Platinum-carbon monoxide adsorption

We have undertaken a series of experiments Involving thin film models of such powdered transition metal catalysts (13,14). In this paper we present a brief review of the results we have obtained to date Involving platinum and rhodium deposited on thin films of tltanla, the latter prepared by oxidation of a tltanliua single crystal. These systems are prepared and characterized under well-controlled conditions. We have used thermal desorption spectroscopy (TDS), Auger electron spectroscopy (AES) and static secondary Ion mass spectrometry (SSIMS). Our results Illustrate the power of SSIMS In understanding the processes that take place during thermal treatment of these thin films. Thermal desorption spectroscopy Is used to characterize the adsorption and desorption of small molecules, In particular, carbon monoxide. AES confirms the SSIMS results and was used to verify the surface cleanliness of the films as they were prepared. 

On the surface of metal electrodes, one also hnds almost always some kind or other of adsorbed oxygen or phase oxide layer produced by interaction with the surrounding air (air-oxidized electrodes). The adsorption of foreign matter on an electrode surface as a rule leads to a lower catalytic activity. In some cases this effect may be very pronounced. For instance, the adsorption of mercury ions, arsenic compounds, or carbon monoxide on platinum electrodes leads to a strong decrease (and sometimes total suppression) of their catalytic activity toward many reactions. These substances then are spoken of as catalyst poisons. The reasons for retardation of a reaction by such poisons most often reside in an adsorptive displacement of the reaction components from the electrode surface by adsorption of the foreign species. 

Dendrimer-protected colloids are capable of adsorbing carbon monoxide while suspended in solution, but upon removal from solution and support on a high surface area metal oxide, CO adsorption was nil presumably due to the collapse of the dendrimer [25]. It is proposed that a similar phenomena occurs on PVP-protected Pt colloids because removal of solvent molecules from the void space in between polymer chains most likely causes them to collapse on each other. Titration of the exposed surface area of colloid solution PVP-protected platinum nanoparticles demonstrated 50% of the total metal surface area was available for reaction, and this exposed area was present as... 

KitamuraF, Takahashi M, Ito M. 1989. Carbon monoxide adsorption on platinum (111) singlecrystal electrode surface studied by infrared reflection - absorption spectroscoy. Surf Sci 223 493-508. 

Kunimatsu K, Golden WG, Seki H, Philpott MR. 1985a. Carbon monoxide adsorption on a platinum electrode studied by polarization modulated FT-IRRAS. 1. Co Adsorbed in the double-layer potential region and its oxidation in acids. Langmuir 1 245 -250. 

Gilman S. 1963. The mechanism of electrochemical oxidation of carbon monoxide and methanol on platinum. I. Carbon monoxide adsorption and desorption and simultaneous oxidation of the platinum surface at constant potential. J Phys Chem 67 1989-1905. 

Large platinum carbonyl clusters have been investigated as models for the adsorption of carbon monoxide on platinum surfaces and on platinum electrodes. An issue is how large the clusters must be before they adopt the properties of the bulk metal. Teo et al. have investigated the magnetic properties of the clusters [Pt6(CO)12]2+, [Pt9(CO)18]2+, [Pt y(CO)22f+, and... 

Adsorbed carbon monoxide on platinum formed at 455 mV in H2S04 presents a thermal desorption spectrum as shown in Fig. 2.4b. As in the case of CO adsorption from the gas phase, the desorption curve for m/e = 28 exhibits two peaks, one near 450 K for the weakly adsorbed CO and the other at 530 K for the strongly adsorbed CO species. The H2 signal remains at the ground level. A slight increase in C02 concentration compared to the blank is observed, which could be due to a surface reaction with ions of the electrolyte. Small amounts of S02 (m/e = 64) are also observed. 

Whereas determination of chemisorption isotherms, e.g., of hydrogen on metals, is a means for calculating the size of the metallic surface area, our results clearly demonstrate that IR studies on the adsorption of nitrogen and carbon monoxide can give valuable information about the structure of the metal surface. The adsorption of nitrogen enables us to determine the number of B5 sites per unit of metal surface area, not only on nickel, but also on palladium, platinum, and iridium. Once the number of B5 sites is known, it is possible to look for other phenomena that require the presence of these sites. One has already been found, viz, the dissociative chemisorption of carbon dioxide on nickel. 

Vibrational Spectroscopic Studies of Adsorbate Competition During Carbon Monoxide Adsorption on Platinum Electrodes... 

Exposure of the clean stepped platinum surface to oxygen caused saturation of the step and kink sites (no adsorption occurred on a 111 surface under identical conditions). The oxygen atom-saturated surface was then exposed to varying amounts of carbon monoxide. Both carbide carbon and CO carbon C Is peaks formed, with a one-to-one correspondence between the growth of carbide and the decrease of surface oxygen atoms. These data are consistent with threee possible reaction schemes ... 

It will be noted that on Langmuir s hypothesis the surface becomes saturated when it is covered with a unimolecular thickness of adsorbed gas. By measuring the adsorption of gases on the surface of mica and of platinum Langmuir showed that with the exception of carbon monoxide, gases such as oxygen, nitrogen and methane apparently when adsorbed to a saturation value covered the surface with a unimolecular thickness of gas. 

Electrooxidation of carbon monoxide to carbon dioxide at platinum has been extensively studied mainly not least because of the technological importance of its role in methanol oxidation in fuel cells [5] and in poisoning hydrogen fuel cells [6]. Enhancing anodic oxidation of CO is critical, and platinum surfaces modified with ruthenium or tin, which favor oxygen atom adsorption and transfer to bound CO, can achieve this [7, 8]. 

Potentiometric techniques have been used to study autonomous reaction rate oscillations over catalysts and carbon monoxide oxidation on platinum has received a considerable amount of attention43,48,58 Possible explanations for reaction rate oscillations over platinum for carbon monoxide oxidation include, (i) strong dependence of activation energy or heat of adsorption on coverage, (ii) surface temperature oscillations, (iii) shift between multiple steady states due to adsorption or desorption of inert species, (iv) periodic oxidation or reduction of the surface. The work of Sales, Turner and Maple has indicated that the most... 

The idea that catalyst surfaces possess a distribution of sites of different energies has been around since the 1920s, but it has not been possible until fairly recently to show that adsorption sites on terraces, steps, and kinks differ in energy. For example, hydrogen shows stronger bonding to steps and kinks on platinum than on the 111 terraces. In addition, the activation energy for H2 dissociation is about zero on the step face and about 8.4 kJ mole-1 on the terrace plane. In addition, carbon monoxide is adsorbed with dissociation on the kinks of Pt, but in the molecular form on the steps and terraces. 

According to UHV investigations (156), the cracking reaction of methanol at Pt surfaces yields strongly adsorbed carbon monoxide. There had been much dispute as to whether the species that blocks the electrocatalyst platinum in methanol-containing electrolytes is really carbon monoxide (157), but today the different schools seem to converge with the opinion that it is CO or CO, some species resembling adsorbed carbon monoxide very closely in its adsorptive, optical, and electrochemical properties. 

A systematic attempt to correlate the catalytic effect of different surfaces with their adsorptive capacity was made by Taylor and his collaborators. Taylor and Burns, for example, investigated the adsorption of hydrogen, carbon dioxide, and ethylene by the six metals nickel, cobalt, palladium, platinum, iron, and copper. All these metals are able to catalyse the hydrogenation of ethylene to ethane, while nickel, cobalt, and palladium also catalyse the reduction of carbon monoxide and of carbon dioxide to methane. 

Carbon monoxide is the molecule whose adsorptive properties have certainly been investigated in most detail. A review of the work prior to 1970 was published by Ford (2) in this series, but in the interim so much additional information has been obtained that a complete compilation of the data would be far beyond the scope of this article. Instead, the main emphasis will be given to a discussion of essential features that fortunately have much in common with different platinum group metals as well as with various crystal planes. 

Now possibilities of the MC simulation allow to consider complex surface processes that include various stages with adsorption and desorption, surface reaction and diffusion, surface reconstruction, and new phase formation, etc. Such investigations become today as natural analysis of the experimental studying. The following papers [282-285] can be referred to as corresponding examples. Authors consider the application of the lattice models to the analysis of oscillatory and autowave processes in the reaction of carbon monoxide oxidation over platinum and palladium surfaces, the turbulent and stripes wave patterns caused by limited COads diffusion during CO oxidation over Pd(110) surface, catalytic processes over supported nanoparticles as well as crystallization during catalytic processes. 

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