Identification of Majorana Modes in Interacting Systems by Local Integrals of Motion.

Recently, there has been substantial progress in methods of identifying local integrals of motion in interacting integrable models or in systems with many-body localization. We show that one of these approaches can be utilized for constructing local, conserved, Majorana fermions in systems with an arbitrary many-body interaction. As a test case, we first investigate a noninteracting Kitaev model and demonstrate that this approach perfectly reproduces the standard results. Then, we discuss how the many-body interactions influence the spatial structure and the lifetime of the Majorana modes. Finally, we determine the regime for which the information stored in the Majorana correlators is also retained for arbitrarily long times at high temperatures. We show that it is included in the regime with topologically protected soft Majorana modes, but in some cases is significantly smaller.

The microelectronic wireless nitrate sensor network for environmental water monitoring.

Quantitative monitoring of water conditions in a field is a critical ability for environmental science studies. We report the design, fabrication and testing of a low cost, miniaturized and sensitive electrochemical based nitrate sensor for quantitative determination of nitrate concentrations in water samples. We have presented detailed analysis for the nitrate detection results using the miniaturized sensor. We have also demonstrated the integration of the sensor to a wireless network and carried out field water testing using the sensor. We envision that the field implementation of the wireless water sensor network will enable "smart farming" and "smart environmental monitoring".

Real-time investigations of Pt(111) surface transformations in sulfuric acid solutions.

We present the first broadband sum-frequency generation (SFG) spectra of adlayers from sulfuric acid solutions on Pt(111) surfaces and reveal surface transformations of (bi)sulfate anions in unprecedented detail. SFG amplitudes, bandwidth, and electrochemical Stark tuning of (bi)sulfate vibrational bands centered at 1250-1290 cm(-1) strongly depend on the applied potential and are correlated with prominent voltammetric features. (Bi)sulfate adlayers on Pt(111) are important model systems for weak, specific adsorption of anions on catalytically active surfaces. Although the existence of surface transformations on Pt(111) in dilute H(2)SO(4) solutions has been established by previous studies, so far they have not been observed with surface vibrational spectroscopy. Our results confirm previous reports of a surface transformation at 0.21 V and provide new information on a second transformation at 0.5 V due to surface hydroxyl formation and rearrangement of the electric double layer.

Sum-frequency generation of acetate adsorption on Au and Pt surfaces: molecular structure effects.

The reversible adsorption of acetate on polycrystalline Au and Pt surfaces was investigated with broadband sum-frequency generation (SFG) and cyclic voltammetry. Specifically adsorbed acetate as well as coadsorbed sulfuric acid anions are observed for the first time with SFG and give rise to dramatically different SFG intensities on Au and Pt surfaces. While similar coverages of acetate adlayers on Au and Pt surfaces are well established by previous studies, an identification of the interfacial molecular structure has been elusive. However, we have applied the high sensitivity of SFG for interfacial polar ordering to identify different acetate structures at Au and Pt surfaces in contact with HClO(4) and H(2)SO(4) electrolytes. Acetate competes with the formation of surface oxides and shifts the oxidation threshold of both Au and Pt electrodes anodically. Effects of the supporting electrolyte on the formation of acetate adlayers are revealed by comparing SFG spectra in HClO(4) and H(2)SO(4) solutions: Sulfuric acid anions modify the potential-dependent acetate adsorption, compete with adsorbed acetate on Au and coadsorb with acetate on Pt surfaces.

Parallel in time dynamics with quantum annealers.

Recent years have witnessed an unprecedented increase in experiments and hybrid simulations involving quantum computers. In particular, quantum annealers. There exist a plethora of algorithms promising to outperform classical computers in the near-term future. Here, we propose a parallel in time approach to simulate dynamical systems designed to be executed already on present-day quantum annealers. In essence, purely classical methods for solving dynamics systems are serial. Therefore, their parallelization is substantially limited. In the presented approach, however, the time evolution is rephrased as a ground-state search of a classical Ising model. Such a problem is solved intrinsically in parallel by quantum computers. The main idea is exemplified by simulating the Rabi oscillations generated by a two-level quantum system (i.e. qubit) experimentally.

Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid.

We report a combined X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and chronoamperometry (CA) study of formic acid electrooxidation on unsupported palladium nanoparticle catalysts in the particle size range from 9 to 40 nm. The CV and CA measurements show that the most active catalyst is made of the smallest (9 and 11 nm) Pd nanoparticles. Besides the high reactivity, XPS data show that such nanoparticles display the highest core-level binding energy (BE) shift and the highest valence band (VB) center downshift with respect to the Fermi level. We believe therefore that we found a correlation between formic acid oxidation current and BE and VB center shifts, which, in turn, can directly be related to the electronic structure of palladium nanoparticles of different particle sizes. Clearly, such a trend using unsupported catalysts has never been reported. According to the density functional theory of heterogeneous catalysis, and mechanistic considerations, the observed shifts are caused by a weakening of the bond strength of the COOH intermediate adsorption on the catalyst surface. This, in turn, results in the increase in the formic acid oxidation rate to CO2 (and in the associated oxidation current). Overall, our measurements demonstrate the particle size effect on the electronic properties of palladium that yields different catalytic activity in the HCOOH oxidation reaction. Our work highlights the significance of the core-level binding energy and center of the d-band shifts in electrocatalysis and underlines the value of the theory that connects the center of the d-band shifts to catalytic reactivity.

Metallic nature and surface diffusion of CO adsorbed on Ru nanoparticles in aqueous media: A 13C NMR study.

We report the first observation of the 13C nuclear magnetic resonance spectroscopy (NMR) of 13CO, adsorbed from 13CO saturated 0.5 M sulfuric acid solutions, onto the surfaces of commercial Ru-black nanoparticles. The 13C NMR spectra consist of a symmetrically broadened peak having a large isotropic shift as compared to CO adsorbed onto supported Ru catalysts. The variation of the spin-lattice relaxation rate follows Korringa behavior, indicating the metallic nature of adsorbed CO, in addition to varying across the spectrum in a Korringa-like manner. Motional narrowing of the NMR spectrum at higher temperatures, together with an additional contribution to the spin-lattice relaxation rate, indicate that adsorbed CO undergoes rapid diffusion on the particle surfaces. A two-band model analysis of the NMR results indicates that the CO adsorption bond is weaker on Ru as compared to either Pt or Pd. This is also supported by a reduction in the activation energy for CO diffusion on Ru vs either Pt or Pd nanoparticles.

Activation of nanoparticle Pt-Ru fuel cell catalysts by heat treatment: a 195Pt NMR and electrochemical study.

(195)Pt NMR spectroscopic and electrochemical measurements were carried out on commercial Pt-Ru alloy nanoparticle samples to investigate the effect of high-temperature annealing in different vacuum/gas-phase environments. Samples annealed at 220 degrees C in Ar gas, or in a vacuum, did not show any demonstrable change in catalytic activity vs electrochemically reduced, room-temperature samples. In contrast, annealing at 220 degrees C in H(2) gas led to a 3-fold increase in reactivity toward methanol oxidation (per surface site). NMR experiments show that annealing at 220 degrees C (in both Ar and H(2)) leads to a slight reduction in the Fermi level local density of states (E(F)-LDOS) at the Pt sites, which we attribute to surface enrichment of Ru. This electronic effect alone, however, appears to be too small to account for the increase in the catalytic activity observed for the H-treated catalyst. By comparing the electrochemical and NMR data of the H- and Ar-treated samples, we conclude that annealing at 220 degrees C in the hydrogen atmosphere reduces surface Ru oxides into metallic Ru, and consequently, the presence of metallic Ru and its enrichment on the surface are essential for the enhanced catalytic activity. In contrast, heat treatment at 600 degrees C in both vacuum and argon atmosphere increases the particle size and reduces the amount of platinum on the nanoparticle surface, thereby increasing the surface Ru content beyond the optimum surface composition values. This causes a large reduction in catalytic activity. Our results suggest that optimizing the amount of surface Ru by heat treatment at temperatures near 200 degrees C, in a hydrogen atmosphere, can be utilized to produce Pt-Ru alloy nanoparticles with high methanol oxidation activity. Finally, our NMR and electrochemical data, taken together with the lattice parameter measurements, lead to a novel model of Pt-Ru alloy nanoparticles having a Ru-rich core and a Pt-Ru alloy overlayer.

Influence of heating time and pressure treatment of potato starch on the generation of radicals: EPR studies.

The influence of heating time and pressurizing time under pressure of 1 GPa on radicals generation in potato starch polymer was investigated by EPR. Potato starch was heated at two temperatures: 413 ± 2 K (140 °C) and 473 ± 2 K (200 °C) for 15, 30, 60, 120, 180, 240, 270 and 300 min and subdued to pressurizing under pressure of 1 ± 0.002 GPa for 6, 60, 300 and 1440 min. In starch heated at 413 K (140 °C) a decrease in the relative intensity of the EPR signal as a function of the pressurizing time can be observed, whereas in starch heated at 473 K (200 °C) such a decrease is not observed. The EPR spectra analysis indicates that they are powder spectra due to the paramagnetic centers leading to Lorentzian line shapes with weak spectroscopic splitting factor g anisotropies and linewidth anisotropies. We have shown that pressurization of starch causes a decrease in the number of radicals in a temperature range in which the polymer is not yet disintegrated. The results of the EPR investigations indicate the existence of a carbon radical center situated at the carbon C1 of the glucose ring. In the EPR spectra of the samples heated with no oxygen access, the hyperfine structure is poorly visible. In the registered EPR spectra of the samples heated with oxygen access, the hyperfine structure is not observed.

Carbon-supported, selenium-modified ruthenium-molybdenum catalysts for oxygen reduction in acidic media.

The stability and oxygen reduction activity of two carbon-supported catalyst materials are reported. The catalysts, Se/Ru and Se/(Ru-Mo), were prepared by using a chemical reduction method. The catalyst nanoparticles were evenly dispersed onto globular amorphous carbon supports, and their average size was ca. 2.4 nm. Thermal treatment at 500 °C for 2 h in an inert argon atmosphere resulted in coarsening of the nanoparticles, and also in some decrease of their activity. A gradual reduction of activity was also observed for Se/Ru during potential-cycle experiments. However, the incorporation of small amounts of Mo into the Se/Ru catalysts considerably improved the stability of the catalyst against dissolution. The Mo-containing samples showed excellent oxygen reduction activities even after cycling the potential 1000 times between 0.7 and 0.9 V. Furthermore, they showed excellent fuel-cell behavior. The performance of the Se/Ru catalysts is greatly improved by the addition of small amounts of elemental Mo. Possible mechanisms responsible for the improvement of the activity are discussed.

A first principles comparison of the mechanism and site requirements for the electrocatalytic oxidation of methanol and formic acid over Pt.

First principles density functional theoretical calculations were carried out to examine and compare the reaction paths and ensembles for the electrocatalytic oxidation of methanol and formic acid in the presence of solution and applied electrochemical potential. Methanol proceeds via both direct and indirect pathways which are governed by the initial C-H and O-H bond activation, respectively. The primary path requires an ensemble size of between 3-4 Pt atoms, whereas the secondary path is much less structure sensitive, requiring only 1-2 metal atoms. The CO that forms inhibits the surface at potentials below 0.66 V NHE. The addition of Ru results in bifunctional as well as electronic effects that lower the onset potential for CO oxidation. In comparison, formic acid proceeds via direct, indirect and formate pathways. The direct path, which involves the activation of the C-H bond followed by the rapid activation of the O-H bond, was calculated to be the predominant path especially at potentials greater than 0.6 V. The activation of the O-H bond of formic acid has a very low barrier and readily proceeds to form surface formate intermediates as the first step of the indirect formate path. Adsorbed formate, however, was calculated to be very stable, and thus acts as a spectator species. At potentials below 0.6 V NHE, CO, which forms via the non-Faradaic hydrolytic splitting of the C-O bond over stepped or defect sites in the indirect path, can build up and poison the surface. The results indicate that the direct path only requires a single Pt atom whereas the indirect path requires a larger surface ensemble and stepped sites. This suggests that alloys will not have the same influence on formic acid oxidation as they do for methanol oxidation.

Aqueous-based synthesis of ruthenium-selenium catalyst for oxygen reduction reaction.

Carbon-supported Se/Ru(Se) catalysts of a broad range of composition were synthesized via a reduction procedure in which a mixture of RuCl3, SeO2 and Black Pearl carbon was treated with NaBH4 in basic media at room temperature. Physical characterization of the catalyst was performed by X-ray diffraction, energy dispersive X-ray spectroscopy and by high resolution transmission electron microscopy. The effect of NaOH addition during the reduction by NaBH4 and the impact of a post-reduction thermal treatment at 500 degrees C were interrogated. The activity of the catalyst towards the oxygen reduction reaction was studied by the use of a rotating disk electrode. It was found that the half-wave potential for the oxygen reduction reaction was about 0.78 V vs. RHE. The Se-to-Ru ratio and metal loading on carbon were optimized for the oxygen reduction reaction and the optimized catalyst was tested at the cathode of a polymer electrolyte fuel cell. The stability of the Se/Ru(Se) catalyst was evaluated by electrochemical cycling and by leaching the catalyst in 0.5 M H2SO4 at 80 degrees C.

Electrocatalysis of oxygen reduction and small alcohol oxidation in alkaline media.

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.

Vibrational recognition of adsorption sites for CO on platinum and platinum-ruthenium surfaces.

We have studied the vibrational properties of CO adsorbed on platinum and platinum-ruthenium surfaces using density-functional perturbation theory within the Perdew-Burke-Ernzerhof generalized-gradient approximation. The calculated C-O stretching frequencies are found to be in excellent agreement with spectroscopic measurements. The frequency shifts that take place when the surface is covered with ruthenium monolayers are also correctly predicted. This agreement for both shifts and absolute vibrational frequencies is made more remarkable by the frequent failure of local and semilocal exchange-correlation functionals in predicting the stability of the different adsorption sites for CO on transition metal surfaces. We have investigated the chemical origin of the C-O frequency shifts introducing an orbital-resolved analysis of the force and frequency density of states, and assessed the effect of donation and backdonation on the CO vibrational frequency using a GGA+molecular U approach. These findings rationalize and establish the accuracy of density-functional calculations in predicting absolute vibrational frequencies, notwithstanding the failure in determining relative adsorption energies, in the strong chemisorption regime.

Methanol dehydrogenation and oxidation on Pt(111) in alkaline solutions.

Adsorption, dehydrogenation, and oxidation of methanol on Pt(111) in alkaline solutions has been examined from a fundamental mechanistic perspective, focusing on the role of adsorbate-adsorbate interactions and the effect of defects on reactivity. CO has been confirmed as the main poisoning species, affecting the rate of methanol dehydrogenation primarily through repulsive interactions with methanol dehydrogenation intermediates. At direct methanol fuel cell (DMFC)-relevant potentials, methanol oxidation occurs almost entirely through a CO intermediate, and the rate of CO oxidation is the main limiting factor in methanol oxidation. Small Pt island defects greatly enhance CO oxidation, though they are effective only when the CO coverage is 0.20 ML or higher. Large Pt islands enhance CO oxidation as well, but unlike small Pt islands, they also promote methanol dehydrogenation. Perturbations in electronic structure are responsible for the CO oxidation effect of defects, but the role of large Pt islands in promoting methanol dehydrogenation is primarily explained by surface geometric structure.

Characterization and methanol electrooxidation studies of Pt(111)/Os surfaces prepared by spontaneous deposition.

Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer oxygen-containing species, at least below 0.5 V vs RHE. Both higher coverage of Os than Ru and the higher potentials are required to provide a sufficient number of active oxygen-containing species for the effective removal of the site-blocking CO from the catalyst surface when the methanol electrooxidation process occurs.

Particle-size effect of nanoscale platinum catalysts in oxygen reduction reaction: an electrochemical and 195Pt EC-NMR study.

Oxygen reduction reaction (ORR) measurements and (195)Pt electrochemical nuclear magnetic resonance (EC-NMR) spectroscopy were combined to study a series of carbon-supported platinum nanoparticle electrocatalysts (Pt/CB) with average diameters in the range of roughly 1-5 nm. ORR rate constants and H(2)O(2) yields evaluated from hydrodynamic voltammograms did not show any particle size dependency. The apparent activation energy of 37 kJ mol(-1), obtained for the ORR rate constant, was identical to that obtained for bulk platinum electrodes. Pt/CB catalysts on Nafion produced only 0.7-1% of H(2)O(2), confirming that the direct four-electron reduction of O(2) to H(2)O is the predominant reaction. NMR spectral features showed characteristic size dependence, and the line shapes were reproduced by using the layer-deconvolution model. Namely, the variations in the NMR spectra with particle size can be explained as due to the combined effect of the layer-by-layer variation of the s-type and d-type local density of states. However, the surface peak position of (195)Pt NMR spectra and the spin-lattice relaxation time of surface platinum atoms showed practically no change with the particle size variation. We conclude that there is a negligible difference in the surface electronic properties of these Pt/CB catalysts due to size variations and therefore, the ORR activities are not affected by the differences in the particle size.

In situ STM study of Au(111)/Os bimetallic surfaces: spontaneous deposition and electrochemical dissolution.

We provide an electrochemical and structural characterization by in situ STM of Au(111)/Os electrodes prepared by spontaneous deposition of Os on Au(111). Surfaces with Os coverage values up to the saturation coverage were examined, from 10%. Using comparisons to previous work on Au(111)/Ru, Pt(111)/Ru, and Pt(111)/Os, we find that we may now generalize that Os deposits spontaneously faster than Ru and has a greater tendency to form 3-D structures. Additionally, the Au(111) substrate shows preferential step and near-step decoration in both cases, although it is less pronounced for Os than Ru. We also investigated the incremental dissolution of the Os from Au(111), to better understand electrochemical dissolution processes in general and to better control the Os deposit structure. The application of controlled electrochemical treatments (cyclic voltammetry up to increasingly positive values) significantly increased the dispersion of the Os deposit by generating smaller, more widely spaced islands. Upon voltammetry up to 0.75 V, the Au(111)/Os surface showed evidence of alloying and the formation of 3-D structures suggestive of strong Os-Os (oxidized) species interactions. The CO stripping results show the Au(111)/Os is not particularly effective for this reaction, but such results help to complete the overall picture of NM-NM catalytic combinations. Although the Au(111)/Os system itself is not catalytically active, the electrochemical manipulation of the deposit structure demonstrated here may be applied to other noble metal/noble metal (NM/NM) catalytic substrates to find optimal deposit morphologies.

An NMR determination of CO diffusion on platinum electrocatalysts.

We report the first direct measurement of CO diffusion on nanoparticle Pt electrocatalysts at the solid/liquid interface, carried out using 13C nuclear magnetic resonance (NMR) with a spin-labeling pulse sequence. Diffusion parameters were measured in the temperature range of 253-293 K for CO adsorbed on commercial Pt-black under saturation coverage. 2H NMR of the same system indicates that the electrolyte remains in the liquid state at temperatures where the CO diffusion experiments were performed. The CO diffusion parameters follow typical Arrhenius behavior with an activation energy of 6.0 +/- 0.4 kcal/mol and a pre-exponential factor of (1.1 +/- 0.6) x 10-8 cm2/s. Exchange between different CO populations, driven by a chemical potential gradient, is suggested to be the main mechanism for CO diffusion. The presence of the electrolyte medium considerably slows down the diffusion of CO as compared to that seen on surfaces of bulk metals under UHV conditions. This work opens up a new approach to the study of surface diffusion of adsorbed molecules on nanoparticle electrode catalysts, including the possibility of correlating diffusion parameters to catalytic activity in real world applications of broad general interest.