(1) Microkinetic Modeling: Decomposition of Formic Acid on Pt(111) and Pd(111) surfaces.

An account of the results obtained from the microkinetic modeling for the decomposition of Formic Acid is given in this report. The results shown here are merely for the purpose of comparison of rates between Pt(111) and Pd(111) surfaces. Although some experimental data for the vapor phase decomposition of Formic Acid on Pd(111) is available, there is no such study on Pt(111) as per our knowledge. No parameter adjustment has been performed to obtain the results given here. The inlet conditions are taken from the literature reporting the vapor phase decomposition on Pd(111), and those values are held constant for the study on Pt(111) to maintain consistency. I have used the flow equations of a transient CSTR reactor to model this reaction. This reactor is generally used to perform initial adjustments to the parameters of the model because of its robustness. This parameter set obtained is then used in the PFR model to finalize the values. Since no adjustments have been made in reporting the results here, only the transient CSTR model has been utilized. Mechanism :
(1) (2) (3) 2 2 2 2 2 2 2 2 (4) (5) (6) (7) (8) 2 2 (9) (10) 2 2 2 (11)

This is just an initial guess for the mechanism, which only has those elementary steps for which we have the converged energy barrier values from Jeys calculations on 3x3 surfaces. A detailed mechanism is given later in this report.

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We do not have any DFT results involving HCO* from Jeys calculations on 3x3 surfaces yet. However, the E for the reaction HCO* H* + CO* has been reported to be -0.96 eV in Pt- WGS paper (Lars). Jey expects the energy barrier for the formation of HCO* from HCOOH* / HCOO* to be very high ( ~ 2 eV) and hence we do not expect the formyl species to play an important role in the reaction. However, the calculations have been started for some elementary steps that involve formyl species. This is the most detailed mechanism for which we have all the relevant information from the DFT calculations performed by Jey. This mechanism does not consider the formation of formyl species, disproportionation reaction resulting in formation of hydroxyl species, and surface reactions involving atomic oxygen, since those reactions have not yet been studied.

Inlet Conditions and Model Description: Flow rate of inlet stream: 51 ml/min Inlet stream composition: Formic Acid(v) = 2.4% (vol/vol) ; Helium(g) = 97.6% (vol/vol). The mechanism describes Formic Acid decomposition as a simple Langmuir Hinshelwood process. A pre exponential factor of 1013(sec-1) is assumed. The reaction enthalpies are calculated based on the gas phase reference, corrected by the temperature dependence using constant pressure heat capacity and the binding energies of the species involved in the reaction. Entropies for adsorbed species are estimated as the difference between their gas-phase entropy and the standard three-dimensional translational entropy. An additional fitting factor Floc, which is common to all species, is used to describe the fraction of rotational and vibrational entropy of the gas-phase molecule that is retained in the adsorbed species. The enthalpies and entropies for gas-phase species were taken from the NIST database. Forward rate constants are calculated using the activation energy barrier values from Jeys calculations and reverse rate constants are then calculated by dividing them with

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the corresponding equilibrium rate constants, to maintain thermodynamic consistency for that particular elementary step. No adjustments are made to any values in obtaining the results reported here.

Results: Comparative results obtained for Pt(111) and Pd(111) are shown below. (1) Turnover Frequency : TOF (1/sec) = Formic Acid in Formic Acid out (where the molar flow rates are normalized by the number of sites)

The e oxidation experiments and some aqueous phase studies (on carbon nanofiber-supported Pt, Pd monometallic particles, Carmen Diaz et al., Applied Catalysis B: Environmental 89 (2009) 375-382) suggest that Pd gives higher conversion at a given temperature.

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This simplified model, however, predicts that Pt is more reactive than Pd at a given temperature. The reason behind such behavior of model is given below. The model predicts that the activation energy barrier for formate formation is less than the carboxyl formation for both Pd (111)[0.60 eV as against 0.72 eV] and Pt(111) [0.53 eV as against 0.80 eV], with respect to the best coadsorbed state. Hence the reaction predominantly follows the formate route, as can be seen from the tables containing values of rates of each elementary step. The energy barrier for the formation of formate is less for Pt(111) [0.53 eV] as compared to Pd(111)[0.60 eV], which contributes to the difference in rates. However the main contribution is from the fact that Pd(111) binds atomic H [-2.88 eV]and CO[-1.95 eV] more strongly than Pt(111) [H = -2.72 eV ] and [CO = -1.74 eV]. Hence there is no vacant site for Pd (111) below 500 K, thus there is no formation of formate species in that range. Same reasoning applies to higher temperature range, where Pt(111) has more vacant sites than Pd(111). xHCOOH=Keq1*PHCOOH*xv rate2=k2*xHCOOH*xv-km2*xHCOO*xH Hence, the higher conversion on Pt(111) based on this simplified model is attributed to the higher number of vacant sites at a given temperature, after some comparative analysis. The graph for surface coverages is given below:

Pd(111) :

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Pt(111)

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(2) Selectivity: Selectivity =(CO2 in outlet)/(CO2 in outlet + CO in outlet)

The above results show that CO2 is nearly the exclusive product formed in the case of Pd(111) over the temperature range, whereas there is a slight increase in the selectivity for Pt(111) at lower temperatures, followed by a comparatively steeper decline as the reaction temperature increases. Note that the scale for this graph is very small, and the selectivity is always more than 96%. Most of the experimental studies (Carmen Diaz et al., Applied Catalysis B: Environmental 89 (2009) 375-382, Dmitri A Bulushev et al., Catal. Today(2010) have suggested that CO2 will be the major C containing product from the reaction with selectivity > 0.96 for all temperature range. However there are studies (G.A. Papapolymerou et al. , Langmuir 1987 , 3 , 10981102) that suggest that CO and CO2 have identical rates of formation on polycrystalline Pt.

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(3) Conversion: Conversion = (Formic Acid in Formic Acid out)/(Formic Acid in)

The results above show that when all the conditions are kept same, Pt(111) is more reactive than Pd(111) at a given temperature. The reaction effectively starts at ~ 400K for Pt(111) and at ~500K for Pd(111). The table below shows the rates for each elementary step at different temperatures. All the rates are in the units of (1/sec)

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(a) Pd(111)

(b) Pt(111)

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These values indicate that the reaction predominantly follows the pathway where formate radical is formed (which is in contradiction with WGS reaction where the predominant pathway is via carboxyl formation and formate is just a spectator species). This is due to the fact that the activation energy barrier for formate is less than that of carboxyl (with respect to the best coadsorbed initial state). This difference in energy barrier is more pronounced in Pt(111) than Pd(111). Also, for Pt(111), at higher temperatures, the carboxyl species does not get converted to CO2 ( as indicated by the negative value of the rate in the table), and hence the selectivity decreases. This phenomenon is not observed for Pd(111). This can be explained by the fact that the equilibrium rate constant (Keq) for this step is 3 orders of magnitude higher on Pd(111) than on Pt(111). The values of the energy barrier for HCOO* COOH* is not known as of now, and no DFT calculations have been performed for this step. The rate determining step, according to this model is step (2), HCOOH* HCOO* + H* for the majority of temperature range.

Detailed Mechanism: A detailed microkinetic model was then prepared based on the structure given above, which included some other possible elementary steps and surface intermediates, for which DFT studies have not been performed by Jey yet. Some of the values are obtained from literature (mostly on 2x2 surface) for this model while others are estimated.
(1) (2) (3) (4) 2 (5) (6) 2 2 (7) (8)

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(9) (10)

2 2

2 2

(11) (12) (13)

(14) (15)

2 2

(16) (17) (18)

(19) (20)

2 2 2

2 2 2

(21) (22) (23)

The H- assisted C-OH bond cleavage in COOH* has been incorporated in the mechanism ( step 15) A working model corresponding to this mechanism is ready and DFT results for the extra steps are awaited.