Yiliu Wang

General synthesis and definitive structural identification of MN 4 C 4 single-atom catalysts with tunable electrocatalytic activities

AbstractSingle-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MN4C4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical prediction of MN4C4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.Atomically dispersed metal catalysts are of increasing importance in many catalytic processes, but clear structural identification is challenging. Here, a general synthesis of metal (nickel, iron and cobalt) single-atom catalysts on nitrogen-doped graphene allows the authors to identify a common structure and furthermore correlate structure with electrocatalytic activity.

The Effect of Thermal Annealing on Charge Transport in Organolead Halide Perovskite Microplate Field-Effect Transistors

Transformation of unipolar n-type semiconductor behavior to ambipolar and finally to unipolar p-type behavior in CH3 NH3 PbI3 microplate field-effect transistors by thermal annealing is reported. The photoluminescence spectra essentially maintain the same features before and after the thermal annealing process, demonstrating that the charge transport measurement provides a sensitive way to probe low-concentration defects in perovskite materials.

Chemical vapor deposition growth of single-crystalline cesium lead halide microplatelets and heterostructures for optoelectronic applications

Organic–inorganic hybrid halide perovskites, such as CH3NH3PbI3, have emerged as an exciting class of materials for solar photovoltaic applications; however, they are currently plagued by insufficient environmental stability. To solve this issue, all-inorganic halide perovskites have been developed and shown to exhibit significantly improved stability. Here, we report a single-step chemical vapor deposition growth of cesium lead halide (CsPbX3) microcrystals. Optical microscopy studies show that the resulting perovskite crystals predominantly adopt a square-platelet morphology. Powder X-ray diffraction (PXRD) studies of the resulting crystals demonstrate a highly crystalline nature, with CsPbCl3, CsPbBr3, and CsPbI3 showing tetragonal, monoclinic, and orthorhombic phases, respectively. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies show that the resulting platelets exhibit well-faceted structures with lateral dimensions of the order of 10–50 μm, thickness around 1 μm, and ultra-smooth surface, suggesting the absence of obvious grain boundaries and the single-crystalline nature of the individual microplatelets. Photoluminescence (PL) images and spectroscopic studies show a uniform and intense emission consistent with the expected band edge transition. Additionally, PL images show brighter emission around the edge of the platelets, demonstrating a wave-guiding effect in high-quality crystals. With a well-defined geometry and ultra-smooth surface, the square platelet structure can function as a whispering gallery mode cavity with a quality factor up to 2,863 to support laser emission at room temperature. Finally, we demonstrate that such microplatelets can be readily grown on a variety of substrates, including silicon, graphene, and other two-dimensional materials such as molybdenum disulfide, which can readily allow the construction of heterostructure optoelectronic devices, including a graphene/perovskite/graphene vertically-stacked photodetector with photoresponsivity > 105 A/W. The extraordinary optical properties of CsPbX3 platelets, combined with their ability to be grown on diverse materials to form functional heterostructures, can lead to exciting opportunities for broad optoelectronic applications.

Scalable solution-phase epitaxial growth of symmetry-mismatched heterostructures on two-dimensional crystal soft template

Lin et al. report 2D layered materials as a soft template for symmetry-mismatched epitaxial growth of PbSe/Bi2Se3 heterostructures. Epitaxial heterostructures with precisely controlled composition and electronic modulation are of central importance for electronics, optoelectronics, thermoelectrics, and catalysis. In general, epitaxial material growth requires identical or nearly identical crystal structures with small misfit in lattice symmetry and parameters and is typically achieved by vapor-phase depositions in vacuum. We report a scalable solution-phase growth of symmetry-mismatched PbSe/Bi2Se3 epitaxial heterostructures by using two-dimensional (2D) Bi2Se3 nanoplates as soft templates. The dangling bond–free surface of 2D Bi2Se3 nanoplates guides the growth of PbSe crystal without requiring a one-to-one match in the atomic structure, which exerts minimal restriction on the epitaxial layer. With a layered structure and weak van der Waals interlayer interaction, the interface layer in the 2D Bi2Se3 nanoplates can deform to accommodate incoming layer, thus functioning as a soft template for symmetry-mismatched epitaxial growth of cubic PbSe crystal on rhombohedral Bi2Se3 nanoplates. We show that a solution chemistry approach can be readily used for the synthesis of gram-scale PbSe/Bi2Se3 epitaxial heterostructures, in which the square PbSe (001) layer forms on the trigonal/hexagonal (0001) plane of Bi2Se3 nanoplates. We further show that the resulted PbSe/Bi2Se3 heterostructures can be readily processed into bulk pellet with considerably suppressed thermal conductivity (0.30 W/m·K at room temperature) while retaining respectable electrical conductivity, together delivering a thermoelectric figure of merit ZT three times higher than that of the pristine Bi2Se3 nanoplates at 575 K. Our study demonstrates a unique epitaxy mode enabled by the 2D nanocrystal soft template via an affordable and scalable solution chemistry approach. It opens up new opportunities for the creation of diverse epitaxial heterostructures with highly disparate structures and functions.

A Solution Processable High‐Performance Thermoelectric Copper Selenide Thin Film

A solid-state thermoelectric device is attractive for diverse technological areas such as cooling, power generation and waste heat recovery with unique advantages of quiet operation, zero hazardous emissions, and long lifetime. With the rapid growth of flexible electronics and miniature sensors, the low-cost flexible thermoelectric energy harvester is highly desired as a potential power supply. Herein, a flexible thermoelectric copper selenide (Cu2 Se) thin film, consisting of earth-abundant elements, is reported. The thin film is fabricated by a low-cost and scalable spin coating process using ink solution with a truly soluble precursor. The Cu2 Se thin film exhibits a power factor of 0.62 mW/(m K2 ) at 684 K on rigid Al2 O3 substrate and 0.46 mW/(m K2 ) at 664 K on flexible polyimide substrate, which is much higher than the values obtained from other solution processed Cu2 Se thin films (<0.1 mW/(m K2 )) and among the highest values reported in all flexible thermoelectric films to date (≈0.5 mW/(m K2 )). Additionally, the fabricated thin film shows great promise to be integrated with the flexible electronic devices, with negligible performance change after 1000 bending cycles. Together, the study demonstrates a low-cost and scalable pathway to high-performance flexible thin film thermoelectric devices from relatively earth-abundant elements.

Gate-Induced Insulator to Band-Like Transport Transition in Organolead Halide Perovskite

Understanding the intrinsic charge transport in organolead halide perovskites is essential for the development of high-efficiency photovoltaics and other optoelectronic devices. Despite the rapid advancement of the organolead halide perovskite in photovoltaic and optoelectronic applications, the intrinsic charge-carrier transport in these materials remains elusive partly due to the difficulty of fabricating electrical devices and obtaining good electrical contact. Here we report the fabrication of organolead halide perovskite microplates with mono- or bilayer graphene as low barrier electrical contact. Systematic charge-transport studies reveal an insulator to band-like transport transition. Our studies indicate that the insulator to band-like transport transition depends on the orthorhombic-to-tetragonal phase-transition temperature and defect densities of the organolead halide perovskite microplates. Our findings not only are important for the fundamental understanding of charge-transport behavior but also offer valuable practical implications for photovoltaics and optoelectronic applications based on the organolead halide perovskite.

Highly-anisotropic optical and electrical properties in layered SnSe

Anisotropic materials are of considerable interest because of their unique combination of polarization- or direction-dependent electrical, optical, and thermoelectric properties. Low-symmetry two-dimensional (2D) materials formed by van der Waals stacking of covalently bonded atomic layers are inherently anisotropic. Layered SnSe exhibits a low degree of lattice symmetry, with a distorted NaCl structure and an in-plane anisotropy. Here we report a systematic study of the in-plane anisotropic properties in layered SnSe, using angle-resolved Raman scattering, optical absorption, and electrical transport studies. The optical and electrical characterization was direction-dependent, and successfully identified the crystalline orientation in the layered SnSe. Furthermore, the dependence of Raman-intensity anisotropy on the SnSe flake thickness and the excitation wavelength were investigated by both experiments and theoretical calculations. Finally, the electrical transport studies demonstrated that few-layer SnSe field-effect transistors (FETs) have a large anisotropic ratio of carrier mobility (∼5.8) between the armchair and zigzag directions, which is a record high value reported for 2D anisotropic materials. The highly-anisotropic properties of layered SnSe indicate considerable promise for anisotropic optics, electronics, and optoelectronics.

Quantum interference mediated vertical molecular tunneling transistors

We report graphene/self-assembly monolayer vertical molecular transistors operating in the quantum tunneling regime. Molecular transistors operating in the quantum tunneling regime represent potential electronic building blocks for future integrated circuits. However, due to their complex fabrication processes and poor stability, traditional molecular transistors can only operate stably at cryogenic temperatures. Here, through a combined experimental and theoretical investigation, we demonstrate a new design of vertical molecular tunneling transistors, with stable switching operations up to room temperature, formed from cross-plane graphene/self-assembled monolayer (SAM)/gold heterostructures. We show that vertical molecular junctions formed from pseudo-p-bis((4-(acetylthio)phenyl)ethynyl)-p-[2,2]cyclophane (PCP) SAMs exhibit destructive quantum interference (QI) effects, which are absent in 1,4-bis(((4-acetylthio)phenyl)ethynyl)benzene (OPE3) SAMs. Consequently, the zero-bias differential conductance of the former is only about 2% of the latter, resulting in an enhanced on-off current ratio for (PCP) SAMs. Field-effect control is achieved using an ionic liquid gate, whose strong vertical electric field penetrates through the graphene layer and tunes the energy levels of the SAMs. The resulting on-off current ratio achieved in PCP SAMs can reach up to ~330, about one order of magnitude higher than that of OPE3 SAMs. The demonstration of molecular junctions with combined QI effect and gate tunability represents a critical step toward functional devices in future molecular-scale electronics.

Solution-processable 2D semiconductors for high-performance large-area electronics

Two-dimensional (2D) materials, consisting of atomically thin crystal layers bound by the van der Waals force, have attracted much interest because of their potential in diverse technologies, including electronics, optoelectronics and catalysis1–10. In particular, solution-processable 2D semiconductor (such as MoS2) nanosheets are attractive building blocks for large-area thin-film electronics. In contrast to conventional zero- and one-dimensional nanostructures (quantum dots and nanowires, respectively), which are typically plagued by surface dangling bonds and associated trapping states, 2D nanosheets have dangling-bond-free surfaces. Thin films created by stacking multiple nanosheets have atomically clean van der Waals interfaces and thus promise excellent charge transport11–15. However, preparing high-quality solution-processable 2D semiconductor nanosheets remains a challenge. For example, MoS2 nanosheets and thin films produced using lithium intercalation and exfoliation are plagued by the presence of the metallic 1T phase and poor electrical performance (mobilities of about 0.3 square centimetres per volt per second and on/off ratios of less than 10)2,12, and materials produced by liquid exfoliation exhibit an intrinsically broad thickness distribution, which leads to poor film quality and unsatisfactory thin-film electrical performance (mobilities of about 0.4 square centimetres per volt per second and on/off ratios of about 100)14,16,17. Here we report a general approach to preparing highly uniform, solution-processable, phase-pure semiconducting nanosheets, which involves the electrochemical intercalation of quaternary ammonium molecules (such as tetraheptylammonium bromide) into 2D crystals, followed by a mild sonication and exfoliation process. By precisely controlling the intercalation chemistry, we obtained phase-pure, semiconducting 2H-MoS2 nanosheets with a narrow thickness distribution. These nanosheets were then further processed into high-performance thin-film transistors, with room-temperature mobilities of about 10 square centimetres per volt per second and on/off ratios of 106 that greatly exceed those obtained for previous solution-processed MoS2 thin-film transistors. The scalable fabrication of large-area arrays of thin-film transistors enabled the construction of functional logic gates and computational circuits, including an inverter, NAND, NOR, AND and XOR gates, and a logic half-adder. We also applied our approach to other 2D materials, including WSe2, Bi2Se3, NbSe2, In2Se3, Sb2Te3 and black phosphorus, demonstrating its potential for generating versatile solution-processable 2D materials.By intercalating large ammonium molecules to exfoliate MoS2 with preservation of the 2H-phase, highly uniform solutionprocessable 2D semiconductor nanosheets are obtained for the scalable fabrication of large-area thin-film electronics.

Ultrathin wavy Rh nanowires as highly effective electrocatalysts for methanol oxidation reaction with ultrahigh ECSA

AbstractDirect methanol fuel cells (DMFCs) have received tremendous research interests because of the facile storage of liquid methanol vs. hydrogen. However, the DMFC today is severely plagued by the poor kinetics and rather high overpotential in methanol oxidation reaction (MOR). Here we report the investigation of the ultrathin Rh wavy nanowires as a highly effective MOR electrocatalyst. We show that ultrathin wavy Rh nanowires can be robustly synthesized with 2–3 nm diameters. Electrochemical studies show a current peak at the potential of 0.61 V vs. reversible hydrogen electrode (RHE), considerably lower than that of Pt based catalysts (~ 0.8–0.9 V vs. RHE). Importantly, with ultrathin diameters and favorable charge transport, the Rh nanowires catalysts exhibit an ultrahigh electrochemically active surface area determined from CO-stripping (ECSACO) of 144.2 m2/g, far exceeding that of the commercial Rh black samples (20 m2/g). Together, the Rh nanowire catalysts deliver a mass activity of 722 mA/mg at 0.61 V, considerably higher than many previously reported electrocatalysts at the same potential. The chronoamperometry studies also demonstrate good stability and CO-tolerance compared with the Rh black control sample, making ultrathin Rh wavy nanowires an attractive electrocatalyst for MOR.