Ultrathin Amorphous/Crystalline Heterophase Rh and Rh Alloy Nanosheets as Tandem Catalysts for Direct Indole Synthesis

Article abstract of DOI:10.1002/adma.202006711

Heterogeneous noble-metal-based catalysis plays an essential role in the production of fine chemicals. Rh-based catalysts are one of the most active candidates for indole synthesis. However, it is still highly desired to develop heterogeneous Rh-based catalysts with high activity and selectivity. In this work, a general, facile wet-chemical method is reported to synthesize ultrathin amorphous/crystalline heterophase Rh and Rh-based bimetallic alloy nanosheets (NSs), including RhCu, RhZn, and RhRu. Impressively, the amorphous/crystalline heterophase Rh NSs exhibit enhanced catalytic activity toward the direct synthesis of indole compared to the crystalline counterpart. Importantly, the obtained amorphous/crystalline heterophase RhCu alloy NSs can further enhance the selectivity to indole of >99.9% and the conversion is 100%. This work demonstrates the importance of phase engineering and metal alloying in the rational design and synthesis of tandem heterogeneous catalysts toward fine chemical synthesis.

Full text of DOI:10.1002/adma.202006711

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Ultrathin Amorphous/Crystalline Heterophase Rh and
Rh Alloy Nanosheets as Tandem Catalysts for Direct
Indole Synthesis
Jingjie Ge, Peiqun Yin, Ye Chen, Hongfei Cheng, Jiawei Liu, Bo Chen, Chaoliang Tan,
Peng-Fei Yin, Hong-Xing Zheng, Qiang-Qiang Li, Shuangming Chen, Wenjie Xu,
Xiaoqian Wang, Geng Wu, Rongbo Sun, Xiang-Huan Shan, Xun Hong, and Hua Zhang*
Owing to the preeminent heterocyclic
Heterogeneous noble-metal-based catalysis plays an essential role in the
production of fine chemicals. Rh-based catalysts are one of the most active
candidates for indole synthesis. However, it is still highly desired to develop
heterogeneous Rh-based catalysts with high activity and selectivity. In
this work, a general, facile wet-chemical method is reported to synthesize
ultrathin amorphous/crystalline heterophase Rh and Rh-based bimetallic
alloy nanosheets (NSs), including RhCu, RhZn, and RhRu. Impressively, the
amorphous/crystalline heterophase Rh NSs exhibit enhanced catalytic activity
toward the direct synthesis of indole compared to the crystalline counterpart.
Importantly, the obtained amorphous/crystalline heterophase RhCu alloy NSs
can further enhance the selectivity to indole of >99.9% and the conversion
is 100%. This work demonstrates the importance of phase engineering and
metal alloying in the rational design and synthesis of tandem heterogeneous
catalysts toward fine chemical synthesis.
motifs, indoles exhibit excellent biological
activity in chemical industry and life sci-
ence, such as pharmaceuticals, agrochem-
icals, and fragrances.[1,2] One of the most
efficient and cost-effective methods to pro-
duce indoles is the direct synthesis via the
tandem reaction,[3–6] i.e., the condensation
between aniline reduced from nitroarene
and its adjacent aldehyde group. Impor-
tantly, Rh-based catalysts are among the
most active catalysts for the indoles syn-
thesis.[7–9] Particularly, heterogeneous Rh-
based catalysts are promising candidates
owing to their stability, recyclability, and
facile segregation.[10,11] However, they still
suffer from the low catalytic activity and
selectivity compared to the homogeneous
Dr. J. Ge, Dr. P. Yin, Dr. Y. Chen, Dr. H. Cheng, J. Liu
Center for Programmable Materials
School of Materials Science and Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore
Dr. C. Tan
Department of Electrical Engineering
City University of Hong Kong
Hong Kong, China
Dr. H.-X. Zheng
Dr. P. Yin, Dr. X. Wang, Dr. G. Wu, R. Sun, Prof. X. Hong
Center of Advanced Nanocatalysis (CAN)
Hefei National Laboratory for Physical Sciences at the Microscale
University of Science and Technology of China
Hefei, Anhui 230026, China
School of Chemistry and Chemical Engineering
Liaocheng University
Liaocheng, Shandong 252059, China
Dr. Q.-Q. Li
School of Physical and Mathematical Sciences
Nanyang Technological University
21 Nanyang Link, Singapore 637371, Singapore
Dr. P. Yin
School of Chemistry and Environmental Engineering
Institute of Low-dimensional Materials Genome Initiative
Shenzhen University
Dr. S. Chen, W. Xu
National Synchrotron Radiation Laboratory
CAS Center for Excellence in Nanoscience
University of Science and Technology of China
Hefei, Anhui 230029, China
Shenzhen 518060, China
Dr. Y. Chen
Department of Chemistry
The Chinese University of Hong Kong
Shatin, N.T., Hong Kong, China
Dr. X.-H. Shan
Department of Chemistry
Dr. B. Chen, Dr. P.-F. Yin, Prof. H. Zhang
Department of Chemistry
University of Science and Technology of China
Hefei, Anhui 230026, China
City University of Hong Kong
Hong Kong, China
Prof. H. Zhang
Hong Kong Branch of National Precious Metals Material
Engineering Research Center (NPMM)
City University of Hong Kong
Hong Kong, China
E-mail: Hua.Zhang@cityu.edu.hk
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202006711.
DOI: 10.1002/adma.202006711
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catalysts.[12–15] Therefore, it is highly desired to develop efficient
Rh-based heterogeneous catalysts for the indole synthesis.
Developing facile synthetic methods for synthesis of noble
metal nanocatalysts has attracted great attention.[11,16] Recent
studies on phase engineering of nanomaterials (PEN)[17] have
revealed the crucial role of phases in determining the proper-
ties, functions, and applications of noble metal heterogeneous
nanocatalysts. As one of important groups of materials in the
field of PEN, heterophase nanomaterials comprising of more
than one phases in individual nanostructures have demon-
strated tremendous potentials in catalysis,[18–22] owing to the
synergistic effect between different phases and the abundant
active sites at the phase boundaries and/or interfaces.[23,24]
For example, amorphous/crystalline heterophase Pd-based
nanosheets (NSs) demonstrate better chemoselectivity than
realized, hindering the exploration of their performances as
tandem catalysts.
Here, we report a surfactant-free, one-pot synthesis of
ultrathin Rh NSs with amorphous/crystalline heterophase
(denoted as a/c-Rh NSs). The crystallinity of Rh NSs can be
tuned by controlling the reaction temperature. Our general
method is also applicable to synthesize Rh-based bimetallic
alloy NSs with amorphous/crystalline heterophase, e.g., RhCu,
RhZn, and RhRu. As a proof-of-concept application, when
used as tandem catalyst for the direct synthesis of indole, the
amorphous/crystalline heterophase Rh NSs outperform their
crystalline counterpart with much higher catalytic activity
toward the indole production. Impressively, via further Cu
alloying, the amorphous/crystalline heterophase RhCu NSs
demonstrate significantly enhanced indole selectivity of over
99.9% with high activity.
The a/c-Rh NSs are prepared by reducing the Rh(acac)3 in
a diluted aqueous formaldehyde solution without any sur-
factant in an autoclave at a mild temperature (90 °C) for
18 h (see the Experimental Section in the Supporting Infor-
mation for experimental details). The Rh nanostructure with
a sheet-assembled flower-like morphology is obtained in high
yield, which was confirmed by the scanning electron micro-
scopy (SEM) (Figure 1a) and dark-field scanning transmis-
sion electron microscopy (DF-STEM) images (Figure 1b).
The formation of flower-like morphology is likely due to the
their crystalline counterpart toward the selective hydrogena-
[23,25]

tion of C C bond in 4-nitrostyrene.
Furthermore, alloying
noble metal catalysts with non-precious metals can reduce
the cost and might also improve the catalytic performance
due to the synergistic effects between different metal compo-
nents.[26–28] For instance, the catalytic activity and selectivity of
Ru catalysts toward the hydrogenation of 4-nitrostyrene[29] and
electrocatalytic hydrogen evolution[30] can be efficiently boosted
by introducing Co atoms and regulating their lattice strain.
However, to the best of our knowledge, the synthesis of het-
erophase Rh and Rh-based alloyed nanomaterials has not been
Figure 1. Characterization of the synthesized a/c-Rh NSs. a) SEM and b) DF-STEM images of Rh NSs. c) TEM image of a typical folded Rh NS, showing
the thickness of ≈1.3 nm. d) A typical aberration-corrected HRTEM image showing the heterophase structure, in which the representative amorphous
and crystalline domains are marked by the red and blue squares, respectively. d1,d2) FFT patterns taken from the red and blue squares in (d), respec-
tively. e) SAED pattern of the a/c-Rh NSs.
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presence of formaldehyde in the hydrothermal synthesis.[31]
The average thickness of the NSs was measured to be about
1.3 nm (Figure 1c; Figure S1, Supporting Information). Aber-
ration-corrected high-resolution transmission electron micro-
scopy (HRTEM) was utilized to investigate the NSs at the
atomic scale. As illustrated in Figure 1d, a typical Rh NS con-
sists of many amorphous and crystalline domains. In a repre-
sentative amorphous region (d1, red square area), Rh atoms are
arranged without obvious long-range order. In a representa-
tive crystalline region (d2, blue square area), the crystal lattice
with a lattice spacing of 2.2 Å is measured, corresponding to
the (111) plane of face-centered cubic (fcc) Rh.[32] The diffuse
ring (Figure 1d1) and the bright spots (Figure 1d2) in the cor-
responding selected-area fast Fourier transform (FFT) patterns
illustrate the amorphous and crystalline phases in the Rh NSs,
respectively. Different from the crystalline Rh NSs (denoted
as c-Rh NSs, Figure S2, Supporting Information) which were
obtained under the same reaction condition except that the
reduction temperature was changed to 170 °C (see the Experi-
mental Section in the Supporting Information for experimental
details), the a/c-Rh NSs possess many amorphous–crystalline
phase boundaries (Figure S3, Supporting Information). More-
over, the low degree of crystallinity in a/c-Rh NSs is reflected
by the weak diffraction ring in the selected area electron dif-
fraction (SAED) pattern (Figure 1e). The X-ray diffraction (XRD)
pattern of the a/c-Rh NSs (Figure S4, Supporting Information)
shows one weak and broad peak at 41.0° ascribed to the diffrac-
tion from the fcc Rh (111) plane, which also indicates the poor
crystallinity of the a/c-Rh NSs. The formation of a/c-Rh NSs at
lower reaction temperature (90 °C) compared to that of c-Rh
NSs (170 °C) is similar to the previous studies on the a/c-Pd
and a/c-PdCu NSs.[23,25]
The chemical state of Rh was confirmed by X-ray
photoelectron spectroscopy (XPS). As shown in Figure 2a, the
binding energy peaks of a/c-Rh NSs at 307.5 and 312.2 eV can
be assigned to Rh 3d5/2 and Rh 3d3/2 of metallic Rh(0), respec-
tively. Compared to the c-Rh NSs (307.2 and 311.9 eV), the Rh
3d peaks of the a/c-Rh NSs slightly shift to higher binding
energy, which could be attributed to the atomic disordering
in the amorphous phase.[33,34] Moreover, X-ray absorption
Figure 2. Structure analysis of the a/c-Rh NSs. a) XPS spectra of a/c-Rh NSs and c-Rh NSs. b) XANES and c) Fourier-transform EXAFS spectra of
a/c-Rh NSs, c-Rh NSs, and Rh foil. Inset in (b): enlarged XANES spectra of Rh K-edge taken from the black dot square. d) RDF profiles of a/c-Rh NSs
and c-Rh NSs.
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near-edge structure (XANES) and extended X-ray absorption
fine structure (EXAFS) spectra of Rh K-edge were collected
to further investigate the valence state and the atomic struc-
ture of the a/c-Rh NSs. As shown in Figure 2b, the Rh K-edge
XANES spectrum of the a/c-Rh NSs displays a similar pattern
but slightly higher energy absorption edge as compared to the
c-Rh NSs and Rh foil, which is consistent with the aforemen-
tioned XPS result. The fitting results of EXAFS spectra of Rh
K-edge for a/c-Rh NSs, c-Rh NSs, and Rh foil (Figure S5 and
Table S1, Supporting Information) show almost identical peak
positions at ≈2.68 Å, which is assigned to the Rh-Rh metallic
bond. Notably, compared with the c-Rh NSs, the peak intensity
of a/c-Rh NSs in the EXAFS spectra is weaker (Figure S5, Sup-
porting Information), and the coordination number of Rh-Rh
in the a/c-Rh NSs is lower (Table S1, Supporting Information),
which can be ascribed to the decreased atomic ordering.[23,35] By
using the azimuthal average function of the profile analysis of
the selected area electron diffraction (PASAD) script in digital
micrograph software, the radial distribution function (RDF)
profile was obtained to further analyze the local structural char-
acteristics of the a/c- and c-Rh NSs (Figure 2d). The two peaks
(Rnea and Rsec) in the RDF profile represent the average distance
of the nearest and the second nearest neighboring Rh atoms,
respectively. Although the Rnea and Rsec peaks of the a/c-Rh NSs
at 2.71 and 4.80 Å, respectively, match well with those of c-Rh
NSs, they are broader and exhibit weaker intensity compared to
those of the crystalline counterpart, further demonstrating their
poor crystallinity.[34]
To demonstrate the universality of our facile synthetic
approach, bimetallic a/c-RhM (M = Cu, Zn, Ru) alloy NSs
were prepared by simply mixing Rh(acac)3 and Cu(acac)2 or
Zn(acac)2 or Ru(acac)3precursors, respectively, in the reaction
solution (see the Experimental Section in the Supporting Infor-
mation for experimental details). Figure 3a–c and Figure S6a–c
(Supporting Information) show the TEM and SEM images of
as-obtained a/c-RhCu, RhZn, and RhRu NSs, respectively,
indicating their high uniformity and purity. Similar to the
a/c-Rh NSs, both amorphous and crystalline domains can be
observed in the a/c-RhM NSs (Figure 3d–f), which were further
confirmed by the diffuse ring (Figure 3d1–f1) and bright spots
(Figure 3d2–f2) in the corresponding FFT patterns, respectively.
The weak rings in the SAED patterns further indicate the low
degree of crystallinity of the a/c-RhM NSs (Figure S7, Sup-
porting Information). Moreover, only weak diffraction peaks
at around 40−45° were observed in the XRD patterns of the
as-prepared RhM NSs (Figure S8, Supporting Information),
indicating their poor crystallinity. The elemental mappings
(Figure 3g–i) show the homogeneous distribution of Rh and the
alloyed metals in the a/c-RhM NSs. By using energy dispersive
X-ray spectroscopy (EDX, Figure S9, Supporting Information),
the Rh/Cu, Rh/Zn, and Rh/Ru atomic ratios are estimated to
be 0.7/0.3, 0.9/0.1, and 0.9/0.1, respectively.
Figure 3. Characterization of the bimetallic a/c-RhM (M = Cu, Zn, Ru) alloy NSs. a–c) TEM and d–f) aberration-corrected HRTEM images of ultrathin
a/c-RhCu, RhZn, and RhRu NSs, respectively. d1–f2) FFT patterns taken from the corresponding orange and cyan square areas in (d–f), respectively.
g–i) DF-STEM images and the corresponding STEM–EDS element mappings of a/c-RhCu, RhZn, and RhRu NSs, respectively.
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Figure 4. Catalytic performances of Rh and RhCu tandem catalysts in the direct synthesis of indole. a) Schematic illustration of the tandem reaction of
2-NPA. Two intermediates in the reaction process are (2-(hydroxyamino)phenyl)acetaldehyde and (2-aminophenyl)acetaldehyde. b) The conversion of
2-NPA and c) the selectivity of products, using a/c-Rh, c-Rh, a/c-RhCu, and c-RhCu NSs as catalysts. d) Recycling test of the a/c-RhCu NSs. Reaction
condition: 2-NPA (0.05 mmol), catalyst (1 mol%), 1 mL of mixed solvent of DMF and H2O (v/v = 5/1), 1 atm H2, 80 °C, and 120 min.
Rh-based materials are promising heterogeneous catalysts
for a variety of tandem reactions.[3,36,37] As a proof-of-concept
application, the catalytic performance of the obtained Rh
NSs was investigated in the tandem catalysis for direct indole
synthesis via the reduction of nitroarenes to anilines and sub-
sequent aldimine condensation.[5,38] The (2-nitrophenyl)acetal-
dehyde (2-NPA), one kind of nitroarene, was first synthesized
(see the Experimental Section in the Supporting Information
for experimental details), and then used as the substrate for the
tandem reaction (Figure 4a), which was conducted in a Schlenk
tube at 80 °C under 1 atm H2 atmosphere (see the Experimental
Section in the Supporting Information for experimental details).
After 120 min of reaction, the conversions of 2-NPA catalyzed
by the a/c-Rh NSs and c-Rh NSs are 100% (Figure 4b, red
curve) and 45% (Figure 4b, blue curve), respectively, indicating
the higher catalytic activity of the a/c-Rh NSs compared to the
c-Rh NSs. As a result, the selectivities of indole are 82% and
52% on the a/c-Rh NSs and c-Rh NSs, respectively (Figure 4c).
Besides indole, by-products, such as 1-hydroxyindole (1-HI),
2-nitrotoluene (2-NT) and 2-aminotoluene (2-AT) shown in grey
in Figure 4a were also detected (Figure 4c; Figures S10a,b and
S11–S14 and Table S2, Supporting Information). It suggests that
more than one pathways took place during the tandem catalytic
process (Figure 4a). Therefore, the selectivity of indole is highly
desired to be further improved.
(Figures S15 and S16, Supporting Information, see the Experi-
mental Section in the Supporting Information for experi-
mental details). Remarkably, the selectivities of indole on the
a/c-RhCu and c-RhCu NSs are improved to >99.9% and 97%,
respectively (Figure 4c; Figure S10c,d and Table S2, Supporting
Information), much higher than those of a/c-Rh NSs (82%)
and c-Rh NSs (52%). Moreover, by using the a/c-RhCu NSs as
catalyst, the conversion of 2-NPA reached 100% within 90 min
(Figure 4b, orange curve), greater than that using the a/c-Rh
(98.7%, Figure 4b, red curve) and c-RhCu catalysts (80.3%,
Figure 4b, cyan curve). The aforementioned results suggest
that alloying Cu can simultaneously improve the selectivity and
activity of the obtained a/c-RhCu NS catalyst. To the best of our
knowledge, the overall catalytic performance of the a/c-RhCu
NSs is superior to the most reported noble-metal-based homo-
geneous and heterogeneous catalysts toward the indole syn-
thesis (Table S3, Supporting Information). Furthermore, the
stability of the a/c-RhCu NSs was evaluated by the recycling
test. As shown in Figure 4d, the a/c-RhCu NSs have been recy-
cled for ten times without significant decay of the catalytic
performance. In addition, the morphology and crystallinity of
the recycled a/c-RhCu NSs catalyst were retained as evidenced
by the TEM image and SAED pattern (Figure S17, Supporting
Information), illustrating their high stability. Therefore, the a/c-
RhCu NSs could be used as excellent heterogeneous catalyst for
the direct synthesis of indole.
Since Cu alloying represents an effective way to enhance
the selectivity of noble metal nanocatalysts,[39–41] the catalytic
performance of the a/c-RhCu NSs was further investigated.
The c-RhCu NSs were also synthesized and used as a catalyst
The high activity and selectivity of the a/c-RhCu NSs toward
the direct synthesis of indole might originate from the unique
amorphous/crystalline heterophase structure and the Rh–Cu
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and Simulation, Nanyang Technological University, Singapore, for use
of their electron microscopy (and/or X-ray) facilities. H.Z. thanks the
support from ITC via Hong Kong Branch of National Precious Metals
Material Engineering Research Center (NPMM), the Start-Up Grant
(Project No. 9380100) and grants (Project Nos. 9610478 and 1886921)
from City University of Hong Kong.
interaction, which could affect the tandem catalytic processes as
follows. First, the amorphous/crystalline heterophase can offer
more abundant active sites. Compared with their crystalline
counterparts (Figures S2c and S15c, Supporting Information),
the a/c-Rh and a/c-RhCu NSs possess more abundant phase
boundaries (Figures S3 and S18, Supporting Information) which
could serve as active sites to boost the hydrogenation rate of the
[42]

nitro group ( NO2) and thus improve the catalytic activity.
Conflict of Interest
The authors declare no conflict of interest.
In addition, the undercoordinated Rh atoms in the amorphous
domains, as confirmed by the fitted EXAFS data (Table S1, Sup-
porting Information), could also serve as the active sites for the
catalytic reactions, further improving their catalytic activity for
hydrogenation process.[10] Second, Cu alloying to form RhCu
NSs could further accelerate the hydrogenation process. As
shown in the XPS spectra (Figure S19, Supporting Information),
the Rh 3d5/2 and 3d3/2 peaks in the a/c-RhCu catalysts shift to
more negative value compared to the a/c-Rh NSs, indicating the
electron donation from Cu to Rh, thus leads to higher electron
density of Rh in the a/c-RhCu NSs.[43,44] The increased electron
density of Rh could result in the weaker surface binding of H
atoms on Rh atoms[23,45–47] further enhancing the hydrogena-
tion activity.[42,48–50] Since H2 only participated in the reduction
of unsaturated bonds, when a/c-RhCu NSs instead of a/c-Rh
NSs are used as the catalyst, the hydrogenation step (Figure 4a)
2-NPA to (2-aminophenyl)acetaldehyde) in the tandem reac-
tion could be greatly promoted, and the decarbonylation rate of
aldehyde group (Figure 4a) 2-NPA to 2-NT, non-hydrogenation
process) would be suppressed. As a result, the obtained amine
intermediate, i.e., (2-aminophenyl)acetaldehyde, can be rapidly
condensed with the adjacent aldehyde group by the tandem pro-
cess, leading to the more favored production of indole.
In summary, we have developed a facile and general wet-chem-
ical strategy for the synthesis of ultrathin amorphous/crystalline
Rh NSs and bimetallic RhM (M = Cu, Zn, Ru) alloy NSs. The het-
erophase and alloying of Cu are found to boost the performance
of the obtained RhCu NSs as efficient heterogeneous tandem cat-
alysts for the direct indole synthesis. Impressively, with the pres-
ence of amorphous-crystalline phase boundaries, the a/c-Rh NSs
exhibit a higher catalytic activity compared with the c-Rh NSs.
By further alloying Cu, 100% conversion and >99.9% selectivity
of indole are obtained on the formed a/c-RhCu NSs. The modi-
fied electronic structure in bimetallic RhCu NSs can weaken the
interaction between Rh and hydrogen, which could be the reason
for the superior selectivity toward indole. Our work demonstrates
the importance of phase engineering of nanomaterials (PEN)
and metal alloying in the rational design of Rh-based catalysts,
providing a new avenue for developing efficient metal nanocata-
lysts for the fine chemical synthesis.
Keywords
amorphous structures, heterophases, indole synthesis, Rh and Rh alloys,
tandem catalysis, ultrathin nanosheets
Received: October 4, 2020
Revised: December 9, 2020
Published online: January 25, 2021
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Acknowledgements
J.G., P.Y., and Y.C. contributed equally to this work. The authors would
like to acknowledge the Facility for Analysis, Characterization, Testing,
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