Atomic Resolution Imaging of Nanoscale Structural Ordering in a Complex Metal Oxide Catalyst

The determination of the atomic structure of a functional material is crucial to understanding its “structure-to-property” relationship (e.g., the active sites in a catalyst), which is however challenging if the structure possesses complex inhomogeneities. Here, we report an atomic structure study of an important MoVTeO complex metal oxide catalyst that is potentially useful for the industrially relevant propane-based BP/SOHIO process. We combined aberration-corrected scanning transmission electron microscopy with synchrotron powder X-ray crystallography to explore the structure at both nanoscopic and macroscopic scales. At the nanoscopic scale, this material exhibits structural and compositional order within nanosized “domains”, while the domains show disordered distribution at the macroscopic scale. We proposed that the intradomain compositional ordering and the interdomain electric dipolar interaction synergistically induce the displacement of Te atoms in the Mo–V–O channels, which determines the geometry of the multifunctional metal oxo-active sites

Defects and Surface Structural Stability of MoTe₂ Under Vacuum Annealing

Understanding the structural stability of transition-metal dichalcogenides is necessary to avoid surface/interface degradation. In this work, the structural stability of 2H-MoTe₂ with thermal treatments up to 500 °C is studied using scanning tunneling microscopy and scanning transmission electron microscopy. On the exfoliated sample surface at room temperature, atomic subsurface donors originating from excess Te atoms are observed and presented as nanometer-sized, electronically-induced protrusions superimposed with the hexagonal lattice structure of MoTe₂. Under a thermal treatment as low as 200 °C, the surface decomposition-induced cluster defects and Te vacancies are readily detected and increase in extent with the increasing temperature. Driven by Te vacancies and thermal energy, intense 60° inversion domain boundaries form resulting in a “wagon wheel” morphology after 400 °C annealing for 15 min. Scanning tunneling spectroscopy identified the electronic states at the domain boundaries and the domain centers. To prevent extensive Te loss at higher temperatures, where Mo₆Te₆ nanowire formation and substantial desorption-induced etching effects will take place simultaneously, surface and edge passivation with a monolayer graphene coverage on MoTe₂ is tested. With this passivation strategy, the structural stability of MoTe₂ is greatly enhanced up to 500 °C without apparent structural defects

Atomic Bonding between Metal and Graphene

To understand structural and chemical properties of metal–graphene composites, it is crucial to unveil the chemical bonding along the interface. We provide direct experimental evidence of atomic bonding between typical metal nano structures and graphene, agreeing well with density functional theory studies. Single Cr atoms are located in the valleys of a zigzag edge, and few-atom ensembles preferentially form atomic chains by self-assembly. Low migration barriers lead to rich dynamics of metal atoms and clusters under electron irradiation. We demonstrate no electron-instigated interaction between Cr clusters and pristine graphene, though Cr has been reported to be highly reactive to graphene. The metal-mediated etching is a dynamic effect between metal clusters and pre-existing defects. The resolved atomic configurations of typical nano metal structures on graphene offer insight into modeling and simulations on properties of metal-decorated graphene for both catalysis and future carbon-based electronics

Atomic Bonding between Metal and Graphene

To understand structural and chemical properties of metal–graphene composites, it is crucial to unveil the chemical bonding along the interface. We provide direct experimental evidence of atomic bonding between typical metal nano structures and graphene, agreeing well with density functional theory studies. Single Cr atoms are located in the valleys of a zigzag edge, and few-atom ensembles preferentially form atomic chains by self-assembly. Low migration barriers lead to rich dynamics of metal atoms and clusters under electron irradiation. We demonstrate no electron-instigated interaction between Cr clusters and pristine graphene, though Cr has been reported to be highly reactive to graphene. The metal-mediated etching is a dynamic effect between metal clusters and pre-existing defects. The resolved atomic configurations of typical nano metal structures on graphene offer insight into modeling and simulations on properties of metal-decorated graphene for both catalysis and future carbon-based electronics

Site-Specific Growth of Au–Pd Alloy Horns on Au Nanorods: A Platform for Highly Sensitive Monitoring of Catalytic Reactions by Surface Enhancement Raman Spectroscopy

Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au–Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au–Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11<i>l</i>} (0.25 < <i>l</i> < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for <i>in situ</i> monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au–Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity

Chiral Transformation: From Single Nanowire to Double Helix

We report a new type of water-soluble ultrathin Au–Ag alloy nanowire (NW), which exhibits unprecedented behavior in a colloidal solution. Upon growth of a thin metal (Pd, Pt, or Au) layer, the NW winds around itself to give a metallic double helix. We propose that the winding originates from the chirality within the as-synthesized Au–Ag NWs, which were induced to untwist upon metal deposition

Atomic Bonding between Metal and Graphene

To understand structural and chemical properties of metal–graphene composites, it is crucial to unveil the chemical bonding along the interface. We provide direct experimental evidence of atomic bonding between typical metal nano structures and graphene, agreeing well with density functional theory studies. Single Cr atoms are located in the valleys of a zigzag edge, and few-atom ensembles preferentially form atomic chains by self-assembly. Low migration barriers lead to rich dynamics of metal atoms and clusters under electron irradiation. We demonstrate no electron-instigated interaction between Cr clusters and pristine graphene, though Cr has been reported to be highly reactive to graphene. The metal-mediated etching is a dynamic effect between metal clusters and pre-existing defects. The resolved atomic configurations of typical nano metal structures on graphene offer insight into modeling and simulations on properties of metal-decorated graphene for both catalysis and future carbon-based electronics

Ru Nanoframes with an fcc Structure and Enhanced Catalytic Properties

Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd–Ru core–frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the reduction of <i>p</i>-nitrophenol by NaBH₄ and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness

Doping Monolayer Graphene with Single Atom Substitutions

Functionalized graphene has been extensively studied with the aim of tailoring properties for gas sensors, superconductors, supercapacitors, nanoelectronics, and spintronics. A bottleneck is the capability to control the carrier type and density by doping. We demonstrate that a two-step process is an efficient way to dope graphene: create vacancies by high-energy atom/ion bombardment and fill these vacancies with desired dopants. Different elements (Pt, Co, and In) have been successfully doped in the single-atom form. The high binding energy of the metal-vacancy complex ensures its stability and is consistent with in situ observation by an aberration-corrected and monochromated transmission electron microscope

Sub-10 nm Tunable Hybrid Dielectric Engineering on MoS₂ for Two-Dimensional Material-Based Devices

The successful realization of high-performance 2D-materials-based nanoelectronics requires integration of high-quality dielectric films as a gate insulator. In this work, we explore the integration of organic and inorganic hybrid dielectrics on MoS₂ and study the chemical and electrical properties of these hybrid films. Our atomic force microscopy, X-ray photoelectron spectroscopy (XPS), Raman, and photoluminescence results show that, aside from the excellent film uniformity and thickness scalability down to 2.5 nm, the molecular layer deposition of octenyltrichlorosilane (OTS) and Al₂O₃ hybrid films preserves the chemical and structural integrity of the MoS₂ surface. The XPS band alignment analysis and electrical characterization reveal that through the inclusion of an organic layer in the dielectric film, the band gap and dielectric constant can be tuned from ∼7.00 to 6.09 eV and ∼9.0 to 4.5, respectively. Furthermore, the hybrid films show promising dielectric properties, including a high breakdown field of ∼7.8 MV/cm, a low leakage current density of ∼1 × 10^–6 A/cm² at 1 MV/cm, a small hysteresis of ∼50 mV, and a top-gate subthreshold voltage swing of ∼79 mV/dec. Our experimental findings provide a facile way of fabricating scalable hybrid gate dielectrics on transition metal dichalcogenides for 2D-material-based flexible electronics applications