Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.

Temperature-Dependent Photoluminescence of g-C3N4: Implication for Temperature Sensing

We report the temperature-dependent photoluminescence (PL) properties of polymeric graphite-like carbon nitride (g-C3N4) and a methodology for the determination of quantum efficiency along with the activation energy. The PL is shown to originate from three different pathways of transitions: sigma*-LP, pi*-LP, and pi*-pi, respectively. The overall activation energy is found to be similar to 73.58 meV which is much lower than the exciton binding energy reported theoretically but ideal for highly sensitive wide-range temperature sensing. The quantum yield derived from the PL data is 23.3%, whereas the absolute quantum yield is 5.3%. We propose that the temperature-dependent PL can be exploited for the evaluation of the temperature dependency of quantum yield as well as for temperature sensing. Our analysis further indicates that g-C3N4 is well-suited for wide-range temperature sensing.

Localized Charge Carrier Transport Properties of Zn1-x Ni (x) O/NiO Two-Phase Composites

We report the localized charge carrier transport of two-phase composite Zn1-x Ni (x) O/NiO (0 a parts per thousand currency sign x a parts per thousand currency sign 1) using the temperature dependence of ac-resistivity rho (ac)(T) across the N,el temperature T (N) (= 523 K) of nickel oxide. Our results provide strong evidence to the variable range hopping of charge carriers between the localized states through a mechanism involving spin-dependent activation energies. The temperature variation of carrier hopping energy epsilon (h)(T) and nearest-neighbor exchange-coupling parameter J (ij)(T) evaluated from the small poleron model exhibits a well-defined anomaly across T (N). For all the composite systems, the average exchange-coupling parameter (J (ij))(AVG) nearly equals to 70 meV which is slightly greater than the 60-meV exciton binding energy of pure zinc oxide. The magnitudes of epsilon (h) (similar to 0.17 eV) and J (ij) (similar to 11 meV) of pure NiO synthesized under oxygen-rich conditions are consistent with the previously reported theoretical estimation based on Green's function analysis. A systematic correlation between the oxygen stoichiometry and, epsilon (h)(T) and J (ij)(T) is discussed.

Adsorption of formaldehyde molecule on the intrinsic and Al-doped graphene: a first principle study

To search for a high sensitivity sensor for formaldehyde (H2CO), We investigated the adsorption of H2CO on the intrinsic and Al-doped graphene sheets using density functional theory (DFT) calculations. Compared with the intrinsic graphene, the Al-doped graphene system has high binding energy value and short connecting distance, which are caused by the chemisorption of H2CO molecule. Furthermore, the density of states (DOS) results show that orbital hybridization could be seen between H2CO and Al-doped graphene sheet, while there is no evidence for hybridization between the H2CO molecule and the intrinsic graphene sheet. Therefore, Al-doped graphene is expected to be a novel chemical sensor for H2CO gas. We hope our calculations are useful for the application of graphene in chemical sensor.

A scaling law of photoelectron angular distributions in one-cycle laser pulses

The photoelectron angular distributions (PADs) from above-threshold ionization of atoms irradiated by one-cycle laser pulses satisfy a scaling law. The scaling law denotes that the main features of the PADs are determined by four dimensionless parameters: (1) the ponderomotive number u(p) = U-p/hw, the ponderomotive energy U-p in units of laser photon energy; (2) the binding number E-b = E-b/h(w), the atomic binding energy E-b in units of laser photon energy; (3) the number of absorbed photons q; (4) the carrier-envelope phase phi(0), the phase of the carrier wave with respect to the envelope. We verify the scaling law by theoretical analysis and numerical calculation, compared to that in long-pulse case. A possible experimental test to verify the scaling law is suggested.

Ionization suppression of diatomic molecules in strong laser fields

The ionization rate of molecules in intense laser fields may be much lower than that of atoms with similar binding energy. This phenomenon is termed the ionization suppression of molecules and is caused by the molecular inner structure. In this paper, we perform a comprehensive study of the ionization suppression of homonuclear diatomic molecules in intense laser fields of linear and circular polarizations. We find that for linear polarization the total ionization rate and the ionization suppression depend greatly on the molecular alignment, and that for circular polarization the ionization suppression of molecules in the antibonding (bonding) shells disappears (appears) for laser intensities around 10(15) W/cm(2). We also find that the molecular photoelectron energy spectra are greatly changed by the interference effect, even though the total ionization rate of molecules remains almost the same as that of their companion atoms.

Measurement of the band bending and surface dipole at chemically functionalized Si(111)/vacuum interfaces

The core-level energy shifts observed using X-ray photoelectron spectroscopy (XPS) have been used to determine the band bending at Si(111) surfaces terminated with Si-Br, Si-H, and Si-CH₃ groups, respectively. The surface termination influenced the band bending, with the Si 2p_3/2 binding energy affected more by the surface chemistry than by the dopant type. The highest binding energies were measured on Si(111)-Br (whose Fermi level was positioned near the conduction band at the surface), followed by Si(111)-H, followed by Si(111)-CH₃ (whose Fermi level was positioned near mid-gap at the surface). Si(111)-CH₃ surfaces exposed to Br₂(g) yielded the lowest binding energies, with the Fermi level positioned between mid-gap and the valence band. The Fermi level position of Br₂(g)-exposed Si(111)-CH₃ was consistent with the presence of negatively charged bromine-containing ions on such surfaces. The binding energies of all of the species detected on the surface (C, O, Br) shifted with the band bending, illustrating the importance of isolating the effects of band bending when measuring chemical shifts on semiconductor surfaces. The influence of band bending was confirmed by surface photovoltage (SPV) measurements, which showed that the core levels shifted toward their flat-band values upon illumination. Where applicable, the contribution from the X-ray source to the SPV was isolated and quantified. Work functions were measured by ultraviolet photoelectron spectroscopy (UPS), allowing for calculation of the sign and magnitude of the surface dipole in such systems. The values of the surface dipoles were in good agreement with previous measurements as well as with electronegativity considerations. The binding energies of the adventitious carbon signals were affected by band bending as well as by the surface dipole. A model of band bending in which charged surface states are located exterior to the surface dipole is consistent with the XPS and UPS behavior of the chemically functionalized Si(111) surfaces investigated herein.

Dynamical stability of nascent neutron stars

This thesis presents a study of the dynamical stability of nascent neutron stars resulting from the accretion induced collapse of rapidly rotating white dwarfs.

Chapter 2 and part of Chapter 3 study the equilibrium models for these neutron stars. They are constructed by assuming that the neutron stars have the same masses, angular momenta, and specific angular momentum distributions as the pre-collapse white dwarfs. If the pre-collapse white dwarf is rapidly rotating, the collapsed object will contain a high density central core of size about 20 km, surrounded by a massive accretion torus extending to hundreds of kilometers from the rotation axis. The ratio of the rotational kinetic energy to gravitational binding energy, β, of these neutron stars is all found to be less than 0.27.

Chapter 3 studies the dynamical stability of these neutron stars by numerically evolving the linearized hydrodynamical equations. A dynamical bar-mode instability is observed when the β of the star is greater than the critical value β_d ≈ 0.25. It is expected that the unstable mode will persist until a substantial amount of angular momentum is carried away by gravitational radiation. The detectability of these sources is studied and it is estimated that LIGO II is unlikely to detect them unless the event rate is greater than 10^-6/year/galaxy.

All the calculations on the structure and stability of the neutron stars in Chapters 2 and 3 are carried out using Newtonian hydrodynamics and gravity. Chapter 4 studies the relativistic effects on the structure of these neutron stars. New techniques are developed and used to construct neutron star models to the first post-Newtonian (1PN) order. The structures of the 1PN models are qualitatively similar to the corresponding Newtonian models, but the values of β are somewhat smaller. The maximum β for these 1PN neutron stars is found to be 0.24, which is 8% smaller than the Newtonian result (0.26). However, relativistic effects will also change the critical value β_d. A detailed post-Newtonian stability analysis has yet to be carried out to study the relativistic effects on the dynamical stability of these neutron stars.

Sequence-function relationships in E. coli transcriptional regulation

Understanding how transcriptional regulatory sequence maps to regulatory function remains a difficult problem in regulatory biology. Given a particular DNA sequence for a bacterial promoter region, we would like to be able to say which transcription factors bind there, how strongly they bind, and whether they interact with each other and/or RNA polymerase, with the ultimate objective of integrating knowledge of these parameters into a prediction of gene expression levels. The theoretical framework of statistical thermodynamics provides a useful framework for doing so, enabling us to predict how gene expression levels depend on transcription factor binding energies and concentrations. We used thermodynamic models, coupled with models of the sequence-dependent binding energies of transcription factors and RNAP, to construct a genotype to phenotype map for the level of repression exhibited by the lac promoter, and tested it experimentally using a set of promoter variants from E. coli strains isolated from different natural environments. For this work, we sought to ``reverse engineer'' naturally occurring promoter sequences to understand how variations in promoter sequence affects gene expression. The natural inverse of this approach is to ``forward engineer'' promoter sequences to obtain targeted levels of gene expression. We used a high precision model of RNAP-DNA sequence dependent binding energy, coupled with a thermodynamic model relating binding energy to gene expression, to predictively design and verify a suite of synthetic E. coli promoters whose expression varied over nearly three orders of magnitude.

However, although thermodynamic models enable predictions of mean levels of gene expression, it has become evident that cell-to-cell variability or ``noise'' in gene expression can also play a biologically important role. In order to address this aspect of gene regulation, we developed models based on the chemical master equation framework and used them to explore the noise properties of a number of common E. coli regulatory motifs; these properties included the dependence of the noise on parameters such as transcription factor binding strength and copy number. We then performed experiments in which these parameters were systematically varied and measured the level of variability using mRNA FISH. The results showed a clear dependence of the noise on these parameters, in accord with model predictions.

Finally, one shortcoming of the preceding modeling frameworks is that their applicability is largely limited to systems that are already well-characterized, such as the lac promoter. Motivated by this fact, we used a high throughput promoter mutagenesis assay called Sort-Seq to explore the completely uncharacterized transcriptional regulatory DNA of the E. coli mechanosensitive channel of large conductance (MscL). We identified several candidate transcription factor binding sites, and work is continuing to identify the associated proteins.

Theory of s-d exchange scattering in dilute magnetic alloys

The problem of s-d exchange scattering of conduction electrons off localized magnetic moments in dilute magnetic alloys is considered employing formal methods of quantum field theoretical scattering. It is shown that such a treatment not only allows for the first time, the inclusion of multiparticle intermediate states in single particle scattering equations but also results in extremely simple and straight forward mathematical analysis. These equations are proved to be exact in the thermodynamic limit. A self-consistent integral equation for electron self energy is derived and approximately solved. The ground state and physical parameters of dilute magnetic alloys are discussed in terms of the theoretical results. Within the approximation of single particle intermediate states our results reduce to earlier versions. The following additional features are found as a consequence of the inclusion of multiparticle intermediate states;

(i) A non analytic binding energy is pre sent for both, antiferromagnetic (J < o) and ferromagnetic (J > o) couplings of the electron plus impurity system.

(ii) The correct behavior of the energy difference of the conduction electron plus impurity system and the free electron system is found which is free of unphysical singularities present in earlier versions of the theories.

(iii) The ground state of the conduction electron plus impurity system is shown to be a many-body condensate state for J < o and J > o, both. However, a distinction is made between the usual terminology of "Singlet" and "Triplet" ground states and nature of our ground state.

(iv) It is shown that a long range ordering, leading to an ordering of the magnetic moments can result from a contact interaction such as the s-d exchange interaction.

(v) The explicit dependence of the excess specific heat of the Kondo systems is obtained and found to be linear in temperatures as T→ o and T ℓnT for 0.3 T_K ≤ T ≤ 0.6 T_K. A rise in (ΔC/T) for temperatures in the region 0 < T ≤ 0.1 T_K is predicted. These results are found to be in excellent agreement with experiments.

(vi) The existence of a critical temperature for Ferromagnetic coupling (J > o) is shown. On the basis of this the apparent contradiction of the simultaneous existence of giant moments and Kondo effect is resolved.

Kinetic investigations of heterogeneously catalyzed reactions on the Ru(001) and Pt(110)-(1x2) surfaces

The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

Performance prediction of graphene nanoribbon and carbon nanotube transistors

Carbon nanotubes (CNTs) and graphene nanoribbons (GNRs) field-effect transistor (FET) can be the basis for a quasi-one- dimensional (Q1D) transistor technology. Recent experiments show that the on-off ratio for GNR devices can be improved to level exploration of transistor action is justified. Here we use the tight-binding energy dipersion approximation, to assess the performance of semiconducting CNT and GNR is qualitatively in terms of drain current drive strength, bandgap and density of states for a specified device. By reducing the maximum conductance 4e2/h by half, we observed that our model has a particularly good fit with 50 nm channel single walled carbon nanotube (SWCNT) experimental data. Given the same bandgap, CNTs outperform GNRs due to valley degeneracy. Nevertheless, the variation of the device contacts will decide which transistor will exhibit better conductivity and thus higher ON currents. © 2011 American Institute of Physics.

The effect of incomplete ionization on the turn-off behavior of FS IGBTs

This letter demonstrates for the first time the effect of the incomplete ionization (I.I.) of the transparent p-anode layer on the static and dynamic characteristics of the field-stop insulated gate bipolar transistors (FS IGBTs). This effect needs to be considered in FS IGBTs TCAD modeling to match accurately the device characteristics across a wide range of temperatures. The acceptor ionization energy (EA) governing the I.I. mechanism for the p-anode is extracted via matching the experimental turn-off waveforms and the static performance with Medici simulator. © 1980-2012 IEEE.

Variational calculations of neutral bound excitons in GaAs quantum-well wires

The binding energy of an exciton bound to a neutral donor (D-0,X) in GaAs quantum-well wires is calculated variationally as a function of the wire width for different positions of the impurity inside the wire by using a two-parameter wavefunction. There is no artificial parameter added in our calculation. The results we have obtained show that the binding energies are closely correlated to the sizes of the wire, the impurity position, and also that their magnitudes are greater than those in the two-dimensional quantum wells compared. In addition, we also calculate the average interparticle distance as a function of the wire width. The results are discussed in detail.

Quantum-dot growth simulation on periodic stress of substrate

InAs quantum dots (QDs) are grown on the cleaved edge of an InxGa1-xAs/GaAs supperlattice experimentally and a good linear alignment of these QDs on the surface of an InxGa1-xAs layer has been realized. The modulation effects of periodic strain on the substrate are investigated theoretically using a kinetic Monte Carlo method. Our results show that a good alignment of QDs can be achieved when the strain energy reaches 2% of the atomic binding energy. The simulation results are in excellent qualitative agreement with our experiments. (C) 2005 American Institute of Physics.