Nanoscale defects like grain boundaries (GBs) would introduce local phonon modes and affect the bulk materials' thermal, electrical, optical, and mechanical properties. It is highly desirable to correlate the phonon modes and atomic arrangements for individual defects to precisely understand the structure-property relation. Here we investigated the localized phonon modes of Al2O3 GBs by combination of the vibrational electron energy loss spectroscopy (EELS) in scanning transmission electron microscope and density functional perturbation theory (DFPT). The differences between GB and bulk obtained from the vibrational EELS show that the GB exhibited more active vibration at the energy range of <50 meV and >80 meV, and further DFPT results proved the wide distribution of bond lengths at GB are the main factor for the emergence of local phonon modes. This research provides insights into the phonon-defect relation and would be of importance in the design and application of polycrystalline materials.
Upcycle polyethylene terephthalate (PET) waste by photoreforming (PR) is a sustainable and green approach to tackle environmental problems but with challenges to obtain valuable oxidation products and high purity hydrogen simultaneously. Noble metal cocatalysts are essential to enhance the overall PR reaction efficacy. In this work, TiO2 nanotubes (TiO2 NTs) decorated with single Pt atoms (Pt1/TiO2) or Pt nanoparticles (PtNPs/TiO2) are used in the photoreforming reaction (in one batch), and the oxidation products from ethylene glycol (EG, hydrolysed product of PET) in liquid phase and hydrogen are detected. With Pt1/TiO2, EG is oxidized to glyoxal, glyoxylate or lactate, and hydrogen evolution rate (r H2) reaches 51.8 µmolâ h-1â gcat-1, that is 30 times higher than that of TiO2. For PtNPs/TiO2 (size of Pt NPs: 1.97 nm), hydrogen evolution reaches 219.1 µmolâ h-1â gcat-1, but with the oxidation product of acetate only. DFT calculation demonstrates that for Pt NPs, the reaction path for hydrogen evolution is preferred thermodynamically, due to the formation of Schottky junction. On the oxidation of EG, theoretical and spectroscopic analysis suggest that bidentate adsorption of EG at the interface is facile on Pt1/TiO2, compared to that on PtNPs/TiO2 (two Pt sites), but oxidation products, adsorb less strongly, compared to PtNPs/TiO2, that eventually regulates the distribution of oxidation products. The results thus demonstrate the bifunctions of Pt in the PR reaction, i.e., electron transfer mediator for hydrogen evolution and reactive sites for molecules adsorption. The oxidation reaction is dominated by the adsorption-desorption behavior of molecules but the reduction reaction is controlled by the electron transfer. In addition, acidification of pretreated PET alkaline solution achieves separation of pure terephthalic acid (PTA), which further improves the reaction efficiency possibly by offering high density of active sites and acidic environment. Our work thus demonstrates that to upcycle PET plastics, an optimized process can be reached by atomic design of photocatalysts and proper treatment on the plastic wastes.
MXenes have aroused intensive enthusiasm because of their exotic properties and promising applications. However, to date, they are usually synthesized by etching technologies. Developing synthetic technologies provides more opportunities for innovation and may extend unexplored applications. Here, we report a bottom-up gas-phase synthesis of Cl-terminated MXene (Ti2CCl2). The gas-phase synthesis endows Ti2CCl2 with unique surface chemistry, high phase purity, and excellent metallic conductivity, which can be used to accelerate polysulfide conversion kinetics and dramatically prolong the cyclability of Li-S batteries. In-depth mechanistic analysis deciphers the origin of the formation of Ti2CCl2 and offers a paradigm for tuning MXene chemical vapor deposition. In brief, the gas-phase synthesis transforms the synthesis of MXenes and unlocks the hardly achieved potentials of MXenes.
The Coulomb explosion and field evaporation are frequently observed physical phenomena for a metallic tip under an external electric field, which can modify the structures of the tip and have broad applications, such as in the atomic-probe tomography and field ion microscopy. However, the mechanistic comprehending of how they change the structures of the tip and the differences between them are not clear. Here, dynamic observations of Coulomb explosions and field evaporations on the positively biased and charged few-layer graphene (FLG) nanoribbon inside a transmission electron microscope are reported. By combining the atomic-scale molecular dynamic simulations, it is shown that the FLG is split into several sheets under Coulomb explosion. It is also observed to break by emitting the carbon ions/segments under the field evaporation. It is further demonstrated that the split and breaking of FLG can be tuned by the shape of the nanoribbon. FLG ribbons with sharp tips have splitting and breaking occur in sequence. FLG with blunt tips break without a split. These results provide a fundamental understanding of Coulomb explosion and field evaporation in graphene nanomaterials and suggest potential methods to engineer graphene-based nanostructures.
Enhancing oxygen activation through defect engineering is an effective strategy for boosting catalytic oxidation performance. Herein, we demonstrate that quenching is an effective strategy for preparing defect-rich Pt/metal oxide catalysts with superior catalytic oxidation activity. As a proof of concept, quenching of α-Fe2O3 in aqueous Pt(NO3)2 solution yielded a catalyst containing Pt single atoms and clusters over defect-rich α-Fe2O3 (Pt/Fe2O3-Q), which possessed state-of-the-art activity for toluene oxidation. Structural and spectroscopic analyses established that the quenching process created abundant lattice defects and lattice dislocations in the α-Fe2O3 support, and stronger electronic interactions between Pt species and Fe2O3 promote the generation of higher oxidation Pt species to modulate the adsorption/desorption behavior of reactants. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) characterization studies and density functional theory (DFT) calculations determined that molecular oxygen and Fe2O3 lattice oxygen were both activated on the Pt/Fe2O3-Q catalyst. Pt/CoMn2O4, Pt/MnO2, and Pt/LaFeO3 catalysts synthesized by the quenching method also offered superior catalytic activity for toluene oxidation. Results encourage the wider use of quenching for the preparation of highly active oxidation catalysts.
Oxides , Platinum , Oxides/chemistry , Platinum/chemistry , Manganese Compounds , Oxygen , Toluene
Grain boundaries (GBs) are considered as the effective sinks for point defects, which improve the radiation resistance of materials. However, the fundamental mechanisms of how the GBs absorb and annihilate point defects under irradiation are still not well understood at atomic scale. With the aid of the atomic resolution scanning transmission electron microscope, we experimentally investigate the atomistic mechanism of point defects absorption by a ∑31 GB in α-Al2O3 under high energy electron beam irradiation. It is shown that a disconnection pair is formed, during which all the Al atomic columns are tracked. We demonstrate that the formation of the disconnection pair is proceeded with disappearing of atomic columns in the GB core, which suggests that the GB absorbs vacancies. Such point defect absorption is attributed to the nucleation and climb motion of disconnections. These experimental results provide an atomistic understanding of how GBs improve the radiation resistance of materials.
Controlling the oxygen content can manipulate the electrical conductivity of transition metal oxides (TMOs). Although the superconductor-metal-insulator transition is useful for functional devices, an electrical path must be developed to manipulate the oxygen deficiency (δ) while maintaining the solid state. YBa2Cu3O7-δ (YBCO, 0 ≤ δ ≤ 1) is a high transition temperature (Tc) TMO that can be modulated from a superconductor (Tc ≈ 92 K when δ = 0) to an insulator (δ ≈ 1). Here, we show a simple and efficient way to manipulate δ in YBCO films using a solid-state electrochemical redox treatment. Applying a negative voltage injects oxide ions to the YBCO films, increasing Tc. Employing a positive voltage suppresses the superconducting transition and modulates the electrical conductivity. The present results demonstrate that the superconductor-metal-insulator transition of YBCO is modulated electrochemically in the solid state, opening possibilities of superconducting oxide-based device applications.
As the lightest solid element and also the simplest metal, lithium (Li) is one of the best representations of quasi-free electron model in both bulk form and the reduced dimensions. Herein, the controlled growth of 2D ultrathin Li nanosheets is demonstrated by utilizing an in situ electrochemical platform built inside transmission electron microscope (TEM). The as-grown freestanding 2D Li nanosheets have strong structure-anisotropy with large lateral dimensions up to several hundreds of nanometers and thickness limited to just a few nanometers. The nanoscale dynamics of nanosheets growth are unraveled by in situ TEM imaging in real-time. Further density-functional theory calculations indicate that oxygen molecules play an important role in directing the anisotropic 2D growth of Li nanosheets through controlling the growth kinetics by their facet-specific capping. The plasmonic optical properties of the as-grown Li nanosheets are probed by cathodoluminescence spectroscopy equipped within TEM, and a broadband visible emission is observed that contains contributions of both in-plane and out-of-plane plasmon resonance modes.
Grain boundary (GB) migration plays an important role in modifying the microstructures and the related properties of polycrystalline materials, and is governed by the atomistic mechanism by which the atoms are displaced from one grain to another. Although such an atomistic mechanism has been intensively investigated, it is still experimentally unclear as to how the GB migration proceeds at the atomic scale. With the aid of high-energy electron-beam irradiation in atomic-resolution scanning transmission electron microscopy, we controllably triggered the GB migration in α-Al2O3 and directly visualized the atomistic GB migration as a stop motion movie. It was revealed that the GB migration proceeds by the cooperative shuffling of atoms on GB ledges along specific routes, passing through several different stable and metastable GB structures with low energies. We demonstrated that GB migration could be facilitated by the GB structural transformations between these low-energy structures.
Grain boundaries (GBs) modulate the macroscopic properties in polycrystalline materials because they have different atomic and electronic structures from the bulk. Despite the progress on the understanding of GB atomic structures, knowledge of the localized electronic band structures is still lacking. Here, we experimentally characterized the atomic structures and the band gaps of four typical GBs in α-Al2O3 by scanning transmission electron microscopy and valence electron energy-loss spectroscopy (EELS). It was found that the band gaps of the GBs are narrowed by 0.5-2.1 eV compared with that of 8.8 eV in the bulk. By combing core-loss EELS with first-principles calculations, we elucidated that the band gap reductions directly correlate with the decrease of the coordination numbers of Al and O ions at the GBs. These results provide in-depth understanding between the local atomic and electronic band structures for GBs and demonstrate a novel electronic-structure analysis for crystalline defects.
Design and synthesis of integrated, interconnected porous structures are critical to the development of high-performance supercapacitors. We develop a novel and facile synthesis technic to construct three-dimensional carbon-bubble foams with hierarchical pores geometry. The carbon-bubble foams are fabricated by conformally coating, via catalytic decomposition of ethanol, a layer of carbon coating onto the surfaces of pre-formed ZnO foams and then the removal of the ZnO template by a reduction-evaporation process. Both the wall thickness and the pore size can be well tuned by adjusting the catalytic decomposition time and temperature. The as-synthesized carbon-bubble foams electrode retains 90.3% of the initial capacitance even after 70 000 continuous cycles under a high current density of 20 A g-1, demonstrating excellent long-time electrochemical and cycling stability. The symmetric device displays rate capability retention of 81.8% with the current density increasing from 0.4 to 20 A g-1. These achieved electrochemical performances originate from the unique structural design of the carbon-bubble foams, which provide not only abundant transport channels for electron and ion but also high active surface area accessible by the electrolyte ions.
As anodes of Li-ion batteries, copper oxides (CuO) have a high theoretical specific capacity (674 mA h g-1 ) but own poor cyclic stability owing to the large volume expansion and low conductivity in charges/discharges. Incorporating reduced graphene oxide (rGO) into CuO anodes with conventional methods fails to build robust interaction between rGO and CuO to efficiently improve the overall anode performance. Here, Cu2 O/CuO/reduced graphene oxides (Cu2 O/CuO/rGO) with a 3D hierarchical nanostructure are synthesized with a facile, single-step hydrothermal method. The Cu2 O/CuO/rGO anode exhibits remarkable cyclic and high-rate performances, and particularly the anode with 25 wt% rGO owns the best performance among all samples, delivering a record capacity of 550 mA h g-1 at 0.5 C after 100 cycles. The pronounced performances are attributed to the highly efficient charge transfer in CuO nanosheets encapsulated in rGO network and the mitigated volume expansion of the anode owing to its robust 3D hierarchical nanostructure.
As a typical immiscible binary system, copper (Cu) and lithium (Li) show no alloying and chemical intermixing under normal circumstances. Here we show that, when decreasing Cu nanoparticle sizes into ultrasmall range, the nanoscale size effect can play a subtle yet critical role in mediating the chemical activity of Cu and therefore its miscibility with Li, such that the electrochemical alloying and solid-state amorphization will occur in such an immiscible system. This unusual observation was accomplished by performing in-situ studies of the electrochemical lithiation processes of individual CuO nanowires inside a transmission electron microscopy (TEM). Upon lithiation, CuO nanowires are first electrochemically reduced to form discrete ultrasmall Cu nanocrystals that, unexpectedly, can in turn undergo further electrochemical lithiation to form amorphous CuLix nanoalloys. Real-time TEM imaging unveils that there is a critical grain size (ca. 6â¯nm), below which the nanocrystalline Cu particles can be continuously lithiated and amorphized. The possibility that the observed solid-state amorphization of Cu-Li might be induced by electron beam irradiation effect can be explicitly ruled out; on the contrary, it was found that electron beam irradiation will lead to the dealloying of as-formed amorphous CuLix nanoalloys.
Interface enhanced magnetism attracts much attention due to its potential use in exploring novel structure devices. Nevertheless, the magnetic behavior at interfaces has not been quantitatively determined. In this study, abnormal magnetic moment reduction is observed in La0.7 Sr0.3 MnO3 (LSMO)/BiFeO3 (BFO) superlattices, which is induced by ferromagnetic (FM)/antiferromagnetic (AFM) coupling in the interface. With reduced repetition of the superlattice's unit cell [(LSMO)n /(BFO)n ]60/n (n = 1, 2, 5, 10) on a SrTiO3 substrate, magnetic moment reduction from 25.5 emu cc-1 ([(LSMO)10 /(BFO)10 ]6 ) to 1.5 emu cc-1 ([(LSMO)1 /(BFO)1 ]60 ) is obtained. Ab initio simulations show that due to the different magnetic domain formation energies, the magnetic moment orientation tends to be paramagnetic in the FM/AFM interface. The work focuses on the magnetic domain formation energy and provides a pathway to construct artificial heterostructures that can be an effective way to tune the magnetic moment orientation and control the magnetization of ultrathin films.
Supported Au nanocatalysts have attracted intensive interest because of their unique catalytic properties. Their poor thermal stability, however, presents a major barrier to the practical applications. Here we report an ultrastable Au nanocatalyst by localizing the Au nanoparticles (NPs) in the interfacial regions between the TiO2 and hydroxyapatite. This unique configuration makes the Au NP surface partially encapsulated due to the strong metal-support interaction and partially exposed and accessible by the reaction molecules. The strong interaction helps stabilizing the Au NPs while the partially exposed Au NP surface provides the active sites for reactions. Such a catalyst not only demonstrated excellent sintering resistance with high activity after calcination at 800 °C but also showed excellent durability that outperforms a commercial three-way catalyst in a simulated practical testing, suggesting great potential for practical applications.
The strong metal-support interaction (SMSI) is of great importance for supported catalysts in heterogeneous catalysis. We report the first example of SMSI between Au nanoparticles (NPs) and hydroxyapatite (HAP), a nonoxide. The reversible encapsulation of Au NPs by HAP support, electron transfer, and changes in CO adsorption are identical to the classic SMSI except that the SMSI of Au/HAP occurred under oxidative condition; the opposite condition for the classical SMSI. The SMSI of Au/HAP not only enhanced the sintering resistance of Au NPs upon calcination but also improved their selectivity and reusability in liquid-phase reaction. It was found that the SMSI between Au and HAP is general and could be extended to other phosphate-supported Au systems such as Au/LaPO4. This new discovery may open a new way to design and develop highly stable supported Au catalysts with controllable activity and selectivity.
An in-depth mechanistic understanding of the electrochemical lithiation process of tungsten oxide (WO3 ) is both of fundamental interest and relevant for potential applications. One of the most important features of WO3 lithiation is the formation of the chemically flexible, nonstoichiometric Lix WO3 , known as tungsten bronze. Herein, we achieved the real-time observation of the deep electrochemical lithiation process of single-crystal WO3 nanowires by constructing inâ situ transmission electron microscopy (TEM) electrochemical cells. As revealed by nanoscale imaging, diffraction, and spectroscopy, it is shown that the rapid and deep lithiation of WO3 nanowires leads to the formation of highly disordered and near-amorphous Lix WO3 phases, but with no detectable traces of elemental W and segregated Li2 O phase formation. These results highlight the remarkable chemical and structural flexibility of the Lix WO3 phases in accommodating the rapid and deep lithiation reaction.
We investigated the strong coupling between the excitons of ZnO nanowires (NWs) and the localized surface plasmons (LSPs) of individual Ag nanoparticles (NPs) by monochromated electron energy loss spectroscopy (EELS) in an aberration-corrected scanning transmission electron microscopy (STEM) instrument. The EELS results confirmed that the hybridization of the ZnO exciton with the LSPs of the Ag NP created two plexcitons: the lower branch plexcitons (LPs) with a symmetrical dipole distribution and the upper branch plexcitons (UPs) with an antisymmetrical dipole distribution. The spatial maps of the LP and UP excitations reveal the nature of the LSP-exciton interactions. With decreasing size of the Ag NP the peak energies of the LPs and UPs showed a blue-shift and an anticrossing behavior at the ZnO exciton energy was observed. The coupled oscillator model explains the dispersion curve of the plexcitons and a Rabi splitting energy of â¼170 meV was deduced. The high spatial and energy resolution STEM-EELS approach demonstrated in this work is general and can be extended to study the various coupling interactions of a plethora of metal-semiconductor nanocomposite systems.
We fabricate carbon nanotube (CNT)-field effect transistors (FETs) with a changeable channel length and investigate the electron transport properties of single-walled, double-walled and triple-walled CNTs under uniaxial strain. In particular, we characterize the atomic structure of the same CNTs in the devices by transmission electron microscopy and correlate the strain-induced electronic property change to the chirality of the CNTs. Both the off-state resistance and on-state resistance are observed to change with the axial strain following an exponential function. The strain-induced band gap change obtained from the maximum resistance change in the transfer curve of the ambipolar FETs is quantitatively compared with the previous theoretical prediction and our DFTB calculation from the chirality of the CNTs. Although following the same trend, the experimentally obtained strain-induced band gap change is obviously larger (57%-170% larger) than the theoretical results for all the six CNTs, indicating that more work is needed to fully understand the strain-induced electronic property change of CNTs.
Few-layer graphene was successfully tailored with smooth edges along crystallographic directions by Joule heating-driven tungsten nanoparticles inside a transmission electron microscope. The dynamic process was monitored in real time at the atomic resolution level. These high-resolution in-situ observations show that the neighboring graphene layers joined together to form closed edges, which is in contrast to the supposed open edges formed with hydrogen passivation. The tungsten nanoparticles transformed to W2C in the intermediate stage of etching and to WC after etching, suggesting that carbon dissolution helped the continuous action of the metal nanoparticles in the catalytic anisotropic etching reaction.
