Coverage dependence and hydroperoxyl-mediated pathway of catalytic water formation on Pt (111) surface

Hydrogen oxidation on Pt (111) surface is modeled by density functional theory (DFT). Previous DFT calculations showed too large O2 dissociation barriers, but we find them highly coverage dependent: when the coverage is low, dissociation barriers close to experimental values (approximately 0.3 eV) are obtained. For the whole reaction, a new pathway involving hydroperoxyl (OOH) intermediate is found, with the highest reaction barrier of only approximately 0.4 eV. This may explain the experimental observation of catalytic water formation on Pt (111) surface above the H2O desorption temperature of 170 K, despite that the direct reaction between chemisorbed O and H atoms is a highly activated process with barrier approximately 1 eV as previous calculations showed.     

Agostic interactions and dissociation in the first layer of water on Pt(111)

Recent quantum mechanical (QM) calculations for a monolayer of H(2)O on Ru(0001) suggested a novel stable structure with half the waters dissociated. However, different studies on Pt(111) suggested an undissociated bilayer structure in which the outer half of the water has the OH bonds toward the surface rather than the O lone pair. Since water layers on Pt are important in many catalytic processes (e.g., the fuel cell cathode), we calculated the energetics and structure of the first monolayer of water on the Pt(111) surface using QM [periodic slab using density functional calculations (DFT) with the PBE-flavor of exchange-correlation functional]. We find that the fully saturated surface ((2)/(3) ML) has half the water almost parallel to the surface (forming a Pt-O Lewis acid-base bond), whereas the other half are perpendicular to the surface, but with the H down toward the surface (forming a Pt-HO agostic bond). This leads to a net bond energy of 0.60 eV/water = 13.8 kcal/mol (the standard ice model with the H up configuration of the water molecules perpendicular to the surface is less stable by 0.092 eV/water = 2.1 kcal/mol). We examined whether the partial dissociation of water proposed for Ru(0001) could occur on Pt(111). For the saturated water layer ((2)/(3) ML) we find a stable structure with half the H(2)O dissociated (forming Pt-OH and Pt-H covalent bonds), which is less favorable by only 0.066 eV/water = 1.51 kcal/mol. These results confirm the interpretation of combined experimental (XAS, XES, XPS) and theoretical (DFT cluster and periodic including spectrum calculations) studies, which find only the H down undissociated case. We find that the undissociated structure leads to a vertical displacement between the two layers of oxygens of approximately 0.42 A (for both H down and H up). In contrast, the partially dissociated system leads to a flat structure with a separation of the oxygen layers of 0.08 A. Among the partially dissociated systems, we find that all subsurface positions for the dissociated hydrogen are less favorable than adsorbing on top of the free Pt surface atom. Our results suggest that for less than (1)/(3) ML, clustering would be observed rather than ordered monolayer structures.     

Membrane-derived fluorinated radicals detected by electron spin resonance in UV-irradiated Nafion and Dow ionomers: effect of counterions and H2O2

Electron spin resonance (ESR) spectroscopy was used to detect and identify radicals formed by UV irradiation of Nafion and Dow perfluorinated membranes partially or fully neutralized by Cu(II), Fe(II), and Fe(III). This method allowed the monitoring of ESR signals from the paramagnetic counterions together with the appearance of membrane-derived radical species. The most surprising aspect of this study was the formation of membrane-derived radical species only in the neutralized membranes, and even in the absence of H2O2 in the case of Nafion/Cu(II) and Nafion/Fe(III). In Nafion/Cu(II), ESR spectra from radicals exhibiting hyperfine interactions with three equivalent 19F nuclei (the "quartet") and with four equivalent 19F nuclei (the "quintet") were detected. In Nafion/Fe(II) exposed to H2O2 solutions, the formation of Fe(III) was detected. Upon UV irradiation, strong signals from the chain-end radical ROCF2CF2* were detected first, followed by the appearance, upon annealing above 200 K, of the quartet signal observed in Nafion/Cu(II). In subsequent experiments with Nafion and Dow membranes neutralized by Fe(III), the ROCF2CF2* radicals were formed even in the absence of H2O2, indicating that the role of H2O2 is oxidation of Fe(II) to Fe(III); moreover, in these systems small amounts of the chain-end radicals were detected even without UV irradiation. This result validates the method used to form the radicals: the role of UV irradiation is to accelerate the formation of a signal that is produced, albeit slowly, even in the dark, and possibly during fuel cell operation. The major conclusion is that cations are involved in degradation processes; the point of attack appears to be at or near the pendant chain of the ionomer. Therefore when studying membrane stability, it is important to consider not only the formation of oxygen radicals, such as HO*, HOO*, and O2*-, that can attack the membrane but also the specific reactivity of counterions.     

Theoretical mechanism study of UF6 hydrolysis in the gas phase

The mechanism of the gas-phase reaction UF 6 + H 2O --> UOF 4 + 2HF is explored using relativistic density functional theory calculations. Initially, H 2O coordinates with UF 6 to form a 1:1 complex UF 6.H 2O. Over an activation energy barrier of about 19 kcal/mol, H 2O transfers a H atom to a nearby ligand F, resulting in UF 5OH + HF. The eliminated HF or another H 2O molecule may form a hydrogen bond with UF 5OH. Starting from UF 5OH, the second HF elimination results in UOF 4. If UF 5OH is in the isolated form, UF 5OH --> UOF 4 + HF takes place over a barrier of 24 kcal/mol. If UF 5OH is hydrogen-bonded with H 2O or HF, the conversion barrier is less than 10 kcal/mol. Once formed, the unstable UOF 4 tends to associate with additional ligands and hydrogen-bonding donors. The calculated binding energies indicate the significance of such interactions, which may have profound impact on further HF eliminating reactions. The IR spectra features can be used to indicate the formation and interaction type of the intermediates and products.     

Temperature dependence of oxygen reduction activity at Nafion-coated bulk Pt and Pt/carbon black catalysts

Oxygen reduction reaction (ORR) activity and H(2)O(2) formation at Nafion-coated film electrodes of bulk-Pt and Pt nanoparticles dispersed on carbon black (Pt/CB) were investigated in 0.1 M HClO(4) solution at 30 to 110 degrees C by using a channel flow double electrode method. We have found that the apparent rate constants k(app) (per real Pt active surface area) for the ORR at bulk-Pt (with and without Nafion-coating) and Nafion-coated Pt/CB (19.3 and 46.7 wt % Pt, d(Pt) = 2.6 to 2.7 nm) thin-film electrodes were in beautiful agreement with each other in the operation conditions of polymer electrolyte fuel cells (PEFCs), i.e., 30-110 degrees C and ca. 0.7 to 0.8 V vs RHE. The H(2)O(2) yield was 0.6-1.0% at 0.7-0.8 V on all Nafion-coated Pt/CB and bulk-Pt and irrespective of Pt-loading level and temperature. Nafion coating was pointed out to be a major factor for the H(2)O(2) formation on Pt catalysts modifying the surface property, because H(2)O(2) production was not detected at the bulk-Pt electrode without Nafion coating.     

Catalytic water formation on platinum: a first-principles study.

The study of catalytic behavior begins with one seemingly simple process, namely the hydrogenation of O to H2O on platinum. Despite the apparent simplicity its mechanism has been much debated. We have used density functional theory with gradient corrections to examine microscopic reaction pathways for several elementary steps implicated in this fundamental catalytic process. We find that H2O formation from chemisorbed O and H atoms is a highly activated process. The largest barrier along this route, with a value of approximately 1 eV, is the addition of the first H to O to produce OH. Once formed, however, OH groups are easily hydrogenated to H2O with a barrier of approximately 0.2 eV. Disproportionation reactions with 1:1 and 2:1 stoichiometries of H2O and O have been examined as alternative routes for OH formation. Both stoichiometries of reaction produce OH groups with barriers that are much lower than that associated with the O + H reaction. H2O, therefore, acts as an autocatalyst in the overall H2O formation process. Disproportionation with a 2:1 stoichiometry is thermodynamically and kinetically favored over disproportionation with a 1:1 stoichiometry. This highlights an additional (promotional) role of the second H2O molecule in this process. In support of our previous suggestion that the key intermediate in the low-temperature H2O formation reaction is a mixed OH and H2O overlayer we find that there is a very large barrier for the dissociation of the second H2O molecule in the 2:1 disproportionation process. We suggest that the proposed intermediate is then hydrogenated to H2O through a very facile proton-transfer mechanism.     

Surface modified multi‐walled carbon nanotubes and Nafion nanocomposite membranes for use in fuel cell applications

The preparation and characterization of the nanocomposite polyelectrolyte membranes, based on Nafion, sulfonated multi‐walled carbon nanotubes (MWCNT‐SO₃H) and imidazole modified multi‐walled carbon nanotubes (MWCNT‐Im), for direct methanol fuel cell applications is described. The results showed that the modification of multi‐walled carbon nanotubes (MWCNT) with proton‐conducting groups (sulfonic acid groups or imidazole groups) could enhance the proton conductivity of the nanocomposite membranes in comparison to Nafion 117. Regarding the interactions between the protonated imidazole groups, grafted on the surface of MWCNT, and the negatively charged sulfonic acid groups of Nafion, new electrostatic interactions can be formed in the interface of the Nafion and MWCNT‐Im, which result in both lower methanol permeability and higher proton conductivity. The physical characteristics of these manufactured nanocomposite membranes were investigated by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, water uptake, methanol permeability, and ion exchange capacity, as well as proton conductivity. The Nafion/MWCNT‐Im membranes showed the higher proton conductivity, lower methanol permeability, and, as a consequence, a higher selectivity parameter in comparison to the neat Nafion or Nafion membrane containing MWCNT‐SO₃H or ─OH functionalized multi‐walled carbon nanotubes (MWCNT‐OH) membranes. The obtained results indicated that the Nafion/MWCNT‐Im membranes could be used as efficient polyelectrolyte membranes for direct methanol fuel cell applications.     

Mechanistic study of the electrochemical oxygen reduction reaction on Pt(111) using density functional theory

Density functional theory (DFT) was used to study the electrolyte solution effects on the oxygen reduction reaction (ORR) on Pt(111). To model the acid electrolyte, an H(5)O(2)(+) cluster was used. The vibrational proton oscillation modes for adsorbed H(5)O(2)(+) computed at 1711 and 1010 cm(-1), in addition to OH stretching and H(2)O scissoring modes, agree with experimental vibrational spectra for proton formation on Pt surfaces in ultrahigh vacuum. Using the H(5)O(2)(+) model, protonation of adsorbed species was found to be facile and consistent with the activation barrier of proton transfer in solution. After protonation, OOH dissociates with an activation barrier of 0.22 eV, similar to the barrier for O(2) dissociation. Comparison of the two pathways suggests that O(2) protonation precedes dissociation in the oxygen reduction reaction. Additionally, an OH diffusion step following O protonation inhibits the reaction, which may lead to accumulation of oxygen on the electrode surface.     

DEA与SDS/n-C5H11OH/H2O微乳液的相互作用

以循环伏安法研究了N,N-二乙基苯胺（DEA）与十二烷基硫酸钠（SDS）/正戊醇（n-C5H11OH）/H2O体系O/W和W/O结构微乳液的相互作用.结果表明,DEA在SDS/n-C5H11OH/H2O体系微乳液中有两种定位方式:其一,DEA分子在微乳液液滴膜相中定位于表面活性剂和助表面活性剂的极性基团附近;其二,DEA分子在微乳液液滴膜相中定位于表面活性剂疏水基团一侧.两种定位的分布与微乳液的结构和组成相关.     

The mechanism of N2O formation via the (NO)2 dimer: a density functional theory study

Catalytic formation of N(2)O via a (NO)(2) intermediate was studied employing density functional theory with generalized gradient approximations. Dimer formation was not favored on Pt(111), in agreement with previous reports. On Pt(211) a variety of dimer structures were studied, including trans-(NO)(2) and cis-(NO)(2) configurations. A possible pathway involving (NO)(2) formation at the terrace near to a Pt step is identified as the possible mechanism for low-temperature N(2)O formation. The dimer is stabilized by bond formation between one O atom of the dimer and two Pt step atoms. The overall mechanism has a low barrier of approximately 0.32 eV. The mechanism is also put into the context of the overall NO + H(2) reaction. A consideration of the step-wise hydrogenation of O(ads) from the step is also presented. Removal of O(ads) from the step is significantly different from O(ads) hydrogenation on Pt(111). The energetically favored structure at the transition state for OH(ads) formation has an activation energy of 0.63 eV. Further hydrogenation of OH(ads) has an activation energy of 0.80 eV.     

Different surface chemistries of water on Ru[0001]: from monomer adsorption to partially dissociated bilayers

Density functional theory has been used to perform a comparative theoretical study of the adsorption and dissociation of H(2)O monomers and icelike bilayers on Ru[0001]. H(2)O monomers bind preferentially at atop sites with an adsorption energy of approximately 0.4 eV/H(2)O. The main bonding interaction is through the H(2)O 1b(1) molecular orbital which mixes with Ru d(z)2 states. The lower-lying set of H(2)O molecules in an intact H(2)O bilayer bond in a similar fashion; the high-lying H(2)O molecules, however, do not bond directly with the surface, rather they are held in place through H bonding. The H(2)O adsorption energy in intact bilayers is approximately 0.6 eV/H(2)O and we estimate that H bonding accounts for approximately 70% of this. In agreement with Feibelman (Science 2002, 295, 99) we find that a partially dissociated OH + H(2)O overlayer is energetically favored over pure intact H(2)O bilayers on the surface. The barrier for the dissociation of a chemisorbed H(2)O monomer is 0.8 eV, whereas the barrier to dissociate a H(2)O incorporated in a bilayer is just 0.5 eV.     

Determination of surface diffusion coefficients of the hydrogen adatom and surface oh radical on platinum electrode

A localized Pt/Nafion interface was established on a planar polycrystalline platinum electrode and the diffusion flux of adsorbed H atoms and OH radical toward the boundary of the interface was measured as the transient current with the cyclovoltammetric technique. Then the surface diffusion coefficients of adsorbed H-atom and OH radical on platinum surface were estimated by solving the differential equation of surface diffusion This article was submitted by the authors in English.     

Adsorption and dissociation of H2O2 on Pt and Pt-alloy clusters and surfaces

The adsorption of H(2)O(2) on Pt and Pt-M alloys, where M is Cr, Co, or Ni, is investigated using density functional theory. Binding energies calculated with a hybrid DFT functional (B3PW91) are in the range of -0.71 to -0.88 eV for H(2)O(2) adsorbed with one of the oxygen atoms on top Pt positions of Pt(3), Pt(2)M, and PtM(2), and enhanced values in the range of -0.81 to -1.09 eV are found on top Ni and Co sites of the Pt(2)M clusters. Adsorption on top sites of Pt(10) yields a weaker binding of -0.48 eV, whereas on periodic Pt(111) and Pt(3)Co(111) surfaces, H(2)O(2) generally dissociates into two OH radicals. On the other hand, attempts to attach H(2)O(2) on bridge sites cause spontaneous dissociation of H(2)O(2) into two adsorbed OH radicals, suggesting that stable adsorptions on bridge sites are not possible for any of the clusters or extended surfaces that are being studied. We also found that the water-H(2)O(2) interaction reduces the strength of the adsorption of H(2)O(2) on these clusters and surfaces.     

A simple Maxwell-Wagner-Butler-Volmer approach to the impedance of the hydrogen electrode in a nafion fuel cell

A simple one-dimensional model of the impedance of a hydrogen/Nafion electrode is set up combining the usual Maxwell-Wagner approach for linear, homogeneous, and isotropic media with the linearized Butler-Volmer equation for the interfacial, electrochemical reaction. Only one relaxation semicircle is normally seen in the Nyquist diagram, but a low-frequency arc may appear at high overvoltages. The model is described by only two dimensionless parameters (in addition to the dimensionless frequency). These parameters are related to the double-layer capacitance and to the interfacial electrochemical reaction rate, respectively. With some adjustments, the model can be used to explain the observed equilibrium impedance from 40 to 70 degrees C of a symmetric cell of the type C/Pt/H(2)|Nafion 117/H(2)/Pt/C. The hydrogen electrodes in this cell were built up as a disperse multiphase region (carbon, platinum grains, Nafion 117, and hydrogen gas) as commonly done in solid polymer fuel cells.     

Preparation of high catalyst utilization electrodes for polymer electrolyte fuel cells

We have developed a novel preparation procedure for an electrocatalyst layer with high utilization of catalyst for polymer electrolyte fuel cells. A commercial Pt catalyst supported on high surface area carbon black (Pt/CB) and Nafion ionomer solution was heated in an autoclave at 200 degrees C, followed by quenching to form the ink of the mixture. It was found that the cathode prepared with the new catalyst ink exhibited very high performance, i.e., high catalyst utilization and improved gas diffusivity. The microstructure analysis indicated that the autoclave treatment promoted an effective introduction of Nafion ionomer into primary pores of Pt/CB agglomerates, in which ca. 90% of Pt catalysts were supported. It was clearly observed by scanning transmission electron microscopy that Nafion ionomer was distributed more uniformly inside Pt/CB agglomerates, compared with those simply mixed with a ball mill in a conventional manner.     

Water desorption from an oxygen covered Pt(111) surface: multichannel desorption

Mixed OH/H2O structures, formed by the reaction of O and water on Pt(111), decompose near 200 K as water desorbs. With an apparent activation barrier that varies between 0.42 and 0.86 eV depending on the composition, coverage, and heating rate of the film, water desorption does not follow a simple kinetic form. The adsorbate is stabilized by the formation of a complete hydrogen bonding network between equivalent amounts of OH and H2O, island edges, and defects in the structure enhancing the decomposition rate. Monte Carlo simulations of water desorption were made using a model potential fitted to first-principles calculations. We find that desorption occurs via several distinct pathways, including direct or proton-transfer mediated desorption and OH recombination. Hence, no single rate determining step has been found. Desorption occurs preferentially from low coordination defect or edge sites, leading to complex kinetics which are sensitive to both the temperature, composition, and history of the sample.     

Electronic states of thiophenyl and furanyl radicals and dissociation energy of thiophene via photoelectron imaging of negative ions

We report photoelectron images and spectra of deprotonated thiophene, C(4)H(3)S(-), obtained at 266, 355, and 390 nm. Photodetachment of the α isomer of the anion is observed, and the photoelectron bands are assigned to the ground X(2)A(') (σ) and excited A(2)A(") and B(2)A(") (π) states of the thiophenyl radical. The photoelectron angular distributions are consistent with photodetachment from the respective in-plane (σ) and out-of-plane (π(?)) orbitals. The adiabatic electron affinity of α-(●)C(4)H(3)S is determined to be 2.05 ± 0.08 eV, while the B(2)A(") term energy is estimated at 1.6 ± 0.1 eV. Using the measured electron affinity and the electron affinity/acidity thermodynamic cycle, the C-H(α) bond dissociation energy of thiophene is calculated as DH(298)(H(α)-C(4)H(3)S) = 115 ± 3 kcal/mol. Comparison of this value to other, previously reported C-H bond dissociation energies, in particular for benzene and furan, sheds light of the relative thermodynamic stabilities of the corresponding radicals. In addition, the 266 nm photoelectron image and spectrum of the furanide anion, C(4)H(3)O(-), reveal a previously unobserved vibrationally resolved band, assigned to the B(2)A(") excited state of the furanyl radical, (●)C(4)H(3)O. The observed band origin corresponds to a 2.53 ± 0.01 eV B(2)A(") term energy, while the resolved vibrational progression (853 ± 42 cm(-1)) is assigned to an in-plane ring mode of α-(●)C(4)H(3)O (B(2)A(")).     

Dissociative photoionization mechanism of methanol isotopologues (CH3OH, CD3OH, CH3OD and CD3OD) by iPEPICO: energetics, statistical and non-statistical kinetics and isotope effects

The dissociative photoionization of energy selected methanol isotopologue (CH(3)OH, CD(3)OH, CH(3)OD and CD(3)OD) cations was investigated using imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy. The first dissociation is an H/D-atom loss from the carbon, also confirmed by partial deuteration. Somewhat above 12 eV, a parallel H(2)-loss channel weakly asserts itself. At photon energies above 15 eV, in a consecutive hydrogen molecule loss to the first H-atom loss, the formation of CHO(+)/CDO(+) dominates as opposed to COH(+)/COD(+) formation. We see little evidence for H-atom scrambling in these processes. In the photon energy range corresponding to the B[combining tilde] and C[combining tilde] ion states, a hydroxyl radical loss appears yielding CH(3)(+)/CD(3)(+). Based on the branching ratios, statistical considerations and ab initio calculations, this process is confirmed to take place on the first electronically excited ?(2)A' ion state. Uncharacteristically, internal conversion is outcompeted by unimolecular dissociation due to the apparently weak Renner-Teller-like coupling between the X[combining tilde] and the ? ion states. The experimental 0 K appearance energies of the ions CH(2)OH(+), CD(2)OH(+), CH(2)OD(+) and CD(2)OD(+) are measured to be 11.646 ± 0.003 eV, 11.739 ± 0.003 eV, 11.642 ± 0.003 eV and 11.737 ± 0.003 eV, respectively. The E(0)(CH(2)OH(+)) = 11.6454 ± 0.0017 eV was obtained based on the independently measured isotopologue results and calculated zero point effects. The 0 K heat of formation of CH(2)OH(+), protonated formaldehyde, was determined to be 717.7 ± 0.7 kJ mol(-1). This yields a 0 K heat of formation of CH(2)OH of -11.1 ± 0.9 kJ mol(-1) and an experimental 298 K proton affinity of formaldehyde of 711.6 ± 0.8 kJ mol(-1). The reverse barrier to homonuclear H(2)-loss from CH(3)OH(+) is determined to be 36 kJ mol(-1), whereas for heteronuclear H(2)-loss from CH(2)OH(+) it is found to be 210 kJ mol(-1).     

Using layer-by-layer assembly of polyaniline fibers in the fast preparation of high performance fuel cell nanostructured membrane electrodes

Membrane electrode assemblies (MEA) for fuel cells require optimization of their nanoscale organization to reach performance parameters, which include enhanced power density, increased catalyst utilization and reduced cost. We applied sprayed layer-by-layer assembly to produce a high activity MEA for H(2)/O(2) fuel cells from polyaniline fibers (PANI-F). This technique produces "fast-prepared" membranes with nanoscale structure, which allows to adequately address specific tuning of their porosity, platinum loading, electronic conductivity, and proton conductivity. Pt nanoparticles were attached to the PANI-F in a reaction of selective heterogeneous nucleation. After functionalization, Pt/PANI-F were assembled with Nafion. Microscopic investigation revealed that functionalized polyaniline fibers formed a highly porous yet tight network of interpenetrating conductors connected to the catalytic Pt particles. The Pt/PANI-F LBL ultrathin MEA demonstrated a power densitiy of 63 mW cm(-2) and yielded a Pt utilization of 437.5 W g(-1) Pt which is comparable to the traditional fuel cell using carbon black as Pt support. Moreover, the amount of Pt used in this work is almost 2 times lower than for usual carbon-supported Pt catalysts.