Porous, Naturally Derived Hafnium Phytate for the Highly Chemoselective Transfer Hydrogenation of Aldehydes with Other Reducible Moieties

Article abstract of DOI:10.1002/cctc.201701521

Both the utilization of naturally occurring compounds to prepare functional materials and the selective conversion of aldehydes with other reducible moieties (ORMs) are very attractive topics. Herein, we synthesized a novel porous material, hafnium phytate (Hf-Phy), by using naturally derived sodium phytate as the building block. Hf-Phy has plenty of mesopores centered around 11.8 nm. Hf-Phy showed excellent performance for the transfer hydrogenation of aldehydes with ORMs by using 2-propanol as the hydrogen source with high selectivities (95–100 %) for alcohols without reducing ORMs. Systematic studies suggested that the oxophilicity of Hf⁴⁺ and the basicity and structure of Hf-Phy contributed significantly to the excellent performance. Additionally, Hf-Phy could be used over at least five cycles without any decrease in activity or selectivity.

Full text of DOI:10.1002/cctc.201701521

Accepted Article
Title: Porous Naturally Derived Hafnium Phytate for Highly
Chemoselective Transfer Hydrogenation of Aldehydes with Other
Reducible Moieties
Authors: Jinliang Song, Zhimin Xue, Chao Xie, Haoran Wu, Shuaishuai
Liu, Lujun Zhang, and Buxing Han
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To be cited as: ChemCatChem 10.1002/cctc.201701521
Link to VoR: http://dx.doi.org/10.1002/cctc.201701521
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10.1002/cctc.201701521
ChemCatChem
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Porous Naturally Derived Hafnium Phytate for Highly
Chemoselective Transfer Hydrogenation of Aldehydes with Other
Reducible Moieties
Jinliang Song,*[a] Zhimin Xue,[b] Chao Xie,[a,c] Haoran Wu,[a,c] Shuaishuai Liu,[a,c] Lujun Zhang,[a,c] and
Buxing Han*[a,c]
Dedication ((optional))
Abstract: Both utilization of naturally occurring compounds to
prepare functional materials and selective conversion of aldehydes
with other reducible moieties (ORM) are very attractive topics.
Herein, we synthesized a novel porous material, hafnium phytate
(Hf-Phy), using naturally derived sodium phytate as the building
block. Hf-Phy had plenty of mesopores centered around 11.8 nm. It
was found that Hf-Phy showed excellent performance for transfer
hydrogenation of aldehydes with ORM using isopropanol as the
hydrogen resource with high selectivities (95-100%) for alcohols
without reducing ORM. Systematic studies suggested that the
oxophilicity of Hf4+, and the basicity and structure of Hf-Phy
contributed significantly to the excellent performance. Additionally,
Hf-Phy could be used at least five cycles without decrease in activity
and selectivity.
complexes or introducing additives, supplemental metal
components, functional supports, and designing special
structures for supported catalysts,[9,11,15,17,27-30] the complex
preparation routes, the relative expensive price, and the stability
and recyclability of these catalytic systems, are still limited their
large scale applications. Undoubtedly, design of simple and
efficient heterogeneous catalysts using cheap and sustainable
precursors for selective reduction of aldehyde groups in the
presence of ORM is still highly desired but very challenging.
Nowadays, utilization of naturally occurring compounds as
catalysts or catalyst precursors has gained increasing
interest.[31,32] Phytic acid (Scheme S1, PhyA) is a naturally
occurring compound in plants. The six phosphate groups in
PhyA structure can coordinate with diverse metal ions to form
functional materials. This characteristics results in great potential
to synthesize efficient Lewis acid catalysts using PhyA for CTH
of aldehydes with ORM considering that Lewis acids are an
important type of catalysts for CTH reaction.[33] Herein, we
designed porous hafnium phytate (denoted as Hf-Phy) for the
first time simply by the reaction of HfCl4 and sodium phytate
(Scheme S1) in hexadecyltrimethyl ammonium bromide
aqueous solution. The obtained Hf-Phy could be used as a
heterogeneous catalyst to efficiently and selectively catalyze the
CTH reaction of aldehydes with ORM toward alcohols without
reducing ORM.
Selective reduction of aldehydes with other reducible moieties
(ORM) towards the corresponding alcohols without reducing the
OMR groups has gained much interest because it is an essential
reaction for the synthesis of various fine chemicals used in
flavorings, perfumes, and pharmaceuticals.[1,2] To dates, direct
hydrogenation using H2 as the reductant and catalytic transfer
hydrogenation (CTH) with secondary alcohols are two commonly
used routes for the reduction of aldehydes with ORM, and great
efforts have been devoted to explore efficient and selective
catalytic systems. In general, some supported transition metals
(e.g., Ru,[3] Pd,[4,5] Au,[6-9] Pt,[10-13] Cu,[14,15] Co,[16,17] Ir,[18-20] or
Ni[21]) and metal complexes[22-26] were the most studied catalysts
for this important transformation, but the selectivities for alcohols
with ORM unreduced are often poor or difficult to be controlled
due to the competitive adsorption and reduction between the
aldehyde group and ORM on the catalytic active centers.
Although the selectivity towards alcohols with ORM unreduced
could be enhanced by designing novel ligands for metal
Hf-Phy was synthesized through the procedure described in
the Supporting Information, and was characterized by various
techniques. The obtained Hf-Phy was a porous material due to
the micellar template effect of hexadecyltrimethyl ammonium
bromide aqueous solution. SEM (Figure S1) and TEM
examinations (Figure 1A) demonstrated that the shape of the as-
prepared Hf-Phy were not uniform with plenty of mesopores
(Figure 1B, the red cycles corresponded to the mesopores).
Meanwhile, the corresponding elemental mappings examined by
HR-TEM confirmed that Hf and P were dispersed in Hf-Phy
uniformly (Figure 1C). FT-IR spectrum of the prepared Hf-Phy
(Figure S2) showed that there was a strong adsorption at 1069
[a]
Dr. J. Song, C. Xie, H. Wu, S. Liu, L. Zhang, Prof. B. Han
Beijing National Laboratory for Molecular Sciences, CAS Key
Laboratory of Colloid and Interface and Thermodynamics, Institute
of Chemistry, Chinese Academy of Sciences, Beijing 100190,
P.R.China
2-
cm-1 belonging to the symmetrical stretching modes of -OPO2
groups,[34a] which could be considered as an evidence for the
structural formation of Hf-Phy.[34b] Meanwhile, peaks around 866
cm-1 and 510 cm-1 were related with the framework vibration of
Hf-O-P and Hf-O bonds, respectively.[34c,d] In addition, the FT-IR
spectrum of Hf-Phy was different with that for sodium phytate
(Figure S3), indicating the formation of Hf-Phy from sodium
phytate and HfCl4. Furthermore, inductively coupled plasma
(ICP) analysis showed that the molar ratio of Hf and P in Hf-Phy
was about 1:2, suggesting one Hf4+ could coordinate with two
phosphate groups. Due to the coordination ability of all the six
phosphate groups and the steric hindrance, the network of Hf-
E-mails: songjl@iccas.ac.cn, hanbx@iccas.ac.cn
Dr. Z. Xue
Beijing Key Laboratory of Lignocellulosic Chemistry, College of
Materials Science and Technology, Beijing Forestry University,
Beijing 100083, China.
C. Xie, H. Wu, S. Liu, L. Zhang, Prof. B. Han
School of Chemistry and Chemical Engineering, University of
Chinese Academy of Sciences, Beijing 100049, P.R.China
[b]
[c]
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/cctc.201701521
ChemCatChem
COMMUNICATION
Phy was mainly generated through a preferred connectivity
pattern (Scheme S2). However, XRD analysis indicated Hf-Phy
had low crystallinity or was poorly ordered (Figure 1D).
Therefore, it can be deduced that many defects or irregular
connectivity were existed in Hf-Phy. As shown in N2 adsorption-
desorption isotherm (Figure 1E), Hf-Phy was a porous material
with mesopores centered around 11.8 nm (the insertion in
Figure 1E), which was consistent with the results determined by
TEM (Figure 1B), and the surface area and pore volume were
266 m2 g-1 and 0.74 cm3 g-1, respectively (Table S1). The low
crystallinity and porous structure suggested that Hf-Phy had
great potential to be a good catalyst.
the rising temperature (Figure 2A) and Hf-Phy amounts (Figure
2B). Nearly full conversion of cinnamaldehyde (97.8%) was
obtained at 100 oC over 0.1 g Hf-Phy. Kinetic experiments
indicated that the conversion enhanced with the prolonging
reaction time, and 6 h was suitable for this Hf-Phy-catalyzed
system (Figure S4). In addition, the selectivity of cinnamyl
alcohol kept nearly constant (97-99%) in these experiments.
Table 1. Catalytic performance of various catalysts for CTH of
cinnamaldehyde.[a]
OH
O
OH
O
+
+
Entry
Catalyst
None
Conversion (%)[b]
Yield (%)[b]
Selectivity (%)
1
2
3
4
5
6
0
0
--
97
97
--
Hf-Phy
Zr-Phy
HfO2
97.8
91.2
2.7
2.1
0
94.9
88.5
2.3
1.5
0
Sn-Phy
Ti-Phy
--
--
[a] Reaction conditions: cinnamaldehyde, 1 mmol; IPA, 4 g; catalyst, 0.1 g;
reaction time, 6 h; reaction temperature, 100 oC; N2 as the protective gas, 0.1
MPa. [b] The conversions and yields were determined by GC using
ethylbenzene as the internal standard.
Figure 1. Characterization of the obtained Hf-Phy. A) TEM image, B) enlarged
TEM image of the red square area in A, C) the corresponding elemental
mappings from HR-TEM, D) powder XRD pattern, and E) N2 adsorption-
desorption isotherm. The insertion in E was the pore size distribution.
Selective CTH of cinnamaldehyde, an aldehyde with
conjugated C=C bonds, to cinnamyl alcohol using isopropanol
(IPA) as the hydrogen resource was selected as a typical model
reaction to evaluate the catalytic performance of Hf-Phy. No
hydrogenation reaction occurred without catalysts (Entry 1,
Table 1). Subsequently, activities of various catalysts were
examined. The prepared Hf-Phy showed the highest catalytic
activity, and a cinnamaldehyde conversion of 97.8% was
achieved with a cinnamyl alcohol selectivity of 97% at 100 oC
(Entry 2, Table 1). In contrast, Zr-Phy provided a slightly lower
conversion of cinnamaldehyde (91.2%, Entry 3, Table 1) than
Hf-Phy. The higher activity of Hf-Phy may be caused by the
higher oxophilicity of Hf than Zr due to the higher dissociation
enthalpies of typical Hf-O (802 KJ mol-1) compared with Zr-O
(776 kJ mol-1),[35] which was beneficial for the activation of the
aldehyde group in cinnamaldehyde (a key step for transfer
hydrogenation[36,37] as discussed below). Moreover, commercial
Figure 2. Effect of reaction temperature (A) and Hf-Phy amount (B) on CTH of
cinnamaldehyde. Reaction conditions: cinnamaldehyde, 1 mmol; IPA, 4 g;
reaction time, 6 h; N2 as the protective gas, 0.1 MPa; Hf-Phy, 0.1 g for A;
reaction temperature, 100 oC for B.
Besides cinnamaldehyde, we used Hf-Phy as the catalyst
for CTH of other aldehydes with ORM. The results in Table 2
indicated that Hf-Phy also showed good activity for conversion of
the examined aldehydes by modifying the reaction conditions.
For other cinnamaldehydes with substituted groups on the
benzene ring, the reactivity could be maintained (Entries 1-3,
Table 2) except for 4-nitro-cinnamaldehyde (Entry 4, Table 2),
which was transformed with a conversion of only 85.9% even
when the reaction time was prolonged to 12 h due to the
electron-withdrawing effect of nitro group. However, when the H
at the α-position of the aldehyde group was substituted, higher
reaction temperature was needed to obtained good performance
in relative short reaction time (Entries 5-8, Table 2). For example,
the transfer hydrogenation should be conducted at 150 oC to
achieve good conversion (>95%) when the substituted groups
were n-pentyl or n-hexyl (Entries 6 and 7, Table 2). Furthermore,
3-phenylpropionaldehyde showed much better reactivity (Entry 9,
Table 2) than cinnamaldehyde due to the conjugation effect
between the double bond and aldehyde group in
cinnamaldehyde. Additionally, Hf-Phy exhibited excellent
catalytic performance for other aldehydes containing ORM,
HfO2 showed very low activity with
a cinnamaldehyde
conversion of only 2.7% (Entry 4, Table 1). Additionally, the
activity of other synthesized metal phytates (Sn-Phy and Ti-Phy)
was very low (Entry 5, Table 1) or inactive (Entry 6, Table 1).
These results suggested that Hf-Phy was a superior catalyst for
selective CTH of cinnamaldehyde.
As important parameters, reaction temperature and catalyst
amounts can affect the overall reaction efficiency significantly.
As expected, the conversion of cinnamaldehyde increased with
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10.1002/cctc.201701521
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COMMUNICATION
including
benzaldehyde,
anisaldehydes,
characterized results for the recovered Hf-Phy through XRD, FT-
IR, SEM, and TEM (Figure S5) indicated that the properties of
Hf-Phy remained unchanged. The atom ratios on the surface
(Table S2) and the statement of Hf (Figure S6) in the recovered
Hf-Phy suggested the surface characteristic was not changed.
Furthermore, N2 adsorption-desorption examination indicated
that textural properties for the recovered Hf-Phy were similar to
the fresh one. The results above showed the stability of Hf-Phy.
In addition, the heterogeneous nature of Hf-Phy was
investigated by hot filtration after reaction for 2 h at 120 oC using
α-methyl-cinnamaldehyde as the reactant, and the reaction
continued to be conducted without solid catalysts. No further
reaction occurred (Figure S7), verifying that Hf-Phy was
heterogeneous. Meanwhile, the concentration of Hf in the
reaction solutions was extremely low (<0.7 ppm) detected by
ICP, suggesting the negligible leaching of active species.
cyclohexanecarboxaldehyde, and citronellal (Entries 10-15,
Table 2). Additionally, control experiments using styrene and
anisole as the substrates indicated no reaction happened,
verifying the inertness of Hf-Phy for transfer hydrogenation of
ORM, which resulted in the high selectivity for the corresponding
alcohols with ORM unreduced. Finally, some aliphatic α,β-
unsaturated aldehydes could also be converted over Hf-Phy
(Entries 16 and 17, Table 2), but the conversion and the
selectivity to the corresponding alcohols were not satisfactory
due to the difference in the conjugation effects from the
unsaturated double bonds.[9]
Table 2. Catalytic activity of Hf-Phy for selective CTH of various aldehydes
with ORM.[a]
O
OH
+
+
R
CH2OH
R
CHO
T
t
C
(%)[b]
Y
(%)[b]
S
(%)[b]
Entry
Reactant
(oC)[b]
(h)[b]
CHO
1
2
3
4
100
100
100
100
6
6
97.8
98.5
94.9
96.7
97
98
CHO
MeO
F
CHO
6
97.2
85.9
96.5
82.3
99
95
CHO
12
O2N
CHO
Figure 3. Reusability of Hf-Phy for CTH of α-methyl-cinnamaldehyde (A) and
3-phenylpropionaldehyde (B). Reaction conditions: substrate, 1 mmol; IPA, 4
g; Hf-Phy, 0.1 g; reaction time, 6 h for A and 3 h for B; reaction temperature,
120 oC for A and 100 oC for B; N2 as the protective gas, 0.1 MPa.
5
6
120
150
6
6
98.5
97.9
97.5
95.4
99
97
4
5
CHO
CHO
7
150
6
97.3
98.7
96.2
98.1
98
99
As discussed above, Hf-Phy showed much better
performance than commercial HfO2, which could result from the
different oxophilicity of Hf, basicity, and structures. First, as the
catalytic center, Hf played the crucial role for CTH of aldehydes
with ORM. The local environment of Hf in Hf-Phy and HfO2 was
examined by XPS. As shown in Figure 4A, the binding energy
values of Hf 4d in Hf-Phy were higher than those of HfO2,
indicating higher positive charge on Hf atoms in Hf-Phy, which
resulted in stronger oxophilicity.[37] The stronger oxophilicity of Hf
in Hf-Phy was helpful for activating the aldehyde groups, which
was the key step for CTH of aldehydes[36,37] with ORM (Figure 5),
and thus improved the reaction. Second, the basicity of the
catalysts could also affect the catalytic activity. As examined by
CO2-TPD, Hf-Phy had higher basicity than HfO2 (Figure 4B),
which may be caused by the higher basicity of phosphate
groups.[37] Higher basicity was favorable to the activation of the
hydroxyl groups in IPA by basic sites (O2-) in the phosphate
groups with the aid of Hf4+ (Figure 5),[37,38] and this effect could
enhance the transfer hydrogenation. Third, as examined by XRD,
Hf-Phy was amorphous with a very low crystallinity, while HfO2
showed better crystallinity (Figure 4C). The lower crystallinity of
Hf-Phy was helpful for the reactants to be in contact with the
catalytic center (Hf). Meanwhile, Hf-Phy had higher BET surface
area, larger pore diameter, and larger pore volume than HfO2
(Table S1), which was beneficial to increasing the diffusion of
reactants to the catalyitc center (Hf). These structure
advantages caused Hf-Phy having a higher catalytic activity.
Br
CHO
CHO
8
9
120
100
6
3
99.5
99.2
97.9
98.5
99.2
97.9
99
CHO
CHO
10
11
100
100
3
3
100
100
MeO
OMe
CHO
12
13
100
100
1.5
2
>99
>99
100
>99
MeO
98.6
98.1
CHO
CHO
14
15
100
100
3
4
>99
>99
100
>99
98.3
97.9
CHO
CHO
16
17
100
100
6
6
63.7
58.2
28.9
24.4
45
42
CHO
[a] Reaction conditions: reactant, 1 mmol; IPA, 4 g; catalyst, 0.1 g; N2 as the
protective gas, 0.1 MPa. [b] T=Temperature, t=time, C=Conversion, Y=Yield,
and S=Selectivity. The conversions and yields were determined by GC using
ethylbenzene as the internal standard.
The reusability of Hf-Phy was evaluated using α-methyl-
cinnamaldehyde and 3-phenylpropionaldehyde as the substrates.
Hf-Phy could be reused at least five times without considerable
change in activity (Figure 3), and the selectivity toward the
corresponding alcohols was always above 98%. The
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COMMUNICATION
This work was supported by National Natural Science
Foundation of China (21673249), National Key Research and
Development Program of China (2017YFA0403003), and Youth
Innovation Promotion Association of CAS (2017043).
Keywords: Selective transfer hydrogenation • porous material •
aldehydes with other reducible moieties • naturally derived
chemicals • hafnium phytate
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10.1002/cctc.201701521
ChemCatChem
COMMUNICATION
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COMMUNICATION
Novel porous hafnium phytate (Hf-
Phy) with mesopores ranging from 2
nm to 20 nm can be synthesized using
naturally derived sodium phytate as
the building block, which is very
efficient and selective for catalytic
transfer hydrogenation of various
aldehydes with other reducible
moieties. Systematic studies suggest
that the excellent performance is
Jinliang Song,* Zhimin Xue, Chao Xie,
Haoran Wu, Shuaishuai Liu, Lujun
Zhang, and Buxing Han*
Page 1 – Page 4
Porous Naturally Derived Hafnium
Phytate for Highly Chemoselective
Transfer Hydrogenation of Aldehydes
with Other Reducible Moieties
significantly
resulted
from
the
oxophilicity of Hf4+, and the basicity
and structure of Hf-Phy.
This article is protected by copyright. All rights reserved.