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Catalysis Today xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Review

A review of catalyst performance and novel reaction engineering

concepts in direct synthesis of hydrogen peroxide
R. Dittmeyer a,∗ , J.-D. Grunwaldt b , A. Pashkova c
a
Karlsruhe Institute of Technology, Institute for Micro Process Engineering (IMVT) and Institute for Catalysis Research and Technology (IKFT),
Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany
b
Karlsruhe Institute of Technology, Institute for Technical Chemistry and Polymer Chemistry (ITCP) and Institute for Catalysis Research and Technology
(IKFT), Engesserstr. 20, D-76131 Karlsruhe, Germany
c
DECHEMA-Forschungsinstitut SBR, Theodor-Heuss-Allee 25, D-60486 Frankfurt am Main, Germany

a r t i c l e i n f o a b s t r a c t

Article history: The recent literature on direct synthesis of H2 O2 is reviewed with respect to two important directions.
Received 20 December 2013 The best catalysts to date are assessed with a view to their composition, e.g., alloys, and regarding the
Received in revised form 20 March 2014 role of the support material and solvent used. Moreover, a number of novel reactor concepts that have
Accepted 21 March 2014
been proposed in literature for direct synthesis of H2 O2 are analyzed with a focus on their potential for
Available online xxx
practical implementation. These include: (i) microchannel process technology for safe mixing and con-
version of the reactants in undiluted gaseous state, (ii) dense palladium-based membranes acting as a
Keywords:
means to prevent gas-phase contact of the reactants while providing a catalytically active interface, (iii)
Hydrogen peroxide
Microchannel process technology
asymmetrically porous catalytic membranes operated in wetted state as an interphase contactor where
Direct Synthesis one reactant is introduced in a controlled way from the gas phase into the liquid reaction medium, (iv)
Palladium microreactors for multiphase operation with improved mass transfer efficiency compared to conven-
Catalytic Membrane tional reactor technologies, and (v) electrocatalytic synthesis, both in electrolysis mode and in fuel cell
mode, which also promise improved safety by avoiding gas-phase mixing of hydrogen and oxygen and
increased selectivity due to improved reaction control.
Concerning the first aim, an acid-pretreated 5 wt.% Pd/C catalyst appears to be the best choice for
methanol as solvent whereas a Pd-Au exchanged Cs-containing heteropolyacid catalyst is the current
benchmark for water as solvent. With proper acid pre-treatment of the Pd/C catalyst or acid function
incorporated into the support (heteropoly acids), no halides and no inorganic acids are needed in the
solvent to prevent hydrogen peroxide decomposition. However, the H2 O2 hydrogenation activity in pure
water is still rather high which limits the selectivity. Among the different reactor concepts, microchannel
process technology seems to offer key advantages in terms of high productivity, selectivity and process
safety. The electrocatalytic approach also looks promising. However, major achievements are still needed,
e.g., successful scale-up of these concepts to relevant throughputs confirming the good performance
obtained in lab scale.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Catalysts, support and solvent effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Choice of active metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.2. Role of oxidation state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3. Rate determining step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.4. Role of oxidic Pd. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.5. Role of support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

∗ Corresponding author. Tel.: +49 721 60823114; fax: +49 721 60823186.
E-mail address: dittmeyer@kit.edu (R. Dittmeyer).

http://dx.doi.org/10.1016/j.cattod.2014.03.055
0920-5861/© 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: R. Dittmeyer, et al., A review of catalyst performance and novel reaction engineering concepts in
direct synthesis of hydrogen peroxide, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.03.055
G Model
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2.6. Comparison of global H2 O2 formation rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

3. Advanced reaction engineering approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Palladium membrane based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Porous catalytic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3. Alternative reaction media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.4. Microreactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.5. Electrocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

and non-chemical processes, whereas for the use in chemical syn-

theses alcohols, e.g., methanol or the like, are often more suitable.
1. Introduction Inorganic acids are added to lower the pH value, because the
decomposition of H2 O2 is favored in a basic environment. Due to
From chemical point of view and as outlined in many rele- the low solubility of hydrogen and oxygen in conventional solvents,
vant papers, e.g., [1–3], H2 O2 is the best single-oxygen donor next high pressures up to more than 100 bar are applied in order to raise
to molecular oxygen. The oxygen is cleanly transferred, and the the productivity. But high pressure, as a downside, also increases
only byproduct is water. In terms of reactivity and selectivity, the hazard potential. The reaction temperature is generally kept
H2 O2 is better than molecular oxygen. On a commercial scale, at low, i.e., below 50 ◦ C, again with a view to limit the decomposition
present, H2 O2 is mainly used as a bleaching agent in the pulp and of the peroxide.
paper industry, as a disinfectant in the cosmetic and pharmaceu- The selectivity issue arises from the fact that water is the ther-
tical industry, and as an oxidant in water treatment and in the modynamically preferred product which can be formed directly in
synthesis of specialty chemicals [4,5]. In highly purified form, it a parallel reaction path from hydrogen and oxygen as well as in two
is also used for etching and cleaning in the electronics industry. consecutive reactions from H2 O2 with and without involvement of
Recently, several large propylene oxide (PO) plants have come on hydrogen, as indicated in Fig. 1.
stream in China (Evonik-Uhde), Belgium (BASF-DOW) and Thailand High selectivity in the direct synthesis reaction requires a cat-
(SCG-DOW) with capacities ranging from 230,000 to 390,000 t/year alyst which, on one hand, can provide appropriate oxygen species
utilizing H2 O2 for catalytic oxidation of propene to PO (HPPO). Due that favor H2 O2 as the primary product and, on the other hand,
to the economics of PO production, the capacity of the H2 O2 plants does promote as little as possible the decomposition and over-
for PO production is by a factor of 2 larger compared to the supply of hydrogenation of the peroxide. The lower the activity for the
the classical markets. Therefore, the start-up of a new HPPO-plant consecutive decomposition of H2 O2 the higher the maximum per-
has a tremendous impact on the global size of the H2 O2 market. oxide concentration that can be obtained. Low decomposition
However, the H2 O2 used by these units is still manufactured by the activity therefore is imperative for obtaining H2 O2 concentrations
AO-process via anthraquinone autoxidation [6]. This now over 70 of practical relevance. In addition, good control of the reaction con-
years old process remains the only one used commercially to pro- ditions in the whole reactor is essential, as the state of the catalyst
duce H2 O2 . Because of its complexity, economics of scale dictate surface is affected by the reaction conditions. For example, the oxy-
the use of large production units on one hand and set a limit to the gen to hydrogen ratio in the reaction medium is known to have a
maximum scale per production train on the other hand. However, strong impact on activity and selectivity as it influences the oxida-
this makes it necessary to transport H2 O2 in concentrated form over tion state of the catalyst. The same holds for the pH value and with
large distances to the consumers. The costs for transport and stor- reservations also for the temperature. Furthermore, from a practi-
age of concentrated H2 O2 solutions add substantially to its price cal point of view, the inside surface of the reactor vessel, all pipes
for the end user. Therefore, despite its advantages as a clean oxi- and downstream installations made from steel in contact with the
dant, H2 O2 is still not economically competitive for the production
of bulk chemicals or for more widespread use in wastewater treat-
ment. For most applications, dilute solutions of H2 O2 are adequate
and an on-site production would be highly desirable as it would
minimize handling and eliminate the need for transportation of
concentrated H2 O2 over long distances.
Among the various alternative approaches to produce H2 O2 , the
direct reaction of hydrogen and oxygen to H2 O2 is conceptually
the most straightforward and therefore most attractive one. How-
ever, despite significant R&D efforts by several academic groups and
major industrial companies, the process has not yet been demon-
strated on commercial scale. Poor economics caused by lower
selectivity combined with only modest savings on the investment
compared to the AO-process as well as challenges for the scale-
up and the safety of the process due to the wide explosive range
of H2 /O2 mixtures (e.g., 4–75 mol% in air, 4–94 mol% in oxygen at
1 atm pressure) are the main reasons.
As H2 O2 is highly unstable under reaction conditions, the reac-
tion is carried out in an appropriate solvent. Water, short-chain
alcohols, or mixtures thereof are most often used as solvents. Water
is generally preferred from an environmental and safety stand- Fig. 1. Reactions involved in direct synthesis of H2 O2 .
point for most applications in bleaching, wastewater treatment Adapted from Ref. [2].

Please cite this article in press as: R. Dittmeyer, et al., A review of catalyst performance and novel reaction engineering concepts in
direct synthesis of hydrogen peroxide, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.03.055
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peroxide solution should be rendered passive by acid cleaning in
order to suppress the decomposition of H2 O2 .
2. Catalysts, support and solvent effects
2.1. Choice of active metal
Most of the catalysts studied for direct synthesis of H2 O2 are
noble metals or combinations of noble metals. They have been
applied on a variety of supports, i.e., most often conventional inor-
ganic types such as alumina, silica, zirconia, titania, and carbon [2].
Pd appears to be the preferred active metal, although by alloying Pd
with Au or Pt, catalysts with better performance than pure Pd have
been obtained. In particular, the system Pd-Au has received a lot of
attention [7–11] while only few publications deal with Pd-Pt sys-
tems [12] despite the fact that Pd-Pt catalysts have been disclosed
in many relevant patents [13–19].
The Pd-Au system was studied on many different support mate-
rials. A ratio of Pd:Au of approximately 1:1 (w/w) showed the best
performance [8]. It was found by extensive characterization that
selective Pd-Au catalysts on oxide supports exhibit core-shell alloy
nanoparticles having an Au core and a Pd-rich shell, although it
is not known whether only part or all of the activity goes back to
these particular structures [7,8]. Moreover, it was found that the
Pd(II)/Pd(0) ratio may play an important role [20], but unlike for
other liquid phase reactions associated with Pd [21,22] none of the
studies have been performed really in situ, which is both for the
alloying proof and the oxidation state pivotal. In contrast, on carbon
the alloy nanoparticles show a homogeneous composition [11]. The
support may have additional influences as described further below.
In the Pd-Pt system Pd16 Pt1 gave the best performance [12].
It was observed that Pd-Pt alloys show enrichment of Pt on the
surface and also that excess Pt quickly deteriorates the catalytic
performance [12]. The authors speculate that tuning the electronic
structure of Pd by the addition of a small amount of Pt may stabilize
dioxygen species on the Pd sites. Adsorbed dioxygen is believed to
be the precursor for the formation of OOH* radicals that react with
atomic and molecular hydrogen to form H2 O2 . Excess Pt, however,
may destabilize OOH* radicals and decompose H2 O2 into H2 O [12].
Au had been identified earlier as the potentially most selec-
tive metal among the noble metals Pd, Pt, Au and Ag for H2 O2
formation, based on theoretical calculations suggesting a compar-
atively high stability of hydroperoxide species on Au surfaces [23].
Various supports were evaluated for Au nanoparticles [24]. The cat-
alytic behavior of these systems was also studied by theoretical
approaches, which revealed that small Au nanoclusters (e.g., 1–13
atoms) indeed can act as viable sites for synthesis of H2 O2 [25–29].
It was found that the rate of H2 O2 formation decreases with an
increase in the mean diameter of the Au nanoparticles. This ten-
dency could be confirmed experimentally with an Au/SiO2 catalyst
prepared by impregnation. For Au particles with a mean diame-
ter of 30 nm only H2 O but no H2 O2 was produced (cf. Ref. [2] and
references therein).
The activity of Au is greatly enhanced by adding Pd. According to
Ref. [30], the role of Au in Pd-Au catalysts is to isolate single Pd sites
that facilitate the coupling of critical surface species to the product,
while inhibiting the formation of undesirable reaction by-products.
In another theoretical study, i.e., using first-principle DFT calcu-
lations for periodic Pd and Pd/Au surfaces, a two-step mechanism
starting from a superoxo precursor state of the oxygen molecule
was proposed as the preferred process on the catalytic surface lead-
ing to H2 O2 [31]. As a competing process the dissociation of oxygen
leading to water formation was found on Pd(111) surfaces. The
presence of Au atoms in the Pd-Au surface is believed to block this
dissociation leading to increased selectivity [31].
Please cite this article in press as: R. Dittmeyer, et al., A review of catalyst performance and novel reaction engineering concepts in
direct synthesis of hydrogen peroxide, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.03.055
3
2.2. Role of oxidation state
It has also been derived from theoretical studies that Pd
nanoparticles possessing a high number of Pd atoms with low
degree of coordination are active and selective catalysts for H2 O2
synthesis (cf. Ref. [2] and references therein). Owing to their
electro-deficiency, these locations appear particularly well-suited
for interacting with promoters present in the reaction medium. This
particular structure of Pd particles may be related to the promoter
effect observed upon adding small amounts of a second metal to Pd
(cf. Ref. [12]). As the proportion of promoter is low, it can be inferred
that the improvement in performance is not associated with alloy
formation between Pd and the second metal [2].
By isotope labeling studies it had been found that H2 O2 is
formed from diatomic oxygen species [1], whereas water formation
obviously requires oxygen dissociation. In the early scientific work
on this reaction, it was concluded that Pd2 0 clusters are respon-
sible for H2 O2 formation [32]. Some of the more recent studies
confirmed that Pd in reduced state is more active and selective for
H2 O2 formation (cf. Ref. [33]). Others, however, reported evidence
that Pd2+ (PdO-like) is the active center forming the H2 O2 , with
adsorbed diatomic oxygen species involved, whereas Pd0 favors
decomposition or over-hydrogenation of the peroxide [1,2,34]. As
Pd2+ is normally reduced in presence of hydrogen at the typical
reaction temperature, one may expect that under reaction condi-
tions a mixed oxidation state prevails, i.e., different Pd atoms in
a metallic particle may have different oxidation states [2]. As the
hydrogen to oxygen ratio generally varies along the reactor in a
continuous-flow system, or with time for batch operation, locally
or temporally different oxidation states may occur leading to vari-
ations of the activity and selectivity.
2.3. Rate determining step
The fact that H2 O2 is derived from diatomic oxygen species
seems to support the earlier postulate that HO2 species exist as
a surface intermediate, which then react with a second hydrogen
atom to give H2 O2 [1,32]. For Pd/C in aqueous solution with H+ and
Br− ions added, a reaction mechanism was derived based on kinetic
analyses claiming a hydrido-hydroperoxy species H-M-OOH as the
key intermediate of H2 O2 formation, direct water formation, and
H2 O2 decomposition [35]. H2 O2 is formed by reductive elimination
whereas ␤-elimination on sites with higher degree of coordinative
unsaturation yields MO and H2 O [35]. Activation of H2 was found
to be rate-determining except at low H2 partial pressure when
the reductive elimination step controlled the overall rate [35]. The
H2 O2 synthesis reaction was found to be inhibited by adsorption of
O2 , which also suppressed H2 O2 decomposition [35]. The authors
further claimed that H+ and Br− adsorb in pair on sites responsible
for ␤-elimination blocking the formation of water. Furthermore, H+
accelerates desorption of H2 O2 preventing its decomposition [35].
In absence of Br− , water is mainly formed by release of O2 from
H-M-OOH and subsequent reaction of the resulting MH2 surface
species with H2 O2 [35].
The role of diatomic oxygen was recently further substantiated
by a detailed DFT study and microkinetic analysis of direct H2 O2
synthesis on Au12 clusters where it was found that the hydrogena-
tion of O2 * to OOH* is the rate limiting step and the selectivity
is determined by competition of hydrogenation and O–O bond
breaking steps [36] (cf. Fig. 2). Adding H atoms reduces the O–O
bond dissociation, and the final surface intermediate H2 O2 * has
a O–O bond breaking barrier that is approximately equal to the
barrier for H2 O2 * desorption. However, the entropy gain due to
desorption of the product leads to quite high selectivity. In aim-
ing at guidelines for catalyst improvement, it could be shown that
the adsorption energy of oxygen is the main reactivity descriptor.
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Fig. 2. H2 O2 reaction network on Au12 (adapted from Ref. [36]). The red and blue numbers next to the arrows give the Ea and E for each step in eV, respectively. The arrow
weights (w) are scaled with the calculated turnover frequency of each elementary step related to the slowest rate in the shown reaction network. Steps that are not kinetically
relevant are not shown.

Whereas the Au12 clusters bind oxygen too strongly, higher coordi-
nated Au-clusters bind oxygen too weakly. Improved performance
is predicted for Au-based alloys with Pd or Ag as minority compo-
nents [36]. This study has been further extended recently on the
basis of Brönstedt-Evens-Polanyi relations [37] and scaling rela-
tions on 12 different alloy systems, underlining the specialty of the
Au-Pd system.
2.4. Role of oxidic Pd
Cationic Pd species have qualified as active catalysts in direct
synthesis also combined with polymers as supports. Catalysts pre-
pared by anchoring Pd2+ ions onto PS-SO3 H ion-exchange resins
were particularly effective with methanol as a solvent. A high H2 O2
productivity and a high selectivity for H2 O2 was observed resulting
in an almost perfectly linear increase of the peroxide concentration
in the reactor with time up to more than 5 wt.%. By photoelectron
spectroscopy it could be shown that the high performance of these
catalytic systems stems from the ability of the sulfonic acid groups
of the resin to interact with and stabilize the Pd2+ ions against
further reduction to metallic Pd [2].
In other studies, colloidal Pd was found to be mainly responsible
for H2 O2 formation when a Pd/silica catalyst or, alternatively, PdCl2
as a salt was added to the solution which was acidified by HCl and
the reaction was carried out at a rather high hydrogen to oxygen
ratio of 1:2 [1,38]. It was claimed that the colloid is formed under
reducing conditions in the acidic solution. Evidence for claiming
the role of colloidal Pd came from comparing the formation rates
of H2 O2 in presence of the supported catalyst and after its removal
from the reaction solution, as well as from direct observation of
colloidal Pd in the solution by TEM, both for addition of Pd/silica
and PdCl2 [38]. More recently, size-controlled nanocolloidal Pd-Au
was reported to be a highly active and selective catalyst for H2 O2
formation in an acidic solution containing NaCl and H2 SO4 [39].
The colloidal catalyst consisted of bimetallic Pd-Au alloy particles
with particle sizes between 2 and 8 nm. It showed higher activity
than Pd-Au supported on rutile-type TiO2 , based on the amount
of Pd. Moreover, an enrichment of Au on the surface was reported
to be beneficial for high selectivity due to an inhibition of H2 O2
decomposition by Au [39].
2.5. Role of support
The role of the support has been studied quite in detail. Its acid-
ity, polarity, and possible metal support interactions may affect
the reaction. It is reported that fluorination or chlorination of the
support prior to the use in the reactor, depending on the type of
support, may inhibit either the decomposition of H2 O2 (PdO/␥-
alumina) or the formation of water directly from the gaseous
reactants (PdO/zirconia) [1]. In both cases the selectivity to H2 O2
is increased. Sulfate ions were less effective in that respect [1]. It is
generally believed that the halide ions block certain active sites by
adsorption, which would otherwise promote the undesired water
forming reactions [1,2]. Halides have also been added to the solvent
as selectivity promoters. In this mode, the effect on the net forma-
tion rate of H2 O2 and on the selectivity differed in part from those
obtained with halide treatment of the support prior to the reac-
tion. Bromide proved to be more effective than chloride and iodide
in this mode while fluoride showed no effect at all [33]. Variation of
the cations did not lead to significant changes of the performance
for any of the halides [33].
However, the interpretation of the results on the different ways
of introducing halide ions suffers from the fact that the acidic prop-
erties of the support play a role as well, i.e., the decomposition of
H2 O2 is promoted in presence of bases [2]. In some cases the halides
had been added/applied in the form of the corresponding inorganic
acids, which is likely to modify the concentration of protons on the
surface (Brønstedt acidity). In addition, adsorbed halide ions also
change the acidity of the support (Lewis acidity). Moreover, phos-
phoric acid has been used in some cases as an additive to stabilize
the H2 O2 . This, however, also modifies the acidity of the support
[2]. For example, the experiments in Ref. [33] have all been carried
out with addition of phosphoric acid.
A third point complicating the analysis of the data on support
effects is the fact that the wettability of the support may be changed
by certain treatments with halides, e.g., fluorine, and this has an

Please cite this article in press as: R. Dittmeyer, et al., A review of catalyst performance and novel reaction engineering concepts in
direct synthesis of hydrogen peroxide, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.03.055
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effect on the selectivity as well. More specifically, the H2 O2 formed
will be repelled by a strong hydrophobicity of the support and
consequently, due to blocked access to the active sites, the decom-
position rate will be lowered. This has been used on purpose [2],
e.g., with hydrophobic carbon as a support material and also when
applying polymeric films designed to prevent contact of the already
formed peroxide with the catalyst on inorganic supports [40] or
catalytic membranes [41].
It should also be mentioned in this context that the pretreat-
ment of the support has also been found to change the particle
size distribution of the active metals. For example, smaller Pd-Au
alloy nanoparticles have been observed after impregnation on car-
bon supports if they had been acid-pretreated before [42]. This has
been observed for pure Au as active metal as well, but not for pure
Pd, and is therefore considered to be related to the specific proper-
ties of Au. These smaller nanoparticles are assumed to decorate and
inhibit the sites for the decomposition of H2 O2 . Hence, when used
for direct synthesis of H2 O2 , the acid-pretreated catalysts gave high
yields of H2 O2 with greater than 95% selectivity.
With a view to industrial application, adding large amounts
of inorganic acids to the solvent would require highly corrosion-
resistant and hence expensive reactor materials. Moreover,
leaching of the active metals is strongly accelerated at low pH
value, which is then expected to speed up the deactivation. There-
fore, in order to limit the amount of inorganic acids to be added
to the solvent, solid acids were evaluated as supports. Examples
described in the scientific and patent literature include silica [43],
tungsten oxide, molybdenum oxide or vanadium oxide on zirco-
nia, heteropoly acids, fluorinated alumina, zeolites, functionalized
carbons with sulfonic acid groups and sulfonic acid functionalized
polystyrene resins (PS-SO3 H) [2] as well as sulfated ceria and sul-
fated zirconia [44].
2.6. Comparison of global H2 O2 formation rates
Following Ref. [2], among those approaches Pd2+ supported on
polystyrene resins showed the most convincing results. The H2 O2
productivity reached up to 1.1 mol H2 O2 h−1 g(Pd)−1 with very lit-
tle decomposition activity, and high H2 O2 concentrations could
be obtained in methanol as solvent [2]. However, comparison of
productivities reported by different groups generally suffers from
the fact that they most often refer to different pressure, tempera-
ture, solvent, additives, H2 to O2 ratio and dilution with inert gas,
and often quite different reaction times have been applied and
conversions have been achieved. In addition, the productivity is
sometimes based on the total catalyst mass and sometimes on the
mass of the active species. For example, zeolite supported Pd-Au
catalysts with 2.5 wt.% Au and 2.5 wt.% Pd have reached productivi-
ties up to 90 mmol H2 O2 h−1 g(cat)−1 in methanol without any acids
and halides added at 2 ◦ C [45,46]. Given the content of active metals
of 5 wt.%, this translates into a productivity per gram of active metal
of 1.8 mol H2 O2 h−1 g(Pd + Au)−1 , which is higher than reported for
the resin-based catalysts. More recently, a Pd-Au catalyst with the
same amount of active metals on a carbon support pretreated with
2% HNO3 and calcined at 400 ◦ C in air before introduction of the
active metals showed a very high H2 O2 selectivity above 98% and
a high productivity of 160 mmol H2 O2 h−1 g(cat)−1 corresponding
to 3.2 mol H2 O2 h−1 g(Pd + Au)−1 . Even higher productivities, i.e., up
to more than 7.5 mol H2 O2 h−1 g(Pd)−1 were demonstrated with a
commercial Pd/C catalyst with 5 wt.% Pd at higher pressure (up to
16.7 MPa), albeit in presence of phosphoric acid as a stabilizer and
NaBr as a promoter [47]. Moreover, this catalyst gave high H2 O2
yields above 80% and high H2 O2 concentrations up to 4 wt.% also in
water pressurized with CO2 or N2 .
Promising results for pure water as solvent, i.e., absence of
acid and halides, were obtained recently with Au-Pd-exchanged
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5
Fig. 3. Contacting of hydrogen and oxygen through a hydrogen permeable metal
membrane and reacting it on the membrane surface to H2 O2 . The membrane surface
is coated with pure Pd to promote formation of H2 O2 and with a polymer layer to
prevent access of H2 O2 from the solution to the active surface.
Concept proposed in Ref. [41].
supported Cs-containing heteropoly acid catalysts with the Keggin
structure [48]. These materials achieved higher H2 O2 productivities
than Au-Pd/C reference catalysts with 5 wt.% of metals under the
same conditions. For example, a system with 0.53 wt.% metal load-
ing reached a H2 O2 productivity of 11.5 mol H2 O2 h−1 g(Pd + Au)−1
at 20 ◦ C. Regrettably, all catalysts showed at least one order of
magnitude higher activity for H2 O2 hydrogenation, which severely
restricts the attainable H2 O2 concentration.
In conclusion to the topic of catalyst performance, it seems
that at present an acid-pretreated 5 wt.% Pd/C catalyst is the best
choice for methanol as solvent whereas a Pd-Au exchanged Cs-
containing heteropoly acid catalyst is the current benchmark for
water as solvent. No halides and no inorganic acids are needed in
order to prevent hydrogen peroxide decomposition in the first case,
whereas in water the H2 O2 selectivity is not yet adequate. In addi-
tion, it must be stressed that these results have all been obtained in
mini autoclaves with very low amounts of catalyst in batch mode,
most likely operating free of mass transport limitations. Successful
transfer of the observed performance to continuous operation and
stability over an extended period of time still have to be demon-
strated.
3. Advanced reaction engineering approaches
In conventional reactors for H2 O2 direct synthesis safety dictates
the use of a large excess of nitrogen as a diluent, which lowers the
reaction rate and leads to an increased mass transport resistance.
In addition, mixing of hydrogen and oxygen in the gas phase is
avoided for safety reasons. As the reaction is carried out in the liq-
uid phase, mass transport from the gas phase via the liquid to the
solid catalyst is slow, which calls for a highly efficient multiphase
reactor design. The importance of the reactor design as to avoid
mass transfer limitation and to limit the decomposition of H2 O2
has also been addressed in a paper on the reaction kinetics [49].
3.1. Palladium membrane based catalysts
Dense Pd-Ag membranes have been proposed as a means to pre-
vent direct contact of hydrogen and oxygen in the gas phase and
thus to increase the safety of the process [41]. A thin Pd-Ag mem-
brane was coated on the inside of a porous ceramic membrane tube
with graded pore size, i.e., coarse on the outside, fine on the inside.
On the outside of the tube hydrogen gas was applied while on the
inside the solvent was placed into which oxygen gas was introduced
as bubbles from the bottom side. The lift of the bubbles was used
to establish a circulating flow of the liquid through the tube (for
details, see [41]).
Hydrogen adsorbs on the inside surface of the Pd-Ag membrane
and is split there into hydrogen atoms which are incorporated into
the membrane and transported to the outside surface. Here they
react with adsorbed oxygen to H2 O2 (Fig. 3). The membrane could
not be made of pure Pd as this suffers from hydrogen embrittlement
due to lattice expansion upon hydrogen uptake and contraction
upon release below 300 ◦ C and would therefore not be stable under
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the conditions of H2 O2 synthesis. Alloying with Ag extends the

working range to lower temperatures, but Pd-Ag was found to show
poor selectivity to H2 O2 . Therefore, the outside membrane surface
was coated with a pure Pd layer that was surface oxidized after-
wards, as Pd2+ is more selective than Pd0 (see above). In addition,
a thin hydrophobic polymer layer (0.5–0.9 ␮m) was applied to the
oxidized Pd surface in order to withhold H2 O2 from the catalyst
surface. In this way H2 O2 decomposition could be suppressed.
With this system, selectivities up to 70% were obtained for com-
plete hydrogen conversion at 25 ◦ C [41]. From a practical point of
view, however, the activity is limited by the hydrogen permeation
through the membrane, which is rather slow in the tempera-
ture window of H2 O2 synthesis. The hydrogen permeation fluxes
found varied between 60 and 190 mmol m−2 h−1 depending on
the membrane configuration and operating conditions. For the
case with 70% selectivity to H2 O2 , the permeation flux reached
ca. 65 mmol m−2 h−1 , which corresponds to a productivity per
membrane area of ca. 45 mmol m−2 h−1 . From this, the specified
hydrogen conversion and H2 O2 selectivity, and the given loading
(thickness) of the Pd-Ag and Pd films one obtains a maximum H2 O2
productivity in the range of 0.9 mmol h−1 g(Pd)−1 , which is 3–4
orders of magnitude lower than the productivity observed with
supported Pd catalysts (see above). Contrary to the case of dispersed
Pd nanoparticles on a high surface area porous support, for the sev-
eral micrometer thick Pd layer here, acting as a barrier between the
gas phase and the liquid phase, by far most of the Pd in the system
does not participate in the reaction. This fact as well as the limited
hydrogen permeance, are the reasons for the inevitably very low
productivity per gram of Pd of such systems. This picture would
only change if one were able to generate much thinner Pd films,
e.g., in the range of 10 nm, which would probably not withstand
the mechanical and chemical stresses in operation. Even though
better than for pure Pd, another downside of this system is still
the limited long-term stability of Pd-Ag alloy films in presence of
hydrogen at room temperature.
3.2. Porous catalytic membranes
Inspired by the limitations of the dense Pd-based catalytic mem-
brane, another membrane-based approach has been developed
where the catalyst was placed in the form of nanoparticles inside
the pores of the top layer of a tubular ceramic membrane instead
of forming a dense metal layer on top of the membrane [50]. This
concept is highlighted in Fig. 4. It relies on a porous ceramic sup-
port, which is wetted on the outside by the solvent. The liquid
penetrates into the top layer, and due to the fact that the pore
diameter increases from the outside surface towards the inside of
the tube, the gas/liquid phase boundary is established within the
porous structure at a position where the gas pressure equals the
liquid pressure plus the capillary pressure. The latter depends on
the pore diameter. Note that in this concept the gas pressure is kept
below the bubble point pressure of the membrane in order to avoid
two phase flow in the reactor with a free gas phase where oxygen
and hydrogen mixtures could occur with compositions within the
explosive range.
By controlling the penetration depth of the liquid via the gas-
liquid differential pressure and employing a membrane with a
rather thin top layer having an appropriate pore size and poros-
ity, high mass transfer coefficients can be established both for the
gas side transport and the liquid side transport. The concept could
be demonstrated successfully in a semi-batch reactor with a H2 O2
productivity up to 6.5 mol h−1 g(Pd)−1 and high selectivity in the
range of 80–90% at 20 ◦ C in methanol as solvent (with addition of
0.01 mol/L of sulfuric acid as a stabilizer and 8 mg/L NaBr as a pro-
moter), e.g., using Pd on titania and on carbon-infiltrated alumina
membranes as catalytic systems [50]. The transfer to a continuous
Fig. 4. Using a graded porous membrane with a catalyst incorporated in the top
layer for reacting a gas species with a species dissolved in the liquid phase.
Adapted from Ref. [50], Pd/X denotes a bimetallic Pd catalyst.
process [51] in lab-scale adopting multichannel membrane ele-
ments used in filtration with supply of oxygen gas on the shell side
and hydrogen-saturated liquid flowing through the channels was
attempted, but has not yet been accomplished due to persistent
difficulties with reliable sealing of all channels at once [52]. Contin-
uous operation with single channel tubes was possible, but resulted
in a low H2 O2 productivity between 0.09 and 0.24 mol h−1 g(Pd)−1 .
This showed that contrary to an outside-coated tube placed in an
autoclave with vigorous stirring of the liquid phase [50], the sys-
tem with (laminar) flow of solvent through inside-coated tubes is
limited by the mass transfer of hydrogen from the bulk flow to the
inside surface where the catalyst is placed [52]. Using the same
type of Pd/TiO2 and Pd/C-Al2 O3 single tube catalytic membranes
as in the semi-batch experiments, the H2 O2 productivity could be
raised by almost one order of magnitude to 1.7 mol h−1 g(Pd)−1 by
installing a bed of inert glass beads inside the tubes, which acted
as a static mixer. The selectivity to H2 O2 varied between 75 and
83%, and the H2 O2 productivity related to the membrane area was
6.1–6.4 mol m−2 h−1 , which is more than two orders of magnitude
higher than reported for the dense Pd-Ag/Pd membrane system
(see above). Moreover, the fact that the productivity per gram of
Pd for the case of stirred liquid around the outside-coated cat-
alytic membrane tube was roughly 5 times higher than for the
case of flow-through mode with an inside-coated catalytic mem-
brane filled with an inert packing indicates that the system still
was affected by mass transfer limitations. Hence, further improve-
ments seem possible with a view to productivity, e.g., by reducing
the inside tube diameter (e.g., capillaries).
3.3. Alternative reaction media
Supercritical CO2 has been proposed as a solvent for H2 O2
synthesis already a decade ago [24]. The main motivation is to
overcome limitations by the solubility of the gaseous reactants
and by the low diffusivity in the liquid phase [53]. Practically,
however, the results obtained with supercritical or liquid CO2
appear to be limited [24,47,54–57] and have not yet led to a break-
through. An increased decomposition rate of H2 O2 due to the higher

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Fig. 5. Principle of a continuous process for production of aqueous H2 O2 solutions using dense CO2 as a solvent.
After Ref. [60].
temperature (i.e., beyond the critical temperature of 31 ◦ C) has been
stated as the main obstacle standing against the exploitation of the
benefits of supercritical CO2 as reaction medium [55]. More recent
results on the use of CO2 together with water as a biphasic solvent,
on the other hand, have shown promise for an improvement of the
synthesis of aqueous H2 O2 solutions [58,59]. Yet these results have
all been obtained in semi-batch mode, so successful transfer to a
continuous process still has to be demonstrated.
One attempt to demonstrate a continuous process with liquid or
supercritical CO2 as a reaction medium has been reported recently
in Ref. [60]. The authors established a loop with two micromix-
ers in series for admixing hydrogen and oxygen separately to a
pressurized liquid CO2 stream, which then was guided through
a coated-wall microreactor followed by an expansion module for
recovery of the produced H2 O2 and H2 O. Fig. 5 shows the princi-
ple. A small amount of ethanol was used as an additional solvent to
trap the produced H2 O2 . The intention behind the use of CO2 as a
solvent, which can easily be removed by pressure relaxation after
the reactor, was to produce aqueous solutions with relatively high
concentration of H2 O2 .
Continuous experiments could be performed with stable cat-
alyst performance over several hours under different conditions
using several promising catalysts pre-selected based on a screening
in semi-batch experiments. The best results were obtained with a
pre-reduced Pd/TiO2 catalyst (1 wt.% Pd) at 40 ◦ C applying a H:O
ratio of 1:1. The pressure typically was 13.5 MPa. The H2 O2 produc-
tivity reached 0.77 mol h−1 g(Pd)−1 albeit at rather low selectivity
of only ca. 10%. Hydrogen conversion (as well as oxygen conversion)
was low under the conditions applied. Interestingly, the results in
continuous mode showed other trends than those from semi-batch
mode despite the same catalysts were used. The reasons have not
been fully understood yet. With a view to the promising results
reported in the recent literature for CO2 as a solvent with a com-
mercial Pd/C catalyst [58,59] and with Pd/TS-1 [57], it seems that
there is potential for implementing a continuous process according
to the scheme given in Fig. 5. However, additional efforts have to be
devoted to catalyst preparation and characterization as well as to
optimization of operating conditions including detailed investiga-
tion of the phase equilibria [61]. Moreover, better understanding of
the modification of the catalyst surface by complex reaction media
such as CO2 containing mixtures seems mandatory as a guide for
catalyst development.
Apart from adding CO2 to the reaction mixture, studies have
been undertaken using biphasic mixtures of an organic solvent
and water where the organic solvent has a high solubility for the
gaseous reactants but is poorly soluble in water, whereas H2 O2 has a
higher affinity to water than to the organic solvent [62]. This causes
the product H2 O2 to be accumulated in the aqueous phase while
the system productivity is not limited by the poor solubility of the
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7
gases in water. It is claimed that with this method H2 O2 concentra-
tions up to several wt.% can be reached with the H2 selectivity up
to ca. 80% and productivities of 4–8 mol h−1 g(Pd)−1 depending on
the particular conditions.
3.4. Microreactors
Several other systems making use of microreaction technol-
ogy have been proposed for direct synthesis of H2 O2 . These
include setups where the gaseous reactants are rapidly mixed in
a micromixer and the resulting gas mixture, whose composition
may fall within the explosion range, is immediately fed to a cat-
alytic reactor installed at the exit of the micromixer to convert it
to H2 O2 [63–65]. Due to the narrow channels inside the mixer and
reactor as well as to the moderate pressure, the propagation of an
uncontrolled reaction is prevented and the process can be executed
within the explosion range. While no detailed data are available in
the literature on the productivity and selectivity reached with such
systems, neither in patents nor in scientific publications, there have
been occasional reports at scientific conferences.
For example, in 2006 UOP reported at the AIChE Spring Meeting
that the process had been run successfully with a 1:1 stoichiom-
etry of H2 :O2 both in a lab-scale system at IMM and in a fully
automated pilot plant at UOP yielding high productivity, 80% H2
conversion and 75% selectivity using methanol as solvent [66]. Hes-
sel et al. [67] report that a special interdigital micromixer from IMM
was used followed by a cartridge filled with catalyst, which acted
as a mini-trickle bed. The term trickle-bed refers to the fact that
the gaseous reactants and the liquid products formed flow con-
currently as a two-phase mixture through a packed catalyst bed.
The system does not represent a classical trickle-bed where down
flow of the liquid is driven by gravity. A noble metal catalyst was
adopted which must be operated in a partially oxidized state in
order to achieve high activity and selectivity. It has been stated
that the catalyst in fully reduced state is not active enough while
in fully oxidized state it catalyzes water formation. A space time
yield of 2 g H2 O2 h−1 g(cat)−1 is reported for undisclosed standard
conditions. Assuming a noble metal content of 5 wt.%, this would
translate into a productivity of 1.2 mol H2 O2 h−1 g(Pd)−1 which falls
behind the best values reported in the literature. However, for
1 wt.% Pd the value would be 5.9 mol H2 O2 h−1 g(Pd)−1 which is at
the upper level of the reported performances for small semi-batch
reactors. Note that a pressure of only 2 MPa and a lower O2 :H2 ratio
were used which leads to savings on oxygen and hence improves
the process economics. A selectivity as high as 85% at 90% H2 con-
version is stated for an O2 :H2 ratio between 1.5 and 3. Based on
the pilot plant data UOP developed the basic engineering of a com-
mercial plant with a capacity of 150,000 t/year. A cost comparison
showed that low-pressure operation within the explosion range
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enabled by micro process technology gives the lowest production
costs for H2 O2 . Yet, as of today, no commercial plant has been built
or announced.
Moreover, a broad patent application by FMC claims the direct
reaction of a hydrogen-containing gas stream and an oxygen-
containing gas stream on a catalyst in presence of a solvent at low
pressure in a microreactor system [68]. This seems to be related to
scientific work carried out at the Stevens Institute of Technology,
Hoboken/NJ who contributed a number of papers on the kinetics of
H2 O2 direct synthesis in a microcapillary reactor [69–72]. A simple
setup consisting of a Teflon micromixer connected to a 765 ␮m i.d.
stainless steel capillary of several centimeters length filled with a
packed bed of catalyst particles with a diameter of 75–150 ␮m was
used. The Teflon micromixer had the task to generate a segmented
flow pattern from the solvent flow and the flow of the already pre-
mixed gaseous reactants, which was then passed through the micro
packed bed. The flow pattern in this catalyst bed should differ from
the one prevailing in the UOP-IMM system described earlier, i.e.,
the total amount of liquid versus gas is higher and distinct gas and
liquid segments flow over the catalyst in an alternating fashion.
However, no detailed studies on the flow patterns and its conse-
quences on the performance are reported. The productivity of a
Pd/silica catalyst with 2 wt.% Pd prepared by a sol-gel technique
reached up to 4 mol H2 O2 h−1 g(Pd)−1 under optimized conditions
in this reactor. The hydrogen conversion was low at a level of 30%
at most, probably as a consequence of the high gas flow used to
establish the segmented flow pattern. With values of up to 60%, the
selectivity also appears to be lower than for typical experiments
in semi-batch reactors under optimized conditions (see above). No
specific actions towards using this technology for the development
of a new process have been reported.
Research groups at AIST, Tsukuba and MIT, Boston have studied
silicon and glass based microchannel reactors for direct synthe-
sis of H2 O2 [73–78]. With single-channel systems made from glass
filled with different fine-grained Pd-based supported catalysts at
a pressure of 1 MPa, aqueous solutions with up to 10 wt.% of H2 O2
could be synthesized, recently [78]. The productivity reached up
to 2 mol H2 O2 h−1 g(Pd)−1 and the H2 selectivity up to 86%. Like
the system presented by the group from the Stevens Institute, in
addition to the gaseous reactants a solvent is fed to the reactor.
However, instead of a defined segmented flow pattern a mixed
two-phase flow has been established. The results achieved with this
system compare favorable, in terms of selectivity, to those obtained
with the stainless-steel microcapillary system described previ-
ously, which may be due to the reactor material, as an insufficient
passivation of the relatively large stainless steel surface inside the
capillary compared to the volume could give rise to decomposition
of H2 O2 . Further, the results agree qualitatively with those obtained
in semi-batch operation with similar catalysts, which seems to indi-
cate that the continuously operated microreactor indeed operated
without mass transfer limitations. However, no specific activities
towards a scale-up of this reactor technology have been reported
so far.
Another group from Japan reported the use of microreactor tech-
nology for direct synthesis of H2 O2 with a view to compact systems
for local production [79]. They used a solid polymer electrolyzer
for obtaining H2 and O2 from water followed by a wall-coated
catalytic microreactor for synthesis of H2 O2 . Two types of microre-
actors were studied, i.e., a silicon microcapillary and a stacked
microreactor consisting of several PMMA plates each with one rect-
angular microchannel inside (1 mm × 0.1 mm) which were stacked
together with silicon plates onto which a 5 wt.% Pd/C catalyst was
coated. The reactors were operated in slug flow mode in order
to enable a high mass transfer rate, and the performance was
observed for varying operating conditions, i.e., temperature, flow
rate, current applied to the electrolyzer. The performance of the two
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systems was similar. Yet from the data given, i.e., 82 mg of catalyst
(4.1 mg Pd) for the stacked microreactor, a flow rate of 3 mm3 /s and
a H2 O2 concentration of up to 8.3 mmol/L, one obtains a productiv-
ity of 0.022 mol H2 O2 h−1 g(Pd)−1 , which is roughly two orders of
magnitude lower than the performance of the systems previously
discussed. No information on the selectivity is provided, most likely
because an aqueous solvent was used, which makes it very difficult
to assess water formation.
Another system making use of the high mass transfer rate
achievable between gas phase, liquid phase and a (solid) catalyst
coated on the wall in a two-phase flow through microchannels has
been described by Wang et al. [80] and later by Ng et al. [81]. In
the earlier paper [80], results from two different microreactors
are compared, i.e., from a single-channel polymethylmethacry-
late (PMMA) system with a channel width of 1 mm and depth of
0.45 mm, where a Pd-zeolite catalyst had been introduced into the
channel by washcoating to form a porous layer with ca. 100 ␮m
thickness on the bottom, as shown in Fig. 6.
The second system was a silicon-based multichannel reactor
having eight parallel channels with 1 mm width and 0.3 mm depth,
where a 200 ␮m thick Pd or Pt-containing zeolite film was grown by
hydrothermal treatment from seed crystals previously deposited in
the channels. Rather high H2 O2 productivities were obtained with
the single channel reactor at ambient temperature and pressure,
e.g., 1.7–6.5 mol h−1 g(Pd)−1 for a 5 wt.% Pd/Silicalite-1 catalyst for
different flow rates and gas compositions and methanol as sol-
vent with addition of HCl (0.1 N). Under the conditions applied, H2
conversion was generally low, i.e., 5.4% at most. The highest H2 O2
selectivity observed was 69% for a catalyst containing 1.7 wt.% of
Pd and 0.3 wt.% of Pt. However, a gradual decrease of the produc-
tivity of 12% within 30 hours was observed, which was attributed
to a loss of active catalyst from the layer (by release of particles
as well as by leaching). The multichannel reactor showed a sub-
stantially reduced productivity, which was quantified in terms of a
channel efficiency of only 25–30% compared to the single channel
as a reference. The performance reduction was mainly attributed to
an uneven distribution of the two-phase flow to the different chan-
nels, which led to an increased mass transfer resistance in channels
with reduced flow velocity or gas holdup, and also to a higher mass
transfer resistance inside the 200 ␮m thick polycrystalline zeolite
film as opposed to the washcoated layer of zeolite crystals.
In the later paper [81], the group used single glass micro-
capillaries with diameters ranging from 0.53 mm to 2 mm which
were inside-coated with a polymer film where Pd nanoparticles
have been incorporated via filling the capillary with a Pd(PPh3 )4 -
containing polymer micelle solution, drying and heat treatment at
150 ◦ C to decompose the Pd organic compound. These systems were
tested in slug-flow operation at ambient temperature and pressure
with methanol as solvent and different additives (inorganic acids,
KBr) for their activity and selectivity. H2 O2 productivities up to
2.3 mol h−1 g(Pd)−1 were achieved. The productivity showed a clear
dependence on the capillary diameter, i.e., the smaller the diame-
ter the higher the productivity, which was explained by increased
gas-liquid mass transfer in thinner capillaries. Results with dif-
ferent metal loadings essentially gave the same productivity per
gram of Pd. Hence it was concluded that the polymer film was
well penetrated by the reactants, and all the Pd was accessible for
the reaction. Moreover, both the activity and the selectivity were
greatly affected by the promoters added to the solvent. Good results
were obtained with H2 SO4 and KBR addition, i.e., 77% H2 selectivity.
Essentially the same approach of operating a single wall-coated
glass microcapillary in slug flow mode with an undiluted mixture
of H2 and O2 was reported very recently also by another group [82],
who used a fused silica capillary of 0.32 mm diameter at a pressure
of 2 MPa. The capillary was inside-coated with an approximately
4 ␮m thick silica layer into which Pd-Au nanoparticles had been
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Fig. 6. Catalyst layer (left) and two-phase flow pattern (right) in a single-channel microreactor.
Adapted from Ref. [80].
introduced. Two different methods were used to prepare catalysts
with an active metal content of 5 wt.%, i.e., impregnation from aque-
ous HAuCl4 and PdCl2 solutions and deposition of stabilized Au-Pd
nanoparticles prepared using a two-phase synthesis method. For
comparison, powder catalysts prepared using the same materials
for support and active phase were studied in an autoclave with
diluted reactants in semi-batch mode. The two-phase method gave
much improved catalyst performance (productivity and selectiv-
ity), which was attributed to improved control of the alloying and
the particle size. It could also be shown that both systems perform
similar, provided the same solvent is used and the partial pressures
and liquid concentrations are similar. However, the microcapillary
can be safely operated with undiluted gas and hence is capable of
delivering a higher productivity, i.e., up to 2.4 mol h−1 g(Pd)−1 with
a H2 selectivity of 60–65%. Catalyst performance was reported to
be stable for several weeks [82].
3.5. Electrocatalysis
H2 O2 can also be synthesized in electrochemical reactors, both
in electrolysis mode (i.e., applying electrical current) and in fuel
cell mode, with co-generation of electricity or without (i.e., short
cut of anode and cathode, see, e.g., Ref. [2] and the references
therein). From a process technology perspective, electrochemical
reactors with the anode and cathode compartments divided by
a solid electrolyte membrane offer the advantage, in H2 O2 syn-
thesis, of keeping hydrogen and oxygen separate. As with dense
metal membranes or porous membranes in bubble-free gas-liquid
contacting mode, this greatly increases the safety of the process.
However, the transport of protons or hydroxide anions through
the electrolyte membrane in general comes with a finite transport
resistance, which may limit the productivity. Therefore, important
prerequisites for the electrodes of such systems are an open three-
dimensional structure with high surface area for easy access of the
reacting phases as well as good electrical conductivity and effective
contacting to the electrolyte membrane.
Electrochemical production of H2 O2 in alkaline solution in
undivided cells in trickle bed operation is established [2]. H2 O2
solutions with a strength of up to 3.4 wt.% can be made in small
stacks rather efficiently with an electrical energy consumption of
2–7 kWh kg(H2 O2 )−1 depending on the current density [83].
However, an attractive alternative to electro-synthesis, which
requires expensive electrical energy, is the use of a fuel cell setup
where H2 O2 can be obtained from H2 and O2 eventually even
together with electrical energy [84–89]. While the first systems
of that kind suffered from rather poor performance [84], in the
meantime the design has been improved. For example, for a cell
equipped with a Nafion 117 membrane and gas diffusion elec-
trodes made from porous carbon materials, PTFE and Pt-black, a
H2 O2 concentration of 6.5 wt.% was reported in batch operation
after 3 h with ambient pressure hydrogen vs. ambient pressure air
[85]. The current efficiency was 88% (i.e., the selectivity based on
H2 consumption), and the system produced 13 mol H2 O2 h−1 m−2 .
Please cite this article in press as: R. Dittmeyer, et al., A review of catalyst performance and novel reaction engineering concepts in
direct synthesis of hydrogen peroxide, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.03.055
9
The Pt loading on the electrodes is not given in the paper but in fuel
cells values up to several mg cm−2 are common. Assuming a load-
ing of 1 mg cm−2 on each of the electrodes (i.e., 2 g m−2 in total)
would result in a productivity of 0.65 mol H2 O2 h−1 g(Pt)−1 which
is not far from the performance of the Pd-based catalysts described
earlier.
In a number of more recent publications it was shown that with
appropriate electrocatalysts, neutral or acidic H2 O2 solutions with
high concentration of H2 O2 can be prepared as well with the fuel
cell system [86,87], albeit at lower current efficiency than in alka-
line medium (NaOH) [88]. For example, a H2 O2 concentration of
13.5 wt.% could be achieved in neutral solution at 42% current effi-
ciency. The (best) cathode electrocatalyst for oxygen reduction in
this case was Co-TPP/VCGF.1 The formation rate of H2 O2 and the
current density increased with increasing amount of electrocat-
alyst; loadings up to 2 mg cm−2 were applied [86]. In an acidic
environment (sulfuric acid) the best choice for the cathode elec-
trocatalyst was MnCl-OEP/AC(723).2 This system achieved a H2 O2
concentration of 6.8 wt% and a current density of 47%. The effects of
the carbon support of the heat-treated Co-porphyrin/carbon elec-
trocatalysts on the formation of H2 O2 and water have been studied
in detail in a very recent publication, concluding that further
efforts should be devoted towards reducing the electrochemical
successive reduction of H2 O2 to improve both the attainable con-
centration of H2 O2 and the current efficiency [89].
However, these data show that promising fuel cell type reactor
systems have been developed for H2 O2 direct synthesis. To carry
this forward from the fundamental research stage to a viable tech-
nology certainly requires strong development efforts focusing not
only on the electrocatalysts themselves, but also on optimizing the
transport in the gas diffusion electrodes. Moreover, the design and
manufacturing of larger cells and stacks, as would be required for
commercial use, have to be developed.
4. Conclusions
The assessment of the published data on different catalysts and
advanced reactor designs proposed for direct synthesis of hydrogen
peroxide reveals that the system performance, i.e., H2 O2 selectivity,
H2 conversion and H2 O2 productivity is strongly influenced by the
reactor design, the reaction conditions and the intrinsic properties
of the active phase. Mass transfer limitations must be minimized at
the catalyst level (porous pellet/layer) and at the reactor level (gas
to liquid, gas and liquid to solid), and the concentration profiles
along the reactor must be optimized to limit H2 O2 decomposi-
tion and hydrogenation, which otherwise decrease selectivity and
productivity.
1
TPP = 5,10,15,20-tetrakis(phenyl)-21H,23H-porphyrin [84], VGCF = vapor grown
carbon fiber [83].
2
OEP = 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin, AC = activated carbon
[84].
G Model
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10 R. Dittmeyer et al. / Catalysis Today xxx (2014) xxx–xxx
Many studies have been devoted to catalyst performance in
semi-batch reactors. They have established that with good cata-
lysts H2 O2 productivities in the range of 2–5 mol h−1 g(Pd)−1 can
be expected in the absence of mass transport limitations. Given a
typical content of active metals of 5 wt.% and support density of
2 g cm−3 (inorganic types), this would translate into a H2 O2 pro-
ductivity related to the catalyst volume of 6.8–17 kg h−1 L−1 , which
means that a reactor with 1 m3 catalyst volume could produce
54,400–136,000 t/a of H2 O2 . However, most catalysts still require
inorganic acids and halides as additives to reach high selectivity for
H2 O2 formation, resp. to prevent H2 O2 decomposition or hydro-
genation, when technically relevant H2 O2 concentrations above
3–5 wt.% are targeted. Moreover, the mechanism is hardly uncov-
ered and here the use of in situ methods like X-ray absorption
spectroscopy or attenuated total reflection infrared spectroscopy
would be of great benefit. Appropriate nanostructuring of the cat-
alysts, e.g., to combine metal, acidic and hydrophobic functions on
the nanoscale, could be of high interest. Dense carbon dioxide as
solvent promises a number of advantages that need to be further
explored in the future.
Microchannel process technology appears to be attractive with a
view to safe and efficient continuous operation. Different concepts
have been proposed for reacting undiluted H2 /O2 gas mixtures in
microchannel systems with or without additional solvents. The
integration of membranes for separate feeding of the reactants into
such systems is another option, which is currently under study
at the IMVT. However, the scale-up of microchannel systems for
multiphase operation so far has not received enough attention in
literature. Severe challenges exist both for equal distribution of a
two-phase flow to a multitude of independent parallel channels
as well as for simultaneous creation of a defined two-phase flow
pattern in parallel channels.
From the standpoint of fundamental research it is of great inter-
est to look for similarities and differences between electrocatalytic
and catalytic reduction of oxygen both with a view to activity and
selectivity for H2 O2 formation.
Acknowledgements
The authors wish to acknowledge the German organizations AiF
(Arbeitsgemeinschaft industrieller Forschungsvereinigungen “Otto
von Guericke” e.V.), DBU (Deutsche Bundesstiftung Umwelt) and
DECHEMA e.V for financial support of the research work on the
direct synthesis of H2 O2 .
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