The direct synthesis of

hydrogen peroxide from H2

royalsocietypublishing.org/journal/rsta
and O2 using Pd–Ni/TiO2
catalysts
Research David A. Crole1 , Ricci Underhill1 , Jennifer K. Edwards1 ,
Cite this article: Crole DA, Underhill R, Greg Shaw1 , Simon J. Freakley2 , Graham J. Hutchings1
Edwards JK, Shaw G, Freakley SJ, Hutchings GJ,
Lewis RJ. 2020 The direct synthesis of hydrogen
and Richard J. Lewis1
peroxide from H2 and O2 using Pd–Ni/TiO2 1 Cardiff Catalysis Institute, School of Chemistry, Cardiff University,
catalysts. Phil. Trans. R. Soc. A 378: 20200062.
Main Building, Park Place, Cardiff CF10 3AT, UK
http://dx.doi.org/10.1098/rsta.2020.0062 2 Department of Chemistry, University of Bath, Claverton Down,

Bath BA2 7AY, UK

Accepted: 5 May 2020
RJL, 0000-0001-9990-7064
One contribution of 14 to a discussion meeting
The direct synthesis of hydrogen peroxide (H2 O2 )
issue ‘Science to enable the circular economy’. from molecular H2 and O2 offers an attractive,
decentralized alternative to production compared to
Subject Areas: the current means of production, the anthraquinone
green chemistry process. Herein we evaluate the performance of
a 0.5%Pd–4.5%Ni/TiO2 catalyst in batch and
Keywords: flow reactor systems using water as a solvent at
hydrogen peroxide, palladium, nickel, ambient temperature. These reaction conditions
nanoparticles, green chemistry are considered challenging for the synthesis of
high H2 O2 concentrations, with the use of sub-
ambient temperatures and alcohol co-solvents typical.
Author for correspondence: Catalytic activity was observed to be stable to
Richard J. Lewis prolonged use in multiple batch experiments or in
e-mail: lewisr27@cardiff.ac.uk a flow system, with selectivities towards H2 O2 of
97% and 85%, respectively. This study was carried
out in the absence of halide or acid additives that are
typically used to inhibit sequential H2 O2 degradation
reactions showing that this Pd–Ni catalyst has the
potential to produce H2 O2 selectively.
This article is part of a discussion meeting issue
‘Science to enable the circular economy’.

1. Introduction
Electronic supplementary material is available
The direct synthesis of hydrogen peroxide (H2 O2 ) would
online at https://doi.org/10.6084/m9.figshare. offer an attractive alternative to the current industrial
c.4982846. means of production, the anthraquinone oxidation (AO)
process and potentially allow decentralized production.

2020 The Author(s) Published by the Royal Society. All rights reserved.
Accounting for more than 95% of global H2 O2 production the AO process is highly optimized.
2
However, there are concerns regarding the requirement for continuous replacement of the
anthraquinone, H2 -carrier, as a result of its over hydrogenation and high energy requirements

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during the extraction and concentration of the formed H2 O2 . Furthermore, the AO process only
proves to be economical on a large scale meaning that production has to be centralized. As a
result H2 O2 , typically produced at initial concentrations of 0.5–2 wt% prior to concentration via
distillation [1], is often transported at high concentrations in the presence of acidic stabilizers,
used to inhibit decomposition to H2 O. However, the use of such stabilizing agents often leads
to decreased reactor lifetime and increased costs associated with their removal from product
streams.
The direct synthesis of H2 O2 from molecular H2 and O2 would offer an attractive alternative
to the AO process, allowing for decentralized H2 O2 production. In particular, applications that
require relatively low concentrations of H2 O2 to be supplied in a continuous manner, such
as the treatment of waste streams [2] and a range of selective chemical oxidations [3] would
benefit from the direct production of H2 O2 . The high activity of Pd-based catalysts for the direct
synthesis reaction has been well known since 1914 [4] and has received significant attention in
the literature [5–9]. However, issues around selectivity have posed a major challenge, with the
suppression of H2 O2 degradation pathways often only achieved through the application of acid
or halide promoters [10–12]. By comparison, AuPd catalysts have been demonstrated to offer
excellent selectivities towards H2 O2 in the absence of stabilizing agents [13–17]. More recently,
we have reported that it is possible to replace Au with more abundant base-metals such as Sn,
Ni, Zn and Co, which through exposure to successive calcination–reduction–calcination heat
treatment can demonstrate selectivities towards H2 O2 in excess of 95%. This has been attributed
to the encapsulation of ultrasmall Pd-rich nanoparticles, responsible for H2 O2 degradation by
the secondary meal oxide [18]. Subsequently, further studies have reported enhanced catalytic
performance can be achieved through the alloying of Pd with a range of secondary non- or semi-
precious metals such as Ag, [19] Sb, [20] Te, [21] Sn [22], Ni [23] and Zn [24]. Enhancement in
selectivity is often attributed to a reduction in the amount of extended Pd ensembles, resulting in
a reduction in the rates of O–O bond scission, preventing the formation of H2 O from H2 O2 via
decomposition or over hydrogenation pathways.
In this work, we focus on the efficacy of our recently reported 4.5%Ni–0.5%Pd/TiO2 catalyst
[18]. In our previous study, we highlighted the excellent selectivity towards H2 O2 that can
be achieved with this catalyst, under conditions optimized for H2 O2 production. Herein we
demonstrate that good catalytic performance can be achieved under conditions less conducive
towards H2 O2 synthesis, namely ambient reaction temperature and a water only reaction medium
while also avoiding the need for acid and halide promoters [25,26]. We further investigate the
efficacy of the 4.5%Ni–0.5%Pd/TiO2 catalyst in a flow regime, with the continual production of
H2 O2 highly desirable for industrial application.

2. Experimental
(a) Catalyst preparation
Bimetallic 5% PdNi/TiO2 catalysts have been prepared on a wt% basis by a conventional wet-
impregnation procedure, based on methodology previously reported in the literature [18]. The
procedure to produce 0.5%Pd–4.5%Ni/TiO2 (1 g) is outlined as follows. Aqueous solutions of
Pd(NO3 )2 (0.833 ml, 6 mg ml−1 , Johnson Matthey) and NiCl2 (5 ml, 9 mg ml−1 , Sigma Aldrich)
were combined with H2 O (HPLC grade), in a 50 ml round bottom flask, so that total volume
was fixed to 16 ml. The resulting mixture was heated to 80°C in a thermostatically controlled
oil bath with stirring (1000 r.p.m.). Upon reaching 80°C TiO2 (0.95 g, Degussa, P25) was added,
the resulting slurry was then stirred continuously until a thick paste was formed. The paste was
dried (110°C, 16 h) and the resulting solid material was ground prior to calcination (500°C, 3 h,
20°C min−1 , static air). This was followed by reduction (200°C, 2 h, 20°C min−1 , 5% H2 /Ar) and
3
re-calcination (400°C, 3 h, 20°C min−1 , static air).

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(b) Direct synthesis of H2 O2 using batch reactor conditions
H2 O2 synthesis was evaluated using a Parr Instruments stainless steel autoclave with an internal
volume of 50 ml, equipped with a PTFE liner so that total volume is reduced to 33 ml, and a
maximum working pressure of 140 bar. The autoclave liner was charged with catalyst (0.01 g)
and solvent (8.5 g H2 O), then purged three times with 5% H2 /CO2 (7 bar) before filling with
5% H2 /CO2 to a gauge pressure of 29 bar, followed by the addition of 25% O2 /CO2 (11 bar). The
reaction was conducted at a temperature of 20°C (controlled using a HAAKE K50 bath/circulator)
for 0.5 h with stirring (1200 r.p.m.) with no continual introduction of reactant gasses. The above
reaction parameters are based on optimum conditions we have previously used for the synthesis
of H2 O2 [25,26]. The concentration of H2 O2 was determined by titrating aliquots of the final
solution after reaction with acidified Ce(SO4 )2 (0.0085 M) in the presence of ferroin indicator. The
conversion of H2 and selectivity towards H2 O2 were determined using a Varian 3800 GC fitted
with TCD and equipped with a Porapak Q column.
H2 conversion (equation (2.1)) and H2 O2 selectivity (equation (2.2)) are defined as follows:
mmolH2 (t(0)) − mmolH2 (t(1))
H2 conversion (% ) = × 100 (2.1)
mmolH2 (t(0))
and
H2 O2 detected (mmol)
H2 O2 selectivity (% ) = × 100. (2.2)
H2 consumed (mmol)

(c) Gas replacement experiments for the direct synthesis of H2 O2 in a batch reactor
An identical procedure to that outlined above for the direct synthesis of H2 O2 is followed for a
reaction time of 0.5 h. After this, stirring is stopped and the reactant gas mixture is vented prior to
replacement with the standard pressures of 5% H2 /CO2 (29 bar) and 25% O2 /CO2 (11 bar). The
reaction is then stirred (1200 r.p.m.) for a further 0.5 h. To collect a series of data points, as in the
case of figure 2, it should be noted that individual experiments are carried out and the reactant
mixture is not sampled online.

(d) Degradation of H2 O2 in a batch reactor

Catalytic activity towards H2 O2 degradation was determined in a similar manner to the direct
synthesis activity of a catalyst. The autoclave liner was charged with H2 O2 (50 wt% 0.69 g), H2 O
(7.82 g) and catalyst (0.01 g), with the solvent composition equivalent to a 4 wt% H2 O2 solution.
From the solution, two 0.05 g aliquots were removed and titrated with acidified Ce(SO4 )2 solution
using ferroin as an indicator to determine an accurate concentration of H2 O2 at the start of the
reaction. The autoclave was pressurised with 29 bar 5% H2 /CO2 (gauge pressure). The reaction
was conducted at a temperature of 20°C, for 0.5 h with stirring (1200 r.p.m.) with no continual
introduction of reactant gasses. After the reaction was complete the catalyst was removed from
the reaction mixture and two 0.05 g aliquots were titrated against the acidified Ce(SO4 )2 solution
using ferroin as an indicator. Catalytic activity towards H2 O2 degradation is reported herein
as percentage degradation and accounts for hydrogenation and decomposition pathways. The
reactor temperature was controlled using a HAAKE K50 bath/circulator using an appropriate
coolant.

(e) Direct synthesis of H2 O2 in a flow reactor

A continuous, fixed bed rector was constructed for the direct synthesis of H2 O2 using Swagelok
fittings with an internal diameter of 1/4 inch. Gas flows of 5% H2 /CO2 and 25% O2 /CO2 were
controlled using Brooks mass flow controllers with the pressure maintained and controlled using
4
a back-pressure regulator at the end of the system. Pressure relief valves were included at various
points throughout the system to release pressure in the case of a blockage. Water (HPLC grade)

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free from acid or halide additives was used as the reaction medium and pumped through the
system using an Agilent 1260 series isocratic HPLC pump, one-way valves were placed after the
MFCs to prevent any liquid from entering the MFCs during the reaction. Liquid was collected
downstream before the back-pressure regulator by emptying a 150 ml gas liquid separator (GLS)
fitted with a valve which acted as a sample collection vessel. A schematic of the reactor is shown
in electronic supplementary material, figure S.1.
We have previously reported that an alternating sequence of gas bubbles and liquid slugs,
termed Taylor flow, have been observed when using a comparable reactor, with catalyst bed
diameter on the order of that used within this study [27]. This may not be surprising when
considering the high gas: liquid flow rates used within this study. Upon introduction of the
catalyst bed a distinct flow of gas and liquid slugs were observed exiting the reactor bed, though
less regular than that observed in an empty tube. This is in keeping with our previous studies into
H2 O2 synthesis over supported AuPd catalysts in a flow regime.
A typical H2 O2 synthesis reaction was carried out using between 0.05 and 0.25 g of catalyst,
which had been pressed into a disk and sieved to a particle size of 425–600 µm, diluted in SiC.
The sample was supported at the bottom of the catalyst bed in the reactor tube by glass wool. The
catalyst was contained within a 10 cm stainless steel tube with an internal diameter of 1/4 inch.
The reactor system was then pressurized, typically to 30 bar, with a 1 : 1 mixture of H2 and O2
from the respective CO2 diluted cylinders. The reactor temperature was controlled using a water
bath at 20°C. When the reaction pressure and gas flows stabilized the solvent flow (typically, 0.25–
5.0 ml min−1 ) was introduced into the system. Both gas and liquid flowed concurrently through
the catalyst bed from top to bottom. Liquid samples were taken from the sample bomb every
10 min, and the concentration of H2 O2 was determined by titration against an acidified dilute
Ce(SO4 )2 solution using ferroin as an indicator. During the study, the amount of H2 O2 was quoted
as the concentration formed in the reaction solution in units of parts per million (ppm). Selectivity
towards H2 O2 synthesis was determined via GC analysis, as discussed above. Evaluation of the
activity of the uncharged (no catalyst) reactor towards H2 O2 degradation and synthesis is found
to be zero in both respects.
Within this work CO2 has been used as a diluent for reactant gases to ensure mixtures do not
enter the explosive region. Furthermore, CO2 provides the additional benefit of improving H2 O2
stability through the formation of carbonic acid in situ, with the decomposition of H2 O2 to H2 O
known to be base-catalysed. We have previously discussed the effect of carbonic acid formation
on the direct synthesis of H2 O2 with a resulting solution pH of 4 reported. Indeed, the effects
of CO2 on catalytic activity are reported to be comparable to that observed when acidifying the
reaction solution to a pH of 4 using HNO3 [28].

(f) Characterization
Metal leaching from supported catalyst was quantified using microwave plasma atomic emission
spectroscopy (MP-AES) via analysis of filtered post reaction solutions, using an Agilent 4100
MP-AES. The concentration responses of Ni and Pd were calibrated using commercial reference
standards (Agilent); in all cases r2 > 0.999.

3. Results and discussion

Our initial work focused on the evaluation of 5%PdNi/TiO2 catalysts with varied Pd:Ni
ratios for the direct synthesis and subsequent degradation of H2 O2. We used water as the
solvent in the absence of halide or acid as promoters and ambient temperature both of which
are not favourable conditions to supress H2 O2 degradation (figure 1) [25,26]. A correlation
between total Pd content and catalytic activity towards H2 O2 synthesis was observed, with
 350 7
5
300 6

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H2O2 degradation (%)
250 5

H2O2 yield (ppm)

200 4

150 3

100 2

50 1

0 0

0 0.2 0.4 0.6 0.8 1.0

Pd content (wt%)

Figure 1. Catalytic activity of 5%PdNi/TiO2 toward H2 O2 synthesis (squares) and its subsequent degradation (triangles) as
a function of Pd content, under batch conditions. H2 O2 direct synthesis reaction conditions: catalyst (0.01 g), H2 O (8.5 g),
5% H2 /CO2 (29 bar), 25% O2 /CO2 (11 bar), 0.5 h, 20°C, 1200 r.p.m. H2 O2 degradation reaction conditions: catalyst (0.01 g), H2 O2
(50 wt%, 0.68 g), H2 O (7.82 g), 5% H2 /CO2 (420 psi), 0.5 h, 20°C, 1200 r.p.m. (Online version in colour.)

the observed concentration of H2 O2 increasing to a maximum of 312 ppm for the 0.75%Pd–
4.25%Ni/TiO2 catalyst before plateauing as the composition was varied to 1%Pd–4%Ni/TiO2
after 30 min of reaction. Interestingly no activity towards H2 O2 degradation, via decomposition
or hydrogenation pathways, was observed for the 0.75%Pd–4.25%Ni/TiO2 catalyst or those
materials with lower Pd loadings, despite their ability to produce H2 O2 . Increasing Pd content
beyond 15% of total metal loading (0.75 wt.%Pd content), does not result in further rise in
H2 O2 concentration, whereas we observe the development of catalytic activity towards H2 O2
degradation (6%) for the 1%Pd–4%Ni/TiO2 catalyst. By comparison we have recently reported
[26] that the well-studied 2.5%Au–2.5%Pd/TiO2 catalyst [29,30] prepared via a conventional wet-
impregnation methodology offers significantly greater rates of H2 O2 degradation (25%), under
identical reaction conditions indicating the beneficial effects of alloying Pd with Ni. It should be
noted that, despite the significantly greater activity of the supported AuPd catalyst towards H2 O2
degradation the concentration of H2 O2 generated (476 ppm) [26] is only slightly greater than that
observed for the 0.75%Pd–4.25%Ni/TiO2 catalyst.
With the requirement for Ni to be present in order to inhibit H2 O2 degradation pathways
clear (electronic supplementary material, table S.1), we next evaluated the efficacy of the 0.5%Pd–
4.5%Ni/TiO2 catalyst over multiple sequential H2 O2 synthesis tests under batch conditions
(figure 2). Initially, over a standard 0.5 h experiment, H2 O2 concentrations comparable to
that reported for the well-studied 0.5%Au–0.5%Pd/TiO2 catalyst are achieved, under identical
reaction conditions [25]. After carrying out five consecutive reactions, where the reactor is
depressurized prior to the introduction of reactant gases at standard pressures, the H2 O2
concentration increased in a linear manner to a value of 552 ppm, with no loss in H2 O2 selectivity
(97%) over sequential synthesis reactions. The high selectivity of the 0.5%Pd–4.5%Ni/TiO2
catalyst is particularly noteworthy given the relatively unfavourable conditions used in this study,
namely the use of ambient temperatures and a water only reaction medium.
Typically the evaluation of catalytic performance towards H2 O2 synthesis has focussed on the
use of high pressure, batch reactors [31,32]. However, the use of such reactors inherently results
in high contact times between the catalyst and synthesized H2 O2 , often leading to increased
degradation via hydrogenation and decomposition pathways. Alternatively a range of membrane
[33,34], fixed bed [35], trickle bed [36–39] and microreactors [40,41] have been used in the direct
synthesis of H2 O2 . Indeed we have previously reported the efficacy of a 0.5%Au–0.5%Pd/TiO2
 800
100 6
700

H2O2 concentration (ppm)

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600 80

selectivity (%)
500
60
400
300 40

200
20
100
0 0
0 1 2 3 4 5
sequential reaction number

Figure 2. Sequential H2 O2 synthesis reactions over the 0.5%Pd–4.5%Ni/TiO2 catalyst, under batch conditions. H2 O2
concentration (bar), selectivity towards H2 O2 (cross). Note: individual reactions are run for 0.5 h and reactant gases are replaced
at 0.5 h intervals. H2 O2 direct synthesis reaction conditions: catalyst (0.01 g), H2 O (8.5 g), 5% H2 /CO2 (29 bar), 25% O2 /CO2 (11 bar),
0.5 h, 20°C, 1200 r.p.m. (Online version in colour.)

catalyst, towards H2 O2 synthesis using a fixed bed reactor, with selectivities of 80% reached when
using optimized reaction conditions [29]. However, it should be noted that when using reaction
conditions similar to those used within this work (water only as solvent and ambient temperature)
the 0.5%Au–0.5%Pd/TiO2 catalyst only displayed a selectivity towards H2 O2 of approximately
20%, with a H2 O2 concentration of 190 ppm produced. With the commercial production of H2 O2
in a continuous mode likely to be favoured, in particular for applications requiring relatively
dilute H2 O2 concentrations, due to minimization of H2 O2 degradation we next investigated the
role of key reaction conditions on the formation of H2 O2 over the 0.5%Pd–4.5%Ni/TiO2 catalyst
in a fixed bed flow reactor.
The effect of varying catalyst mass from 0.05 to 0.25 g was first investigated (figure 3), with
H2 O2 concentration increasing in a linear manner with catalyst content, up to a catalyst mass of
0.1 g, beyond which H2 O2 concentration continues to increase but nonlinearly, in a similar fashion
to H2 conversion (electronic supplementary material, table S.2). This in part may be related to a
slight rise in activity towards the degradation of H2 O2 , as indicated by the marginal decrease
in H2 O2 selectivity at larger catalyst masses. Which in turn results from increased contact time
between reactant gases and the catalyst. Indeed, the relationship between H2 O2 degradation
activity and H2 O2 concentration is well known [18]. However, it is suggested that the observed
differences in catalytic selectivity are not significant. It is possible, given the relatively high flow
rates used within this study, that the plateau observed in H2 O2 concentration can be related to
limitations associated with reactant gas diffusion to the catalyst. Alternatively, it is also possible
that as the liquid and gas flow rates were held constant during these experiments and in turn
residence time across the catalyst bed is modified (electronic supplementary material, table S.2)
that in fact H2 O2 synthesis and degradation rates are equivalent, resulting in a plateauing of
observable H2 O2 concentration. Regardless, selectivity towards H2 O2 is seen to remain high,
exceeding 85%.
The effect of total reaction pressure was next investigated (figure 4), while maintaining all
other reaction conditions. As expected, an enhancement in H2 O2 concentration was observed
with increasing pressure. These results show that pressure had no effect on catalytic selectivity,
which remains constant at 85%. This is in keeping with our previous observations into supported
AuPd nanoparticles, under both flow [27] and batch [30] regimes, where both H2 O2 synthesis and
degradation pathways increase proportionally with pressure. The first order dependence of H2 O2
 100 100 7

H2O2 concentration (ppm)

80 80

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H2O2 selectivity (%)
60 60

40 40

20 20

0 0

0 0.05 0.10 0.15 0.20 0.25

catalyst mass (g)

Figure 3. Effect of catalyst mass on catalytic activity towards H2 O2 synthesis, under flow conditions. H2 O2 concentration as ppm
(squares), selectivity towards H2 O2 (cross). Reaction conditions: 20°C, H2 O liquid flow rate, 1 ml min−1 , 30 bar total pressure,
5% H2 /CO2 (175 ml min−1 ), 25% O2 /CO2 (35 ml min−1 ). (Online version in colour.)

100 100
H2O2 concentration (ppm)

80 80

H2O2 selectivity (%)

60 60

40 40

20 20

0 0

0 5 10 15 20 25 30
total pressure (bar)

Figure 4. Effect of pressure on catalytic activity towards H2 O2 synthesis, under flow conditions. H2 O2 concentration as ppm
(squares), selectivity towards H2 O2 (cross). Reaction conditions: 20°C, catalyst mass (0.25 g) H2 O liquid flow rate, 1 ml min−1 ,
5% H2 /CO2 (175 ml min−1 ), 25% O2 /CO2 (35 ml min−1 ). (Online version in colour.)

formation with respect to H2 partial pressure suggests that H2 O2 concentration scales linearly
with increasing H2 pressure. However, we observe a slight divergence away from this correlation,
with similar observations previously reported by Izumi et al. [41], at pressures comparable to that
studied within this work (see electronic supplementary material, table S.3). In this case, we ascribe
the nonlinear relationship between reactant gas pressure and H2 O2 concentration to diffusion
issues associated with inefficient reactor dynamics and catalyst packing. Indeed, it can be seen
(electronic supplementary material, figure S.2) that when using a lower catalyst mass (0.1 g) the
relationship between reactant gas pressure and H2 O2 concentration is close to linear.
The effect of solvent flow rate was next investigated while maintaining all other reaction
conditions (figure 5). Perhaps unsurprisingly, due to effects of dilution, we observe a decrease
in H2 O2 concentration with increasing flow rate. However, calculation of the moles of H2 O2
produced revealed that this metric increased with solvent flow, with a maximum (0.004 mmol)
observed at 3 ml min−1 solvent flow. Increasing flow rate beyond 3 ml min−1 resulted in no further
 160 0.0045
8
140 0.0040

H2O2 concentration (ppm)

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0.0035

(mmolH O (ml min–1))

...............................................................
120

H2O2 concentration
0.0030
100
0.0025
80
0.0020

2 2
60
0.0015
40
0.0010
20 0.0005
0 0
0 1 2 3 4 5
solvent flow (ml min–1)

Figure 5. Effect of solvent flow rate on catalytic activity towards H2 O2 synthesis, under flow conditions. H2 O2 concentration
as ppm (squares), H2 O2 concentration as mmolH2 O2 mlmin−1 (triangles). Reaction conditions: 20°C, catalyst mass (0.25 g) H2 O,
30 bar total pressure, 5% H2 /CO2 (175 ml min−1 ), 25% O2 /CO2 (35 ml min−1 ). (Online version in colour.)

100 100
H2O2 concentration (ppm)

80 80

H2O2 selectivity (%)

60 60

40 40

20 20

0 0
0 2 4 6 8 10
time (h)

Figure 6. Catalytic activity of the 0.5%Pd–4.5%Ni/TiO2 catalyst over 10 h onstream. H2 O2 concentration as ppm (squares),
selectivity towards H2 O2 (cross). Reaction conditions: 20°C, catalyst mass (0.25 g) H2 O liquid flow rate, 1 ml min−1 , 30 bar total
pressure, 5% H2 /CO2 (175 ml min−1 ), 25% O2 /CO2 (35 ml min−1 ). (Online version in colour.)

increase in H2 O2 concentration, with similar results observed regardless of total catalyst mass
used (electronic supplementary material, figure S.3). This is ascribed to mass transfer limitations,
where greater solvent flow rates and shorter residence times inhibit diffusion of reagent gases to
catalytically active sites, with similar conclusions previously made by Biasi et al. [42,43]. As more
solvent is passed through the catalyst bed the residence time of H2 O2 is reduced through dilution
of the solution. With the extent of H2 O2 degradation proportional to residence time, increasing
solvent flow rates will also result in a decrease in the rate of these subsequent reactions, leading
to increased selectivity. Indeed, we have previously reported, using similar reaction conditions,
that with increasing solvent flow rates H2 conversion remains constant, while selectivity towards
H2 O2 increases significantly.
Finally with the requirement to re-use a catalyst successfully at the heart of green chemistry
and the activity of homogeneous species towards H2 O2 synthesis well known [44], we next
investigated catalytic activity of the 0.5%Pd–4.5%Ni/TiO2 catalyst towards H2 O2 synthesis for
extended periods of time, under flow conditions (figure 6). Over 10 h on-stream, we observe
9
no loss in either activity, with 80 ppm H2 O2 produced consistently, or selectivity towards H2 O2 ,
indicative of the high stability of the catalyst. Furthermore, analysis of the post reaction effluent

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via MP-AES (electronic supplementary material, table S.4) reveals no leaching of either Pd or
Ni from the catalyst surface. It should be noted that comparable concentrations of H2 O2 to that
produced over the 0.5%Pd–4.5%Ni/TiO2 catalyst have previously been reported to offer excellent
biocidal activity, with Ronen et al. [2] reporting the high efficacy of preformed H2 O2 in the
remediation of greywater. As such we propose that the continuous production of relatively low
concentrations of H2 O2 may find applications in sectors, such as the treatment of waste streams.

4. Conclusion
With a focus on reaction conditions considered unfavourable to H2 O2 formation, we have
evaluated the efficacy of supported PdNi catalysts exposed to a successive calcination–reduction–
calcination heat treatment towards the direct synthesis of H2 O2 . Catalytic activity in both a stirred
autoclave reactor and using flow conditions is found to be stable, with a selectivity towards H2 O2
exceeding 95% and 85% in batch and flow regimes, respectively. We consider that these catalysts
represent a promising basis for further exploration of the direct synthesis of H2 O2 under realistic
industrial conditions.
Data accessibility. Information on the data underpinning the results presented here, including how to access
them, can be found at http://doi.org/10.17035/d.2020.0101908221.
Authors’ contributions. All authors provided substantial contributions to the conception and design, or acquisition
of data, or analysis and interpretation of data, drafting the article or revising it critically for important
intellectual content and final approval of the version to be published.
Competing interests. The authors declare no competing interests.
Funding. D.A.C. and R.U. wish to acknowledge the Selden Research Limited for financial support. J.K.E,
G.S., G.J.H. and R.J.L. gratefully acknowledge the Cardiff University for financial support, in addition
S.J.F. acknowledges the financial support and the award of a Prize Research Fellowship from the from the
University of Bath.
Acknowledgments. The authors wish to acknowledge the Selden Research Limited for useful discussion
throughout.

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