Local Charge Separation Research Articles

Ionically Charged Topological Defects in Nematic Fluids

Charge profiles in liquid electrolytes are of crucial importance for applications, such as supercapacitors, fuel cells, batteries, or the self-assembly of particles in colloidal or biological settings. However, creating localised (screened) charge profiles in the bulk of such electrolytes, generally requires the presence of surfaces -- for example, provided by colloidal particles or outer surfaces of the material -- which poses a fundamental constraint on the material design. Here, we show that topological defects in nematic electrolytes can perform as regions for local charge separation, forming charged defect cores and in some geometries even electric multilayers, as opposed to the electric double layers found in isotropic electrolytes. Using a Landau-de Gennes-Poisson-Boltzmann theoretical framework, we show that ions highly effectively couple with the topological defect cores via ion solvability, and with the local director-field distortions of the defects via flexoelectricity. The defect charging is shown for different defect types -- lines, points, and walls -- using geometries of ionically screened flat isotropic-nematic interfaces, radial hedgehog point defects and half-integer wedge disclinations in the bulk and as stabilised by (charged) colloidal particles. More generally, our findings are relevant for possible applications where topological defects act as diffuse ionic capacitors or as ionic charge carriers.

A coating strategy to achieve effective local charge separation for photocatalytic coevolution

Semiconductors of narrow bandgaps and high quantum efficiency have not been broadly utilized for photocatalytic coevolution of H2 and O2 via water splitting. One prominent issue is to develop effective protection strategies, which not only mitigate photocorrosion in an aqueous environment but also facilitate charge separation. Achieving local charge separation is especially challenging when these reductive and oxidative sites are placed only nanometers apart compared to two macroscopically separated electrodes in a photoelectrochemical cell. Additionally, the driving force of charge separation, namely the energetic difference in the barrier heights across the two type of sites, is small. Herein, we used conformal coatings attached by nanoscale cocatalysts to transform two classes of tunable bandgap semiconductors, i.e., CdS and GaInP2, into stable and efficient photocatalysts. We used hydrogen evolution and redox-mediator oxidation for model study, and further constructed a two-compartment solar fuel generator that separated stoichiometric H2 and O2 products. Distinct from the single charge-transfer direction reported for conventional protective coatings, the coating herein allows for concurrent injection of photoexcited electrons and holes through the coating. The energetic difference between reductive and oxidative catalytic sites was regulated by selectivity and local kinetics. Accordingly, the charge separation behavior was validated using numerical simulations. Following this design principle, the CdS/TiO2/Rh@CrOx photocatalysts evolved H2 while oxidizing reversible polysulfide redox mediators at a maximum rate of 90.6 μmol⋅h-1⋅cm-2 by stacking three panels. Powered by a solar cell, the redox-mediated solar water-splitting reactor regenerated the polysulfide repeatedly and achieved solar-to-hydrogen efficiency of 1.7%.

Enhanced Photocatalytic Activity from Tungsten and Fluoride Dual Modified Titanium Dioxide

Possessing promoted chemical reactions under ultraviolet or visible light, photocatalysis is one of the most promising and feasible technologies in advanced oxidation processes. Due to the advantages of low cost, earth-abundance, non-toxicity and high resistance to corrosion/photocorrosion, titanium dioxide has become an excellent candidate for environmental and sustainable applications in our daily life and industrial sectors. TiO2 nanoparticles with large specific surface area offer abundant active sites and suitable band edge position, which makes them one of the most desired materials for photocatalytic applications. In the current work, a dual functional one-pot synthesis strategy involving tungsten doping and trace-level fluorination has been developed. Combined characteristic analyses and density functional calculation (DFT) suggest that the noteworthily improved photocatalysis under both ultraviolet and visible lights can be attributed to rapid charge separation and transfer due to the successfully narrowed bandgap from tungsten doping and a localized spatial charge separation by surface F-adsorption.

Trace-Level Fluorination of Mesoporous TiO2 Improves Photocatalytic and Pb(II) Adsorbent Performances.

Fluorination is an effective way of tuning the physicochemical property and activity of TiO2 nanocrystallites, which usually requires a considerable amount of hydrofluoric acid (or NH4F) for a typical F/Ti molar ratio, RF, of 0.5-69.0 during synthesis. This has consequential environmental issues due to the high toxicity and hazard of the reactants. In the present work, an environmentally benign fluorination approach is demonstrated that uses only a trace amount of sodium fluoride with an RF of 10-6 during synthesis. While it maintained the desirable high surface area (102.4 m2/g), the trace-level fluorination enabled significant enhancements on photocatalytic activities (e.g., a 56% increase on hydrogen evolution rate) and heavy metal Pb(II) removal (31%) of the mesoporous TiO2. This can be attributed to enriched Ti3+ and localized spatial charge separation due to fluorination as proved by X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR), and density functional theory (DFT) analyses.

Anisotropic ultracold plasma expansion

Based on fluid model, the three-dimensional expansion of ultracold plasma is studied. The model considered both thermal pressure and ambipolar potential rising due to the local charge separation. By using isothermal assumption and quasi-neutrality condition, the time dependent asymetric expansion parametric investigation is conducted for two different ultracold plasma ion species (Sr+ and Ca+). It is found that ion temperature, in the range of ultracold limit, did not affect strongly the expanding profile but decreases the expanding density by an amount of ∼0.5% to ∼7%.The ion inertia is also found to enhance the asymetric aspect of the anisotrpic plasma expansion.

Design of Advanced Functional Materials Using Nanoporous Single-Site Photocatalysts.

Nanoporous silica solids can offer opportunities for hosting photocatalytic components such as various tetra-coordinated transition metal ions to form systems referred to as "single-site photocatalysts". Under UV/visible-light irradiation, they form charge transfer excited states, which exhibit a localized charge separation and thus behave differently from those of bulk semiconductor photocatalysts exemplified by TiO2 . This account presents an overview of the design of advanced functional materials based on the unique photo-excited mechanisms of single-site photocatalysts. Firstly, the incorporation of single-site photocatalysts within transparent porous silica films will be introduced, which exhibit not only unique photocatalytic properties, but also high surface hydrophilicity with self-cleaning and antifogging applications. Secondary, photo-assisted deposition (PAD) of metal precursors on single-site photocatalysts opens up a new route to prepare nanoparticles. Thirdly, visible light sensitive photocatalysts with single and/or binary oxides moieties can be prepared so as to use solar light, the ideal energy source.

Surface-Halogenation-Induced Atomic-Site Activation and Local Charge Separation for Superb CO2 Photoreduction.

Solar-energy-driven CO2 conversion into value-added chemical fuels holds great potential in renewable energy generation. However, the rapid recombination of charge carriers and deficient reactive sites, as two major obstacles, severely hampers the photocatalytic CO2 reduction activity. Herein, a desirable surface halogenation strategy to address the aforementioned concerns over a Sillén-related layer-structured photocatalyst Bi2 O2 (OH)(NO3 ) (BON) is demonstrated. The surface halogen ions that are anchored on the Bi atoms by replacing surface hydroxyls on the one hand facilitate the local charge separation, and, on the other hand, activate the hydroxyls that profoundly boost the adsorption of CO2 molecules and protons and facilitate the CO2 conversion process, as evidenced by experimental and theoretical results collectively. Among the three series of BON-X (X = Cl, Br, and I) catalysts, BON-Br shows the most substantially enhanced CO production rate (8.12 µmol g-1 h-1 ) without any sacrificial agents or cocatalysts, ≈73 times higher than that of pristine Bi2 O2 (OH)(NO3 ), also exceeding that of the state-of-the-art photocatalysts reported to date. This work presents a surface polarization protocol for engineering charge behavior and reactive sites to promote photocatalysis, which shows great promise to the future design of high-performance materials for clean energy production.

Surface P atom grafting of g-C3N4 for improved local spatial charge separation and enhanced photocatalytic H2 production

A new surface P atom-grafted g-C3N4 is developed, and the existence form and function of P atom is presented.

An STM – SEM setup for characterizing photon and electron induced effects in single photovoltaic nanowires

Vertical arrays of semiconductor nanowires show great potential for material-efficient and high-performance solar cells. The characterization and correlation between material structure and properties of the individual nanowires are crucial for the continued performance improvement of such devices. In this work, we developed a method with a scanning tunneling microscope (STM) probe inside a scanning electron microscope (SEM) to enable the studies of single photovoltaic nanowires. The STM probe is used to contact individual nanowires in ensembles. We combine the STM-SEM with an in situ light emitting diode (LED) illumination source to study both the electrical and photovoltaic properties of vertical GaAs nanowires with radial p-i-n junctions. We also illustrate that the local charge separation ability within the nanowires can be studied by electron beam induced current (EBIC) measurements. The in situ SEM setup allows the correlation between properties and nanowire structure. The data show that the quality of the electrical contact to the semiconductor nanowire is crucial to be able to investigate the inherent properties of the nanowires. We have established a procedure to make high-quality ohmic contacts to the nanowires with the STM probe. We also show that the effect of mechanical strain on the electrical properties can be investigated by the STM-SEM setup.

Local spatial charge separation and proton activation induced by surface hydroxylation promoting photocatalytic hydrogen evolution of polymeric carbon nitride

Polymeric carbon nitride as an intriguing earth-abundant visible light photocatalyst for H2 evolution has projected huge potentials. A high-performance polymeric carbon nitride photocatalyst system always requires fabrication of nanostructure or assistance of other semiconductors for ample reactive sites or rapid carrier migration/charge separation. Here, we disclose that hydroxylation as an efficient surface polarization decoration tactic without involving nanostructure or other semiconductors can substantially promote local spatial charge separation and proton activation of polymeric carbon nitride, thus achieving high photocatalytic H2 evolution. The post-hydrothermal treatment allows polymeric carbon nitride surface controllable grafting of abundant hydroxyls (-OH) on the -C≡N sites, which not only extends the 2D conjugate electron system of polymeric carbon nitride to 3D space to realize local spatial charge separation, but also polarizes the neighboring N atoms (C-N=C) to promote the proton adsorption and activation on them, further contributing to the high H2 evolution performance. The deep hydroxylation offered by introduction of basic ammonium salts discloses a pH-dependent hydroxylation-level mechanism and renders a ~ 11-fold enhancement in H2 generation rate with an AQY of 9.1% at 420 ± 15 nm. The finding may bring a new opportunity for developing highly-efficient HER materials base on surface polarization of functional groups.

Few-Layer WSe2 Schottky Junction-Based Photovoltaic Devices through Site-Selective Dual Doping.

Ultrathin sheets of two-dimensional (2D) materials like transition metal dichalcogenides have attracted strong attention as components of high-performance light-harvesting devices. Here, we report the implementation of Schottky junction-based photovoltaic devices through site-selective surface doping of few-layer WSe2 in lateral contact configuration. Specifically, whereas the drain region is covered by a strong molecular p-type dopant (NDP-9) to achieve an Ohmic contact, the source region is coated with an Al2O3 layer, which causes local n-type doping and correspondingly an increase of the Schottky barrier at the contact. By scanning photocurrent microscopy using green laser light, it could be confirmed that photocurent generation is restricted to the region around the source contact. The local photoinduced charge separation is associated with a photoresponsivity of up to 20 mA W-1 and an external quantum efficiency of up to 1.3%. The demonstrated device concept should be easily transferrable to other van der Waals 2D materials.

Electric Double Layer Composed of an Antagonistic Salt in an Aqueous Mixture: Local Charge Separation and Surface Phase Transition.

We examine an electric double layer containing an antagonistic salt in an aqueous mixture, where the cations are small and hydrophilic but the anions are large and hydrophobic. In this situation, a strong coupling arises between the charge density and the solvent composition. As a result, the anions are trapped in an oil-rich adsorption layer on a hydrophobic wall. We then vary the surface charge density σ on the wall. For σ>0 the anions remain accumulated, but for σ<0 the cations are attracted to the wall with increasing |σ|. Furthermore, the electric potential drop Ψ(σ) is nonmonotonic when the solvent interaction parameter χ(T) exceeds a critical value χ_{c} determined by the composition and the ion density in the bulk. This leads to a first-order phase transition between two kinds of electric double layers with different σ and common Ψ. In equilibrium such two-layer regions can coexist. The steric effect due to finite ion sizes is crucial in these phenomena.

Excitonic complexes in GaN/(Al,Ga)N quantum dots

Here we report a theoretical investigation of excitonic complexes in polar GaN/(Al,Ga)N quantum dots (QDs). A sum rule between the binding energies of charged excitons is used to calculate the biexciton binding energy. The binding energies of excitonic complexes in GaN/AlN are shown to be strongly correlated to the QD size. Due to the large hole localization, the positively charged exciton energy is found to be always blueshifted compared to the exciton one. The negatively charged exciton and the biexciton energy can be blueshifted or redshifted according to the QD size. Increasing the size of GaN/AlN QDs makes the identification of charged excitons difficult, and the use of an Al0.5Ga0.5N barrier can be advantageous for clear identification. Our theoretical results for the binding energy of exciton complexes are also confronted with values deduced experimentally for InAs/GaAs QDs, confirming our theoretical prediction for charged excitonic complexes in GaN/(Al,Ga)N QDs. Finally, we realize that the trends of excitonic complexes in QDs are significantly related to competition between the local charge separation (whatever its origin) and the correlation effect. Following our findings, entangled photons pairs can be produced in QDs with careful control of their size in order to obtain zero exciton–biexciton energy separation.

On the generation of double layers from ion- and electron-acoustic instabilities

A plasma double layer (DL) is a nonlinear electrostatic structure that carries a uni-polar electric field parallel to the background magnetic field due to local charge separation. Past studies showed that DLs observed in space plasmas are mostly associated with the ion acoustic instability. Recent Van Allen Probes observations of parallel electric field structures traveling much faster than the ion acoustic speed have motivated a computational study to test the hypothesis that a new type of DLs—electron acoustic DLs—generated from the electron acoustic instability are responsible for these electric fields. Nonlinear particle-in-cell simulations yield negative results, i.e., the hypothetical electron acoustic DLs cannot be formed in a way similar to ion acoustic DLs. Linear theory analysis and the simulations show that the frequencies of electron acoustic waves are too high for ions to respond and maintain charge separation required by DLs. However, our results do show that local density perturbations in a two-electron-component plasma can result in unipolar-like electric field structures that propagate at the electron thermal speed, suggesting another potential explanation for the observations.

Unusual high oxygen reduction performance in all-carbon electrocatalysts.

Carbon-based electrocatalysts are more durable and cost-effective than noble materials for the oxygen reduction reaction (ORR), which is an important process in energy conversion technologies. Heteroatoms are considered responsible for the excellent ORR performance in many carbon-based electrocatalysts. But whether an all-carbon electrocatalyst can effectively reduce oxygen is unknown. We subtly engineered the interfaces between planar graphene sheets and curved carbon nanotubes (G-CNT) and gained a remarkable activity/selectivity for ORR (larger current, and n = 3.86, ~93% hydroxide + ~7% peroxide). This performance is close to that of Pt; and the durability is much better than Pt. We further demonstrate the application of this G-CNT hybrid as an all-carbon cathode catalyst for lithium oxygen batteries.We speculate that the high ORR activity of this G-CNT hybrid stems from the localized charge separation at the interface of the graphene and carbon nanotube, which results from the tunneling electron transfer due to the Fermi level mismatch on the planar and curved sp2 surfaces. Our result represents a conceptual breakthrough and pioneers the new avenues towards practical all-carbon electrocatalysis.

Propagator Computational Method for Drift‐Diffusion Equations to Describe Plasma‐Wall Interaction

AbstractPlasmas evolve under sharp conditions such as localized currents, charge separation and absorption or emission of particles. The plasma‐wall interaction is one of these singularities. Numerical methods based upon differences usually fail under these abrupt boundary conditions leading to new spurious noise and singularities of numerical nature. Here, we extend the path‐sum integral numerical method to account for abrupt boundary conditions in plasma drift‐diffusion equations. The boundary‐path‐integral solution also shows the advantages of the smoothing affects of the diffusive short‐time propagators for unbounded domains. The proposed scheme is free of artificial numerical smoothing functions to mask sharp behaviours. This stable, robust and grid‐free algorithm is applied to test cases of plasma‐wall interaction with an advancing scheme that simultaneously copes with disparate electron and ion time scales. (© 2014 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

Local CP-violation and electric charge separation by magnetic fields from lattice QCD

We study local CP-violation on the lattice by measuring the local correlation between the topological charge density and the electric dipole moment of quarks, induced by a constant external magnetic field. This correlator is found to increase linearly with the external field, with the coefficient of proportionality depending only weakly on temperature. Results are obtained on lattices with various spacings, and are extrapolated to the continuum limit after the renormalization of the observables is carried out. This renormalization utilizes the gradient flow for the quark and gluon fields. Our findings suggest that the strength of local CP-violation in QCD with physical quark masses is about an order of magnitude smaller than a model prediction based on nearly massless quarks in domains of constant gluon backgrounds with topological charge. We also show numerical evidence that the observed local CP-violation correlates with spatially extended electric dipole structures in the QCD vacuum.

Response to “Comment on ‘Three-dimensional numerical investigation of electron transport with rotating spoke in a cylindrical anode layer Hall plasma accelerator’” [Phys. Plasmas 20, 014701 (2013)

The numerical simulation described in our paper [D. L. Tang et al., Phys. Plasmas 19, 073519 (2012)] shows a rotating dense plasma structure, which is the critical characteristic of the rotating spoke. The simulated rotating spoke has a frequency of 12.5 MHz with a rotational speed of ∼1.0 × 106 m/s on the surface of the anode. Accompanied by the almost uniform azimuthal ion distribution, the non-axisymmetric electron distribution introduces two azimuthal electric fields with opposite directions. The azimuthal electric fields have the same rotational frequency and speed together with the rotating spoke. The azimuthal electric fields excite the axial electron drift upstream and downstream due to the additional Eθ x B field and then the axial shear flow is generated. The axial local charge separation induced by the axial shear electron flow may be compensated by the azimuthal electron transport, finally resulting in the azimuthal electric field rotation and electron transport with the rotating spoke.

Plasmon Inducing Effects for Enhanced Photoelectrochemical Water Splitting: X-ray Absorption Approach to Electronic Structures

Artificial photosynthesis using semiconductors has been investigated for more than three decades for the purpose of transferring solar energy into chemical fuels. Numerous studies have revealed that the introduction of plasmonic materials into photochemical reaction can substantially enhance the photo response to the solar splitting of water. Until recently, few systematic studies have provided clear evidence concerning how plasmon excitation and which factor dominates the solar splitting of water in photovoltaic devices. This work demonstrates the effects of plasmons upon an Au nanostructure-ZnO nanorods array as a photoanode. Several strategies have been successfully adopted to reveal the mutually independent contributions of various plasmonic effects under solar irradiation. These have clarified that the coupling of hot electrons that are formed by plasmons and the electromagnetic field can effectively increase the probability of a photochemical reaction in the splitting of water. These findings support a new approach to investigating localized plasmon-induced effects and charge separation in photoelectrochemical processes, and solar water splitting was used herein as platform to explore mechanisms of enhancement of surface plasmon resonance.

Three-dimensional numerical investigation of electron transport with rotating spoke in a cylindrical anode layer Hall plasma accelerator

The effects of increased magnetic field and pressure on electron transport with a rotating spoke in a cylindrical anode layer Hall plasma accelerator are investigated by three-dimensional particle-in-cell numerical simulation. The azimuthal rotation of electron transport with the spoke has a frequency of 12.5 MHz. It propagates in the direction of the E × B drift at a speed of ∼1.0 × 106 m/s (about 37% of the E × B drift speed). Local charge separation occurs because the azimuthal local electron density concentration is accompanied by an almost uniform azimuthal ion distribution. The non-axisymmetrical electron density concentration and axisymmetrical ion distribution introduce two azimuthal electric fields with opposite directions in the plasma discharge region. The axial electron shear flow is excited under the additional Eθ × B field. The anomalous electron transport with the rotating spoke may be attributed to the axial electron shear flow induced by the two azimuthal electric fields with opposite directions as a result of the azimuthal local electron density concentration.