Gold-Containing Catalysts Based on Mesoporous Metal–Organic Frameworks of the MIL Type for Regioselective Hydroamination Reaction of Phenylacetylene

Article abstract of DOI:10.1134/S0965544120080058

Abstract: Catalyst systems based on gold nanoparticles introduced into the matrices of mesoporous metal–organic frameworks of the MIL type based on trivalent metal ions (Al, Fe) manifest activity in the regioselective hydroamination of phenylacetylene with aniline according to the Markovnikov rule. The activity of the synthesized gold-containing systems significantly depends on the nature of organic and inorganic building units, metal ions, and organic linkers, which form the framework, as well as on the catalyst preparation procedure.

Full text of DOI:10.1134/S0965544120080058

ISSN 0965-5441, Petroleum Chemistry, 2020, Vol. 60, No. 8, pp. 895–902. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Sovremennye Molekulyarnye Sita, 2020.
Gold-Containing Catalysts Based on Mesoporous Metal–Organic
Frameworks of the MIL Type for Regioselective Hydroamination
Reaction of Phenylacetylene
V. I. Isaevaa, *, L. M. Kustova, b, **, G. I. Kapustina, G. S. Deikoa, E. V. Belyaevaa,
A. Zizganovaa, and O. P. Tkachenkoa
aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
bFaculty of Chemistry, Moscow State University, Moscow, 119991 Russia
*e-mail: sharf@ioc.ac.ru
**e-mail: LMK@ioc.ac.ru
Received November 20, 2019; revised April 5, 2020; accepted April 10, 2020
Abstract—Catalyst systems based on gold nanoparticles introduced into the matrices of mesoporous metal–
organic frameworks of the MIL type based on trivalent metal ions (Al, Fe) manifest activity in the regioselec-
tive hydroamination of phenylacetylene with aniline according to the Markovnikov rule. The activity of the
synthesized gold-containing systems significantly depends on the nature of organic and inorganic building
units, metal ions, and organic linkers, which form the framework, as well as on the catalyst preparation pro-
cedure.
Keywords: hydroamination, Markovnikov addition rule, metal–organic frameworks, nanoparticles, catalysis,
gold
DOI: 10.1134/S0965544120080058
INTRODUCTION
of heterogeneous systems affect the activity and selec-
tivity of M/MOF nanomaterials. On the other hand,
metal–organic frameworks utterly correspond to the
task of finding the effect of the method of preparation
on the catalytic properties of heterogeneous systems
due to a set of characteristics such as the topology and
functionality of the network, porosity, and structural
properties variable in a wide range. In this connection,
the development of simple methods for the immobili-
zation of precious metal nanoparticles in MOF matri-
ces for obtaining active and selective catalyst materials
is an important and at the same time unconventional
problem.
The aim of this work consisted in the preparation of
gold-containing nanomaterials based on metal–
organic frameworks (Au/MOF). Special attention was
paid to studying the effect of their preparation method
on the dispersity and localization of gold nanoparti-
cles in the metal–organic matrices, and, thus, on the
catalytic properties of the nanohybrids being formed.
In view of the above, Au nanoparticles were intro-
duced into highly porous MOF supports according to
two alternative procedures, namely, incipient wetness
(dry) impregnation and wet impregnation.
In the recent decade, metal–organic frameworks
(MOFs) have attracted the attention of researchers as
carriers of heterogeneous catalysts [1]. Metal–organic
frameworks are a class of ordered zeolite-like materi-
als, the structure of which is formed by inorganic and
organic building units, metal ions, and polydentate
organic linker molecules bound into a three-dimen-
sional framework by coordination bonds [2]. The
unique characteristics of these inorganic–organic
materials create conditions for fine tuning and con-
trolling heterogeneous catalyst systems based on them.
In particular, a high specific surface area and a high
pore volume with uniform size and shape distribution
make these systems promising materials for stabilizing
active metal nanoparticles that are labile under other
conditions [3]. The application of metal–organic
frameworks as matrices for the introduction of metal
nanoparticles promotes their uniform distribution and
guarantee of high dispersity. These characteristics of
supported metal nanoparticles create conditions for
enhancing the catalytic properties of thereby obtained
nanohybrids [4].
It is known that the method of introduction of a
metal into porous MOF matrices determines to a sig-
nificant extent the location and dispersity of the intro- nanoparticles depends on their size to a greater extent
duced nanoparticles [5]. In turn, these characteristics than in the case of nanoparticles of other metals, e.g.,
It is known [6] that the catalytic activity of Au
895

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ISAEVA et al.
Table 1. Metal–organic frameworks of the MIL type—the supports of Au nanoparticles
Specific surface area,
MIL
Composition
Porous structure
SBET, m2/g
MIL-100(Fe)
Fe3O(OH)(btc)2
btc = benzene-1,3,5-tricarboxylate
“Windows” of 0.55–0.86 nm
and voids of 2.5–2.9 nm
1665
2100
NH2–MIL-101(Al) Al3O(abdc)3
abdc = 2-aminobenzene-1,4-dicarboxylate
“Windows” of 1.2–1.6 nm
and voids of 2.9–3.4 nm
palladium. In this connection, one of the key prob- homogenous catalyst systems for carrying out this
lems for gold-containing catalysts is controlling the reaction have been developed [8]; however, published
particle size distribution in the corresponding range. sources contain only sporadic information about
As has been noted above, the use of metal–organic hydroamination in the presence of catalysts based on
frameworks with a certain topology of the framework MOF matrices [9].
structure and high porosity and specific surface area as
matrices for the encapsulation of gold nanoparticles
makes it possible to solve this problem. From this per-
spective, an important direction of this research was to
reveal the contribution from the characteristics of the
metal–organic frameworks (structure, topology) to
the stabilization of Au nanoparticles in these matrices
and the catalytic properties of the Au/MOF nanohy-
brids obtained. For this purpose, MIL-100(Fe) and
NH2–MIL-101(Al) mesoporous frameworks based
The synthesized MIL matrices and gold-contain-
ing catalysts based on them were characterized by a set
of instrumental methods, such as X-ray diffraction
(XRD) analysis, diffuse reflectance infrared Fourier-
transform spectroscopy (DRIFTS), and low-tem-
perature adsorption of nitrogen.
EXPERIMENTAL
Synthesis of MIL Samples and Gold-Containing
Catalysts on Their Basis
on Fe3+ and Al3+ ions and benzene-1,3,5-tricarboxyl-
ate and 2-aminobenzene-1,4-dicarboxylate linkers,
respectively, were used as the carriers of gold nanopar-
ticles (Table 1). These matrices were chosen due to the
large size of the pores in the form of nanocavities (2.4–
3.4 nm, Table 1). The presence of these voids limited
by small “windows” in NH2–MIL-101(Al) and MIL-
100(Fe) matrices makes it possible to provide a limit-
ing effect of the porous structure of the framework
with respect of gold nanoparticles.
The samples of MIL-100(Fe) and NH2–MIL-
101(Al) were prepared under solvothermal conditions
under autogenous pressure generated by solvent
vapors at an elevated temperature in a closed volume.
NH2–MIL-101(Al) [Al3O(abdc)3]. The sample
was synthesized according to a modified procedure
[10]. The synthesis conditions were modified as fol-
lows: the reaction temperature (110°C) was decreased
in comparison with the published procedure (130°C).
The mixture of the reactants AlCl3 · 6H2O (0.51 g,
2.11 mmol), 2-aminobenzene-1,4-dicarboxylic acid
(0.56 g, 3.09 mmol), and DMF (40 mL) was stirred
with a magnetic stirrer until complete dissolution of
the reactants and heated in a thermostat (110°C, 72 h).
The product was isolated on a centrifuge (4000 rpm),
rinsed with DMF (3 × 20 mL), and treated with ace-
tone (3 × 20 mL) followed by ethanol (3 × 20 mL).
The yellow crystalline substance was evacuated using
an oil pump (1 × 10−3 torr) for 2–4 h (20°C) and then
at a gradually increasing temperature: 90°C for 3 h,
120°C for 2 h, and 160°C for 4 h. A finely dispersed
yellow powder was obtained after evacuation.
To increase the efficiency of the metal–support
interactions, a NH2–MIL-101(Al) framework modi-
fied by amino groups in the organic linkers, which
may promote the stabilization of gold nanoparticles in
the pores and prevent their aggregation during and
after the catalytic reaction, was chosen. The MIL-
100(Fe) framework is of interest due to the coordina-
tively unsaturated sites, Fe3+ ions, which may provide
a synergistic effect in combination with Au nanoparti-
cles in the case of using Au/MIL-100(Fe) as a catalyst.
The regioselective hydroamination reaction of
phenylacetylene by aniline was chosen for testing the
catalytic properties of the Au/MIL obtained nanohy-
brids. It should be noted that the hydroamination
reaction attracts increased attention of researchers as a
direct way for forming the C–N bond with the prepa-
ration of valuable products and intermediate products
of fine chemical synthesis and physiologically active
MIL-100(Fe) [Fe3O(OH)(btc)2]. The sample of
MIL-100(Fe) was synthesized under hydrothermal
conditions according to a published procedure [11].
Anhydrous iron chloride (0.487 g, 1.0 mmol) and
(CH3O)3btc (0.499 g, 0.66 mmol) were dissolved in
compounds [7]. By now, various heterogeneous and 17 mL of distilled water. The resulting solution was
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GOLD-CONTAINING CATALYSTS BASED ON MESOPOROUS METAL–ORGANIC
897
placed into a 60-mL Teflon liner that was transferred uum, the adsorption of nitrogen on the sample was
into a steel autoclave. The autoclave with the reaction measured at −196°C. Different gas pressures were
mixture was heated in a drying oven at 130°C for 72 h. used to obtain the nitrogen adsorption isotherm. The
The precipitate formed was isolated by centrifuging, analysis was performed at a relative pressure of nitro-
rinsed with distilled water (3 × 10 mL), and then gen N2 P/P0 in the range of 0.01 to 0.99.
treated with dehydrated acetone (20 mL) under stir-
ring (24 h). It was further isolated on a centrifuge and
dried in vacuum (7 h, 60°C, 10−2 torr).
Catalytic Testing Experiments
Prior to introducing gold nanoparticles, the sam-
ples of mesoporous frameworks were activated in vac-
uum to remove the “guest” molecules of the reactants
and solvent (DMF), captured during the synthesis,
from the pores (150°C, 7 h, 10−2 torr).
A reaction mixture containing a catalyst (0.1 g,
0.05–2.5% mmol metal), phenylacetylene (1 mmol),
aniline (1 mmol), toluene (1 mL), and undecane (a
chromatographic standard, 0.07 mL, 0.3 mmol) was
stirred in a glass reactor with a magnetic stirrer in an air
atmosphere (110°C, 8–24 h).
The preparation of catalysts by incipient wetness
impregnation. Gold (3.7–5 wt %) was deposited by
mixing 1.2 g of a sample of MIL with a solution of
The composition of the reaction solution was stud-
ied by gas–liquid chromatography (GLC) (Kristally-
HAuCl4 · 3H2O (11–13 mg) in absolute ethanol uks chromatograph equipped with FID) on a capillary
column (OV-1 phase, 25 m) under programmed heat-
ing (100–170°C).
Recycling experiments. After carrying out the reac-
tion, the catalyst (5%Au/NH2–MIL-101(Al)) was
(0.30 mL). The samples containing the gold precursor
were dried under reduced pressure (90°C, 5 h) and
then subjected to vacuum heat treatment (100°C, 4 h,
10−2 torr).
Wet impregnation. The activated support (100 mg) separated by centrifugation, rinsed with toluene (3 ×
was mixed with a solution of HAuCl4 · 3H2O (50 mg) 1 mL), refluxed in 1 mL of toluene, and then the cat-
alyst was repeatedly isolated by centrifugation and
reused under the same conditions of the catalytic reac-
tion.
in deionized water (5 mL) at 50°C (24 h).
Gold nanoparticles introduced into the MIL-
100(Fe)
and
NH2–MIL-101(Al)
matrices
were obtained by reduction with a sodium borohy-
dride solution in ethanol (22°C). Then, the gold-con-
taining hybrid nanomaterials based on the MIL matri-
ces (Au/MIL) were dried in a vacuum (150°C, 5 h,
10−2 torr).
RESULTS AND DISCUSSION
The samples of MIL synthesized under solvother-
mal conditions are distinguished by a high specific
surface area, the value of which coincides with the
published data [10, 11] (Table 1).
Gold nanoparticles were introduced into the
matrices of the mesoporous MIL structures by the
postsynthesis modification of the preliminarily syn-
thesized metal–organic frameworks. According to the
published data, the deposition of a metal by wet
impregnation leads to the formation of particles inside
the support pores, whereas the nanoparticles are
mainly localized on the support surface in the case of
incipient wetness impregnation [3].
Instrumental Characterization of MIL Samples
and Au/MIL Catalysts Based on Them
X-ray diffraction analysis. To confirm the phase
composition of the samples, X-ray diffraction mea-
surements were performed at room temperature on an
EMPYREAN powder diffractometer (PANalytical,
the Netherlands) (nickel-filtered CuKα radiation, an
X’Celerator linear detector, Bragg–Brentano geome-
try) in the 2θ angle range of 7°–40° .
Infrared (IR) spectra of the samples were obtained
on a Nicolet Protege 460 spectrometer by the diffuse
scattering procedure. The Fourier-transform IR spec-
tra were recorded at a resolution of 2 cm−1. The data
acquisition and processing were performed using the
OMNIC software package. The adsorption of CO
(10 torr) was carried out at room temperature followed
by its desorption in a vacuum.
Physical adsorption of nitrogen. The porous struc-
ture and surface area of the synthesized materials were
characterized using a Micromeritics ASAP-2020-Plus
instrument by volumetric measurement of nitrogen
Instrumental Studies of Mesoporous MIL-100(Fe)
and NH2–MIL-101(Al) Frameworks and Au/MIL
Nanomaterials Based on Them
The morphology of the synthesized NH2–MIL-
101(Al) sample was identified by comparing the exper-
imental X-ray diffraction pattern with the theoretical
X-ray diffraction pattern by the known crystal lattice
parameters (cubic cell Fd-3m, a = 87.536(27) Å [12]
(Fig. 1)).
The morphology of the obtained sample of MIL-
adsorption; the parameters of the porous structure 100(Fe) was identified by comparing the experimental
were calculated by the Brunauer–Emmett–Teller X-ray diffraction pattern with the theoretical X-ray
(BET) equation. After degassing at 150°C in a vac- diffraction pattern by the known crystal lattice param-
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ISAEVA et al.
40000
35000
30000
25000
20000
15000
10000
5000
1
3
2
0
10
20
2ꢀ
Fig. 1. (1) X-ray diffraction pattern of the synthesized sample of NH –MIL-101(Al). (3) Calculated X-ray diffraction pattern.
2
(2) Difference curve on the structure refinement.
600000
1
500000
400000
300000
200000
2
100000
0
3
10
20
30
40
2ꢀ
Fig. 2. (1) X-ray diffraction pattern of the synthesized sample of MIL-100(Fe). (3) Calculated X-ray diffraction pattern. (2) Dif-
ference curve on the structure refinement.
eters (cubic cell Fd-3m, a = 72.1 Å, V = 388000 Å [11]
Probably, the presence of the functional amino
group in the 2-aminobenzene-1,4-dicarboxylate
linker of the mesoporous support stabilizes the
charged Aun+ particles in this case, thereby preventing
their further reduction. In addition, the specific topol-
ogy of the framework structure, the presence of large
voids limited by small “windows” (see Table 1), in
combination with the method of preparation of the
5%Au/NH2–MIL-101(Al) nanohybrid by wet
impregnation promotes the predominant localization
of the gold particles in the volume of the metal–
organic matrix.
(Fig. 2)).
The XRD study of the obtained Au/MIL nanohy-
brids indicate that the introduction of gold nanoparti-
cles preserves their crystal structure (Fig. 3a). In the
case of the samples prepared by incipient wetness
impregnation, there is the formation of large (up to
~25 nm) gold nanoparticles on the surface of the MIL
supports (Fig. 3b). Probably, in the near-surface layers
of the metal–organic matrix, its limiting effect in rela-
tion to gold nanoparticles is not as pronounced as in its
bulk.
The electronic state of the gold particles localized
in the NH2–MIL-101(Al) mesoporous matrix was
studied by IR spectroscopy of adsorbed CO as a probe
molecule The study of the 5%Au/NH2–MIL-101(Al)
nanohybrid prepared by impregnation in a solvent
excess showed that gold in the oxidized state was pres-
Phenylacetylene Hydroamination by Aniline
over Au/MIL Nanohybrids
The synthesized Au/MIL nanohybrids demon-
strate a quite high activity in the regioselective
ent in the form of Aun+ particles on the amine-modi- hydroamination of phenylacetylene by aniline accord-
fied support (Fig. 4).
ing to the Markovnikov rule (Scheme 1).
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GOLD-CONTAINING CATALYSTS BASED ON MESOPOROUS METAL–ORGANIC
899
600000
500000
400000
300000
200000
100000
0
(a)
1
3
2
0
10
2ꢀ
80000
60000
40000
20000
0
(b)
1
3
2
30
40
50
60
70
80
2ꢀ
Fig. 3. (a) X-ray diffraction patterns of an Au/MIL-100(Fe) gold-containing nanohybrid in the region of small angles: (1) experi-
mental and (2) theoretical. (3) Difference curve on the structure refinement. (b) X-ray diffraction patterns of an Au/MIL-100(Fe)
gold-containing nanohybrid in the region of high angles: (1) experimental and (2) theoretical. (3) Difference curve on the structure
refinement. The average diameter of the gold nanoparticles localized on the surface of MIL-100(Fe) is ~25 nm.
0.5
2177
Au0+
CO, 10 Torr, 20ꢁC
Vacuum, 20ꢁC, 30 min
0.4
0.3
0.2
0.1
0
2200
2100
2000
1800
2300
Wavelength, cm−1
Fig. 4. Spectrum of CO adsorbed on the 5%Au/NH –MIL-101(Al) gold-containing nanohybrid prepared by the impregnation
2
in an excess of a solvent.
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ISAEVA et al.
NH2
HN
+
O
NH2
N
H2O
+
Scheme 1. Hydroamination of phenylacetylene by aniline.
Depending on the nature of the metal–organic posite obtained by dry impregnation. Apparently, the
support and the method for preparing the gold-con-
taining nanocatalyst, almost quantitative conversion is
observed over 19–30 h (Table 2). The activity of the
synthesized Au/MIL catalyst systems is determined to
a significant extent by the nature of the organic linker
and inorganic building unit (metal ion) in the compo-
sition of the framework, as well as by the framework
preparation procedure. The highest rate of hydroami-
nation (expressed in TOF) is achieved over gold-con-
taining MIL-100(Fe) obtained by dry impregnation.
This method of preparation promotes the accessibility
of the active sites, Au nanoparticles, localized near the
surface of the MIL-100(Fe) framework, for the sub-
strates phenylacetylene and aniline. In addition, in the
amino groups in the organic linkers of the NH2–MIL-
101(Al) framework promote the stabilization of the
active sites in the bulk of the metal–organic matrix.
The method of preparation by wet impregnation has
an additional effect in relation to the immobilization
of Au nanoparticles in the intracrystalline space of the
framework. Such a specific location of the active sites
inside the pores of the support complicates the mass
transport (internal diffusion) of the bulky molecules of
the reactants and products to them.
All the synthesized Au/MIL catalytic nanomateri-
als demonstrate high imine (target product) selectivity
in the hydroamination reaction (Table 2). The selec-
case of the MIL-100(Fe) matrix based on Fe3+ ions, a tivity of gold-containing catalyst systems depends on
synergistic effect of the second metal (iron) that
increases the activity of the Au/MIL-100(Fe) nano-
hybrid and yield of the imine (hydroamination prod-
uct) is possible.
both the method of introduction of Au nanoparticles
and the framework functionality. In particular, the
highest imine selectivity of the reaction of ~95–99% is
achieved in the case of the 5%Au/NH2–MIL-101(Al)
catalyst system prepared by wet impregnation. On the
opposite, the imine selectivity of hydroamination is
noticeably lower (30.4%) over the 3.7%Au/MIL-
The lowest activity and yield of the target product
(imine) are observed for the gold-containing catalyst
based on the NH2–MIL-101(Al) framework prepared
by wet impregnation. When carrying out the hydroam- 100(Fe) nanohybrid based on the MIL-100(Fe)
ination over this sample (5%Au/NH2–MIL-
101(Al)*), the yield of the target product and the con-
version of the reactants are lower than those in the
presence of the 5%Au/NH2–MIL-101(Al) nanocom-
framework. The increased selectivity of the Au/NH2–
MIL-101(Al) nanohybrid is probably due to the effect
of the amino group in the organic linker. This func-
tional group may facilitate the uniform distribution of
Table 2. Hydroamination of phenylacetylene over Au/MIL nanohybrids. Catalyst (0.1 g, 2.5% mmol metal), phenylacety-
lene (1 mmol), aniline (1 mmol), Treact = 110°C
TOF × 103, Reaction Conversion, Yield of imine, Yieldofketone, Imine selectivity,
Nanohybrid
s−1
time, h
%
%
%
%
5%Au/NH2–MIL-101(Al)*
5%Au/NH2–MIL-101(Al)
3.7%Au/MIL-100(Fe)
0.3
2.9
10.6
81.0
22.0
20.0
52.4
75.0
99.0
41.3
75.0
30.0
11.1
0.0
69.0
78.8
99.0
30.4
* The catalyst is synthesized by wet impregnation.
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GOLD-CONTAINING CATALYSTS BASED ON MESOPOROUS METAL–ORGANIC
901
1
4000
2
3000
2000
1000
10
15
20
2ꢀ
25
30
35
0
5
Fig. 5. X-ray diffraction patterns of a 5%Au/NH –MIL-101(Al) nanohybrid (1) before and (2) after carrying out the catalytic
2
reaction.
gold particles in the bulk of the metal–organic matrix agreement with the results of the XRD study of the
and thus provide the uniformity of the active sites.
morphological stability of the 5%Au/NH2–MIL-
101(Al) nanohybrid under the conditions of the
hydroamination reaction. Comparing the X-ray dif-
fraction patterns of this heterogeneous system before
and after catalysis (Fig. 5) shows the preservation of
the morphology of the NH2–MIL-101(Al) metal–
organic framework. In addition, the intensity of the
reflection at a high angle of ~38°, which corresponds
to gold nanoparticles, remains unchanged after carry-
ing out the phenylacetylene hydroamination by aniline
over 5%Au/NH2–MIL-101(Al). This indicates the
absence of the undesired “leaching” of the active
phase under these conditions.
Catalytic Stability of the 5%Au/NH2–
MIL-101(Al) Nanohybrid
The stability of the 5%Au/NH2–MIL-101(Al)
heterogeneous system was studied in three catalytic
cycles of hydroamination of phenylacetylene with ani-
line. It should be noted that the difference in the val-
ues of aniline conversion in the first catalytic cycle
(Table 3) in comparison with the results presented in
Table 2 is apparently explained by the different con-
centrations of the catalyst (5%Au/NH2–MIL-
101(Al)) in both cases. Indeed, we earlier showed that
the catalyst concentration in the reaction mixture
should be 2.5 mmol % Au under the optimum condi-
tions. It is seen from Table 3 that the conversion of ani-
line decreased by 50% in the third catalytic cycle. This
phenomenon may be associated with the increased
adsorption of the unreacted aniline and the product
imine in the support pores despite the treatment of the
catalyst with toluene after the completion of the reac-
tion. The imine selectivity decreases in the second and
third catalytic cycles. Possibly, the partial shielding of
the amino groups in the organic linkers of the NH2–
MIL-101(Al) matrix by the products, which, in turn,
leads to a change in the microenvironment of the
active sites (gold nanoparticles) in the pores of the
metal–organic support, makes a certain contribution
to the decline in the selectivity.
The obtained data on the reuse of the 5%Au/NH2–
MIL-101(Al) catalyst system indicate the need for fur-
ther optimization of the experimental conditions of
the catalytic hydroamination reaction and regenera-
tion of the Au/MIL heterogeneous systems, first of all,
provision of the conditions for the effective desorption
of the reaction products from the pores of the metal–
organic matrices.
In summary, the regioselective hydroamination of
phenylacetylene with aniline was carried out in the
presence of Au/MIL gold-containing hybrid nanoma-
terials for the first time. The activity and selectivity of
the gold nanoparticles fixed in the matrices of the
mesoporous metal–organic frameworks in the reac-
tion under study substantially depend on the method
of preparation of the gold-containing nanocatalysts, as
well as on the nature of the metal–organic framework
including the inorganic building units (metal ions)
and on the functionality of pore walls. The XRD data
indicate the retention of the morphology of the
Au/NH2–MIL-101(Al) nanohybrid after the
The assumption that the decrease in the conversion
of the heterogeneous system under study in the cata-
lytic cycles is associated with the blocking of active
sites in the support pores, rather than with the
decrease in the concentration of the active phase, is in
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ISAEVA et al.
4. M. Meilikhov, K. Yusenko, D. Esken, et al., Eur. J.
hydroamination reaction. The highest rate of
hydroamination of phenylacetylene by aniline is
achieved in the case of using the Au-containing MIL-
100(Fe) nanomaterial obtained by incipient wetness
impregnation. Conversely, the Au/NH2–MIL-
101(Al) hybrid nanomaterials exhibit increased selec-
tivity in comparison with the Au/MIL-100(Fe) nano-
catalyst. Therefore, the use of Au/MIL nanohybrids
makes it possible to control their catalytic properties in
the practically important reaction under study.
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PETROLEUM CHEMISTRY
Vol. 60
No. 8
2020