Boosting Catalysis of Pd Nanoparticles in MOFs by Pore Wall Engineering: The Roles of Electron Transfer and Adsorption Energy

Article abstract of DOI:10.1002/adma.202000041

The chemical environment of metal nanoparticles (NPs) possesses significant influence on their catalytic performance yet is far from being well understood. Herein, tiny Pd NPs are encapsulated into the pore space of metal–organic frameworks (MOFs), UiO-66-X (X = H, OMe, NH₂, 2OH, 2OH(Hf)), affording Pd@UiO-66-X composites. The surface microenvironment of the Pd NPs is readily modulated by pore wall engineering, via the functional group and metal substitution in the MOFs. Consequently, the catalytic activity of Pd@UiO-66-X follows the order of Pd@UiO-66-OH > Pd@UiO-66-2OH(Hf) > Pd@UiO-66-NH₂ > Pd@UiO-66-OMe > Pd@UiO-66-H toward the hydrogenation of benzoic acid. It is found that the activity difference is not only ascribed to the distinct charge transfer between Pd and the MOF, but is also explained by the discriminated substrate adsorption energy of Pd@UiO-66-X (–OH < –2OH(Hf) < –NH₂ < –OMe < –H), based on CO-diffuse reflectance infrared Fourier transform spectra and density-functional theory (DFT) calculations. The Pd@UiO-66-OH, featuring a high Pd electronic state and moderate adsorption energy, displays the highest activity. This work highlights the influence of the surface microenvironment of guest metal NPs, the catalytic activity of which is dominated by electron transfer and the adsorption energy, via the systematic substitution of metal and functional groups in host MOFs.

Full text of DOI:10.1002/adma.202000041

CommuniCation
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Boosting Catalysis of Pd Nanoparticles in MOFs by
Pore Wall Engineering: The Roles of Electron Transfer
and Adsorption Energy
Dongxiao Chen, Weijie Yang, Long Jiao, Luyan Li, Shu-Hong Yu, and Hai-Long Jiang*
reactions because of their high activity.[1]
The chemical environment of metal nanoparticles (NPs) possesses significant
influence on their catalytic performance yet is far from being well understood.
Herein, tiny Pd NPs are encapsulated into the pore space of metal–organic
However, small metal NPs are prone
to aggregate during the reaction due to
their high surface energy, and their cata-
lytic activity is severely influenced by
surrounding chemical environment. To
address the above issues, there are two
common solutions: (1) protecting metal
NPs with various ligands or surfactants,
where the accessibility of metal sites is
usually hampered by these surface pro-
tectors; (2) stabilizing metal NPs onto
supports, where the interface interaction
between the support and metal NPs is lim-
ited, thus causing stability and selectivity
concerns. In fact, the surface microenvi-
ronment modulation of metal NPs based
on conventional supports, such as metal
oxides, is far from satisfaction and dif-
frameworks (MOFs), UiO-66-X (X = H, OMe, NH , 2OH, 2OH(Hf)), affording
2
Pd@UiO-66-X composites. The surface microenvironment of the Pd NPs
is readily modulated by pore wall engineering, via the functional group and
metal substitution in the MOFs. Consequently, the catalytic activity of Pd@
UiO-66-X follows the order of Pd@UiO-66-OH > Pd@UiO-66-2OH(Hf) > Pd@
UiO-66-NH > Pd@UiO-66-OMe > Pd@UiO-66-H toward the hydrogenation
2
of benzoic acid. It is found that the activity difference is not only ascribed to
the distinct charge transfer between Pd and the MOF, but is also explained
by the discriminated substrate adsorption energy of Pd@UiO-66-X (–OH <
–
2OH(Hf) < –NH < –OMe < –H), based on CO-diffuse reflectance infrared
2
Fourier transform spectra and density-functional theory (DFT) calculations. The
Pd@UiO-66-OH, featuring a high Pd electronic state and moderate adsorption
energy, displays the highest activity. This work highlights the influence of the
surface microenvironment of guest metal NPs, the catalytic activity of which is
dominated by electron transfer and the adsorption energy, via the systematic
substitution of metal and functional groups in host MOFs.
[2]
ficult to achieve. In this context, encap-
sulating metal NPs into porous materials
has been recently recognized to be an
[
2a–c]
effective strategy,
where the hosts are
able to stabilize metal NPs in small sizes
and make them well accessible to the sub-
strates thanks to the interconnected pores.
Catalysis has greatly promoted the progress of human life and
industrial production, where the catalyst plays the key role.
Metal nanoparticles (NPs) as an important class of heteroge-
neous catalysts have been widely used in various reactions; for
example, Pd NPs are most commonly used in hydrogenation
The substrate can be even enriched inside the nanoreactor via
capillary action, accelerating the catalysis. Moreover, it is pos-
sible to regulate the microenvironment around metal active
sites via pore wall engineering of the porous hosts.
To meet this target, metal–organic frameworks (MOFs), a
class of crystalline porous materials featuring well-tailorable
[
3]
linkers, clusters and pore spaces, would be ideal host mate-
rials. MOFs with permanent porosity offer inherent advantages
to confine metal NPs and the resultant metal NPs@MOF com-
posites have demonstrated their great potential and integrated
D. Chen, Dr. L. Jiao, L. Li, Prof. S.-H. Yu, Prof. H.-L. Jiang
Hefei National Laboratory for Physical Sciences at the Microscale
CAS Key Laboratory of Soft Matter Chemistry
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
E-mail: jianglab@ustc.edu.cn
Dr. W. Yang
School of Energy and Power Engineering
North China Electric Power University
Baoding, Hebei 071003, P.R. China
[4]
merits of both components for enhanced catalysis. In recent
years, there have been quite a few reports on metal NPs@MOF
catalysis, most of which concern about the high activity and
[
4]
recyclability of tiny metal NPs stabilized by MOF hosts. In
fact, the chemical microenvironment around guest metal NPs
can be easily regulated, by the linker functional group altera-
[2c,5]
tion or metal substitution in MOFs, to improve the activity.
However, the current limited investigations are almost related
[
5]
to linker or metal alteration only, and the microenvironment
influence figure of metal NPs for catalysis remains largely
unclear. To the best of our knowledge, there has never been a
report on the systematic interaction regulation between guest
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202000041.
DOI: 10.1002/adma.202000041
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The phase purity and crystallinity of all UiO-66-X and Pd@
UiO-66-X have been examined by powder X-ray diffraction
(
XRD, Figure S1, Supporting Information). All Pd@UiO-66-X
well inherit the structure from UiO-66 while do not show any
diffraction peak for Pd NPs, revealing that Pd NPs could be
small. The Brunauer–Emmett–Teller (BET) surface area and
pore size distribution of Pd@UiO-66-X have been investigated
by nitrogen sorption at 77 K (Figures S2 and S3 and Table S1,
Supporting Information). The decreased surface area upon
introducing different functional groups is caused by the partial
pore occupation of functional groups in MOFs. In reference to
the parent UiO-66-X, the slight decreased surface of Pd@UiO-
6
6-X is possibly due to the occupied pore space and increased
[
7b]
weight by Pd NPs. Meanwhile, all Pd@UiO-66-X catalysts
show similar pore size distributions, making them ideal can-
didates to investigate the influence of chemical environment
exclusively (Figure S3b, Supporting Information). Transmission
electron microscopy (TEM) observation for Pd@UiO-66-NH2
as a representative suggests that very tiny Pd NPs are highly
dispersed with mean sizes less than 1.1 nm throughout the
entire MOF particle (Figure 1a,b; Figures S4–S7, Supporting
Information). This is further approved by the elemental energy-
dispersive X-ray (EDX) mapping (Figure 1c). It is reasonably
considered that most of Pd NPs with sizes similar to or less
than the diameter of the MOF cages are successfully confined
in the MOF as predesigned. The inductively coupled plasma
atomic emission spectroscopy (ICP-AES) results reveal that the
Pd contents in Pd@UiO-66-X are similar and fall in the range
of 2.13–2.84 wt % (Table S1, Supporting Information).
Scheme 1. Schematic illustration showing the preparation process of
Pd@UiO-66-X and highlighting their tailorable pore walls.
metal NPs and host MOFs by changing both linker and metal
clusters for catalysis.
In this work, isoreticular MOFs with the UiO-66 structural
[
6]
prototype featuring alterable linker groups and metal clusters
are employed to encapsulate Pd NPs via the ultrasound-assisted
double-solvent approach (DSA),[ affording Pd@UiO-66-X
7]
(
X = H, OMe, NH , 2OH, 2OH(Hf); X represents the alter-
Upon demonstrating the similar structure and components of
Pd@UiO-66-X, we set out to explore their catalytic performance
toward hydrogenation of benzoic acid (Table 1). The selective
2
able group grafting onto the linker benzene ring, Hf means
the Hf-oxo or otherwise the Zr-oxo cluster; Scheme 1). The
obtained Pd@UiO-66-X exhibits distinctly different activities in
the hydrogenation reaction of benzoic acid, in which Pd@UiO-
6
2
6
6-2OH possesses the highest activity followed by Pd@UiO-66-
OH(Hf), Pd@UiO-66-NH , Pd@UiO-66-OMe, and Pd@UiO-
2
6, in a decreasing order of activity. Remarkably, the activity of
Pd@UiO-66-2OH is around 14 times higher than that of Pd@
UiO-66. The distinct activity is not only ascribed to the different
electron transfer from Pd to the MOFs, but also due to the dis-
criminated substrate adsorption energy of Pd@UiO-66-X, as
elucidated by density-functional theory (DFT) calculations. This
is the first finding that electron transfer and substrate adsorp-
tion energy codominate the activity in metal NPs/MOF catalytic
system.
The UiO-66-X frameworks, formulated M O (OH) (BDC-X)
6
4
4
6
(
2
BDC = benzene-1,4-dicarboxylate; M = Zr, X = H, NH , OMe,
2
OH; M = Hf, X = 2OH),[ as the representative MOFs, was
6]
employed as hosts. UiO-66-X features a 3D network with two
types of cages with diameters of 0.8 and 1.1 nm, high physico-
chemical stability, suitable for stabilizing tiny metal NPs. The
five isoreticular UiO-66-X with pore sizes of 7–12 Å have been
synthesized according to the previous methods with slight
modifications (Scheme 1).[ To prevent the formation of Pd
NPs on the MOF external surface, avoid Pd aggregation and
6]
Figure 1. a,b) Representative low-magnification (a) and high-magnifica-
achieve sufficient contact between Pd and the MOF, an ultra-
tion (b) TEM images of Pd@UiO-66-NH . c) High-angle annular dark-
sound assisted DSA[7] was adopted to rationally incorporate Pd
2
field scanning transmission electron microscopy (HAADF-STEM) image
NPs to afford Pd@UiO-66-X (Scheme 1; also see experimental
details in the Supporting Information).
of Pd@UiO-66-NH , and the corresponding Zr, N, Pd, and overlapped
2
elemental mapping for the selected area.
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Table 1. The preliminary optimization experiments for the hydrogenation of benzoic acid.
Entrya)
Catalyst
H2 Pressure [bar]
Solvent
water
water
water
water
water
DMF
Conv.
0%
Sel.
—
Temperature [°C]
1
no
10
10
10
1
85
85
85
85
50
85
85
2
3
4
5
6
7
UiO-66-2OH
0%
—
Pd@UiO-66-2OH
Pd@UiO-66-2OH
Pd@UiO-66-2OH
Pd@UiO-66-2OH
Pd@UiO-66-2OH
>99%
12%
6%
100%
100%
100%
—
10
10
10
0%
dioxane
0%
—
a)Reaction conditions: 0.1 mmol benzoic acid, 5 mL solvent, 15 mg catalyst, 8 h at different temperatures or H2 pressures. Catalytic products were analyzed and identified
by gas chromatography.
hydrogenation of benzoic acid to cyclohexanecarboxylic acid
CCA) not only affords highly desired chemical intermediate
in a fixed amount, have been attempted for the selective
hydrogenation of benzoic acid. Strikingly, they show distinctly
different catalytic activity, although they have similar compo-
nents and structures. The Pd@UiO-66-2OH affords nearly
complete conversion (>99%) in 8 h and the reaction proceeds
efficiently in the first order rate (Figure 2a). By contrast, Pd@
(
for the synthesis of pharmaceuticals such as praziquantel, but
also is a significant process in the synthesis of caprolactam from
toluene.[ The preliminary optimization experiments have been
conducted to obtain optimized reaction conditions (Table 1). No
product can be detected in the absence of catalyst or in the pres-
ence of pure MOF catalyst only (entry 1–2). In sharp contrast,
Pd@UiO-66-2OH gives complete conversion under the iden-
tical conditions (in water at 85 °C and 10 bar, entry 3), which
unambiguously indicates that Pd NPs behave as the catalytic
centers for this process. Interestingly, the conversion quickly
decreases when the reaction pressure or temperature goes down
8]
UiO-66-NH , Pd@UiO-66-OMe, and Pd@UiO-66 give gradu-
2
ally decreased conversions of 73%, 30%, and 7%, respectively,
under the same conditions (Figure 2b). Interestingly, upon
changing the Zr-oxo to Hf-oxo cluster, the resulting Pd@UiO-
66-2OH(Hf) exhibits moderate activity with a conversion of
79%. To our delight, all these catalysts are able to convert ben-
zoic acid to CCA product with complete selectivity (Figure 2b).
More importantly, no apparent loss of MOF crystallinity and
no identifiable peak for Pd NPs are observed in the powder
XRD pattern after catalysis (Figure S8, Supporting Informa-
tion). The results suggest the retained integrity of UiO-66-2OH
framework and the absence of Pd agglomeration, which is
(entry 4–5). It is delighted to find that the most favorable green
solvent, water, is optimal for this reaction; no product is surpris-
ingly detectable in DMF and dioxane (entry 6–7).
With the above optimized reaction parameters, the Pd@
UiO-66-X with different functional groups and metal clusters,
Figure 2. a) Time-dependent conversion of selective benzoic acid hydrogenation over Pd@UiO-66-2OH. b) Conversion and selectivity of catalytic
hydrogenation of benzoic acid over Pd@UiO-66-X. Reaction conditions: 0.1 mmol BA, 5 mL water, 15 mg catalyst, 8 h, 85 °C, 10 bar H2.
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further approved by the TEM observation (Figure S9, Sup-
porting Information), demonstrating the great MOF confine-
ment effect and structural stability of the composite catalysts.
In addition, the durability of Pd@UiO-66-2OH has been fur-
ther examined with the reaction carried out by using three
times larger amount of benzoic acid. As expected, no apparent
activity drop of Pd@UiO-66-2OH can be observed during the
reaction; the reaction proceeds efficiently and reaches complete
conversion within 22 h (Figure S10, Supporting Information).
To verify the nature of the heterogeneous catalysis of Pd@UiO-
and UiO-66, featuring fixed framework topology yet altered
functional groups on the BDC linker or exchanged metals
in the M-oxo cluster, are 2.62, 2.57, 2.63, 2.68, and 2.89,
respectively (Figure 3a). As expected, such a trend is well con-
sistent with the activity sequence for all the UiO-66-X struc-
tures with Zr-oxo clusters, implying that the charge transfer
between Pd and the MOFs is responsible for their discrimi-
nated activities. On the basis of the electron density distribu-
tion profile, it is obvious that electron transfer mainly takes
place at the region between Pd NPs and linkers. To be spe-
cific, the accumulation of electron density is mostly located at
the bond of Pd and linkers, whereas the reduction of electron
density is mostly located at Pd NPs and linkers (Figure 3a
inset; Figure S13, Supporting Information), indicating that the
MOFs are able to hold Pd NPs firmly. Meanwhile, the Pd NPs
lose electrons, presenting positive charge, which is in con-
sistent with the analysis of Bader charge.
6
6-2OH, the filtration test has been performed. It can be seen
that no further conversion of benzoic acid can be detected upon
the removal of the catalyst, reflecting the heterogeneous fea-
ture of the catalytic process (Figure S11, Supporting Informa-
tion). Furthermore, only a tiny amount of Pd leaching (≈3.9%)
is observed from the catalyst after reaction and the activity of
Pd@UiO-66-2OH shows very slight drop in the three consecu-
tive cycles (Figure S12, Supporting Information).
To further understand the above different electron transfer
numbers and probe into the surface electron property of Pd
NPs encapsulated in UiO-66-X, the diffuse reflectance infrared
Fourier transform (DRIFT) spectra of CO adsorption has been
carried out to evaluate the adsorption behavior of CO molecule
on the Pd NPs (Figure 3b). The main adsorption peaks of all
Although water possibly participates in the hydrogenation
reaction by providing proton as the reductant,[ it is safe to
conclude that such effect from water would not contribute
to the catalytic differences in our work, as all reactions have
been carried out under the same conditions. It is assumed
that surface electronic properties of confined Pd NPs are
responsible for the activity difference. To understand the real
reason behind this significant activity difference among Pd@
UiO-66-X and elucidate the corresponding Pd surface elec-
tronic states, DFT calculations have been adopted to obtain
the Bader charge and d-band center of these composite cata-
lysts, using the Vienna Ab initio Simulation Package (VASP)
with plane-wave pseudo potential method.[ On the basis of
the optimized geometries of Pd @UiO-66-X, the numbers of
8b]
−
1
five samples falls into the range of 2020–2075 cm , which are
assigned to the C–O vibrations of linearly adsorbed CO. The
adsorption mode of CO of all five samples is the same which
suggests that Pd NPs in these sample are of the same structure
−1
and situation. No bridge-bonded peaks (1850−1950 cm ) are
observable from the spectra. The small peaks around 2121 cm−
are possibly due to CO adsorbed on the partially oxidized Pd
1
9]
[10]
NPs. The main adsorption peaks of all five samples exhibit
apparent redshift, assignable to the electron-donating effect of
functional groups on the linkers in the host MOFs to the guest
Pd NPs. The electron donation degree follows the order of
2
8
electron transfer from Pd clusters to the host frameworks in
UiO-66-2OH, UiO-66-2OH(Hf), UiO-66-NH , UiO-66-OMe,
2
Figure 3. a) The calculated number of electron transfer from Pd clusters to the MOF host in Pd@UiO-66-X (inset: electron density distribution profile
of Pd@UiO-66-2OH as a representative). b) The DRIFT spectra of CO adsorption on Pd@UiO-66-X at 298 K.
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Pd@UiO-66-2OH
>
Pd@UiO-66-2OH(Hf)
>
Pd@UiO-
benzoic acid derivatives has been further investigated (Table S2,
Supporting Information). To our delight, all para-substituted
benzoic acids with both electron-drawing and -donating groups
6
6-NH > Pd@UiO-66-OMe > Pd@UiO-66, which provides per-
2
fect explanation (i.e., charge compensation from the functional
groups to Pd NPs) on the reversed order of electron transfer
numbers in the above calculated results.
(–Cl, –Br, –CH ) have shown excellent conversion and selectivity
3
(entry 1–3). The hydrogenation of phenyl acetic acid, a homolo-
gous compound of benzoic acid, also gives complete conver-
sion (entry 4). Moreover, the benzoic acid derivatives, methyl
benzoate and benzamide afford very high conversions of 99%
and 95%, respectively (entry 5–6). Their similarly high activities
well illuminate the general applicability of Pd@UiO-66-2OH,
tolerating various benzoic acid derivatives.
In addition, the position of the center of the d-band states
(εd) of Pd NPs (using Pd28 as a representative structural model)
encapsulated in different UiO-66-X frameworks was calculated
as follows
+
∫−∞
∞
E ⋅D(E)dE
(1)
ε
d
=
In summary, isoreticular UiO-66-X with various linker
groups and altered M-oxo clusters have been synthesized.
The ultrafine Pd NPs are incorporated into these MOF pores,
which create modulated chemical microenvironment for Pd
sites based on the MOF pore wall engineering. The selective
hydrogenation of benzoic acid to CCA, a vital process in petro-
leum industry, has been selected to investigate the catalytic
performance of Pd@UiO-66-X. Remarkably, their activities
are distinctly different, among which Pd@UiO-66-2OH is not
only 14 times higher than that of Pd@UiO-66 but also exhibits
excellent conversions toward diverse benzoic acid derivatives.
The different Pd electronic states in Pd@UiO-66-X, attributed
to the differentiated charge transfer interactions between Pd
and the isoreticular MOFs, should be responsible for the above
results. Furthermore, the calculated d-band center results reveal
that the discriminative adsorption energy of these Pd@UiO-
66-X catalysts also accounts for their distinct activities. As
far as we know, this is the first work tailoring electronic state
and adsorption energy of metal NPs by means of linker group
change and metal substitution in isoreticular MOF hosts.
This work provides significant insight in the design of hetero-
geneous catalysts and will open up an avenue to the rational
control of chemical microenvironment surrounding active sites
for optimizing catalytic performance. We believe this micro-
environment effect on catalysis would be extendable to other
metal/MOF catalytic systems, and even other heterogeneous
catalytic systems.
+
∫−∞
∞
D(E)dE
where D(E) is the density of d-states function of the Pd atoms
and E is the energy relative to the Fermi level.
According to the theory of d-band center,
d-band center location (less electrons in the d-orbital) results
in shifting up of antibonding states through the Fermi level
and lower occupancy of anti-bonding states, leading to the
stronger interaction between the adsorbate and the catalyst
surface. The d-band center of Pd cluster is estimated to be
[9,11]
a higher
−
1.82, −1.81, −1.78, −1.75, and −1.73 eV for Pd@UiO-66-2OH,
Pd@UiO-66-2OH(Hf), Pd@UiO-66-NH2, Pd@UiO-66-OMe,
and Pd@UiO-66, respectively. It is well known that, when the
d-band center gets closer to zero (Fermi level), the interaction
between the reactant and the surface will be stronger, accord-
ingly larger adsorption energy. Therefore, according to the
d-band center data above, the adsorption strength sequence of
substrates on Pd @UiO-66-X should be Pd@UiO-66-2OH <
2
8
Pd@UiO-66-2OH(Hf) < Pd@UiO-66-NH < Pd@UiO-66-OMe
2
<
Pd@UiO-66 (Figure 4), which is exactly reverse to that of
catalytic activity. Given that appropriate adsorptive strength
between substrate and active center/catalyst is favorable, and
too strong strength is detrimental to catalytic reactions, based
on the Sabatier principle,[ these adsorption energy results
well explain and should account for the order of experimental
activity (Figure 4).
12]
Encouraged by the above theoretical and characteriza-
tion elucidations, the general applicability of the optimized
Pd@UiO-66-2OH catalyst for selective hydrogenation of diverse
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
D.C., W.Y., and L.J. contributed equally to this work. This work was
supported by the National Natural Science Foundation of China
(
21725101, 21871244, 21673213, and 21521001), the China Postdoctoral
Science Foundation (2019M660151, 2019TQ0298), and Fujian Institute
of Innovation (CAS). The authors gratefully thank all reviewers for their
insightful comments and valuable suggestions, Dr. X. Liu at University
of Science and Technology of China for discussions.
Conflict of Interest
The authors declare no conflict of interest.
Figure 4. Schematic plot guiding the relationship between adsorption
strength and catalytic activity.
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