The study of organic semiconductor/ferromagnet interfaces in organic spintronics: A short review of recent progress

An overview is given on recent results in organic spintronic research. In particular, so‐called spinterfaces, spin‐injecting interfaces involving organic semiconductor (OSC) molecules and ferromagnetic metals, are discussed. The interfaces are classified in different categories depending on the type and strength of interface interaction and the relevant physics concerning energy level alignment and spin polarization of interface states are explained. Examples are given on characterization of both interface energetics and spin‐related properties obtained from a wide variety of experimental techniques, highlighting the different ways contacting can modify the electronic and magnetic properties of the OSC molecules and the ferromagnetic metals at the resulting spinterfaces. Finally, models for spin injection at spinterfaces are presented and discussed, followed by some speculations on consequences for device design and performance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Photocatalytic Enhancement Strategy with the Introduction of Metallic Bi: A Review on Bi/Semiconductor Photocatalysts

Semiconductor photocatalysis has great potential in the fields of solar fuel production and environmental remediation. Nevertheless, the photocatalytic efficiency still constrains its practical production applications. The development of new semiconductor materials is essential to enhance the solar energy conversion efficiency of photocatalytic systems. Recently, the research on enhancing the photocatalytic performance of semiconductors by introducing bismuth (Bi) has attracted widespread attention. In this review, we briefly overview the main synthesis methods of Bi/semiconductor photocatalysts and summarize the control of the micromorphology of Bi in Bi/semiconductors and the key role of Bi in the catalytic system. In addition, the promising applications of Bi/semiconductors in photocatalysis, such as pollutant degradation, sterilization, water separation, CO2 reduction, and N2 fixation, are outlined. Finally, an outlook on the challenges and future research directions of Bi/semiconductor photocatalysts is given. We aim to offer guidance for the rational design and synthesis of high-efficiency Bi/semiconductor photocatalysts for energy and environmental applications.     

The magnetoresistance of metal-rich Ag2+xSe – A prototype nanoscale metal/semiconductor dispersion?

The magnetoresistance (MR) effect of the low temperature phase of silver selenide (-Ag_2+δSe) is studied with both bulk and thin film samples within a wide range of composition, i.e. metal content. Homogeneous bulk silver selenide shows the ordinary magnetoresistance (OMR) effect, which can be explained by the two-band model of a classical semiconductor. Heterogeneous silver selenide forms a semiconductor/metal dispersion which shows completely different MR effects, depending on the microstructure of the samples. XRD and TEM studies of thin film samples prove the two-phase character of the silver-rich material, and also offer new insights into the microstructure of the low temperature phase of silver selenide: Two selenide phases appear and form a “nano-parquet” of two coexisting selenide phases with both coherent twin boundaries and incoherent large angle grain boundaries. This microstructure is discussed as the possible reason for the observed MR effects.     

Molecular modeling and photovoltaic applications of porphyrin-based dyes: A review

In this review, the introduction of solar cells is presented. Old and new generation solar cells are briefly described. Quantum dot solar cells (QDSCs), perovskite solar cells, and dye-sensitized solar cells (DSSCs) are concisely introduced. The sensitization mechanism in DSSCs is discussed in detail concerning the spectral and electron injection properties of different dyes. An analysis of the intramolecular charge transfer process in the excited dye molecule is also provided. The use of porphyrin-based dyes as sensitizers in DSSCs is then reviewed. The design, synthesis, and photovoltaic application of a wide variety of porphyrin-based dyes as well as porphyrin dyads are presented and discussed. Theoretical studies of the spectral and electronic properties of different porphyrin-based dyes using DFT and TD-DFT methods are described. The different possibilities for improving the light-to-electrical energy conversion performance are discussed, such as structural modifications through introducing push-pull moieties, which in turn tunes the HOMO-LUMO energy gap of the sensitizing dye used in the DSSC. Experimental, as well as theoretical calculations of adsorption energies of the sensitizing dyes, are crucial for predicting the relative performance and efficiency of the dyes.     

Recent progress in TiO2-based photocatalysts for hydrogen evolution reaction: A review

TiO₂ has gained tremendous attention as a cutting-edge material for application in photocatalysis. The performance of TiO₂ as a photocatalyst depends on various parameters including morphology, surface area, and crystallinity. Although TiO₂ has shown good catalytic activity in various catalysis systems, the performance of TiO₂ as a photocatalyst is generally limited due to its low conductivity and a wide optical bandgap. Numerous different studies have been devoted to overcome these problems, showing significant improvement in photocatalytic performance. In this study, we summarize the recent progress in the utilization of TiO₂ for the photocatalytic hydrogen evolution reaction (HER). Strategies for modulating the properties toward the high photocatalytic activity of TiO₂ for HER including structural engineering, compositional engineering, and doping are highlighted and discussed. The advantages and limitations of each modification approach are reviewed. Finally, the remaining obstacles and perspective for the development of TiO₂ as photocatalysts toward high efficient HER in the near future are also provided.     

Twisted molecular geometry and localized electronic structure of the triplet excited gem-diphenyltrimethylenemethane biradical: substituent effects on thermoluminescence and related theoretical calculations

Substituent effects on the energies of electronic transitions (ETs) between the triplet excited and ground states of gem-diphenyltrimethylenemethane biradicals (³2a) were explored by using thermoluminescence (TL) spectroscopy and density functional theory (DFT) including time-dependent (TD) DFT. Linear free energy (Hammett) analyses of TL energies of a variety of para-substituted aryl derivatives of ³2* gave reasonable correlations with the substituent constant, σ. The slope of Hammett plots of the data are nearly identical to one obtained from a similar analysis of the photoluminescence (PL) energies of the structurally-related 1,1-diarylethyl radicals (3*). The results suggest that TL of ³2* and PL of 3* derive from a common diarylmethyl radical fluorophore. This interpretation is also supported by the DFT and TDDFT calculated electronic structures and ET energies of ³2 and 3. Thermodynamic and kinetic analyses of the charge recombination (CR) process between 2⁺ and 1⁻, which generates ³2*, revealed that substituents not only alter the TL energies but also the TL intensities of ³2*. The observations made in this effort demonstrate that ³2* as well as ³2 and 2⁺ have greatly twisted molecular geometries and highly localized electronic structures.     

A review of transition metal chalcogenide/graphene nanocomposites for energy storage and conversion

Recent advances in the applications of transition metal chalcogenides/graphene (TMC/graphene) nanocomposites in future energy storage and conversion are reviewed. The synthesis processes and structures of TMC/graphene, workingpriciple of evergy energy device, and the electrochemical performances are summarized.     

Interfacial electron transfer at TiO2 nanostructured electrodes modified with capped gold nanoparticles: The photoelectrochemistry of water oxidation

We have studied the photoelectrochemical behavior of nanostructured anatase electrodes modified with gold nanoparticles stabilized either with citrate (Au_cit) or with tetraoctylammonium bromide (Au_TOAB). An increase both in photocurrent and in photopotential was observed in 0.05 M NaOH upon modification with Au_TOAB. This behavior is attributed to an efficient hole consumption at the gold nanoparticles, which implies an effective hole transport to them from the TiO₂ nanostructure, probably facilitated by the capping agent. Once in the Au particles, the holes would promote an oxidation process (O₂ generation), which requires that the Au nanoparticles attain a high enough local electrode potential. This is possible as long as the Au_TOAB nanoparticles may behave as nanocapacitors with a very low capacity (ca. 1 aF) and thus the accumulation of a few holes may induce important changes in their potential. In acidic medium or in the presence of 0.1 M CH₃OH no enhancement was detected. In the case of TiO₂ modified with Au_cit, no increase of the photoelectrochemical response was observed in any case. It is suggested that a proper design of the metal/semiconductor nanojunctions may lead to an enhanced charge separation and to the eventual development of photoinduced metal electrocatalysis.     

GW/BSE Nonadiabatic Dynamics Simulations on Excited-State Relaxation Processes of Zinc Phthalocyanine-Fullerene Dyads: Roles of Bridging Chemical Bonds

In this work, we employ electronic structure calculations and nonadiabatic dynamics simulations based on many-body Green function and Bethe-Salpeter equation (GW/BSE) methods to study excited-state properties of a zinc phthalocyanine-fullerene (ZnPc-C\begin{document}$ _{60} $\end{document}) dyad with 6-6 and 5-6 configurations. In the former, the initially populated locally excited (LE) state of ZnPc is the lowest S\begin{document}$ _1 $\end{document} state and thus, its subsequent charge separation is relatively slow. In contrast, in the latter, the S\begin{document}$ _1 $\end{document} state is the LE state of C\begin{document}$ _{60} $\end{document} while the LE state of ZnPc is much higher in energy. There also exist several charge-transfer (CT) states between the LE states of ZnPc and C\begin{document}$ _{60} $\end{document}. Thus, one can see apparent charge separation dynamics during excited-state relaxation dynamics from the LE state of ZnPc to that of C\begin{document}$ _{60} $\end{document}. These points are verified in dynamics simulations. In the first 200 fs, there is a rapid excitation energy transfer from ZnPc to C\begin{document}$ _{60} $\end{document}, followed by an ultrafast charge separation to form a CT intermediate state. This process is mainly driven by hole transfer from C\begin{document}$ _{60} $\end{document} to ZnPc. The present work demonstrates that different bonding patterns (i.e. 5-6 and 6-6) of the C\begin{document}$ - $\end{document}N linker can be used to tune excited-state properties and thereto optoelectronic properties of covalently bonded ZnPc-C\begin{document}$ _{60} $\end{document} dyads. Methodologically, it is proven that combined GW/BSE nonadiabatic dynamics method is a practical and reliable tool for exploring photoinduced dynamics of nonperiodic dyads, organometallic molecules, quantum dots, nanoclusters, etc.     

A Fullerene/Lipid Electrode Device: Reversible Electron Transfer Reaction of C60 Embedded in a Cast Film of an Artificial Ammonium Lipid on an Electrode in Aqueous Solution

Two reversible one-electron transfers are observed for an electrode device made from C₆₀ and an artificial lipid (see schematic drawing). Cyclic voltammetric studies reveal that the redox couples are unchanged even after 50 cycles, thus indicating that the C₆₀ radical monoanion and the C₆₀ dianion generated in aqueous solution are very stable.     

A temporal study of the surface enhanced Raman bond polarizabilities of ethylene thiourea on the Ag electrode: The electromagnetic and charge transfer mechanisms

Based on the surface enhanced Raman intensities of ethylene thiourea on the silver electrode, the temporal bond polarizabilities are elucidated to offer important information of the surface enhancement mechanisms. The results demonstrated that both the electromagnetic and charge transfer mechanisms are responsible for the large enhancement. The relaxation rates of the various bond polarizabilities are displayed. All obey a single exponentially decaying function, independent of potentials and mechanisms. The characteristic time for the relaxation due to charge transfer mechanism is larger than that via the electromagnetic mechanism due to that its relaxation requires longer time for the charges to re-distribute.     

The role of the nano-environment of supported gold catalysts in the activity control. Modification of Au/Al2O3 catalysts by redox-type metal oxides

Au/Al₂O₃ catalysts were modified by different redox metal oxides, such as FeO_x, MnO_x and CoO_x, resulting in a pronounced activity increase in CO oxidation.     

The effect of high pressure on the ion pair equilibrium constant of alkali metal fluorides: A spectrophotometric study

Bromophenol blue indicator was used in UV-visible spectrophotometric measurements to study ion association constants of alkali metal fluorides. The equilibrium constants for the ion pair formation of the alkali metal fluorides were determined as a function of ionic strength at one atmosphere pressure and 25°C. The effect of pressure on these association constants was measured at a constant total ionic strength of 1.0 mol-kg^–1 over a pressure range of 1 to 2000 atmospheres at 25°C. The pressure dependences of the stoichiometric association constants of the alkali metal fluorides are given by: lnK _LiF ^* =0.77–2.47×10^–4P–2.12×10^–8P²; lnK _NaF ^* =0.53–1.08×10^–4P–1.66×10^–8P²; lnK _KF ^* =0.24–4.41×10^–5P–7.15×10^–8P²; lnK _RbF ^* =–0.17–8.65×10^–5P–4.51×10^–8P²; and lnK _CsF ^* = –0.37–1.14×10^–4P–6.82×10^–8P², where P is the pressure in atmospheres. The stoichiometric molar volume and compressibility changes for ion pair formation of the alkali metal fluorides were evaluated from the pressure dependence of K _MF ^* data. The thermodynamic association constants were also calculated making use of activity coefficient data from the Pitzer equations. The partial molal volume and compressibility changes for ion pair formation of each alkali metal fluoride are reported.     

The role of local structure on formic acid decomposition in supercritical water: A hybrid quantum mechanics/Monte Carlo study

We explored water-assisted decompositions of formic acid in supercritical water in terms of local structure near reactant. A hybrid quantum mechanics/molecular mechanics (QM/MM) simulation used in this paper includes QM part as first solvation shell members around the reactant. A present QM/MM approach can simulate supercritical water solution with a reasonable computational load while keeping the simulation preciseness because a density functional theory of B3LYP/6-31+G(d) level was iterated at every 1000 Monte Carlo solute moves. The formic acid converts mainly decarboxylation by water-assisted mechanism, and the coordinated water molecules play an important role for understanding supercritical water density dependence of the reaction. We analyzed a contour map based on the solute–solvent interaction energy along with the reaction pathway. Coordinated water molecule restricted the dehydration pathway by means of hydrogen bond with formic acid, however, the coordinated water promotes the decarboxylation pathway by means of stabilization of the transition state structure with one catalytic water molecule. The contour map of the pair interaction energy along the reaction path elucidates the role of local structure on reactions in supercritical water.     

The adsorption of acidic gaseous pollutants on metal and nonmetallic surface studied by first-principles calculation: A review

Recent advances of SO₂, NO_x, H₂S and CO₂ adsorption on metal and nonmetallic surfaces by first-principles calculation are reviewed, and the common adsorption properties and calculation methods are summarized.     

The adsorption of acidic gaseous pollutants on metal and nonmetallic surface studied by first-principles calculation: A review

The acidic gases such as SO₂, NO_x, H₂S and CO₂ are typical harmful pollutants and greenhouse gases in the atmosphere, which are also the main sources of PM_2.5. The most widely used method of treating these gas molecules is to capture them with different adsorption materials, i.e., metal and nonmetallic materials such as MnO₂, MoS₂ and carbon-based materials. And doping transition metal atoms in adsorption materials are beneficial to the gas adsorption process. The first-principles calculation is a powerful tool for studying the adsorption properties of contaminant molecules on different materials at the molecular and atomic levels to understand surface adsorption reactions, adsorption reactivity, and structure-activity relationships which can provide theoretical guidance for laboratory researches and industrial applications. This review introduces the adsorption models and surface properties of these gas molecules on metal and nonmetallic surfaces by first-principles calculation in recent years. The purpose of this review is to provide the theoretical guidance for experimental research and industrial application, and to inspire scientists to benefit from first-principles calculation for applying similar methods in future work.     

The interface effect on the lithiation of silicon/graphene composites: The first principles study

To reveal the interaction mechanism between lithium (Li) and silicon/graphene (Si/Gra) interface at the atomic scale, it was calculated that the energy band structure, density of states, charge transfer, radial distribution function and Li diffusion coefficient based on the first principles. The results indicated that the volume expansion of Si was effectively limited by the Si/Gra interface during Li insertion. There appeared the interface effect of Si/Gra on the combination of Li and Si atoms, according to the longer Li-C (2.9 Å) and the larger electron cloud near the Li atom at the Si/Gra interface. The better diffusion channel for Li atoms was constructed at the Si/Gra interface, due to the lower diffusion energy barrier (0.42–0.44 eV) and higher diffusion coefficient (D_Li = 0.784 × 10⁻⁴ cm²/s) for Li⁺ diffusion.     

Effects of different alkali metal ions on the cationization of poly(ethylene glycol)s in matrix-assisted laser desorption/ionization mass spectrometry: a new selectivity parameter

The cationization of poly(ethylene glycol)s, PEG 4000 and PEG 6000, under matrix-assisted laser desorption/ionization conditions was studied by using different concentration ratios of the sodium ion, as the reference ion, and another alkali metal ion (Li(+), K(+), Rb(+), Cs(+)). A linear correlation was found between the intensity ratio of the sodiated PEGs and PEGs cationized with alkali metal ions versus the initial concentration ratio of sodium and alkali metal ions. The slopes of these straight lines are proposed as a novel selectivity ratio for the ionization process. The intensity distribution of the cationized PEGs was also investigated. It was found that the cationized oligomers follow Poisson statistics. The M(n) and M(w) values were also evaluated. An explanation for the observed effects is given.     

Multifrequency electron paramagnetic resonance and theoretical studies of a Mn(II) (S = 5/2) complex: The role of geometrical elements on the Zero Field Splitting parameters

The Zero Field Splitting (ZFS) parameters of the mononuclear Mn(II) (S = 5/2) compound [Mn(Ac4Ph)₂], where HAc4Ph stands for 4-phenyl-2-acetylpyridine thiosemicarbazone, are determined by dual mode X-band and high field/high frequency electron paramagnetic resonance spectroscopy. Density functional theory (DFT) calculations reproduce both the sign and absolute value of the axial parameter D of the ZFS tensor, whose distribution is quantitatively correlated to distribution on geometrical elements of the complex.