Studies in Surface Science and Catalysis, Vol.

139
J.J. Spivey, G.W. Roberts and B.H. Davis (Editors) 327
9 2001 Elsevier Science B.V. All rights reserved.

Quinone Mediated Stabilization of a Palladium Catalyst for the Synthesis

of Hydrogen Peroxide from Carbon Monoxide, Water and Oxygen

Daniele Bianchi, Rossella Bortolo, Cecilia Querci, Rino D'Aloisio, and Marco Ricci

EniChem - Centro Ricerche Novara "Istituto G. Donegani"

Via Fauser 4, 1-28100 Novara (Italy)

An improved method for the synthesis of hydrogen peroxide from carbon monoxide, water
and oxygen catalyzed by palladium complexes in presence of a quinone co-catalyst is
described. The use of 1,4-naphthoquinone and 1,10-phenanthroline as palladium ligand
resulted in a marked catalyst stabilization against deactivation processes such as polynuclear
species formation and Pd-black precipitation, which are very fast operating in the absence of
quinone.

1. INTRODUCTION

Hydrogen peroxide is a chemical used in large volumes for chlorine free bleaching and in a
wide variety of chemical processes as environmentally friendly oxidant, mainly due to its
unique feature of producing water as the only by-product [ 1].
Industrially, hydrogen peroxide is almost universally produced by the alternate
hydrogenation and oxidation with air of an alkylanthraquinone [2]. Although the process is
efficient from a yield standpoint, it is quite complex and is carried out in two separate steps,
using a stoichiometric amount of expensive high molecular weight quinones (e.g. 2-
ethylanthraquinone).
In a previous paper [3] we reported a new method for the synthesis of hydrogen peroxide
from CO/H20/O2 catalyzed by homogeneous palladium complexes with bidentate nitrogen"
ligands.

CO + H20 + 0 2 ~ CO 2 + H202

In particular, the palladium complex with 2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline,

was selected as the most efficient catalyst. The presence of the methyl substitution in 2,9-
positions was necessary to avoid the formation ofbinuclear complexes like 1 (detected using
1,10-phenanthroline as palladium ligand), which are stable in reaction conditions and are
responsible of the fast irreversible deactivation of the catalyst.
The proposed reaction pathway (Figure 1) is likely to involve:/) the reduction of the Pd(II)
complex 2 via hydride intermediate 3, by carbon monoxide and water, affording carbon
dioxide and a Pd(0) species 4; ii) the oxidation of this Pd(0) species by oxygen with
fonnation of a Pd(II) peroxo-complex 5; iii) the reaction of the latter species with an acid,
producing hydrogen peroxide and restoring the initial Pd(II) complex [4].
328

CO + HzO CO:, + HX
X \) H
L2Pd~X
2

H202"~
2HXJ[ 9 co

-2CO co
L2Pd~/IO
O <
CO DEACTIVATION
4 P A T H W A Y1

l
- 2 CO DEACTIVATION
PATHWAY 2

Pd-black

Fig. 1. Deactivation pathways

[L2 = bidentate nitrogen ligand]

As shown in Figure 1 (deactivation pathway 1), the inactive complex 1 is probably generated
by the coupling between the hydride species 3 and the Pd(0) species 4.
Using 1,10-phenanthroline as the palladium ligand, a red solid was isolated which structure
was assigned on the basis of MS and ~H-NMR analysis as the binuclear hydride species 1.

2. EXPERIMENTAL SECTION

General procedure for the synthesis of hydrogen peroxide

Pd(OAc)2 (5.6 mg, 0.025 mmol), 1,10-phenanthroline (67.5 mg, 0.375 retool), and
C7FlsCOOH(414 mg, 1 mmol) were dissolved in a mixture of toluene (3 ml) and 1-butanol
(7 ml), and stirred for 6 hours at 25~ The resulting complex solution was added to water"
(10 ml) to form a biphasic system.
1,4-Naphthoquinone (198 mg, 1,25 mmol) was added and the mixture was poured into an
autoclave containing a glass liner. The reactor was then pressured to 60 bar partial pressure
of air and 10 bar partial pressure of CO in order to form a non-flammable gas mixture and
the reaction was carried out for 1 hour at 70~ At the end of the reaction, the hydrogen
peroxide concentration was evaluated by titration with potassium permanganate.

3. RESULTS AND DISCUSSION

In spite of the high efficiency displayed by the catalyst, the selected 2,9 substituted ligand is
quite expensive, therefore, for the development of an industrial process, the use of a simple
and cheap ligand, such as the 1,10-phenanthroline, should be desirable.
 329

With the aim to prevent the formation of the inactive binuclear complex 1, which is very fast
using 1,10-phenanthroline, a possible way is the addition to the reaction media of a
competitor of carbon monoxide in binding the reduced palladium species.
We found that, using 1,10-phenanthroline as a palladium ligand, a great enhancement of the
catalyst stability was obtained operating in presence of a suitable quinone, acting as a
cocatalyst [5].

3.1 Stabilization against the deactivation pathway 1

In order to evaluate the effect of quinones on our system, we tested the series of compounds
listed in table 1, using the complex Pd(phenanthroline)X2 as a catalyst, operating under
reducing reaction conditions (CO/H20, in absence of 02) which favors the formation of the
inactive complexes.
The reactions were carried out in the biphasic system previously selected for the synthesis of
hydrogen peroxide (1-butanol/chlorobenzene/water).
Since the hydrophilic ligand phenanthroline (1) afforded a complex soluble in the aqueous
phase, the catalyst was moved into the organic phase by using a highly hydrophobic acid co-
catalyst (perfluorooctanoic acid) acting as a phase transfer anion (the partition of the
complex in the organic layer was <1% and >99% with trifluoroacetate and
perfluorooctanoate anion, respectively). Operating under these conditions, we found that
quinones 6-9, added in excess with respect to the palladium (quinone/Pd molar ratio = 100)
not only prevented the formation of red, inactive species, but were also reduced in a catalytic
way to the corresponding hydroquinones [6]. On the contrary, quinones 10 and 11 did not
bind to the reduced palladium (probably because of their steric hindrance) and failed in
preventing the formation of the red inactive species.

O quinone
2 CO /CO
L2Pd~ ~ 8 #,~ ~ L2PdxcO
0 ]2

2HX

+ L2P<x
X
OH 8a 2

Fig. 2. Stabilizing effect of the quinone-cocatalyst

[L2 = bidentate nitrogen ligand]

Figure 2 shows the reaction of quinone 8 that is reduced to 1,4-dihydroxynaphthalene (8a) in

the presence of Pd(phenanthroline)(CTH~sCOO)2 catalyst. In the new pathway, the
intermediate complex L2Pd(0)-quinone (12) is formed instead of the complex 4, which is the
330

precursor of the deactivated catalyst 1 [7-8]. The complex 12 is not stable under the reaction
conditions and gives 8a with regeneration of the starting Pd(II) complex 2.
The same quinones series was tested in the presence of oxygen (CO/H20/O_~) under the
reaction conditions suitable for the synthesis of hydrogen peroxide.
As reported in Table 1, the only quinone really effective in promoting the formation of
hydrogen peroxide was the 1,4-naphthoquinone 8.
In all the other cases we observed the fast formation of the red inactive species. The analysis
of the final reaction mixtures showed that the quinones 6 and 7 were quantitatively reduced
to the corresponding hydroquinones, not effective in the stabilization of reduced palladium
species. Quinones 10 and 11 were not transformed, confirming the results obtained operating
under reducing conditions in absence of oxygen. Also the quinone 8 was recovered
unaltered, but in this case we observed the vigorous formation of hydrogen peroxide and the
maintenance of the palladium catalyst in the active form.
These findings can be explained by the ability of 1,4-dihydroxynaphthalene 8a, resulting
from the first reduction step, to react with oxygen to give hydrogen peroxide, thus
regenerating the starting quinone 8 which can reenter into the catalytic cycle (Figure 3).
Conversely, hydroquinone and phenylhydroquinone arising from the reduction of quinones 6
and 7 respectively, have a too high reduction potential (E ~ and cannot undergo the oxidation
process.

Table 1
Selection of the quinone-cocatalyst

Quinone lal Eo TOF Quinone E~ TOF

(V) ibl (hour") I~i (V) (hour ~)
0 i i
0
6 ~ 0.712 5 Idl 9 ~)k,,~M e 0.422 20 I,,I
v y
O o

7 % 0.698 13 [al 10 Me~~4e O

0.466 0 I,,]
Me" ~ 'Me
O 0
O O
8 @ 0.484 263 11 ~~/~Et 0.150 0 Idl
v-y-v
0 O
[a] 1,10-Phenanthroline/CTF~sCOOH/quinone/Pd molar ratio" 5/20/50/1; solvent: 1-
butanol/chlorobenzene/water 35/15/50 (v/v/v); temperature: 70~ Pco" 6 bar; Po_~" 64
bar.
[b] Reduction potential
[e] Tumover frequency (moles of hydrogen peroxide per mole of palladium per hour).
[d] The formation of red inactive complexes was observed.
 331

CO + H20 CO2 + HX

\ N / ~X N" ~X
2 3

HX
O

12 O

9a 02 H202 9

Fig. 3. Reaction mechanism in presence of quinones

[L_, = bidentate nitrogen ligand]

2-Methyl-l,4-dihydroxynaphthalene, coming from the reduction of 2-methylnaphthoquinone

9, was easily oxidized but, due to the steric hindrance of its methyl group, quinone 9 showed
a low binding capability towards the Pd(0) species and failed in preventing the fomaation of
the inactive complex.
Even if the reaction balance is formally the same, the mechanism of formation of hydrogen
peroxide in the new process is completely different to that proposed for the reaction carried
out in absence of quinones (Figure 1). In the former case, Pd(0) species 4 is likely to be
oxidized by oxygen, and hydrogen peroxide is formed upon hydrolysis of the resulting
peroxo-complex. On the contrary, in the presence of the quinone, Pd(0) species 4 is oxidized
by the quinone itself, and hydrogen peroxide is formed upon auto-oxidation of the resulting
hydroquinone (Figure 3).
The different mechanism was confirmed by studying the ligand effect on the reaction carried
out in absence and in presence of quinones.
Table 2 reports the catalytic activities of a series of palladium complexes with the bidentate
nitrogen ligands in the synthesis of hydrogen peroxide carried out in presence or in absence
of the selected quinone 8 (used in catalytic amount).
332

Table 2
Selection of the palladium ligand

Pd ligand I~J TOF (hour")lb~ TOF (h'our-')

in absence of quinone in presence of quinone 8
0 Icl 225

0 ic~ 263

434 90

528 75

[a] Ligand/C7FIsCOOH/quinone 8/Pd molar ratio: 5/20/50/1; solvent: 1-butanol/chloro

benzene/water 35/15/50 (v/v/v); temperature: 70~ Pco: 6 bar; Po2:64 bar.
[b] Turnover frequency (moles of hydrogen peroxide per mole of palladium per hour).
[c] The formation of red inactive complexes was observed.

Perfluorooctanoic acid were used as acid co-catalysts for both hydrophobic and hydrophilic
ligands, in order to ensure the segregation of the catalysts into the organic layer of the
biphasic system.
As shown in the table, the complexes with 2,9-unsubstituted ligands resulted inactive in
absence of quinones due to the formation of red inactive binuclear species, but became active
in presence of 8. Conversely, the complexes with 2,9-dimethyl substituted ligands, which
were strongly effective in absence of quinones, displayed a lower activity in presence of 8.
Thus, this behavior seems to confirm the presence of two different reaction pathways, and
consequently different reaction rates, if palladium is oxidized by the oxygen or the quinone."
After selection of 1,10-phenanthroline as the most effective ligand, the reaction conditions
were optimized in order to improve the catalyst efficiency and stability. The
ligand/perfluorooctanoic acid/quinone 8/Pd(OAc)2 molar ratio was tuned to 15/40/50/1,
achieving an increase of tumover frequency (TOF) higher than 500 moles of hydrogen
peroxide per mole of palladium per hour. The best catalyst stability was obtained operating
in a chlorine free reaction medium (1-butanol/toluene/water) [9].

3.2 Stabilization against the deactivation pathway 2

In the case of the process carried out in the absence of quinone, the use of a large excess of
oxygen in the gas phase was necessary in order to prevent the precipitation of reduced
palladium (Figure 1: deactivation pathway 2) which becomes predominant under reducing
conditions (operating with pure oxygen, the maximum allowed CO fraction was 8.5%) [4].
In the new process, the strong stabilizing effect exerted by the quinone on Pd(0) species,
allowed to use air instead of oxygen and to increase the CO fraction up to 14%.
 333

800

600
A

400
U.
oi-.

200

0 5 10 15
co (%)

Fig. 4. Effect of the gas phase composition

Gas phase composition: carbon monoxide/air; pressure 70 bar; temperature 70~
I"1 Pd Ligand: 2,9-dimethyl-4,7-diphenyl-l,10-phenanthroline; quinone: none.
!1 Pd Ligand: 1,10-phenanthroline; quinone 8.
[*] The partial precipitation of Pd-black was detected.

As reported in Figure 4, this resulted in a higher catalytic activity (TOF = 680) and in safer
reaction conditions, being the Lower Explosion Limit (LEL) of carbon monoxide in air
(17,5%) higher than that in pure oxygen (12,5%).
In a preliminary study, the stability of the catalytic system was evaluated by running a series
of reaction cycles in a discontinuous operation mode (Figure 5).

5.000

4.000

3.000

2.000

1.000

0 1 2 3 4 5 6 7 8 9 10
Reaction cycle (n*)

Fig. 5. Catalyst stability

Reaction conditions: phenanthroline/CTFlsCOOH/quinone 8/Pd molar ratio: 15/40/50/1;
solvent: 1-butanol/toluene/water 35/15/50 (v/v/v); temperature: 70~ Pco: 10 bar; Pair: 60
bar.
334

At the end of each cycle the aqueous phase, containing the produced hydrogen peroxide, was
removed by decantation and replaced with pure water. The organic layer, containing the
catalyst, the quinone and the acid co-catalyst, was then reused in a following cycle. After 10
consecutive cycles (carried out in 10 hours) an overall turnover number (TON) of 4500
moles of hydrogen peroxide per mole of palladium was achieved and the catalyst did not
show any appreciable loss of activity.
However, in the aqueous phase we detected traces of phthalic acid, produced by the partial
oxidation of the quinone 8: thus, quinones more stable under oxidizing conditions are highly
desirable.

4. CONCLUSIONS

The use of palladium complexes with 1,10-phenanthroline in the presence of a catalytic

amount of a suitable quinone, provides a stable and efficient catalyst for the synthesis of
hydrogen peroxide from carbon monoxide, oxygen and water.
The features of an effective quinone co-catalyst should be: i) a reduction potential value (E ~
ranging between 0,4 and 0,5 V, to make possible both the reduction and oxidation processes;
ii) the absence of substituents in positions 2 and 3 on the ring to allow an efficient Pd(0)
binding and stabilization; iii) the presence of hydrophobic substituents to ensure a selective
partition of the quinone in the organic layer of the biphasic system; iv) its high stability
toward oxidation.
The development of a continuous process, based on the above reported improvement, is
presently under consideration.

REFERENCES

[1] G. Strukul, in G. Strukul (eds.), Catalytic Oxidations with Hydrogen Peroxide as

Oxidant, Kluver, Dordrecht, 1992, pp. 1.
[2] G. Goor, ibid., pp. 13.
[3] D. Bianchi, R. Bortolo, R. D'Aloisio, M. Ricci, Angew. Chem. Int. Ed., 38 (1999) 706.
[4] D. Bianchi, R. Bortolo, R. D'Aloisio, M. Ricci, J. Mol. Cat. A: Chem. 150 (1999) 87.
[5] B. Milani, A. Anzilutti, L. Vicentini, A. Sessanta o Santi, E. Zangrando, S. Geremia,
G. Mestroni, Organometallics, 16 (1997) 5064.
[6] A. B. Fasman, V. A. Golodov, D. V. Sokol'skii, Dokl. Akad. Nauk. SSSR English
Translation, 155 (1964) 298.
[7] R. A. Klein, C. J. Elsevier, F. Hartl, Organometallics, 16 (1997) 1284.
[8] M. Hiramatsu, K. Shiozaki, T. Fujinami, S. Sakai, J. Organometal. Chem., 246 (1983)
203.
[9] D. Bianchi, R. Bortolo, R. D'Aloisio, C. Querci, M. Ricci, in B. Dehnon and G. F.
Forment (Eds.), Catalyst Deactivation, Elsevier, Amsterdam 1999, pp. 481.