Surface-Amine-Implanting Approach for Catalyst Functionalization: Prominently Enhancing Catalytic Hydrogen Generation from Formic Acid

Article abstract of DOI:10.1002/ejic.201701108

Highly efficient hydrogen generation from formic acid is a vital process in the clean energy and chemical industry fields. In this work, a universal and efficient surface-amine-implanting approach (SAIA) was proposed to fabricate highly active nanocatalysts with controllable nucleation and growth of small-sized metal nanoparticles (NPs) and desired environments around the active sites. The highly dispersed ultrafine palladium NPs supported by the amine-implanted porous carbon (Pd/APC) exhibited catalytic activity that was increased nearly threefold relative to that of the unmodified catalyst and showed high selectivity for the dehydrogenation of formic acid under mild conditions. Detailed investigations demonstrated that the amine species densely implanted on the pore surface of carbon by hydrothermal treatment with ammonium hydroxide played an important role in dispersing the metal NPs and in promoting the catalytic processes. The presented approach provides powerful entry into highly active catalysts to elicit enhanced catalytic performance for various catalytic reactions and to promote the dehydrogenation of formic acid for practical applications.

Full text of DOI:10.1002/ejic.201701108

A Journal of
Accepted Article
Title: Surface Amine-Implanting Approach for Catalyst
Functionalization: Prominently Enhancing Catalytic Hydrogen
Generation from Formic Acid
Authors: Qi-Long Zhu, De-Jie Zhu, Yue-Hong Wen, Qiang Xu, and Xin-
Tao Wu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201701108
Link to VoR: http://dx.doi.org/10.1002/ejic.201701108

10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
Surface Amine-Implanting Approach for Catalyst
Functionalization: Prominently Enhancing Catalytic Hydrogen
Generation from Formic Acid
De-Jie Zhu,[a,b] Yue-Hong Wen,[a] Qiang Xu,[c] Qi-Long Zhu,*[a] and Xin-Tao Wu[a]
Abstract: The highly efficient hydrogen generation from formic acid
is a vital process in clean energy and chemical industry fields. In this
work, a universal and efficient surface amine-implanting approach
(SAIA) has been proposed for fabricating highly active nanocatalysts
with controllable nucleation and growth of downsized metal
nanoparticles (NPs) and desired environments around the active
sites. The highly dispersed ultrafine palladium NPs supported by the
amine-implanted porous carbon (Pd/APC) exhibited superior
catalytic activity and high selectivity for the dehydrogenation of
formic acid under mild conditions, which afford nearly three-fold
increase of the catalytic activity. Detailed investigation demonstrates
that the amine species densely implanted on the pore surface of
carbon by hydrothermal treatment with ammonium hydroxide play
important roles in both dispersing the metal NPs and promoting the
catalytic processes. The approach provides a powerful entry into
highly active catalysts to elicit enhanced catalytic performance for
various catalytic reactions and promote the dehydrogenation of
formic acid for practical applications.
that the catalytic performance of the immobilized metal NPs
significantly depends on the nature of the support materials. The
rational modification of surface nature of supports not only can
downsize and prevent aggregation of the metal NPs, but also
can optimize their surface electronic properties.[5] Recently, N-
functionalized carbon materials has attracted particular attention
for heterogeneous catalytic applications.[6] The ultrafine metal
NPs can be anchored by the N-sites of the functionalized carbon
to realize higher dispersion, strong synergetic effects between
metal and N-contained sites, which may accelerate the catalytic
7]
reaction rates and improve the reaction selectivity.[2c,
Particularly, the incorporation of the electron-rich and alkaline
amine groups into a carbon may further strengthen these
advantages, which, however, is rarely reported. Although
several efforts have been made for incorporating N-contained
species to carbon supports, the tedious, complex and poor
manoeuvrability of the modification processes restrain the
widespread applications. Therefore, the strategies for facile and
efficient surface implanting of the amine groups onto the pore
surface of carbons for significantly enhancing the catalytic
performance and providing necessary environments for catalysis
are highly desired.
Introduction
Hydrogen is considered as a most sustainable and clean
energy carrier without any damage for environment during use.[5]
However, gaseous hydrogen is hard to be stored by condensing
because of its low boiling point and low gravimetric capacity
under atmospheric conditions.[8, 2b] Liquid chemical hydrides with
high potential for hydrogen storage and generation have been
extensively studied by researchers due to their significant
advantages including high volumetric/gravimetric hydrogen
density, easy transportation, and safety.[9] Formic acid (FA,
HCOOH) has been identified as an excellent liquid hydrogen
carrier due to theirs high hydrogen content (4.4 wt.-%), high
volumetric hydrogen density (53 g L-1), safe storage and
transportation, nontoxicity, excellent stability.[9a] Furthermore, FA
could be yielded in large scale by biomass processes and
catalytic hydrogenation of CO2 generated from industrial
processes.[10] In the past few years, several studies have been
done for the dehydrogenation of FA.[11] However, the challenges
of highly efficient and selective dehydrogenation of FA to H2 +
CO2 without CO generation under ambient conditions still remain.
Hence, it is imperative to design and synthesis of excellent
performance catalysts by a simple and efficient method for
hydrogen generation from FA.
Herein, we reported an simple but effective surface amine-
implanting approach (SAIA) to functionalize the inner surface of
porous carbon, which shows great ability to disperse and
immobilize the ultrafine metal NPs and provides strong metal–
molecular support interactions. The ultrafine Pd NPs
immobilized on the amine-implanted porous carbon (APC)
showed remarkably enhanced catalytic activity for the hydrogen
generation from FA. For optimizing the properties of supports to
realize better catalytic activity, APCs with different contents of
amine groups were prepared by altering ammonium hydroxide
concentration, time and temperature of the hydrothermal
The supported metal nanoparticles (NPs) have been
aroused substantial attention due to their excellent performance
in many fields, especially in heterogeneous catalytic reactions.[1]
There are plenty of researches showing that the metal NP size,
support materials and their synergetic effect are crucial to
facilitate the heterogeneous catalysis system. It is well accepted
that ultrafine metal NPs possess greatly abundant catalytic
active sites due to their small size effect and quantum size
effect.[2] However, their large fraction of exposed surface atoms,
high specific surface area and surface energy make them tend
to aggregation, which is detrimental to their catalytic application.
Several endeavors have been made for preparing and stabilizing
the ultrafine metal NPs; however, the synthesis of ligand-free
ultrafine and stable metal NPs still encounters many challenges
and limitations.[3] Supporting metal NPs on the high-surface-area
supports, such as porous carbon, silica, metal oxides, and
metal‒organic frameworks (MOFs), is an efficient way to support
and disperse the metal NPs.[1d, 4] Moreover, it is widely known
[a]
D.-J. Zhu, Dr. Y.-H. Wen, Prof. Dr. Q.-L. Zhu, Prof. Dr. X.-T. Wu
State Key Laboratory of Structure Chemistry
Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences
Fuzhou, Fujian 350002, P. R. China
E-mail: qlzhu@fjirsm.ac.cn
[b]
[c]
D.-J. Zhu
University of the Chinese Academy of Sciences
Beijing, P. R. China
Prof. Dr. Q. Xu
National Institute of Advanced Industrial Science and Technology
(AIST)
Ikeda, Osaka 563-8577, Japan
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
treatment with ammonium hydroxide, respectively. Detailed
studies imply that the amine species of APC not only can benefit
to the dispersion and downsizing of Pd NPs, but also provide
necessary local environments to promote the deprotonation of
FA, absorption between reactants and catalysts, and thereby the
overall catalytic process.[12]
Coupled Plasma Optical Emission Spectrometer (ICP-OES)
measurement, while 4.37 wt.-% Pd was loaded onto PPC (Table
S2), demonstrating that the implanted amine species can
promote Pd precursors and/or Pd NPs to anchor on porous
carbon supports.[14a] The Pd content of the recycled Pd/APC
catalyst was determined to be 4.58 wt.-%, indicating no leaching
of Pd from catalyst during the catalysis. N2 adsorption/desorption
isotherms were measured at 77 K to determine porous structure
information of the samples. The calculated Brunner-Emmett-
Teller (BET) surface areas of PPC, APC, Pd/PPC and Pd/APC
were 1643, 1483, 1117 and 868 m2 g-1, respectively (Figure S8).
Compared to the carbon supports, the appreciable decreases of
surface areas of Pd/PPC and Pd/APC demonstrate that part of
Pd NPs has been successfully embedded into the pores of
carbon frameworks. In addition, APC shows slightly lower BET
surface areas than that of PPC, which could be attributed to the
incorporation of N-contained species into the pores of carbon by
amine-implanting approach.[12b]
Results and Discussion
Scheme 1. Schematic Illustration for Preparing Pd/APC Nanocatalyst.
The preparation of Pd/APC nanocatalyst by SAIA is
illustrated in Scheme 1. Briefly, 100 mg pristine porous carbon
(PPC) was hydrothermally treated at 200 °C for 10 h with 25
wt% ammonium hydroxide, resulting in the formation of APC.
Then, aqueous K2PdCl4 solution was injected into aqueous
suspension of the resultant APC with ultrasonic treatment for 30
min. Finally, rapid addition of NaBH4 aqueous to the above
suspension afforded the ultrafine Pd NPs immobilized on APC.
For the comparison, Pd/PPC was synthesized by using PPC
instead of APC.
The crystallinity of as-synthesized catalysts was
characterized by powder X-ray diffraction (PXRD) patterns. The
characteristic peaks of Pd0 were observed, indicating that the Pd
NPs were successfully immobilized on porous carbon support
(Figure S1). The X-ray photoelectron spectroscopic (XPS)
measurements confirm that the electron-rich amine species
successfully implanted onto the pore surface of APC. The N 1s
signal at 399.9 eV could be attributed to amine groups (e.g., -
NH-, -NH2) (Figures 1c and S2d).[13] The binding energy for Pd in
Pd/APC at Pd 3d5/2 level is observed at 336.0 eV, which can be
assigned to Pd0, while the Pd 3d5/2 level at 337.5 eV could be
ascribed to Pd2+ caused by oxygenizing of highly active surface
atoms of Pd NPs and/or strong interaction between Pd
precursors and amine species of APC making Pd2+ difficult to be
reduced to Pd0 (Figures 1d and S3b).[14] The Pd loading in
Pd/APC was determined to be 4.62 wt.-% by Inductively
Figure 1. XPS survey spectrum (a) and high-resolution XPS spectra of C 1s
(b), N 1s (c) and (d) Pd 3d for Pd/APC.
The morphologies and microstructures of the as-prepared
catalysts were characterized by transmission electron
microscopy (TEM) and high angle annular dark field scanning
TEM (HADDF-STEM). The TEM and HADDF-STEM images of
Pd/APC show that the Pd NPs well dispersed on the APC
support with rare aggregation and an average particle size of
about 2.3 nm (Figures 2a, c and S4b, d). However, the PPC
supported Pd NPs show a larger average particle size of 3.2 nm
with inferior dispersion (Figures 2b, d and S4a, c). Therefore, it
further demonstrates that the implanting of amine group to
carbon support can downsize the Pd NPs and improve their
dispersion, implying that Pd/APC could exert a better catalytic
activity.
The catalytic performance of the as-synthesized catalysts
for hydrogen generation from FA was tested. Remarkably, the
Pd/APC exhibited tremendously enhanced catalytic performance
for the dehydrogenation of FA at FA-SF system at ambient
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10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
conditions, compared with Pd/PPC (Figure 3). It is worth noted
that the Pd/APC catalyst presented an exceptional TOF of 2230
h–1 at 50 °C, which is almost three times higher than the
counterpart without amine functionality, and among the highest
values ever reported for heterogeneously catalyzed hydrogen
generation from FA at ambient conditions. Such catalyst can
efficiently catalyze the hydrogen generation from FA at relatively
low temperatures, which may significantly decrease costs and
be conveniently operated during industrial process. The average
rates of H2 generation during FA dehydrogenation process could
be calculated as 17 L H2 min-1 gPd-1, corresponding to the
appreciably high energy density (~30 W min-1 gPd-1), which
promisingly facilitates FA as a competitive hydrogen carrier for
practical applications. The catalytic selectivity of Pd/APC for the
dehydrogenation of FA was confirmed by chromatography (GC)
analysis (Figure S9). No CO was detected by GC in the released
gaseous product, indicating highly selective decomposition of FA
to H2 and CO2 over Pd/APC and strictly restraint of the
undesired dehydration pathway (HCOOH → H2O + CO), which
is crucial for its practical applications, such as proton exchange
membrane fuel cells (PEMFCs). The catalyst poison experiment
was conducted and found that the catalytic activity of Pd/APC
decreased sharply after exposure of the catalyst to CO,
suggesting the low tolerance of the catalysts to CO (Figure S17).
Moreover, the catalytic performance of the dehydrogenation of
pure FA over Pd/PPC and Pd/APC was further conducted
(nPd/nFA = 0.011, 50 °C), which also elucidated that Pd/APC
possesses higher catalytic performance for hydrogen generation
from FA (Figure S13).
Figure 3. Volume of the generated gas (CO2 + H2) versus time for the
dehydrogenation of FA over (a) Pd/APC and (b) Pd/PPC (nPd/nFA = 0.011,
FA/SF = 1:1, 50 °C). Inset: TOF values of dehydrogenation of FA over Pd/APC
and Pd/PPC.
The rate of hydrogen generation from FA over Pd/APC
highly depends on operation temperature. The catalytic
reactions were completed in 10.3, 6.3, 3.6 and 3.3 minutes at 30,
40, 50 and 55 °C (FA/SF= 1:1, nPd/nFA= 0.011), respectively. The
apparent activation energy of Pd/APC and Pd/PPC was
calculated to be 46.31 KJ mol-1 and 41.37 KJ mol-1 by fitting
Arrhenius plot of lnTOF vs 1/T (Figures 4a and S15). In addition,
it is noted that the molar ratio of FA/SF has profound effect on
the activity of the as-prepared catalyst. The activity of the
catalyst increases initially until FA/SF = 1:1 and then slightly
decreases with further increasing SF molar percentage in FA/SF
mixed solution (Figure S14). Therefore, it can be concluded that
the best molar ratio of FA/SF for hydrogen generation over this
catalyst is 1:1.
Figure 2. TEM and HADDF-STEM images of (a,c) Pd/APC and (b,d) Pd/PPC.
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10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
amine-implanted porous support plays another indispensable
role to provide the alkaline and electron-donating environments
around the active sites for promoting the de-protonation of FA,
absorption between reactants and catalyst. Another catalyst,
Pd/APC*, with mean particle size of 3.5 nm also has been
prepared by using the APC support. Despite the larger particle
size, the Pd/APC* catalyst displayed a much higher catalytic
activity than that of Pd/PPC, further confirming that amine
species doped within carbon supports can promote the
dehydrogenation of formic acid (Figures S18 and S21). The
possible pathway of hydrogen generation over amine-implanted
porous carbon supported Pd NPs could be speculated that the
amine species on the supports acts as proton scavengers
providing alkalized environment, which promote O-H bond
dissociation in FA to produce -[H2NH]+ and Pd-formate
7a]
species.[15,
Subsequently, Pd-formate species undergo β-
hydride elimination to produce CO2 and palladium hydride
species.[15a] The H2 release followed by the combination of -
[H2NH]+ and palladium hydride species. On the basis of above
analysis, the assist of the amine species and synergetic effects
between Pd NPs and alkaline supports are responsible for the
significantly enhanced catalytic activity.
From the views of practical applications, the stability and
recyclability of catalyst plays a crucial role in industrial process.
The stability and recyclability of the as-synthesized catalyst were
evaluated at 50 °C (nPd/nFA = 0.011, FA/SF = 1:1). The catalytic
activity displayed slightly loss after 4 runs of reaction, which
indicated the excellent recyclability of the Pd/APC catalyst
(Figure S16). No obvious change was found for Pd NP
crystalline phase and size after catalysis as indicated by PXRD,
TEM measurements (Figures S19 and S20), suggesting the high
stability of the catalyst during hydrogen generation from FA. In
addition, the performance of Pd/APC after 4-cycle tests still
hugely surpass Pd/PPC, suggesting amine-implanted porous
carbon supported ultrafine Pd NPs are much more competitive.
Figure 4. (a) Volume of the released gas (H2 + CO2) versus time and (b)
corresponding TOF values for the dehydrogenation of FA at different
temperatures over Pd/APC (nPd/nFA = 0.011, FA/SF= 1:1, 50 °C). Insert:
Arrhenius plot (lnTOF vs. 1/T).
Conclusions
To gain more details about the effects of the amine groups
in APCs on the enhancement of catalytic performance of the
Pd/APC catalysts, various comparative experiments were
carried out. With the increases of temperature, time and
ammonium hydroxide concentration for hydrothermal treatment
of the porous carbon by ammonium hydroxide; the TOF values
achieved by the corresponding Pd/APC catalysts initially
increased, and then a similar maximum value was reached and
maintained (Figures S10, S11 and S12), which is consistent with
the changes of the amine contents of APC determined by
elemental analysis (Table S3). Consequently, the catalytic
performance of Pd/APC is highly dependent on the content of
amine group in APC. Fundamentally, the explanation for the
prominent enhancement of the catalytic performance of Pd/APC
could be down to the high dispersion of ultrafine Pd NPs and
strong metal–molecular support interactions. On the one hand,
the amine groups on the pore surface can disperse and
downsize Pd NPs immobilized on APC by enhancing the
interactions between metal precursors/NPs and electron-rich
supports.[5a] On the other hand, the weakly alkalization of the
In summary, a universal and efficient SAIA approach has
been successfully developed to prepare amine-implanted porous
carbon supported metal NPs. Compared with pristine porous
carbon, the amine-implanted ones can afford more highly
dispersed Pd NPs with necessary local catalytic environments,
which exhibited much more preferable catalytic activity and
excellent recyclability with 100% selectivity for hydrogen
generation from FA under mild conditions, giving a TOF value
among the best yet reported. The superior catalytic performance
of Pd/APC could be ascribed to the improved affinity between
amine-implanted carbon supports and metal precursor/NPs, and
thus the prevention of the aggregation and over-growth of Pd
NPs and the enhanced metal–molecular support interactions.
Moreover, the alkalization of the carbon supports with amine
groups could further facilitate the decomposition of FA to release
hydrogen. The catalyst functionalization method and results are
expected to not only promote the fabrication of efficient
nanocatalysts, but also expand the practical applications of
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10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
generation from FA. Such test cycles of the catalyst for the
hydrogen storage and generation using FA as hydrogen carrier
for fuel cells and other energy fields of chemical industry.
dehydrogenation of FA were carried out for 4 runs at 50 °C (nPd/nFA
0.011, FA/SF = 1:1).
=
Catalyst poison experiment: The as-synthesized Pd/APC was used for
catalyst poison test. Typically, the CO gas flow was pumped into the two-
necked reaction tube (50 mL) placed with Pd/APC or Pd/PPC for 30 min.
Then, the procedures for the dehydrogenation of FA were carried out.
Experimental Section
Preparation of catalysts
Synthesis of amine-implanted porous carbon supports: Typically,
100 mg pristine porous carbon (PPC) powder was dispersed in 25 wt %
ammonium hydroxide (15 mL). Subsequently, the mixture was
transferred into a Teflon-lined steel autoclave and heated under 200 °C
for 10 h. Finally, the amine-implanted porous carbon (APC) was obtained
by filtering and wishing with de-ionized water for several times and then
dried at 50 °C for 5 h in vacuum.
Acknowledgements
We thank the Recruitment Program of Global Youth Experts, the
NSFC (21233009), the Strategic Priority Research Program of
CAS (XDB20010200), and the 973 Program (2014CB845603)
for financial support.
Control experiments were conducted to explore the optimum conditions
for the treatment of porous carbon. The PPC samples were treated at
80 °C , 120 °C , 180 °C and 200 °C for 10 h with 25 wt.-% ammonium
hydroxide, named as APC-80 °C , APC-120 °C , APC-180 °C and APC-
200 °C , respectively. The PPC samples were treated with hydrothermal
reaction at 200 °C with 25 wt.-% ammonium hydroxide for 2 h, 6 h, 10 h
and 14 h, named as APC-2 h, APC-6 h, APC-10 h and APC-14 h,
respectively. The PPC samples were treated with hydrothermal reaction
with 5 wt.-%, 10 wt.-%, 15 wt.-% and 25 wt.-% ammonium hydroxide at
200 °C for 10 h, named as APC-5 %, APC-10 %, APC-15 % and APC-
25 %, respectively.
Keywords: heterogeneous catalyst • functionalized carbon •
hydrogen generation • formic acid • metal nanoparticles
[1]
a) Y.-Z. Chen, Y.-X. Zhou, H. Wang, J. Lu, T. Uchida, Q. Xu, S.-H. Yu,
H.-L. Jiang, ACS Catal. 2015, 5, 2062-2069; b) L. Li, H. Zhao, J. Wang,
R. Wang, ACS Nano, 2014, 8, 5352-5364; c) Y.-B. Huang, Q. Wang, J.
Liang, X. Wang, R. Cao, J. Am. Chem. Soc. 2016, 138, 10104-10107;
d) M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu, H. Zhao, Z.
Tang, Nature 2016, 539, 76-80; e) S. Zeng, L. Zhang, X. Zhang, Y.
Wang, H. Pan, H. Su, Int. J. Hydrogen Energy 2012, 37, 9994-10001.
Synthesis of Pd/APC and Pd/PPC: The Pd NPs supported by APC
[2] a) H. Yin, H. Tang, D. Wang, Y. Gao, Z. Tang, ACS Nano 2012, 6, 8288-
8297; b) K. Mori, T. Hara, T. Mizugaki, K. Ebitani, K. Kaneda, J. Am.
Chem. Soc. 2004, 126, 10657-10666; c) Q.-Y. Bi, J.-D. Lin, Y.-M. Liu,
H.-Y. He, F.-Q. Huang, Y. Cao, J. Power Sources 2016, 328, 463-471;
d) J. Li, W. Chen, H. Zhao, X. Zheng, L. Wu, H. Pan, J. Zhu, Y. Chen, J.
Lu, J. Catal. 2017, 352, 371-381; e) X. Yang, D. Yu, B. Cao, A.C. To,
ACS Appl. Mater. Interf. 2017, 9, 29-35; f) D.A. Bulushev, M. Zacharska,
E.V. Shlyakhova, A.L. Chuvilin, Y. Guo, S. Beloshapkin, A.V. Okotrub,
L.G. Bulusheva, ACS Catal. 2016, 6, 681-691.
were synthesized by
a facile sodium hydroxide-assisted reduction
approach.[4a] Firstly, the as-obtained APC (100 mg) was dispersed in de-
ionized water (2.5 mL), and mixed with an aqueous solution of K2PdCl4
(0.30 M, 0.30 mL). Then, the resulted aqueous suspension was further
homogenized by sonicating 0.5 h. Subsequently, NaBH4 (20 mg)
dissolved in NaOH aqueous (0.5 M, 0.50 mL) was rapidly injected into
the above obtained aqueous suspension. The mixture was stirred for
another half an hour at room temperature to fully deposit the metallic Pd
NPs onto the support. Finally, the desired Pd/APC catalyst was collected
by centrifuging and washing with de-ionized water for three times, and
then dried in vacuum at room temperature for further catalytic activity
tests. In addition, the reduction temperature was further increased from
room temperature to 50 °C , and the resultant catalyst was denoted as
Pd/APC*. For comparison, Pd/PPC was prepared following the same
synthetic procedures, except that PPC was used instead of APC.
[3]
a) Z. Guo, C. Xiao, R. V. Maligal-Ganesh, L. Zhou, T. W. Goh, X. Li, D.
Tesfagaber, A. Thiel, W. Huang, ACS Catal. 2014, 4, 1340-1348; b) J.
Chen, R. Liu, Y. Guo, L. Chen, H. Gao, ACS Catal. 2015, 5, 722-733; c)
H.-j. Jeon, Y.-M. Chung, Appl. Catal. B: Environ. 2017, 210, 212-222; d)
Q.-L. Zhu, Q. Xu, Chem 2016, 1, 220-245; e) S. Akbayrak, S. Özkar,
ACS Appl. Mater. Interfaces 2012, 4, 6302-6310.
[4]
a) Q.-L. Zhu, N. Tsumori, Q. Xu, Chem. Sci. 2014, 5, 195-199; b) Y.
Zhu, T. Nakanishi, K. Kanamori, K. Nakanishi, S. Ichii, K. Iwaida, Y.
Masui, T. Kamei, T. Shimada, A. Kumamoto, Y. H. Ikuhara, M. Jeon, G.
Hasegawa, M. Tafu, C. W. Yoon, T. Asefa, ACS Appl. Mater. Interfaces.
2017, 9, 36-41; c) N. Yi, H. Saltsburg, M. Flytzani-Stephanopoulos,
ChemSusChem 2013, 6, 816-819; d) Q.-Y. Bi, J.-D. Lin, Y.-M. Liu, F.-Q.
Huang, Y. Cao, Int. J. Hydrogen Energy 2016, 41, 21193-21202; e) Q.
Yao, W. Shi, G. Feng, Z.-H. Lu, X. Zhang, D. Tao, D. Kong, X. Chen, J.
Power Sources 2014, 257, 293-299.
Catalytic Activity Testing
Procedures for the dehydrogenation of formic acid: Reaction
apparatus for measuring the H2/CO2 evolution from the FA/SF system is
the same as previously reported.[4a] In general, a mixture of as-
synthesized catalyst and distilled water (2 mL) was placed in a two-
necked reaction tube (50 mL), which was placed in a water bath at a
preset temperature (30-55 °C) under ambient atmosphere. A gas burette
filled with water was connected to the reaction flask to measure the
volume of released gas (temperature kept constant at 25 °C during
measurements). The reaction started when 1.5 mL of the mixed aqueous
solution containing FA (5.5 M) and SF with different molar ratios was
injected into the mixture. The molar ratios of Pd/FA were theoretically
fixed at 0.011 in all the catalytic reactions. The volume of the evolved gas
was monitored by recording the displacement of water in the gas burette.
[5]
[6]
a) F.-Z. Song, Q.-L. Zhu, N. Tsumori, Q. Xu, ACS Catal. 2015, 5, 5141-
5144; b) N. Wang, Q. Sun, R. Bai, X. Li, G. Guo, J. Yu, J. Am. Chem.
Soc. 2016, 138, 7484-7487; c) Z.-H. Lu, J. Li, A. Zhu, Q. Yao, W.
Huang, R. Zhou, R. Zhou, X. Chen, Int. J. Hydrogen Energy 2013, 38,
5330-5337.
a) Q.-Y. Bi, J.-D. Lin, Y.-M. Liu, H.-Y. He, F.-Q. Huang, Y. Cao, Angew.
Chem. Int. Ed. 2016, 128, 12028-12032; b) X.-H. Li, X. Wang, M.
Antonietti, Chem. Sci. 2012, 3, 2170-2174; c) X. Xu, Y. Li, Y. Gong, P.
Zhang, H. Li, Y. Wang, J. Am. Chem. Soc. 2012, 134, 16987-16990; d)
R. V. Jagadeesh, H. Junge, M.-M. Pohl, J. Radnik, A. Brückner, M.
Beller, J. Am. Chem. Soc. 2013, 135, 10776-10782; e) Z.-L. Wang, J.-
Recyclability testing of the catalysts: For the recyclability test, the
Pd/APC catalyst was recycled for the next test cycle by washing with de-
ionized water for several times after the completion of the hydrogen
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10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
M. Yan, Y.-F. Zhang, Y. Ping, H.-L. Wang, Q. Jiang, Nanoscale, 2014,
Miele, Chem. Mater. 2014, 26, 3249-3255; f) E. Petit, P. Miele, U. B.
Demirci, ChemSusChem 2016, 9, 1777-1780.
6, 3073-3077.
[7]
a) R. Arrigo, M. E. Schuster, Z. Xie, Y. Yi, G. Wowsnick, L. L. Sun, K. E.
Hermann, M. Friedrich, P. Kast, M. Hävecker, A. Knop-Gericke, R.
Schlögl, ACS Catal. 2015, 5, 2740-2753; b) R. Arrigo, S. Wrabetz, M. E.
Schuster, D. Wang, A. Villa, D. Rosenthal, F. Girsgdies, G. Weinberg, L.
Prati, R. Schlogl, D. S. Su, Phys. Chem. Chem. Phys. 2012, 14, 10523-
10532; c) K. Wan, G.-F. Long, M.-Y. Liu, L. Du, Z.-X. Liang, P.
Tsiakaras, Appl. Catal. B: Environ. 2015, 165, 566-571; d) C. N. R. Rao,
K. Gopalakrishnan, A. Govindaraj, Nano Today 2014, 9, 324-343; e) Y.
Gao, G. Hu, J. Zhong, Z. Shi, Y. Zhu, D. S. Su, J. Wang, X. Bao, D. Ma,
Angew. Chem. Int. Ed. 2013, 52, 2109-2113; f) M. Armbrüster, M.
Behrens, F. Cinquini, K. Föttinger, Y. Grin, A. Haghofer, B. Klötzer, A.
Knop-Gericke, H. Lorenz, A. Ota, S. Penner, J. Prinz, C. Rameshan, Z.
Révay, D. Rosenthal, G. Rupprechter, P. Sautet, R. Schlögl, L. Shao, L.
Szentmiklósi, D. Teschner, D. Torres, R. Wagner, R. Widmer, G.
Wowsnick, ChemCatChem 2012, 4, 1048-1063.
[10] a) S. Ott, Science 2011, 333, 1714-1715; b) K. Tedsree, T. Li, S. Jones,
C. W. A. Chan, K. M. K. Yu, P. A. J. Bagot, E. A. Marquis, G. D. W.
Smith, S. C. E. Tsang, Nat. Nanotech. 2011, 6, 302-307; c) Z. Li, Q. Xu,
Acc. Chem. Res. 2017, 50, 1449-1458; d) W.-H. Wang, Y. Himeda, J. T.
Muckerman, G. F. Manbeck, E. Fujita, Chem. Rev. 2015, 115, 12936-
12973; e) Y. Himeda, S. Miyazawa, T. Hirose, ChemSusChem 2011, 4,
487-493.
[11] a) A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H. Junge, P. J.
Dyson, G. Laurenczy, R. Ludwig, M. Beller, Science 2011, 333, 1733-
1736; b) Q. Liu, X. Yang, Y. Huang, S. Xu, X. Su, X. Pan, J. Xu, A.
Wang, C. Liang, X. Wang, T. Zhang, Energy Environ. Sci. 2015, 8,
3204-3207; c) X. Yang, P. Pachfule, Y. Chen, N. Tsumori, Q. Xu, Chem.
Commun. 2016, 52, 4171-4174.
[12] a) J. H. Lee, J. Ryu, J. Y. Kim, S.-W. Nam, J. H. Han, T.-H. Lim, S.
Gautam, K. H. Chae, C. W. Yoon, J. Mater. Chem. A 2014, 2, 9490-
9495; b) F. Wang, J. Xu, X. Shao, X. Su, Y. Huang, T. Zhang,
ChemSusChem 2016, 9, 246-251.
[8]
[9]
a) L. Schlapbach, A. Zuttel, Nature 2001, 414, 353-358; b) M. Aresta, A.
Dibenedetto, A. Angelini, Chem. Rev. 2014, 114, 1709-1742; c) A.
Gutowska, L. Li, Y. Shin, C. M. Wang, X. S. Li, J. C. Linehan, R. S.
Smith, B. D. Kay, B. Schmid, W. Shaw, M. Gutowski, T. Autrey, Angew.
Chem. Int. Ed. 2005, 44, 3578-3582; d) Z. Huang, T. Autrey, Energy
Environ. Sci. 2012, 5, 9257-9268.
[13] B. Liu, H. Yao, W. Song, L. Jin, I. M. Mosa, J. F. Rusling, S. L. Suib, J.
He, J. Am. Chem. Soc. 2016, 138, 4718-4721.
[14] a) Z. Li, X. Yang, N. Tsumori, Z. Liu, Y. Himeda, T. Autrey, Q. Xu, ACS
Catal. 2017, 7, 2720-2724; b) Q.-L. Zhu, N. Tsumori, Q. Xu, J. Am.
Chem. Soc. 2015, 137, 11743-11748.
a) Q.-L. Zhu, Q. Xu, Energy Environ. Sci. 2015, 8, 478-512; b) H.-L.
Jiangꢀ, S. K. Singhꢀ, J.-M. Yanꢀ, X.-B. Zhang, Q. Xu, ChemSusChem
2010, 3, 541-549; c) D. Mellmann, P. Sponholz, H. Junge, M. Beller,
Chem. Soc. Rev. 2016, 45, 3954-3988; d) Grasemann, M., G.
Laurenczy, Energy Environ. Sci. 2012, 5, 8171-8181; e) R. Moury, U. B.
Demirci, V. Ban, Y. Filinchuk, T. Ichikawa, L. Zeng, K. Goshome, P.
[15] a) M. Martis, K. Mori, K. Fujiwara, W.-S. Ahn, H. Yamashita, J. Phys.
Chem. C, 2013, 117, 22805-22810; b) K. Koh, J. E. Seo, J. H. Lee, A.
Goswami, C. W. Yoon, T. Asefa, J. Mater. Chem. A, 2014, 2, 20444-
20449
This article is protected by copyright. All rights reserved.

10.1002/ejic.201701108
European Journal of Inorganic Chemistry
COMMUNICATION
COMMUNICATION
A universal and efficient surface
amine-implanting approach (SAIA)
has been proposed for fabricating
highly active nanocatalysts, which
exhibited superior catalytic
Heterogeneous catalysis
De-Jie Zhu,[a, b] Yue-Hong Wen,[a] Qiang
Xu,[c] Qi-Long Zhu,*[a] and Xin-Tao Wu[a]
Page No. – Page No.
performance for the dehydrogenation
of formic acid under mild conditions.
The amine species densely implanted
on the pore surface of carbon play
important roles for enhancing the
catalytic activity.
Title: Surface Amine-Implanting
Approach for Catalyst
Functionalization: Prominently
Enhancing Catalytic Hydrogen
Generation from Formic Acid
This article is protected by copyright. All rights reserved.