Self-healing of fractured diamond.

Materials that possess the ability to self-heal cracks at room temperature, akin to living organisms, are highly sought after. However, achieving crack self-healing in inorganic materials, particularly with covalent bonds, presents a great challenge and often necessitates high temperatures and considerable atomic diffusion. Here we conducted a quantitative evaluation of the room-temperature self-healing behaviour of a fractured nanotwinned diamond composite, revealing that the self-healing properties of the composite stem from both the formation of nanoscale diamond osteoblasts comprising sp2- and sp3-hybridized carbon atoms at the fractured surfaces, and the atomic interaction transition from repulsion to attraction when the two fractured surfaces come into close proximity. The self-healing process resulted in a remarkable recovery of approximately 34% in tensile strength for the nanotwinned diamond composite. This discovery sheds light on the self-healing capability of nanostructured diamond, offering valuable insights for future research endeavours aimed at enhancing the toughness and durability of brittle ceramic materials.

Stabilizing Single-Atomic Pt by Forming PtFe Bonds for Efficient Diboration of Alkynes.

Precisely tailoring the oxidation state of single-atomic metal in heterogeneous catalysis is an efficient way to stabilize the single-atomic site and promote their activity, but realizing this approach remains a grand challenge to date. Herein, a class of stable single-atomic catalysts with well-tuned oxidation state of Pt by forming PtFe atomic bonds is reported, which are supported by defective Fe2 O3  nanosheets on reduced graphene oxide (PFARFNs). These as-synthesized materials can greatly enhance the catalytic activity, stability, and selectivity for the diboration of alkynes. The PFARFNs exhibit high conversion of 99% at 100 °C with an outstanding turnover frequency (TOF) of 545 h-1 , and a relatively high conversion of 58% at room temperature (25 °C) with a TOF of 310 h-1 , which has been hardly achieved previously. Through both experimental and theoretical investigation, it is demonstrated that the fast electron transfer from Fe to Pt in Fe-Pt-O atomic sites in PFARFNs can not only stabilize the single-atomic Pt, but also significantly improve their catalytic activity.

Multiscale engineered artificial tooth enamel.

Tooth enamel, renowned for its high stiffness, hardness, and viscoelasticity, is an ideal model for designing biomimetic materials, but accurate replication of complex hierarchical organization of high-performance biomaterials in scalable abiological composites is challenging. We engineered an enamel analog with the essential hierarchical structure at multiple scales through assembly of amorphous intergranular phase (AIP)-coated hydroxyapatite nanowires intertwined with polyvinyl alcohol. The nanocomposite simultaneously exhibited high stiffness, hardness, strength, viscoelasticity, and toughness, exceeding the properties of enamel and previously manufactured bulk enamel-inspired materials. The presence of AIP, polymer confinement, and strong interfacial adhesion are all needed for high mechanical performance. This multiscale design is suitable for scalable production of high-performance materials.

Strong structural occupation ratio effect on mechanical properties of silicon carbide nanowires.

Materials' mechanical properties highly depend on their internal structures. Designing novel structure is an effective route to improve materials' performance. One-dimensional disordered (ODD) structure is a kind of particular structure in silicon carbide (SiC), which highly affects its mechanical properties. Herein, we show that SiC nanowires (NWs) containing ODD structure (with an occupation ratio of 32.6%) exhibit ultrahigh tensile strength and elastic strain, which are up to 13.7 GPa and 12% respectively, approaching the ideal theoretical limit. The ODD structural occupation ratio effect on mechanical properties of SiC NWs has been systematically studied and a saddle shaped tendency for the strength versus occupation ratio is firstly revealed. The strength increases with the increase of the ODD occupation ratio but decreases when the occupation ratio exceeds a critical value of ~ 32.6%, micro twins appear in the ODD region when the ODD segment increases and soften the ODD segment, finally results in a decrease of the strength.

Hierarchically structured diamond composite with exceptional toughness.

The well known trade-off between hardness and toughness (resistance to fracture) makes simultaneous improvement of both properties challenging, especially in diamond. The hardness of diamond can be increased through nanostructuring strategies1,2, among which the formation of high-density nanoscale twins - crystalline regions related by symmetry - also toughens diamond2. In materials other than diamond, there are several other promising approaches to enhancing toughness in addition to nanotwinning3, such as bio-inspired laminated composite toughening4-7, transformation toughening8 and dual-phase toughening9, but there has been little research into such approaches in diamond. Here we report the structural characterization of a diamond composite hierarchically assembled with coherently interfaced diamond polytypes (different stacking sequences), interwoven nanotwins and interlocked nanograins. The architecture of the composite enhances toughness more than nanotwinning alone, without sacrificing hardness. Single-edge notched beam tests yield a toughness up to five times that of synthetic diamond10, even greater than that of magnesium alloys. When fracture occurs, a crack propagates through diamond nanotwins of the 3C (cubic) polytype along {111} planes, via a zigzag path. As the crack encounters regions of non-3C polytypes, its propagation is diffused into sinuous fractures, with local transformation into 3C diamond near the fracture surfaces. Both processes dissipate strain energy, thereby enhancing toughness. This work could prove useful in making superhard materials and engineering ceramics. By using structural architecture with synergetic effects of hardening and toughening, the trade-off between hardness and toughness may eventually be surmounted.

Hierarchical Nanoassembly of MoS2/Co9S8/Ni3S2/Ni as a Highly Efficient Electrocatalyst for Overall Water Splitting in a Wide pH Range.

The design of low-cost yet high-efficiency electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) over a wide pH range is highly challenging. We now report a hierarchical co-assembly of interacting MoS2 and Co9S8 nanosheets attached on Ni3S2 nanorod arrays which are supported on nickel foam (NF). This tiered structure endows high performance toward HER and OER over a very broad pH range. By adjusting the molar ratio of the Co:Mo precursors, we have created CoMoNiS-NF- xy composites ( x: y means Co:Mo molar ratios ranging from 5:1 to 1:3) with controllable morphology and composition. The three-dimensional composites have an abundance of active sites capable of universal pH catalytic HER and OER activity. The CoMoNiS-NF-31 demonstrates the best electrocatalytic activity, giving ultralow overpotentials (113, 103, and 117 mV for HER and 166, 228, and 405 mV for OER) to achieve a current density of 10 mA cm-2 in alkaline, acidic, and neutral electrolytes, respectively. It also shows a remarkable balance between electrocatalytic activity and stability. Based on the distinguished catalytic performance of CoMoNiS-NF-31 toward HER and OER, we demonstrate a two-electrode electrolyzer performing water electrolysis over a wide pH range, with low cell voltages of 1.54, 1.45, and 1.80 V at 10 mA cm-2 in alkaline, acidic, and neutral media, respectively. First-principles calculations suggest that the high OER activity arises from electron transfer from Co9S8 to MoS2 at the interface, which alters the binding energies of adsorbed species and decreases overpotentials. Our results demonstrate that hierarchical metal sulfides can serve as highly efficient all-pH (pH = 0-14) electrocatalysts for overall water splitting.

Room-temperature superplasticity in Au nanowires and their atomistic mechanisms.

We report experimental observation of room-temperature superplasticity and the distinct nanosize effect on the deformation mechanisms of Au nanowires. The Au nanowires were subjected to in situ tensile straining in a transmission electron microscope by using a home-made strain actuator, and a super large plastic strain with ∼150% uniform elongation and ∼260% total strain were observed before fracture. The plastic deformation started through full dislocation slip and was followed by the activities of stacking fault ribbons (or dissociated full dislocations) that were generated from surface sources and disappeared at the other end surfaces. With the reduction of the diameter of Au nanowires, the deformation changed to the twinning mode through partial dislocation emissions from sample surfaces. The mechanisms behind the observed phenomena are discussed in detail. These results shed light on the size-controlled plasticity of nano-metals.

Dual-Phase Super-Strong and Elastic Ceramic.

Ceramic materials exhibit very high stiffness and extraordinary strength, but they typically suffer from brittleness. Amorphization and size confinement are commonly used to reinforce materials. However, the inverse Hall-Petch effect and the shear-band softening effect usually limit further improvement of their performance under a critical size. With an optimum structure design, we demonstrate that dual-phase zirconia nanowires (DP-ZrO2 NWs) with nanocrystals embedded in an amorphous matrix as a strengthening phase can overcome these problems simultaneously. As a result of this structure, in situ tensile tests demonstrate that the mechanical properties have been enormously improved in a way that does not follow both the inverse Hall-Petch effect and the shear band softening effect. The elastic strain approaches ∼7%, and the ultimate strength is 3.52 GPa, accompanied by a high toughness of ∼151 MJ m-3, making the DP-ZrO2 NW composite the strongest and toughest ZrO2 ever achieved. The findings provide a way to improve the mechanical properties of ceramics in a controllable manner, which may serve as a pervasive approach to be broadly applied to a variety of materials.

Effects of twin orientation and spacing on the mechanical properties of Cu nanowires.

The role of twin orientation in mechanical behaviors of nanomaterials is drawing increasing attention. In this paper, atomistic simulations on the tensile deformation of twinned Cu nanowires (NWs) are implemented to investigate the twin orientation and spacing effects. The results of numerical simulations reveal that the tensile deformation mechanisms can be divided into three types with the twin orientation varying from 0° to 90°: dislocations slip intersecting with twin boundary (TB), stacking faults formed parallel to the TB and TB migration. Detail analysis about dislocation motion is carried out to illustrate the plastic deformation mechanisms. In addition, with the increasing of the TB spacing, there is a transition from yield with strain hardening to yield with nearly constant flow stress. The peak stress decreases with the increase of TB spacing, which can be attributed to surface roughness caused by crystal reorientation. Our findings also suggest a possible approach to tune the mechanical behaviors of low dimensional nanostructures.

Sub-1 nm Nanowire Based Superlattice Showing High Strength and Low Modulus.

Polymers possess special dimension-dependent processing flexibility which is always absent in inorganic materials. Traditional inorganic nanowires own similar dimensions to polymers, but usually lack near-molecular diameters and the related properties. Here we report that inorganic nanowires with sub1 nm diameter and microscale length can be electrospinningly processed into superstructures including smooth fibers and large-area mat by tuning the viscosity and surface tension of the colloidal nanowires solution. These superstructures have shown both flexible texture and excellent mechanical properties (712.5 MPa for tensile strength, 10.3 GPa for elastic modulus) while retaining properties arising from inorganic components.

In Situ Observation of Twin Boundary Sliding in Single Crystalline Cu Nanowires.

Using a homemade, novel, in situ transmission electron microscopy (TEM) double tilt tensile device, plastic behavior of single crystalline Cu nanowires of around 150 nm are studied. Deformation twins occur during the tests as predesigned before the experiments. In situ observation of twin boundary sliding (TBS) caused by full dislocation (extended dislocation) is first revealed at the atomic scale which is confirmed by molecular dynamics (MD) simulation results. Combined with twin boundary migration and multiple dislocations nucleated from surface, TBS causes a superlarge fracture strain which is over 166% and a severe necking which is over 93%, far beyond the typical values for most nanomaterials without twins.

A General Bioinspired, Metals-Based Synergic Cross-Linking Strategy toward Mechanically Enhanced Materials.

Creating lightweight engineering materials combining high strength and great toughness remains a significant challenge. Despite possessing-enhanced strength and stiffness, bioinspired/polymeric materials usually suffer from clearly reduced extensibility and toughness when compared to corresponding bulk polymer materials. Herein, inspired by tiny amounts of various inorganic impurities for mechanical improvement in natural materials, we present a versatile and effective metal ion (Mn+)-based synergic cross-linking (MSC) strategy incorporating eight types of metal ions into material bulks that can drastically enhance the tensile strength (∼24.1-70.8%), toughness (∼18.6-110.1%), modulus (∼21.6-66.7%), and hardness (∼6.4-176.5%) of multiple types of pristine materials (from hydrophilic to hydrophobic and from unary to binary). More importantly, we also explore the primarily elastic-plastic deformation mechanism and brittle fracture behavior (indentation strain of >5%) of the synergic cross-linked graphene oxide (Syn-GO) paper by means of in situ nanoindentation SEM. The MSC strategy for mechanically enhanced integration can be readily attributed to the formation of the complicated metals-based cross-linking/complex networks in the interfaces and intermolecules between functional groups of materials and various metal ions that give rise to efficient energy dissipation. This work suggests a promising MSC strategy for designing advanced materials with outstanding mechanical properties by adding low amounts (<1.0 wt %) of synergic metal ions serving as synergic ion-bonding cross-linkers.

Ca2+ Enhanced Nacre-Inspired Montmorillonite-Alginate Film with Superior Mechanical, Transparent, Fire Retardancy, and Shape Memory Properties.

Inspired by nacre, this is the first time that using the cross-linking of alginate with Ca ions to fabricate organic-inorganic nacre-inspired films we have successfully prepared a new class of Ca2+ ion enhanced montmorillonite (MMT)-alginate (ALG) composites, realizing an optimum combination of high strength (∼280 MPa) and high toughness (∼7.2 MJ m-3) compared with other MMT based artificial nacre. Furthermore, high temperature performance of the composites (with a maximum strength of ∼170 MPa at 100 °C) along with excellent transmittance, fire retardancy, and unique shape memory response to alcohols could greatly expand the application of the mutilfunctional composites, which are believed to show competitive advantages in transportion, construction, and insulations, protection of a flammable biological material, etc.

Atomic scale observation of oxygen delivery during silver-oxygen nanoparticle catalysed oxidation of carbon nanotubes.

To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars-van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes.

Study of the Mechanical Behavior of Radially Grown Fivefold Twinned Nanowires on the Atomic Scale.

In situ bending tests and dynamic modeling simulations are for the first time revealing the mechanical behavior of copper nanowires (NW) with radially grown fivefold twin structures on the atomic scale. Combining the simulations with the experimental results it is shown that both the twin boundaries (TBs) and the twin center act as dislocation sources. TB migration and L-locks are readily observed in these types of radially grown fivefold-twin structures.

Cloning Nacre's 3D Interlocking Skeleton in Engineering Composites to Achieve Exceptional Mechanical Properties.

Ceramic/polymer composite equipped with 3D interlocking skeleton (3D IL) is developed through a simple freeze-casting method, exhibiting exceptionally light weight, high strength, toughness, and shock resistance. Long-range crack energy dissipation enabled by 3D interlocking structure is considered as the primary reinforcing mechanism for such superior properties. The smart composite design strategy should hold a place in developing future structural engineering materials.

Strong and Tough Layered Nanocomposites with Buried Interfaces.

In nacre, the excellent mechanical properties of materials are highly dependent on their intricate hierarchical structures. However, strengthening and toughening effects induced by the buried inorganic-organic interfaces actually originate from various minerals/ions with small amounts, and have not drawn enough attention yet. Herein, we present a typical class of artificial nacres, fabricated by graphene oxide (GO) nanosheets, carboxymethylcellulose (CMC) polymer, and multivalent cationic (M(n+)) ions, in which the M(n+) ions cross-linking with plenty of oxygen-containing groups serve as the reinforcing "evocator", working together with other cooperative interactions (e.g., hydrogen (H)-bonding) to strengthen the GO/CMC interfaces. When compared with the pristine GO/CMC paper, the cross-linking strategies dramatically reinforce the mechanical properties of our artificial nacres. This special reinforcing effect opens a promising route to strengthen and toughen materials to be applied in aerospace, tissue engineering, and wearable electronic devices, which also has implication for better understanding of the role of these minerals/ions in natural materials for the mechanical improvement.

Ternary Artificial Nacre Reinforced by Ultrathin Amorphous Alumina with Exceptional Mechanical Properties.

A novel ternary artificial nacre is developed through a vacuum-assisted filtration method, with reinforced ultrathin amorphous alumina that is grown in situ on the surface of GO. This ternary artificial nacre simultaneously shows exceptional strength and toughness, which have, up to now, been considered to be mutually exclusive. This novel material will play a role in the structuring of future materials.

Binary Synergy Strengthening and Toughening of Bio-Inspired Nacre-like Graphene Oxide/Sodium Alginate Composite Paper.

A crucial requirement for most engineering materials is the excellent balance of strength and toughness. By mimicking the hybrid hierarchical structure in nacre, a kind of nacre-like paper based on binary hybrid graphene oxide (GO)/sodium alginate (SA) building blocks has been successfully fabricated. Systematic evaluation for the mechanical property in different (dry/wet) environment/after thermal annealing shows a perfect combination of high strength and toughness. Both of the parameters are nearly many-times higher than those of similar materials because of the synergistic strengthening/toughening enhancement from the binary GO/SA hybrids. The successful fabrication route offers an excellent approach to design advanced strong integrated nacre-like composite materials, which can be applied in tissue engineering, protection, aerospace, and permeable membranes for separation and delivery.

Synthesis of concave gold nanocuboids with high-index facets and their enhanced catalytic activity.

Novel concave gold nanocuboids bounded by 24 high-index {611} facets are synthesized using the seed-mediated growth method via an overgrowth mechanism. The as-synthesized products demonstrated greatly enhanced catalytic activity for the electro-oxidation of glucose and the reduction of 4-nitrothiophenol (4-NTP) under a laser.