Mechanism of H2O2 Decomposition by Triphenylphosphine Oxide.

A decomposition mechanism of H2O2 by triphenylphosphine oxide (TPPO) is presented. TPPO is often incorporated in proton-exchange membrane electrolytes as a moiety to inhibit the H2O2-induced degradation of the membranes. However, it has not been revealed how TPPO decreases the concentration of free H2O2 in the membranes. Following the experimental X-ray structures, the TPPO dimer capturing two H2O2 molecules was used as the calculation model. The vibrational spectrum calculations for various hydration numbers show that this model correctly reproduces the spectral peaks of TPPO capturing H2O2. On the basis of this model, the H2O2 decomposition mechanism by the TPPO dimer was searched. It was consequently found that this reaction proceeds through three steps: (1) Hydrogen transfer from H2O2 to the P=O bond of TPPO, (2) Hydrogen transfer from the -OOH group to the -OH group, and (3) O-O bond formation between O2 groups. The calculated vibrational spectra for the reactants and intermediates indicated that the first and second steps are activated by vibrational excitations. Moreover, the third step giving low barrier heights is considered to proceed through two reaction paths: directly producing the O2 molecule or going through an HOOOH intermediate. Interestingly, this reaction mechanism was found to use the violation of the octet rule for the P=O double bond, resulting in the strong H2O2 binding of TPPO.

Introduction

Degradation of the proton-exchange electrolyte membrane is a central factor determining the durability of fuel cells.[1,2] Proton-exchange membranes are known to be deteriorated by hydrogen peroxide, H2O2, coming from the oxygen O2 crossover.[3−5] That is, H2O2 is thought to cleave chemical bonds in membranes. For many years, it has been accepted that the H2O2-induced bond cleavage proceeds through the production of hydroxyl OH radicals. Recent studies have, however, reported that the OH radical-induced mechanism is inconsistent with actual membrane degradations: the ratio of the decomposition fragment products in the Fenton test, which is considered to produce OH radicals, is significantly different from that in the actual degradation of fuel cells.[6,7] Very recently, we theoretically proposed that a H2O2-induced decomposition mechanism also causes the degradation of membranes under actual fuel cell operation conditions.[8] That is, we proposed an H2O2-induced degradation mechanism, in which the H2O2 molecule, which is hydrated in the protonated water cluster of the doubly hydrated sulfonic acid groups of the Nafion membrane, directly attacks the ether bond of the membrane. What should be noted is that despite the fact that H2O2 certainly deteriorates proton-exchange membranes, only a few reliable methods have been suggested to remove H2O2 from proton-exchange membranes while maintaining the performance of the membranes.

The use of phosphine oxides, X3P=O (X is a group such as phenyl group), is one of the available methods for decreasing the amount of free H2O2 in proton-exchange membranes.[9] Although phosphine oxides are produced as unavoidable useless byproducts in some reactions such as the Wittig,[10] Staudinger,[11] and Appel[12] reactions, they are often used to detect oxygen in the production of phosphines because of the strong P=O bond. This P=O double bond has attracted attentions from a theoretical standpoint due to the clear violation of the octet rule, which establishes the tendency of atoms to prefer to have eight electrons in the valence shells.[13,14] For consistency with this rule, the P=O bond had been interpreted as an ionic bond for many years.[15−19] Theoretical studies, however, have revealed that this P=O double bond is not an ionic bond and is formed by the donation of the lone electron pair of the oxygen atom to the X–P σ* bond.[14,20−22] This P=O bond is also known to strongly bind to H2O2 molecules. Thierbach et al. found that triphenylphosphine, Ph3P=O, forms very short hydrogen bonds with the hydrogen of halogen acids[23−25] and H2O2,[26] indicating the strong O–H bonds between the P=O and H groups. Hillard et al. recently investigated the reactions of the tertiary phosphine oxides, X3P=O, for X = methyl (Me), butyl (Bu), octyl (Oct), cyclohexanyl (Cy), and phenyl (Ph) groups with H2O2 to produce X3P=O·(H2O2) (0.5 ≤ x ≤ 1.0) to explore the purification of phosphine oxides.[27] By means of single-crystal X-ray measurements, they found a cyclic dimeric structure, (Cy3P=O·H2O2)2 for the H2O2 adduct of tricyclohexanylphosphine oxide, Cy3P=O. They also found in the infrared (IR) spectra of tributylphosphine oxide, Bu3P=O, that the bound H2O2 is partially decomposed after 4 h in toluene at 80 °C, and the produced H2O is efficiently and quantitatively removed to yield clean phosphine oxides. This strongly suggests that the phosphine oxides could reduce H2O2 in proton-exchange membranes.

Note that a phosphine oxide moiety, triphenylphosphine oxide (TPPO) moiety, has already been introduced in proton-exchange membranes to decrease the degradation of the membranes. Fu et al. first inserted the TPPO moiety in the hydrophobic group of the sulfonated poly(arylene ether sulfone) proton-exchange membrane to enhance its water uptake and consequently found that this moiety leads to strong intermolecular interactions and high oxidative stability.[28] Miyake et al. used a sulfonated TPPO moiety in the hydrophilic group of block copolymer proton-exchange membranes and succeeded to improve their hydrophilic/hydrophobic phase separation and oxidative stability.[29] The TPPO moiety is considered to bind and/or decompose H2O2 in the proton-exchange membranes. These results seem to indicate that phosphine oxides decompose H2O2 molecules even in the form of moiety of the membranes. However, it has never been revealed how TPPO molecules accelerate the decomposition of H2O2. H2O2 decomposition is known to significantly depend on the presence or absence of catalysts. Although H2O2 is very slowly decomposed in supercritical water in the absence of such catalysts, it is rapidly decomposed into water and O2 molecules in the presence of catalysts such as metal ions. Many conventional decomposition mechanisms have assumed the initial production of OH radicals in, for example, the following reactions[30]

Since there are many water molecules in the channels of proton-exchange membranes, OH radicals are considered to be very unstable: the lifetime of OH radicals is 100 ns in aquo. H2O2 also requires 50.2 kcal/mol to dissociate into OH radicals.[31,32] As mentioned above, the H2O2 decomposition rapidly proceeds in the presence of metal ions. However, it needs no TPPO to proceed. H2O2 is, therefore, thought to be decomposed without producing OH radicals in membranes with TPPO moieties, although the decomposition mechanism has not yet been revealed.

In this study, we theoretically propose a decomposition mechanism of hydrated H2O2 molecules by TPPO. On the basis of the past experimental studies, we assume that H2O2 is decomposed through the cyclic dimeric structure of TPPO, (Ph3P=O·H2O2)2 (see Figure ). After detailing the computational methods, we first explore the optimized hydration structures of the TPPO dimer capturing H2O2 and their vibrational spectra. Then, we calculate several steps of the H2O2 decomposition reaction by TPPO and the associated reactions. We finally investigate the overall decomposition reaction mechanism focusing on why TPPO decomposes H2O2.

Figure 2

Optimized structures of hydrated TPPO dimer + two H2O2 molecules for λ = 0–3. LC-BLYP/cc-pVDZ is used in the geometry optimizations.

Computational Details

All calculations have been performed using the long-range correction[33] of Becke 1988 exchange[34] plus Lee–Yang–Parr correlation[35] (LC-BLYP) functional (single parameter, μ = 0.47[36]) with the cc-pVDZ basis set.[37,38] On the basis of the experimental X-ray structure,[27] we have adopted the TPPO dimer capturing two H2O2 molecules for the hydration numbers of λ = 0–3 as the calculation model (Figure ). The small hydration numbers (λ = 0–3) are selected to model the hydration condition near the anode of the proton-exchange membrane fuel cell, where H2O2 molecules are produced and actively decompose the membranes under the low humidity condition.[8] Geometry optimizations of the hydrated structures have been carried out for several initial structures maximizing the number of hydrogen bonds. The optimum geometries of the hydrated TPPO dimer with two H2O2 molecules are illustrated in Figure . Using these optimum geometries as the initial structures, we have optimized the geometries of the TPPO dimer + 2H2O2 models by varying the bond distance contributing to each reaction step: O–H bond distance of H2O2 (step 1), P=O bond distance (step 2), and bridging O–O bond distance (step 3). The Gaussian 09 suite of programs[39] has been used to perform all of the LC-BLYP calculations. All of the optimized structures have been checked to ensure that they yield positive, real frequencies. Transition-state calculations have been performed by the quadratic synchronous transition method.[40,41] The predictor–corrector integration method[42,43] was used to calculate the intrinsic reaction coordinates (IRCs) of the reactions. The vibrational modes contributing to the IR spectra and their assignments were analyzed using GaussView 5.0.8.[44]

Figure 1

Chemical structure of the calculation model of TPPO + two H2O2 and 2λ H2O molecules, where λ is the hydration number.

Calculated Results and Discussion

Hydrated Structures and Vibrational Spectra of TPPO Capturing H2O2

First, let us explore the hydration structures of TPPO capturing H2O2 molecules for four hydration numbers: λ = 0 through 3. As the calculation model of H2O2-adsorbed TPPO, we used an X-ray cyclic dimeric structure, in which tricyclohexanylphosphine oxide, Cy3P=O, captures two H2O2 molecules.[27]Figure illustrates the optimized structures of the hydration models: TPPO dimer capturing two H2O2 molecules with λ hydration water molecules. As shown in the figure, the H2O2 molecules make hydrogen bonds with hydrated water molecules between the TPPO molecules. The cross-linked structure using two H2O2 molecules is mediated by hydration water molecules in the presence of water molecules. Note, however, that the oxygen atoms of the phosphine oxides are attached to the H2O2 molecules in all of these hydrated structures. These findings suggest that the P=O group of the TPPO and hydration water molecules may play a significant role in the decomposition of H2O2.

Using these hydration structures, we next calculated the vibrational spectra of the hydrated TPPO dimer capturing the H2O2 molecules. Figure a displays the vibrational spectra of the TPPO dimer before and after the binding of two H2O2 molecules with no hydration water molecule. The figure clearly shows that the H2O2 binding produces sharp peaks in the 3200–3500 cm–1 range. Table summarizes the peak energies and the corresponding vibrational modes of the TPPO dimer capturing two H2O2 molecules for the hydration numbers of λ = 0 and 3. As shown in the table, the peaks in the 3200–3500 cm–1 range correspond to the O–H stretching modes of the H2O2 molecules. Note that similar broad, strong absorption peaks appear in the experimental IR spectra of neat Bu3P=O (Bu is n-butyl group) before and after H2O2 binding around 3217 cm–1, which are also assigned to the O–H stretching modes.[27] This indicates that the O–H stretching modes of H2O2 molecules are activated by IR photoabsorption in the 3200–3500 cm–1 range. The source of IR photoabsorption may be questioned. The main source of IR photoabsorption is molecular collisions. The temperature increase heats materials. According to classical statistical thermodynamics, a temperature upshift increases the frequency of molecular collisions, and consequently the collisions activate the vibrational motions of materials. In quantum mechanics, molecular collision-induced vibrational excitations are interpreted to transfer (IR) light (or in other words, corresponding energy) to excite molecular vibrational eigenstates by a translation–vibration coupling. The transition probability of the molecular collision-induced vibrational excitations is proportional to that of the IR light-induced excitations, that is, IR spectral peak strengths.[45] Note also that there are other sources of IR light: for example, the background photoradiation of materials and their reflections and transmissions. Dependent only on the temperature, IR light is known to be radiated in the range of 2.5–100 μm (100–4000 cm–1) at 300 K (room temperature). We consider that molecular collisions and background IR photoradiation enhance the H2O2 decomposition, as mentioned later.

Figure 3

Vibrational spectra of (a) TPPO dimer before and after capturing two H2O2 molecules without hydration (λ = 0) and (b) TPPO dimer capturing two H2O2 molecules before and after hydration (λ = 0 and 3). LC-BLYP/cc-pVDZ is used.

Table 1

Peak Energies and the Corresponding Peak Assignments of IR Spectra of Dehydrated and Hydrated TPPO Dimer Capturing Two H2O2 Molecules for λ = 0 and 3a

dehydrated TPPO dimer + 2H2O2 (λ = 0)		hydrated TPPO dimer + 2H2O2 (λ = 3)
peak energy (cm–1)	assignments	peak energy (cm–1)	assignments
3205	C–H stretching	3021, 3465, 3521, 3584, 3596, 3648, 3715, 3740	O–H stretching of H2O
		3135, 3176, 3323, 3333, 3398	O–H stretching of H2O2
3395, 3475, 3495, 3534	O–H stretching of H2O2	1709, 1722, 1741	H2O scissoring
		1515	H2O swinging
1183, 1184, 1195	symmetric C–C and P=O stretching	1189, 1195	symmetric C–C and P=O stretching
1120, 1131	asymmetric C–C and P=O stretching	1127, 1130	asymmetric C–C and P=O stretching
799, 822	H2O2 swinging	870, 874, 895, 952, 1113	H2O2 swinging
		793	C–H swinging
568, 569	asymmetric C–C and P–C stretching	555, 579, 676	H2O wagging and swinging

Only the peaks of more than 10–38 esu2 cm2 peak strengths are listed. The peak assignments corresponding to the vibrations of H2O2 are in bold.

Figure b depicts the vibrational spectra of the TPPO dimer capturing two H2O2 molecules with zero (λ = 0) and three (λ = 3) hydration water molecules. As shown in the figure, the hydration of this system provides sharp peaks in the 1700–1800 and 3000–3800 cm–1 ranges. Table indicates that these peaks are assigned to the scissoring modes and antisymmetric stretching modes of hydrated water molecules, respectively. These sharp peaks also appear after hydration in the experimental IR spectra of neat Bu3P=O with predecomposed H2O2 at 1647.2, 3219.2, and 3408.2 cm–1.[27] This correspondence indicates that the present model correctly reproduces the hydration structure of this phosphine oxide, and therefore, it is appropriate to investigate the H2O2 decomposition mechanism by TPPO.

H2O2 Decomposition Reaction Mechanism

Using the authenticated calculation model, we next searched for the H2O2 decomposition reaction mechanism by the TPPO dimer. As a result, we found that this reaction proceeds through the following three steps:

Hydrogen transfer from H2O2 to the P=O bond of TPPO: 2Ph3PO–H2O2 (MIN1) → 2Ph3P(OH)OOH (MIN2),

Hydrogen transfer from the −OOH group to the −OH group: 2Ph3P(OH)OOH (MIN2) → 2Ph3P(H2O)O2 (MIN3), and

O–O bond formation between O2 groups: 2Ph3P(H2O)O2 (MIN3) → 2Ph3PO + O2 + 2H2O (MIN4).

Figure illustrates four minima of this decomposition reaction for the hydration number of λ = 3. We adopted the most stable reaction paths in the ones that were calculated, which are given in several geometry optimizations, to specify this reaction mechanism. If OH radicals are used as a substitute for H2O2, we will obtain much different reaction mechanisms, with lower reaction barriers. However, we chose reaction mechanisms, to which H2O2 directly contributes, because OH radicals require large energies to be generated, as mentioned above. In this section, we explore the reaction mechanisms in these three steps.

Figure 4

Optimized structures of the minima of the H2O2 decomposition reaction by TPPO, 2Ph3PO–H2O2 → 2Ph3PO + O2 + 2H2O, for λ = 3. MIN1 and MIN4 indicate the reactant and the product, and MIN2 and MIN3 indicate the intermediate products. The dotted circles indicate the H2O2 molecules and their decomposed fragments. The fixed bond distances in the optimization of step 1 are shown in the structure of MIN1. LC-BLYP/cc-pVDZ is used.

Step 1: Hydrogen Transfer from H2O2 to the P=O Bond of TPPO

In the first step of the H2O2 decomposition reaction, that is, MIN1 → MIN2, the oxygen atom of the P=O bond abstracts a hydrogen atom from H2O2. Figure compares the potential energy curves of the first step for λ = 0 through 3. The horizontal axis indicates the structural parameter ratio of MIN2. After mixing the structural parameters of MIN1 and MIN2 at this rate, the geometries at each point on the reaction coordinate were optimized by fixing the O–O and O–H distances, which are shown in Figure . The figure shows that the dehydrated TPPO dimer provides the lowest barrier (∼46 kcal/mol), whereas the hydrated ones give high barriers, 56–60 kcal/mol. Note, however, that even the barrier of the dehydrated TPPO dimer, ∼46 kcal/mol, is too high for the decomposition reaction to proceed easily at room temperature condition. It is interesting to compare this barrier to that of the H2O2 decomposition reaction in water, which is experimentally known to be 43–48 kcal/mol.[30] Recently, we also calculated this barrier height by the same method and found that it is evaluated to be 48–50 kcal/mol under hydration. The small difference between the barrier heights seems to suggest that the contribution of the TPPO dimer to the reactivity of the H2O2 decomposition is not important. We should, however, note that the OH stretching modes of H2O2 are considered to contribute to this reaction step when attached to the TPPO dimer, whereas these modes may be relaxed by other vibrational modes of water molecules when hydrated in aqueous solution. As mentioned in the previous section, this system provides sharp peaks corresponding to the O–H stretching modes of H2O2 in the 3200–3500 cm–1 (9.2–10.0 kcal/mol) range. This indicates that the stretching modes of the captured H2O2 molecules are activated by vibrational excitations in this region. Note that the stretching mode of H2O2 proceeds toward the direction of the reaction process in this step, and therefore, enhances the reaction process through the vibrational excitations. Although the stretching modes of H2O2 are also activated in aquo, they are relaxed by the vibrational modes of water molecules around H2O2. We, therefore, conclude that this reaction step slowly proceeds by the assistance of the vibrational excitations.

Figure 5

Potential energy curves of H2O2 decomposition reaction by TPPO dimer in the first step, 2Ph3PO–H2O2 → 2Ph3P(OH)OOH, with respect to the structural parameter ratio of the product of this step (MIN2) on the IRC from the reactant (MIN1) to MIN2. The dotted circles indicate the fixed O–O and O–H bond distances. LC-BLYP/cc-pVDZ is used.

Step 2: Hydrogen Transfer from −OOH Group to the −OH Group

The second step of the H2O2 decomposition, that is, MIN2 → MIN3, is the hydrogen transfer from the −O–OH group to the −OH group, both of which bind to the P atom. Figure plots the potential energy curves of this step in terms of the P–O distance of the P–OH bond for λ = 0 through 3. The geometry optimizations were performed by fixing only the P–O distance. This figure shows that the dehydrated TPPO dimer provides the lowest barrier with ∼27 kcal/mol, whereas the hydrated one gives a higher barrier, 30–33 kcal/mol. However, this step is not thought to be rate-determining because of the lower barriers than those in the first step. We should also note that this barrier estimate includes the barriers for two molecules because this step is an intramolecular reaction. Interestingly, this step is driven by the P–O stretching of the P–OH group. In the vibrational spectrum of MIN2 for λ = 0 (see the Supplementary Information), a strong peak corresponding to this stretching mode appears at 949 cm–1, with a very strong peak corresponding to the O–H stretching of the P–OH group at 2697 cm–1, which supports the backward process toward MIN1 in step 1. This suggests that vibrational excitations also induce this step to proceed, although it simultaneously activates the backward process of step 1. Furthermore, the vibrational spectrum of MIN3 for λ = 0 (see the Supplementary Information) gives a strong peak corresponding to the OH stretching of H2O, which supports the backward process of step 2 at 3069, 3516, and 3810 cm–1. We, therefore, propose that the vibrational excitations activate this step for both forward and backward processes, as well as step 1.

Figure 6

Potential energy curves of H2O2 decomposition reaction by TPPO dimer in the second step, 2Ph3P(OH)OOH → 2Ph3P(H2O)OO, with respect to the P–O distance of the P–OH bond. The dotted circles indicate the fixed P–O bond distances. LC-BLYP/cc-pVDZ is used.

Step 3: O–O Bond Formation between O2 Groups

In the third step, an O2 molecule is formed from two O2 molecules attached to the P atoms of MIN3 to regenerate the TPPO dimer: MIN3 → MIN4. Note that the H2O2 decomposition can be interpreted to be terminated in step 2 because oxygen and water molecules are already produced in this step. Although this interpretation is surely acceptable, the H2O2 decomposition is not a catalytic reaction in this case because it does not regenerate the TPPO dimer, probably in contradiction to the experimental results. Since the O2 molecules attached to the P atoms are radicals in MIN3, they are considered to form an O2 molecule rapidly when approaching each other. The reaction barrier of this step is, therefore, the energy required to bring two O2 molecules together. Figure depicts the potential energy curves of step 3 with respect to the O–O distance between two O2 molecules attached to the P atoms of the TPPO dimer. As shown in the figure, two reaction paths are obtained for this step: one path directly produces an O2 molecule (path 1) and the other path forms an HOOOH molecule before producing an O2 molecule (path 2).

Figure 7

Potential energy curves of H2O2 decomposition reaction by TPPO dimer in the third step, 2Ph3P(H2O)O2 → 2Ph3PO + O2 + 2H2O, with respect to the O–O distance. The dotted circles indicate the fixed O–O bond distances. LC-BLYP/cc-pVDZ is used.

For path 1, the systems of small hydration numbers (λ = 0 and 1) provide lower barriers than those of large hydration numbers (λ = 2 and 3): the barrier height energies are less than 15 kcal/mol for the former, whereas they are 25–30 kcal/mol for the latter. Since the barrier heights of the former are much lower than those in step 1 and 2, step 3 may naturally proceed under dehydrated conditions. The reaction energies also tend to be large for the small hydration numbers: they are 64.5, 56.1, 44.5, and 49.3 kcal/mol for λ = 0 through 3, respectively. We, therefore, conclude that, similar to step 1 and 2, step 3 rapidly proceeds under the dehydrated condition, whereas it proceeds slowly under the hydrated condition.

The second path proceeds via the production of an HOOOH molecule. The potential energy curves of this path intersect with those of path 1 in decreasing the O–O bond distance between two O2 molecules and have a minima at an O–O bond distance of about 2.2 Å. We consider that a significant proportion of this step falls into the potential well of this path, producing an HOOOH molecule. Therefore, we also explored the subsequent reaction process after which the HOOOH production would proceed. Figure illustrates the decomposition reaction potential energy curve of HOOOH by two water molecules to O2 + H2O on the normalized IRC. The figure shows that this decomposition reaction requires only less than 10 kcal/mol to proceed. This indicates that HOOOH is easily decomposed under the hydrated condition. Being different from steps 1 and 2, step 3 is not enhanced by vibrational excitations because MIN3 provides no sharp peaks corresponding to the O–O stretching modes. We therefore suppose that the HOOOH production may be an alternative path for step 3 because it requires a very small barrier to proceed.

Figure 8

Decomposition reaction potential energy curve of HOOH: HOOOH + 2H2O → O2 + 3H2O on the normalized IRC, which is calculated by LC-BLYP/cc-pVDZ. The reactant energy is set to be zero.

Overall Mechanism of TPPO-Induced H2O2 Decomposition Reaction

Finally, let us clarify the overall picture of the H2O2 decomposition reaction mechanism for steps 1 through 3. Figure integrates the reaction potential energy curves and schematic diagrams of these steps. The figure shows high reaction barriers and small (or negative) reaction energies as a whole. Actually, the reaction barrier energies were evaluated to be about 71, 84, 78, and 79 kcal/mol, and the reaction energies are given to be 1.0, −3.8, −4.7, and −2.7 kcal/mol for λ = 0 through 3, respectively. This seems to suggest that the TPPO-induced H2O2 decomposition reaction is very slow. However, the results also indicate that the first and second steps are activated by vibrational excitations, and the third step has two paths giving very low barrier heights, as mentioned above. Moreover, even the highest barriers of step 1 in this reaction are lower than those of the H2O2 decomposition reaction in aquo without any catalyst such as a metal ion. We therefore consider that this decomposition reaction proceeds faster than it appears in the potential energy curves.

Figure 9

Potential energy curve of the whole process of 2H2O2 → O2 + 2H2O by TPPO dimer. LC-BLYP/cc-pVDZ is used. The IRCs are normalized for each reaction step.

The present results also clarify some features of TPPO. The reaction mechanism shows that the H2O2 decomposition uses the violation of the octet rule, that is, the P atom of TPPO forms five bonds in the reaction process. As mentioned in the introduction, it has been discussed whether the P=O double bond is an ionic bond satisfying the octet rule or not. This reaction mechanism indicates that the P atom of TPPO clearly violates the octet rule, and the P=O bond is, therefore, not ionic. Furthermore, this result explains the reason as to why H2O2 molecules strongly bind to the P=O double bond. The H2O2 molecules and the P=O bond exchange hydrogen atoms through the O–H stretching modes that have high vibrational excitation probabilities. Therefore, TPPO is useful as an inhibitor for chemical attack by H2O2 because of the strong adsorption ability, even if the decomposition reaction would be slow.

Conclusions

In this study, we have theoretically investigated the decomposition mechanism of hydrogen peroxide, H2O2, by TPPO, which is often incorporated in the proton-exchange membranes for fuel cells. As a result, by reference to an experimental study, we found a decomposition reaction mechanism, which uses the TPPO dimer and is activated by the vibrational excitations in the initial processes.

On the basis of the experimental X-ray spectrum analysis,[27] we first determined the hydration structures of the TPPO dimer capturing two H2O2 molecules for the hydration numbers of λ = 0 through 3. We calculated the vibrational spectra of these hydrated systems and found that the vibrational spectra accurately provide sharp peaks corresponding to the vibrational modes of H2O2 and H2O attached to the TPPO dimer, and therefore, the calculational models are considered to be correct.

We next explored the H2O2 decomposition reaction mechanism of the TPPO dimer, using the authenticated models. Consequently, we found that this decomposition reaction proceeds through three steps: (1) hydrogen transfer from H2O2 to the P=O bond of TPPO, (2) hydrogen transfer from the −OOH group to the −OH group, and (3) O–O bond formation between O2 groups. For the first and second steps, we revealed that the reactions are activated by vibrational excitations because of the sharp peaks corresponding to the vibrational modes, enhancing the reaction rates for these steps for both forward and backward processes. The decomposition reaction was shown to proceed at a higher rate under dehydrated condition than that under hydrated conditions. We also found that the third step provides two reaction paths: one directly produces an O2 molecule and the other forms HOOOH prior to the O2 production. For both paths, we obtained low barrier heights, indicating the smooth progress of the reactions.

In conclusion, we proposed a TPPO-induced H2O2 decomposition mechanism activated by vibrational excitations. This reaction mechanism makes use of the violation of the octet rule and the resulting strong H2O2 binding to the P=O double bond. We expect that this study will lead to the development of a new catalyst for H2O2 decomposition.