Cation , surface protonation

Fontes tt al. [224,225 addressed the acid—base effects of the zeolites on enzymes in nonaqueous media by looking at how these materials affected the catalytic activity of cross-linked subtilisin microcrystals in supercritical fluids (C02, ethane) and in polar and nonpolar organic solvents (acetonitrile, hexane) at controlled water activity (aw). They were interested in how immobilization of subtilisin on zeolite could affected its ionization state and hence their catalytic performances. Transesterification activity of substilisin supported on NaA zeolite is improved up to 10-fold and 100-fold when performed under low aw values in supercritical-C02 and supercritical-ethane respectively. The increase is also observed when increasing the amount of zeolite due not only to a dehydrating effect but also to a cation exchange process between the surface proton of the enzyme and the sodium ions of the zeolite. The resulting basic form of the enzyme enhances the catalytic activity. In organic solvent the activity was even more enhanced than in sc-hexane, 10-fold and 20-fold for acetonitrile and hexane, respectively, probably due to a difference in the solubility of the acid byproduct. 

Figure 6.1 A simple electrostatic adsorption mechanism illustrating the protonation-deprotonation chemistry of surface hydroxyl groups on oxide surfaces (which are neutral at the PZC) and the corresponding uptake of anionic or cationic complexes. Proton transfer to or from the surface can significantly affect the solution pH.

Similarly, surface protonation tends to increase the dissolution rate, because it leads to highly polarized interatomic bonds in the immediate proximity of the surface central ions and thus facilitates the detachment of a cationic surface group into the solution. On the other hand, a surface coordinated metal ion, e.g., Cu2+ or Al3+, may block a surface group and thus retard dissolution. An outer-sphere surface complex has little effect on the dissolution rate. Changes in the oxidation state of surface central ions have a pronounced effect on the dissolution rate (see Chapter 9). 

But factors other than the surface charge can become important such as the effects of specific adsorption of cations and anions on the degree of surface protonation (see Example 5.1). 

Effect of ligands and metal ions on surface protonation of a hydrous oxide. Specific Adsorption of cations and anions is accompanied by a displacement of alkalimetric and acidimetric titration curve (see Figs. 2.10 and 3.5). This reflects a change in surface protonation as a consequence of adsorption. This is illustrated by two examples ... 

In essence, aqueous titration of surface acidity is an ion-exchange process in which hydrated surface protons are replaced by other hydrated cations (e.g., Na+, NIV") during the course of the titration. The procedure is straightforward. It usually consists of the direct titration of an aqueous suspension of the sample of powdered solid with a dilute base (e.g., sodium hydroxide) to a neutral endpoint. Another commonly used procedure consists of noting the pH of an appropriate salt solution (e.g., ammonium acetate), adding the sample, and measuring the amount of di-... 

In a subsequent calculational study [HF and MP2 levels of theory with 6-31G(d) basis set and MP4(SDQ)], Szabo and Cremer849 explored the he C7Hn+ potential energy surface. Cation 487 (tricyclo[4.1,0.01,3]heptyl cation), the protonated ethano-bridged derivative of spirocyclopentyl cation, was considered to be the missing link between the bicyclo[3.2.0]hept-3-yl cation 488 and the 7-norbomyl cation 489. It is a kinetically stabilized species separated from cations 488 and 489 by 18.9 and 15.9 kcal mol-1, respectively. 

Formic acid, HCOOH, was studied several years ago, but more recently the cation H2COH+ (protonated formaldehyde) and the surface for the reaction (10)172 have... 

Having emphasized the importance of the pH parameter, it should be recognized that its measurement is in itself a difficult task [90]. When the surface is charged, the overall ion concentrations are not constant close to the oxide-fluid interface. For instance, above the IEP, i.e. for negatively charged surfaces, there is an increase in cation and proton concentrations at the surface. Therefore, the pH is lower than in the bulk of the solution. The situation is reversed at a pH lower than the IEP. This is a typical compensation effect of the pH. 

Keggin-type heteropoly compounds have attractive and important characteristics in terms of catalysis. They consist of heteropolyanions and counter-cations such as H, Cs or NHT When the counter-cations are protons, they are called heteropolyacids (HPA). An important characteristic of HPAs, such as 12-tungstophos-phoric acid (H3PW12O40), is the presence of very strong Bronsted acid sites. But the characteristics of HPAs strongly depend on temperature and relative humidity. When they are used in heterogeneous catalysis, it is often necessary to support them on high-surface-area oxides or activated carbons, in order to increase the surface contact with the reactants. 

Scherer and Willig (65) have studied the rate enhancement, due to cations and protons, of electron transfer from the surface of an organic insulator crystal, such as perylene, to oxidized ions, such as [Fe(CN)g] and fMo(CN)g] ", in solution. In an electrochemical method such as this, the saturation current directly renders the rate constant for electron transfer at the crystal surface. Furthermore, electron transfer on [Fe(CN)6l or [Mo(CN)g] can be studied in the absence of reduced forms, whereas the salt effect can be measured up to the solubility limit. They found that for the same concentration of added electrolyte, rate constants increased with the increased charge of the cation. Up to s 1M rate enhancement was of the order Li < Na < Cs but at salt concentrations >3.5 M a reversal that could be explained by different hydrations of the cations took place. They also found a good linear correlation in the shift to higher redox potentials (simultaneously increasing rate constants) with higher salt concentrations. 

For silica, the protons on the surface silanols are only weakly acidic, therefore ion exchange of these protons for a cation complex must be assisted by the use of a Lewis base to activate the surface protons as ... 

The base can be a co-solvent, such as trialkylamine, or the Lewis base function can be designed into the metal complex using O-bearing ligands such as al-koxyamines, acetylacetonates, etc. The optimum amount of co-solvent is 1-2 equivalents of the metal complex present in the solvent. The nitrogen atoms in ethylenediamine are not sufficiently basic to activate the surface protons from silica, but ethylenediamine complexes of some metal cations, such as Cu(II), readily exchange for the protons in zeolites which are more acidic than silanol protons. ... 

Adduct formation may occur between Lewis base sites on the cluster and cations on the surface (Lewis cations or protonic M—OH) ... 

F ure 9.21. The net charge at the hydrous oxide surface is established by the proton balance (adsorption of or OH and their complexes) at the interface and specifically bound cations or anions. This charge can be determined from an alkalimetric-acidi-metric titration curve and from a measurement of the extent of adsorption of specifically adsort)ed ions. Specifically adsorbed cations (anions) increase (decrease) the pH of the point of zero charge (pzc) or the isoelectric point but lower (raise) the pH of the zero net proton condition (pznpc). Addition of a ligand, at constant pH, increases surface protonation while the addition of a metal ion (i.e., specifically adsorbed) lowers surface protonation. (Adapted from Hohl et al., 1980.)... 

Temperature-programmed reduction and desorption (TPR, TPD) have been applied to study the stability of Pt-Co bimetallic particles entrapped in NaY zeolite cages upon O2 oxidation and reaction with surface protons generated during the reduction of transition metal cations. Oxidation of Pt/NaY catalyst with O2 at 573 K causes shift of TPR peak to lower temperature due to formation of partially oxidized Pt particles. Similar treatment for Pt-Co/NaY bimetallic catalysts results in complete isolation of Pt and Co in Pt-Co particles, leaving Pt and Co in supercages and sodalite cages, respectively. 

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