Multivariate analysis of ATR-IR spectroscopic data: applications to the solid-liquid catalytic interface

It is demonstrated that attenuated total reflection infrared (ATR-IR) spectroscopy coupled with multivariate data analysis can be effectively used for in situ investigation of supported catalyst-liquid interfaces. Both formaldehyde adsorption/dissociation in water and acetonitrile adsorption in hexane on thin (ca 10 mum) films of 5 wt % Pt/gamma-Al(2)O(3) deposited on a germanium waveguide have been investigated. The multivariate analysis applies classical least squares (CLS) and partial least squares (PLS) methods to the ATR-IR data in order to correlate spectral changes with known sources of experimental variation (i.e., time, concentration of solution species, etc.). The formaldehyde adsorption experiments revealed no spectroscopic evidence for adsorbed molecular formaldehyde under the conditions examined. However, the dissociation product carbon monoxide was observed to form in atop configuration on Pt, likely on edges and terrace sites. Isotope labeling experiments suggest that a pair of peaks observed at 1990 and 2060 cm(-)(1) during treatments of Pt in H(2)-saturated water arise at least in part from nu(Pt)(-)(H) stretching of adsorbed atomic hydrogen. Acetonitrile was found to adsorb on the Pt catalyst by sigma-bonding of the CN group with the platinum, yielding apparent surface peaks that are almost identical to that observed in the liquid phase. A peak at 1641 cm(-)(1) was observed which was assigned to the adsorption of the CN group in a tilted configuration involving a combination of end-on and pi interaction with the surface. This species was found to be reactive toward hydrogen, suggesting that it might play a role in nitrile hydrogenation. The prospects of using this approach to examine solid-catalyzed liquid-phase reactions are discussed in light of these findings.     

Competition at chiral metal surfaces: fundamental aspects of the inversion of enantioselectivity in hydrogenations on platinum

O-Phenylcinchonidine (PhOCD) is known to efficiently induce inversion of enantioselectivity with respect to cinchonidine (CD) in the enantioselective hydrogenation of various activated ketones on Pt/Al(2)O(3). To understand the origin of the switch of enantioselective properties of the catalyst, the adsorption of PhOCD has been studied by in situ ATR-IR spectroscopy, in the presence of organic solvent and dissolved hydrogen, i.e., under conditions used for catalytic hydrogenation. The adsorption structures and energies of the anchoring group of CD and PhOCD were calculated on a Pt 38 cluster, using relativistically corrected density functional theory (DFT). Both approaches indicate that both modifiers are adsorbed via the quinoline ring and that the spatial arrangement of the quinuclidine skeleton is critical for the chiral recognition. New molecular level information on the conformation of CD relative to PhOCD adsorbed on a surface is extracted from the ATR spectra and supported by DFT calculations. The result is a clearer picture of the role played by the phenyl group in defining the chiral space created by the modifiers on Pt. Moreover, when CD was added to a pre-equilibrated adsorbed layer of PhOCD, a chiral adsorbed layer was formed with CD as the dominant modifier, indicating that CD adsorbs more strongly than PhOCD. Conversely, when PhOCD was added to preadsorbed CD, no significant substitution occurred. The process leading to nonlinear effects in heterogeneous asymmetric catalysis has been characterized by in situ spectroscopy, and new insight into a heterogeneous catalytic R-S switch system is provided.     

Surface processes occurring on Rh/alumina during chiral modification by cinchonidine: an ATR-IR spectroscopy study

Cinchona alkaloids are frequently used for chiral modification of supported noble metal catalysts employed in heterogeneous enantioselective hydrogenation. In order to gain molecular insight into the surface processes occurring at the metal/liquid interface, cinchonidine (CD) adsorption on vapor-deposited Rh/Al2O3 films has been studied in the presence of solvent and hydrogen by means of attenuated total reflection infrared (ATR-IR) spectroscopy. The spectrum of CD adsorbed on Rh exhibited two dominant signals at 1593 and 1511 cm(-1), which are characteristic of a surface species having a quinoline ring tilted with respect to the metal. Interestingly, no adsorbed modifier in the flat geometry (quinoline parallel to the metal plane) was observed. During desorption, these signals vanished, and a new prominent signal appeared at 1601 cm(-1) which belongs to a species with the quinoline ring hydrogenated on the heteroaromatic side. Concentration-dependent experiments and the reversibility of the observed phenomenon indicate that CD was readily hydrogenated to 1',2',3',4',10,11-hexahydrocinchonidine (CDH(6)) on Rh. The ATR-IR spectra also reveal that the flat species was indeed immediately hydrogenated when CD was provided from solution, and the only visible adsorbed species was the tilted species, which displaced the hydrogenation product from the metal surface. In the absence of dissolved CD, during desorption, the tilted species was converted to the flat species and rapidly hydrogenated. The hydrogenation product was stable on the metal surface only in the absence of CD. Therefore, the adsorption strength of the different species is as follows: flat > tilted > CDH(6). Evidence for the formation of the flat species and its role as an intermediate to the hydrogenation product is given by an experiment in which CD was adsorbed in the absence of dissolved hydrogen after surface cleaning. The adsorption and hydrogenation of CD on Rh deviate significantly from that observed earlier on Pt and Pd under similar conditions, where the flat species could be observed even in the presence of hydrogen. This difference is attributed to the weaker interaction and lower hydrogenation rate occurring on Pt and Pd.     

Light at the interface: the potential of attenuated total reflection infrared spectroscopy for understanding heterogeneous catalysis in water

IR spectroscopy has been an important tool for studying detailed interactions of reactants and reaction-intermediates with catalyst surfaces. Studying reactions in water is, however, far from trivial, due to the excessive absorption of infrared light by water. One way to deal with this is the use of Attenuated Total Reflection spectroscopy (ATR-IR) minimizing the path length of infrared light through the water. Moreover, ATR-IR allows for a direct comparison of reactions in gas and water on the same sample, which bridges the gap between separate catalyst investigations in gas and liquid phase. This tutorial review describes recent progress in using ATR-IR for studying heterogeneous catalysts in water. An overview is given of the important aspects to be taken into account when using ATR-IR to study heterogeneous catalysts in liquid phase, like the procedure to prepare stable catalyst layers on the internal reflection element. As a case study, CO adsorption and oxidation on noble metal catalysts is investigated with ATR-IR in gas and water. The results show a large effect of water and pH on the adsorption and oxidation of CO on Pt/Al(2)O(3) and Pd/Al(2)O(3). From the results it is concluded that water affects the metal particle potential as well as the adsorbed CO molecule directly, resulting in higher oxidation rates in water compared to gas phase. Moreover, also pH influences the metal particle potential with a clear effect on the observed oxidation rates. Finally, the future outlook illustrates that ATR-IR spectroscopy holds great promise in the field of liquid phase heterogeneous catalysis.     

Interaction between ketopantolactone and chirally modified Pt investigated by attenuated total reflection IR concentration modulation spectroscopy

The combination of ATR-IR and modulation spectroscopy allowed for the study of the interaction of ketopantolactone with Pt/Al2O3 films chirally modified by cinchonidine under hydrogenation conditions. The spectra reveal a significant influence of ketopantolactone on the adsorption of the modifier and indicate a N-H-O hydrogen bond between modifier and reactant. The latter was corroborated by a comparative study with N-methyl cinchonidine chloride modified Pt/Al2O3.     

红外光谱法考察苯加氢过程中的氢溢流效应

以点状Pt/η-Al_2O_3催化剂作为产生溢流氢的“源”, 用原位红外光谱观察η-Al_2O_3上苯的加氢过程, 发现溢流氢在η-Al_2O_3表面上可以迁移相当长的距离, 它的迁移速度是苯加氢反应的控制步骤。结合TPSR-MS数据, 认为苯的加氢是分步进行的, 它先被加氢成环已二烯, 再转化成环已烯, 最终形成环已烷脱附。这些反应都是快速反应。     

Supercritical carbon dioxide: an inert solvent for catalytic hydrogenation?

Various surface species originating from the reaction between CO2 and H2 over Al2O3-supported Pt, Pd, Rh, and Ru model catalysts were investigated by attenuated total reflection infrared (ATR-IR) spectroscopy under high-pressure conditions. Two different spectroscopic cells were used: a variable-volume view cell equipped with ATR-crystal and transmission IR windows (batch reactor) and a continuous-flow cell also equipped with a reflection element for ATR-IR spectroscopy. The study corroborated that CO formation from dense CO2 in the presence of hydrogen occurs over all Pt-group metals commonly used in heterogeneous catalytic hydrogenations in supercritical CO2 (scCO2). In the batch reactor cell, formation of CO was detected on all metals at 50 and 90 degrees C, with the highest rate on Pt. Additional surface species were observed on Pt/Al2O3 at 150 bar under static conditions. It seems that further reaction of CO with hydrogen is facilitated by the higher surface concentration at higher pressure. In the continuous-flow cell, CO coverage on Pt/Al2O3 was less prominent than that in the batch reactor cell. A transient experiment in the continuous-flow cell additionally revealed CO formation on Pt/Al2O3 at 120 bar after switching the feed from a H2-ethane to a H2-CO2 mixture. The in situ ATR-IR measurements indicate that CO formation in CO2-H2 mixtures is normally a minor side reaction during hydrogenation reactions on Pt-group metal catalysts, and dense ("supercritical") CO2 may be considered as a relatively "inert" solvent in many practical applications. However, blocking of specific sites on the metal surface by CO and consecutive products can affect structure sensitive hydrogenation reactions and may be at the origin of unexpected shifts in the product distribution.     

In situ investigation of acetonitrile adsorption on Al2O3-coated CaF2 using sum-frequency spectroscopy

Sum-frequency spectroscopy (SFS) has been used to probe the interface between a model catalyst support (Al(2)O(3)-coated CaF(2)) and liquid consisting of neat acetonitrile and acetonitrile in ethanol. Vibrational features associated with both CN stretching ( approximately 2242 and 2281) and C-H stretching ( approximately 2942 and 2989) are observed for adsorbed nitrile. The peak positions are only slightly shifted from the bulk values, indicating weak adsorption to the model support. In the case of the neat liquid, the C-H stretching vibrations have also been probed using various polarization combinations of the sum frequency, visible and infrared beams in order to determine the orientation of the nitrile with respect to the surface. The average molecular angle calculated ( approximately 39 degrees ) shows the off-normal alignment of acetonitrile on the surface of the model support. Finally, an attempt has been made to obtain qualitative information about the adsorption isotherm of acetonitrile on Al(2)O(3)/CaF(2). The lack of curvature in the isotherm indicates the lack of affinity for the surface by acetonitrile in ethanol.     

Computational study of the adsorption energetics and vibrational wavenumbers of NH3 Adsorbed on the Ni(111) Surface

The structure and stabilities of NH(3) adsorbed on different sites of a Ni(111) surface are compared based on density functional, plane-waves calculations within a periodic framework. The surface has been modeled by 4- and 5-layer slabs with 2 x 2 and 3 x 3 unit cells. Calculated results are in good agreement with available experimental data, confirming the atop adsorption site to be the most favorable, with no preferred azimuthal orientation for the H atoms. For NH(3) adsorbed at the atop site, the one-dimensional potential energy profiles along the N-H and N-Ni bonds and the coupling between adjacent N-H bond oscillators have been calculated and fitted to an analytical expression using an accurate anharmonic potential model. Variational calculations have been performed to obtain frequencies for the N-H and N-Ni stretching vibrations and N-H stretching line widths. The model for calculating line widths has also been tested with CO adsorbed at the hcp hollow of the Ni(111) surface.     

红外光谱研究Pt-Re/Al2O3重整催化剂的表面结构

CO和NO吸附或两者竞争吸附在Pt／Al2O3，Re／Al2O3和Pt－Re／Al2O3催化剂上的红外光谱可以给出Pt和Re的表面结构信息．本文研究的催化剂为低金属载量的Pt／Al2O3，Re／Al2O3和工业型Pt－Re／Al2O3，其中Pt含量0．22％，Re含量0．43％（质量分数）．实验结果表明，用NO与CO双分子竞争吸附的红外光谱实验方法可分别表征还原态Pt－Re／Al2O3重整催化剂上Pt表面和Re表面，并视需要可对Pt表面和Re表面进行半定量分析．在还原态工业型Pt－Re／Al2O3重整催化剂表面上，没有明显迹象表明有Pt－Re合金形成．     

担载型钌催化剂吸附CO性能的原位红外研究

用原位红外研究了ＣＯ的吸附与脱附，ＣＯ／Ｈ２的共吸附及反应，考察了焙烧温度对Ｒｕ／Ａｌ２Ｏ３及Ｒｕ／ＳｉＯ２催化剂的影响，结果表明，经不同温度焙烧的催化剂样品，其吸附性能有很大差别。随着焙烧温度的升高，金属－载体相互作用增强，导致ＣＯ吸附量减少。Ｒｕ／Ａｌ２Ｏ３吸附的ＣＯ较稳定，而Ｒｕ／ＳｉＯ２吸附的ＣＯ在高温易脱附。各不同ＣＯ吸会态间、多重态更易发生反应。在未焙烧的Ｒｕ／ＳｉＯ２低ＣＯ／Ｈ２反应     

Chirally modified platinum generated by adsorption of cinchonidine ether derivatives: towards uncovering the chiral sites

The adsorption behavior of O-methyl and O-trimethylsilyl derivatives of cinchonidine (CD), employed as chiral modifiers for heterogeneous enantioselective hydrogenations on supported Pt catalysts, has been investigated by using attenuated total reflection infrared spectroscopy (ATR-IR) and density functional theory (DFT) electronic structure calculations. The ATR-IR spectroscopic investigation provided detailed insight of the adsorbed modifiers under conditions close to those employed during catalytic processes, and electronic structure calculations were used as a complement to the experiments to uncover the implications of conformational changes in generating the topology of the surface chiral site. The structural investigation of the adsorbed modifiers revealed a relationship between the spatial positions of the ether substituents and the enantiodifferentiation induced by the modified catalyst observed in the hydrogenation of alpha-activated ketones. Experiments and calculations corroborate a model, according to which the addition of a bulky ether group to CD reshapes the chiral sites, thus generating catalytic chiral surfaces with different and, in some cases (e.g. hydrogenation of ketopantolactone), even opposite enantioselective properties to those obtained with CD without altering the absolute configuration of the modifier. The study also confirms that active surface conformations of cinchona modifiers are markedly different from those existing in vacuum and in solution, thus underlying the necessity of investigating the surface-modifier interaction in order to understand enantioselectivity.     

Infrared emission and theoretical study of carbon monoxide adsorbed on alumina-supported Rh, Ir, and Pt catalysts

The infrared emission spectra of CO adsorbed on alumina-supported 1, 3, and 5 wt % Rh, Ir, and Pt metal-containing catalysts were studied at 423 and 473 K. While CO is adsorbed in dicarbonyl (dimer), linearly (on-top) bonded and bridged carbonyl forms on rhodium and platinum, the dimer form is dominant on iridium. The relative intensity of Rh-CO and Ir-CO linear bands decrease with increasing temperature compared to the intensity of the dicarbonyl bands; the corresponding bands on Pt behave the opposite way. Two dicarbonyl and two linear Pt-CO bands were identified in the infrared spectra of Pt/Al(2)O(3) catalysts. The surface structure (kinked or planar Pt atoms), the dispersity of the metal, the temperature, and the quantity of adsorbed CO on the surfaces all have an effect on the fine structure of the Pt-CO stretching bands. The metal-carbon and CO stretching force constants were calculated for surface dicarbonyl, linearly bonded CO, and bridged carbonyl species. The metal-carbon stretching wavenumbers and force constants were predicted and compared between surface species and metal carbonyl complexes. The iridium-carbon bonds were found always stronger than the Rh-C and Pt-C ones in all surface species. The observed stretching wavenumbers and force constants seem to support the idea that CO and metal-carbon bonds are always stronger in metal carbonyl complexes than in adsorbed surface species. The distribution and mode of CO adsorption on surface metal sites can be effectively studied by means of infrared emission spectroscopy.     

不同载体负载的铂催化剂在丙酮酸乙酯不对称氢化反应中的活性及其铂流失率比较

以介孔树脂材料FDU-14和介孔碳材料CMK-3为载体制备了两种负载型铂催化剂, 用N₂气吸附、X射线衍射及CO化学吸附等手段对这两种催化剂进行了表征, 并将这两种不同的负载型铂催化剂在丙酮酸乙酯不对称氢化反应中的催化性能及其铂流失率与商品化Pt/Al₂O₃催化剂进行了比较. 研究结果表明, 尽管Pt/Al₂O₃催化剂的初始活性和光学选择性均较高, 然而相同反应条件下乙酸溶剂中Pt/FDU-14和Pt/CMK-3催化剂的铂流失率比Pt/Al₂O₃催化剂的低. 通过对催化剂进行CO吸附原位傅里叶变换红外漫反射光谱(DRIFTS)表征, 从载体的不同表面电子性质角度解释了不同载体负载的铂催化剂在丙酮酸乙酯不对称氢化反应中的活性和铂流失率的差异.     

In situ ATR-IR spectroscopic and reaction kinetics studies of water-gas shift and methanol reforming on Pt/Al2O3 catalysts in vapor and liquid phases

Reaction kinetics measurements of the water-gas shift reaction were carried out at 373 K on Pt/Al2O3 in vapor phase to investigate the effects of CO, H2, and H2O partial pressures. Results of in situ ATR-IR studies conducted in vapor phase under similar conditions suggest that the Pt surface coverage by adsorbed CO is high (approximately 90% of the saturation coverage), leading to a negligible effect of the CO pressures on the rate of reaction. The negative reaction order with respect to the H2 pressure is caused by the increased coverage of adsorbed H atoms, and the fractional positive order with respect to the water pressure is consistent with non-equilibrated H2O dissociation on Pt. Results of in situ ATR-IR studies carried out at 373 K show that the presence of liquid water leads to a slight decrease in the Pt surface coverage by adsorbed CO (approximately 80% of the saturation coverage) when the CO partial pressure is the same as in the vapor-phase studies. The rate of the WGS reaction in the presence of liquid water is comparable to the rate under complete vaporization conditions when other factors (such as CO partial pressure) are held constant. Reaction kinetics measurements of methanol reforming were carried out at 423 K over a total pressure range of 1.36-5.84 bar. In situ ATR-IR studies were conducted at 423 K to determine the Pt surface coverage by adsorbed CO in completely vaporized methanol feeds and in aqueous methanol solutions. The decomposition of methanol is found to be slower during the reforming of methanol in liquid phase than in vapor phase, which leads to a lower rate of hydrogen production in liquid phase (0.08 min(-1) at 4.88 bar) than in vapor phase (0.23 min(-1) at 4.46 bar). The lower reaction order with respect to methanol concentration observed for vapor-phase versus liquid-phase methanol reforming (0.2 versus 0.8, respectively) is due to the higher extent of CO poisoning on Pt for reforming in vapor phase than in liquid phase, based on the higher coverage by adsorbed CO observed in completely vaporized methanol feeds (55-60% of the saturation coverage) than in aqueous methanol feed solutions (29-40% of the saturation coverage).     

甲基环戊烷在铂催化剂上氢解的动力学研究

研究了甲基环戊烷在负载型铂催化剂上的氢解动力学，建立了新的动力学模型，在Ｐｔ／ＳｉＯ２上，两个平行反应（一个生成正己烷，另一个生成甲基戊烷）在甲基环戊烷吸附脱氢过程中存在显著的焓变差异，而Ｃ－Ｃ键断裂活化能则相近，在Ａｌ２Ｏ３负载铂催化剂上，反应的表现活经能仅是在Ｐｔ／ＳｉＯ２上的一半，这是由于Ｃｌ离子的存在，改变了铂的催化性能，导致缺电子铂颗粒的形成，使反应速率的控制步骤从在Ｐｔ／ＳｉＯ２上的Ｃ     

Time-lapse STM studies of diastereomeric cinchona alkaloids on platinum metals

The adsorption of cinchonidine (CD) and cinchonine (CN) on Pt(111) and Pd(111) single crystals has been investigated by means of scanning tunneling microscopy (STM) in an ultrahigh vacuum system. In time-lapse series the mobilities of different adsorption species have been determined on a single molecule basis and with varying hydrogen background pressures in the system. The diastereomeric cinchona alkaloids, CD and CN, which are widely used as chiral modifiers of platinum group metals in catalytic enantioselective hydrogenation, showed similar adsorption modes and diffusion behavior on Pt(111), except that the flatly adsorbed CN molecules which were free (not in a dimer/cluster) were significantly more mobile than their CD analogues. CD adsorbed on Pd(111) showed similar adsorption modes as observed on Pt(111) but at considerably higher mobility of the flatly absorbed species already in the low-pressure region. The observed adsorption behaviors are discussed in the context of independent ATR-IR measurements and theoretical calculations. Special emphasis is put on the nonlinear effect observed in hydrogenation reactions with CD/CN mixtures. Our observations corroborate that this effect is mainly a consequence of the different adsorption strengths of CD and CN on Pt.     

Identification of catalyst surface species during asymmetric platinum-catalysed hydrogenation in a "supercritical" solvent

In situ attenuated total reflection infrared spectroscopy studies during the enantioselective hydrogenation of ethyl pyruvate in "supercritical" ethane over a chirally modified Pt/Al(2)O(3) catalyst show the preferential adsorption of ethyl pyruvate as cis-conformer and indicate a hydrogen bond interaction of this species with the co-adsorbed modifier cinchonidine.     

CO在担载Ru催化剂上的吸脱附作用及其表面加氢反应

研究了担载于Al_2O_3和ZrO_2上的以Ru_3(CO)_(12)为前体的[Ru]和以RuCl_3为前体的Ru催化剂的TPR特性、CO吸脱附行为及其表面加H_2反应。担载于Al_2O_3上的[Ru]和Ru催化剂上部分物相较担载于ZrO_2上者难于还原。CO在氧化[Ru]催化剂上主要以Ru(CO)yO_2表面络合物形式存在,在还原[Ru]和Ru、以及氧化Ru催化剂上CO以吸附物种形式存在。在Ru离子上的CO比在Ru原子上者难于脱附。以ZrO_2为载体的[Ru]和Ru催化剂上的CO加H_2生成CH_4的性能显著优于以Al_2O_3为载体者,担载[Ru]催化剂上的CO加H_2性能略优于担载Ru催化剂。     

An in situ attenuated total reflection infrared study of a chiral catalytic solid-liquid interface: cinchonidine adsorption on pt.

An in situ attenuated total reflection study of the chiral solid-liquid interface created by cinchonidine adsorption on a Pt/Al(2)O(3) model catalyst is presented. Experiments were performed in the presence of dissolved hydrogen, that is under conditions used for the heterogeneous enantioselective hydrogenation of alpha-functionalized ketones. Cinchonidine adsorbs via the quinoline moiety. The adsorption mode is coverage dependent and several species coexist on the surface. At low concentration (10(-6)M) a predominantly flat adsorption mode prevails. At increasing coverage two different tilted species, alpha-H abstracted and N lone pair bonded cinchonidine, are observed. The latter is only weakly bound and in a fast dynamic equilibrium with dissolved cinchonidine. At high concentration (10(-4)-10(-3) M) all three species coexist on the Pt surface. A slow transition from an adsorbate layer with a high fraction of alpha-H abstracted cinchonidine to one with a high fraction of N lone pair bonded cinchonidine is observed with the cinchonidine concentration being the driving force for the process. The reverse transition in the absence of dissolved cinchonidine is fast. Cinchonidine competes with solvent decomposition products for adsorption sites on the Pt, which may contribute to the observed solvent dependence of the heterogeneous enantioselective hydrogenation of ketones by cinchonidine-modified Pt.