorods in nanomolding process or modulating the necking temperature. Molecular dynamics simulation reveals that the formation of the nanotip geometry is determined by the interplay between dislocation-based and diffusion-based deformation mechanisms, intrinsically arising from the nonlinear dependence of atom diffusion on temperature and sample size. The good controllability, mass production and low cost of the developed nanomolding-necking technology make it highly promising in developing nanodevices for a wide range of applications, such as probing, sensing, antireflection coating and nanoindentation.

Robust structural superlubricity under gigapascal pressures.

Structural superlubricity (SSL) is a state of contact with no wear and ultralow friction. SSL has been characterized at contact with van der Waals (vdW) layered materials, while its stability under extreme loading conditions has not been assessed. By designing both self-mated and non-self-mated vdW contacts with materials chosen for their high strengths, we report outstanding robustness of SSL under very high pressures in experiments. The incommensurate self-mated vdW contact between graphite interfaces can maintain the state of SSL under a pressure no lower than 9.45 GPa, and the non-self-mated vdW contact between a tungsten tip and graphite substrate remains stable up to 3.74 GPa. Beyond this critical pressure, wear is activated, signaling the breakdown of vdW contacts and SSL. This unexpectedly strong pressure-resistance and wear-free feature of SSL breaks down the picture of progressive wear. Atomistic simulations show that lattice destruction at the vdW contact by pressure-assisted bonding triggers wear through shear-induced tearing of the single-atomic layers. The correlation between the breakdown pressure and material properties shows that the bulk modulus and the first ionization energy are the most relevant factors, indicating the combined structural and electronic effects. Impressively, the breakdown pressures defined by the SSL interface could even exceed the strength of materials in contact, demonstrating the robustness of SSL. These findings offer a fundamental understanding of wear at the vdW contacts and guide the design of SSL-enabled applications.

Carbon nanotube fibers with dynamic strength up to 14 GPa.

High dynamic strength is of fundamental importance for fibrous materials that are used in high-strain rate environments. Carbon nanotube fibers are one of the most promising candidates. Using a strategy to optimize hierarchical structures, we fabricated carbon nanotube fibers with a dynamic strength of 14 gigapascals (GPa) and excellent energy absorption. The dynamic performance of the fibers is attributed to the simultaneous breakage of individual nanotubes and delocalization of impact energy that occurs during the high-strain rate loading process; these behaviors are due to improvements in interfacial interactions, nanotube alignment, and densification therein. This work presents an effective strategy to utilize the strength of individual carbon nanotubes at the macroscale and provides fresh mechanism insights.

Fabricating Ultrastrong Carbon Nanotube Fibers via a Microwave Welding Interface.

Liquid crystal wet-spun carbon nanotube fibers (CNTFs) offer notable advantages, such as precise alignment and scalability. However, these CNTFs usually suffer premature failure through intertube slippage due to the weak interfacial interactions between adjacent shells and bundles. Herein, we present a microwave (MW) welding strategy to enhance intertube interactions by partially carbonizing interstitial heterocyclic aramid polymers. The resulting CNTFs exhibit ultrahigh static tensile strength (6.74 ± 0.34 GPa) and dynamic tensile strength (9.52 ± 1.31 GPa), outperforming other traditional high-performance fibers. This work provides a straightforward yet effective approach to strengthening CNTFs for advanced engineering applications.

Data-driven discovery of ultraincompressible crystals from a universal correlation between bulk modulus and volumetric cohesive energy.

Bulk modulus and cohesive energy are two important quantities of condensed matter. From the interatomic energy landscape, we here derived a correlation between the bulk modulus (B) and the volumetric cohesive energy (ρe), i.e.B= 2(ln2)2ρe/9ϵs2=kρe, whereϵsandkare the strain-to-failure of interatomic bonds and the factor of proportionality, respectively. By analyzing numerous crystals from first principles calculations, it was shown that this correlation is universally applicable to various crystals including simple substances and compounds. Most interestingly, it was found thatϵsof crystals with a similar structure are almost a constant, resulting in a linear relationship betweenBandρe. Furthermore, we found that the value ofkfor any compound can be determined based on the rule of mixtures, i.e.k= ∑xiki, wherexiandkiare the atomic fraction and the factor of proportionality for each element in this compound, respectively. Finally, this correlation was used to predict the bulk moduli for a vast number of crystals with knownρein databases. After first principles verification of the top 50 crystals with the highest predicted bulk modulus, 25 ultraincompressible crystals with a bulk modulus greater than 400 GPa that can rival diamond (436 GPa) were discovered.

Atomic stiffness for bulk modulus prediction and high-throughput screening of ultraincompressible crystals.

Determining bulk moduli is central to high-throughput screening of ultraincompressible materials. However, existing approaches are either too inaccurate or too expensive for general applications, or they are limited to narrow chemistries. Here we define a microscopic quantity to measure the atomic stiffness for each element in the periodic table. Based on this quantity, we derive an analytic formula for bulk modulus prediction. By analyzing numerous crystals from first-principles calculations, this formula shows superior accuracy, efficiency, universality, and interpretability compared to previous empirical/semiempirical formulae and machine learning models. Directed by our formula predictions and verified by first-principles calculations, 47 ultraincompressible crystals rivaling diamond are identified from over one million material candidates, which extends the family of known ultraincompressible crystals. Finally, treasure maps of possible elemental combinations for ultraincompressible crystals are created from our theory. This theory and insights provide guidelines for designing and discovering ultraincompressible crystals of the future.

The Stiffest and Strongest Predicted Material: C2 N Atomic Chains Approach the Theoretical Limits.

Though linear atomic chains exhibit extreme properties, it is presently unclear how these properties can be maximized by the choice of elemental composition. Considering that boron, carbon, and nitrogen can form high modulus and high strength atomic chains, here an algorithm is developed to construct 143 possible atomic chains of these elements with 6 or fewer atoms in the primitive cell and explore their stabilities and mechanical properties by first-principles calculations. It is found that the gravimetric modulus (1032 GPa g-1 cm3 ) and strength (108 GPa g-1 cm3 ) of the C2 N chain significantly exceed those of any known material, including the previously stiffest predicted material (C chain, 945 GPa g-1 cm3 ) and the previously strongest predicted material (BC chain, 92 GPa g-1 cm3 ), and also approach the theoretical limits of gravimetric modulus (1036 GPa g-1 cm3 ) and strength (130 GPa g-1 cm3 ). Mechanistic analyses demonstrate that the higher gravimetric modulus and strength of the C2 N chain, compared with the C and BC chains, originate from its short, stiff chemical bonding and the abnormal decrease in bond length alternation under tension. The likely ease of fabrication and potential synthesis routes for C2 N chains are discussed.

Fabricating strong and tough aramid fibers by small addition of carbon nanotubes.

Synthetic high-performance fibers present excellent mechanical properties and promising applications in the impact protection field. However, fabricating fibers with high strength and high toughness is challenging due to their intrinsic conflicts. Herein, we report a simultaneous improvement in strength, toughness, and modulus of heterocyclic aramid fibers by 26%, 66%, and 13%, respectively, via polymerizing a small amount (0.05 wt%) of short aminated single-walled carbon nanotubes (SWNTs), achieving a tensile strength of 6.44 ± 0.11 GPa, a toughness of 184.0 ± 11.4 MJ m-3, and a Young's modulus of 141.7 ± 4.0 GPa. Mechanism analyses reveal that short aminated SWNTs improve the crystallinity and orientation degree by affecting the structures of heterocyclic aramid chains around SWNTs, and in situ polymerization increases the interfacial interaction therein to promote stress transfer and suppress strain localization. These two effects account for the simultaneous improvement in strength and toughness.

An iron-base oxygen-evolution electrode for high-temperature electrolyzers.

High-temperature molten-salt electrolyzers play a central role in metals, materials and chemicals production for their merit of favorable kinetics. However, a low-cost, long-lasting, and efficient high-temperature oxygen evolution reaction (HT-OER) electrode remains a big challenge. Here we report an iron-base electrode with an in situ formed lithium ferrite scale that provides enhanced stability and catalytic activity in both high-temperature molten carbonate and chloride salts. The finding is stemmed from a discovery of the ionic potential-stability relationship and a basicity modulation principle of oxide films in molten salt. Using the iron-base electrode, we build a kiloampere-scale molten carbonate electrolyzer to efficiently convert CO2 to carbon and oxygen. More broadly, the design principles lay the foundations for exploring cheap, Earth-abundant, and long-lasting HT-OER electrodes for electrochemical devices with molten carbonate and chloride electrolytes.

More Powerful Twistron Carbon Nanotube Yarn Mechanical Energy Harvesters.

Stretching a coiled carbon nanotube (CNT) yarn can provide large, reversible electrochemical capacitance changes, which convert mechanical energy to electricity. Here, it is shown that the performance of these "twistron" harvesters can be increased by optimizing the alignment of precursor CNT forests, plastically stretching the precursor twisted yarn, applying much higher tensile loads during precoiling twist than for coiling, using electrothermal pulse annealing under tension, and incorporating reduced graphene oxide nanoplates. The peak output power for a 1 and a 30 Hz sinusoidal deformation are 0.73 and 3.19 kW kg-1 , respectively, which are 24- and 13-fold that of previous twistron harvesters at these respective frequencies. This performance at 30 Hz is over 12-fold that of other prior-art mechanical energy harvesters for frequencies between 0.1 and 600 Hz. The maximum energy conversion efficiency is 7.2-fold that for previous twistrons. Twistron anode and cathode yarn arrays are stretched 180° out-of-phase by locating them in the negative and positive compressibility directions of hinged wine-rack frames, thereby doubling the output voltage and reducing the input mechanical energy.

Computational Prediction of Superlubric Layered Heterojunctions.

Structural superlubricity has attracted increasing interest in modern tribology. However, experimental identification of superlubric interfaces among the vast number of heterojunctions is a trial-and-error and time-consuming approach. In this work, based on the requirements on the in-plane stiffnesses of layered materials and the interfacial interactions at the sliding incommensurate interfaces of heterojunctions for structural superlubricity, we propose criteria for predicting structural superlubricity between heterojunctions. Based on these criteria, we identify 61 heterojunctions with potential superlubricity features from 208 candidates by screening the data of first-principles calculations. This work provides a universal route for accelerating the discovery of new superlubric heterojunctions.

Generation of atomic hydrogen by Ni-Fe hydroxides: Mechanism and activity for hydrodechlorination of trichloroethylene.

Atomic hydrogen (H•) is highly reactive for the hydrodechlorination of trichloroethylene (TCE). In this work, we found that the coprecipitation of Ni2+ and Fe2+ at neutral pH led to an unprecedented catalytic generation of H•. The generated H• effectively dechlorinate TCE to nontoxic ethylene and ethane, and Fe2+ is the only electron donor. The abundant adsorbed H• produced with a Ni/Fe ratio of 0.4 enhances hydrogen evolution reaction causing a low efficiency for hydrodechlorination. In contrast, the active absorbed H• is generated in the crystal lattice of Ni-Fe hydroxides with a Ni/Fe ratio of 3.0 causing highly efficient hydrodechlorination of TCE. This work not only reveals the mechanism of catalytic hydrodechlorination by Ni-Fe hydroxides at neutral pH, but also provides a novel approach to detoxify TCE in contaminated water using facile precipitated Ni-Fe hydroxides.

Electrochemical reductive remediation of trichloroethylene contaminated groundwater using biomimetic iron-nitrogen-doped carbon.

Electrochemical dechlorination is a prospective strategy to remediate trichloroethylene (TCE)-contaminated groundwater. In this work, iron-nitrogen-doped carbon (FeNC) mimicking microbiological dechlorination coenzymes was developed for TCE removal under environmentally related conditions. The biomimetic FeNC-900, FeNC-1000, and FeNC-1100 materials were synthesized via pyrolysis at different temperatures (900, 1000, and 1100 °C). Due to the synergistic effect of Fe-N4 active sites and graphitic N sites, FeNC-1000 had the highest electron transfer efficiency and the largest electrochemical active surface area among the as-synthesized FeNC catalysts. The pseudo-first-order rate constants for TCE reduction using FeNC-1000 catalyst are 0.19, 0.28 and 0.36 h-1 at potentials of -0.8 V, -1.0 V and -1.2 V, respectively. Active hydrogen and direct electrons transfer both contribute to the dechlorination from TCE to C2H4 and C2H6. FeNC maintain a high reactivity after five reuse cycles. Our study provides a novel approach for the dechlorination of chlorinated organic contaminants in groundwater.

Core-Shell Magnetic Micropillars for Reprogrammable Actuation.

Stimuli-responsive micro/nanostructures that exhibit not only programmable but also reprogrammable actuation behaviors are highly desirable for various advanced engineering applications (e.g., anticounterfeiting, information encoding, dynamic imaging and display, microrobotics, etc.) but yet to be realized with state-of-the-art technologies. Here we report a concept and a corresponding experimental technique for core-shell magnetic micropillars enabling simultaneously programmable and reprogrammable actuations using a simple magnetic field. The micropillars are composed of elastomeric hollow shells for shaping encapsulated with liquid magnetic nanocomposite resin cores for actuating. The spatial distribution of the magnetic nanoparticles inside the resin channels can be dynamically modulated within individual micropillars, which consequently regulates the magnetomechanical responses of the pillars upon actuation (bending deformation varied near 1 order of magnitude under the same actuation field). We demonstrate that the micropillars with contrasting bending responses can be configured in an arbitrary spatial pattern by direct magnetic writing, and the written pattern can then be easily magnetically erased to facilitate next-round rewriting and reconfiguration. This reprogrammable actuation capability of the micropillars is further demonstrated by their potential applications for rewritable paper and recyclable displays, where various microscale characteristics can be controlled to dynamically appear and disappear at the same or different locations of one single micropillar array. The core-shell magnetic micropillars reported here provide a universal prototype for reprogrammable responsive micro/nanostructures through rational design and facile fabrication from conventional materials.

Out-of-Plane Deformations Determined Mechanics of Vanadium Disulfide (VS2) Sheets.

The rapid development of two-dimensional (2D) materials has significantly broadened the scope of 2D science in both fundamental scientific interests and emerging technological applications, wherein the mechanical properties play an indispensably key role. Nevertheless, particularly challenging is the ultrathin nature of 2D materials that makes their manipulations and characterizations considerably difficult. Herein, thanks to the excellent flexibility of vanadium disulfide (VS2) sheets, their susceptibility to out-of-plane deformation is exploited to realize the controllable loading and enable the accurate measurements of mechanical properties. In particular, the Young's modulus is estimated to be 44.4 ± 3.5 GPa, approaching the lower limit for 2D transition metal dichalcogenides (TMDs). We further report the first measurement of thickness-dependent bending rigidity of VS2, which deviates from the prediction of the classical continuum mechanics theory. Additionally, a deeper understanding of the mechanics within two dimensions also facilitates the modulation of strain-coupled physics at the nanoscale. Our Raman measurements showed the Grüneisen parameters for VS2 were determined for the first time to be γE2g1 ≈ 0.83 and γA1g ≈ 0.32.

Predicted Confinement-Enhanced Stability and Extraordinary Mechanical Properties for Carbon Nanotube Wrapped Chains of Linear Carbon.

The demand for high-modulus, high-strength, lightweight materials has continuously driven the bottom-up assembly of carbon nanostructures into high-performance bulk carbon materials, such as graphene sheets and carbon nanotube yarns. Carbyne, often called linear carbon, has a higher predicted gravimetric modulus and gravimetric strength than any other form of carbon, but possibly reacts under near-ambient conditions because of the extended sp1 hybridization. The successful fabrication of carbon nanotube wrapped single carbyne chain (Shi et al. Nat. Mater. 2016, 15, 634) suggests the possibility of carbyne's bulk production. Herein, we designed a type of carbon assembly that includes a possibly large array of carbyne chains confined within a single-walled nanotube sheath (nanotube wrapped carbynes, NTWCs), in which carbyne chains act as reinforcing building blocks, and the carbon nanotube sheath protects the multiple carbyne chains against chemical or topochemical reaction. We showed that NTWCs exhibit confinement-enhanced stabilities, even when they contain multiple neighboring carbyne chains. We developed a mechanics model for exploring the mechanical properties of NTWCs. On the basis of this model, the gravimetric modulus (and strength) of NTWCs was predicted to increase from 356.4 (50.25) to 977.2 GPa·g-1·cm3 (71.20 GPa·g-1·cm3) as the mass ratio of carbyne carbons to sheath carbons increases, which is supported by atomistic simulations. The highest calculated gravimetric modulus and strength of NTWCs are 174.2% and 41.7%, respectively, higher than those of either graphene or carbon nanotubes. The corresponding highest values of engineering modulus and strength of NTWCs with a density of 1.54 g·cm-3 are 1505 and 109.6 GPa, respectively. Hence, NTWCs are promising for uses in high-modulus, high-strength, lightweight composites.