Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters.

Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O(2) pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O(2) activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C(16)O-(18)O(2)-(16)O(2) reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O(2) activation steps involve direct O(2)* (or O(2)) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO(2) and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O(2). These CO-assisted O(2) dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O(2) dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O(2) reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with (12)CO-(13)CO mixtures showed that the binding, dynamics, and thermodynamics of CO chemisorbed at saturation coverages do not depend on Pt cluster size in a range that strongly affects the coordination of Pt atoms exposed at cluster surfaces. These data and their theoretical and mechanistic interpretations indicate that the remarkable structure insensitivity observed for CO oxidation reactions reflects average CO binding properties that are essentially independent of cluster size. Theoretical estimates of rate and equilibrium constants for surface reactions and CO adsorption show that both parameters increase as the coordination of exposed Pt atoms decreases in Pt(201) cluster surfaces; such compensation dampens but does not eliminate coordination and cluster size effects on measured rate constants. The structural features and intrinsic non-uniformity of cluster surfaces weaken when CO forms saturated monolayers on such surfaces, apparently because surfaces and adsorbates restructure to balance CO surface binding and CO-CO interaction energies.

Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls.

The acid-catalyzed formation of carbon-carbon bonds from C1 precursors via CO insertion into chemisorbed methyl groups occurs selectively within eight-membered ring (8-MR) zeolite channels. This elementary step controls catalytic carbonylation rates of dimethyl ether (DME) to methyl acetate. The number of O-H groups within 8-MR channels was measured by rigorous deconvolution of the infrared bands for O-H groups in cation-exchanged and acid forms of mordenite (M,H-MOR) and ferrierite (H-FER) after adsorption of basic probe molecules of varying size. DME carbonylation rates are proportional to the number of O-H groups within 8-MR channels. Na+ cations selectively replaced protons within 8-MR channels and led to a disproportionate decrease in carbonylation turnover rates (per total H+). These conclusions are consistent with the low or undetectable rates of carbonylation on zeolites without 8-MR channels (H-BEA, H-FAU, H-MFI). Such specificity of methyl reactivity upon confinement within small channels appears to be unprecedented in catalysis by microporous solids, which typically select reactions by size exclusion of bulkier transition states.

Experimental Raman spectra of dilute and laser-light-sensitive [Rh(4)(CO)(9)(mu-CO)(3)] and [(mu(4)-eta(2)-3-hexyne)Rh(4)(CO)(8)(mu-CO)(2)]. Comparison with theoretically predicted spectra.

The reaction of [Rh(4)(CO)(9)(mu-CO)(3)] with 3-hexyne to form the butterfly cluster [(mu(4)-eta(2)-3-hexyne)Rh(4)(CO)(8)(mu-CO)(2)] was monitored viain-situ Raman spectroscopy using an NIR laser source, at room temperature and under atmospheric argon using n-hexane as solvent. The collected raw spectra were deconvoluted using band-target entropy minimization (BTEM). The pure component mid-Raman spectra of the [Rh(4)(CO)(9)(mu-CO)(3)] and the butterfly cluster [(mu(4)-eta(2)-3-hexyne)Rh(4)(CO)(8)(mu-CO)(2)], were reconstructed with a high signal-to-noise ratio. Full geometric optimization and Raman vibrational prediction were carried out using DFT. The experimental and predicted Raman spectra were in good agreement. In particular, the far-Raman vibrational modes in the region 100-280 cm(-1) provided characterization of the metal-metal bonds and direct confirmation of the structural integrity of the polynuclear frameworks in solution.

The direct determination of partial molar volumes and reaction volumes in ultra-dilute non-reactive and reactive multi-component systems using a combined spectroscopic and modified response surface model approach.

Two experimental multi-component organometallic systems were studied, namely, (1) a non-reactive system consisting of [Mo(CO)(6)], [Mn(2)(CO)(10)], and [Re(2)(CO)(10)] in toluene under argon at 298.15 K and 0.1 MPa and (2) a reactive system consisting of [Rh(4)(CO)(12)] + PPh(3)--> [Rh(4)(CO)(11)PPh(3)] + CO in n-hexane under argon at 298.15 K and 0.1 MPa. The mole fractions of all solutes were less than 140 x 10(-6) in system (1) and less than 65 x 10(-6) in system (2). Simultaneous in-situ FTIR spectroscopic measurements and on-line oscillatory U-tube density measurements were performed on the multi-component solutions. A newly developed response surface methodology was applied to the data sets to determine the individual limiting partial molar volumes of all constituents present as well as the reaction volume. The limiting partial molar volumes obtained for system (1) were 176.4 +/- 2.5, 265.1 +/- 2.4, and 276.8 +/- 2.4 cm(3) mol(-1) for [Mo(CO)(6)], [Mn(2)(CO)(10)], and [Re(2)(CO)(10)], respectively and are consistent with independent binary experiments. The limiting partial molar volumes obtained for system (2) were 310.7 +/- 2.7, 219.8 +/- 2.2 and 461.5 +/- 4.5 cm(3) mol(-1) for [Rh(4)(CO)(12)], PPh(3) and [Rh(4)(CO)(11)PPh(3)], respectively. In addition, a reaction volume Delta(r)V equal to -17.0 +/- 5.7 cm(3) mol(-1) was obtained. The present results demonstrate that both partial molar volumes and reaction volumes can be obtained directly from multi-component organometallic solutions. This development provides a new tool for physico-chemical determinations relevant to a variety of solutes and their reactions.

Spectral resolution of fluxional organometallics. The observation and FTIR characterization of all-terminal [Rh4(CO)12].

In situ FTIR spectroscopy at 1 cm(-1) resolution was conducted on n-hexane solutions of the bridged [Rh4(CO)9(mu-CO)3] in the interval T= 268-288 K and P(T)= 0.1-7.0 MPa using either helium or carbon monoxide as dissolved gas. Analysis of the spectral data sets was conducted using band-target entropy minimization (BTEM), in order to recover the pure component spectra. A new spectral pattern was recovered with terminal vibrations at 2075, 2069.8, 2044.6 and 2042 cm(-1). The new spectrum is consistent with an all-terminal [Rh4(CO)12] species with a C(3v) anticubeoctahedron structure where 2 different [Rh(CO)3] moieties exist, although the presence of some Td structure can not be entirely excluded. The equilibrium between all-terminal [Rh4(CO)12] and the bridged [Rh(4)(CO)9(mu-CO)3] was determined in the presence of both helium and CO. The equilibrium constant K(eq)=[Rh4(CO)12]/[Rh4(CO)9(mu-CO)3] at 275 K was ca. 0.011 and the determined equilibrium parameters were Delta(r)G= 12.63 +/- 4.8 kJ mol(-1), Delta(r)H=-21.45 +/- 2.3 kJ mol(-1) and Delta(r)S=-114.3 +/- 8.35 J mol(-1) K(-1). The free energy indicates a very small difference between the bridged and terminal geometry, and the lower entropy is consistent with a higher symmetry. This finding helps to address a long-standing issue concerning the existence of various [M4(CO)12] symmetries. In a more general context, the present study illustrates the considerable utility of quantitative infrared spectroscopy (occurring on a fast vibrational timescale) combined with sophisticated deconvolution techniques in order to resolve systems which have been demonstrated to be fluxional on the NMR timescale.