Showing papers in "Physical Chemistry Chemical Physics in 2007"

Studying Disorder in Graphite-Based Systems by Raman Spectroscopy

Abstract: Raman spectroscopy has historically played an important role in the structural characterization of graphitic materials, in particular providing valuable information about defects, stacking of the graphene layers and the finite sizes of the crystallites parallel and perpendicular to the hexagonal axis Here we review the defect-induced Raman spectra of graphitic materials from both experimental and theoretical standpoints and we present recent Raman results on nanographites and graphenes The disorder-induced D and D′ Raman features, as well as the G′-band (the overtone of the D-band which is always observed in defect-free samples), are discussed in terms of the double-resonance (DR) Raman process, involving phonons within the interior of the 1st Brillouin zone of graphite and defects In this review, experimental results for the D, D′ and G′ bands obtained with different laser lines, and in samples with different crystallite sizes and different types of defects are presented and discussed We also present recent advances that made possible the development of Raman scattering as a tool for very accurate structural analysis of nano-graphite, with the establishment of an empirical formula for the in- and out-of-plane crystalline size and even fancier Raman-based information, such as for the atomic structure at graphite edges, and the identification of single versus multi-graphene layers Once established, this knowledge provides a powerful machinery to understand newer forms of sp2 carbon materials, such as the recently developed pitch-based graphitic foams Results for the calculated Raman intensity of the disorder-induced D-band in graphitic materials as a function of both the excitation laser energy (Elaser) and the in-plane size (La) of nano-graphites are presented and compared with experimental results The status of this research area is assessed, and opportunities for future work are identified

Carbon materials for supercapacitor application.

Abstract: The most commonly used electrode materials for electrochemical capacitors are activated carbons, because they are commercially available and cheap, and they can be produced with large specific surface area. However, only the electrochemically available surface area is useful for charging the electrical double layer (EDL). The EDL formation is especially efficient in carbon pores of size below 1 nm because of the lack of space charge and a good attraction of ions along the pore walls. The pore size should ideally match the size of the ions. However, for good dynamic charge propagation, some small mesopores are useful. An asymmetric configuration, where the positive and negative electrodes are constructed from different materials, e.g., activated carbon, transition metal oxide or conducting polymer, is of great interest because of an important extension of the operating voltage. In such a case, the energy as well as power is greatly increased. It appears that nanotubes are a perfect conducting additive and/or support for materials with pseudocapacitance properties, e.g. MnO2, conducting polymers. Substitutional heteroatoms in the carbon network (nitrogen, oxygen) are a promising way to enhance the capacitance. Carbons obtained by one-step pyrolysis of organic precursors rich in heteroatoms (nitrogen and/or oxygen) are very interesting, because they are denser than activated carbons. The application of a novel type of electrolyte with a broad voltage window (ionic liquids) is considered, but the stability of this new generation of electrolyte during long term cycling of capacitors is not yet confirmed.

Layer-by-Layer Assembly as a Versatile Bottom-Up Nanofabrication Technique for Exploratory Research and Realistic Application

Abstract: The layer-by-layer (LbL) adsorption technique offers an easy and inexpensive process for multilayer formation and allows a variety of materials to be incorporated within the film structures. Therefore, the LbL assembly method can be regarded as a versatile bottom-up nanofabrication technique. Research fields concerned with LbL assembly have developed rapidly but some important physicochemical aspects remain uninvestigated. In this review, we will introduce several examples from physicochemical investigations regarding the basics of this method to advanced research aimed at practical applications. These are selected mostly from recent reports and should stimulate many physical chemists and chemical physicists in the further development of LbL assembly. In order to further understand the mechanism of the LbL assembly process, theoretical work, including thermodynamics calculations, has been conducted. Additionally, the use of molecular dynamics simulation has been proposed. Recently, many kinds of physicochemical molecular interactions, including hydrogen bonding, charge transfer interactions, and stereo-complex formation, have been used. The combination of the LbL method with other fabrication techniques such as spin-coating, spraying, and photolithography has also been extensively researched. These improvements have enabled preparation of LbL films composed of various materials contained in well-designed nanostructures. The resulting structures can be used to investigate basic physicochemical phenomena where relative distances between interacting groups is of great importance. Similarly, LbL structures prepared by such advanced techniques are used widely for development of functional systems for physical applications from photovoltaic devices and field effect transistors to biochemical applications including nano-sized reactors and drug delivery systems.

Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability

Abstract: The objective of this work is the further systematic improvement of the accuracy of Double-Hybrid Density Functionals (DHDF) that add non-local electron correlation effects to a standard hybrid functional by second-order perturbation theory (S. Grimme, J. Chem. Phys., 2006, 124, 034108). The only known shortcoming of these generally highly accurate functionals is an underestimation of the long-range dispersion (van der Waals) interactions. To correct this deficiency, we add a previously developed empirical dispersion term (DFT-D) to the energy expression but leave the electronic part of the functional untouched. Results are presented for the S22 set of non-covalent interaction energies, the G3/99 set of heat of formations and conformational energies of a phenylalanyl–glycyl–glycine peptide model. We furthermore propose seven hydrocarbon reactions with strong intramolecular dispersion contributions as a benchmark set for newly developed density functionals. In general, the proposed composite approach is for many chemically relevant properties of similar quality as high-level coupled-cluster treatments. A significant increase of the accuracy for non-covalent interactions is obtained and the corrected B2PLYP DHDF provides one of the lowest ever obtained Mean Absolute Deviations (MAD) for the S22 set (0.2–0.3 kcal mol−1). Unprecedented high accuracy is also obtained for the relative energies of peptide conformations that turn out to be very difficult. The significant improvements found for the G3/99 set (reduction of the MAD from 2.4 to 1.7 kcal mol−1) underline the importance of intramolecular dispersion effects in large molecules. In all tested cases the results from the standard B3LYP approach are also significantly improved, and we recommend the general use of dispersion corrections in DFT treatments.

Anodic electron transfer mechanisms in microbial fuel cells and their energy efficiency

Abstract: The performance of a microbial fuel cell (MFC) depends on a complex system of parameters. Apart from technical variables like the anode or fuel cell design, it is mainly the paths and mechanisms of the bioelectrochemical energy conversion that decisively determine the MFC power and energy output. Here, the electron transfer from the microbial cell to the fuel cell anode, as a process that links microbiology and electrochemistry, represents a key factor that defines the theoretical limits of the energy conversion. The determination of the energy efficiency of the electron transfer reactions, based on the biological standard potentials of the involved redox species in combination with the known paths (and stoichiometry) of the underlying microbial metabolism, is an important instrument for this discussion. Against the sometimes confusing classifications of MFCs in literature it is demonstrated that the anodic electron transfer is always based on one and the same background: the exploitation of the necessity of every living cell to dispose the electrons liberated during oxidative substrate degradation.

Electrocatalysis of oxygen reduction and small alcohol oxidation in alkaline media

Abstract: We present here a critical review of several technologically important electrocatalytic systems operating in alkaline electrolytes. These include the oxygen reduction reaction (ORR) occurring on catalysts containing Pt, Pd, Ir, Ru, or Ag, the methanol oxidation reaction (MOR) occurring on Pt-containing catalysts, and the ethanol oxidation reaction (EOR) occurring on Ni–Co–Fe alloy catalysts. Each of these catalytic systems is relevant to alkaline fuel cell (AFC) technology, while the ORR systems are also relevant to chlor-alkali electrolysis and metal-air batteries. The use of alkaline media presents advantages both in electrocatalytic activity and in materials stability and corrosion. Therefore, prospects for the continued development of alkaline electrocatalytic systems, including alkaline fuel cells, seem very promising.

Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode.

Abstract: We present results of density functional theory calculations on a Pt(111) slab with a bilayer of water, solvated protons in the water layer, and excess electrons in the metal surface. In this way we model the electrochemical double layer at a platinum electrode. By varying the number of protons/electrons in the double layer we investigate the system as a function of the electrode potential. We study the elementary processes involved in the hydrogen evolution reaction, 2(H+ + e−) → H2, and determine the activation energy and predominant reaction mechanism as a function of electrode potential. We confirm by explicit calculations the notion that the variation of the activation barrier with potential can be viewed as a manifestation of the Bronsted–Evans–Polanyi-type relationship between activation energy and reaction energy found throughout surface chemistry.

Distance measurements on spin-labelled biomacromolecules by pulsed electron paramagnetic resonance

Abstract: The biological function of protein, DNA, and RNA molecules often depends on relative movements of domains with dimensions of a few nanometers. This length scale can be accessed by distance measurements between spin labels if pulsed electron paramagnetic resonance (EPR) techniques such as electron-electron double resonance (ELDOR) and double-quantum EPR are used. The approach does not require crystalline samples and is well suited to biomacromolecules with an intrinsic flexibility as distributions of distances can be measured. Furthermore, oligomerization or complexation of biomacromolecules can also be studied, even if it is incomplete. The sensitivity of the technique and the reliability of the measured distance distribution depend on careful optimization of the experimental conditions and procedures for data analysis. Interpretation of spin-to-spin distance distributions in terms of the structure of the biomacromolecules furthermore requires a model for the conformational distribution of the spin labels.

Hydrogen storage: the remaining scientific and technological challenges

Abstract: To ensure future worldwide mobility, hydrogen storage in combination with fuel cells for on-board automotive applications is one of the most challenging issues. Potential solid-state solutions have to fulfil operating requirements defined by the fuel cell propulsion system. Important requirements are also defined by customer demands such as cost, overall fuel capacity, refuelling time and efficiency. It seems that currently none of the different storage solid state materials can reach the required storage densities for a hydrogen-powered vehicle. New strategies for storage systems are necessary to fulfil the requirements for a broad introduction of automotive fuel cell powertrains to the market. The combination of different storage systems may provide a possible solution to store sufficiently high amounts of hydrogen.

Size-dependent structural transformations of hematite nanoparticles. 1. Phase transition.

Abstract: Using Fourier Transform InfraRed (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), and Transmission Electron Microscopy (TEM), we characterize the structure and/or morphology of hematite (α-Fe2O3) particles with sizes of 7, 18, 39 and 120 nm. It is found that these nanoparticles possess maghemite (γ-Fe2O3)-like defects in the near surface regions, to which a vibrational mode at 690 cm−1, active both in FTIR and Raman spectra, is assigned. The fraction of the maghemite-like defects and the net lattice disorder are inversely related to the particle size. However, the effect is opposite for nanoparticles grown by sintering of smaller hematite precursors under conditions when the formation of a uniform hematite-like structure throughout the aggregate is restricted by kinetic issues. This means that not only particle size but also the growth kinetics determines the structure of the nanoparticles. The observed structural changes are interpreted as size-induced α-Fe2O3 ↔ γ-Fe2O3 phase transitions. We develop a general model that considers spinel defects and absorbed/adsorbed species (in our case, hydroxyls) as dominant controls on structural changes with particle size in hematite nanoparticles, including solid-state phase transitions. These changes are represented by trajectories in a phase diagram built in three phase coordinates—concentrations of spinel defects, absorbed impurities, and adsorbed species. The critical size for the onset of the α → γ phase transition depends on the particle environment, and for the dry particles used in this study is about 40 nm. The model supports the existence of intermediate phases (protohematite and hydrohematite) during dehydration of goethite. We also demonstrate that the hematite structure is significantly less defective when the nanoparticles are immersed in water or KBr matrix, which is explained by the effects of the electrochemical double layer and increased rigidity of the particle environment. Finally, we revise the problem of applicability of IR spectroscopy to the lattice vibrations of hematite nanoparticles, demonstrating that structural comparison of different samples is much more reliable if it is based on the Eu band at about 460 cm−1 and the spinel band at 690 cm−1, instead of the A2u/Eu band at about 550 cm−1 used in previous work. The new methodology is applied to analysis of the reported IR spectra of Martian hematite.

Non-covalent interactions in biomacromolecules

Abstract: Non-covalent interactions play an important role in chemistry, physics and especially in biodisciplines. They determine the structure of biomacromolecules such as DNA and proteins and are responsible for the molecular recognition process. Theoretical evaluation of interaction energies is difficult; however, perturbation as well as variation (supermolecular) methods are briefly described. Accurate interaction energies can be obtained by complete basis set limit calculations providing a large portion of correlation energy is covered (e.g. by performing CCSD(T) calculations). The role of H-bonding and stacking interactions in the stabilisation of DNA, oligopeptides and proteins is described, and the importance of London dispersion energy is shown.

Mesoporous and nanowire Co3O4 as negative electrodes for rechargeable lithium batteries

Abstract: The conversion reactions associated with mesoporous and nanowire Co3O4 when used as negative electrodes in rechargeable lithium batteries have been investigated. Initially, Li is intercalated into Co3O4 up to x ∼ 1.5 Li in LixCo3O4. Thereafter, both materials form a nanocomposite of Co particles imbedded in Li2O, which on subsequent charge forms CoO. The capacities on cycling increase on initial cycles to values exceeding the theoretical value for Co3O4 + 8 Li+ + 8e− → 4 Li2O + 3 Co, 890 mAhg−1, and this is interpreted as due to charge storage in a polymer layer that forms on the high surface area of nanowire and mesoporous Co3O4. After 15 cycles, the capacity decreases drastically for the nanowires due to formation of grains that are separated one from another by a thick polymer layer, leading to electrical isolation. In contrast, the mesoporous Co3O4 losses its mesoporosity and forms a morphology similar to bulk Co3O4 (Co particles imbedded in Li2O matrix) with which it exhibits a similar capacity on cycling. In contrast to mesoporous lithium intercalation compounds, which show superior capacity at high rates compared to bulk materials, mesoporosity does not seem to improve the capacity of conversion reactions on extended cycling. If, however, mesoporosity could be retained during the conversion reaction, then higher capacities could be obtained in such systems.

A well-tempered density functional theory of electrons in molecules

Abstract: This Invited Article reports extensions of a recently developed approach to density functional theory with correct long-range behavior (R. Baer and D. Neuhauser, Phys. Rev. Lett., 2005, 94, 043002). The central quantities are a splitting functional gamma[n] and a complementary exchange-correlation functional E[n]. We give a practical method for determining the value of gamma in molecules, assuming an approximation for E is given. The resulting theory shows good ability to reproduce the ionization potentials for various molecules. However it is not of sufficient accuracy for forming a satisfactory framework for studying molecular properties. A somewhat different approach is then adopted, which depends on a density-independent gamma and an additional parameter w eliminating part of the local exchange functional. The values of these two parameters are obtained by best-fitting to experimental atomization energies and bond lengths of the molecules in the G2(1) database. The optimized values are gamma = 0.5 a and w = 0.1. We then examine the performance of this slightly semi-empirical functional for a variety of molecular properties, comparing to related works and experiment. We show that this approach can be used for describing in a satisfactory manner a broad range of molecular properties, be they static or dynamic. Most satisfactory is the ability to describe valence, Rydberg and inter-molecular charge-transfer excitations.

Dye-sensitized nanocrystalline solar cells

Abstract: The basic physical and chemical principles behind the dye-sensitized nanocrystalline solar cell (DSC: also known as the Gratzel cell after its inventor) are outlined in order to clarify the differences and similarities between the DSC and conventional semiconductor solar cells. The roles of the components of the DSC (wide bandgap oxide, sensitizer dye, redox electrolyte or hole conductor, counter electrode) are examined in order to show how they influence the performance of the system. The routes that can lead to loss of DSC performance are analyzed within a quantitative framework that considers electron transport and interfacial electron transfer processes, and strategies to improve cell performance are discussed. Electron transport and trapping in the mesoporous oxide are discussed, and a novel method to probe the electrochemical potential (quasi Fermi level) of electrons in the DSC is described. The article concludes with an assessment of the prospects for future development of the DSC concept.

Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR

Abstract: Among microporous systems metal organic frameworks are considered promising materials for molecular adsorption. In this contribution infrared spectroscopy is successfully applied to highlight the positive role played by coordinatively unsaturated Cu2+ ions in HKUST-1, acting as specific interaction sites. A properly activated material, obtained after solvent removal, is characterized by a high fraction of coordinatively unsaturated Cu2+ ions acting as preferential adsorption sites that show specific activities towards some of the most common gaseous species (NO, CO2, CO, N2 and H2). From a temperature dependent IR study, it has been estimated that the H2 adsorption energy is as high as 10 kJ mol−1. A very complex spectral evolution has been observed upon lowering the temperature. A further peculiarity of this material is the fact that it promotes ortho–para conversion of the adsorbed H2 species.

Understanding the kinetics of spin-forbidden chemical reactions

Abstract: Many chemical reactions involve a change in spin-state and are formally forbidden. This article summarises a number of previously published applications showing that a form of Transition State Theory (TST) can account for the kinetics of these reactions. New calculations for the emblematic spin-forbidden reaction HC + N2 are also reported. The observed reactivity is determined by two factors. The first is the critical energy required for reaction to occur, which in spin-forbidden reactions is often defined by the relative energy of the Minimum Energy Crossing Point (MECP) between potential energy surfaces corresponding to the different spin states. The second factor is the probability of hopping from one surface to the other in the vicinity of the crossing region, which is largely defined by the spin–orbit coupling matrix element between the two electronic wavefunctions. The spin-forbidden transition state theory takes both factors into account and gives good results. The shortcomings of the theory, which are largely analogous to those of standard TST, are discussed. Finally, it is shown that in cases where the surface-hopping probability is low, the kinetics of spin-forbidden reactions will be characterised by unusually unfavourable entropies of activation. As a consequence, reactions involving a spin-state change can be expected to compete poorly with spin-allowed reactions at high temperatures (or energies).

Vapourisation of ionic liquids.

Abstract: Eight common imidazolium based ionic liquids have been successfully evaporated in ultra-high vacuum, their vapours analysed by line of sight mass spectrometry and their heats (enthalpy) of vapourisation determined. They were found to evaporate as ion pairs, with heats of vapourisation which depend primarily on the coulombic interactions within the liquid phase and the gas phase ion pair. An electrostatic model is presented relating the heats of vapourisation to the molar volumes of the ionic liquids.

In situ solid state 11B MAS-NMR studies of the thermal decomposition of ammonia borane: mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material

Abstract: The mechanism of hydrogen release from solid state ammonia borane (AB) has been investigated via in situ solid state 11B and 11B{1H} MAS-NMR techniques in external fields of 7.1 T and 18.8 T at a decomposition temperature of 88 °C, well below the reported melting point. The decomposition of AB is well described by an induction, nucleation and growth mechanistic pathway. During the induction period, little hydrogen is released from AB; however, a new species identified as a mobile phase of AB is observed in the 11B NMR spectra. Subsequent to induction, at reaction times when hydrogen is initially being released, three additional species are observed: the diammoniate of diborane (DADB), [(NH3)2BH2]+[BH4]−, and two BH2N2 species believed to be the linear (NH3BH2NH2BH3) and cyclic dimer (NH2BH2)2 of aminoborane. At longer reaction times the sharper features are replaced by broad, structureless peaks of a complex polymeric aminoborane (PAB) containing both BH2N2 and BHN3 species. The following mechanistic model for the induction, nucleation and growth for AB decomposition leading to formation of hydrogen is proposed: (i) an induction period that yields a mobile phase of AB caused by disruption of the dihydrogen bonds; (ii) nucleation that yields reactive DADB from the mobile AB; and (iii) growth that includes a bimolecular reaction between DADB and AB to release the stored hydrogen.

Perturbation of water structure due to monovalent ions in solution

Abstract: The ion induced modification to the tetrahedral structure of water is a topic of much current interest. We address this question by interpreting neutron diffraction data from monovalent ionic solutions of NaCl and KCl using a computer assisted structural modeling technique. We investigate the effect that these ions have on the water–water O–O, O–H and H–H radial distribution functions as a function of ionic concentration. It is found that the O–H and H–H functions are only marginally affected by ionic composition, signaling that hydrogen bonding between water molecules remains largely intact, even at the highest concentrations. On the other hand the O–O functions are strongly modified by the ions. In particular the position of the second peak in gOO(r), is found to move inwards with increasing salt concentration, in a manner closely analogous to what happens in pure water under pressure. Furthermore by recalculating gOO(r) after excluding all the water molecules in the first hydration shell of each ion, we show that this structural perturbation exists outside the first hydration shell of the ions.

Fructose/dioxygen biofuel cell based on direct electron transfer-type bioelectrocatalysis

Abstract: One-compartment biofuel cells without separators have been constructed, in which d-fructose dehydrogenase (FDH) from Gluconobacter sp. and laccase from Trametes sp. (TsLAC) work as catalysts of direct electron transfer (DET)-type bioelectrocatalysis in the two-electron oxidation of d-fructose and four-electron reduction of dioxygen as fuels, respectively. FDH adsorbs strongly and stably on Ketjen black (KB) particles that have been modified on carbon papers (CP) and produces the catalytic current with the maximum density of about 4 mA cm(-2) without mediators at pH 5. The catalytic wave of the d-fructose oxidation is controlled by the enzyme kinetics. The location and the shape of the catalytic waves suggest strongly that the electron is directly transferred to the KB particles from the heme c site in FDH, of which the formal potential has been determined to be 39 mV vs. Ag|AgCl|sat. KCl. Electrochemistry of three kinds of multi-copper oxidases has also been investigated and TsLAC has been selected as the best one of the DET-type bioelectrocatalyst for the four-electron reduction of dioxygen in view of the thermodynamics and kinetics at pH 5. In the DET-type bioelectrocatalysis, the electron from electrodes seems to be transferred to the type I copper site of multi-copper oxidases. TsLAC adsorbed on carbon aerogel (CG) particles with an average pore size of 22 nm, that have been modified on CP electrodes, produces the catalytic reduction current of dioxygen with a density of about 4 mA cm(-2), which is governed by the mass transfer of the dissolved dioxygen. The FDH-adsorbed KB-modified CP electrodes and the TsLAC-adsorbed CG-modified CP electrodes have been combined to construct one-compartment biofuel cells without separators. The open-circuit voltage was 790 mV. The maximum current density of 2.8 mA cm(-2) and the maximum power density of 850 microW cm(-2) have been achieved at 410 mV of the cell voltage under stirring.

Femtosecond quantum control of molecular dynamics in the condensed phase

Abstract: We review the progress in controlling quantum dynamical processes in the condensed phase with femtosecond laser pulses. Due to its high particle density the condensed phase has both high relevance and appeal for chemical synthesis. Thus, in recent years different methods have been developed to manipulate the dynamics of condensed-phase systems by changing one or multiple laser pulse parameters. Single-parameter control is often achieved by variation of the excitation pulse’s wavelength, its linear chirp or its temporal subpulse separation in case of pulse sequences. Multiparameter control schemes are more flexible and provide a much larger parameter space for an optimal solution. This is realized in adaptive femtosecond quantum control, in which the optimal solution is iteratively obtained through the combination of an experimental feedback signal and an automated learning algorithm. Several experiments are presented that illustrate the different control concepts and highlight their broad applicability. These fascinating achievements show the continuous progress on the way towards the control of complex quantum reactions in the condensed phase.

Intermediate temperature proton conductors for PEM fuel cells based on phosphonic acid as protogenic group: A progress report

Abstract: The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the “spacer concept”, which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming “bulky” hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below σ = 10–3 S cm–1 at T = 150 °C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC >10 meq g–1) may allow for high proton conductivities in the intermediate temperature range (T ∼ 120 –160 °C).

Adsorption of sulfur dioxide on hematite and goethite particle surfaces

Abstract: The adsorption of sulfur dioxide (SO2) on iron oxide particle surfaces at 296 K has been investigated using X-ray photoelectron spectroscopy (XPS). A custom-designed XPS ultra-high vacuum chamber was coupled to an environmental reaction chamber so that the effects of adsorbed water and molecular oxygen on the reaction of SO2 with iron oxide surfaces could be followed at atmospherically relevant pressures. In the absence of H2O and O2, exposure of hematite (α-Fe2O3) and goethite (α-FeOOH) to SO2 resulted predominantly in the formation of adsorbed sulfite (SO32−), although evidence for adsorbed sulfate (SO42−) was also found. At saturation, the coverage of adsorbed sulfur species was the same on both α-Fe2O3 and α-FeOOH as determined from the S2p : Fe2p ratio. Equivalent saturation coverages and product ratios of sulfite to sulfate were observed on these oxide surfaces in the presence of water vapor at pressures between 6 and 18 Torr, corresponding to 28 to 85% relative humidity (RH), suggesting that water had no effect on the adsorption of SO2. In contrast, molecular oxygen substantially influenced the interactions of SO2 with iron oxide surfaces, albeit to a much larger extent on α-Fe2O3 relative to α-FeOOH. For α-Fe2O3, adsorption of SO2 in the presence of molecular oxygen resulted in the quantitative formation of SO42− with no detectable SO32−. Furthermore, molecular oxygen significantly enhanced the extent of SO2 uptake on α-Fe2O3, as indicated by the greater than two-fold increase in the S2p : Fe2p ratio. Although SO2 uptake is still enhanced on α-Fe2O3 in the presence of molecular oxygen and water, the enhancement factor decreases with increasing RH. In the case of α-FeOOH, there is an increase in the amount of SO42− in the presence of molecular oxygen, however, the predominant surface species remained SO32− and there is no enhancement in SO2 uptake as measured by the S2p : Fe2p ratio. A mechanism involving molecular oxygen activation on oxygen vacancy sites is proposed as a possible explanation for the non-photochemical oxidation of sulfur dioxide on iron oxide surfaces. The concentration of these sites depends on the exact environmental conditions of RH.

Scanning electrochemical microscopy in the 21st century

Abstract: The fundamentals of and recent advances in scanning electrochemical microscopy (SECM) are described. The focus is on applications of this method to studies of systems and processes of active current interest ranging from nanoelectrochemistry to electron transfer reactions and electrocatalysis to biological imaging.

Dynamics of efficient electron-hole separation in TiO2 nanoparticles revealed by femtosecond transient absorption spectroscopy under the weak-excitation condition.

Abstract: The transient absorption of nanocrystalline TiO2 films in the visible and IR wavelength regions was measured under the weak-excitation condition, where the second-order electron–hole recombination process can be ignored. The intrinsic dynamics of the electron–hole pairs in the femtosecond to picosecond time range was elucidated. Surface-trapped electrons and surface-trapped holes were generated within ∼200 fs (time resolution). Surface-trapped electrons, which gave an absorption peak at around 800 nm, and bulk electrons, which absorbed in the IR wavelength region, decayed with a 500-ps time constant due to relaxation into deep bulk trapping sites. It is already known that, after this relaxation, electrons and holes survive for microseconds. We interpreted these long lifetimes in terms of the prompt spatial charge separation of electrons in the bulk and holes at the surface.

Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory.

Abstract: By varying the external electric field in density functional theory (DFT) calculations we have estimated the impact of the local electric field in the electric double layer on the oxygen reduction reaction (ORR). Potentially, including the local electric field could change adsorption energies and barriers substantially, thereby affecting the reaction mechanism predicted for ORR on different metals. To estimate the effect of local electric fields on ORR we combine the DFT results at various external electric field strengths with a previously developed model of electrochemical reactions which fully accounts for the effect of the electrode potential. We find that the local electric field only slightly affects the output of the model. Hence, the general picture obtained without inclusion of the electric field still persists. However, for accurate predictions at oxygen reduction potentials close to the volcano top local electric field effects may be of importance.

Taxonomy of periodic nets and the design of materials.

Abstract: The concept of a natural tiling for a periodic net is introduced and used to derive a transitivity associated with the structure. It is accordingly shown that the transitivity provides a useful method of classifying polyhedra and nets. For design of materials to serve as targets for synthesis, structures with one kind of edge (edge transitive) are particularly important. Edge-transitive polyhedra, layers and 3-periodic nets are then described. Some other nets of special importance in crystal chemistry are also identified.

Quintuple-ζ quality coupled-cluster correlation energies with triple-ζ basis sets

Abstract: The explicitly-correlated coupled-cluster method CCSD(T)(R12) is extended to include F12 geminal basis functions that decay exponentially with the interelectronic distance and reproduce the form of the average Coulomb hole more accurately than linear-r12. Equations derived using the Ansatz 2 strong orthogonality projector are presented. The convergence of the correlation energy with orbital basis set for the new CCSD(T)(F12) method is studied and found to be rapid, 98% of the basis set limit correlation energy is typically recovered using triple-ζ orbital basis sets. The performance for reaction enthalpies is assessed via a test set of 15 reactions involving 23 molecules. The title statement is found to hold equally true for total and relative correlation energies.

Semiconductor and ceramic nanoparticle films deposited by chemical bath deposition

Abstract: Chemical bath deposition (CBD) has been used to deposit films of metal sulfides, selenides and oxides, together with some miscellaneous compounds, beginning nearly 140 years ago. While it is a well-known technique in a few specific areas (notably photoconductive lead salt detectors, photoelectrodes and more recently, thin film solar cells), it is by and large an under-appreciated technique. The more recent interest in all things ‘nano’ has provided a boost for CBD: since it is a low temperature, solution (almost always aqueous) technique, crystal size is often very small. This is evidenced by the existence of size quantization commonly found in CBD semiconductor films. The intention of this review is to provide readers, many of whom may not even be aware of the CBD technique, with an overview of how the technique has been used to fabricate nanocrystalline semiconductor (this terminology also includes oxides often classified as ceramics) films and some properties of these films. The review begins, after a short introduction, with a general description of the CBD method, designed to give the reader a basic knowledge of the technique. The rest of the review then focuses on nanocrystalline (or, in the few cases of amorphous deposits, nanoparticle) films. The various factors which determine crystal size are first discussed. This is followed by some of the many examples of size quantization observed in the films. Since CBD films are usually porous, surface effects can be very important, and various surface-dependent properties (light emission and surface states) as well as surface modification, are treated: (although some properties, like emission, can be strongly dependent on both surface and ‘bulk’). Because of the fact that many CBD films have been made specifically for use as photoelectrodes in photoelectrochemical cells, there is next a chapter on this topic with a few examples of such photoelectrodes. Film structure and morphology follows with examples of patterning, porosity and crystal shape. The review concludes with some of the author’s opinions as to what the near future holds for CBD development in general.

Theory and computation of nuclear magnetic resonance parameters.

Abstract: The art of quantum chemical electronic structure calculation has over the last 15 years reached a point where systematic computational studies of magnetic response properties have become a routine procedure for molecular systems. One of their most prominent areas of application are the spectral parameters of nuclear magnetic resonance (NMR) spectroscopy, due to the immense importance of this experimental method in many scientific disciplines. This article attempts to give an overview on the theory and state-of-the-art of the practical computations in the field, in terms of the size of systems that can be treated, the accuracy that can be expected, and the various factors that would influence the agreement of even the most accurate imaginable electronic structure calculation with experiment. These factors include relativistic effects, thermal effects, as well as solvation/environmental influences, where my group has been active. The dependence of the NMR spectra on external magnetic and optical fields is also briefly touched on.