Formic acid, decomposition

As early as 1923 Hinshelwood and Topley (27) noted the exceptionally erratic behavior of palladium foil catalyst in the formic acid decomposition reaction within 140-200°C. The initially very high catalytic activity decreased 102 times during the exposure of palladium to hydrogen, which is a product of the reaction. Though the interpretation does not concern the /3-hydride formation, the authors observation deserves mentioning. 

Fig. 8. Arrhenius plots for the formic acid decomposition on palladium foil (1) and small pieces of this foil (2) at a higher temperature range, when hydrogen evolving as a product of the reaction was absorbed by Pd and transformed into the /3-Pd-H hydride phase. At the lower temperature range the reaction proceeds on the a-Pd-H phase, with a higher activation energy when the foil was hydrogen pretreated (2a), and a lower activation energy for a degassed Pd foil (3a). After Brill and Watson (57).

Volter and Alsdorf (52) obtained a relation of a very similar character for the dependence of the catalytic activity in formic acid decomposition on the composition of the nickel-copper alloys. However, extending the times of the alloy annealing for their better homogenization caused the maxima on the catalytic activity curves to disappear. 

Figure 12.14 SFG spectra of the carbonyls formed during formic acid decomposition on a Pt(lll) electrode in 0.1 M H2SO4 electrolyte containing 0.1 M formic acid. The spectral position is typical of atop CO on the Pt(l 11) surface. Times at which the spectra have been recorded are from 2 to 496 s, yielding HCOOH decomposition kinetics at three electrode potentials, -0.200, -0.025, and 0.225 V vs. Ag/AgCl.

Overall, we demonstrated electrode potential- and time-dependent properties of the atop CO adsorbate generated from the formic acid decomposition process at three potentials, and addressed the issues of formic acid reactivity and poisoning [Samjeske and Osawa, 2005 Chen et al., 2003,2006]. There is also a consistency with the previous kinetic data obtained by electrochemical methods the maximum in formic acid decomposition rates was obtained at —0.025 V vs. Ag/AgCl or 0.25 V vs. RHE (cf. Fig. 12.7 in [Lu et al., 1999]). However, the exact path towards the CO formation is not clear, as the main reaction is the oxidation of the HCOOH molecule ... 

Lu G-Q, Crown A, Wieckowski A. 1999. Formic acid decomposition on polycrystalline platinum and palladium electrodes. J Phys Chem B 103 9700-9711. 

Electron micrographs of Pd-Au films used for formic acid decomposition (69) showed two main differences due to change in composition ... 

Gold forms a continuous series of solid solutions with palladium, and there is no evidence for the existence of a miscibility gap. Also, the catalytic properties of the component metals are very different, and for these reasons the Pd-Au alloys have been popular in studies of the electronic factor in catalysis. The well-known paper by Couper and Eley (127) remains the most clearly defined example of a correlation between catalytic activity and the filling of d-band vacancies. The apparent activation energy for the ortho-parahydrogen conversion over Pd-Au wires wras constant on Pd and the Pd-rich alloys, but increased abruptly at 60% Au, at which composition d-band vacancies were considered to be just filled. Subsequently, Eley, with various collaborators, has studied a number of other reactions over the same alloy wires, e.g., formic acid decomposition 128), CO oxidation 129), and N20 decomposition ISO). These results, and the extent to which they support the d-band theory, have been reviewed by Eley (1). We shall confine our attention here to the chemisorption of oxygen and the decomposition of formic acid, winch have been studied on Pd-Au alloy films. 

Fig. 20. Apparent activation energy, Ek, for formic acid decomposition over Pd-Au alloy films deposited and annealed at 450°C (O) pure Pd film deposited at — 196°C and annealed at 200°C ( ) (69).

The points for Ag and Pd-Ag alloys lie on the same straight line, a compensation effect, but the pure Pd point lies above the Pd-Ag line. In fact, the point for pure Pd lies on the line for Pd-Rh alloys, whereas the other pure metal in this series, i.e., rhodium is anomalous, falling well below the Pd-Rh line. Examination of the many compensation effect plots given in Bond s Catalysis by Metals (155) shows that often one or other of the pure metals in a series of catalysts consisting of two metals and their alloys falls off the plot. Examples include CO oxidation and formic acid decomposition over Pd-Au catalysts, parahydrogen conversion (Pt-Cu) and the hydrogenation of acetylene (Cu-Ni, Co-Ni), ethylene (Pt-Cu), and benzene (Cu-Ni). In some cases, where alloy catalysts containing only a small addition of the second component have been studied, then such catalysts are also found to be anomalous, like the pure metal which they approximate in composition. 

Jacobs, G., Patterson, P.M., Graham, U.M., Crawford, A.C., Dozier, A., and Davis, B.H. 2005. Catalytic links among the water-gas shift, water-assisted formic acid decomposition, and methanol steam reforming reactions over Pt-promoted thoria. J. Catal. 235 79. 

In reviews on formic acid decomposition, Mars and coworkers194,198 wrote that the formation and decomposition of formate anions were monitored by infrared spectroscopy. These studies were carried out by Fahrenfort, Sachtler, and coworkers188,193 for the case of formates on metals produced by formic acid adsorption—Cu, Ni, Pd, Rh, Pt, and Zn and in the case of metal oxides, Hirota et al. investigated ZnO,187,189,190,197 while Scholten et al. studied MgO.199,200 The infrared... 

FIGURE9.t. Volcano Plot of formic acid decomposition. Abscissa Calculated A HadsofHCOOH Ordinate Temperature at which rate of HCOOH decomposition reaches the same value for all metals. 

B. Results for Formic Acid Decomposition on Clean Metals. 21... 

Metal-Oxygen and Metal-Hydrogen Surface Bond Strengths Compared to TPRS Peak Temperature for Formic Acid Decomposition"... 

The autocatalytic process observed on Ni(l 10) was very similar to results reported previously on nickel powder (82). In that work the rate of decomposition was measured as a function of the amount of formic acid adsorbed and the formic acid pressure. At 60°C and pressures from 0.4 to 1.4 Torr the rate of decomposition decreased as the formate coverage increased. Such behavior can be accounted for if the attractive interactions between the adsorbed species observed for the formic acid decomposition on Ni(llO) or... 

D. Reactions for Formic Acid Decomposition ON Metal-Adlayer Surfaces... 

Temperature programmed desorption studies of formic acid decomposition by metals was reviewed recently by Madix (7d) the significance of formate formation is paramount to the discussion. This is also apparent in the recent electron energy loss spectra of formic acid adsorption on Cu(lOO) reported by Sexton (77). 

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