Formaldehyde adsorption

The most commonly used emulsifiers are sodium, potassium, or ammonium salts of oleic acid, stearic acid, or rosin acids, or disproportionate rosin acids, either singly or in mixture. An aLkylsulfate or aLkylarenesulfonate can also be used or be present as a stabilizer. A useful stabilizer of this class is the condensation product of formaldehyde with the sodium salt of P-naphthalenesulfonic acid. AH these primary emulsifiers and stabilizers are anionic and on adsorption they confer a negative charge to the polymer particles. Latices stabilized with cationic or nonionic surfactants have been developed for special apphcations. Despite the high concentration of emulsifiers in most synthetic latices, only a small proportion is present in the aqueous phase nearly all of it is adsorbed on the polymer particles. 

Highly active catalysts have been produced by adsorption of lipases onto macroporous acrylate beads, polypropylene particles and phenol-formaldehyde weak anion exchange resins. Protein is bound, presumably essentially as a monolayer, within the pores of the particles. The large surface area of the particles (10m2 g 1) means that substantial amounts of protein can be adsorbed, and the pores are of sufficient size to allow easy access of reactants to this adsorbed protein. 

Figure 3b. The sticking probability of methanol on a Cu(llO) surface predosed with half a monolayer of oxygen. There is an induction period to adsorption taking place and formaldehyde is evolved coincidentally with the sticking. Adsorption temperature of 353 K.

Nakabayashi, S., Sugiyama, N., Yagi, 1. and Uosaki, K. (1996) Dissociative adsorption dynamics of formaldehyde on a platinum electrode surface onedimensional domino Chem. Phys., 205, 269-275. 

Adsorption of formaldehyde on Pt (111) and Pt(lOO) electrodes cyclic voltammetry and scanning tunneling microscopy. Langmuir, 21, 4964—4970. 

Methanol, Formaldehyde, and Formic Acid Adsorption/Oxidation on a Carbon-Supported Pt Nanoparticle Fuel Cell Catalyst A Comparative Quantitative OEMS Study... 

In the following, after a brief description of the experimental setup and procedures (Section 13.2), we will first focus on the adsorption and on the coverage and composition of the adlayer resulting from adsorption of the respective Cj molecules at a potential in the Hup range as determined by adsorbate stripping experiments (Section 13.3.1). Section 13.3.2 deals with bulk oxidation of the respective reactants and the contribution of the different reaction products to the total reaction current under continuous electrolyte flow, first in potentiodynamic experiments and then in potentiostatic reaction transients, after stepping the potential from 0.16 to 0.6 V, which was chosen as a typical reaction potential. The results are discussed in terms of a mechanism in which, for methanol and formaldehyde oxidation, the commonly used dual-pathway mechanism is extended by the possibility that reaction intermediates can desorb as incomplete oxidation products and also re-adsorb for further oxidation (for the formic acid oxidation mechanism, see [Samjeske and Osawa, 2005 Chen et al., 2006a, b Miki et al., 2004]). 

In this section, we will present and discuss cyclic voltammetry and potential-step DBMS data on the electro-oxidation ( stripping ) of pre-adsorbed residues formed upon adsorption of formic acid, formaldehyde, and methanol, and compare these data with the oxidative stripping of a CO adlayer formed upon exposure of a Pt/ Vulcan catalyst to a CO-containing (either CO- or CO/Ar-saturated) electrolyte as reference. We will identify adsorbed species from the ratio of the mass spectrometric and faradaic stripping charge, determine the adsorbate coverage relative to a saturated CO adlayer, and discuss mass spectrometric and faradaic current transients after adsorption at 0.16 V and a subsequent potential step to 0.6 V. 

Figure 13.6 Potential-step electro-oxidation of formaldehyde on a Pt/Vulcan thin-film electrode (7 p,gpt cm, geometric area 0.28 cm ) in 0.5 M H2SO4 solution containing 0.1 M HCHO upon stepping the potential from 0.16 to 0.6 V (electrolyte flow rate 5 pL at room temperature). (a) Solid line, faradaic current transients dashed line, partial current for HCHO oxidation to CO2 dotted line, difference between the net faradaic current and that for CO2 formation, (b) Solid line, m/z = 44 ion current transients gray line potential-step oxidation of pre-adsorbed CO derived upon HCHO adsorption at 0.16 V, in HCHO-free sulfuric acid solution, (c) Current efficiency transients for CO2 formation (dashed line) and formic acid formation (dotted line).

With regard to the second question, while COad formation from methanol is slow at potentials in the H pd region, formaldehyde adsorption transients on a Pt film electrode showed rapid COad formation under these condition [Chen et al., to be published]. Furthermore, Korzeniewski and Childers [1998] reported increasingly... 

The reaction sequence of formaldehyde formation and subsequent COad formation can proceed either as sequential reactions of adsorbed species, or it can involve formation and desorption of formaldehyde into the electrol5d e and subsequent re-adsorption and further decomposition of formaldehyde to COad. Considering the significant transport and catalyst loading effects discussed above, it is clear that desorption and subsequent re-adsorption plus dehydrogenation of formaldehyde will play an important role also for COad formation, although a direct reaction of adsorbed RIad species can not be ruled out. 

Similar ideas can be applied to formaldehyde oxidation. For bulk formaldehyde oxidation, we found predominant formic acid formation under current reaction conditions rather than CO2 formation. Hence, it cannot be ruled out, and may even be realistic, that formaldehyde is first oxidized to formic acid, which can subsequently be oxidized to CO2. The steady-state product distribution at 0.6 V is much more favorable for such a mechanism as in the case of methanol oxidation. On the other hand, because of the high efficiency of COad formation from formaldehyde, this process is likely to proceed directly from formaldehyde adsorption rather than via formation and re-adsorption of formic acid. Alternatively, the second oxygen can be introduced via formaldehyde hydration to methylene glycol, which could be further oxidized to formic acid and finally to CO2 (see the next paragraph). 

The adsorption and oxidation of the Ci molecules methanol, formaldehyde, and formic acid over a carbon-supported Pt/C fuel cell catalyst under continuous electrolyte flow have been investigated in a quantitative, comparative online DBMS study. 

Chen Y-X, Heinen M, Jusys Z, Behm RJ. Dissociative adsorption and oxidation of formaldehyde on a Pt film electrode under controlled mass-transport conditions, an in-situ spectro-electrochemical flow-cell study. To he published. 

Loucka T, Weber J. 1968. Adsorption and oxidation of formaldehyde at the platinum electrode in acid solutions. J Electroanal Chem 21 329-344. 

Mai C-F, Shue C-H, Yang Y-C, Yang L-YO, Yau S-L, Itaya K. 2005. Adsorption of formaldehyde on Pt(lll) and Pt(lOO) electrodes Cyclic voltammetry and scaniung tinmeUng microscopy. Langmuir 21 4964-4970. 

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