One-pot tandem catalysis over Pd@MIL-101: boosting the efficiency of nitro compound hydrogenation by coupling with ammonia borane dehydrogenation

Article abstract of DOI:10.1039/c5cc03102h

The hydrogenation efficiency of nitro compounds was found to be greatly boosted by coupling with dehydrogenation of ammonia borane. The Pd@MIL-101 with tiny Pd NPs is exceptionally efficient and recyclable in the tandem reactions and diverse nitro compounds can be selectively reduced to the corresponding amines in 1.5-5 min with quantitative yields.

Full text of DOI:10.1039/c5cc03102h

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One-Pot Tandem Catalysis over Pd@MIL-101:
Boosting Efficiency of Nitro Compound Hydrogenation
by Coupling with Ammonia Borane Dehydrogenation
Cite this: DOI: 10.1039/x0xx00000x
‡,a
‡,a
b
c
Received 00th January 2012,
Accepted 00th January 2012
Qihao Yang, YuꢀZhen Chen, Zhiyong U. Wang, Qiang Xu, and HaiꢀLong
Jiang*
,a
DOI: 10.1039/x0xx00000x
www.rsc.org/
The hydrogenation efficiency of nitro compounds was found To solve this problem, the encapsulation/confinement of tiny metal
NPs inside porous materials has been recognized as an effective
way.
to be greatly boosted by coupling with dehydrogenation of
ammonia borane. The Pd@MIL-101 with tiny Pd NPs is
exceptionally efficient and recyclable in the tandem reactions
and diverse nitro compounds can be selectively reduced to the
corresponding amines in 1.5-5 min with quantitative yields.
7
As a relatively new class of porous material, metalꢀorganic
8
frameworks (MOFs), possess exceptionally high porosity and
exhibit promising applications in diverse fields including gas storage
9
and separation, sensing, catalysis, etc. Porous MOFs have been
demonstrated to be ideal candidates to stabilize fine metal NPs for
10
Aniline and its derivatives are important chemical raw materials with catalysis. However, the metal NPs@MOF has been rarely reported
11
production of more than 4,000,000 tons every year. They are used for tandem catalysis, particularly, among which almost all are
widely for the synthesis of dyes, polymers, agroꢀchemicals, based on synergistic effect between MOF acidity/basicity and metal
1
pharmaceuticals, and various fine chemicals. One common route for NPs, while tandem catalysis over metal NPs alone remains
their preparation is the reduction of the corresponding nitro unexplored thus far.
derivatives. The reduction of nitro compounds is generally achieved2
In this work, a Pd precursor was rationally introduced into a
mesoporous MOF, MILꢀ101, via a double solvents approach (DSA)
in the presence of noble metal catalysts under hydrogen atmosphere.
However, hydrogen gas is hardly dissolvable in the solution of nitro followed by in situ reduction by NH BH to afford tiny Pd NPs of
3
3
compounds, thus making the reduction of nitro compounds by ∼3 nm in diameter mainly confined inside the cavities of MILꢀ101.
hydrogenation relatively slow. To improve the efficiency of the The obtained Pd@MILꢀ101 exhibits excellent catalytic performance
reaction, it is crucial to enable sufficient contact between hydrogen in tandem dehydrogenation of ammonia borane and reduction of
gas and the substrate (nitro compounds). In this regard, a system nitro compounds (Scheme 1). Especially, the turnover frequency
where in situ hydrogen generation is coupled with nitro group (TOF) value for the hydrogenation of nitrobenzene is as high as 97
ꢀ
1
ꢀ1
reduction could provide an effective solution, since the hydrogen molnitrobenzene·molPd ·min , to the best of our knowledge, which
produced throughout the reaction system will be able to well contact surpasses all previously reported Pd catalytic activity in this
and react with nitro group immediately, thus to greatly boost the conversion. In addition, this is the first work of metal NPs@MOF
reaction rate.
Ammonia borane (NH BH , AB) is a versatile reducing agent due active sites.
catalyzing a tandem reaction with monometallic NPs as the sole
3
3
to its high hydrogen content of 19.6 wt%, stability, nonꢀtoxicity, and
3,4
high solubility in water and methanol. As a high quality of
hydrogen source, dehydrogenation of ammonia borane in water
or/and methanol can be effectively catalyzed over fine metal
4,5
nanoparticles (NPs). Therefore, it is possible to achieve highly
efficient reduction of nitro compounds by taking advantage of in situ
generated hydrogen from NH BH in the presence of a suitable
3
3
catalyst.
Palladium NPs have been previously demonstrated to be effective
catalysts for both NH BH dehydrogenation and hydrogenation of Rꢀ
3
3
2+
5,6
Scheme 1 Schematic illustration showing the in situ reduction of Pd
NO to RꢀNH . It is well known that the catalytic activity of noble
2
2
incorporated into MILꢀ101 and the subsequent tandem catalysis of the
dehydrogenation of ammonia borane and hydrogenation of nitro compounds.
metal NPs is closely relevant to their sizes. While small size
typically corresponds to enhanced catalytic activity of metal NPs, it
also results in high surface energies. Thus smallꢀsize metal NPs tend
The mesoporous MOF, MILꢀ101, a chromiumꢀbased MOF with
to aggregate/fuse, resulting in the reduction of their catalytic activity. the molecular formula Cr F(H O) O[(O C)C H (CO )] ·nH O
3
2
2
2
6
4
2
3
2
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(
where n is ∼25), is chosen due to its high stability in water and give a homogeneous solution. The reaction proceeded smoothly and
methanol, large surface area (BET, >3600 m /g), and two giant nitrobenzene was converted to aniline very rapidly as short as 1.5
2
cavities (2.9 and 3.4 nm) accessible through pore windows of ca. 1.2 min with real Pd/nitro compound molar ratio of ~0.007:1 at room
12
and 1.6 nm. To avoid the deposition of Pd NPs onto the external temperature (Table 1, entry 1). The turnover frequency (TOF) was
ꢀ
1
ꢀ1
surface of the MOF and their possible aggregation, double solvents calculated to be 97 molnitrobenzene·molPd ·min . As far as we know,
approach (DSA) was adopted herein. An aqueous Pd(NO ) solution this is the highest value for the reduction of nitrobenzene over
3
2
with a volume slightly less than MILꢀ101 pore volume was pumped diverse Pd catalysts reported thus far (Table S1).
dropwise into the MILꢀ101 suspension in the hydrophobic solvent nꢀ
With the optimized conditions, the catalytic results for the tandem
hexane. Given the hydrophilic nature of the inner pore environment reaction with diverse RꢀNO
substrates over Pd@MILꢀ101 are
2
of MILꢀ101, the aqueous Pd(NO ) solution was readily absorbed summarized in Table 1. All aromatic or aliphatic nitro compounds
3
2
into the pores of activated MILꢀ101 by capillary force during the examined were converted into the corresponding primary amines
1
0k,11f,13
2+
impregnation process.
The Pd
loaded MILꢀ101 was with excellent conversion yields (>99%) at room temperature.
subsequently reduced in situ by NH BH to give Pd@MILꢀ101.
Aliphatic nitro compounds such as nitroꢀmethane and nitroꢀethane
were reduced in excellent yields in 1.5 min (entries 2, 3). A variety
of aromatic nitro compounds with electronꢀrich groups can be
efficiently reduced in the same fashion. For example, nitrobenzenes
bearing the oꢀmethyl, mꢀmethyl, pꢀmethyl, pꢀmethylol, pꢀhydroxyl,
oꢀamino, mꢀamino and pꢀamino were reduced to the corresponding
amine products in 1.5 min (entries 4ꢀ11). Moreover, the slight space
steric hindrance was tolerated well to the hydrogenation of nitro
compounds (entries 4ꢀ6 and 9ꢀ11). Electronꢀdeficient substituents,
such as fluoroꢀ and nitro groups slow down the reduction a little bit
3
3
(
entries 12, 13), but the reaction are still very fast from the practical
Fig. 1 (a) Powder XRD patterns of simulated MILꢀ101, asꢀsynthesized MILꢀ
point of view.
1
1
01 and Pd@MILꢀ101. (b) N
01 at 77 K. Filled and open symbols represent adsorption and desorption
2
sorption isotherms for MILꢀ101 and Pd@MILꢀ
Table 1 Tandem Reaction Results for Dehydrogenation of NH BH
3
3
branches, respectively.
and Hydrogenation of Various RꢀNO
2
Compounds over Pd@MILꢀ
a
1
01.
The powder Xꢀray diffraction (PXRD) pattern for Pd@MILꢀ101
shows that the crystallinity and structure of MILꢀ101 remain well
upon loading Pd NPs (Fig. 1a). The absence of identifiable
diffraction peak of Pd NPs implies that the Pd NPs are tiny. The
Yield
Time
(min)
Entry
Substrate
Product
c
(%)
impact of metal loading on the porosity of MILꢀ101 (BET: 3660
2
m /g) has been established by measuring N sorption at 77 K, which
>99
>99
>99
1.5
1.5
1.5
2
1
2
3
reveals that Pd@MILꢀ101 still remains highly porous with a BET
surface area of 1597 m /g. The appreciable decrease in N sorption
2
2
amount and surface area indicates that the cavities of the host
framework are occupied by dispersed NPs or/and blocked by the
NPs located on the surface (Fig. 1b). Transmission electron
microscopy (TEM) image demonstrates that the Pd NPs are well
dispersed with average sizes of ∼2.5 nm (Fig. 2). The inductively
coupled plasmaꢀatomic emission spectroscopy (ICPꢀAES) indicates
the actual Pd content (0.86 wt%) is close to the nominal value (1.00
wt%).
NH2
CH3
4
>99
1.5
5
6
7
8
>99
>99
>99
>99
1.5
1.5
1.5
1.5
9
>99
1.5
1
0
>99
>99
1.5
1.5
Fig. 2 (a) TEM image of Pd@MILꢀ101 and (b) size distribution for Pd NPs.
11
With Pd@MILꢀ101 in hands, we proceeded to investigate the
catalytic performance of Pd NPs for the tandem reaction of ammonia
borane dehydrogenation and nitro compound hydrogenation. The
reaction was initiated by adding NH BH to the solution in flask
containing Pd @MILꢀ101 and nitro compounds under magnetic
stirring. Nitrobenzene was first employed as a model compound in
the tandem catalysis over Pd@MILꢀ101 to explore the optimized
1
1
2
3
>99
>99
>99
3
5
3
3
2+
b
1
4
30
a
Reaction conditions: 0.4 mmol nitro compound, 0.875 mmol NH
3
BH
BH
3
, 34
was
o
b
mg 0.86 wt% Pd@MILꢀ101, 8 mL MeOH, 12 mL H
2
O, 25 C. NH
3
3
reaction parameters. Given the great solubility of RꢀNO in methanol
2
c
replaced by 1 bar hydrogen. Catalytic reaction products were analyzed and
identified by gas chromatography.
but not in water, a mixture of methanol and water (v:v = 2:3) was
adopted to dissolve the nitro compounds and ammonia borane to
2
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To explore the possible reason for this extremely efficient hydrogen dispersed throughout the reaction system, which
reduction of nitro compounds, the uncoupled dehydrogenation of greatly facilitates the contact between hydrogen and nitro
NH BH in a mixture of methanol and water (v:v = 2:3) over compounds, thus boosting the reaction rate. A variety of
3
3
Pd@MILꢀ101 was conducted and the reaction was completed in 27 aliphatic and aromatic nitro compounds with different groups
min (Pd/NH BH molar ratio of ~0.003:1) (Fig. S1), where were able to be reduced to the respective primary amines with
3
3
theoretical maximal amount of hydrogen was generated (H /NH BH
≈
excellent conversion yields (>99%) in very short reaction time
3). When additional nitro compounds were introduced into the (1.5ꢀ5 min). Six consecutive runs of the tandem catalysis
2
3
3
reaction system, unexpectedly, the generation of H2 was greatly unambiguously demonstrate the great stability and recyclability
accelerated, especially in the initiation stage (Fig. S2). Although the of Pd@MILꢀ101 catalyst. Compared to other reported reduction
reason behind this phenomenon currently remains unclear, we systems for nitro compounds, the current tandem manner does
believe the extremely rapid hydrogen generation kinetics certainly not require stored/pressurized hydrogen and it is therefore not
contributes to the boosting reduction of nitro compounds. Moreover, only more efficient but also much safer. We envision the
there is clearly a synergistic effect when both the NH BH3 strategy with tandem catalysis in this work opens an avenue
3
dehydrogenation and nitro compounds reduction are coupled. We to the improvement of catalytic efficiency for other related
also attempted to change the hydrogen source for the reduction of reactions.
nitro compounds. Strikingly, when ammonia borane was replaced
with hydrogen flow while other conditions remained unaltered (with
Pd@MILꢀ101 catalyst preꢀreduced by ammonia borane), the reaction
was completed after 30 min (entry 14), 20 times slower than that of
the above NH BH ꢀengaged tandem process. Our experiments
This work is supported by the NSFC (21371162 and
1301159), the 973 program (2014CB931803), NSF of Anhui
Province (1408085MB23), the Recruitment Program of Global
Youth Experts, the Scientific Research Foundation for the
Returned Overseas Chinese Scholars, the State Education
5
3
3
support that the content of dissolved hydrogen in the reaction
solution as well as sufficient contact between hydrogen and nitro Ministry, and the Fundamental Research Funds for the Central
compounds jointly control the reduction rate of the nitro group, for Universities (WK2060190026).
which the coupling of in situ dehydrogenation and reduction
reactions has been proved to be a very effective approach.
The stability and reusability of catalysts are of great importance
Notes and references
a
for their practical application. It can be seen that the activity,
selectivity and framework integrity of Pd@MILꢀ101 were well
retained during six consecutive runs without any treatment or
activation for the catalyst (Fig. 3a, S3), clearly demonstrating the
recyclability and reusability of the catalyst. In addition, the Pd NPs
remain high dispersion and their sizes are almost retained even after
Hefei National Laboratory for Physical Sciences at the Microscale, Key
Laboratory of Soft Matter Chemistry, Chinese Academy of Sciences,
Collaborative Innovation Center of Suzhou Nano Science and
Technology, Department of Chemistry, University of Science and
Technology of China, Hefei, Anhui 230026, P.R. China. Eꢀmail:
6
runs, revealing the good confinement effect of MILꢀ101 based on jianglab@ustc.edu.cn; Webpage: http://staff.ustc.edu.cn/~jianglab/
b
its porous structure (Fig. 3b). The ICPꢀAES result shows negligible
Pd species can be detected in the reacted solution, which reveals the
leaching of active sites almost does not occur during the reaction.
Department of Chemistry and Physics, Troy University, Troy, AL
3
c
6082, USA.
National Institute of Advanced Industrial Science and Technology
(
AIST), Ikeda, Osaka 563ꢀ8577, Japan.
Electronic Supplementary Information (ESI) available: See
DOI: 10.1039/c000000x/
†
‡
1
These authors contributed equally to this work.
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ammonia borane dehydrogenation and nitrobenzene hydrogenation. Reaction
,
2
5
conditions: 0.4 mmol nitrobenzene, 0.875 mmol NH
3
BH
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3
, 34 mg 0.86 wt%
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(a
o
Pd@MILꢀ101, 8 mL MeOH, 12 mL H
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b
6
Inset: size distribution for Pd NPs in Pd@MILꢀ10 after 6 cycles of tandem
reactions.
5
(a
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b
,
In summary, a tandem process has been developed to
successfully improve the reaction rate of the hydrogenation of
nitro compounds by coupling with the hydrogen generation
from NH BH . The tandem reaction exhibits exceptionally high
c
3
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d
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f
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) the extremely rapid kinetics of hydrogen generation from
NH BH enables the generation of local highꢀconcentration
3
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| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5CC03102H
Graphical Abstract
The hydrogenation efficiency of nitro compounds is greatly boosted by coupling with
ammonia borane dehydrogenation over rationally synthesized Pd@MIL-101 with Pd
NPs in ~3 nm.