Fast Generation of Hydroxyl Radicals by Rerouting the Electron Transfer Pathway via Constructed Chemical Channels during the Photo-Electro-Reduction of Oxygen

A strategy for the fast generation of hydroxyl radicals (HO·) via photo-electro-reduction of oxygen by rerouting the electron transfer pathway was proposed. The rate-determining step of HO· production is the formation of H2O2 and the simultaneous reduction of H2O2. Engineering of F-TiO2 with single atom Pd bonded with four F and two O atoms favored the electrocatalytic 2-electron oxygen reduction to H2O2 with as high as 99% selectivity, while the additional channel bond HO–O···Pd–F–TiO2 facilitates the photogenerated electron transfer from the conduction band to single atom Pd to reduce Pd···O–OH to HO·. The optimized HO· production rate is 9.18 μ mol L–1 min–1, which is 2.6–52.5 times higher than that in traditional advanced oxidation processes. In the application of wastewater treatment, this proposed photoelectrocatalytic oxygen reduction method, respectively, shows fast kinetics of 0.324 and 0.175 min–1 for removing bisphenol A and acetaminophen. Around 93.2% total organic carbon and 99.3% acute toxicity removal were achieved. Additionally, the degradation efficiency was less affected by the water source and pH value because of the evitable usage of metallic active sites. This work represents a fundamental investigation on the generation rate of HO·, which would pave the way for the future development of photoelectrocatalytic technologies for water purification

Real-Space Imaging of Orbital Selectivity on SrTiO₃(001) Surface

Real-space access of the orbital degree of freedom in complex oxides is still challenging due to intricate electronic hybridization. Here, we report a direct observation of reproducible orbital-selective tunneling on a novel SrTiO3(001) surface by scanning tunneling microscopy. The electronic structures reversibly switch between two different sets of symmetries depending on the sample bias, which is accompanied by a remarkable change in energy-dependent spectroscopy data. Tunneling spectrum combined with density functional theory calculations elucidates that symmetry-breaking at the surface determines the crystal-splitting field of eg/t2g orbitals with a strong in-plane anisotropy so that electrons alternatingly fill eg and t2g orbitals during the imaging process with different biases. This surface superstructure provides a new strategy toward understanding orbital textures and orbital selectivity in complex oxides

Purely Electric-Field-Driven Perpendicular Magnetization Reversal

If achieved, magnetization reversal purely with an electric field has the potential to revolutionize the spintronic devices that currently utilize power-dissipating currents. However, all existing proposals involve the use of a magnetic field. Here we use phase-field simulations to study the piezoelectric and magnetoelectric responses in a three-dimensional multiferroic nanostructure consisting of a perpendicularly magnetized nanomagnet with an in-plane long axis and a juxtaposed ferroelectric nanoisland. For the first time, we demonstrate a full reversal of perpendicular magnetization via successive precession and damping, driven purely by a perpendicular electric-field pulse of certain pulse duration across the nanoferroelectric. We discuss the materials selection and size dependence of both nanoferroelctrics and nanomagnets for experimental verification. These results offer new inspiration to the design of spintronic devices that simultaneously possess high density, high thermal stability, and high reliability

Atomically Resolved Edge States on a Layered Ferroelectric Oxide

The emerging surface/edge electronic phases driven by broken symmetry effects have attracted great attention in low-dimensional electronic systems. However, experimental proof on their existence in ferroelectric oxides at the atomic scale is still missing. In this work, metallic surface states are observed on layered Bi2WO6 by scanning tunneling microscopy/spectroscopy. Differential conductance is remarkably enhanced near the step edge compared with that on the terrace, forming a one-dimensional edge state. Density functional theory calculations verify that symmetry breaking at the surface determines the electronic structures and O 2p orbitals contribute the most to the density of states around the Fermi level. Our discovery provides a new strategy toward the hidden phases on other correlated oxide surfaces

Controllable Ferroelastic Switching in Epitaxial Self-Assembled Aurivillius Nanobricks

Layered perovskites with Aurivillius phase have drawn tremendous attention recently, owing to their high ferroelectric Curie temperatures, large spontaneous polarization, and fatigue-free and environment-friendly characteristics. Bi2WO6 is one of the simplest members in the Aurivillius family with superior ferroelastic and photo-electrochemical behaviors. The self-assembly fabrication of its nanoarchitectures and strategic modulation of their ferroelastic switching are crucial toward highly efficient nanoscale applications. In this work, Bi2WO6 nanobrick arrays were epitaxially grown along the orthorhombic direction in a self-assembled way. Such a nanoscale topology supports out-of-plane and in-plane vectors of ferroelectric polarizations, enabling a perpendicular voltage manipulation of these emerging ferroelectric/elastic domains. Combining the scanning probe technique and transmission electron microscopy, we confirmed the in-plane polarization vectors of 78.6 and 101.4° within the crystallographic axes of the nanobricks with respect to the (110) plane of the substrate. Thus, this work provides new opportunities for ferroelectric/elastic engineering in Bi2WO6 nanostructures for a wide range of applications, such as sensing, actuating, and catalysis

Unusual Behaviors of Electric-Field Control of Magnetism in Multiferroic Heterostructures via Multifactor Cooperation

Electric-field control of magnetism (EFCM) is very important for the exploration of high-density, fast, and nonvolatile random-access memory with ultralow energy consumption. Here, we report the electric-field-induced ferroelectric phase transitions in Pb­(Mg1/3Nb2/3)0.82Ti0.18O3 (PMN-0.18PT) and symmetry breaking of EFCM behaviors for corresponding directions in multiferroic heterostructures composed of amorphous ferromagnetic Co40Fe40B20 (CoFeB) and PMN-0.18PT. We uncover a new mechanism behind the unusual phenomena, involving coupling between CoFeB and PMN-0.18PT via complex cooperation of electric-field-induced ferroelectric phase transitions, competition of different ferroelectric domains, and internal electric field in PMN-0.18PT. The deterministic EFCM with reversible and nonvolatile nature opens up a new avenue for exploring EFCM in multiferroic heterostructures and is also significant for applications

Visualizing Atomic Quantum Defects in Ultrathin 1T-PtTe₂

Defects are of significant importance to determine and improve the distinct properties of 2D materials, such as electronic, optical, and catalytic performance. In this report, we observe four types of point defects in atomically thin flakes of 1T-PtTe2 by using low-temperature scanning tunnelling microscopy and spectroscopy (STM/S). Through the combination of STM imaging and simulations, such defects are identified as a single tellurium vacancy from each side of the top PtTe2 layer and a single platinum vacancy from the topmost and next layer. The density functional theory (DFT) calculations reveal that the platinum vacancies from both the monolayer and bilayer exhibit a local magnetic moment. In bilayer PtTe2, the interlayer coulomb screening effect reduces the local magnetic momentum of the single platinum vacancy. Our research provides meaningful guidance for further experiments about the effects of intrinsic defects on potential functions of thin 1T-PtTe2, such as catalysis and spintronic applications

Photoenhanced Electroresistance at Dislocation-Mediated Phase Boundary

Ferroelectric tunneling junctions have attracted intensive research interest due to their potential applications in high-density data storage and neural network computing. However, the prerequisite of an ultrathin ferroelectric tunneling barrier makes it a great challenge to simultaneously implement the robust polarization and negligible leakage current in a ferroelectric thin film, both of which are significant for ferroelectric tunneling junctions with reliable operating performance. Here, we observe a large tunneling electroresistance effect of ∼1.0 × 104% across the BiFeO3 nanoisland edge, where the intrinsic ferroelectric polarization of the nanoisland makes a major contribution to tuning the barrier height. This phenomenon is beneficial from the artificially designed tunneling barrier between the nanoscale top electrode and the inclined conducting phase boundary, which is located between the rhombohedral-island and tetragonal-film matrix and arranged with the dislocation array. More significantly, the tunneling electroresistance effect is further improved to ∼1.6 × 104% by the introduction of photoinduced carriers, which are separated by the flexoelectric field arising from the dislocations

Nanoscale Bandgap Tuning across an Inhomogeneous Ferroelectric Interface

We report nanoscale bandgap engineering via a local strain across the inhomogeneous ferroelectric interface, which is controlled by the visible-light-excited probe voltage. Switchable photovoltaic effects and the spectral response of the photocurrent were explored to illustrate the reversible bandgap variation (∼0.3 eV). This local-strain-engineered bandgap has been further revealed by <i>in situ</i> probe-voltage-assisted valence electron energy-loss spectroscopy (EELS). Phase-field simulations and first-principle calculations were also employed for illustration of the large local strain and the bandgap variation in ferroelectric perovskite oxides. This reversible bandgap tuning in complex oxides demonstrates a framework for the understanding of the optically related behaviors (photovoltaic, photoemission, and photocatalyst effects) affected by order parameters such as charge, orbital, and lattice parameters

Visualizing Atomic Quantum Defects in Ultrathin 1T-PtTe₂

Defects are of significant importance to determine and improve the distinct properties of 2D materials, such as electronic, optical, and catalytic performance. In this report, we observe four types of point defects in atomically thin flakes of 1T-PtTe2 by using low-temperature scanning tunnelling microscopy and spectroscopy (STM/S). Through the combination of STM imaging and simulations, such defects are identified as a single tellurium vacancy from each side of the top PtTe2 layer and a single platinum vacancy from the topmost and next layer. The density functional theory (DFT) calculations reveal that the platinum vacancies from both the monolayer and bilayer exhibit a local magnetic moment. In bilayer PtTe2, the interlayer coulomb screening effect reduces the local magnetic momentum of the single platinum vacancy. Our research provides meaningful guidance for further experiments about the effects of intrinsic defects on potential functions of thin 1T-PtTe2, such as catalysis and spintronic applications