Catalysis Surveys from Asia (2023) 27:115–131

https://doi.org/10.1007/s10563-022-09382-8

REVIEW ARTICLE

The Metal-Based Catalysts for Selective Hydrogenation

of Anthraquinone to Produce Hydrogen Peroxide
Chenglin Miao1 · Rongxin Zhang1 · Tianli Hui2 · Gaoshan Zang1 · Jieguang Wang1

Received: 31 May 2022 / Accepted: 22 October 2022 / Published online: 11 November 2022
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2022

Abstract
Selective hydrogenation of anthraquinone is critical in producing H2O2, the strong oxidant widely used in most industrial
areas. More efforts were made on the selective hydrogenation of C=O in the anthraquinone process because the sides-product
will negatively affect continuous H2O2 production and significantly reduce the project economics. A crucial step toward high
H2O2 yield is the rational design of heterogeneous catalysts. In this review, the metal-based catalyst design for the selec-
tive anthraquinone hydrogenation is cataloged into two significant strategies: active metal regulation and support property
regulation. Research accomplished in the past decade on the catalyst design for selective anthraquinone hydrogenation is
systematically reviewed. The focus is on the catalytic performance-enhancing mechanism and the factors that influence
the mechanism. In addition, the limitations and barriers encountered for supported catalysts in the current study, as well as
potential research trends, are discussed.

Keywords Selective hydrogenation · Catalyst design · H2O2 production · Anthraquinone method

1 Introduction The anthraquinone catalytic hydrogenation method uses

Hydrogen peroxide (H2O2) is a green and environmentally
friendly molecular, widely used in food, paper, textile, and
wastewater treatment industries. Its redox product is water
and thus will not cause secondary pollution to the environ-
ment. Since the early twenty-first century, the application of
H2O2 in producing some bulk chemicals, such as caprolac-
tam, propylene oxide, and epichlorohydrin, has significantly
promoted the growth of H2O2 demand. Recently, with the
improvement of the environmental protection requirements,
the replacement of non-green oxidants will be compelled.
Thus, the need for H2O2 surely will further increase year by
year. Among several methods of H2O2 production, catalytic
anthraquinone hydrogenation, which possesses the advan-
tages of low energy consumption and low cost, has become
the mainstream method, and almost 99% of H2O2 in the
world is produced by this method.
* Chenglin Miao
244487055@qq.com
1
SINOPEC, Research Institute of Petroleum Processing,
Beijing 100083, People’s Republic of China
2
State Key Laboratory of Heavy Oil Processing, China
University of Petroleum, Beijing 102249, China
a reduction–oxidation cycle process in industrial produc-
tion. Initially, the 2-ethyl-9,10-anthraquinone (eAQ) dis-
solved in a mixed solvent is mainly hydrogenated to 2-ethyl-
9,10-anthrahydroquinone (eAQH2), in which the C=O bonds
of the eAQ is transferred into C–OH bonds with the effect
of catalyst (shown in Scheme 1). [1–4] Then, the obtained
eAQH2 is oxidized by air/O2 through an autoxidation pro-
cess to produce the desired H2O2 and regenerate the origi-
nal eAQ. During the hydrogenation process, besides the
main reaction, the obtained eAQH2 can undergo further
reaction in the presence of a catalyst to give various prod-
ucts. On one hand, the C=C bonds of aromatic rings in the
obtained eAQH2 are successively hydrogenated to gener-
ated 2-ethyl-5,6,7,8-tetrahydro-9,10-anthrahydroquinone
(H4eAQH2) and 2-ethyl-1,2,3,4,5,6,7,8-octahydro-9,10-an-
thrahydroquinone (H8eAQH2) [6, 7]. On the other hand, the
2-ethyl-9-anthrone/2-ethyl-10-anthrone (eAN), which can
be further hydrogenated into 2-ethyl-5,6,7,8-tetrahydro-
9-anthrone/2-ethyl-5,6,7,8-tetrahydro-10-anthrone (H4eAN),
can be obtained undergoes the hydrogenolytic cleavage of
C-O bonds [6, 8–10]. All the side products cannot be trans-
formed back to the original eAQ during the hydrogenation
process, causing the loss of the eAQ in the reduction–oxi-
dation cycle, thus leading to huge economic damage. It is

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Scheme 1 Anthraquinone hydrogenation/oxidation process for manu-
facturing H2O2
worth mentioning that all side products are expected to be
kept at a low concentration. Although the H4eAQH2 can be
oxidized to produce desired H2O2, it shows a slower oxida-
tion rate than eAQH2, leading to lower efficiency in H2O2
production, which is also an undesired product. According to
the process of the eAQ method, it is not difficult to tell that
the key point of it is the hydrogenation rate and the selec-
tivity of the target product, eAQH2 [11]. More specifically,
the most important index that determines the yield of H2O2
lies in the activation efficiency of the catalyst to the eAQ
molecular and the selectivity towards C=O bonds.
At the very beginning, skeletal Ni catalysts were applied
for the catalytic eAQ hydrogenation process and played an
essential role in the early development of the H2O2 indus-
try due to its good selective towards eAQH2 and H4eAQH2
(these two products are named as active quinones) [12–14].
However, its shortcoming of being extremely easily oxi-
dized in the air, the environmentally unfriendly preparation
process, and the finite space for its catalytic performance
improvement limit its further development. Gradually, the
metal-supported catalysts are mainly used in industry instead
of skeletal Ni due to their higher activity, selectivity, stabil-
ity, and safety. In the past 20 years, there has been exten-
sive work on the catalytic performance of metal-supported
catalysts for selective eAQ hydrogenation. Significant find-
ings include the intrinsic activity and selectivity of the met-
als, and the effect of the second components and supports
were reported [6–21]. In earlier years, Ni-based supported
catalysts were investigated for application in catalytic eAQ
hydrogenation to overcome the shortage of skeletal Ni cata-
lysts. However, the activity is still lower, which is due to the
intrinsic properties of Ni metals. Afterward, bimetal/alloy
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C. Miao et al.
catalysts are developed to improve intrinsic activity. Second
components, such as La, Mo, Cr, and even P, modify the Ni
metal to obtain the enhanced catalytic activity [13, 15–17]
Compared with the Ni-based supported catalysts, the Pd-
based catalysts possess intrinsic activity for the hydrogena-
tion of eAQ molecular, which have been widely applied in
industrial production. Various Pd-based supported catalysts
have been made and regulated to improve production capac-
ity and efficiency, focusing on eAQ molecular adsorption,
selectivity C=O activation, and hydrogen activation/dis-
sociation capacity [18–20]. Moreover, as for the supported
catalysts, besides the characteristics of active metals, the
surface properties of support are another factor affecting
the catalytic performance of eAQ hydrogenation. Acid/
alkali modified support, such as Si, La and Cs modified alu-
mina (Al2O3), are fabricated to tune the capability for eAQ
adsorption and thus enhance the subsequent reactant mol-
ecules activation. In addition, the molecular volume of the
reactant molecules and solvent molecules is large. Therefore,
the mass transfer resistance will significantly affect the cata-
lytic performance. To minimize the mass transfer resistance,
catalysts with controllable pore structures (SBA, MCM, and
AAO) are applied to the hydrogenation process [14, 21].
Despite many related publications in the last 20 years, the
subject has not been reviewed much. Thus, in this review,
we focus on the catalyst reported for selective eAQ hydro-
genation, which covered the factors that influence catalytic
activity and selectivity, kinetics and modeling, and the fun-
damental mechanism of this reaction. Those latest advances
and progress of this reaction are systematically summarized
based on the regulation method of active metals/supports,
emphasizing the catalytic performance-enhancing mecha-
nism and the factors that influence the mechanism. We also
point out some potential research trends and suggest a few
approaches to improve the yield of H2O2 further. In addition,
we hope that this Review can help researchers better under-
stand the development of selective eAQ hydrogenation and
offer some new ideas for industrial catalyst design.
2 The Effect of Active Metals on Catalytic
Performance
Active metals, the indispensable part of the catalysts, play a
decisive role in the catalytic performance of almost all reac-
tions. Generally, Ni and Pd are applied for selective catalytic
hydrogenation of eAQ due to their excellent hydrogenation
activity during this process. Ni-based catalyst is an impor-
tant research direction for the fabrication of high-perfor-
mance eAQ hydrogenation catalysts due to their low cost
and good activity. The Pd-based catalyst has become the
primary catalyst for industrial production due to its higher
catalytic performance. Some outstanding and exciting results
The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen…
have been reported in recent studies regarding these metal
catalysts, and the hydrogenation performance of the reported
catalysts has been summarized in Table 1.
2.1 Ni-Based Catalysts
2.1.1 Ni Alloy Catalysts
Industrially, the Raney Ni catalyst is initially explored in
the application for selective eAQ hydrogenation. However,
Raney Ni is fragile, rapidly deactivated, and quickly causes
excessive hydrogenation. Firstly, the skeletal alloy catalyst
was fabricated to improve the catalytic performance of the
Ni catalysts to overcome the drawbacks of the Raney Ni
catalyst. Liu and Fan et al. reported a Rapidly Quenched
Ni–Al alloy (RQ-Ni) catalyst, which possesses a higher
surface area, porosity, pore diameter, and the amorphous
structure characters [13]. Compared with the Raney Ni cata-
lyst, the RQ-Ni catalyst exhibits a 97% yield of H2O2 and
then levels off, while that of the Raney Ni catalyst is only
67% and dropped after prolonged reaction time. More inter-
estingly, after the reduction–oxidation cycle, the evolution
of H4eAQ over the RQ catalyst is much slower than that
of the Raney catalyst, which indicates that the RQ catalyst
exhibits a higher selectivity than that of the Raney catalyst
in C=O bonds hydrogenation, thus leading to the preferred
catalytic performance (shown in Fig. 1A). The enhanced
performance could be attributed to the defect sites driven
by the amorphous characters of the RQ catalyst, which can
tightly bond with hydrogenation. Thus, it shows high activ-
ity in the C=O bonds hydrogenation. Although the catalyst
exhibits improved catalytic performance, 18% of eAQ in
the RQ catalyst system is converted to H4eAQ, while 3% of
eAQ deteriorates. The bimetallic skeletal NiB and NiCrB
catalysts, showing improved selectivity towards C=O bonds,
were further synthesized by Fan group [12]. Besides the
coordinatively unsaturated nature of the amorphous alloys,
the added Cr species can act as Lewis acid sites, which could
activate the C=O bonds by accepting the lone electron pair
on the oxygen and thus exhibits the superior selectivity.
The activation favors the nucleophilic attack of the carbon
by hydrogen dissociative adsorbed on metal, leading to
enhanced hydrogenation activity of the carbonyl group and
consequently superior selectivity in eAQ hydrogenation to
eAQH2. Similar results were obtained over the amorphous
NiB alloy catalysts doped with the second metal M (M = La,
Mo etc.) [12, 14–16]. The second M component acts as the
Lewis acid site and functions as the electron acceptor, which
transfers the electron to Ni metal sites. The electron-enriched
Ni sites could also strengthen the adsorption of C=O bonds
by increasing the backdonation into πCO*, which is another
reason for the improved selectivity. More importantly, the
addition of second metal could enhance the thermal stability
117
of the skeletal Ni catalyst while effectively dispersing the
surface Ni atoms (shown in Fig. 1B) simultaneously.
2.1.2 Supported Ni-based catalysts. The use of a large
number of strong bases in the production process of skel-
etal Ni catalysts would cause severe environmental pollution
and higher production costs. Thus, the more environmentally
friendly supported Ni-based catalysts were developed for
this industrial process. The alumina-supported NiB amor-
phous alloy was further reported by Wang group [21]. The
effect of the La loading on the catalytic performance of the
supported NiLaB alloy catalyst was also explored. As shown
in Fig. 1C and D, the hydrogenation activity increases upon
La incorporation up. The TOF of the NiLaB catalyst with the
1.02% La loading is almost two times that of the NiB cata-
lyst. The boosting activity can be attributed to two aspects:
on the one hand, the addition of La can induces the strong
metal-support interaction (SMSI) between alloy metals and
alumina support, leading to the higher dispersed Ni active
center. On the other hand, after doping, the electron will
transfer from La to Ni and thus obtain the electron-enriched
Ni sites, which can weaken the adsorption of eAQ molecu-
lar and strengthen the activation of adsorbed hydrogenation.
Moreover, when the La loading is too much, the hydrogena-
tion activity would significantly reduce due to excessive La
covering the surface Ni active centers (shown in insert figure
of Fig. 1C). However, it is worth mentioning that although
the catalytic stability is viral important for the eAQ catalyst,
the above works have not conducted in-depth research on
the catalytic stability and structural ability of the Ni-based
catalyst.
2.2 Pd-Based Catalysts
2.2.1 Supported Pd Monometallic Catalysts
Pd-based are the most widely used catalysts for the eAQ
selectivity hydrogenation due to their higher activity and
selectivity, as shown in Table 1. The properties of Pd par-
ticles, such as the size, crystal face, and electronic struc-
ture, fundamentally determine the catalytic performance of
Pd-based catalysts for the eAQ hydrogenation. Pd/Al2O3
was prepared via one-step synthesis (Pd-situ/Al2O3), and
impregnation (Pd-im/Al2O3) synthesis was applied for the
selective hydrogenation of eAQ reaction; 98.9% and 98.3%
of active quinones (eAQ and H4eAQ) with 15.0 and 12.4 g/L
hydrogenation efficiency obtained, respectively. The higher
hydrogenation efficiency of the Pd-situ/Al2O3 can be attrib-
uted to its smaller particle size, which led to a higher number
of surface Pd sites [4]. Zhang et al. reported the supported
face-controlled Pd nanocrystal catalysts for the eAQ hydro-
genation performance [5]. The Pd-Cube/Al2O3 catalyst with
exposed Pd (100) face possesses two times TOF in the eAQ
selective hydrogenation than the Pd-Octa/Al2O3 catalyst
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Table 1 Representative results for the selective hydrogenation of eAQ over Ni/Pd based catalyst
Entry Catalyst Reaction conditions TOF (s−1) Selec. eAQ Selec. H4eAQ Selec. Deg.c Activity Ref.
o a

13
T ( C) PH2 (Mpa) t (h) solvent Catal.
Cons.b (g)

1 Raney Ni 50 0.3 1.3 TOPd + TMBd 1.0 0.56 15.0% 60.5% 24.5% 67e [12]
2 RQ-Ni 50 0.3 1.4 TOP + TMB 1.0 0.60 81.0% 15.6% 3.4% 97e
3 NiCrB alloy 50 0.3 1.0 TOP + TMB 0.5 – 99.3% 0.7% – ~ 100e [13]
4 NiB alloy 50 0.3 3.0 TOP + TMB 0.5 – – 1.9% – 98e [17]
5 NiCrB alloy 50 0.3 1.0 TOP + TMB 0.5 – – ~ 0% – ~ 100e
6 NiMoB alloy 65 – 2.0 TOP + TMB 0.2 – – – – 6.9f [16]
7 NiLaB alloy 65 – 2.0 TOP + TMB 0.2 – – – – 7.4f [15]
8 NiB/Al2O3 65 – 2.0 – 0.5 1.0 – – – 0.5f [23]
9 NiLaB/Al2O3 65 – 2.0 – 0.5 1.9 – – – 2.4f
10 Pd/Al2O3 62 4.8 Xylene + Octanol 0.28 – – 58% 40% 405 g [10]
11 Pd/SiO2 62 0.1 5.0 Xylene + Octanol 0.28 – – 39% 20% 315 g
12 Pd/C 62 0.1 5.0 Xylene + Octanol 0.28 – – 59% 29% 405 g
13 Pd-Cube/ Al2O3 50 0.3 0.25 TOP + TMB 1.2 9.9 – 5.0 mmol 5.2 mmol 13.9 h [5]
14 Pd-Cuboct/ Al2O3 50 0.5 0.25 TOP + TMB 1.2 7.3 – 6.2 mmol 5.5 mmol –
15 Pd-Octa/ Al2O3 50 0.45 0.25 TOP + TMB 1.2 5.3 – 7.2 mmol 5.4 mmol –
16 Au/Al2O3 60 0.3 – TOP + TMB 1.2 – 100%k 0 1.1 h [6]
17 Pd/Au/Al2O3 60 0.3 – TOP + TMB 1.2 – 99.6%k 0.4% 14.3 h
18 Au/Pd/Al2O3 60 0.3 – TOP + TMB 1.2 – 98.1%k 1.9% 12.8 h
19 Pd-Au/Al2O3 60 0.3 – TOP + TMB 1.2 – 97.7%k 2.3% 11.2 h
20 PdGa/Al2O3 60 0.3 0.25 TOP + TMB 0.6 – 99.6%k 0.4% 11.9 h [24]
21 PdIr/Al2O3 (alloy) 50 0.3 1.5 TOP + TMB 0.25 – – 0.12 mmol – 92.1e [25]
22 PdIr/Al2O3 (Mesocrystal) 50 0.3 1.5 TOP + TMB 0.25 – – 0.05 mmol – 7.7 h [26]
23 PdRu/Al2O3 60 0.3 0.25 TOP + TMB 0.3 – 99.5%k 0.5% 12.1 h [27]
24 PdAg/Al2O3 70 0.3 0.3 TOP + TMB 0.3 – 98.9% 0.4% 0.7% 5.2 m [19]
25 PdCu/Al2O3 70 0.3 0.3 TOP + TMB 0.3 – 98.8% 0.4% 0.8% 5.5 m
26 PdCo/Al2O3 70 0.3 0.3 TOP + TMB 0.3 – – – – 0.3 m
27 PdNi/SiO2/COR 80 0.1 – TOP + C9 aromatics – 1.21 95.3%k 4.7% 7.5 h [28]
28 PdFe/SiO2/OR 80 0.1 – TOP + C9 aromatics – 0.99 80.6%k 19.4% 5.5 h
29 PdMn/SiO2/COR 80 0.1 – TOP + C9 aromatics – 0.78 63.7%k 36.3% 4.35 h
30 PdCu/SiO2/COR 80 0.1 – TOP + C9 aromatics – 0.56 40.4%k 59.6% 3.1 h
a
The time to reach the highest conversion of eAQ, reflecting the catalyst activity. bCatal. Cons. are defined as the catalyst consumption (g). cThe selectivity towards degradation products. dTOP
and TMB are represented as trioctylphosphate and trimethyl benzene, respectively. eThe yield of H2O2 (%), which is expressed as the ratio of tol H2O2 to the initial number of mol eAQ in the
reactor. fExpressed as the amount of hydrogen peroxide produced per gram of catalyst per minute (gH2O2/gcat/min × 103). gThe hydrogen consumption for hydrogenation of eAQ (mol × 10–5).
h
The hydrogenation efficiency (g/L). kThe selectivity of active quinones, which involve eAQ and H4eAQ. mThe rate of H2 consumption, which represents the reactof ion rate of EAQ hydrogena-
C. Miao et al.

tion over the catalysts

The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen…
Fig. 1 The H2O2 yield over Raney Ni and RQ Ni catalysts (A)
[13]; The TEM images of the NiB and NiCrB alloy catalysts (B)
[12]; The catalytic activities and TOF values of NiLaB/γ-Al2O3
with exposed Pd (111) face. At the same time, the selectiv-
ity is similar, indicating the ability towards eAQ activation,
especially the C=O bonds, is quite different. The ability
of the Pd (100) and Pd (111) to activate the C=O in the
eAQ was studied by the density functional theory (DFT)
calculations. As shown in Fig. 2, the calculated adsorption
energy of the eAQ molecule on the Pd (100) face is larger
than that of on the Pd (111) face, indicating the adsorption
configuration of the eAQ molecule on the Pd (100) face is
more stable. More importantly, the distance between the C/O
atom in the C=O bond of eAQ and the nearest Pd atom
(2.19/2.18 Å) on the Pd (100) face is much closer than the
that of the Pd (111) face (2.29/2.85 Å) indicated that the
ability of Pd (100) face to activate the eAQ molecule are
stronger. Further, the activation ability of the Pd (100) and
Pd (111) to activate C–O and C=C bonds of eAQH2, which
is the hydrogenation product of eAQ, was also studied to
explore the crystal-face effect of the excessive hydrogena-
tion. The changes of each C=C bond length in aromatic on
the Pd (100) face (Δ < 0.03 Å) are more minor than that on
the Pd (111) face (Δ > 0.05 Å), demonstrating that the (111)
face are more favored in the activation of C=C bonds in
eAQH2, whereas, the changes of the two C-O bonds length
on two crystal face shows little difference (Δ≈0.06/0.03 Å),
119
catalysts, the La loading among 0% to 3.0% (C) [14]; The data of
H2-chemisorption, cm3g−1 STP, and the corresponding calculated, 10
[19] Ni atoms gCAT−1 (D) [14]
indicating the activation ability towards C-O in the eAQH2
between two Pd face are similar.
The degradation process of the main product of the eAQ
hydrogenation, eAQH2, was reported by Drelinkiewicz
group [9]. Besides the H4eAQH2, one of the active quinones,
the obtained eAQH2 is transformed into the intermediate
product and eAN, in which the former will also transfer to
eAN during the catalytic process over the Pd/Al2O3 catalyst.
More importantly, the transformation of eAN to by-products
proceeds even before the complete consumption of eAQH2,
whereas the hydrogenation of the second aromatic ring pro-
ducing fully saturated non-active H8eAQH2 is observed only
after complete consumption of hydroquinone eAQH2. The
experimental result explains to a certain extent that main-
taining a low eAQ conversion is beneficial to the keep of the
high selectivity in industry production. The more refined
hydrogenation process for the eAQ and the hydrogenated
products was studied by DFT calculation [17]. As shown in
Fig. 2C, the O atoms in the C=O bonds of the eAQ molecu-
lar are hydrogenated to produce eAQH2 with an activation
barrier of 16.1 kcal/mol. In comparison, the activation bar-
rier for the hydrogenation of eAQH2 to the hydrogenated
intermediate is 26.8 kcal/mol, which is much higher than
that of the main reaction. Therefore, the results of the DFT
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120
Fig. 2 TEM and the corresponding HRTEM images of Pd nanocrys-
tals: (a) cube, (b) octahedron. The insets show the edge length distri-
bution, structural diagram, and FFT pattern (A) [9]; Optimized struc-
tures of eAQ adsorbed on the (a) Pd (100) and (b) Pd (111) surfaces.
calculation reveal that the advantage of the Pd-based cat-
alysts in the eAQ selective hydrogenation lies in its good
selectivity towards the activation of C=O bonds. However,
the calculation results also pointed out that the activation
barrier of the dehydrogenation of eAQH2 is 16.2 kcal/mol,
indicating that the formation of eAN and the corresponding
degradation products is more accessible, which can explain
the appearance of experimentally observed degradation
products during the long reaction time.
2.2.2 Supported Pd-Based Bimetallic Catalysts
Although many efforts have been made to fabricate the mon-
ometallic Pd catalyst with improved catalytic performance,
the degradation products (eAN, H8eAQ et al.) are inevita-
bly produced. Thus, more works were explored to fabricate
the catalyst with high activity and selectivity towards active
quinones. Tailoring the composition and morphology of the
active component plays an essential role in incrementing
13
C. Miao et al.
The Eads = -(Etotal-EeAQ-Ecatalyst) (B) [9]; Optimized structures and rel-
ative activation barrier for the hydrogenation of (a) eAQ, (b) eAQH2,
and the (c) dehydrogenation of eAQH2 on the Pd surface (C) [17].
The unit is Å and kcal/mol
catalytic performance. Bimetallization may offer opportu-
nities for synergistic inter-metallic interactions so that it
exhibits advantages over the monometallic catalyst. Hong
et al. have reported PdIr/Al2O3 bimetallic catalysts for eAQ
hydrogenation [24]. Detailed studies have shown that the
strong interaction between Pd and Ir benefits the dispersion
of Pd, and the added Ir atoms isolate contiguous Pd sites.
Therefore, the bimetallic catalyst possesses more isolated
Pd sites. Moreover, the strong interaction promotes the
electron transfer from Pd to Ir, and thus the Pd sites with
lower electron density are obtained, as shown in Fig. 3A.
Profit from the synergistic effects between Pd and Ir, the
bimetallic catalyst affords significantly higher H2O2 yields
than the monometallic Pd catalyst, while the concentration
of H4eAQ is also much lower. The enhanced activity can
be attributed to increased Pd sites that provide more active
sites for eAQ. The preferred selectivity can be attributed to
the improved electronic effect that facilitates the desorption
of eAQH2. A series of PdRu/Al2O3 bimetallic catalysts with
The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen…
Fig. 3 The XPS spectra (a) of PdIr catalysts and (b) the proposed
model for the eAQ hydrogenation mechanism over the PdIr alloy
catalyst (A) [24]; the H2-TPD patterns of the PdRu samples (a) and
enhanced activity and high selectivity in the eAQ hydro-
genation process was reported by Han group [26]. Besides
the geometric and electronic effects, they were surprised to
find that the bimetallic system shows stronger hydrogen des-
orption behavior (as shown in Fig. 3B) that may be devoted
to enhancing activity. More importantly, the Ru4+ sites with
the electrophilic characteristic may act as the active sites
for the adsorption and activation of C=O bonds on the eAQ
molecule through the lone electron pair of the oxygen atoms,
known as the “electrophilic C=O activation” mechanism,
which can favor the hydrogenation of C=O. Therefore, the
PdRu/Al2O3 bimetallic catalyst shows superior performance
for eAQ hydrogenation.
As an industrialization-oriented catalytic reaction, the
economy of the catalyst is an important aspect to be con-
sidered. For the Pd-based catalysts, the effective substitu-
tion of Pd has always been a hot topic in this field. More
economical bimetallic catalysts were thus fabricated for
the application in the eAQ selective hydrogenation pro-
cess. Wang et al. reported more economical bimetal-
lic Pd-based catalysts, such as PdAg, PdCo, and PdCu
bimetallic catalysts, and the effect of the mass ratio of the
121
(b) the proposed mechanism of promoting effect of a second metal in
bimetallic PdRu catalyst and the preferential modes of eAQ activation
on the surface (B) [26]
second metal and the reduction temperature on the cata-
lytic performance has also been explored [18]. As shown
in Fig. 4A, when the M/Pd ratio = 0.25, the bimetallic
catalysts show improved catalytic performance. However,
the reaction rate decreases with the further increasing the
addition amount of the second metal (M/Pd ratio > 1).
More interestingly, the catalytic activity of bimetallic cata-
lysts (PdAg and PdCo catalysts) reduced by hydrogenation
at low-temperature increases by order of magnitude com-
pared to Pd/Al2O3 monometallic catalyst. In contrast, the
bimetallic catalysts reduced at high temperatures give the
opposite results. The superior catalytic performance is due
to the synergistic effect of the Pd-Mα+ structure, which is
induced by the low reduction temperature. Kinetic analysis
indicates that the Pd-Mα+ structure could enhance the sur-
face reaction of eAQ hydrogenation. Compared with the
monometallic catalysts, the surface reaction rate constant
(k*) of PdCo and PdAg bimetallic catalysts substantially
increases from 0.74 mol/L/min to 5.58 mol/L/min and
5.06 mol/L/min, respectively. It is worth mentioning that
the strong repulsion between the aromatic furan ring and
Cu atoms is induced by the overlap of the anti-bonding
13
122
Fig. 4 Reaction rate (r) of eAQ hydrogenation over the catalysts reduced in H2 at 80 °C and 310 °C, and the reaction conditions are listed in
Table 1 (A) [18]; the DFT optimized structure of eAQ adsorbed on Pd (111), Pd3Ni1 (111), Pd3Fe1 (111) and Pd3Cu1 (111) (B) [19]
orbital of the aromatic ring, and the 3d band of the Cu
atoms might be responsible for the poor catalytic perfor-
mance of PdCu bimetallic catalysts. Lei et al. reported
the PdNi, PdFe and PdMn bimetallic catalysts with the
enhanced activity (TOF = 1.21, 0.99 and 0.78 s −1) and
selectivity (active quinones: 95.3%, 80.6% and 63.7%) in
contrast of Pd catalyst (TOF = 0.69 s−1; active quinones:
42.2%) [19]. The DFT calculations were further conducted
to investigate the effect of the bimetallic catalyst on the
eAQ adsorption and activation. Compared with the Pd
monometallic catalyst, the adsorption energies of eAQ on
Pd3Ni1, Pd3Fe1, and Pd3Mn1 slightly decreased from 61.4
to 59.9, 50.7, and 44.5 kcal/mol, while the C-O bonds of
the adsorbed eAQ molecular elongated from 1.285/1.286
to 1.313/1.286, 1.291/1.331 and 1.275/1.341 Å, respec-
tively. It indicated that the addition of second metal (Ni,
Fe, and Mn) weakened the adsorption of the benzene rings
and enhanced the binding of the carbonyl group of eAQ
molecular. As for the PdCu catalyst, although the adsorp-
tion energy changes a little more, the C-O bonds of the
adsorbed eAQ are almost unchanged. This indicates the
addition of Cu is attributed to the inhibition of adsorption
13
C. Miao et al.
of eAQ, which is unfavorable for the hydrogenation of
C=O groups and leads to lower catalytic activity.
In addition to the composition of bimetallic catalysts,
the diverse structure with the same composition also sig-
nificantly impacts the catalytic performance of the eAQ
hydrogenation. You et al. prepared a series of bimetal-
lic PdAu bimetallic catalysts with different structures by
changing the loading sequence of Pd and Au (shown in
Fig. 5A) [5]. The Pd 3d spectra of all bimetallic catalysts
show a shift towards lower binding energy than the mon-
ometallic Pd catalyst due to the charge transfer caused
by the inter-metallic interactions between Au and Pd
atoms. Moreover, the addition of Au benefits the reduc-
tion of Pd 2+, elevating the ratio of Pd 0. Thus, the Pd/
Au/Al2O3 and Au/Pd/Al2O3 catalysts with more exposed
Pd 0 sites show higher hydrogenation efficiency (14.27
and 12.79 g/L) and selectivity towards active quinones
(99.59% and 98.16%) than Pd/Al 2O3 catalyst (12.04 g/L
and 96.33%). However, the Pd@Au/Al2O3 catalyst exhib-
its a bimetallic CoreAu-shellPd structure with lower disper-
sion in which fewer Pd0 atoms are exposed on the surface.
Therefore, although the Pd@Au/Al2O3 catalyst possesses
The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen…
Fig. 5 HRTEM image of Pd/Au/Al2O3 (a), Au/Pd/Al2O3 (b), and
Pd@Au/Al2O3 (c) catalysts, d is the average particle size (A) [5];
HRTEM image of PdIr mecrocrystals (a), the grain boundaries (b)
better selectivity (97.76%) due to the preferred elec-
tronic structure, it shows lower hydrogenation efficiency
(11.21 g/L) owing to the lack of active sites. Li group also
fabricated PdIr mesocrystal catalyst with enhanced cata-
lytic performance, compared with the PdIr alloy catalyst,
by tuning the synthetic conditions for the eAQ hydro-
genation process [25]. Profit by the abundant defect sites
at the grain interface of the mesocrystal catalyst (shown
in Fig. 5B), the hydrogen activation capacity is highly
improved, which is the main reason for preferable activity
and selectivity.
Overall, various metal catalysts were applied in the
selective hydrogenation of eAQ, especially the Pd-based
catalyst, and most of them showed excellent catalytic
performance. The effect of the active metals on catalytic
performance can be concluded into two aspects: optimiz-
ing the activation behavior of eAQ molecules, includ-
ing creating more adsorption sites for eAQ molecules,
fabricating profitable electronic structure for the C=O
bonds activation; enhancing the hydrogen activation/dis-
sociation ability. However, the cost of Pd-based metal
catalysts was high, and the degradation products are inev-
itably even on the most selectable motivation. Therefore,
the preparation of highly selective and active catalysts
with high economy always focuses on the eAQ selective
hydrogenation field.
123
caused by grain rotation in the mecrocrystals and H2-TPD profiles of
PdIr alloy catalyst and PdIr mesocrystal catalyst (c) (B) [25]
3 The Effect of Supports on Catalytic
Performance
As the component of a supported metal catalyst, supports
are generally considered an integral part of the immobili-
zation and dispersion of active metals. However, increas-
ing studies have found that the nature of support also plays
a vital role in the catalytic reaction. The performance of
the catalysts can be enhanced by regulating the surface
properties of support, such as acidity and alkalinity. Simul-
taneously, for some catalytic systems with apparent mass/
heat transfer resistance, the pore structure and morphology
control are vital for optimizing catalytic performance. The
catalytic performance of the Pd catalyst supported on dif-
ferent supports is listed in Table 2.
3.1 Surface Acidity and Alkalinity
As illustrated above, the electron-enriched metal sites can
act as the adsorption sites for the eAQ molecular, which
will significantly enhance the catalytic performance. How-
ever, some acid/basic/metal sites on the support surface
may play the same role in adsorption and auxiliary activa-
tion of reactants. Spherical Pd/SiO2-Al2O3 catalysts with
13
 Table 2 Representative results for the selective hydrogenation of eAQ over supported catalyst
124
Entry Catalyst Reaction conditions Selec. eAQ Selec. H4eAQ Selec. Deg Activity Ref.
o
T ( C) PH2 (Mpa) Solvent Catal. Cons. (g) Pd loading (%)

13
1 Pd/Al2O3 50 – TOP + TMB 10 0.30 – – – 8.5a [29]
2 Pd/2wt%-SiO2-Al2O3 50 – TOP + TMB 10 0.30 – – – 8.7a
3 Pd/5wt%-SiO2-Al2O3 50 – TOP + TMB 10 0.30 – – – 9.0a
4 Pd/8wt%-SiO2-Al2O3 50 – TOP + TMB 10 0.30 – – – 10.1a
5 Pd/Al2O3-Na2SiO3-Sh 50 0.5 TOP + TMB – 1.04 – 0.294 2.53 70b [23]
6 Pd/Al2O3-Na2SiO3-Lg 65 0.5 TOP + TMB – 0.81 – 0.153 1.56 68b
7 Pd/Al2O3-Na2SiO3-Vc 65 0.5 TOP + TMB – 0.70 – 0.342 2.53 74b
8 Pd/Al2O3-Na2SiO3-Vc 65 0.5 TOP + TMB – 1.20 – 0.353 2.64 –
9 Pd/Al2O3-Na2SiO3-Vc 65 0.5 TOP + TMB – 1.60 – 0.342 2.80 –
10 Pd/Al2O3-Na2SiO3-Vc 65 0.5 TOP + TMB – 2.00 – 0.377 2.57 –
11 Pd/ZrO2-Al2O3 45 0.2 – – 0.3 – – – 9.11a [30]
12 Pd/Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 1.29 0.29 76c [9]
13 Pd/Li-Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 0.78 0.30 100c
14 Pd/Na-Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 0.59 0.25 146c
15 Pd/K-Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 0.54 0.18 143c
16 Pd/0.5Cs-Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 0.59 – 86c
17 Pd/Cs-Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 0.44 0.10 160c
18 Pd/4Cs-Al2O3 55 – Xylene + diisobutyl carbinol 0.45 2.00 – 0.20 0.05 180c
19 Pd/Al2O3 40 30d Xylene + Octanol 0.1 0.50 0.89e 0.01e – [21]
20 Pd/Al2O3-HCl 40 30d Xylene + Octanol 0.1 0.50 0.96e 0.02e –
21 Pd/Al2O3-NaOH 40 30d Xylene + Octanol 0.1 0.50 0.97e 0.04e –
22 Pd/Al2O3-Na2CO3 40 30d Xylene + Octanol 0.1 0.50 0.98e 0.02e –
23 Pd/Al2O3-Na2SiO3 40 30d Xylene + Octanol 0.1 0.50 0.99e 0.03e –
24 Pd/Al2O3 60 0.3 TOP + TMB 0.6 0.50 94.5 – 5.5 7.0a [31]
25 Pd/Al2O3-1P 60 0.3 TOP + TMB 0.6 0.49 96.0 – 4.0 9.8a
26 Pd/Al2O3-5P 60 0.3 TOP + TMB 0.6 0.54 96.0 – 4.0 5.5a
27 Pd/Al2O3 50 – TOP + TMB 5.0 0.30 82.0 0.10e 0.045e 3.3 [32]
28 Pd/AAO-10.3 nm 50 – TOP + TMB 5.0 0.29 93.0 0.01e 0.013e 10.1
29 Pd/AAO-14.5 nm 50 – TOP + TMB 5.0 0.28 96.0 0.008e 0.008e 8.4
30 Pd/AAO-24.5 nm 50 – TOP + TMB 5.0 0.29 97.0 0.004e 0.002e 6.8
31 Pd/AAO-6 μm 50 – TOP + TMB 5.0 0.29 96.0 0.003e 0.004e 6.7
32 Pd/AAO-12 μm 50 – TOP + TMB 5.0 0.29 97.0 0.003e 0.005e 7.8
33 Pd/AAO-18 μm 50 – TOP + TMB 5.0 0.29 97.0 0.004e 0.01e 8.2
34 Pd/NiO/Al-1 50 – TOP + TMB 5.0 0.0184 99.2 – – 107.5f [33]
35 Pd/NiO/Al-1 50 – TOP + TMB 5.0 0.0686 99.0 – – 21.1f
36 Pd/NiO/Al-1 50 – TOP + TMB 5.0 0.0485 94.5 – – 28.9f

a
The hydrogenation efficiency (g/L). bThe yield of H2O2 (%), which is expressed as the ratio of mol H2O2 to the initial number of mol eAQ in the reactor. cThe reaction time required for 50%
eAQ conversion (min). dThe flow rate of hydrogenation (mL/min). eThe concentration of H4eAQ/degradation (mol/L). fExpressed as the amount of hydrogen peroxide produced per gram of
C. Miao et al.

catalyst per hour (gH2O2/gcat/h)

The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen…
different silica contents have been synthesized by Feng
et al. [28]. As shown in Fig. 6A, the weak acid amount of
silica-modified catalyst is significantly higher than that of
pristine alumina catalyst, while the medium acid amount
decreased. The slight increased total acid amount (sum
of weak and medium acid amount) implies that although
the addition of silica could reduce the intensity of acid-
ity sites, the total acidity of Al2O3 is enhanced with the
increase of silica content. Moreover, the addition of sil-
ica resulted in the increment of surface area due to the
increased phase change temperature of alumina after dop-
ing, which leads to the higher dispersion and active surface
area of Pd. Thus, the preferred hydrogenation efficiency
of SiO2-Al2O3 supported Pd catalysts can be attributed to
parts: the higher specific surface area of support enhances
the dispersion of Pd, resulting in more active centers; the
increased acid sites on the catalyst surface might accel-
erate the hydrogenation rate because it can also act as
the adsorption sites for eAQ molecular. The effect of the
silica species modification on the degradation of active
quinones was further studied [22]. The addition of silica
species influences the activity in reducing eAQ to eAQH2
and exhibits an essential role in consuming eAQH2. The
hydrogenolysis reactions of C-O bonds in the eAQH2 and
the tautomerization of eAQH2 to oxanthrone (OXO) are
restricted on the silica-modified catalysts. Therefore, the
degradation product is not detectable. Li and Sun group
reported the CeO and ZrO doped alumina supported Pd
catalysts with increased surface acidity [29, 33]. After
doping, the Lewis acid sites are formed due to the positive
charge imbalance resulting from the Zr4+/Ce4+ inserted
into the Al3+ lattice. Besides improving the catalytic per-
formance, the crushing strength and thermal stability of
doped catalysts significantly improve, leading to enhanced
catalytic stability.
Furthermore, Huang and Li et al. studied the effect of the
pretreatments of Al2O3 supports with HCl, NaOH, Na2CO3,
and Na2SiO3 on the catalytic performance [20]. Compared
with the unpretreated support (shown in Fig. 6B), the pre-
treated alumina-supported catalysts showed much higher
H2O2 yield, and the formation of degradation products was
also strongly inhibited. This result reminds us that not only
the acid modification can promote the activation of eAQ
molecules, but also the alkali modifiers play an essential role
in the hydrogenation of eAQ. The role of the alkali modi-
fiers (Li, Na, K, Cs) in Pd/Al2O3 catalysts for eAQ hydro-
genation was reported by Drelinkiewicz [8]. The alkaline
modifiers exhibit multiple effects on the eAQ hydrogenation
process. As for the activity, the hydrogen uptake rate of the
alkali-modified catalysts in the hydrogenation stage of eAQ
to eAQH2 (before 30 min) increases, whereas the rate in the
“deep hydrogenation” stage remarkably decreases. As for
the selectivity, the enhanced alkalinity of catalysts favors
125
the formation of OXO, the isomer of hydroquinone. And
the conversion of the observed OXO to eAN over the alkali-
modified catalysts is strongly inhibited on alkali-doped cata-
lysts, which greatly enhances the selectivity toward active
quinones. These effects are ascribed to stronger interac-
tions between the alkali-modified catalyst and reagents and
may concern especially the OXO molecule. Moreover, the
nature of the alkali promotes, and its content in the catalyst
is important. The effects will become stronger as the alkalin-
ity of the promoter increases.
3.2 Pore Structure and Morphology of Supports
In the eAQ process, support plays a crucial role in dispers-
ing active components. It significantly affects the improve-
ment of the diffusion process since the main reaction of eAQ
hydrogenation is controlled by mass diffusion. However, the
spherical alumina, widely used as the support in a fixed-bed
process to produce the H2O2, usually suffers from a broad
pore size distribution. And thus, the mass transfer limita-
tion could be substantial, which results in the low catalytic
performance. Some works have revealed the relationship
between the pore structure and catalytic performance and
exploits new supports to enhance mass transfer by eliminat-
ing the transfer resistance. Wang et al. reported a series of
Pd/Al2O3/cordierite monolithic catalysts with different Pd
penetrating depths for the eAQ hydrogenation [34]. Com-
pared with the catalyst with a deeper Pd penetrating depth,
which possesses the longer internal mass transfer distance
for products, the catalyst with less penetrating depth shows
higher activity and selectivity towards active quinones.
Benefit for the enhanced ability for the product desorption
driven by the shorter internal mass transfer distance, the
concentration of H4eAQ over the catalyst with less Pd pen-
etrating depth increased much slower meanwhile the con-
centration of H8eAQ, eAN, and H4eAN shows a similar ten-
dency, compared with the catalyst with deeper penetrating
depth. Li group prepared a Pd/Al2O3 catalyst with optimized
pore structure via template-polymerization method for the
hydrogenation process [35]. Using acrylic ammonium as a
template, the spherical alumina obtained after calculation
shows a much narrower pore size distribution (3–20 nm)
than the unmodified spherical alumina (2–50 nm). Profit
from the more concentrated pore distribution, the surface
area of the supports increased by 30%, leading to higher
Pd distribution after supporting Pd active metals. Thus, the
modified catalyst shows improved hydrogenation efficiency
and catalytic stability.
To explore the effect of pore structure on the catalytic
performance of eAQ more specifically, Hong et al. pre-
pared the anodic alumina oxide (AAO) with controlla-
ble uniform pore size and depths as support (shown in
Fig. 7) for the catalytic hydrogenation process in which
13
126
Fig. 6 The dispersion of palladium, active surface area, analysis of
acid sites, and the hydrogenation efficiency in anthraquinone hydro-
genation on Pd/xwt.%-SiO2-Al2O3 catalysts (x = 0, 2, 5, and 8) (A)
[28]; Effect of pretreatment of the support on the H2O2 yield and the
the AAO support was shaped into θ-ring and then support
Pd nanoparticles [31] . Compared with the spherical Pd/
Al2O3 catalyst, the θ ring-shaped Pd/AAO catalysts show
dramatic, enhanced hydrogenation efficiency and improved
selectivity towards active quinones due to the advances in
mass transfer the θ-ring shape and the uniform cylindri-
cal pores of catalysts. Owing to the confinement effect of
AAO, with the pore size decreasing, the size of Pd parti-
cles filled in the channels became smaller, which enhanced
the activity of eAQ hydrogenation. However, deep-hydro-
genation happened more easily on smaller AAO pores,
resulting in decreased H2O2 productivity. Similar to pore
size, the pore depth of AAO also affects Pd nanoparti-
cle dispersion. The H 2O 2 productivity increased while
selectivity slightly declined as the pore depth increased.
Further, the pore shape of the support determined by the
morphologies also plays a vital role in the mass transfer,
which was also investigated by Li group [32]. As shown
in Fig. 7D-F, three kinds of array-typed NiO/Al materials
13
C. Miao et al.
active anthraquinone content (Conditions: 0.5 wt.% Pd/γ-Al2O3 cata-
lysts 0.1 g, hydrogenated time 1.5 h, working solution volume 10 mL,
H2 flow rate 30 mL/min and temperature 40 °C.) (B) [22]
with morphologies of nest-like, face-to-face packed, and
dandelion-like structures were synthesized as support for
Pd catalysts. Since different morphologies possess differ-
ent pore structures (shown in the insert figure in Fig. 7E),
three catalysts have distinct catalytic performances. On the
basis of ensuring effective collision of reactant molecules,
the outer opening pores (20–100 nm) could decrease dif-
fusion barriers of eAQ/eAQH2, which improves active site
accessibility for eAQ and benefits desorption of eAQH2.
Thus, the catalyst with nest-like and dandelion-like struc-
ture shows enhanced selectivity towards active quinones.
In addition, the interaction between the appropriate weak
basic sites Ni2+-OH with Pd nanoparticles improves the
surface electronic density of active metals, leading to the
enhanced hydrogen activation ability. Therefore, the nest-
like catalyst with the suitable pore structure and surface
acidic/basic property exhibits higher catalytic performance
(space–time yield of 107.5 g/gPd/h, > 99% selectivity of
active quinones).
The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen…
In summary, the regulation of surface acidic/basic prop-
erty and pore structure of spherical alumina support has
always been the focus of the eAQ selective hydrogenation
process. The key to improving the production efficiency
of H2O2 is to optimize the pore structure while ensuring
the uniform and high dispersion of active metals, which
is the guarantees to eliminate the mass transfer resistance
and improve the activity and selectivity. Meanwhile, the
majorization of surface properties should also be consid-
ered, which is one of the factors in improving the intrinsic
activity.
4 Future Perspectives
This review summarizes representative publications in
the recent 20 years about the selective eAQ hydrogena-
tion reactions over the supported metal catalysts, espe-
cially Pd and Ni-based catalysts. The Pd-based supported
catalysts showed higher activity and selectivity towards
active quinones. Meanwhile, they exhibited higher com-
petitiveness compared to other catalysts in the industry.
We also summarize three main catalyst design strategies
from those publications. The first was to create more domi-
nant sites conducive to activating the C=O bond in the
eAQ molecules. The methods include but are not limited
to constructing catalysts with high Pd dispersion, expos-
ing the dominant crystal surface for the reaction of C=O
bonds, and constructing new sites for C=O bond reaction,
such as Mα+. The second one was to adjust the electronic
structure of the active center to realize the preferential
activation of the C=O bond and the timely desorption of
Fig. 7 The cross-section SEM view of AAO support with the 6 μm
pore depth (A) [31]; Top view SEM images of AAO support with
24.5 nm pore size (B) [31]; HRTEM images of Pd particles filled in
127
hydrogenation products, such as the construction of alloy
structure, support doping, etc. The third was to construct
the support with an optimized pore structure, conducive
to the diffusion of reactions and products and reducing
the mass transfer resistance during the catalytic process.
In summary, since the activation of eAQ is the rate-deter-
mining step in the selective hydrogenation process, the
design principle of high catalytic performance catalysts is
the enhance the reaction rate of C=O bond in eAQ molec-
ular while avoiding the deep hydrogenation of C=C bonds
in the benzene ring.
Based on the above literature, the possible reaction
pathway for the preparation of hydrogen peroxide by
anthraquinone process over metal-based catalyst can be
proposed, as shown in Fig. 8. Initially, the C=O bonds
of eAQ molecular connect with the active sites (Ni or
Pd sites, as reported by most of the literature) to form
active intermediates under the effect of the alloy/crystal
plane/metal-support interaction, which is considered the
rate-determining step in eAQ hydrogenation. Then, the H
species are activated over the same active sites or over-
flowed from the Pd surface to attack the intermediates.
Subsequently, the intermediate adsorbed on the active sites
undergoes Pd-Cδ+ bond cleavage, and the O atom of the
activated C=O bonds acts as an acceptor of active H spe-
cies to form the eAQH2 after a sterol rearrangement step.
Finally, oxidation of eAQH2 by O2 results in the formation
of H2O2 and regeneration of the original eAQ.
Although these excellent results were achieved for sup-
ported metal catalysts through these preparation approaches,
some challenges and barriers still exist and need to be solved
in the future.
the internal channels (C) [31]; the SEM images of the top view of
Ni(OH)2/Al-1 (D), Ni(OH)2/Al-2 (E), the insert figure is the pore size
distributions of supports) and Ni(OH)2/Al-3 (F) [32]
13
128
Fig. 8 The possible pathways
for the preparation of hydrogen
peroxide by anthraquinone
process over Pd/MgAl-LDH
catalyst [6]. (The green route
is the eAQ hydrogenation pro-
cess, and the blue route is the
oxidation process) (Color figure
online)
Firstly, accurate identification of the active sites for eAQ
molecular in the catalyst is significant for the distinct under-
standing of the hydrogenation mechanism. As discussed in
parts 2 and 3, some catalysts have shown excellent catalytic
performance in the hydrogenation of eAQ, but the mecha-
nism of the hydrogenation process is still ambiguous. The
unclear identification of active sites makes designing cata-
lysts with higher performance more difficult. Recently, our
group has reported an LDH-derived supported Pd catalyst
with the vacancy-rich sandwich structure (IE catalyst) [6].
Its TOF in the eAQ hydrogenation process is 2.7 times that
of catalyst prepared by the traditional method (IM catalyst),
while the selectivity towards active quinones can maintain
above 99%. The structure–activity relationship and hydro-
genation mechanism are further studied with excellent cata-
lytic performance. Interestingly, the vacancy-riched interface
structure between the active metals and supports is asso-
ciated with the preferred performance (shown in Fig. 9A).
A series of technology prove that the Pd-riched oxygen
vacancy (Vo) interface sites changes the adsorption form
of C=O bonds in eAQ, which is beneficial to the selective
activation of C=O bonds. The effect of the interface site
has also been reported by the Guo group, latterly [23]. The
PdGa bimetallic catalyst with Ga2O3/Pd interface shows
much higher hydrogenation efficiency than the Pd catalyst.
As shown in Fig. 9B, the DFT calculation results indicate
that the C=O bonds of eAQ are strongly adsorbed on the
Ga2O3/Pd interface, which facilitates the activation of eAQ.
The above researches remind us that the functions of active
metals and supports are usually not separated from the sup-
ported catalysts. For the selective eAQ hydrogenation reac-
tion, which requires multiple sites (metal sites for the activa-
tion of hydrogen, acid/base/metal sites for the activation of
the C=O bond), the interface structure, especially the unsat-
urated sites in the interface, might be the real active reaction
sites. Those works remind us that the synergistic effect of the
multi-active sites in the catalyst should be considered in the
catalyst design process for eAQ hydrogenation.
13
C. Miao et al.
Secondly, novel support materials with the optimized
pore structure and appropriate acid properties need to be
explored. As illustrated above, alumina is the most widely
used support for the eAQ selectivity hydrogenation process
in the industry. However, the poor structure and lack of sur-
face inhibit the improvement of the catalytic performance.
Although some related works have reported the performance
of alumina-supported catalysts can be enhanced by some
methods, such as modification, doping, or template addi-
tion, few of them are suitable for the application in indus-
trial H2O2 production. Therefore, it is desired to develop
a method for the preparation of novel support materials
that can meet the growing needs of the industry. Besides
the pore structure and the surface acid/basic properties,
the hydrophobicity of support has also been another fac-
tor affecting the rate and selectivity. Wang et al. found that
the Pd/SBA-15 catalyst with high hydrophobicity exhibited
a high hydrogenation rate and selectivity towards eAQH2
[36, 37]. The hydrophobicity of the catalyst, which is con-
ducive to the adsorption of eAQ from the working solution,
might be one of the reasons for the superior catalytic perfor-
mance. Recently, a series of modified Pd/SBA-15 catalysts
with excellent catalytic performance, which combines the
advantages of hydrophobicity, surface acidity, and long-
range ordered pore structure (shown in Fig. 10), is further
reported by them [10]. Those works provide a novel direc-
tion for designing the high-performance eAQ selectivity
hydrogenation catalyst for industrial production.
Last but not least, the more economical catalysts with
high catalytic performance are desirable for industrial appli-
cations. To keep the excellent catalytic performance of eAQ
hydrogenation and reduce the cost of catalyst production as
much as possible, the Co-active components are added to the
catalyst by supporting doping or the alloying of the active
metal. The main function of the Co-active component is to
adjust the hole number of d-band of active metal to make it
adaptive to the number of electron transfers during the reac-
tion process to improve the catalytic performance. In recent
The Metal-Based Catalysts for Selective Hydrogenation of Anthraquinone to Produce Hydrogen… 129

Fig. 9 The possible pathways for the anthraquinone hydrogenation process over the IE-Pd/MgAl-LDH catalyst (A) [6]; The possible structures
optimized by DFT of EAQ adsorbed on Pd (111) and Ga2O3/Pd (111) (B) [23]

Fig. 10 The initial hydrogen

consumption rate for eAQ
hydrogenation and selectivity
to eAQH2 over (NH4)3AlF6
treated Pd/SBA-15, unmodified
Pd/SBA-15 and (NH4)2SiF6
treated Pd/SBA-15 catalysts,
and the proposed model for the
eAQ hydrogenation mechanism
over the modified Pd/SBA-15
catalysts [36, 37].

years, the price of precious metals has soared, and the cost catalysts, some cheaper components, such as Au, Ir, Ru, Co,
of Pd has increased the most. Under the current situation, to and Cs, etc., are applied to the Pd-based catalysts. However,
improve the catalytic performance of “expensive” Pd-based among all those Co-active components, the better catalytic

13
130
performance means a higher cost of catalyst, which the
related literature can clearly conclude. Therefore, to further
improve the industrial utilization of bicomponent catalysts,
more economical catalysts should be fabricated. Recently,
Guo and Belykh groups developed the P-modified alumina-
supported Pd catalyst and Pd-P catalyst for the eAQ hydro-
genation, respectively [3, 30]. The co-active component, P,
is much “cheaper” than the other metal components, show-
ing equal or better co-catalysis, indicating the potential for
industrial application and cost reduction. The above results
encourage us to focus on the no-metal modifier. Moreover,
some research suggested that the no-metal incorporation
(such as S, N, C, etc.) could improve the surface acid–base
property and increase the reducibility of Pd nanoparticles,
which enhanced the catalytic performance in the hydrogena-
tion process [38–41] s. Therefore, the non-metal-doped Pd
catalyst may become a potential candidate for eAQ hydro-
genation. Moreover, few investigations about no-metal modi-
fiers for eAQ hydrogenation have been published.
Acknowledgements The authors gratefully acknowledge the funding
of the National Natural Science Fundation of China (22202235).
Author contributions CM, as the first and corresponding author, wrote
this manuscript and led the discussion,TH and RZ contribute to a part
of the discussion and future perspectives,GZ makes contributions to
selecting the topic and gives specific guidance during the manuscript
preparing stage,Jieguang Wang gives guidance on manuscript writing.
Declarations
Competing interest The authors declare no competing interest.
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