Bioinspired Hollow Nanoreactor: Catalysts that Carry Gaseous Hydrogen for Enhanced Gas-Liquid-Solid Three-Phase Hydrogenation Reactions

Article abstract of DOI:10.1002/cctc.201902049

For conventional gas-liquid-solid three-phase heterogeneous hydrogenation reactions, hydrogen must be dissolved into the solvent to be a participating reactant, restricting the reaction rates. In this study, we demonstrate that gaseous hydrogen could be directly involved in gas-liquid-solid hydrogenation reactions through a bioinspired hollow nanoreactor with superaerophilic surface to enhance the reaction rates. We produce Pd@meso-SiO₂ hollow nanoreactor, whose external surface is modified with perfluorodecyltriethoxysilane (PFDTS). In aqueous solutions, H₂ gas could be spread quickly on the surface and stored in the cavity of hollow spheres, and participated in hydrogenation reactions, thereby enhancing H₂ concentration around Pd nanoparticles. In hydrogenation of olefin reactions, such three-phase interface allows rapid and direct transportation of H₂ bubbles to the surface of Pd nanoparticles rather than through diffusion of dissolved H₂ in liquid phase, leading to an enhanced catalytic rate. This strategy is expected to be useful for designing and developing new catalytic systems of gas-liquid-solid three-phase reaction.

Full text of DOI:10.1002/cctc.201902049

Accepted Article
Title: Bioinspired hollow nanoreactor: catalysts that carry gaseous
hydrogen for enhanced gas-liquid-solid three-phase
hydrogenation reactions
Authors: Wei-Guo Song, Zhaohua Li, Zhongpeng Zhu, Changyan Cao,
and Lei Jiang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201902049
Link to VoR: http://dx.doi.org/10.1002/cctc.201902049
A Journal of
www.chemcatchem.org

10.1002/cctc.201902049
ChemCatChem
COMMUNICATION
Bioinspired hollow nanoreactor: catalysts that carry gaseous
hydrogen for enhanced gas-liquid-solid three-phase
hydrogenation reactions
Zhaohua Li,[a,c] Zhongpeng Zhu,[b,c] Changyan Cao*[a,c], Lei Jiang[b,c] and Weiguo Song*[a,c]
Abstract:
For
conventional
gas-liquid-solid
three-phase
In order to address such mass transfer issue, some original
approaches including Pickering emulsions and microfluidic
devices have been developed for the water/oil bi-phase
system.[5] For gas-liquid-solid three-phase reactions, it is
desirable for gas phase reactant to directly be adsorpted onto
the catalyst. However, allowing liquid and gas reactants to
simultaneously approach catalyst surface is rarely reported in
heterogeneous catalyst, as it required precise control of the
wettability of catalyst surface against liquid and gas
simultaneously.[6] The key feature of such wettability matched
catalyst is the presence of both aerophilicity and hydrophilicity
on the same catalyst.
Underwater superaerophilicity was first reported and proposed
when air bubbles quickly bursting within several milliseconds on
a “self-cleaning” lotus leaf.[7] The superaerophilicity of a lotus
leaf in water is attributed to the unique micro/nanohierarchical
rough structures and the chemical component with low interface
energy. Air pockets captured in the nanostructure of the lotus
leaf could easily coalesce with air bubbles, and microstructure
provides enough space for air-bubble spreading. Therefore, gas
bubbles completely spread on superaerophilic surface within
very short time, and thus high concentration of gases on solid
surface could be directly obtained while the solid particle is in
the water. Inspired by this gas storage mechanism in water,
researchers have fabricated artificial underliquid superaerophilic
materials and used in electrocatalysis[8] and photocatalysis[9] to
enhance the gas concentration on catalysts surface and catalytic
efficiency.
In this work, we report a bioinspired hollow nanoreactor with
superaerophilic/hydrophobic surface outside the shell. Such
structure allows gas reactant to be stored inside the hollow
space, and directly participate the reaction on shell, where active
sites are located. Such design will enhance the catalytic
efficiency in gas-liquid-solid three-phase hydrogenation
reactions. As shown in Scheme 1, through surface modifying
with PFDTS, Pd@meso-SiO2@PFDTS hollow nanoreactor with
superaerophilic surface is obtained. Because of the hydrophobic
property of PFDTS layer, water cannot penetrate into the
nanoreactor while H2 could be spread quickly and stored in the
cavity, thereby enhancing H2 concentration around Pd
nanoparticles. At the same time, liquid olefin reactant molecules
could wet the PFDTS layer and across mesoporous SiO2 layer
to reach active Pd nanoparticles, thereby resulting in the
formation of gas-liquid-solid three-phase interface around Pd
nanoparticles for catalytic reactions. Such three-phase reaction
interface allows the rapid and direct transportation of H2 bubbles
to the surface of Pd nanoparticles rather than diffusion through
dissolution H2 in the liquid phase, leading to an approximate
double enhancement of catalytic rate in hydrogenation of
styrene as compared to conventional Pd@meso-SiO2 liquid-solid
diphase reaction system.
heterogeneous hydrogenation reactions, hydrogen must be
dissolved into the solvent to be a participating reactant, restricting
the reaction rates. In this study, we demonstrate that gaseous
hydrogen could be directly involved in gas-liquid-solid hydrogenation
reactions through
a
bioinspired hollow nanoreactor with
superaerophilic surface to enhance the reaction rates. We produce
Pd@meso-SiO2 hollow nanoreactor, whose external surface is
modified with perfluorodecyltriethoxysilane (PFDTS). In aqueous
solutions, H2 gas could be spread quickly on the surface and stored
in the cavity of hollow spheres, and participated in hydrogenation
reactions, thereby enhancing H2 concentration around Pd
nanoparticles. In hydrogenation of olefin reactions, such three-phase
interface allows rapid and direct transportation of H2 bubbles to the
surface of Pd nanoparticles rather than through diffusion of dissolved
H2 in liquid phase, leading to an enhanced catalytic rate. This
strategy is expected to be useful for designing and developing new
catalytic systems of gas-liquid-solid three-phase reaction.
Gas-liquid-solid three-phase catalytic reactions, such as
hydrogenation reaction and oxidation reaction, play important
role in heterogeneous catalysis and have widely applications in
the chemical and pharmaceutical industries.[1] Although
numerous state-of-the-art catalysts with high activity have been
developed, the reaction conditions are usually harsh and
efficiency are still low when compared to homogeneous
reactions, partially because of unmatched mass transfer of
different phases, especially for gas-solid interface.[2] In general,
gaseous reactants are participated in reactions as dissolution
form in the liquid, making gas-liquid-solid three phase reactions
actually liquid-solid biphase reactions. However, the solubility of
gases in liquid are usually quite low,[3] resulting in the low
concentration of gaseous reactants, and thus lowering the
efficiency of gas-liquid-solid three-phase catalytic reactions.[4]
[a]
Z. Li, Dr C. Cao, Prof. W. Song
Beijing National Laboratory for Molecular Sciences, CAS
Research/Education Center for Excellence in Molecular Sciences,
CAS Key Laboratory of Molecular Nanostructure and
Nanotechnology, Institute of Chemistry, Chinese Academy of
Sciences
Zhongguancun North First Street 2, 100190 Beijing (P.R. China)
E-mail: cycao@iccas.ac.cn; wsong@iccas.ac.cn
Z. Zhu, Prof. L. Jiang
Key Laboratory of Bio-inspired Materials and Interfacial Science,
Technical Institute of Physics and Chemistry, Chinese Academy of
Sciences
Zhongguancun East Road 29, 100190 Beijing (P.R. China)
Z. Li, Z. Zhu, Dr C. Cao, Prof. L. Jiang, Prof. W. Song
University of Chinese Academy of Sciences
100049 Beijing (P.R. China)
[b]
[c]
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902049
ChemCatChem
COMMUNICATION
H2
H2
H2
H2
H2
H2
H2
H2
H2
H2
H2
gas
H2
H2
H2
H2
H2
H2
H2
H2
H2
H2
Water
SiO2
PFDTS
Aerophobic Water
Pd NPs
Superaerophilic
Reactant
Water
H2
DissolvedH2
Scheme 1. Schematic illustration of gas-liquid-solid three-phase reaction
interface.
Figure 1. TEM images, water contact angles and H2 bubble adhesion
behaviours of Pd@meso-SiO2 (a, c, d) and Pd@meso-SiO2@PFDTS (b, e, f).
Pd@meso-SiO2 hollow nanoreactor with Pd nanoparticles
located on the inside wall was first prepared according to our
previous method,[10] which exhibited hydrophilic property in air
with water contact angle of 6.3º (Figure 1c). After surface
modifying with PFDTS, Pd@meso-SiO2@PFDTS hollow
nanoreactor showed hydrophobic surface with water contact
angle of about 146.9º (Figure 1e). Energy dispersive
spectroscopy (EDS) mapping showed that fluorine was uniformly
distributed on the surface of Pd@meso-SiO2@PFDTS (Figure
S1), indicating uniform PFDTS modification on external surface.
Compared to Pd@meso-SiO2 (844 m2 g-1), the BET surface area
of Pd@meso-SiO2@PFDTS decreased to 601 m2 g-1 due to the
PFDTS coating (Figure S2). All these results suggested that
PFDTS was successfully coated on the surface of Pd@meso-
SiO2 and Pd@meso-SiO2@PFDTS hollow nanoreactor with
hydrophobic surface was prepared.
Table 1. Structural parameters and catalytic properties of different kinds of
catalysts for hydrogenation of styrene
Pd content Pd dispersion Conv. Time TOF
Catalyst
(wt%)
(%)
(%) (min) (h-1)
Pd@meso-SiO2
3.0
3.2
2.8
71
93
85
81
30
30
30
10
3148
6733
5221
1173
Pd@meso-SiO2@PFDTS
2.1
C/Pd@meso-SiO2@PFDTS 2.1
3.3
meso-SiO2/Pd
3.0
29.4
meso-SiO2/Pd@PFDTS
Pd/C
2.5
4.3
28.0
21.0
64
90
10
10
1168
1273
Pd/C@PFDTS
3.4
19.4
52
10
1007
Reaction conditions: catalyst (5 mg), styrene (0.1 mmol), mesitylene (0.1
The aerophilic/aerophobic properties of both unmodified
mmol), H2O (4 mL), 35 ℃, H2 balloon.
Pd@meso-SiO2
and
modified
Pd@meso-SiO2@PFDTS
underwater were then studied. Due to its hydrophilic surface, H2
bubble showed “pinning” state for as long as 30 seconds on
unmodified Pd@meso-SiO2 (Figure 1d). For comparison, after
PFDTS modification, H2 bubble exhibited “bursting” behavior and
could be completely spread in about 107 ms (Figure 1f),
indicating the surface of Pd@meso-SiO2@PFDTS was
superaerophilic. In this case, H2 could be spread quickly and
stored in the cavity of the hollow structure, thereby enhancing
the H2 concentration around Pd nanoparticles, which should be
favorable for catalysis.
Hydrogenation of styrene was first selected as the model
reaction to investigate the performance of catalysts before and
after modification. Since only accessible Pd can be regarded as
active sites, temperature programmed desorption with CO (CO-
TPD) as probing molecule was used to determine the dispersion
of Pd on these catalysts. All structural parameters and catalytic
properties were summarized in Table 1. It can be seen that the
TOF value of the unmodified aerophobic catalyst Pd@meso-
SiO2 was 3148 h-1. By contrast, Pd@meso-SiO2@PFDTS
exhibited higher activity with a TOF value of 6733 h-1 under the
same conditions, more than twice of the TOF value of
Pd@meso-SiO2.
different reaction interfaces. For unmodified Pd@meso-SiO2
catalyst, the hydrophilic surface keeps H2 bubbles kept “pinning”
state, and thereby H2 can only participant in the reaction as the
dissolved species in water, while the solubility of hydrogen in
water is very low at ambient pressure. For comparison, modified
Pd@meso-SiO2@PFDTS with superaerophilic surface in the
reaction system could adsorb H2 quickly and store it in the cavity,
thereby enhancing H2 concentration around Pd nanoparticles. At
the same time, styrene molecules could wet the PFDTS layer
and diffuse across mesoporous SiO2 layer to contact active Pd
nanoparticles, thereby resulting in the formation of gas-liquid-
solid three-phase interface for reaction. Such three-phase
reaction interface allows the rapid and direct transformation of
H2 bubbles to the surface of Pd nanoparticles rather than
diffusion of dissolved H2 species in water.
It is worth noting that the cavity of Pd@meso-SiO2@PFDTS
nanoreactor is beneficial for storing and delivering H2 to the
reaction interface. To validate the importance, a controlled
catalyst without cavity while other parameter maintain the same
as Pd@meso-SiO2@PFDTS hollow nanoreactor was prepared
(denoted as C/Pd@meso-SiO2@PFDTS). The detail synthesis
procedures and characterizations were shown in the supporting
information. TEM and EDS mapping images showed Pd
The difference in performance of these two catalysts can be
attributed to their difference surface properties leading to
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902049
ChemCatChem
COMMUNICATION
nanoparticles were located at the inner wall of mesoporous SiO2
and the solid carbon sphere (Figure S3). Water and H2 bubble
contact angle tests confirmed it exhibited similar hydrophobicity
in air (~ ca. 145.7º) and superaerophilicity under water with H2
bubble contact angle of ca. 0º (Figure S4). When used for the
hydrogenation of styrene, the TOF value was 5221 h-1, which is
lower than that of Pd@meso-SiO2@PFDTS. With hollow cavity,
there was larger space for storing H2 gases in Pd@meso-
SiO2@PFDTS nanoreactor for reaction, resulting in higher
catalytic rate.
Table 2. Catalytic activities of Pd@meso-SiO2@PFDTS for hydrogenation of
olefins
In addition, the location of Pd nanoparticles at the inner wall of
the hollow spheres is also very important for Pd@meso-
SiO2@PFDTS hollow nanoreactor. Another controlled catalyst in
which Pd nanoparticles were loaded on the outer surface of
mesoporous hollow SiO2 sphere and then modified with PFDTS
was prepared (denoted as meso-SiO2/Pd@PFDTS). Contact
angle tests confirmed that it also exhibited similar hydrophobicity
in air (~ ca. 154.6º) and superaerophilic under water (Figures
S5e-S5f). When used for the hydrogenation of styrene, the TOF
value was only 1168 h-1, which is one fifth of that of Pd@meso-
SiO2@PFDTS.
On
meso-SiO2/Pd@PFDTS,
since
Pd
nanoparticles were located at the outer surface of the hollow
sphere, most active sites of Pd were covered by PFDTS during
the modification process, resulting in spatial restriction for
relative large styrene molecules. This was further confirmed with
catalyst in which Pd nanoparticles were supported on the
surface of meso-SiO2 hollow sphere without PFDTS modification
(denoted as meso-SiO2/Pd). It can be seen in Table 1,
unmodified meso-SiO2/Pd catalyst showed similar activity (TOF,
1173 h-1) with that of meso-SiO2/Pd@PFDTS. The accessible
Pd active sites and mass transportation on meso-SiO2/Pd were
better than those of meso-SiO2/Pd@PFDTS, but hydrogen
reactant must be dissolved to reach the Pd active sites. Such
trade-off between unmodified meso-SiO2/Pd and modified meso-
SiO2/Pd@PFDTS resulted in low reaction rate for both catalysts.
Therefore, Pd nanoparticles being located on the inner wall of
mesoporous SiO2 is crucial for Pd@meso-SiO2@PFDTS hollow
nanoreactor, where all Pd sites are accessible even after
PFDTS coating.
Based on the above catalysis analysis, the superior catalytic
property of Pd@meso-SiO2@PFDTS hollow nanoreactor for
gas-liquid-solid three-phase hydrogenation reactions can be
attributed to the following three characteristics: (1) the
superaerophilic surface ensures H2 gas to be adsorbed quickly;
(2) the unique hollow structure provides a cavity for gas storage
and ensures sufficient gas concentration for the reaction; and (3)
Pd nanoparticles located on the inner wall of the catalyst.
This stratagy can be expanded for other gas-liquid-solid three-
phase heterogeneous catalysis. For example, Au@meso-
SiO2@PFDTS catalyst was also prepared and used for selective
oxidation of styrene with O2. Au@meso-SiO2@PFDTS exhibited
higher activity with a TOF value of 575 h-1 owing to the
superaerophilic surface, which enables O2 bubbles bursting and
thus enhancing O2 concentration around active sites for reaction
(Figure S9, Table S1).
In summary, we have shown that the catalytic rate of
matched gas-liquid-solid three-phase hydrogenation reactions
could be enhanced through a bioinspired hollow nanoreactor
with superaerophilic surface to rapidly and directly transfer gas
bubbles to the active sites, and thereby enhancing the gas
concentration for the interface reaction.
Experimental Section
Pd@meso-SiO2@PFDTS was further used for hydrogenation
of other olefins, including aromatic olefins, cyclic olefins and an
aliphatic olefin. As shown in Table 2, the superaerophilic catalyst
exhibited excellent catalytic activity for all tested olefins.
Moreover, Pd@meso-SiO2@PFDTS exhibited good recyclability.
As shown in Figure S6, no obvious loss of activity was observed
after five consecutive runs. TEM image and contact angle test of
the recovered catalyst were similar to the fresh one (Figures S7).
In addition, commercial Pd/C and modified Pd/C@PFDTS
catalysts were also test for comparison (Figure S8). The results
showed that the TOFs were obviously lower than that of
Pd@meso-SiO2@PFDTS under the same conditions.
Synthesis of Pd@meso-SiO2@PFDTS.
Pd@meso-SiO2 was first synthesized according to the literature.[10] 10
mg of Pd@meso-SiO2 was dispersed in 4 mL of toluene and sonicated
for 30 min. 20 μL of PFDTS was dispersed in 2 mL of toluene and
sonicated for 30 min. PFDTS/toluene was added to the Pd@meso-
SiO2/toluene and the mixture was stirred for another 30 min. The product
was obtained after centrifugation, washing with ethanol and vacuum
drying.
Hydrogenation of olefins.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902049
ChemCatChem
COMMUNICATION
Catalyst (5 mg), substrate (0.1 mmol), mesitylene (internal standard, 0.1
mmol) and water (4 mL) were added into a 10 mL glass round-bottom
flask. The air in the reactor was replaced by H2. Then the reaction
mixture was stirred in a 35 ℃ water bath for the desired time. After
reaction, the mixture was extracted with ethyl acetate and the catalyst
was separated from the system by centrifugation. The organic phase was
analyzed by a GC (Shimadzu GC-2010) equipped with a flame ionization
detector (FID) and a Rtx-5 capillary column (0.25 mm in diameter, 30 m
in length).
Senthamarai, M. Sohail, A. S. Alshammari, M. M. Pohl, M. Beller, R. V.
Jagadeesh, Chem. Sci. 2018, 9, 8553-8560; e) F. K. Scharnagl, M. F.
Hertrich, F. Ferretti, C. Kreyenschulte, H. Lund, R. Jackstell, M. Beller,
Sci. Adv. 2018, 4, eaau1248; f) S. B. Tian, W. B. Gong, W. X. Chen, N.
Lin, Y. Q. Zhu, Q. C. Feng, Q. Xu, Q. Fu, C. Chen, J. Luo, W. S. Yan, H.
J. Zhao, D. S. Wang, Y. D. Li, ACS Catal. 2019, 9, 5223-5230.
Hydrogen and deuterium, Vol. 5/6 (Ed.: IUPAC Solubility data series),
Pergamon Press, OXford, England, 1981
[3]
[4]
a) D. D. Dionysiou, A. A. Burbano, M. T. Suidan, Environ. Sci. Technol.
2002, 36, 3834-3843; b) A. Mills, J. S. Wang, D. F. Ollis, J. Catal. 2006,
243, 1-6; c) P. Kang, S. Zhang, T. J. Meyer, M. Brookhart, Angew.
Chem. Int. Ed. 2014, 53, 8709-8713; Angew. Chem. 2014, 126, 8853-
8857.
Characterizations.
Transmission electron microscopy (TEM) was carried out on a JEOL
2100F electron microscope operated at 200 kV. The surface area of the
products were measured by the Brunauer-Emmett-Teller (BET) method
using N2 adsorption and desorption isotherms on Micromeritics ASAP
2460 Surface Area and Porosity Analyzer at 77 K. The loading content of
Pd was determined by inductively coupled plasma atomic emission
spectroscopy (ICP-AES, Shimadzu ICPE-9000). The dispersion of Pd
was determined by a chemisorption analyzer (AutoChem Ⅱ 2920). The
water contact angle (WCA) and gas bubble adhesion behavior was
[5]
a) A. Günther, S. A. Khan, M. Thalmann, F. Trachsel, K. F. Jensen, Lab.
Chip. 2004, 4, 278-286; b) J. Kobayashi, Y. Mori, K. Okamoto, R.
Akiyama, M. Ueno, T. Kitamori, S. Kobayashi, Science 2004, 304,
1305-1308; c) Y. H. Yu, L. M. Fu, F. W. Zhang, T. Zhou, H. Q. Yang,
ChemPhysChem 2014, 15, 841-848; d) T. Y. Yang, L. J. Wei, L. Y. Jing,
J. F. Liang, X. M. Zhang, M. Tang, M. J. Monteiro, Y. I. Chen, Y. Wang,
S. Gu, D. Y. Zhao, H. Q. Yang, J. Liu, G. Q. M. Lu, Angew. Chem. Int.
Ed. 2017, 56, 8459-8463; Angew. Chem. 2017, 129, 8579-8583; e) C.
H. Han, P. Meng, E. R. Waclawik, C. Zhang, X. H. Li, H. Q. Yang, M.
Antonietti, J. S. Xu, Angew. Chem. Int. Ed. 2018, 57, 14857-14861;
Angew. Chem. 2018, 130, 15073-15077; f) Q. Q. Zhao, X. Zhao, H.
Peng, Y. Liu, L. H. Yang, J. Sun, L. Yang, Y. F. Shen, Catal. Sci.
Technol. 2019, 9, 3445-3453.
measured by
a contact angle meter (OCA25, Dataphysics). The
conversion of olefins were measured by a gas chromatograph (Shimadzu
GC-2010) equipped with a flame ionization detector (FID) and a Rtx-5
capillary column (0.25 mm in diameter, 30 m in length).
[6]
a) J. P. Huang, F. Q. Cheng, B. P. Binks, H. Q. Yang, J. Am. Chem.
Soc. 2015, 137, 15015-15025; b) Z. H. Li, C. Y. Cao, Z. P. Zhu, J. Liu,
W. G. Song, L. Jiang, Adv. Mater. Interfaces 2018, 5, 1801259; c) Z. H.
Li, C. Y. Cao, Z. P. Zhu, L. Jiang, W. G. Song, ChemCatChem 2019,
10.1002/cctc.201900918.
Acknowledgements
The authors thank the National Natural Science Foundation of
China (NSFC 21932006, 21573245), National Key R&D
Program of China (Grant No. 2018YFA0208504) and the Youth
Innovation Promotion Association of CAS (2017049).
[7]
[8]
J. M. Wang, Y. M. Zheng, F. Q. Nie, J. Zhai, L. Jiang, Langmuir 2009,
25, 14129-14134.
a) Z. Y. Lu, W. W. Xu, J. Ma, Y. J. Li, X. M. Sun, L. Jiang, Adv. Mater.
2016, 28, 7155-7161; b) P. W. Wang, T. Hayashi, Q. A. Meng, Q. B.
Wang, H. Liu, K. Hashimoto, L. Jiang, Small 2017, 13, 1601250; c) W.
W. Xu, Z. Y. Lu, X. M. Sun, L. Jiang, X. Duan, Accounts Chem. Res.
2018, 51, 1590-1598; d) M. Qiao, M. M. Titirici, Chem. Eur. J. 2018, 24,
18374-18384; e) J. Li, G. X. Chen, Y. Y. Zhu, Z. Liang, A. Pei, C. L. Wu,
H. X. Wang, H. R. Lee, K. Liu, S. Chu, Y. Cui, Nat. Catal. 2018, 1, 592-
600; f) M. Qiao, G. A. Ferrero, L. Fernández Velasco, W. Vern Hor, Y.
Yang, H. Luo, P. Lodewyckx, A. B. Fuertes, M. Sevilla, M. M. Titirici,
ACS Appl. Mater. Interfaces 2019, 11, 11298-11305; g) J. Y. Zheng, Y.
H. Lyu, M. Qiao, R. L. Wang, Y. Y. Zhou, H. Li, C. Chen, Y. F. Li, H. J.
Zhou, S. P. Jiang, S. Y. Wang, Chem 2019, 5, 617-633; h) Y. J. Li, H. C.
Zhang, N. N. Han, Y. Kuang, J. F. Liu, W. Liu, H. H. Duan, X. M. Sun,
Nano Res. 2019, 12, 177-182; i) Z. Cai, Y. S. Zhang, Y. X. Zhao, Y. S.
Wu, W. W. Xu, X. M. Wen, Y. Zhong, Y. Zhang, W. Liu, H. L. Wang, Y.
Kuang, X. M. Sun, Nano Res. 2019, 12, 345-349; j) Y. S. Zhang, Z. Cai,
Y. X. Zhao, X. M. Wen, W. W. Xu, Y. Zhong, L. Bai, W. Liu, Y. Zhang, Y.
Zhang, Y. Kuang, X. M. Sun, Nanoscale Horiz. 2019, 4, 490-494.
a) D. Aebisher, D. Bartusik, Y. Liu, Y. Y. Zhao, M. Barahman, Q. F. Xu,
A. M. Lyons, A. Greer, J. Am. Chem. Soc. 2013, 135, 18990-18998; b)
Y. Y. Zhao, Y. Liu, Q. F. Xu, M. Barahman, D. Bartusik, A. Greer, A. M.
Lyons, J. Phys. Chem. A 2014, 118, 10364-10371; c) Y. Y. Zhao, Y. Liu,
Q. F. Xu, M. Barahman, A. M. Lyons, ACS Appl. Mater. Interfaces 2015,
7, 2632-2640; d) X. Sheng, Z. Liu, R. S. Zeng, L. P. Chen, X. J. Feng, L.
Jiang, J. Am. Chem. Soc. 2017, 139, 12402-12405; e) A. Q. Zhu, J.
Zhang, F. Y. Guan, H. M. Tang, X. J. Feng, ACS Omega 2019, 4, 3534-
3538; f) J. X. Liu, R. Li, X. Zu, X. C. Zhang, Y. F. Wang, Y. W. Wang, C.
M. Fan, Chem. Eng. J. 2019, 371, 796-803.
Keywords: Superaerophilic • surface • heterogeneous catalysis
• nanoreactor • bursting
[1]
a) F. Chen, A. E. Surkus, L. He, M. M. Pohl, J. Radnik, C. Topf, K.
Junge, M. Beller, J. Am. Chem. Soc. 2015, 137, 11718-11724; b) M. T.
Zhao, K. Yuan, Y. Wang, G. D. Li, J. Guo, L. Gu, W. P. Hu, H. J. Zhao,
Z. Y. Tang, Nature 2016, 539, 76-80; c) Q. C. Feng, S. Zhao, Y. Wang,
J. C. Dong, W. X. Chen, D. S. He, D. S. Wang, J. Yang, Y. M. Zhu, H. L.
Zhu, L. Gu, Z. Li, Y. X. Liu, R. Yu, J. Li, Y. D. Li, J. Am. Chem. Soc.
2017, 139, 7294-7301; d) D. Formenti, F. Ferretti, F. K. Scharnagl, M.
Beller, Chem. Rev. 2019, 119, 2611-2680; e) D. I. Enache, J. K.
Edwards, P. Landon, B. Solsona-Espriu, A. F. Carley, A. A. Herzing, M.
Watanabe, C. J. Kiely, D. W. Knight, G. J. Hutchings, Science 2006,
311, 362-365; f) N. Agarwal, S. J. Freakley, R. U. McVicker, S. M.
Althahban, N. Dimitratos, Q. He, D. J. Morgan, R. L. Jenkins, D. J.
Willock, S. H. Taylor, C. J. Kiely, G. J. Hutchings, Science 2017, 358,
223-226; g) X. Q. Jia, J. P. Ma, F. Xia, Y. M. Xu, J. Gao, J. Xu, Nat.
Commun. 2018, 9, 933; h) X. J. Zhu, Q. S. Guo, Y. F. Sun, S. J. Chen,
J. Q. Wang, M. M. Wu, W. Z. Fu, Y. Q. Tang, X. Z. Duan, D. Chen, Y.
Wan, Nat. Commun. 2019, 10, 1428.
[9]
[2]
a) L. Kesavan, R. Tiruvalam, M. H. Ab Rahim, M. I. bin Saiman, D. I.
Enache, R. L. Jenkins, N. Dimitratos, J. A. Lopez-Sanchez, S. H. Taylor,
D. W. Knight, C. J. Kiely, G. J. Hutchings, Science 2011, 331, 195-199;
b) R. V. Jagadeesh, A. E. Surkus, H. Junge, M. M. Pohl, J. Radnik, J.
Rabeah, H. M. Huan, V. Schünemann, A. Brückner, M. Beller, Science
2013, 342, 1073-1076; c) X. Wang, W. X. Chen, L. Zhang, T. Yao, W.
Liu, Y. Lin, H. X. Ju, J. C. Dong, L. R. Zheng, W. S. Yan, X. S. Zheng, Z.
J. Li, X. Q. Wang, J. Yang, D. S. He, Y. Wang, Z. X. Deng, Y. Wu, Y. D.
Li, J. Am. Chem. Soc. 2017, 139, 9419-9422; d) K. Murugesan, T.
[10] Z. Chen, Z. M. Cui, P. Li, C. Y. Cao, Y. L. Hong, Z. Y. Wu, W. G. Song,
J. Phys. Chem. C 2012, 116, 14986-14991.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201902049
ChemCatChem
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 2:
COMMUNICATION
Zhaohua Li, Zhongpeng Zhu, Changyan
Cao*, Lei Jiang and Weiguo Song*
H2
H2
H2
H2
H2
H2
H2
H2
H2
Superaerophilic
Modification
Reactant
gas
H2
Page No. – Page No.
H2
H2
H2
H2
Water
Water
Biphase
Water
Triphase
H2
Bioinspired hollow nanoreactor:
catalysts that carry gaseous
hydrogen for enhanced gas-liquid-
solid three-phase hydrogenation
reactions
SiO2
Pd NPs
PFDTS
Dissolved H2
The catalytic rate of matched gas-liquid-solid three-phase hydrogenation reactions
could be enhanced through a bioinspired hollow nanoreactor with superaerophilic
surface to rapidly and directly transfer gas bubbles to the active sites, and thereby
enhancing the gas concentration for the interface reaction.
This article is protected by copyright. All rights reserved.