Materials Letters 234 (2019) 58–61

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

An efficient Pd/C catalyst design based on sequential ligand exchange

method for the direct synthesis of H2O2
Seungsun Lee, Young-Min Chung ⇑
Department of Nano & Chemical Engineering, Kunsan National University, 558 Daehak-ro, Kunsan 573-701, Republic of Korea

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

Article history: A new catalyst preparation method involving the sequential ligand exchange of anionic palladium com-
Received 22 July 2018 plexes to cationic complexes via the formation of palladium hydroxide intermediates is proposed. The
Received in revised form 4 September 2018 novel method enables the electrostatic adsorption of an anionic palladium complex on the negatively
Accepted 13 September 2018
charged carbon surface, and therefore makes it possible to obtain small and highly dispersed Pd nanopar-
Available online 14 September 2018
ticles. The H2O2 productivity and H2 selectivity of the ligand-exchanged catalyst were 16 and 3.6 times
higher than those of the Pd/C catalyst prepared by using the same anionic palladium precursor. The strik-
Keywords:
ingly different activities mainly attributed to the difference in the nanoparticle size and the oxidation
Sequential ligand exchange
Electrostatic adsorption
state of Pd, which clearly indicates that the activity of Pd/C catalyst for the direct synthesis of H2O2
Pd/C can be greatly improved by the sequential ligand exchange method.
Direct synthesis of H2O2 Ó 2018 Elsevier B.V. All rights reserved.

Although Pd/C catalysts have been extensively studied for the
direct synthesis of H2O2, the formation of large, polydisperse Pd
nanoparticles (NPs) resulting from the non-selective physisorption
of an anionic palladium precursor on the carbon surface with neg-
ative charge, persists as a stubborn problem to obtain a high H2O2
yield. Therefore, a suitable preparation method enabling the for-
mation of small Pd NPs is highly needed. For this purpose, the elec-
trostatic adsorption of metal precursor ions on a support is very
important. The weakly physisorbed metal ions may aggregate on
the support or grow in solution, which results in the formation of
large, polydisperse Pd NPs after reduction [1]. Thus, it is preferable
to use a cationic palladium precursor because the surface of an
activated carbon is mostly negatively charged over a wide range
of pH values. In addition, the incorporation of the cationic nitrogen
groups on the carbon surface may offer electrostatic adsorption
sites for anionic palladium precursors. Alternatively, the immobi-
lization of ready-made colloidal Pd NPs on the carbon surface is
possible. However, all these methods have drawbacks.
The first method using a cationic palladium precursor has
apparent advantages such as the formation of small NPs, simple
electrostatic adsorption without surface modification, and high
reproducibility. However, the relatively high cost and complex
preparation steps have limited its use to specific industrial applica-
tions. The second method is capable of selectively adsorbing anio-
nic ions, and thus obtaining small NPs [2]. However, even though
⇑ Corresponding author.
E-mail address: ymchung@kunsan.ac.kr (Y.-M. Chung).
the positively charged nitrogen groups may provide electrostatic
adsorption sites for anionic metal precursors, simultaneous non-
selective physisorption is inevitable because a large portion of
the carbon surface remains negatively charged. Furthermore, the
incorporated basic sites may accelerate unfavorable H2O2 decom-
position [3]. In addition, while the preparation of colloidal Pd
NPs offers superior NP size control, the stabilizing ligand may sig-
nificantly affect the H2O2 yield by increasing the mass transfer
resistance of reactants or by modifying the binding modes of the
reactive intermediates [4].
Herein, we propose a new Pd/C catalyst design for the direct
synthesis of H2O2 adopting the sequential ligand exchange method
for the electrostatic adsorption of an anionic palladium complex on
a negatively charged carbon surface.
Fig. 1 shows the reaction routes and the visual and UV–vis
absorption spectra changes during the sequential ligand exchange
of an anionic palladium complex. The exact ligand exchange con-
sist of two pathways through the formation of palladium hydrox-
ides as intermediates. In the first exchange step, the pH of the
metal precursor solution is critical because uncontrollable rapid
nucleation and subsequent precipitation of the insoluble palladium
hydroxide species will occur at high hydroxide ion concentrations.
Therefore, ammonia plays a dual function in the slow generation of
hydroxide ions and subsequent ligand exchange with the hydrox-
ide ions in these sequential ligand exchange reactions.
The ligand exchange of the palladium complex was monitored
by the color change of the solution (Fig. 1(b)). At pH 8, the brown
anionic palladium precursor solution (i) turned pale pink, implying

https://doi.org/10.1016/j.matlet.2018.09.068
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 S. Lee, Y.-M. Chung / Materials Letters 234 (2019) 58–61 59

Fig. 1. Sequential ligand exchange of an anionic palladium precursor: (a) reaction pathways and (b) visual and UV–vis absorption changes during the sequential ligand
exchange process.

Fig. 2. TEM images of Pd/C catalysts and the Pd NP size distributions.

60 S. Lee, Y.-M. Chung / Materials Letters 234 (2019) 58–61
the formation of palladium hydroxide species (ii), and the disap-
pearance of the pale pink color of (iii) after additional stirring at
353 K is indicative of the ligand exchange of the hydroxide ion with
ammonia. Changes in the UV–vis absorption spectra of the metal
precursor solution during the sequential ligand exchange reactions
closely matched the visual color changes. After the addition of an
aqueous ammonia solution, the characteristic absorption bands
of [PdCl4]2 at 210 and 238 nm were completely substituted by a
broad Pd(OH)x band around 300 nm. The appearance of a strong
absorption band in the far-UV region after additional stirring
implies the second ligand exchange reaction from hydroxide to
ammonia [5].
Fig. S1 shows the catalyst preparation schemes using different
strategies. The Pd/C#A catalyst was prepared by the sequential
[PdCl4]2 ion adsorption and Pd(OH)x deposition method. In the
case of Pd/C#Ex, the anionic palladium ions were first converted
to the cationic complexes by the sequential ligand exchange
method. After then, the electrostatic adsorption of the ligand-
exchanged cationic palladium complex was performed in the
absence of hydroxide ions to suppress unfavorable non-selective
adsorption. The preparation method for the Pd/C#C catalyst was
similar to that of Pd/C#Ex, except for the direct use of a cationic
palladium precursor.
Fig. 2 shows the TEM images of the Pd/C catalysts. While large
and polydisperse NPs (4.8 ± 1.5 nm) were obtained in the case of
Pd/C#A, very small, monodisperse NPs were observed for Pd/C#C
and Pd/C#Ex catalysts (2.1 ± 0.3 and 1.9 ± 0.2 nm, respectively)
(Fig. S2). The result demonstrates that the electrostatic adsorption
of palladium complexes is prerequisite for the production of extre-
mely small, monodisperse Pd NPs. Moreover, the similar Pd NP
sizes of Pd/C#Ex to those of Pd/C#C suggests that the anionic pal-
ladium complex can be adsorbed on the carbon surface exhibiting
same negative charge via the sequential ligand exchange process.
The similar Pd content of Pd/C#Ex (0.45 wt%) with that of
Pd/C#C (0.41 wt%) indicates that there was no appreciable loss
during the sequential ligand exchange. Cheng et al. reported that
an anionic palladium precursor ion could be converted to a cationic
complex through the formation of palladium hydroxides as inter-
mediates [6]. However, the formation of large and polydisperse
Pd NPs suggests that the rapid and heterogeneous deposition of
various Pd complexes occurred by the addition of hydroxide ions
Fig. 3. Catalytic activity of the Pd/Cs in the direct synthesis of H2O2.
during catalyst preparation, even when a cationic palladium pre-
cursor was used.
The PXRD patterns and XPS analysis of the Pd/C catalysts are
presented in Fig. S3. The intense and sharp Pd [1 1 1] peak
observed for the Pd/C#A implies the formation of large Pd NPs with
high crystallinity. There was no distinguishable difference in the
PXRD patterns between the Pd/C#C and Pd/C#Ex, indicating their
similar crystal structure and crystallinity. In the XPS analysis, the
two broad bands observed for the Pd(3d5/2) and Pd(3d3/2) in the
334–340 and 340–346 eV regions suggest the presence of both
Pd2+ and Pd0, which indicates that total reduction was not
achieved, regardless of the preparation methods. However, the
degree of reduction was dependent on the preparation method,
and the smaller Pd0/Pd2+ ratio observed in the deconvoluted XPS
peaks of the Pd/C#C and Pd/C#Ex catalysts suggest that a large pro-
portion of the palladium exists in an oxidized form (Table S2).
The direct synthesis of H2O2 was performed using the Pd/C cat-
alysts, and the results are presented in Fig. 3. In the presence of the
Pd/C#A catalyst, poor H2O2 productivity and H2 selectivity were
obtained, although the H2 conversion was high. In contrast, Pd/
C#C and Pd/C#Ex showed excellent reaction performance, and
the H2O2 productivity and H2 selectivity reached as high as ca.
21000 mmol-H2O2/g-Pd.h and 94%, respectively.
Recently, theoretical and experimental studies reported the
importance of the active metal particle size [7,8]. While small Pd
NPs may be advantageous for the selective formation of H2O2, lar-
ger Pd NPs may promote unfavorable O2 dissociation, resulting in
the formation of H2O. Furthermore, Table 1 shows that the Pd/
C#A catalyst having larger Pd NPs with more metallic nature, as
revealed by XPS and TEM analyses, accelerated the unfavorable
H2O2 decomposition, which resulted in the low H2O2 yield [9,10].
Table 1
H2O2 decomposition in the presence of the Pd/C
catalysts.
Catalyst Decomposition
(mmol-H2O2/g-Pd.h)
Pd/C#A 1085
Pd/C#C 703
Pd/C#Ex 785
 S. Lee, Y.-M. Chung / Materials Letters 234 (2019) 58–61
The result clearly shows that the superior catalytic activity of Pd/
C#C and Pd/C#Ex may be attributed to the formation of highly dis-
[2]
persed tiny Pd NPs with a high population of Pd2+.
In summary, an efficient Pd/C catalyst design based on the
sequential ligand exchange approach was developed. The excellent
activity of the ligand-exchanged catalyst clearly shows that the [3]
low activity of conventional Pd/C catalyst for the direct synthesis
of H2O2 can be greatly improved by the new method. Moreover,
the virtually identical physicochemical properties and activity of [4]
the Pd/C#Ex to those of the Pd/C#C prepared by using a cationic
palladium complex demonstrate the effectiveness of the sequential
ligand exchange method for the electrostatic adsorption of an anio- [5]
nic metal complex on a negatively charged surface.
Acknowledgement [6]
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded [7]
by the Ministry of Education (2016R1D1A3B02006928).
Appendix A. Supplementary data [8]
Supplementary data to this article can be found online at [9]
https://doi.org/10.1016/j.matlet.2018.09.068.
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