Photoinduced surface dynamics of CO adsorbed on a platinum electrode

The surface dynamics of adsorbed CO molecules formed by dissociative adsorption of HCHO at a polycrystalline Pt electrode/electrolyte solution interface was studied by picosecond time-resolved sum-frequency generation (TR-SFG) spectroscopy. A SFG peak at 2050-2060 cm(-1) was observed at the Pt electrode in HClO(4) solution containing HCHO at 0-300 mV (vs Ag/AgCl), indicating the formation of adsorbed CO at an atop site of the Pt surface as a result of dissociative adsorption of HCHO. The peak position varied with potential by approximately 33 cm(-1)/V, as previously found in an infrared reflection absorption spectroscopy (IRAS) study. Irradiation of an intense picosecond visible pulse (25 ps, 532 nm) caused an instant intensity decrease and broadening of the CO peak accompanied by the emergence of a new broad peak at approximately 1980 cm(-1) within the time resolution of the system. These results suggest a decrease and increase in the populations of CO adsorbed on atop and bridge sites, respectively, upon visible pump pulse irradiation.     

Vibrational sum frequency generation studies of the (2 x 2)-->(radical19 x radical19) phase transition of CO on Pt(111) electrodes

The potential-dependent (2x2)-3CO-->(radical19x radical19)R23.4 degrees-13CO adlayer phase transition on Pt(111) with 0.1M H(2)SO(4) electrolyte was studied using femtosecond broadband multiplex sum frequency generation (SFG) spectroscopy combined with linear scan voltammetry. Across the phase boundary the SFG atop intensity jumps, and at the same time the SFG spectrum of threefold CO sites is transformed into a bridge site spectrum with a small decrease in integrated SFG intensity. The SFG atop intensity jump and three fold-to-bridge intensity drop are noticeably different from what would be expected for these structures on the basis of coverage alone. This occurs because the SFG signal is sensitive to both the coverage and changes in the local field that result from a changing adlayer structure. We derive an equation that allows us to correct the SFG intensities for these effects using information derived from infrared absorption-reflection spectroscopy (IRAS) and second-harmonic generation (SHG) measurements. With this correction, the SFG results agree well with what would be expected for a transition between perfect adlattices. A small (approximately 20%) discrepancy in the SFG determination of atop coverage is attributed to either a small amount of surface disorder or uncertainties in the SFG, SHG, and IRAS measurements. SFG is also used to examine the reversibility hysteresis and kinetics of the phase transition and its dependence on electrolyte composition. The phase transition is reversible with an approximately 150 mV anodic overpotential and the forward (2x2)-->(radical19x radical19) transition is slower than the reverse. Repeated cycles of phase transition indicate that the 25 microm electrolyte layer used here does not appreciably distort the potential-coverage relationships.     

Pt/glassy carbon model catalysts prepared from PS-b-P2VP micellar templates

Poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was used as a micellar template to fabricate arrays of Pt nanoparticles on mica and glassy carbon (GC) supports. Polymer micellar deposition yields Pt nanoparticles with tunable particle size and surface number density on both mica and GC. After deposition of precursor-loaded micelles onto GC, oxygen plasma etching removes the polymer shell, followed by thermal treatment with H2 gas to reduce the Pt. Etching conditions were optimized to maximize removal of the polymer while minimizing damage to the GC. Arrays of Pt nanoparticles with controlled size and surface number density can be prepared on mica (for particle size characterization) and GC to make Pt/GC model catalysts. These model catalysts were characterized by tapping mode atomic force microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry to measure activity for oxidation of carbon monoxide or methanol. Cyclic voltammetry results demonstrate the existence of a correlation between Pt particle size and electrocatalytic properties including onset potential, tolerance of carbonaceous adsorbates, and intrinsic activity (based on active Pt area from CO stripping voltammetry). Results obtained with Pt/GC model catalysts duplicate prior results obtained with Pt/porous carbon catalysts therefore validating the synthesis approach and offering a new, tunable platform to study catalyst structure and other effects such as aging on proton exchange membrane fuel cell (PEMFC) reactions.     

Polarization-Dependent Sum-Frequency-Generation Spectroscopy for In Situ Tracking of Nanoparticle Morphology

The surface structure of oxide-supported metal nanoparticles can be determined via characteristic vibrations of adsorbed probe molecules such as CO. Usually, spectroscopic studies focus on peak position and intensity, which are related to binding geometries and number of adsorption sites, respectively. Employing two differently prepared model catalysts, it is demonstrated that polarization-dependent sum-frequency-generation (SFG) spectroscopy reveals the average surface structure and shape of the nanoparticles. SFG results for different particle sizes and morphologies are compared to direct real-space structure analysis by TEM and STM. The described feature of SFG could be used to monitor particle restructuring in situ and may be a valuable tool for operando catalysis.     

Promotion effects in the oxidation of CO over zeolite-supported Pt nanoparticles

Well-defined Pt-nanoparticles with an average diameter of 1 nm supported on a series of zeolite Y samples containing different monovalent (H+, Na+, K+, Rb+, and Cs+) and divalent (Mg2+, Ca2+, Sr2+, and Ba2+) cations have been used as model systems to investigate the effect of promotor elements in the oxidation of CO in excess oxygen. Time-resolved infrared spectroscopy measurements allowed us to study the temperature-programmed desorption of CO from supported Pt nanoparticles to monitor the electronic changes in the local environment of adsorbed CO. It was found that the red shift of the linear Pt-coordinated CO vibration compared to that of gas-phase CO increases with an increasing cation radius-to-charge ratio. In addition, a systematic shift from linear (L) to bridge (B) bonded CO was observed for decreasing Lewis acidity, as expressed by the Kamlet-Taft parameter alpha. A decreasing alpha results in an increasing electron charge on the framework oxygen atoms and therefore an increasing electron charge on the supported Pt nanoparticles. This observation was confirmed with X-ray absorption spectroscopy, and the intensity of the experimental Pt atomic XAFS correlates with the Lewis acidity of the cation introduced. Furthermore, it was found that the CO coverage increases with increasing electron density on the Pt nanoparticles. This increasing electron density was found to result in an increased CO oxidation activity; i.e., the T(50%) for CO oxidation decreases with decreasing alpha. In other words, basic promotors facilitate the chemisorption of CO on the Pt particles. The most promoted CO oxidation catalyst is a Pt/K-Y sample, which has a T(50%) of 390 K and a L:B intensity ratio of 2.7. The obtained results provide guidelines to design improved CO oxidation catalysts.     

CoPt nanoparticles and their catalytic properties in electrooxidation of CO and CH(3)OH studied by in situ FTIRS

CoPt nanoparticles supported on a glassy carbon electrode (denoted as CoPt/GC) were prepared by galvanic replacement reaction between electrodeposited Co nanoparticles and K(2)PtCl(6) solution. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were both employed to characterize the CoPt nanoparticles. It was shown that the CoPt nanoparticles have irregular shapes and most of them exhibit a core-shell structure with a porous Co core and a shell of Pt tiny particles. The composition of the CoPt nanoparticles was analyzed by energy-dispersive X-ray spectroscopy (EDX), which depicts a Co : Pt ratio of ca. 21 : 79. Studies of cyclic voltammetry (CV) demonstrated that CoPt/GC possesses a much higher catalytic activity towards CO and methanol electrooxidation than a nanoscale Pt thin film electrode. In situ FTIR spectroscopic studies have revealed for the first time, that a CoPt nanoparticles electrode exhibits abnormal IR effects (AIREs) for IR absorption of CO adsorbed on it. In comparison with the IR features of CO adsorbed on a bulk Pt electrode, the direction of the IR bands of CO adsorbed on the CoPt/GC electrode is inverted completely, and the intensity of the IR bands has been enhanced up to 15.4 times. The AIREs is significant in detecting the adsorbed intermediate species involved in electrocatalytic reactions. The results demonstrated a reaction mechanism of CH(3)OH oxidation on CoPt/GC in alkaline solutions through evidencing CO(L), CO(M), HCOO(-), CO(3)(2-), HCO(3)(-) and CO(2) as intermediate and product species by in situ FTIRS.     

核-壳结构Au-Pt纳米粒子的光谱表征和电催化性能

用化学还原法合成了核-壳结构Au-Pt纳米粒子.紫外可见光谱(UV-Vis)、电化学循环伏安(CV)和透射电子显微镜(TEM)表征结果指出，所合成的核-壳结构Au-Pt纳米粒子为球形，平均直径为27 nm.以CO为分子探针，结合透射红外光谱研究，发现CO以孪生吸附态形式(COT)吸附在Au-Pt纳米粒子上，在2110 cm－1和2063 cm－1附近分别给出对称和反对称红外吸收峰. CV研究结果指出Au-Pt/GC电极对CO的氧化有较高的催化活性，起始氧化电位较本体Pt电极提前了0.45 V，峰电位提前了0.11 V.     

DFT investigation of CO adsorption on Pt(211) and Pt(311) surfaces from low to high coverage

Adsorption of CO on Pt(211) and Pt(311) surfaces has been investigated by the density functional theory (DFT) method (periodic DMol3) with full geometry optimization. Adsorption energies, structures, and C-O stretching vibrational frequencies are studied by considering multiple possible adsorption sites and comparing them with the experimental data. The calculated C-O stretching frequencies agree well with the experimental ones, and precise determination of adsorption sites can be carried out. For Pt(211), CO adsorbs at the atop site on the step edge at low coverage, but CO adsorbs at the atop and bridge sites simultaneously on both the step edge and the terrace with further increasing CO coverage. The present results interpret the reflection adsorption infrared (RAIR) spectra of Brown and co-workers very well from low to high coverage. For Pt(311), CO adsorbs also at the atop site on the step edge at low coverage. The lifting of reconstruction by CO adsorption occurs also for Pt(311), whereas the energy gain for lifting the reconstruction of the Pt(311) surface is smaller than that for Pt(110). The largest difference between the stepped Pt(211)/Pt(311) and Pt(110) surfaces is the occupation on the edge sites at higher coverage. For the stepped surfaces, the bridge site begins to be occupied at higher coverage, whereas the atop site is always occupied for the Pt(110) surface.     

Effect of adsorption site, size, and composition of Pt/Au bimetallic clusters on the CO frequency: a density functional theory study

Density functional theory (DFT) calculations were performed to investigate the C-O stretching frequency changes when a CO molecule was adsorbed to Pt/Au clusters of 2-4 atoms. Our calculations show that the adsorption site is the most sensitive quantity to the C-O stretching frequency shifts. All the bridge site adsorptions yield a CO frequency band of 1737-1927 cm-1 with the CO bond distance of 1.167-1.204 A regardless of cluster composition and size, and all the atop site adsorptions yield a CO frequency band of 2000-2091 cm-1 with the CO bond distance of 1.151-1.167 A. More detailed analysis of the two frequency bands shows that each band may consist of two emerging subbands with the lower frequencies corresponding to the CO adsorption to Pt atoms and the higher frequencies to the CO adsorption to Au atoms. The insensitivity of the CO frequency shift to the cluster size indicates that the trend discussed here for small clusters may be used to interpret the experimental observations for nanoparticles. Our results also illustrated that the Fourier transform infrared spectroscopy measurement may be used as a sensitive tool to identify adsorption sites of the Pt/Au nanoparticles using CO adsorption as the probe.     

Effect of Co doping on catalytic activity of small Pt clusters

Platinum is the most widely used catalyst in fuel cell electrodes. Designing improved catalysts with low or no platinum content is one of the grand challenges in fuel cell research. Here, we investigate electronic structures of Pt(4) and Pt(3)Co clusters and report a comparative study of adsorption of H(2), O(2), and CO molecules on the two clusters using density functional theory. The adsorption studies show that H(2) undergoes dissociative chemisorption on the tetrahedral clusters in head on and side on approaches at Pt centers. O(2) dissociation occurs primarily in three and four center coordinations and CO prefers to adsorb on Pt or Co atop atoms. The adsorption energy of O(2) is found to be higher for the Co doped cluster. For CO, the Pt atop orientation is preferred for both Pt(4) and Pt(3)Co tetrahedral clusters. Adsorption of CO molecule on tetrahedral Pt(3)Co in side on approach leads to isomerization to planar rhombus geometry. An analysis of Hirshfeld charge distribution shows that the clusters become more polarized after adsorption of the molecules.     

Electrochemical characters and structure changes of electrochemically treated Pt nanoparticles

In this paper, the surface and electrochemical characters of the Pt/CNT electrode before and after voltammetric cyclings were studied using high resolution transmission electron microscopy imaging (HRTEM), X-ray photon electron spectroscopy (XPS) and cyclic voltammetry measurements of CO and methanol oxidation. It was found that Pt nanoparticles were not stable and formed the linked and agglomerated structures. The changes of the crystallites led to the peak multiplicity, the negative shift of CO oxidation peaks, and the increase of the current density of methanol oxidation. We considered the specific activities were due to the increases of oxygen species and defect sites on Pt.     

Preferential oxidation of carbon monoxide catalyzed by platinum nanoparticles in mesoporous silica

Preferential oxidation (PROX) of CO is an important practical process to purify H2 for use in polymer electrolyte fuel cells. Although many supported noble metal catalysts have been reported so far, their catalytic performances remain insufficient for operation at low temperature. We found that Pt nanoparticles in mesoporous silica give unprecedented activity, selectivity, and durability in the PROX reaction below 353 K. We also studied the promotional effect of mesoporous silica in the Pt-catalyzed PROX reaction by infrared spectroscopy using the isotopic tracer technique. Gas-phase O2 is not directly used for CO oxidation, but the oxygen of mesoporous silica is incorporated into CO2. These results suggest that CO oxidation is promoted by the attack of the surface OH groups to CO on Pt without forming water.     

Studies of CO adsorption on Pt(100), Pt(410), and Pt(110) surfaces using density functional theory

Adsorption of CO on Pt(100), Pt(410), and Pt(110) surfaces has been investigated by density functional theory (DFT) method (periodic DMol(3)) with full geometry optimization and without symmetry restriction. Adsorption energies, structures, and vibrational frequencies of CO on these surfaces are studied by considering multiple possible adsorption sites and comparing them with the experimental data. The same site preference as inferred experiments is obtained for all the surfaces. For Pt(100), CO adsorbs at the bridge site at low coverage, but the atop site becomes most favorable for the c(2 x 2) structure at 1/2 monolayer. For Pt(410) (stepped surface with (100) terrace and (110) step), CO adsorbs preferentially at the atop site on the step edge at 1/4 monolayer, but CO populates also at other atop and bridge sites on the (100) terrace at 1/2 monolayer. The multiple possible adsorption sites probably correspond to the multiple states in the temperature-programmed desorption spectra for CO desorption. For Pt(110), CO adsorbs preferentially at the atop site on the edge for both the reconstructed (1 x 2) and the un-reconstructed (1 x 1) surfaces. When adjacent sites along the edge row begin to be occupied, the CO molecules tilt alternately by ca. 20 degrees from the surface normal in opposite directions for both the (1 x 2) and (1 x 1) surfaces.     

Hydrothermal growth of mesoporous SBA-15 silica in the presence of PVP-stabilized Pt nanoparticles: synthesis, characterization, and catalytic properties

A novel high surface area heterogeneous catalyst based on solution phase colloidal nanoparticle chemistry has been developed. Monodisperse platinum nanoparticles of 1.7-7.1 nm have been synthesized by alcohol reduction methods and incorporated into mesoporous SBA-15 silica during hydrothermal synthesis. Characterization of the Pt/SBA-15 catalysts suggests that Pt particles are located within the surfactant micelles during silica formation leading to their dispersion throughout the silica structure. After removal of the templating polymer from the nanoparticle surface, Pt particle sizes were determined from monolayer gas adsorption measurements. Infrared studies of CO adsorption revealed that CO exclusively adsorbs to atop sites and red-shifts as the particle size decreases suggesting surface roughness increases with decreasing particle size. Ethylene hydrogenation rates were invariant with particle size and consistent with a clean Pt surface. Ethane hydrogenolysis displayed significant structure sensitivity over the size range of 1-7 nm, while the apparent activation energy increased linearly up to a Pt particle size of approximately 4 nm and then remained constant. The observed rate dependence with particle size is attributed to a higher reactivity of coordinatively unsaturated surface atoms in small particles compared to low-index surface atoms prevalent in large particles. The most reactive of these unsaturated surface atoms are responsible for ethane decomposition to surface carbon. The ability to design catalytic structures with tunable properties by rational synthetic methods is a major advance in the field of catalyst synthesis and for the development of accurate structure-function relationships in heterogeneous reaction kinetics.     

An unexpected enhancement in methanol electro-oxidation on an ensemble of Pt(111) nanofacets: a case of nanoscale single crystal ensemble electrocatalysis

Pt nanoparticles having the same size ( approximately 10 nm) but different shapes (cubic or octahedral/tetrahedral), as determined by transmission electron microscopy, were synthesized via a polyol-based synthetic procedure. Their respective electrocatalytic activities for methanol oxidation were characterized by cyclic voltammetry and chronoamperometry in both sulfuric and perchloric acid electrolytes, which showed clear shape (surface orientation) dependences. Furthermore, the octahedral/tetrahedral Pt nanoparticles displayed an unexpectedly large enhancement in methanol electro-oxidation activity; about 3-fold increase in transient intrinsic activity and 10-fold increase in CO tolerance steady-state activity when compared to commercial Pt black. Gaseous and methanolic CO adsorption on the synthesized nanoparticles were also investigated by surface-enhanced IR absorption spectroscopy in perchloric acid electrolyte, which suggested that the different trends observed might be related to the electronic effects specific to a given ensemble of the nanofacets.     

A spectroscopic proof of a surface equilibrium between on top and bridge bonded CO at Pt(1 1 0) in acid solution

According to most of works in the literature, adsorbed carbon monoxide at Pt(1 1 0) electrodes in acid media presents only linear bonded (CO_L) so-called, atop geometry. In the present work, the formation of bridge bonded carbon monoxide (CO_B) is shown via in situ infrared FT spectra, measured on a Pt(1 1 0) electrode covered with 25% CO, in HClO₄ solutions. For the first time, the inter conversion between atop and bridge bonded CO at potentials in the hydrogen adsorption region is reported in acid solution. Band intensity and band center frequency indicate dipole–dipole coupling effects in spite of the low CO total coverage.     

Sum frequency generation studies of surfaces of high-surface-area powdered materials

We report the first observation of sum frequency generation (SFG) photons on high-surface-area powders, critically important materials in heterogeneous catalysis. We utilize SFG in total internal reflection (TIR) geometry and show that the TIR-SFG approach markedly reduces the destructive interference associated with nonlinear optical spectroscopy of small particle surfaces, making SFG studies of high-surface-area powders possible. The index of refraction of materials and their distance from the TIR-SFG prism are key parameters in generating and detecting the sum frequency signal. We find that TIR-SFG is highly sensitive to capillary condensation. To demonstrate the capability of the TIR-SFG technique, we measure the thermodynamics of methanol adsorption and desorption on high-surface-area SiO2.     

IR spectroscopic observation of molecular transport through Pt@CoO yolk-shell nanostructures

FTIR spectroscopy has been used to monitor the transport of CO to the Pt cores of Pt@CoO nanoparticles forming CO/Pt species. It was found that external Pt sites are not present on the outer surfaces of the approximately 10 nm diameter nanostructures and that CO transports to Pt adsorption sites by an activated surface diffusion process through the CoO shells surrounding approximately 2 nm diameter Pt cores. The CO transport process is not due to gas-phase transport below 300 K. The weakly bound adsorbed CO/CoO species responsible for transport was directly observed at approximately 2147 cm(-1) during transport through the CoO shells.     

Rh和Pt超薄层电极上的CO吸附行为(英文)

利用沉积在粗糙金电极上的过渡金属超薄层电极技术 ,我们获得了氢及一氧化碳在Rh和Pt表面上吸附的拉曼信号 ,并对两者之间的相互作用进行了分析 ..我们还进行了二氧化碳在这两种金属表面的还原行为的初步研究 ,以及对不同方式获得的一氧化碳吸附拉曼信号的特点进行了分析 .     

Particle size dependent adsorption and reaction kinetics on reduced and partially oxidized Pd nanoparticles

Combining scanning tunneling microscopy (STM), IR reflection absorption spectroscopy (IRAS) and molecular beam (MB) techniques, we have investigated particle size effects on a Pd/Fe(3)O(4) model catalyst. We focus on the particle size dependence of (i) CO adsorption, (ii) oxygen adsorption and (iii) Pd nanoparticle oxidation/reduction. The model system, which is based on Pd nanoparticles supported on an ordered Fe(3)O(4) film on Pt(111), is characterized in detail with respect to particle morphology, nucleation, growth and coalescence behavior of the Pd particles. Morphological changes upon stabilization by thermal treatment in oxygen atmosphere are also considered. The size of the Pd particles can be varied roughly between 1 and 100 nm. The growth and morphology of the Pd particles on the Fe(3)O(4)/Pt(111) film were characterized by STM and IRAS of adsorbed CO as a probe molecule. It was found that very small Pd particles on Fe(3)O(4) show a strongly modified adsorption behavior, characterized by atypically weak CO adsorption and a characteristic CO stretching frequency around 2130 cm(-1). This modification is attributed to a strong interaction with the support. Additionally, the kinetics of CO adsorption was studied by sticking coefficient experiments as a function of particle size. For small particles it is shown that the CO adsorption rate is significantly enhanced by the capture zone effect. The absolute size of the capture zone was quantified on the basis of the STM and sticking coefficient data. Finally, oxygen adsorption was studied by means of MB CO titration experiments. Pure chemisorption of oxygen is observed at 400 K, whereas at 500 K partial oxidation of the particles occurs. The oxidation behavior reveals strong kinetic hindrances to oxidation for larger particles, whereas facile oxidation and reduction are observed for smaller particles. For the latter, estimates point to the formation of oxide layers which, on average, are thicker than the surface oxides on corresponding single crystal surfaces.