Maximizing the Catalytic Activity of Nanoparticles through Monolayer Assembly on Nitrogen-Doped Graphene

Article abstract of DOI:10.1002/anie.201709815

We report a facile method for assembly of a monolayer array of nitrogen-doped graphene (NG) and nanoparticles (NPs) and the subsequent transfer of two layers onto a solid substrate (S). Using 3 nm NiPd NPs as an example, we demonstrate that NiPd-NG-Si (Si=silicon wafer) can function as a catalyst and show maximum NiPd catalysis for the hydrolysis of ammonia borane (H₃NBH₃, AB) with a turnover frequency (TOF) of 4896.8 h^?1 and an activation energy (E_a) of 18.8 kJ mol^?1. The NiPd-NG-S catalyst is also highly active for catalyzing the transfer hydrogenation from AB to nitro compounds, leading to the green synthesis of quinazolines in water. Our assembly method can be extended to other graphene and NP catalyst materials, providing a new 2D NP catalyst platform for catalyzing multiple reactions in one pot with maximum efficiency.

Full text of DOI:10.1002/anie.201709815

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Accepted Article
Title: Maximizing Catalysis of Nanoparticles via Their Monolayer
Assembly on Nitrogen-doped Graphene
Authors: Chao Yu, Xuefeng Guo, Mengqi Shen, Bo Shen, Michelle
Muzzio, Zhouyang Yin, Qing Li, Zheng Xi, Junrui Li,
Christopher Takakazu Seto, and Shouheng Sun
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709815
Angew. Chem. 10.1002/ange.201709815
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10.1002/anie.201709815
Angewandte Chemie International Edition
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Maximizing Catalysis of Nanoparticles via Their Monolayer
Assembly on Nitrogen-doped Graphene
Chao Yu†, Xuefeng Guo†, Mengqi Shen, Bo Shen, Michelle Muzzio, Zhouyang Yin, Qing Li, Zheng Xi,
Junrui Li, Christopher T. Seto* and Shouheng Sun*
Abstract: We report a facile interface assembly method to assemble
monolayer array of nitrogen-doped graphene (NG) and
nanoparticles (NPs) and then to transfer the dual monolayers onto a
solid substrate. Using nm NiPd NPs as an example, we
then a monolayer assembly of NPs (Figure 1b). By lifting a solid
substrate (S) from a water phase, we can transfer the monolayer
assembly of NPs and NG onto S, giving NPs-NG-S (Figure 1c).
The assembly method can be extended to G in general, but
pristine G cannot stabilize NPs well enough to survive the NP
activation process tested in this paper for catalysis. NG is a
better choice for anchoring/stabilizing NPs for catalytic studies
due to the N-doping induced disruption of the π-electron cloud
a
3
demonstrate that NiPd-NG-Si can function as a catalyst probe and
show maximum NiPd catalysis for the hydrolysis of ammonia borane
(H3NBH3, AB) with its TOF = 4896.8 h-1 and Ea = 18.8 kJ/mol. The
NiPd-NG-Si is also highly active for catalyzing transfer
hydrogenation from AB to -NO2, leading to the green chemistry
synthesis of quinazolines in water. Our assembly method can be
extended to other graphene and NP catalyst materials, providing a
new 2D NP catalyst platform for catalyzing multiple reactions in one-
pot with maximum efficiency.
7]
on the G surface.[2f, When proper NPs are chosen for the
assembly, the NPs-NG-S can serve as a convenient catalyst
“probe”: Inserting the probe into a solution containing all required
reactants will trigger a series of cascade reactions, while pulling
the probe away from the solution will stop the reactions (Figure
1c). In this way, we can achieve rational control of reaction
kinetics and product formation.
The recent push for green chemistry syntheses of functional
molecules and materials requires new and efficient catalysts that
are able to catalyze multiple chemical reactions. Such catalysts
can also serve as models for developing a better understanding
of how to design and optimize multifunctional catalysts. One way
that this problem has been addressed is to have catalysts
arranged in a two-dimensional (2D) array so that each single
catalyst unit is exposed to reactants equally for a specific
reaction. This is conventionally achieved by using the
lithography process in which a catalytically active material is
deposited on
a
pre-patterned substrate.[1] Recently, self-
Figure 1. a) Schematic illustration of the interface assembly of monolayer NG.
b) Interface assembly of NPs-NG. c) Assembled NPs-NG on both sides of S
as a probe to catalyze a solution phase reaction with “on” representing the
probe insertion to trigger the catalytic reaction, and “off” indicating the pulling
of the probe from the solution to stop the reaction.
assembly techniques have advanced to a level that functional
nanoparticles (NPs) can be deposited on a flat surface[2] and
serve as a catalyst layer to achieve higher catalytic activity.[3]
However, this approach has been limited to NP deposition on
bulk solid surfaces. Efforts to deposit NPs on a flat nanoscale
support, such as graphene (G), have met with only limited
success for catalytic applications because of difficulties in
controlling monodisperse NP deposition on a flat G surface,[2f, 4]
or in unfolding the NP-modified G into a flat NP-G array.[5]
Here we report a facile assembly approach to consecutive
monolayer assembly of nitrogen-doped G (NG) and NPs to
achieve a monolayer NP deposition on NG and further on a flat
solid substrate, as outlined in Figure 1. Our assembly strategy is
based on liquid/liquid self-assembly of NPs reported as a way
for rapid fabrication of 2D nanostructures.[6] By controlling
solvent types and solvent evaporation on the water phase, we
are able to assemble a monolayer array of NG (Figure 1a), and
We first demonstrate our new strategy to prepare NPs-NG-S.
NG was synthesized as reported,[8] and was dispersed in ethanol.
Representative NPs of 3 nm Ni30Pd70 (denoted as NiPd in this
paper),[9] 8 nm Fe3O4[10] and 9 nm Pd[11] were also prepared as
reported. We modified a previous report on the assembly of
[6b. 12]
graphene oxide (GO)
and performed our assembly by
dropping pentane (5 mL) onto a water (5 mL) surface (20 cm2) to
create a pentane-water inter-surface. Then we added 1 mL of
ethanol dispersion of NG (0.05 mg/mL) via a syringe into the
water phase without disrupting the interface. Evaporation of half
of the pentane at room temperature led to formation of a
reflective NG film at the interface. When we added 2.5 mL of NP
pentane dispersion (0.012 mg/mL) dropwise at this stage and let
the pentane completely evaporate, we obtained a monolayer
array of NPs directly on the NG film. The film was collected on a
SiO-coated Cu grid or a silicon wafer by lifting the substrate up
through the water phase, and dried in air. During this process,
lifting the substrate at different stages can give us either NG-Si
or NPs-NG-Si.
[*]
Dr. C. Yu,[†] X. Guo,[†] M. Shen, B. Shen, M. Muzzio, Z. Yin, Z. Xi, J.
Li, Prof. C. T. Seto and Prof. S. Sun
Department of Chemistry, Brown University
Providence, RI, 02912 (United State)
E-mail: christopher_seto@brown.edu
ssun@brown.edu
Prof. Q. Li
The NG-Si was characterized by atomic force microscope
School of Materials Science and Engineering, Huazhong University
of Science and Technology
(AFM, Figure 2a, Figure S1). Line scanning across
a
Wuhan, Hubei 430074 (China)
[†]
These authors contributed equally to this work
Supporting information for this article is given via a link at the end of
the document.
1
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10.1002/anie.201709815
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representative sheet gave a height profile and film thickness of
0.6 nm, corresponding to the thickness of a single layer of NG.[8,
aggregation (Figure 2d). The AFM image of a representative
patch of the annealed sample shows nearly the same height (3.0
nm) when compared to the height measured for a freshly-
deposited, unannealed sample (Inset of Figure 2c). However,
the NiPd NPs in the NiPd-G-Si structure shows signs of stacking
after this annealing treatment (Figure S6). These observations
indicate that the NG indeed provides anchoring sites that
stabilize the NPs during the NP activation process.
13]
The transmission electron microscope (TEM) images clearly
show the monolayer assembly of 3 nm NiPd NPs (Figure 2b), as
well as 9 nm Pd and 8 nm Fe3O4 NPs (Figure S2&3) on NG. The
NP arrays can be further characterized by AFM analysis (Figure
2c). For example, the average thickness of the NiPd-NG is
measured to be 3.1 nm. Subtracting the NG thickness of 0.6 nm
(Inset of Figure 2a) gives a NP height of 2.5 nm, close to the
average NP size measured by TEM, indicating the successfully
preparation of a dual-monolayer assembly of NPs and NG (AFM
measurements often give smaller dimensions than TEM
measurements, especially for NPs with dimensions less than 10
]
nm due to tip-sample interactions).[14 Under these assembly
conditions with
a
properly controlled NP dispersion
concentration, we did not observe NP deposition on the non-NG
area of S, indicating that our assembly approach is very
selective for the formation of NPs-NG. However, increasing the
NP concentration to 0.016 mg/mL or higher caused the NPs to
stack in multilayers at the interface (Figure S4a), denoted as
(NiPd)>1-NG-Si, while reduction of the NP dispersion
concentration to 0.008 mg/mL or below resulted in patchy NP
assemblies on the NG surface (Figure S4b), denoted as
(NiPd)<1-NG-Si.
Figure 3. a) Stoichiometric hydrogen evolution from AB hydrolysis catalyzed
by NiPd-S prepared via different assembly methods ([AB] = 300 mM, T = 298
K. For NiPd-NG-Si or NiPd-G-Si, [NiPd] = 1.5 ppm and 1.7 ppm, respectively.
For (NiPd)<1-NG-Si and (NiPd)>1-NiPd-NG-Si, [NiPd] = 1.0 ppm and 2.1 ppm,
respectively. For NiPd+Support, [NiPd] = 0.15 mg/mL). b) TOF values of NiPd-
S
prepared via different assembly methods. c) Stoichiometric hydrogen
evolution at different temperatures ([AB] = 300 mM, [NiPd] = 1.5 ppm). d) TOF
values of NiPd-NG at different temperatures. Inset: Arrhenius plot of ln TOF vs
(1/T).
We first tested the assembled NiPd NPs as a catalyst for the
hydrolysis of ammonia borane (AB) (the assembled Pd and
Fe3O4 NPs were much less active than the NiPd NPs). We used
the reaction condition that has been optimized for the NiPd NP
catalyst (10 mL of 300 mM AB at 298 K)[9] for the comparison
purpose, and plotted the data in Figure 3a,b. Compared with
other controls, the NiPd-NG-Si catalyst shows much-enhanced
activity for AB hydrolysis. (NiPd)>1-NG-Si, (NiPd)<1-NG-Si and
even NiPd-G-Si are all less active than the monolayer assembly
NiPd-NG-Si. NiPd + NG (or G) is much less active than the
NiPd-NG-Si and requires that the NiPd loading be increased to
0.15 mg/mL for the rate of H2 production to be comparable with
the NiPd-NG-Si (1.5 ppm). These results indicate that 1)
monolayer assembly can indeed maximize NiPd catalysis; and
2) the presence of NG enhances the NiPd catalysis due to the
NG’s role in stabilizing the NiPd NPs and activating NH3-BH3
bonding by the NG-BH3 interaction. The temperature
dependence of the catalytic reaction from 298 K-328 K was also
measured as shown in Figure 3c. From the slope of the linear
plot of ln TOF versus 1/T in Figure 3d, we calculated the
activation energy for H2 evolution from AB to be Ea = 18.8 kJ/mol,
and TOF to be 4896.8 molH2 molNiPd-1 min-1. The NiPd-NG-Si has
the lowest Ea and highest initial TOF ever reported for AB
hydrolysis.[16]
Figure 2. a) AFM image of NG-S (S = Si). Inset: line profile of scanning across
the NG. b) TEM image of 3 nm NiPd-NG-S (S = SiO Type-A supported Cu
grid). c) AFM image of NiPd-NG-Si. Inset: line profile of scanning across part
of the NiPd-NG-Si. d) TEM image of 3 nm NiPd-NG-S (S = SiO Type-A
supported Cu grid) annealed at 400 °C. e) AFM image of the annealed NiPd-
NG-Si. (f) AFM height profile of line scanning across the annealed NiPd-NG-Si
in e).
Monolayer assembly of NPs on NG allows maximum
exposure of NPs for catalysis. The NG serves as a Lewis basic
support, providing anchoring sites not only for the NPs, but also
for Lewis acidic reactants, facilitating the enhancement of NP
catalysis.[15] For comparison purposes, we also prepared NiPd-
G-Si (Figure S5), as well as physical mixture of NiPd+NG (or G)
by mixing NPs and NG (or G) (mass ratio 3/5) in hexane
followed by hexane washing. These NPs were activated by
annealing in Ar at 400 °C for 2 h. The NiPd-NG-Si shows no NP
2
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10.1002/anie.201709815
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COMMUNICATION
>95% (Figure 4c) and no obvious change of catalyst morphology
(Figure S7), indicating that the NiPd-NG-Si catalyst is not only
active, but also stable under the reaction conditions.
We further performed three control experiments (Figure S8)
to study the possible reaction mechanism. From control
experiment 1, we can see that the reaction without aldehyde
gave aromatic amines. The formation of –NH2 and =NH groups
shows that the hydrolysis of AB provides both H2 and NH3 for
the reactions. Control experiment 2 indicates that NH3 is a
reaction component required for the formation of quinazoline.
Control experiment 3 confirms that the catalyst is active for
dehydro-aromatization, and can further catalyze
a second
transfer hydrogenation reaction to C=C of styrene. Based on
these control experiments and previous reports,[19] we can
propose a possible mechanism to explain how the reactions
proceed to form the final product (Scheme S1). Overall,
compared with previous syntheses of quinazolines,[20] our new
catalyst probe shows maximum activity for catalyzing one-pot
cascade reactions for the formation of quinazolines in water
under mild condition without the addition of any other additives
or oxidants.
We have developed a facile interfacial assembly method to
prepare a monolayer array of NG and NPs consecutively, and to
transfer the NPs-NG onto a solid substrate (S), obtaining the
dual NP and NG assemblies on S, NPs-NG-S. This NPs-NG-S
can be used as a catalyst probe to turn a catalytic reaction “on”
by inserting the probe into the reaction solution and “off” by
pulling the probe out of the solution. Using 3 nm NiPd NPs as an
example, we have demonstrated that the monolayer NiPd-NG-Si
shows the maximum catalysis not only for AB hydrolysis, but
also for the following transfer hydrogenation, imine formation,
and condensation of aromatic nitro-compounds and aldehydes,
leading to the one-pot, high-yield synthesis of quinazolines in
water with only 0.016 mol% catalyst loading. Our assembly
method can be extended to other G and NPs, providing a new
2D NP platform for catalyzing reactions with optimum efficiency.
Figure 4. a) Reaction results of 2-nitroacetophenone and various aldehydes.
Reaction conditions: 2-nitroacetophenone (1 mmol), aromatic or aliphatic
aldehyde (1.2 mmol), NiPd-NG-Si (0.016 mol%), water (20 mL) and AB (3
mmol), 60 °C, 8 h. b) Schematic photos showing the NiPd-NG-catalyzed one-
pot synthesis of quinazolines using AB in water. c) Separation yields of
quinazoline 1a in successive runs using recycled NiPd-NG-Si).
Since AB hydrolysis has been used directly in transfer
,
hydrogenation reactions for organic reductions,[3b 17] we explored
the advantages of our new catalyst probe for the AB-initiated
transfer hydrogenation and for the high-yield synthesis of
quinazolines - the key components present in heterocycle
compounds for displaying antibacterial, antifungal and
anticancer activities.[18] Our NiPd-NG-Si catalyzed the one-pot
synthesis of quinazolines from o-nitroacetophenone and
benzaldehydes with AB hydrolysis providing the necessary H2
+
and NH3 (NH4
NH3 + H+) sources, as summarized in
Figure 4a. We screened reaction conditions and found that
reaction in water at 60 °C for 8 h to be optimal (Table S1 and
Table S2). The NiPd-NG-Si was the most active catalyst, giving
4-methyl-2-phenylquinazoline in an excellent yield of 99% in the
presence of only 0.016 mol% of NiPd. We tested the NiPd-NG-
Si catalyst for similar reactions and found it to be equally active
in producing quinazoline derivatives (1a-5a) regardless of the
presence of electron-donating or electron-withdrawing groups on
the benzaldehyde. Furthermore, an aliphatic aldehyde, which is
much less active under conventional reaction conditions, also
reacts well to give 6a in 84% yield. In the synthesis, we simply
inserted the NiPd-NG-Si probe into the solution to initiate the
one-pot reaction. From the reaction system photos (Figure 4b),
we can see that after the probe is inserted into the reaction
solution, the balloon expands quickly due to the fast release of
H2 from AB hydrolysis. As the reaction proceeds, the balloon
shrinks due to the consumption of H2 during the subsequent
transfer hydrogenation and other reactions. We can pull the
catalyst probe out from the reaction system to stop the reaction
and to separate the reaction product. Using the reaction leading
to the formation of 1a, we tested stability of the NiPd-NG-Si
catalyst after 5 consecutive reaction runs. In each case, after
pulling the catalyst from the reaction solution and washing it with
water, the catalyst was ready for the next round of reaction. We
found no significant loss of catalytic activity (1a yield stayed
Experimental Section
Monolayer Assembly of NPs-NG-S: Pentane (5 mL) was firstly added on
the top of water (5 mL) to form a biphasic interface between pentane and
water phase. NG was mixed with ethanol (0.05 mg/mL) and 1 mL of this
solution was injected into the water phase. Once half of the pentane was
evaporated at room temperature, 2.5 mL of NPs/pentane solution (0.012
mg/mL for Ni30Pd70, 0.02 mg/mL for Fe3O4, 0.02 mg/mL for Pd) was
added dropwise to the pentane phase. After pentane evaporation, a large
monolayer array was assembled on the surface of the NG, and was then
transferred onto S (14 mm x 6 mm silicon wafer or SiO Type-A supported
Cu grid) for characterizations. Other experimental details were given in
the supporting information.
Acknowledgements
The work was supported by the U.S. Army Research Laboratory and the
U.S. Army Research Office under grant W911NF-15-1-0147 (S.S.), by
Strem Chemicals (S.S.), by National Natural Science Foundation of
China (21603078) and National Materials Genome Project
(2016YFB0700600) (Q.L.), as well as by the National Science
Foundation Graduate Research Fellowship under Grant No. 1644760
(M.M.).
Keywords: Interfacial assembly • Dual-monolayer •
Nanoparticles • Hydrogen Transfer • Heterogeneous catalyst •
3
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[1]
a) V. Flauraud, M. Mastrangeli, G. D. Bernasconi, J. Butet, D. T. L.
Alexander, E. Shahrabi, O. J. F. Martin, J. Brugger, Nat. Nanotechnol.
2017, 12, 73-80; b) T. G. W. Edwardson, K. L. Lau, D. Bousmail, C. J.
Serpell, H. F. Sleiman, Nat. Chem. 2016, 8, 162-170; c) S. H. Etschel, L.
Portilla, J. Kirschner, M. Drost, F. Tu, H. Marbach, R. R. Tykwinski, M.
Halik, Angew. Chem. Int. Edit. 2015, 54, 9235-9238; d) Y. H. Zheng, C.
H. Lalander, T. Thai, S. Dhuey, S. Cabrini, U. Bach, Angew. Chem. Int.
Edit. 2011, 50, 4398-4402; e) J. H. Zhang, Y. F. Li, X. M. Zhang, B.
Yang, Adv. Mater. 2010, 22, 4249-4269; f) K. Q. Peng, Y. Wu, H. Fang,
[6]
a) W. Han, Z. Q. Lin, Angew. Chem. Int. Edit. 2012, 51, 1534-1546; b) F.
M. Chen, S. B. Liu, J. M. Shen, L. Wei, A. D. Liu, M. B. Chan-Park, Y.
Chen, Langmuir 2011, 27, 9174-9181; c) S. Biswas, L. T. Drzal, Nano
Lett. 2009, 9, 167-172.
[7]
[8]
a) Q. Li, W. L. Zhu, J. J. Fu, H. Y. Zhang, G. Wu, S. H. Sun, Nano Energ.
2016, 24, 1-9; b) B. Li, F. Dai, Q. F. Xiao, L. Yang, J. M. Shen, C. M.
Zhang, M. Cai, Energ. Environ. Sci. 2016, 9, 102-106.
Z. H. Sheng, L. Shao, J. J. Chen, W. J. Bao, F. B. Wang, X. H. Xia, ACS
Nano 2011, 5, 4350-4358.
X. Y. Zhong, Y. Xu, J. Zhu, Angew. Chem. Int. Edit. 2005, 44, 2737- [9]
2742; g) V. Santhanam, R. P. Andres, Nano Lett. 2004, 4, 41-44; h) Y.
Cui, M. T. Bjork, J. A. Liddle, C. Sonnichsen, B. Boussert, A. P. [10]
Alivisatos, Nano Lett. 2004, 4, 1093-1098.
H. Goksu, S. F. Ho, O. Metin, K. Korkmaz, A. M. Garcia, M. S. Gultekin,
S. H. Sun, ACS Catal. 2014, 4, 1777-1782.
P. X. Xi, K. Cheng, X. L. Sun, Z. Z. Zeng, S. H. Sun, Chem. Commun.
2012, 48, 2952-2954.
[2]
a) P. S. Toth, M. Velicky, M. A. Bissett, T. J. A. Slater, N. Savjani, A. K. [11]
Rabiu, A. M. Rakowski, J. R. Brent, S. J. Haigh, P. O'Brien, R. A. W.
Dryfe, Adv. Mater. 2016, 28, 8256-8264; b) M. P. Arciniegas, F. Di [12]
Stasio, H. B. Li, D. Altamura, L. De Trizio, M. Prato, A. Scarpellini, I.
Moreels, R. Krahne, L. Manna, Adv. Funct. Mater. 2016, 26, 4535-4542; [13]
c) P. S. Toth, M. Velicky, Q. M. Ramasse, D. M. Kepaptsoglou, R. A. W.
Dryfe, Adv. Funct. Mater. 2015, 25, 2899-2909; d) L. R. Xu, X. Zhou, W. [14]
Q. Tian, T. Gao, Y. F. Zhang, S. B. Lei, Z. F. Liu, Angew. Chem. Int. Edit.
2014, 53, 9564-9568; e) K. H. Lee, H. J. Shin, B. Kumar, H. S. Kim, J.
Lee, R. Bhatia, S. H. Kim, I. Y. Lee, H. S. Lee, G. H. Kim, J. B. Yoo, J. Y.
Choi, S. W. Kim, Angew. Chem. Int. Edit. 2014, 53, 11493-11497; f) Z. L.
Li, J. H. Liu, C. G. Xia, F. W. Li, ACS Catal. 2013, 3, 2440-2448; g) X. [15]
Huang, Z. Y. Zeng, S. Y. Bao, M. F. Wang, X. Y. Qi, Z. X. Fan, H. Zhang,
Nat. Commun. 2013, 4, doi:10.1038/ncomms3239; h) A. Reina, X. T. Jia,
J. Ho, D. Nezich, H. B. Son, V. Bulovic, M. S. Dresselhaus, J. Kong,
Nano Lett. 2009, 9, 30-35.
G. M. Jiang, H. Y. Zhu, X. Zhang, B. Shen, L. H. Wu, S. Zhang, G. Lu, Z.
B. Wu, S. H. Sun, ACS Nano 2015, 9, 11014-11022.
Y. P. Wang, H. L. Fu, Q. W. Huang, Y. Cui, Y. Sun, L. H. Jiang, Energy
2015, 93, 854-863.
C. Y. He, Z. S. Li, M. L. Cai, M. Cai, J. Q. Wang, Z. Q. Tian, X. Zhang, P.
K. Shen, J. Mater. Chem. A 2013, 1, 1401-1406.
a) M. Cargnello, N. L. Wieder, T. Montini, R. J. Gorte, P. Fornasiero, J.
Am. Chem. Soc. 2010, 132, 1402-1409; b) A. Mechler, J. Kopniczky, J.
Kokavecz, A. Hoel, C. G. Granqvist, P. Heszler, Phys. Rev. B 2005, 72,
doi: 10.1103/PhysRevB.72.125407; c) Y. Ebenstein, E. Nahum, U. Banin,
Nano Lett. 2002, 2, 945-950.
a) X. J. Cui, Y. H. Li, S. Bachmann, M. Scalone, A. E. Surkus, K. Junge,
C. Topf, M. Beller, J. Am. Chem. Soc. 2016, 138, 457-457; b) Q. Y. Bi, J.
D. Lin, Y. M. Liu, H. Y. He, F. Q. Huang, Y. Cao, Angew. Chem. Int. Edit.
2016, 55, 11849-11853; c) 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; d) Y. Zheng, Y. Jiao, L. Ge, M. Jaroniec, S. Z. Qiao,
Angew. Chem. Int. Edit. 2013, 52, 3110-3116.
[3]
a) J. Zhao, Z. Chen, J. Am. Chem. Soc. 2017, 139, 12480–12487; b) C.
Yu, J. J. Fu, M. Muzzio, T. L. Shen, D. Su, J. J. Zhu, S. H. Sun, Chem.
Mater. 2017, 29, 1413-1418; c) Y. Huang, M. Zhao, S. Han, Z. Lai, J. [16]
Yang, C. Tan, Q. Ma, Q. Lu, J. Chen, X. Zhang, Z. Zhang, B. Li, B. Chen,
Y. Zong, H. Zhang, Adv. Mater. 2017, 29, doi: 10.1002/adma.201700102; [17]
d) D. H. Deng, K. S. Novoselov, Q. Fu, N. F. Zheng, Z. Q. Tian, X. H.
Bao, Nat. Nanotechnol. 2016, 11, 218-230; e) Y. X. Yao, Q. Fu, Y. Y.
Zhang, X. F. Weng, H. Li, M. S. Chen, L. Jin, A. Y. Dong, R. T. Mu, P.
Jiang, L. Liu, H. Bluhm, Z. Liu, S. B. Zhang, X. H. Bao, P. Natl. Acad. Sci.
USA 2014, 111, 17023-17028; f) X. F. Chen, J. S. Zhang, X. Z. Fu, M.
a) W. W. Zhan, Q. L. Zhu, Q. Xu, ACS Catal. 2016, 6, 6892–6905. b) A.
Rossin, M. Peruzzini. Chem. Rev. 2016, 116, 8848–8872.
a) Z. H. Shao, S. M. Fu, M. F. Wei, S. L. Zhou, Q. Liu, Angew. Chem.
Int. Edit. 2016, 55, 14653-14657; b) S. Rej, C. F. Hsia, T. Y. Chen, F. C.
Lin, J. S. Huang, M. H. Huang, Angew. Chem. Int. Edit. 2016, 55, 7222-
7226; c) H. C. Brown, J. Chandrasekharan, J. Am. Chem. Soc. 1984,
106, 1863-1865; d) G. E. Ryschkewitsch, J. Am. Chem. Soc. 1960, 82,
3290-3294.
Antonietti, X. C. Wang, J. Am. Chem. Soc. 2009, 131, 11658-11659.
a) S. C. Xu, B. Y. Man, S. Z. Jiang, J. H. Wang, J. Wei, S. D. Xu, H. P.
Liu, S. B. Gao, H. L. Liu, Z. H. Li, H. S. Li, H. W. Qin, ACS. Appl. Mater.
Inter. 2015, 7, 10977-10987; b) Y. Y. Lv, Y. Fang, Z. X. Wu, X. F. Qian, Y.
F. Song, R. C. Che, A. M. Asiri, Y. Y. Xia, B. Tu, D. Y. Zhao, Small. 2015,
11, 1003-1010; c) D. C. Geng, H. P. Wang, G. Yu, Adv. Mater. 2015, 27,
[18]
a) V. Colotta, D. Catarzi, F. Varano, O. Lenzi, G. Filacchioni, C. Costagli,
A. Galli, C. Ghelardini, N. Galeotti, P. Gratteri, J. Sgrignani, F. Deflorian,
S. Moro, J. Med. Chem. 2006, 49, 6015-6026; b) Z. Z. Ma, Y. Hano, T.
Nomura, Heterocycles 2005, 65, 2203-2219; c) P. A. Ple, T. P. Green, L.
F. Hennequin, J. Curwen, M. Fennell, J. Allen, C. Lambert-van der
Brempt, G. Costello, J. Med. Chem. 2004, 47, 871-887.
[4]
2821-2837; d) J. W. Liu, R. T. Lu, G. W. Xu, J. Wu, P. Thapa, D. Moore, [19]
Adv. Funct. Mater. 2013, 23, 4941-4948; e) X. Z. Zhou, X. Huang, X. Y.
Qi, S. X. Wu, C. Xue, F. Y. C. Boey, Q. Y. Yan, P. Chen, H. Zhang, J.
Phys. Chem. C 2009, 113, 10842-10846.
a) C. Yu, X. F. Guo, Z. Xi, M. Muzzio, Z. Y. Yin, B. Shen, J. R. Li, C. T.
Seto, S. H. Sun, J. Am. Chem. Soc. 2017, 139, 5712-5715; b) L. Tang,
X. H. Zhao, G. D. Zou, Y. Q. Zhou, X. K. Yang, Asian J. Org. Chem.
2016, 5, 335-339; c) L. Tang, Y. Yang, L. X. Wen, S. Zhang, Z. G. Zha,
Z. Y. Wang, Org. Chem. Front. 2015, 2, 114-118; d) L. Tang, X. F. Guo,
Y. Yang, Z. G. Zha, Z. Y. Wang, Chem. Commun. 2014, 50, 6145-6148.
a) Z. Y. Chen, J. X. Chen, M. C. Liu, J. C. Ding, W. X. Gao, X. B. Huang,
H. Y. Wu, J. Org. Chem. 2013, 78, 11342-11348; b) Y. Z. Yan, Y. H.
Zhang, C. T. Feng, Z. G. Zha, Z. Y. Wang, Angew. Chem. Int. Edit. 2012,
51, 8077-8081; c) X. W. Liu, H. Fu, Y. Y. Jiang, Y. F. Zhao, Angew.
Chem. Int. Edit. 2009, 48, 348-351; d) J. R. Li, X. Chen, D. X. Shi, S. L.
Ma, Q. Li, Q. Zhang, J. H. Tang, Org. Lett. 2009, 11, 1193-1196.
[5]
a) L. H. Wu, J. J. Willis, I. S. McKay, B. T. Diroll, J. Qin, M. Cargnello, C.
J. Tassone, Nature 2017, 548, doi:10.1038/nature23308; b) E. A.
Gaulding, B. T. Diroll, E. D. Goodwin, Z. J. Vrtis, C. R. Kagan, C. B. [20]
Murray, Adv. Mater. 2015, 27, 2846-2851; c) A. G. Dong, J. Chen, P. M.
Vora, J. M. Kikkawa, C. B. Murray, Nature 2010, 466, 474-477; d) T. P.
Bigioni, X. M. Lin, T. T. Nguyen, E. I. Corwin, T. A. Witten, H. M. Jaeger,
Nat Mater. 2006, 5, 265-270; e) M. Li, H. Schnablegger, S. Mann, Nature
1999, 402, 393-395.
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This article is protected by copyright. All rights reserved.

10.1002/anie.201709815
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
A
simple interfacial assembly
Chao Yu†, Xuefeng Guo†, Mengqi
method
assemble
nanoparticles and nitrogen-doped
graphene (NG) onto solid
substrate. The as-prepared NiPd-
NG-Si serves as a robust and
highly efficient catalyst probe for
the hydrolysis of ammonia borane
and for the following up tandem
reactions that lead to the high yield
synthesis of quinazolines in water.
was
a
developed
monolayer
to
of
Shen, Bo Shen, Michelle Muzzio,
Zhouyang Yin, Qing Li, Zheng Xi,
Junrui Li, Christopher T. Seto* and
Shouheng Sun*
a
Page No. – Page No.
Maximizing Catalysis of
Nanoparticles via Their Monolayer
Assembly on Nitrogen-doped
Graphene
5
This article is protected by copyright. All rights reserved.