Elucidating the Bioinspired Synthesis Process of Magnetosomes-Like Fe3O4 Nanoparticles.

Iron oxide nanoparticles are a kind of important biomedical nanomaterials. Although their industrial-scale production can be realized by the conventional coprecipitation method, the controllability of their size and morphology remains a huge challenge. In this study, a kind of synthetic polypeptide Mms6-28 which mimics the magnetosome protein Mms6 is used for the bioinspired synthesis of Fe3O4 nanoparticles (NPs). Magnetosomes-like Fe3O4 NPs with uniform size, cubooctahedral shape, and smooth crystal surfaces are synthesized via a partial oxidation process. The Mms6-28 polypeptides play an important role by binding with iron ions and forming nucleation templates and are also preferably attached to the [100] and [111] crystal planes to induce the formation of uniform cubooctahedral Fe3O4 NPs. The continuous release and oxidation of Fe2+ from pre-formed Fe2+-rich precursors within the Mms6-28-based template make the reaction much controllable. The study affords new insights into the bioinspired- and bio-synthesis mechanism of magnetosomes.

Single Carbon Vacancy Traps Atomic Platinum for Hydrogen Evolution Catalysis.

The coordinated configuration of atomic platinum (Pt) has always been identified as an active site with high intrinsic activity for hydrogen evolution reaction (HER). Herein, we purposely synthesize single vacancies in a carbon matrix (defective graphene) that can trap atomic Pt to form the Pt-C3 configuration, which gives exceptionally high reactivity for HER in both acidic and alkaline solutions. The intrinsic activity of Pt-C3 site is valued with a turnover frequency (TOF) of 26.41 s-1 and mass activity of 26.05 A g-1 at 100 mV, respectively, which are both nearly 18 times higher than those of commercial 20 wt % Pt/C. It is revealed that the optimal coordination Pt-C3 has a stronger electron-capture ability and lower Gibbs free energy difference (ΔG), resulting in promoting the reduction of adsorbed H+ and the acceleration of H2 desorption, thus exhibiting the extraordinary HER activity. This work provides a new insight on the unique coordinated configuration of dispersive atomic Pt in defective C matrix for superior HER performance.

A medium-range structure motif linking amorphous and crystalline states.

Amorphous materials have no long-range order, but there are ordered structures at short range (2-5 Å), medium range (5-20 Å) and even longer length scales1-5. While regular6,7 and semiregular polyhedra8-10 are often found as short-range ordering in amorphous materials, the nature of medium-range order has remained elusive11-14. Consequently, it is difficult to determine whether there exists any structural link at medium range or longer length scales between the amorphous material and its crystalline counterparts. Moreover, an amorphous material often crystallizes into a phase of different composition15, with very different underlying structural building blocks, further compounding the issue. Here, we capture an intermediate crystalline cubic phase in a Pd-Ni-P amorphous alloy and reveal the structure of the medium-range order, a six-membered tricapped trigonal prism cluster (6M-TTP) with a length scale of 12.5 Å. We find that the 6M-TTP can pack periodically to several tens of nanometres to form the cube phase. Our experimental observations provide evidence of a structural link between the amorphous and crystalline phases in a Pd-Ni-P alloy at the medium-range length scale and suggest that it is the connectivity of the 6M-TTP clusters that distinguishes the crystalline and amorphous phases. These findings will shed light on the structure of amorphous materials at extended length scales beyond that of short-range order.

Breaking Material Property Trade-offs via Macrodesign of Microstructure.

Many properties of materials are incompatible with each other or even completely exclusive. Here, we proposed a new concept in view of the trade-off paradox of material properties, which is to macrodirectionally design the microstructure of materials according to their specific service requirements to accurately use the properties of materials to the extreme. By using this concept, we successfully solved the paradox of high strength and high conductivity of copper contact wire in a high-speed train. Our concept can be used to solve the other property paradoxes of functional and structural materials.

Revealing Solute Clusters in Coalescence by Atom Probe Tomography Analysis.

Experimentally revealing dynamic evolution and growth behavior of small solute clusters in alloys remains a technical challenge. To date, the coalescence of the solute clusters has seldom been experimentally addressed. To address the challenge, we used atom probe tomography (APT) to access boundary information of solute clusters and identify those in close contact. By systematically investigating the population and size evolution of the clusters in close contact with aging time, we unveiled important information regarding the clusters in coalescence with the exsitu experimental technique. In this work, the maximum separation method was employed to identify clusters in APT datasets of naturally aged Al­Zn­Mg alloy. Coalescence was found to significantly contribute to the growth of small clusters and remained predominant for the formation and growth of large Guinier­Preston II ${\rm \lpar G}{\rm P}_{{\eta }^{\prime}}\rpar$ zones after 3 months aging.

Understanding the Activity of Co-N4-x Cx in Atomic Metal Catalysts for Oxygen Reduction Catalysis.

Atomic metal catalysis (AMC) provides an effective way to enhance activity for the oxygen reduction reaction (ORR). Cobalt anchored on nitrogen-doped carbon materials have been extensively reported. The carbon-hosted Co-N4 structure was widely considered as the active site; however, it is very rare to investigate the activity of Co partially coordinated with N, for example, Co-N4-x Cx . Herein, the activity of Co-N4-x Cx with tunable coordination environment is investigated as the active sites for ORR catalysis. The defect (di-vacancies) on carbon is essential for the formation of Co-N4-x Cx . N species play two important roles in promoting the intrinsic activity of atomic metal catalyst: N coordinated with Co to manipulate the reactivity by modification of electronic distribution and N helped to trap more Co to increase the number of active sites.

Achieving High Thermoelectric Figure of Merit in Polycrystalline SnSe via Introducing Sn Vacancies.

Thermoelectric power generation technology has emerged as a clean "heat engine" that can convert heat to electricity. Recently, the discovery of an ultrahigh thermoelectric figure of merit in SnSe crystals has drawn a great deal of attention. In view of their facile processing and scale-up applications, polycrystalline SnSe materials with ZT values comparable to those of the SnSe crystals are greatly desired. Here we achieve a record high ZT value ∼2.1 at 873 K in polycrystalline Sn1-xSe with Sn vacancies. We demonstrate that the carrier concentration increases by artificially introducing Sn vacancies, contributing significantly to the enhancements of electrical conductivity and thermoelectric power factor. The detailed analysis of the data in the light of first-principles calculations results indicates that the increased carrier concentration can be attributed to the Sn-vacancy-induced Fermi level downshift and the interplay between the vacancy states and valence bands. Furthermore, vacancies break translation symmetry and thus enhance phonon scattering, leading to extralow thermal conductivity. Such high ZT value ∼2.1 is achieved by synergistically optimizing both electrical- and thermal-transport properties of polycrystalline SnSe. The vast increase in ZT for polycrystalline SnSe may accelerate practical applications of this material in highly effective solid-state thermoelectric devices.

Deep learning-assisted analysis of HRTEM images of crystalline nanoparticles.

Accurate analysis of high-resolution transmission electron microscopy (HRTEM) images is important for the characterization and design of materials. However, conventional analyses rely mostly on manual procedures, which are time-consuming and lack accuracy, especially when the image contrast is low. Here, we propose an advanced analysis method for extracting crystal features from HRTEM images based on a 2D fast Fourier transform and U-Net based deep learning model. By using HRTEM images of iron oxide nanoparticles as examples, we show that our method is capable of providing information on the crystallinity profile, distribution of crystal planes, phases and defects automatically with high accuracy. In an era of data-driven technological development, we believe that deep learning based analysis tools will facilitate great progress in fundamental research on crystalline materials.

Enhanced Density of States Facilitates High Thermoelectric Performance in Solution-Grown Ge- and In-Codoped SnSe Nanoplates.

SnSe single crystals have gained great interest due to their excellent thermoelectric performance. However, polycrystalline SnSe is greatly desired due to facile processing, machinability, and scale-up application. Here, we report an outstanding high average ZT of 0.88 as well as a high peak ZT of 1.92 in solution-processed SnSe nanoplates. Nanosized boundaries formed by nanoplates and lattice strain created by lattice dislocations and stacking faults effectively scatter heat-carrying phonons, resulting in an ultralow lattice thermal conductivity of 0.19 W m-1 K-1 at 873 K. Ultraviolet photoelectron spectroscopy reveals that Ge and In incorporation produces an enhanced density of states in the electronic structure of SnSe, resulting in a large Seebeck coefficient. Ge and In codoping not only optimizes the Seebeck coefficient but also substantially increases the carrier concentration and electrical conductivity, helping to maintain a high power factor over a wide temperature range. Benefiting from an enhanced power factor and markedly reduced lattice thermal conductivity, high average ZT and peak ZT are achieved in Ge- and In-codoped SnSe nanoplates. This work achieves an ultrahigh average ZT of 0.88 in polycrystalline SnSe by adopting nontoxic element doping, potentially expanding its usefulness for various thermoelectric generator applications.

Thermoelectric performance of nanostructured In/Pb codoped SnTe with band convergence and resonant level prepared via a green and facile hydrothermal method.

SnTe is considered as a promising alternative to the conventional high-performance thermoelectric material PbTe, which inspired the thermoelectric community for a while. Here, we design a green, facile and low-energy-intensity hydrothermal route without involving any toxic or unstable chemicals to fabricate SnTe-based thermoelectric materials. Ultralow lattice thermal conductivity and enhanced thermoelectric performance are achieved via the combination of band engineering and nanostructuring. Enhanced Seebeck coefficient and power factor are induced by converging the band structure and creating resonant levels due to Pb and In doping. More importantly, due to the reduced grain sizes, nanoparticles, and dual-atom point defect scattering, ultralow lattice thermal conductivity was obtained in the bulk samples fabricated by the hydrothermal route. Benefiting from the enhanced power factor and significantly reduced thermal conductivity, the peak ZT is enhanced to ∼0.7 in In/Pb codoped SnTe, a 60% improvement over pure SnTe.

A General Approach to Direct Growth of Oriented Metal-Organic Framework Nanosheets on Reduced Graphene Oxides.

Ultrathin metal-organic framework nanosheets (UMOFNs) deposited on graphene are highly attractive, however direct growth of UMOFNs on graphene with controlled orientations remains challenging. Here, a low-concentration-assisted heterogeneous nucleation strategy is reported for the direct growth of UMOFNs on reduced graphene oxides (rGO) surface with controllable orientations. This general strategy can be applied to construct various UMOFNs on rGO, including Co-ZIF, Ni-ZIF, Co, Cu-ZIF and Co, Fe-ZIF. When UMOFNs are mostly attached perpendicularly on rGO, a 3D foam-like hierarchical architecture (named UMOFNs@rGO-F) is formed with an open pore structure and excellent conductivity, showing excellent performance as electrode materials for Li-ion batteries and oxygen evolution. The contribution has provided a strategy for improving the electrochemical performance of MOFs in energy storage applications.

Core-Shell Prussian Blue Analogs with Compositional Heterogeneity and Open Cages for Oxygen Evolution Reaction.

Here, a reduction-cation exchange (RCE) strategy is proposed for synthesizing Fe-Co based bimetallic Prussian blue analogs (PBAs) with heterogeneous composition distribution and open cage nanocage architecture. Specially, bivalent cobalt is introduced into a potassium ferricyanide solution containing hydrochloric acid and polyvinyl pyrrolidone. The uniform PBAs with opened cages are formed tardily after hydrothermal reaction. Time-dependent evolution characterization on composition elucidating the RCE mechanism is based on the sequential reduction of ferric iron and cation exchange reaction between divalent iron and cobalt. The PBA structures are confirmed by electron tomography technology, and the heterogeneous element distribution is verified by energy-dispersive X-ray spectroscopy elemental analysis, leading to the formation of core-shell PBAs with compositional heterogeneity (Fe rich shell and Co rich core) and open cage architecture. When the PBA catalysts are used to boost the oxygen evolution reaction (OER), superior OER activity and long-term stability (low overpotential of 271 mV at 10 mA cm-2 and ≈5.3% potential increase for 24 h) are achieved, which is attributed to the unique compositional and structural properties as well as high special surface areas (576.2 m2 g-1). The strategies offer insights for developing PBAs with compositional and structural multiplicity, which encourages more practical catalytic applications.

Electrospun mulberry-like hierarchical carbon fiber web for high-performance supercapacitors.

In this work, we have fabricated a kind of N-doped hierarchal carbon fiber web by electrospinning hollow mesoporous carbon spheres (HMCSs) into fibrous structure. The as-synthesized carbon fiber web with novel mulberry-like morphology, thus denoted as MC-FW, possesses micro/meso/macroporous porosity, large surface area, high conductivity and multi-level structure, which are highly desired for supercapacitor electrode materials. The electrochemical measurements demonstrate that the designed MC-FW shows high capacitance (298.6 F g-1), favorable capacitance retention (71.0%) and long cycle life (97.3% capacitance retention after 5000 cycles). Notably, the capacitance of 298.6 F g-1 for MC-FW is higher than the capacitance reported so far for many hollow carbon spheres and carbon fibers, which may contribute to the synergistic effect between the merits of HMCSs (e.g. micro/meso/macroporous hierarchal structure, large surface area, high pore volume) and advantages of 1D carbon fiber (e.g. large aspect ratio and high conductivity). It is believed that this distinctive carbon fiber web may show promising prospects as advanced energy storage materials and catalyst.

A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage.

Sodium transition metal oxides with layered structures are attractive cathode materials for sodium-ion batteries due to their large theoretical specific capacities. However, these layered oxides suffer from poor cyclability and low rate performance because of structural instability and sluggish electrode kinetics. In the present work, we show the sodiation reaction of Mn3O4 to yield crystal water free NaMnO2-y-δ(OH)2y, a monoclinic polymorph of sodium birnessite bearing Na/Mn(OH)8 hexahedra and Na/MnO6 octahedra. With the new polymorph, NaMnO2-y-δ(OH)2y exhibits an enlarged interlayer distance of about 7 Å, which is in favor of fast sodium ion migration and good structural stability. In combination of the favorable nanosheet morphology, NaMn2-y-δ(OH)2y cathode delivers large specific capacity up to 211.9 mAh g-1, excellent cycle performance (94.6% capacity retention after 1000 cycles), and outstanding rate capability (156.0 mAh g-1 at 50 C). This study demonstrates an effective approach in tailoring the structural and electrochemical properties of birnessite towards superior cathode performance in sodium-ion batteries.

Realizing High Thermoelectric Performance below Phase Transition Temperature in Polycrystalline SnSe via Lattice Anharmonicity Strengthening and Strain Engineering.

We report the high thermoelectric performance of p-type polycrystalline SnSe obtained below the phase transition temperature by harnessing Pb doping and introducing Sn vacancies. The enhanced carrier concentration induced by Pb doping and introducing Sn vacancies contributes to enhancements of electrical conductivity and power factor of polycrystalline SnSe. We demonstrate that the lattice anharmonicity is strengthened by Pb substitution and Sn vacancies through forming weaker bonds. We find that Pb substitution introduces huge stress field in the interior of the SnSe grains. The thermal conductivity can be greatly reduced by lattice anharmonicity strengthening and applying huge stress field. The lattice thermal conductivity is reduced to as low as 0.18 W m-1 K-1 in the Sn0.92Pb0.03Se sample at 773 K. As a result, a remarkable high ZT of ∼1.4 was achieved at 773 K in the Sn0.93Pb0.02Se sample through lattice anharmonicity strengthening and strain engineering.

Two-dimensional antimonene single crystals grown by van der Waals epitaxy.

Unlike the unstable black phosphorous, another two-dimensional group-VA material, antimonene, was recently predicted to exhibit good stability and remarkable physical properties. However, the synthesis of high-quality monolayer or few-layer antimonenes, sparsely reported, has greatly hindered the development of this new field. Here, we report the van der Waals epitaxy growth of few-layer antimonene monocrystalline polygons, their atomical microstructure and stability in ambient condition. The high-quality, few-layer antimonene monocrystalline polygons can be synthesized on various substrates, including flexible ones, via van der Waals epitaxy growth. Raman spectroscopy and transmission electron microscopy reveal that the obtained antimonene polygons have buckled rhombohedral atomic structure, consistent with the theoretically predicted most stable ß-phase allotrope. The very high stability of antimonenes was observed after aging in air for 30 days. First-principle and molecular dynamics simulation results confirmed that compared with phosphorene, antimonene is less likely to be oxidized and possesses higher thermodynamic stability in oxygen atmosphere at room temperature. Moreover, antimonene polygons show high electrical conductivity up to 104 S m-1 and good optical transparency in the visible light range, promising in transparent conductive electrode applications.