Hybrid Catalyst of a Metal-Organic Framework, Metal Nanoparticles, and Oxide That Enables Strong Steric Constraint and Metal-Support Interaction for the Highly Effective and Selective Hydrogenation of Cinnamaldehyde

Article abstract of DOI:10.1021/acs.inorgchem.8b01922

In this work, we designed a hybrid catalyst composed of a metal-organic framework (MOF), Pt nanoparticles (NPs), and ferric oxide, namely, Co-MOF-74@(Pt@Fe₂O₃), which enables not only high turnover frequencies of up to 245.7 h^-1 but also ultrahigh 100% selectivity toward cinnamyl alcohol in the hydrogenation of cinnamaldehyde under mild conditions. This excellent performance is attributed to the fact that such a hybrid catalyst enables not only strong steric constraint to provide the favored C-O adsorption of cinnamaldehyde but also strong metal-support interaction to lower the electron density of Pt NPs.

Full text of DOI:10.1021/acs.inorgchem.8b01922

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Hybrid Catalyst of a Metal−Organic Framework, Metal
Nanoparticles, and Oxide That Enables Strong Steric Constraint and
Metal−Support Interaction for the Highly Effective and Selective
Hydrogenation of Cinnamaldehyde
†
†
Li-Xiao Yang, Hui-Qiong Wu, Heng-Ya Gao, Jian-Qiang Li, Yuan Tao, Wen-Hui Yin, and Feng Luo*
State Key Laboratory for Nuclear Resources and Environment, School of Biology, Chemistry and Material Science, East China
University of Technology, Nanchang, Jiangxi 344000, China
*
S Supporting Information
high temperature and pressure (H ) were also employed
2
ABSTRACT: In this work, we designed a hybrid catalyst
composed of a metal−organic framework (MOF), Pt
nanoparticles (NPs), and ferric oxide, namely, Co-MOF-
because of their special contributions to both the efficiency
and selectivity. However, from the viewpoint of safety and low
energy consumption, mild reaction conditions such as room
7
4@(Pt@Fe O ), which enables not only high turnover
2 3
temperature and 1 bar of H are highly desirable.
2
−
1
frequencies of up to 245.7 h but also ultrahigh 100%
selectivity toward cinnamyl alcohol in the hydrogenation
of cinnamaldehyde under mild conditions. This excellent
performance is attributed to the fact that such a hybrid
catalyst enables not only strong steric constraint to pro-
vide the favored CO adsorption of cinnamaldehyde but
also strong metal−support interaction to lower the electron
density of Pt NPs.
Metal−organic frameworks (MOFs), built on metal ions and
organic ligands, have become some of the most promising
material platforms because of their structural diversity, highly
designable organic ligands, uniform pores, high surface areas,
11−14
and open-metal sites (OPSs).
During the past decade, we
have witnessed flourishing development in MOFs, and broad
applications involving, but not limited to, storage, gas separation,
15−20
catalysis, and luminescence, have been disclosed.
Recent
advances also revealed MOFs as promising support materials for
catalytic purposes because of the fact that MOFs enable out-
standing steric constraints from size effects or unique OPSs.
21
elective hydrogenation on the structure-sensitive molecule
S
of α,β-unsaturated aldehydes presents one of the most
challenging topics in catalysis because hydrogenation on a CC
bond is more thermodynamically and kinetically preferable than
As a result, size-selective and chemically selective catalyses were
observed. However, cases of MOF-supported catalysts showing
high catalytic efficiency and selectivity for the hydrogenation of
CAL under mild reaction conditions are still extremely scarce.
In this work, we propose a synergic approach to enable high
1
,2
that on a CO bond.
As a typical example, selective hydrogenation of cinnamalde-
3
hyde (CAL) has received extensive interest. CAL holds two
efficiency and selectivity at room temperature and 1 bar of H
2
.
unsaturated and conjugated alkene (CC) and carbonyl (CO)
groups, which allow for further hydrogenation reaction. Gener-
ally speaking, without an effective catalyst, complete hydro-
genation would produce hydrocinnamyl alcohol. By contrast,
with a suitable catalyst, selective hydrogenation can be achieved,
leading to the desired products of hydrocinnamaldehyde (HCAL)
and cinnamyl alcohol (COL). Both HCAL and COL are
important materials in the flavoring, perfume, and pharmaceu-
tical industries. However, achieving 100% selectivity for the
In a previous report, a Fe support was found to give favorable
O
2 3
steric constraint on the CO group of CAL, leading to enhance-
3,22
ment in the selectivity toward COL. On the other hand, some
evidence also supports the contribution of enhancement in the
3
,9
selectivity toward COL from the OPSs in MOFs. In this
regard, integration of both Fe - and OPS-containing MOF
supports is expected to largely enhance the catalytic selectivity.
The catalyst of Co-MOF-74@(Pt@Fe O ) was prepared
O
3
2
2
3
by a step-by-step approach. First, to avoid the use of poly-
vinylpyrrolidone) (PVP), which was often employed to prevent
4
,5
(
desired product is still a challenging task.
the aggregation of metal nanoparticles (NPs) and finally must be
annealed to release from the surface of metal NPs, consequently
leading to serious decrease in the catalytic performance, a spray
approach in an automatic manner is, for the first time, utilized to
prepare Pt NPs. As shown in Figure 1, the homemade spray
equipment is composed of two basic components, viz., inner and
outer capillaries, which are used to deliver solution and air,
respectively. The velocity of air was controlled by a flowmeter at
To this end, many efforts have been devoted to noble-metal-
based catalysts such as Os, Ir, Ru, Rh, Pt, Pd, and Au because of
6
their high catalytic activity. However, their poor selectivity,
especially toward COL, seriously restricts their practical appli-
cations. Thus, modification is demanded. Previous researches
have disclosed several elegant methods to modify the undesir-
7
able activity site, for example, surface ligands, noble-metal-based
8
3,9
10
alloys, steric constraints, and metal−support interactions.
5
00 mL/min. The H PtCl and NaBH concentration was
However, such selective enhancement is usually accompanied by
a sacrifice of the catalytic efficiency. For an ideal catalyst, both
the catalytic efficiency and selectivity are highly important.
Moreover, in the literature, extreme reaction conditions such as
2
6
4
Received: July 10, 2018
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b01922
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
Figure 1. Spray approach for fabricating Pt NPs: (i) a schematic
description of the spray approach; (ii) a proposed mechanism for
generating Pt NPs by the spray approach.
6
mmol/L. The NaBH solution was used to produce the foglike
4
droplet. For comparison, generation of Pt NPs by the commonly
used dropping method with or without PVP was also carried out.
UV−vis spectroscopy was used to trace the formation of Pt NPs,
and transmission electron microscopy (TEM) was employed to
characterize the resulting Pt NPs (Figure 2a−f). As shown in
Figure 2, it is clear that both the spray approach and common
method with or without PVP can produce a black Pt solution,
indicative of the generation of Pt NPs. In the UV−vis spectra
Figure 2. UV−vis and TEM comparison of Pt NPs synthesized by three
distinct methods: (a, c, and e) UV−vis spectra; (b, d, and f) TEM
images of the Pt NPs obtained by the commonly used dropping method
without and with PVP and our spray approach, respectively. The inset
images in parts a, c, and e are of the resultant Pt NP solution after the
(
Figure 2a,c,e), an obvious absorption at 260 nm belonging to
23
the H PtCl solution was observed. For the dropping method
2
6
without PVP, the disappearance of absorption at 260 nm, due to
rapid transformation from a Pt(II) solution to Pt NPs and then
serious aggregation of Pt NPs, was observed if more than 2 mL of
addition of 10 mL of a NaBH solution. Clearly, both the commonly
4
used dropping method with PVP and our spray approach can obtain a
transparent and dispersed Pt NP solution, whereas the commonly used
dropping method without PVP would result in seriously aggregated
bulk Pt at the bottom of vessel, well consistent with the TEM result (b).
The corresponding particle size histograms of Pt NPs are shown in parts
d and f (see the insets).
23
the NaBH solution was added (Figure 2a). This is well
4
consistent with the TEM result (Figure 2b). However, with
PVP, more than 6 mL of the NaBH solution was required
4
23
(
Figure 2c) because, as suggested in the literature, PVP can
effectively prevent the aggregation of Pt NPs. Monodispersed Pt
NPs with a size of 3.0 ± 0.3 nm were observed (Figure 2d).
By contrast, even after the addition of more than 8.3 mL of the
To combine both Fe O and the MOF support together and
2
3
enhance the metal−support interactions, the loading of Pt NPs
onto mixed supports was implemented by our recently devel-
NaBH solution, the peak at 260 nm does not disappear when
4
+
25
+
oped MOF technique. Note that the MOF technique can
significantly prevent reaggregation during the loading of Pt NPs
onto the support, leading to well-dispersed loading with a size of
our spray approach was used (Figure 2e), leading to generation
of monodispersed Pt NPs with a uniform size of 2.4 ± 0.3 nm
(
Figure 2f), strongly suggesting its superior ability in preventing
2
.6 ± 0.3 nm (Figure 3). Such a value is comparable with that of
the aggregation of Pt NPs. Ultrahigh stability, even saving for
weeks at ambience, was also observed for the resulting Pt NP
2
solution prepared by our spray approach (Figure S3). All of the
above results, including the absence of a protecting agent such as
PVP, automated production, and comparable or superior out-
come, suggest that our spray approach even exceeds the com-
monly used PVP protecting method, indicative of its superior
application in the preparation of monodispersed metal NPs.
To disclose the formation mechanism of Pt NPs by means of the
spray approach, TEM was employed to trace the whole forma-
tion process. Also, as shown in Figure S4, a possible “droplet-
nucleation-growth-monodispersed Pt NPs” formation mecha-
Figure 3. TEM image of Co-MOF-74@(Pt@Fe O ) and the particle
size histogram of Pt NPs.
2
3
24
nism, similar to the well-established microemulsion technique,
is proposed. Initially, the nanoscopic droplets stabilized by an
air/water interface were generated by the spray approach. Then,
the formation of Pt NPs proceeds in two steps: first a nucleation
the presynthesized Pt NPs (2.4 ± 0.3 nm) by the spray approach,
+
indicative of well maintenance. In principle, the MOF technique
4
+
process outside the droplet due to the reduction of Pt by
is similar to the previously established coprecipitation method for
26
NaBH and then growth to form the final NPs.
the preparation of supported Au, Pd, and Pt catalysts. The
4
B
DOI: 10.1021/acs.inorgchem.8b01922
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
difference is the iron oxide. In our MOF technique, its forma-
Communication
+
3
84.5% selectivity under 54.5% conversion. In this regard, it is
reasonable that a mixed support composed of both Fe O and
3
+
tion is in an in situ manner because of the surface reaction of Fe
2
3
25
and Co-MOF-74, whereas in the established coprecipitation
method, its formation is tuned by the temperature and pH
Co-MOF-74 in the present catalyst could result in a significant
synergic effect to give strong steric constraint for the CO
groups of CAL, thus leading to unprecedented 95% selectivity
under 90% conversion.
To evaluate the metal−support interaction, we further carried
out analysis of the electronic structure of Pt NPs on the support
by high-resolution XPS. As shown in Figure S13, the Pt 4f7/2 and
4f 2 peaks of Pt NPs synthesized by the spray approach are
2
6
values. The resulting composite was further characterized by
powder X-ray diffraction (PXRD; Figure S5), TEM (Figure 3),
high-resolution TEM (Figure S6), X-ray photoelectron spectros-
copy (XPS; Figure S7), and N adsorption at 77 K (Figure S8),
2
suggesting the composition of Fe O , Pt NPs, and Co-MOF-74.
2
3
We know that the aperture of Co-MOF-74 is about 1.1 nm,
which suggests that the loading of Pt NPs must occur on the
surface of the Co-MOF-74 samples rather than within the pore
because of the big size of the as-synthesized Pt NPs (2.4 ±
5
/
located at 70.75 and 74.07 eV, respectively, corresponding to the
0
8
typical metallic Pt . The samples of Pt/Co-MOF-74 show two
corresponding peaks at higher level of 70.91 and 74.33 eV,
indicating that some electrons were transferred from Pt NPs to
Co-MOF-74. However, another set of peaks at 72.42 and
76.08 eV emerge, corresponding to Pt species, which implies
some oxidation of the Pt NPs due to the reaggregation of Pt NPs
on the support resulting from weak metal−support interactions.
By contrast, shifting to a higher level at 71.10 and 74.41 eV was
0
.3 nm). As disclosed in our recent reports, the formation of
3+
8
Fe O due to the surface reaction of Fe and Co-MOF-74 also
occurred on the surface of the Co-MOF-74 samples, while as
observed in the literature, coprecipitation facilitates generation
of the Pt-encapsulated hybrid composite. In this regard, in this
system the formation of Pt@Fe O on the surface of the
2
3
25
2+
26
2
3
Co-MOF-74 samples is expected; thus, the resulting material
can be viewed as Co-MOF-74@(Pt@Fe O ).
observed for Co-MOF-74@(Pt@Fe
O ), suggesting more elec-
2 3
8
tron transfer from Pt NPs to both Co-MOF-74 and Fe
O .
3
2
3
2
The highly controlled nature, well-dispersed loading of Pt
NPs, and unique combination of mixed Fe O - and OPS-con-
Impressively, there is no observation of the oxidation of Pt NPs.
Thereby, strong metal−support interactions in the Co-MOF-
74@(Pt@Fe O ) catalyst can be deduced from these facts like
maintenance of the size, dispersity, and oxidation state of Pt NPs
and significant electron transfer from Pt NPs to the support.
In conclusion, we demonstrate in this work a novel multi-
component catalyst composed of Fe O , Pt NPs, and Co-MOF-
74. The synthesis of such a catalyst is extremely simple through
2
3
taining MOF supports entice us to explore its catalytic hydro-
genation performance on CAL. The catalytic reaction was
2 3
carried out at room temperature and 1 bar of H . Impressively,
2
Co-MOF-74@(Pt@Fe O ) shows not only ultrahigh selectivity
2
3
(
100%) toward hydrogenation on the CO group with COL as
2 3
the only product under 63% conversion of CAL but also high
catalytic efficiency, as evidenced by turnover frequency values as
high as 245.7 h−1 (Table S1). Most importantly, when the
reaction time is prolonged up to 5 h, the selectivity just gives a
little reduction, leading to 95% selectivity under 90% con-
version. The slight decrease of the selectivity is mainly due to the
fact that, along with higher conversion, some overhydrogenation
occurred. Furthermore, such a catalyst shows good stability after
three recycle runs (Figure S9). Also, this claim was further
confirmed by PXRD (Figure S10) and TEM (Figure S11).
Moreover, no leaching of Pt from the catalyst during the catalytic
reaction was observed, as evidenced by the solution without the
detection of Pt by means of inductively coupled plasma mass
+
our recently developed MOF technique. The results show that
this catalyst enables an outstanding catalytic performance for the
selective hydrogenation of CAL (Table S1) and should present
the first one showing both high catalytic efficiency and selectivity
under mild reaction conditions. The origin is mainly due to the
fact that such a unique multicomponent catalyst can not only
enable strong steric constraint toward the CO group of CAL
from both the Fe O and Co-MOF-74 components but also
2
3
show strong metal−support interaction.
ASSOCIATED CONTENT
■
*
S
Supporting Information
27−32
spectrometry after the catalytic reaction.
The Supporting Information isavailable free of charge onthe ACS
Publications website at DOI: 10.1021/acs.inorgchem.8b01922.
To verify the catalytic mechanism, several control experi-
ments were executed. Clearly, Co-MOF-74 and Co-MOF-74@
Fe O shows no catalytic activity (Table S1) because of the lack
Materials involved in the synthesis and additional figures
2
3
and tables (PDF)
of catalytic active metals of Pt NPs. Note that without support
the as-synthesized Pt NPs catalyst through the spray approach
just shows low 28.7% selectivity under 24% conversion. By
contrast, the MOF-supported catalyst of the Pt/Co-MOF-74
catalyst (Figure S12) prepared by a direct-wetness-method
impregnation of Co-MOF-74 in the as-synthesized Pt NPs
solution gives 43.8% selectivity under 65% conversion. This
strongly suggests that the support of Co-MOF-74 can improve
the selectivity. A similar trend was observed in the sandwich
Co-MOF-74@Pt@Co-MOF-74 structure that enables 70.1%
AUTHOR INFORMATION
■
Corresponding Author
E-mail: ecitluofeng@163.com.
*
ORCID
Feng Luo: 0000-0001-6380-2754
Author Contributions
†
L.-X.Y. and H.-Q.W. contributed equally to this work.
3
selectivity under 35% conversion. Also, the origin as suggested
Notes
in the literature is primarily due to the steric constraint of the
coordination interaction between the OPSs in Co-MOF-74 and
The authors declare no competing financial interest.
3
the CO groups of CAL. Previous research disclosed that the
ACKNOWLEDGMENTS
Fe O support can also provide steric constraint for the CO
■
2
3
3
,22
groups of CAL, consequently improving the selectivity.
This work was supported by the NSF of China (21871047), and
the Innovation Fund Designated for Graduate Students of East
China University of Technology (DH YC-201825).
For example, the Au@Fe O catalyst displayed 65.8% selectivity
2
3
2
2
under 70.2% conversion, while the Pt@Fe O catalyst afforded
2
3
C
DOI: 10.1021/acs.inorgchem.8b01922
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
H.; Jiang, H. L. Singlet oxygen-engaged selective photo-oxidation over
Pt nanocrystals/ porphyrinic MOF: the roles of photothermal effect
and Pt electronic state. J. Am. Chem. Soc. 2017, 139, 2035−2044.
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