Intermediates in Surface Reactions

If an adsorbed species, e.g. an intermediate in a catalytic reaction cycle, decomposes into products that desorb instantaneously, TPD can be used to monitor the reaction step. 

This is illustrated by the TPD spectra of formate adsorbed on Cu(lOO). To prove that formate is a reaction intermediate in the synthesis of methanol from CO2 and H2, a Cu(lOO) surface was subjected to methanol synthesis conditions and the TPD spectra recorded (lower traces of Fig. 7.13). For comparison, the upper traces represent the decomposition of formate obtained by dosing formic acid on the surface. As both CO2 and H2 desorb at significantly lower temperatures than those of the peaks in Fig. 7.13, the measurements represent decomposition-limited desorptions. Hence, the fact that both decomposition profiles are identical is strong evidence that formate is present under methanol synthesis conditions. 

In principle, TPD can also be applied to high-surface area catalysts in plug-flow reactors. Often, however, the curves are seriously broadened by mass-transport phenomena. Hence, the use of single crystals or particles on planar supports offers great advantages for these investigations. 

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To rationally govern the selectivity of a catalytic process, the elementary reaction steps on real catalyst surfaces must be identified. The use of well-defined organometallic compounds (possible intermediates in surface reactions) can be very useful in the determination of these steps. The use of kinetic modelling techniques combined with statistical analysis of kinetic... 

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