Chemoselective hydrogenation of α,β-unsaturated aldehydes over Rh nanoclusters confined in a metal-organic framework

Article abstract of DOI:10.1039/d0ta01845g

Selective hydrogenation of α,β-unsaturated aldehydes to achieve high selectivity towards a desirable product is still a great challenge mainly because of the complex conjugate system. Herein, Rh nanoclusters encapsulated in MIL-101 (Cr), synthesized by the double solvent method, are able to selectively hydrogenate C-C of cinnamaldehyde, an α,β-unsaturated aldehyde and achieve over 98percent selectivity with a conversion of 98percent to a saturated aldehyde under mild conditions. Fourier transform infrared spectroscopy confirms that MIL-101 acts as an aldehyde protector to suppress the reactivity of C-O, and the X-ray photoelectron spectroscopy (XPS) data indicate that the electropositive Rh, owing to the electron transfer from Rh to MIL-101, preferentially absorbs C-C rather than C-O leading to -improvement of the selectivity towards saturated aldehydes. In addition, Rh@MIL-101 can also efficiently catalyse hydrodefluorination of aryl fluorides with good stability. This work provides a basic strategy to develop other selective heterogeneous catalystsviastructural modulation for synergetic catalysis.

Full text of DOI:10.1039/d0ta01845g

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DOI: 10.1039/D0TA01845G
PAPER
Chemoselective hydrogenation of α, β-unsaturated
aldehyde over Rh nanoclusters confined in metal-
organic framework †
Received 00th February 20xx,
Accepted 00th February 20xx
a
a
a
a
a
DOI: 10.1039/x0xx00000x
Qinglin Liu, Yinle Li, Yanan Fan, Cheng-Yong Su and Guangqin Li*
Selective hydrogenation of α, β-unsaturated aldehyde to achieve high selectivity towards a desirable product is
still a great challenge, mainly because of the complex conjugate system. Herein, Rh nanoclusters encapsulated in
MIL-101 (Cr), synthesized by double solvents method, are able to selectively hydrogenate C=C of α, β-unsaturated
aldehyde cinnamaldehyde and achieve over 98% selectivity with conversion of 98% to saturated aldehyde in mild
condition. The Fourier transform infrared spectroscopy confirms that MIL-101 acts as aldehyde protector to
suppress the reactivity of C=O, and the X-ray photoelectron spectroscopy (XPS) data indicates that the
electropositive Rh, owing to the electron transfer from Rh to MIL-101, preferentially absorbs C=C rather than C=O
leading to improvement of the selectivity of saturated aldehyde. In addition, Rh@MIL-101 can also efficiently
hydrodefluorinate of aryl fluoride with good stability. This work gives out a basic strategy to develop other selective
heterogeneous catalysts via structure modulation for synergetic catalysis.
speculated that Rh element may be a superior candidate for selective
hydrogenation of α, β-unsaturated aldehydes.
Metal-organic frameworks (MOFs) are well-known for their large
internal surface areas, stable chemical structure and appropriate size
Introduction
To hydrogenate α, β-unsaturated aldehyde towards high yields of
saturated aldehyde or unsaturated alcohol is significantly important
for industrial manufacture, such as petrochemicals, pharmaceuticals
and perfume.1-4 Because the complex conjugate system including two
active functional groups of C=C and C=O, it is difficult to accurately
crack only one functional conjugate bond.5-8 Cinnamaldehyde (CAL),
a classical α, β-unsaturated aldehyde with both C=O bond and C=C
bond, is a complex conjugated system. A great amount of noble metals
based catalysts (such as Pt, Pd) for selective hydrogenation CAL to
hydrocinnamaldehyde (HCAL) have been reported recently,9-14
of pores.26-31 Owing to these outstanding characteristics, MOFs have
been attached great attention in heterogeneous catalysis, especially for
compound combined MOFs with metal particles.32-36 Metal particles
can be confined into MOFs, which will keep the metal from
aggregating or losing for long durability with high activity.37-41 In
addition, the organic linkers or the metal nods of MOFs can be a sort
of Lewis acid site, which may accelerate the reaction process and
improve the selectivity of the desired product.39, 41-44
Herein, we report
a highly efficient and chemoselective
heterogeneous catalyst Rh@MIL-101 which has been prepared by
double solvents method. The obtained Rh@MIL-101 exhibits
excellent performance in selective hydrogenation of CAL with 98%
conversion in 5 h and over 98% selectivity of HCAL, much better than
commercial Rh/C and other M@MIL-101 (M=Pt, Pd), and maintains
stable activity after 6 successive cycles. More importantly, the Lewis
acid site from MIL-101 and significant C=C bond hydrogenation
ability from Rh nanoclusters may promote the selective hydrogenation.
however, the selectivity is usually lower than 90% over 1 MPa H
2
gas.15-17 Moreover, the hydrogenation of C=C or C=O is easily over
hydrogenated to saturated alcohol.18-20 Hence, to find out a kind of
catalysts with a powerful ability to hydrogenate only C=C or C=O in
the conjugated compounds is still a great strategy. Although Rh-based
catalyst applied for selective hydrogenation of α, β-unsaturated
aldehydes is rarely reported, it has been applied in unsaturated
aldehydes hydrogenation, such as benzaldehyde, exhibiting excellent
activity and selectivity towards saturated aldehyde.21-25 Thus, it can be
Experimental
a
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of
Materials.
Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275,
P. R. China. E-mail: liguangqin@mail.sysu.edu.cn.
Chromic chloride hexahydrate (CrCl
3
·6H
2
O), terephthalic acid
RhCl ), and sodium
†
Electronic
Supplementary
Information
(ESI)
available.
See
(H
2
BDC), sodium hexachlororhodate (III) (Na
3
6
DOI: 10.1039/x0xx00000x
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J Po lue ran sael od fo Mn aot te rai ad l js u Cs ht emm ai rs gt ri yn sA
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Journal of Materials Chemistry A
4
) were purchased from Aladdin (Shanghai, Hydrodefluorization of aryl chlorides.
borohydride (NaBH
View Article Online
China). All the chemicals were used without any further purification.
DOI: 10.1039/D0TA01845G
.1 mmol aryl chlorides and 10 mg catalyst were added to 5 mL water
0
and kept ultrasound for 5 min to obtain a homogeneous solution
before transferred into a 25 mL round-bottom flask. Removed the air
Preparation of Rh@MIL-101.
The MIL-101 (Cr) was synthesized according to the literature reported in the round-bottom flask and then kept the final H
before.5 Rh nanoclusters were confined within MIL-101 (Cr) by 0.1MPa using a H
balloon. After finishing the reaction, the solution
double solvents method. Briefly, 100 mg MIL-101 was dispersed in was extracted by ethyl acetate and then analyzed by GC-MS.
0 mL of n-hexane, 180µL deionized water containing 0.05 mmol
Na RhCl was added dropwise within 20 min, under vigorously
2
pressure at
2
2
3
6
stirring. After stirring for 3h, the solid powder was settled down in the
bottom and then the supernatant was decanted, allowed the powder
get dried in air at room temperature. The as-synthesis sample was
further dried at 150 ⁰C under vacuum for 10 h. After removing
n-hexane and water in MIL-101, Rh ion was reduced by adding 5 mL
Result and discussion
To produce Rh nanoclusters confined in metal-organic framework,
MIL-101 (Cr) was firstly synthesized by the hydrothermal method as
reported (Fig. S1†).2a The double solvents method was adopted to
0
4
.6 M NaBH , after vigorously stirring for 30 min, the grey product
prepare the Rh@MIL-101 catalyst, and morphology was analyzed by
transmission electron microscopy (TEM). As shown in Fig. 1, Rh
nanoclusters homogeneously dispersed in the MIL-101, with the mean
diameter of 1.7 nm (Fig. 1a and Fig. S2†). The high resolution
transmission electron microscopy (HRTEM) image showed the lattice
fringe of 0.22 nm, which was corresponding to the (111) plane of Rh
element (Fig. 1b). To test the element distribution of Rh@MIL-101,
energy-dispersive X-ray spectroscopy (EDS) element mappings were
carried out, and Rh element was distributed homogeneously in the
entire MIL-101 (Fig. 1c). To confirm the structure of as-prepared
materials, X-ray diffraction (XRD) was examined and shown in Fig.
S3†. The obviously diffraction peaks of Rh@MIL-101 were
corresponding to pristine MIL-101, no diffraction peaks from the
structure of face-centered-cubic (fcc) Rh were observed, due to the
low amount of Rh loading and ultrafine size of the particles, which
was collected by centrifuging and washed by water for 3 times, and
was dried at 60 ⁰C under vacuum overnight.
Preparation of Rh nanoparticles.
Rh nanoparticles were synthesized by directly reduced using NaBH
as reductant. Briefly, 0.1 mmol Na RhCl was dissolved in 5 mL water,
mmol NaBH was added and stirred for 30min. The products were
4
3
6
3
4
obtained after washing with double-distilled water for several times
and dispersed in 1ml EtOH for further use.
Characterization.
The morphology and microstructure were tested by field-emission
scanning electron microscopy (FESEM, SU8010, Hitachi) and
transmission electron microscopy (TEM, JEM-1400 Plus, JEOL).
High resolution images and element mappings were carried out on
high-resolution transmission electron microscopy (HRTEM,
ARM200P, JEOL). The crystalline structures of samples were
characterized by powder X-ray diffraction (XRD, Rigaku, SmartLab),
with Cu Kα radiation under operation conditions of 40 kV and 30 mA.
X-ray photoelectron spectroscopy (XPS) spectra were tested by a VG
ESCALABMKII instrument. Fourier transform infrared (FT-IR)
spectra were detected on Bruker Alpha spectrometer. Metal content of
the catalysts was analyzed by inductively coupled plasma mass
was consistent with TEM images.39,45 The N
2
adsorption isotherms of
MIL-101 and Rh@MIL-101 both showed a mixture of type I and IV
curves (Fig. S4†). The Brunauer–Emmett–Teller (BET) surface area
2
-1
3
-1
and total pore volume of MIL-101 were 3735 m g and 1.63 cm g ,
respectively. Compared to pure MIL-101, the BET surface area and
2
-1
3
pore volume of Rh@MIL-101 decreased to 1715 m g and 0.63 cm
g-1, indicating that the cavities of MIL-101 were partially occupied by
highly dispersed Rh nanoclusters.46,47 The Fourier transform infrared
(FT-IR) spectrum of Rh@MIL-101 still preserved the characteristics
of MIL-101 (Fig. S5†). The actual metal amount of catalyst was 4.4
wt%, confirmed by inductively coupled plasma mass spectrometry
2
spectrometry (ICP-MS, Themo Fisher Scientific). The N adsorption-
desorption isotherms were determined by Quantachrome Instruments
Autosorb-iQ2-MP at 77K.
Chemoselective hydrogenation of cinnamaldehyde.
In a typical procedure, 5 mg catalyst was dispersed in 3 mL ethanol
then 100 µL cinnamaldehyde (CAL) was added to the mixture in a
high-pressure reaction glass vial. The glass vial was purged with pure
2 2
H for at least 3 time to remove the air, and eventually kept the H
pressure at 1 MPa. The reaction was carried out at desired time and
temperature, and kept stirring with the speed of 600 rpm. After
finishing the reaction, the solution was centrifuged and then analyzed
by gas chromatography - mass spectrometry (GC-MS, SHIMAZU
QP 2010) with a flame ionization detector (FID).
Fig. 1 (a) TEM image (b) HRTEM image and (c) HAADF-STEM-
EDS element mappings of Rh@MIL-101.
J. Mater. Chem. A, 2020, X, XXXXX-XXXXX
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(
ICP-MS), listed in Table S1†. Taking account for the EDS mapping over 98%. This implies that Rh@MIL-101 could giVvieewoAurtticlaelOmnolinset
result, XRD and ICP-MS, Rh nanoclusters dispersed homogeneously single hydrogenation product and avoid overDhOyId:r1o0g.1e0n3a9t/iDn0gT. A01845G
in the MIL-101 have been successfully synthesized. For comparison, Pt@MIL-101, Pd@MIL-101 were synthesized by
To investigate the activity and selectivity of α, β-unsaturated the same recipe, and the XRD patterns and morphology images had
aldehydes hydrogenation, cinnamaldehyde was selected to evaluate no significant difference with Rh@MIL-101 (Fig. S3 and S6†). Then,
the performance of Rh@MIL-101. Since both of the selectivity pure Rh nanoparticles were prepared by directly reduced using NaBH .
4
hydrogenation products, hydrocinnamaldehyde (HCAL) and Obviously, Rh nanoparticles with mean diameter of 5.7 nm were
cinnamyl alcohol (COL), are widely used as perfume or reaction larger than Rh nanoclusters within MIL-101 from TEM image (Fig.
intermediate, there is a great desire to develop catalysts with S7†), further demonstrating the significance of confinement effects of
wonderful activity and selectivity, to solely hydrogenate C=O bond or the MIL-101. These four kinds of catalysts were performed CAL
C=C bond.48-51 The hydrogenation reaction here was carried out in hydrogenation under the same condition as Rh@MIL-101, and the
relatively mild conditions, and the results were displayed in Fig. 2. results were shown in Fig. 2e. Pt@MIL-101 showed the unsatisfied
The schematic of CAL hydrogenation is shown in Fig. 2a, activity (55%) and the Pd@MIL-101 presented 92% conversion of
cinnamaldehyde is firstly hydrogenated to HCAL or COL, and CAL, but generated 27% of over hydrogenation product. As for
sequentially experienced over hydrogenating to undesired product commercial Rh/C, with the average particle size of 2.3 nm (Fig. S8†),
HCOL. Then, the impact of temperature towards the hydrogenation merely achieved 53% of CAL conversion. Pure Rh NPs performed
reaction was explored (Fig. 2b). The conversion could reach more even worse (merely 20% conversion) in hydrogenation reaction,
than 98% with high selectivity from 30 ℃ to 90 ℃, which means that
the catalyst retains an impressive performance in a wide range of
temperature. Hence, 30 ℃ was chosen as a proper temperature in the
following tests. And the time-source hydrogenation reaction data (Fig.
mainly due to the large size and severe aggregation. MIL-101 had
less than 5% selectivity of HCAL, which could be thought as a
negligible influence for Rh@MIL-101 hydrogenation reaction. The
detailed catalysis results including turnover frequency (TOF) based
on metal loading were calculated to evaluate intrinsic reactivity, and
2
c) showed that the reaction conversion raised from 42% in first 0.5 h
to 98% after 5 h, and the selectivity for HCAL kept in a high level (＞ listed in the Table S2†. It should be noted that Rh@MIL-101
8%) in 5 h. When the reaction time was extended to 6 h, the presented the best activity and selectivity compared to other noble
selectivity was well remained, indicating the over hydrogenation metal catalysts and commercial Rh/C, indicating the support MIL-101
hardly happened. Furthermore, reaction under different H pressures accelerated the reaction process and may act as active site for aldehyde
9
2
was carried out (Fig. 2d). With increasing the gas pressure, reaction protector to enhance HCAL selectivity.
conversion raised rapidly, while the selectivity of HCAL was always
Fig. 2 (a) Schematic of CAL hydrogenation. (b) Activity and
selectivity changes of Rh@MIL-101 for hydrogenation of CAL with
different temperature after 5 h. (c) different time at 30 ℃ after 5 h
2
and (d) different H pressure after 5 h. (e) The activity and selectivity
changes for hydrogenation of CAL with different catalysts after 5 h
at 30 °C. (f) The stability test of Rh@MIL-101 for hydrogenation of
CAL (reaction conditions: 100 µL CAL, 5mg catalysts, 30 °C, 5 h,
1
2
MPa H ).
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Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/D0TA01845G
a
b
Conversion
Sel phenol
Table 1 Selective Hydrogenation of Different α, β - Unsaturated
Sel cyclohexanone
Sel
cyclohexanol
a
Aldehydes over Rh@MIL-101.
c
d
Time Conv.
Sel.
(%)
Entry
Substrate
Product
(h)
(%)
1
2
3
99
98
98
Fig. 3. (a) HCAL and COL hydrogenation performances of Rh@MIL-
5
99
101. (b) FT-IR spectra of CAL adsorption on the Rh@MIL-101. (c)
possible mechanism for CAL hydrogenation over Rh@MIL-101 with
MIL-101 as aldehyde protector.
4
F i3g . (a) Schematic of p-fluorophenol 1h 2y drodef 8l u0 orizatio 9n 5.
(b) Hydrodefluorization performance over Rh@MIL-101 within
04 min. (c) Catalytic activity and selectivity of dif 6f erent c a9 t 0a lysts. ( 8d 1)
Stability test of Rh@MIL-101 for p-fluorophenol hydrodefluorization.
9
Recycle ability is necessary to be considered to fully evaluate the
catalytic performance. Thereby the stability test of Rh@MIL-101
for selective hydrogenation was carried out. Even after 6 successive
cycles of CAL hydrogenation reaction, Rh@MIL-101 still retained
great activity and selectivity to HCAL, as shown in Fig. 2f. The
structure and morphology of reused catalyst were detected to be
maintained (Fig. S9†), indicating that MIL-101 kept the Rh
nanoclusters from aggregation and presented the excellent catalytic
performance and recycle ability.
Reaction condition: room temperature, H
p-fluorophenol.
2
balloon, 90min, 0.1mmol
5
6
93
92
6
4
99
99
a
Reaction condition: α, β - unsaturated aldehydes (0.5 mmol),
2
catalyst (5mg), Ethanol (3 mL), 30 °C, 1 MPa H , monitored by gas
To investigate the universality of Rh@MIL-101, different α, β-
unsaturated aldehydes were hydrogenated to corresponding
saturated aldehyde by Rh@MIL-101. As shown in Table 1, almost
all the substrates can reach over 90% conversion within 6 h reaction,
accompanied by high selectivity towards saturated aldehyde products.
Due to the steric hindrance brought by ethyl, β-ethylcinnamaldehyde
achieved only 80% conversion even after 12 h reaction, but still
remained high selectivity for C=C bond hydrogenation product. It
suggests that Rh@MIL-101 is an excellent catalyst for selective
hydrogenation of α, β-unsaturated aldehydes.
To further understanding the reason for high selectivity of CAL
hydrogenation over Rh@MIL-101, the COL and HCAL
hydrogenation reactions were explored over Rh@MIL-101 (Fig. 3a).
COL was completely hydrogenated to HCOL within 1 h. On the
contrary, HCAL hardly converted to HCOL in the entire reaction,
indicating that Rh@MIL-101 can actively transform CAL to HCAL,
chromatography-mass spectrometry (GC-MS).
shown in Fig. 3b, the obvious C=O stretching vibration peak (1679
-1
cm ) can be found in the spectra of pure CAL. When the catalyst
Rh@MIL-101 was added and stirred for only 1min, the absorbance of
C=O stretching vibration peak was severely weakened and the peak
-1
was red shift to 1672 cm . After stirring for 30 min, it became much
-1
weaker and further red shift (1670 cm ), which may be attributed to
interaction between the Lewis acid sites of MIL-101 and one of the
oxygen lone pairs,5, 59,60 as the similar adsorption behavior was found
on the bare MIL-101 (Fig. S11†). The interaction between aldehyde
group and MIL-101 inhibited the hydrogenation of C=O bond. This
reveals that the synergistic effect of electropositive Rh nanoclusters
and aldehyde protector MIL-101 is the key to avoid over
but inhibit C=O bond hydrogenation, leading to the high yield of hydrogenation and keeps high selectivity of saturated aldehyde.
HCAL.
Encouraged by these promising results, we believe that Rh@MIL-
Since the surface electronic property is related to the selectivity of 101 may be also a good candidate catalyst for other heterogeneous
catalyst to a great extent,52-55 the chemical state of Rh@MIL-101 was reaction. Here the catalytic activity of Rh@MIL-101 for the
characterized by X-ray photoelectron spectroscopy (XPS). As shown hydrodefluorination of aryl fluorides was further examined in mild
in Fig. S10†, the strong peak at 307.5 eV and 312.1 eV were condition. As shown in Fig. 4, p-fluorophenol was completely
0
corresponding to Rh 3d5/2 and 3d3/2 of pure Rh NPs, respectively. hydrodefluorinated within 30 min over Rh@MIL-101, and produced
0
After combining with MIL-101, the peak of Rh shifted to 307.9 eV 92% of final product cyclohexanol after 90 min reaction. Rh@MIL-
and 312.5 eV. In addition, the peak of Cr 2p3/2 obviously shifted from 101 performed much better than other catalysts (Table S3†), and
5
77.9 eV to 577.3 eV after immobilization of Rh NPs, indicating the retained stable activity even after eight rounds of hydrodefluorination
electron transfer happened from Rh to MIL-101.56,57 Since C atom in reaction (Fig. 4d and S12†). In addition, Rh@MIL-101 was also
the C=O is electropositive, electropositive Rh in MIL-101 may be able suitable for catalyzing some other aryl fluorides and presented
to absorb the C=C bond rather than C=O, result in the high selectivity excellent activity (Table S4†). In brief, Rh@MIL-101 is thought as an
towards HCAL.9, 58
outstanding catalyst for hydrodefluorination, which would be benefit
To deeply explore the mechanism for selective hydrogenation, FT- to degrade the excess fluorochemical in the environment.61-62
IR was used to examine the adsorption of CAL on Rh@MIL-101. As
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1
497.
Conclusions
View Article Online
1
1
1
1 W. Lin, H. Cheng, L. He, Y. Yu and F. ZhDaOo,I:J1.0C.10a3ta9l/.D, 02T0A1031,834053G,
10-116.
1
To conclude, Rh nanoclusters confined with MIL-101 have been
synthesized for selective hydrogenation of α, β-unsaturated aldehyde.
Rh@MIL-101 presents excellent performance in selective
hydrogenation of cinnamaldehyde with 98% conversion in 5 h and
over 98% selectivity towards saturated aldehyde. Because Lewis acid
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Conflict of interest
The authors declare no conflict of interest.
22 Y. Cao, M. Tang, M. Li, J. Deng, F. Xu, L. Xie and Y. Wang, ACS
Sustain. Chem. Eng., 2017, 5, 9894-9902.
2
3 D. J. M. Snelders, N. Yan, W. Gan, G. Laurenczy and P. J. Dyson,
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This work was supported by National Key R&D Program of China
(
2018YFA0108300), High Level Talent of China and Guangdong 25 M. Ibrahim, R. Poreddy, K. Philippot, A. Riisager and E. J. Garcia-
Province, The 100 Talents Plan Foundation of Sun Yat-sen University,
Suarez, Dalton Trans., 2016, 45, 19368-19373.
the Program for Guangdong Introducing Innovative and 26 L. Chen, R. Luque and Y. Li, Chem. Soc. Rev., 2017, 46, 4614-
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