Porous Zirconium–Furandicarboxylate Microspheres for Efficient Redox Conversion of Biofuranics

Article abstract of DOI:10.1002/cssc.201601898

Biofuranic compounds, typically derived from C₅ and C₆ carbohydrates, have been extensively studied as promising alternatives to chemicals based on fossil resources. The present work reports the simple assembly of biobased 2,5-furandicarboxylic acid (FDCA) with different metal ions to prepare a range of metal–FDCA hybrids under hydrothermal conditions. The hybrid materials were demonstrated to have porous structure and acid–base bifunctionality. Zr-FDCA-T, in particular, showed a microspheric structure, high thermostability (ca. 400 °C), average pore diameters of approximately 4.7 nm, large density, moderate strength of Lewis-base/acid centers (ca. 1.4 mmol g^?1), and a small number of Br?nsted-acid sites. This material afforded almost quantitative yields of biofuranic alcohols from the corresponding aldehydes under mild conditions through catalytic transfer hydrogenation (CTH). Isotopic ¹H NMR spectroscopy and kinetic studies verified that direct hydride transfer was the dominant pathway and rate-determining step of the CTH. Importantly, the Zr-FDCA-T microspheres could be recycled with no decrease in catalytic performance and little leaching of active sites. Moreover, good yields of C₅ (i.e., furfural) or C₄ products [i.e., maleic acid and 2(5H)-furanone] could be obtained from furfuryl alcohol without oxidation of the furan ring over these metal–FDCA hybrids. The content and ratio of Lewis-acid/base sites were demonstrated to dominantly affect the catalytic performance of these redox reactions.

Full text of DOI:10.1002/cssc.201601898

Accepted Article
Title: Porous zirconium-furandicarboxylate microspheres for efficient
redox conversion of biofuranics
Authors: Hu Li, Xiaofang Liu, Tingting Yang, Wenfeng Zhao,
Shunmugavel Saravanamurugan, and Song Yang
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To be cited as: ChemSusChem 10.1002/cssc.201601898
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10.1002/cssc.201601898
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Porous zirconium-furandicarboxylate microspheres for efficient
redox conversion of biofuranics
Hu Li,[a] Xiaofang Liu,[a] Tingting Yang,[a] Wenfeng Zhao,[a] Shunmugavel Saravanamurugan,[b] Song
Yang[a]*
Abstract: Biofuranic compounds, typically derived from C5 and C6
carbohydrates, have been extensively studied as promising
alternatives to fossil fule-based chemicals. The present work reports
the simple assembly of bio-based 2,5-furandicarboxylic acid (FDCA)
with different metal ions to prepare a range of metal-FDCA hybrids
under hydrothermal conditions, which were demonstrated to have
porous structure and acid-base bifunctionality. Especially, Zr-FDCA-
T showed microspheric structure, high thermostability (ca. 400 ºC),
ampliative average pore diameters (ca. 4.7 nm), large density and
moderate strength of Lewis base/acid centers (ca. 1.4 mmol/g) and
few content of Bronsted acid sites, and was able to afford almost
quantitative yields of biofuranic alcohols from corresponding
aldehydes under mild conditions via catalytic transfer hydrogenation
(CTH). Isotopic 1H NMR and kinetic studies verified the direct
hydride transfer to be the dominant pathway and rate-determining
step of the CTH reactions. Importantly, the Zr-FDCA-T microspheres
could be recycled with no decrease in catalytic performance and little
leaching of active sites. Moreover, good yields of C5 (i.e., furfural) or
C4 products (i.e., maleic acid and 2(5H)-furanone) could be obtained
from furfuryl alcohol without oxidation of the furan ring over these
renewable metal-FDCA hybrids. The content and ratio of Lewis
acid/base sites were demonstrated to dominantly affect the catalytic
performance of these redox reactions.
active for the valorization of biomass involving the processes of
hydrogenation and oxidation [3]. Cheap transition-metal particles
and oxides are deemed to be preferable candidates for both
types of reactions, but they often suffer from some drawbacks
such as need of harsh conditions, and relatively low stability and
reusability [4]
.
Metal-organic frameworks (MOFs), which are typically
composed of metal species and organic ligands to generate
porous and crystalline polymers, have been illustrated to be
most potentially applied in a variety of research fields such as
substance separation, gas adsorption, sensing, energy storage
and drug delivery[5]. Particularly, an increasing attention has
been placed on the use of MOFs containing flexible organic
moieties and coordinatively unsaturated metal sites for
heterogeneously catalyzing organic transformations and
biomass conversions in recent years[6]. To a great extent, the
high surface areas and rich micropores of MOFs can
significantly increase the contact probability of active sites to the
substrates, especially for those dependent on shape selectivity[7].
However, the microporous network may on the other hand
impede the access of bulky molecules to the cavities of MOFs[8]
and their thermal and chemical stability are relatively lower than
most commercial solid materilas (e.g., zeolites)[9], both of which
probably inhibit the catalytic applications of MOFs in wide-range
and large-scale production.
Introduction
The development of functional and structural materials from
natural composites has been considered to be one of important
areas in material chemistry [10]. Starting from lignocellulose, a
large number of porous carbonaceous materials prepared by
calcination and grafted with different functional groups were
demonstrated to show attractive prospects in catalysis,
drug/gene delivery, and fuel cell [11]. As a more facile and
controllable alternative to conventional preparative routes, the
assembly of organic molecules derived from natural materials
(e.g., phytic acid, polyphenol and porphyrin) with metal ions (e.g.,
Zr4+, Cu2+ and Fe3+) can not only mimic natural structures but
also form a range of functions with enhanced stability [12]. Similar
to the basic structure of terephthalic acid that is often used as
organic ligand for MOFs preparation, FDCA has two -COOH
Over the past decades, renewable lignocellulosic biomass has
been explored to be the most abundant and promissing
feedstock for producing biofuels and valuable chemicals [1]. In
the presence of acidic catalysts, simultaneously coupled with
basic/metallic sites, sugar and lignin components can be
selectively converted to a wide range of products like polyols
(e.g., sorbitol, mannitol, xylitol and ethylene glycol), organic
acids (e.g., levulinic acid and lactic acid), furanic compounds
(e.g., 5-hydroxymethylfurfural (HMF), 5-ethoxymethylfurfural
(EMF), 2,5-dimethylfuran (DMF), 2,5-diformylfuran (DFF) and
2,5-furandicarboxylic acid (FDCA)), and phenolics (e.g., vanillin
and veratraldehyde) [2]. Commonly, noble metal catalysts are
groups at the para position of the ring, showing convenient
[2f,2g]
[a]
Dr. H. Li, X. Liu, T. Yang, W. Zhao, Prof. S. Yang
State-Local Joint Engineering Lab for Comprehensive Utilization of
Biomass, State Key Laboratory Breeding Base of Green Pesticide
and Agricultural Bioengineering (Ministry of Education), Center for
R&D of Fine Chemicals, Guizhou University
Guiyang, Guizhou 550025, China
E-mail: jhzx.msm@gmail.com
Dr. S. Saravanamurugan
Center of Innovative and Applied Bioprocessing (CIAB)
Mohali 160 071, Punjab, India
replacement with each other in production of polymers
.
Inspired by these grand findings, the present work is to design
and prepare mesoporous acid-base bifunctional nanohybrids
from bio-based FDCA and different metal ions under
hydrothermal conditions for redox conversion of biofuranics in
high efficiency. Moreover, studies on reaction parameters
optimization, structure-activity relationship, catalyst recyclability,
reaction mechanism, and catalytic kinetics are also carried out.
To the best of our knowledge, this is the first report on the
[b]
application of FDCA as
a renewable organic ligand for
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cssc.201601898
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synthesizing acid-base bifunctional MOFs-type materials that
can be used as stable and heterogeneous redox catalysts.
HAADF (scanning transmission electron microscope and high-
angle annular dark-field) image in Fig. 3.
Results and Discussion
Catalyst charaterization
FT-IR spectra of ZrO2, Zr-FDCA and Zr-FDCA-T in Fig. 1A show
the characteristic of Zr−O bonds at 800 cm−1,[2e] while the
enhanced transmittance at wavenumbers of 1420 cm−1 and
1610-1700 cm−1 for both Zr-FDCA and Zr-FDCA-T reveals the
−
symmetric and asymmetric stretching vibration of the −CO2
group, respectively [13]. A splitting of around 190 cm−1 between
these two peaks further indicates that the coordination mode of
FDCA to Zr is bridging, rather than monodentate and bidentate
modes (Fig.S1), which is consistent with the structure of UiO-
66(Zr) [14]. In the case of ZrO2, the bands at 1630 cm−1 and 3450
cm−1 are possibly belonged to water bending vibrations and the
stretches of surface OH groups, respectively [2e]. The FT-IR
spectra for Zr-FDCA and Zr-FDCA-T also exhibit a small broad
peak at ~3200 cm−1, which can contribute to the OH groups of
monodentate FDCA molecules that may be incompletely
coordinated to Zr by leaving some protonated carboxylic
(−CO2H) groups [14]. It should be noted that the use of CTAB and
mesitylene as structure-directing agent for preparation of Zr-
FDCA-T is most likely to enhance the binding ability of
carboxylate to Zr, which can be well supported by its relatively
weaker band at ~3200 cm−1, as compared with Zr-FDCA.
Fig.2. HR-TEM images of ZrO2 (A), Zr-FDCA (B) and Zr-FDCA-T (C), as well
as TEM diffraction pattern (D), TEM image (E) and SEM image (F) of Zr-
FDCA-T
Fig.3. STEM-HAADF image (a), and Zr (b), C (c) and O (d) elemental
mappings of Zr-FDCA-T
Fig.1. FT-IR spectra (A) and XRD patterns (B) of ZrO2, Zr-FDCA and Zr-
FDCA-T
Nitrogen adsorption-desorption isotherms of ZrO2, Zr-FDCA and
Zr-FDCA-T are shown in Fig. S3. The simultaneous presence of
micro- and mesopores in ZrO2 could be primarily resulted from
the aggregate particles. Interestingly, the introduction of organic
species (i.e., FDCA) was able to greatly increase the adsorbed
quantity of N2 and generate more centered distribution of
mesopores, which might be the results of evenly assembled
organic-inorganic networks (Fig. 3), especially in the case of Zr-
FDCA-T. Table 1 collects the texture data of ZrO2, Zr-FDCA, Zr-
FDCA-T and UiO-66(Zr), including BET surface areas, pore
volumes, and average pore diameters. UiO-66(Zr) has the
highest surface area (1446 m2/g) and pore volume (0.61 m3/g),
as shown in Table 1 and Fig. S4, while its pore dimension is only
limited to microporous scale (1.7 nm). In contrast, Zr-FDCA and
Zr-FDCA-T with much lower suface areas (ca. 200 m2/g) but
show larger average pore sizes of 3.5 and 4.7 nm, respectively,
which may facilitate the access of active sites to the substrate.
For the amphoteric nature of the hybrids, it’s interesting to find
that Zr-FDCA and Zr-FDCA-T possess relatively higher
Fig. 1B illustrates the XRD patterns of ZrO2, Zr-FDCA and Zr-
FDCA-T. It can be seen that all these Zr-containing materials are
amorphorous with only a few broad diffractions, although Zr-
FDCA and Zr-FDCA-T have an obvious peak at 2θ of ~7.5° with
strong intensity, which is the typical (111) reflection of UiO-
66(Zr) (Fig.S2) [15]. HR-TEM images of ZrO2, Zr-FDCA and Zr-
FDCA-T further confirm their poor crystalline structure (Fig. 2A-
C). Fig. 2C shows the introduction of CTAB and mesitylene for
Zr-FDCA-T preparation leading to the formation of wormlike
feature, which may thus increase the surface area and porous
structure despite the absence of lattice plane (Fig. 2D). Notably,
the TEM and SEM images of Zr-FDCA-T demonstrate the slight
aggregation of microspheres in nano size (80-120 nm; Fig. 2E-
F), while the Zr, O and C compositions (i.e., Zr4+ and −CO2
−
moities) in Zr-FDCA-T were evenly connected and dispersed, as
observed from corresponding elemental mappings and STEM-
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10.1002/cssc.201601898
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hydrophobicity than neat ZrO2, which can be well supported by
the contact angles of a water droplet on their surfaces (Fig. 4 &
Fig.S5) [16]. This character of Zr-FDCA and Zr-FDCA-T can
further confirm the even connection of zirconium and
carboxylate species with less free protonated −CO2H groups,
which is in agreement with the results of FT-IR (Fig. 1A) and
elemental mappings (Fig. 3).
was most likely to promote the formation of more acid and base
sites, as compared with neat ZrO2 (Table S1, Table 1). More
interestingly, the assembly of Zr with FDCA for preparing Zr-
FDCA and Zr-FDCA-T hybrids could increase the contents of
Lewis acid sites (coordinated Zr; 1430-1450 cm–1) through
consuming Bronsted acid sites (free –COOH; 1530-1545 cm–1),
to some extent, as proved by pyridine-adsorbed FT-IR spectra
(Fig. 5B).
Table 1. Texture and acid-base properties of Zr-containing catalysts
Basicity
(mmol/
g)[d]
Acidity
(mmol/
g)[d]
Base/
acid
ratio
SBET
Vpore
Dpore
Catalyst
(m2/g)[a]
(m3/g)[b]
(nm)[c]
Zr-FDCA
Zr-FDCA-T
ZrO2
170
207
86
0.15
0.24
0.12
0.61
3.5
4.7
5.5
1.7
0.80
0.79
0.37
0.69
0.67
0.59
0.34
0.77
1:0.8
1:0.7
1:0.9
1:1.1
UiO-66(Zr)
1446
[a] BET surface area was determined by N2 adsorption isotherm.
[b] Pore volume was estimated by BJH adsorption cumulative volume of pores.
[c] Adsorption average pore diameter (4V/A by BET).
[d] Basicity and acidity was determined by NH3- and CO2-TPD, respectively.
Fig.5. TG curves (A) and pyridine-adsorbed FT-IR spectra (B) of Zr-containing
catalytic materials
CTH of FUR to FFA with different catalysts
Furfural (FUR) is one of important components in bio-oils, which
is generally derived from C5 sugars via dehydration under
hydrothermal conditions [18]. However, the –CHO groups in FUR
are susceptible to be condensed to humins, and much attention
has been thus laid on the stabilization of FUR by selective
hydrogenation to furfuryl alcohol (FFA) over noble metals (e.g.,
Pt, Pd and Ru) [19]. Therefore, CTH of FUR to FFA in 2-PrOH
was initially chosen to examine the catalytic performance of
different metal-FDCA hybrids (Table 2). Almost no reaction took
place in the absence of any catalyst at 140 ºC after 4 h (entry 1).
With the addition of metal-FDCA catalyst (i.e., Al-FDCA, Cr-
FDCA, Fe-FDCA, and Cu-FDCA) into the reaction system, low
FFA yields (1–14%) along with even more downstream products
including 2-(isopropoxy)methyl furan (IPMA; 2–19% yields) and
isopropyl levulinate (IPL; 5–8% yields) were observed (entries 2-
5). The existence of more acid sites with high strength
(base/acid site ratio: 1/2.4–1/11.6; Table S1) in these metal-
FDCA hybrids seemed to promote further etherification of FFA to
IPMA and even alcoholysis to give IPL (Scheme S1), while the
lack of enough base sites that are favorable for the process of
hydrogen tranfer (HT) failed to catalyze FUR being converted to
Fig.4. Contact angle (CA) of a water droplet on the surface of Zr-FDCA (A)
and Zr-FDCA-T (B)
Prior to determining the basicity (derived from O species in the
framework of M–O–C) and acidity (from metal and –COOH
moieties) of the metal-FDCA hybrids, the thermal stability of
selected Zr-FDCA and Zr-FDCA-T samples was initially
measured by TG analysis. Fig. 5A clearly demonstrates that
both Zr-FDCA and Zr-FDCA-T hybrids are not decomposed until
the temperature reaches to 400 ºC. In order to obtain the
accurate results of acid/base site contents for these solid bybrids
by using NH3/CO2-TPD, the maximum desorption temperature
was set at 300 ºC (Figs. S6-S7). The basicity and acidity of
different metal-FDCA hybrids (i.e., Al-FDCA, Cr-FDCA, Fe-
FDCA, Cu-FDCA, and Zr-FDCA) were supplied in Table S1,
wherein the type of metal ions was found to significantly affect
the base/acid site distribution and contents, as well as their
strength that can be directly evaluated on the basis of the
desorption temperature [17]. In the case of Zr-containing catalysts,
the inroduction of the organic species FDCA assembled with Zr
FFA in high efficiency [16]
.
Table 2. CTH of FUR to FFA with ZrO2, UiO-66(Zr) and metal-FDCA hybrids[a]
Entry
Catalyst
Blank
FFA yield(%)
FFA selec.(%)
FUR conv.(%)
TOF (h-1)[b]
--
0.7
0.2
0.7
<0. 1
2.7
10-6×k (s-1)[c]
1.4
IPMA yield(%)
IPL yield(%)
1
2
3
4
5
6
7
8
9
0
14
3
13
<1
78
96
41
72
0
<2
39
18
47
9
83
98
52
86
--
14
5
19
2
3
1
8
3
--
7
6
8
5
<1
<1
2
Al-FDCA
Cr-FDCA
Fe-FDCA
Cu-FDCA
Zr-FDCA
Zr-FDCA-T
ZrO2
36
17
28
10
94
98
79
84
34.3
13.8
44.1
6.5
123.1
271.7
50.9
3.5
2.9
2.5
UiO-66(Zr)
136.5
<1
[a] Reaction conditions: 2 mmol FUR, 0.1 g catalyst, 10 mL 2-PrOH, T = 140 ºC, and t = 4 h. [b] TOF = (mole of FFA) / (mole of acid/base sites × time). [c]
Reaction rate constant k is obtained from –ln (1 – FUR conversion) vs time [18b]. FFA: furfuryl alcohol; FUR: furfural; IPMA: 2-(isopropoxy)methyl furan; IPL:
isopropyl levulinate
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Gratifyingly, Zr-FDCA had more weak base sites (i.e., 0.63 and
0.17 mmol/g centered at the desorption temperature of 94 and
280 ºC, respectively) and comparable density of acidic sites in
weak to moderate strength (i.e., 0.54 and 0.13 mmol/g centered
at the desorption temperature of 116 and 269 ºC, respectively)
to other metal-FDCA hybrids (Scheme S1), and was able to
catalyze FUR being transformed to FFA in a relatively higher
yield of 78% with an enhanced TOF (2.7 h-1) which was 4-27
times higher than that of Al-FDCA, Cr-FDCA, Fe-FDCA and Cu-
FDCA (0.1-0.7 h-1; Table 2, entries 2-6). Further modification of
Zr-FDCA (base/acid ratio 1:0.8) with CTAB to prepare Zr-FDCA-
T microspheres (Fig. 2F) bearing an increased surface area and
pore size (Table 1) could ulteriorly accelerate the base/acid site
ratio to 1:0.7 (Table S1). As a result, the optimal Zr-FDCA-T
hybrid afforded a much higher FFA yield (96%), and TOF (3.5 h-
1) and k (2.7 × 10-4 s-1) increased by a magnitude of 1.3 and 2.2
times, respectively, as compared with Zr-FDCA (Table 2, entries
6 & 7). In contrast, either ZrO2 with lower surface area (86 m2/g)
and base/acid site contents (0.37 and 0.34 mmol/g) or UiO-
66(Zr) with smaller average pore diameter (1.7 nm; Table 1)
showed inferior activity to Zr-FDCA-T (Table 2, entries 7-9).
These results clearly demonstrate that the content of base/acid
sites in an appropriate molar ratio, surface area, and pore size
are all positively correlated with the pronounced performance of
the catalyst.
FDCA-T and UiO-66(Zr) could be concluded to be also helpful
for selective production of FFA from FUR by getting rid of
forming condensation products from either FUR or FFA
mediated by strong base [16]
.
It’s worth noting that the in situ generated acetone from 2-PrOH
during CTH of FUR with Zr-FDCA-T was much less than that
from pure 2-PrOH, which is in good agreement with a previous
report [21]. As compared with 2-PrOH, FUR seemed to show
superior availability to the relatively hydrophobic surface of Zr-
FDCA-T (Fig. 4), which could also be verified by the adsorption
energy of FUR (–2.4 eV) > FFA (–1.8 eV) > acetone (–1.1 eV) >
[22]
2-PrOH (–1.0 eV)
, thus significantly restraining the
dehydrogenation rate of 2-PrOH during the CTH system.
Notably, Zr-FDCA-T exhibited comparable and even higher
catalytic performance in CTH of FUR to FFA (Table S2), as
compared with noble and transition metal particles (e.g., Pt, Cu,
Ni, Co, and Fe) by using either H2 or alcohol as hydrogen-donor
(H-donor) [23]. These results demonstrate that porous acid-base
bifunctional Zr-FDCA-T simply prepared from the assembly of
bio-based molecule FDCA with Zr display promising applications
in CTH reactions.
Effect of reaction temperature and time on CTH of FUR
In the presence of the Zr-FDCA-T microshperes, the effect of
reaction temperature (i.e., 80, 100, 120, 140, and 160 ºC) on
product distribution in CTH of FUR was further investigated after
reacting for 4 h (Fig. 7A). At a relatively low temperature of 80 ºC,
IPMA (12% yield) formed by etherification of FFA with 2-PrOH
was found to be the major byproduct during CTH of FUR,
implying that etherification and transfer hydrogenation of 2-PrOH
are most likely to be two competitive reactions. With the
increase of reaction temperature from 80 to 140 ºC, the yield of
IPMA gradually decreased to aound 1%, which clearly indicated
the acceleration of relatively high temeprature (i.e., 140 ºC) on
the transfer hydrogenation process for selective production of
FFA from FUR (Fig. 7A). When the reaction temeprature further
increased to 160 ºC, the downstream product (i.e., IPL) derived
from IPMA was observed to be the dominant byproduct, as
identified by GC-MS in Fig.S8. Therefore, it can be
unambiguously perceived that a relatively high temperature of
140 ºC is more favorable for the exclusive formation of FFA from
FUR in 2-PrOH.
Fig.6. XPS spectra of Zr 3d (A) and O 1s (B) in ZrO2, Zr-FDCA, Zr-FDCA-T
and UiO-66(Zr)
It was also not difficult to find that UiO-66(Zr) having micropores
centered at 1.7 nm could still give a moderate FFA yield of 72%
from CTH of FUR, which was comparable to that obtained over
Zr-FDCA (78%) and higher than ZrO2 (41%), respectively (Table
2). Apart from the promotional effect of larger suface area (1446
m2/g) and comparable base/acid sites (0.69 and 0.77 mmol/g in
a ratio of 1/1.1) to Zr-FDCA-T (Table 1), the strength of acid and
base sites could be another crucial factor in affecting CTH of
FUR to FFA [12d]. To elucidate this speculation, Zr 3d and O 1s in
ZrO2, Zr-FDCA, Zr-FDCA-T and UiO-66(Zr), separately
corresponding to Lewis acid and base centers, were recorded
with XPS (Fig. 6). A higher Zr 3d binding energy means a larger
positive charge of Zr species, thus indicating the Zr centers to
have much stronger Lewis acidity (Fig. 6A) [20]. In turn, a lower O
1s binding energy illustrates a higher negative charge and
basicity of oxygen in C-O-Zr (Fig. 6B) [8c]. Therefore, the Lewis
acidity and basicity of these catalysts are in the order of Zr-
FDCA-T > UiO-66(Zr) > Zr-FDCA > ZrO2 and Zr-FDCA > Zr-
Fig.7. CTH of FUR to FFA at different reaction temperatures after 4 h (A) and
in different reaction times at 140 ºC (B); Reaction conditions: 2 mmol FUR, 0.1
g Zr-FDCA-T, and 10 mL 2-PrOH.
FDCA-T
> ZrO2 > UiO-66(Zr), respectively. Besides high
contents and appropriate molar ratios of acid/base sites, the
predominant acidity but low to moderate base strength of Zr-
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In line with the effect of reaction temperature on product
distribution in CTH of FUR to FFA, either IPMA or IPL was found
to be primarily formed as the byproduct in yields of up to 7%, by
in yields of 91-96% at almost complete FUR conversions under
the optimized reaction conditions (Fig. S9). At relatively low FUR
conversions of around 50%, Zr-FDCA-T was also able to
varying reaction time in the range of 0.5–10 h at 140 ºC (Fig. 7B). catalyze FUR being converted to FFA with a slight decrease in
IPMA seemed to be not stable after long reaction duration (≥4 h), yields by no more than 4% after five cycles (Fig.S10). These
which could be reversibly converted to FFA, or further
transformed into IPL. However, a certain amount of unkown
propducts (<5% in total) was formed after reacting for 10 h,
results confirmed the robust active sites and high durability of Zr-
FDCA-T in CTH of FUR to FFA.
which was possibly caused by some FFA-involved side
To accurately investigate the structural changes in Zr-FDCA-T
before and after CTH reactions for six cycles, a variety of
characterization techniques including TG analysis, nitrogen
adsorption-desorption, pyridine-adsorbed FT-IR, CO2-TPD, FT-
IR, XRD, and SEM have been adopted (Fig. 9, Figs.S11-S13). A
slight reduction of surface area (from 207 to 185 m2/g) was
detected (Fig. 9A), which could be ascribed to the adsorption of
organic species into cavities of Zr-FDCA-T during the reactions
(Fig. 9B, Fig.S11). Only minor leaching of Zr species (~3% of
total Zr content) was observed, as determined by ICP-OES
analysis. Although the total acidity of Zr-FDCA-T was almost in
constant contents of 0.55-0.59 mmol/g after recycling for six
times, the distribution of Lewis and Bronsted acid sites was
changed a little bit by consuming the former ones to generate
the latter (Fig. 9C). The slightly increased intensity of the
adsoption at around 3200 cm−1 for reused Zr-FDCA-T could be
assigned to the in situ formed OH groups of monodentate FDCA
molecules (Fig.S12), implying the possible dissociation of
coordinated Zr and carboxylate groups to liberate −CO2H, to a
small degree. Surprisingly, the basicity of the reused Zr-FDCA-T
increased by about 0.1 mmol/g (Fig. 9D), which might be
resulted from the adsorbed basic organic species (e.g., 2-
propoxide) and the generated rough surfaces of the recovered
catalyst (Fig.S13) to facilitate the access of CO2 by TPD analysis.
[24]
reactions like oligomerization and condensation
. The
optimized reaction time (4 h) and temeprature (140 ºC) were
thus selected and used for the subsequent studies.
Catalyst recyclability in CTH of FUR to FFA
Prior to the recycling study of Zr-FDCA-T, the effect of catalyst
dosage on CTH of FUR to FFA was initially examined (Fig. 8A).
It was interesting to note that the selectivity toward FFA
increased from 63% to 98% with the addition of more Zr-FDCA-
T
(25-100 mg). During these catalytic processes, the
hemiacetalization of FUR with 2-PrOH was found to be the
dominant reaction route to consume the substrate [22], thus
resulting in low to moderate FFA selectivities at relatively high
FUR conversions by using relatively low catalyst dosages (25-75
mg). Although Zr-FDCA-T with a large dosage of 200 mg could
promote the complete conversion of FUR (Fig. 8A) without
producing the hemiacetal byproduct, the downstream products
of FFA (e.g., IPMA and IPL) catalyzed by excess acid and base
sites were formed instead.
Fig.8. Effect of Zr-FDCA-T dosage on FUR-to-FFA conversion at 140 ºC for 4
h (A), and catalytic behavior study of Zr-FDCA-T in FUR-to-FFA conversion at
140 ºC by varying reaction time (B)
To study the catalytic behavior of Zr-FDCA-T for CTH of FUR to
FFA in 2-PrOH at 140 ºC, two parallel experiments by using the
solid catalyst in an optimal dosage of 100 mg with or without
separating the catalyst from the hot reaction mixture after 1 h
were conducted (Fig. 8B). After stirring for another 5 h under
identical conditions, Zr-FDCA-T could smoothly catalyze FUR
being converted to FFA, while almost no reaction was observed
to take place for the reaction system being filtered out the
catalyst. ICP-OES analysis showed both filtrates containing <1
ppm of zirconium species, clearly manifesting the intactness and
heterogeneous catalysis of Zr-FDCA-T in the CTH reactions.
Fig.9. Nitrogen adsorption-desorption isotherms (A), TG curves (B), pyridine-
adsorbed FT-IR spectra (C), and CO2-TPD patterns of fresh and reused Zr-
FDCA-T microspheres for six cycles
CTH of other biofuranics and selected deuterium labeling
experiments
The reusability of a solid catalyst is one of important indexes to
evaluate its potential application in industrial production [25]. Over
six consecutive cycles, Zr-FDCA-T could be simply recovered by
washing with DMF and ethanol, and capable of producing FFA
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10.1002/cssc.201601898
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FULL PAPER
[27]
Encouraged by the predominant catalytic performance of Zr-
FDCA-T microspheres in CTH of FUR to FFA, other biofuranics
including 5-hydromethylfurfural (HMF) and 5-methylfurfural (MF)
derived from C6 sugars have also been used as substrates to
produce corresponding alcohols 2,5-bis(hydroxymethyl)furan
(BHMF) and 5-methylfurfuryl alcohol (MFA). High yields of
BHMF (87%) and MFA (95%) at almost complete substrate
conversions could be achieved at 140 ºC after reacting for 8 and
6 h, respectively (Table S3).
simultaneous presence of oxidizable C=C and C=O groups
.
In this study, all metal-FDCA hybrids were demonstrated to
significantly suppress the furan ring oxidation. Notably, Zr-
FDCA-T with moderate Lewis basicity and acidity could
selectively catalyze FFA being incompletely oxidized to FUR (up
to 41% yield), while Cr-FDCA and Cu-FDCA with superior Lewis
acidity afforded high yields of maleic acid and 2(5H)-furanone
(~60% in total). These results further confirmed the role of acid
and base sites in controlling the distribution of products derived
from furanic compounds via redox reactions.
To elucidate the reaction mechanism, CTH of HMF to BHMF in
2-PrOH (d8) was monitored at varying times by ex situ nuclear
magnetic resonance (NMR) spectrometer (JEOL-ECX 500), as
shown in Fig. 10. The obtained 1H NMR spectra show the proton
in aldehyde group (i.e., −CHO) of HMF (1a) gradually
disappeared by increasingly adding deuterium (D) from 2-PrOH
(d8) to its C=O bond. Accordingly, the methylene (−CH2−) and
methine (−CH−) groups of HMF were separately shifted to 2b
and 1b in D-labeled BHMF (Fig. 10). GC-MS spectrum for CTH
of HMF in 2-PrOH (d8) illustrates the formed BHMF having two
almost equivalent molecular ion peaks with additional 2 and 3
amu (i.e., m/z = 130 and 131), respectively (Fig.S14), which can
be caused by the direct hydrogen transfer and proton exchange
between HMF and 2-PrOH (d8) in the column during GC-MS
analysis (Scheme S2) [16]. The reaction rate of HMF-to-BHMF
conversion in normal (kH) and isotopic (kD) 2-PrOH was
indepentently determined under identical conditions, and the
kH/kD value was found to be 2.1. These unequal rate constants
further proved the CTH reaction proceeding through the direct
Conclusions
A range of porous acid-base bifunctional metal-FDCA hybrids
(i.e., Cr-FDCA, Cu-FDCA, Al-FDCA, Fe-FDCA, Zr-FDCA, and
Zr-FDCA-T) were successfully prepared from simple assembly
of bio-based FDCA with corresponding metal ions under
hydrothermal conditions, and demonstrated to be highly efficient
for redox conversions of biofuranics without breaking C=C bond
of the furan ring. In the presence of Zr-FDCA-T microspheres,
CTH of biofuranic aldehydes to corresponding alcohols could be
achieved with almost quantitative yields, and the direct hydride
transfer was verified to be the dominant reaction pathway and
the rate-determining step by isotopic 1H NMR and kinetic studies.
Importantly, Zr-FDCA-T microspheres were able to be reused
with no significant decrease in catalytic activity and little leaching
of active sites. Moreover, these metal-FDCA hybrids were also
found to show high selectivity in catalytic oxidation of FFA to
either C5 or C4 products with moderate yields. This type of bio-
based functional catalysts shows great potential in organic
synthesis and biomass valorization, and the simple preparation
methods may be used for developing other renewable catalytic
materials.
hydride transfer as the rate-determining step [26]
.
Experimental Section
Materials
2,5-Furandicarboxylic acid (FDCA, 98%), p-phthalic acid (99%),
zirconium chloride (ZrCl4, ≥99.5%), aluminum chloride (AlCl3, 99%),
chromium chloride hexahydrate (CrCl3·6H2O, 98%), iron chloride (FeCl3,
98%), copper chloride (CuCl2, 98%), hexadecyl trimethyl ammonium
bromide (CTAB, 99%), hydrogen peroxide solution (30 wt% H2O2 in
water), 2-propanol (99.5%) and N,N-dimethylformamide (DMF, 99.8%)
were brought from Aladdin Industrial Inc. (Shanghai). Furfural (FUR,
99%), furfuryl alcohol (FFA, 98%), 5-methylfurfural (MF, 99%), 5-
methylfurfuryl alcohol (MFA, 97%), 5-hydroxymethylfurfural (HMF, 99%),
2,5-bis(hydroxymethyl)furan (BHMF, 98%), 2(5H)-furanone (98%), maleic
acid (MA, 99%), mesitylene (>98%), and 2-propanol-d8 (2-PrOH-d8, 99.5
atom% D) were purchased from J&K Scientific Ltd. (Beijing). All other
reagents (analytical grade) were utilized as recieved without any
treatment, unless otherwise mentioned.
Fig.10. 1H NMR spectra of HMF-to-BHMF conversion in isotopic 2-PrOH (d8)
at varying times
Catalytic oxidation of furfuryl alcohol
In addition to the hydrogenation reactions, catalytic oxidations of
FFA with H2O2 over different metal-FDCA hybrids were also
investigated at 45 ºC for 2 h, and the results are shown in Table
S4. It was reported that a range of C4 compounds (e.g., maleic
acid and 2(5H)-furanone), acetic acid, and humins would be
formed in H2O2-mediated oxidation of FUR owing to the
Catalyst preparation
All metal-biofuranic catalysts (M-FDCA; M = Zr, Al, Cr, Fe, and Cu) were
prepared from the self-assembly of 2,5-furandicarboxylic acid (FDCA)
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10.1002/cssc.201601898
ChemSusChem
FULL PAPER
with equivalent corresponding metal chloride (i.e., ZrCl4, AlCl3, CrCl3,
FeCl3, or CuCl2) in DMF under hydrothermal conditions. In a typical
procedure, 1.5 mmol FDCA (0.23 g) and 1.5 mmol ZrCl4 (0.35 g) were
dissolved in 15.5 mL DMF (0.2 mol) in a 25 mL teflon-lined stainless steel
autoclave by stirring at room temperature for 10 min. The tightly sealed
autoclave was kept in an oven (JZ-4-1200, Shanghai Jingzhao
Mechanical Equipment Co. Ltd.) under static conditions at 120 ºC for 24
h. Upon completion, the resulting white precipitates were filtered out and
successively washed with DMF and ethanol for 5-8 times until colorless
transparent filtrate was observed, followed by drying at 100 ºC overnight
to afford the target sample Zr-FDCA. To further extend the aperture
structure of Zr-FDCA, CTAB (0.45 mmol) and mesitylene (0.45 mmol)
were added as co-reagents under other identical conditions, and the
obtained material was denoted as Zr-FDCA-T. For comparison, ZrO2
(calcined at 150 ºC for 12 h) and UiO-66(Zr) were also synthesized,
CTH reactions of bio-based carbonyl compounds with 2-propanol (2-
PrOH) were all conducted in a 15 mL Ace pressure tube (Synthware,
Beijing) under oil-heating conditions. In a general procedure, 2.0 mmol
furfural (FUR), 0.1 g catalyst, and 10 mL 2-PrOH were added into the
reactor, and then placed into the preheated oil bath at a desired
temperature of 80-160 ºC, followed by magnetically stirring for a specific
reaction time (i.e., 0.5-10 h) at 600 rpm. Upon completion, the tube was
quenched by cold water in a beaker, and the liquid mixture was
quantitatively analyzed by gas chromatography (GC).
Catalytic oxidation of furfuryl alcohol
To a 15 mL Ace pressure tube, 1 mmol furfuryl alcohol (FFA), 2 mL 30
wt% H2O2, and 0.05 g catalyst were added. The resulting mixture was
then put into the oil bath under vigorously stirring, and heated to 45 ºC for
2 h. After the reaction, the aqueous solution was quantitatively analyzed
by high performance liquid chromatography (HPLC).
according to previously reported procedures [28]
.
Catalyst characterization
Catalyst recycling
Wide angle XRD (X-ray diffraction) patterns in a range of 5-90º were
recorded on a D8 Advance X-ray powder diffractometer with a Cu Kα
radiation source (Bruker, Germany). FT-IR (Fourier transform-infrared)
spectroscopy was conducted using a Nicolet 6700 spectrometer (Thermo
Fisher Scientific, US) in a thin KBr disk. Pyridine adsorbed FT-IR spectra
For recycling the catalyst, the solid residue in the solution after each
cycle was separated by centrifugation, successively washed with DMF
and ethanol for 5 times, dried at 120 ºC for 5 h, and directly employed for
the next run. To examine the leaching content of active species, the
reaction mixture after filtering out the catalyst and volumetrically diluting
with deionized water was sent for ICP-OES (inductively coupled plasma-
optical emission spectroscopy) analysis with a PerkinElmer Optima 8000
instrument.
were measured with
a Bruker VERTEX V70v system, wherein a
temperature-programmed desorption of pyridine-adsorbed sample at 250
ºC for 1 h (from 25 ºC with a heating ramp of 5 ºC min-1) was
implemented before FT-IR analysis. SEM (scanning electron microscopy;
MERLIN Compact, ZEISS, Germany) and HR-TEM (high resolution-
transmission electron microscope; Tecnai G2 F20, FEI, US) were used to
the morphologies of catalytic materials. STEM-HAADF (Scanning
transmission electron microscope and high-angle annular dark-field)
imaging was obtained from an aberration corrected (S)TEM (JEM-
1200EX, JEOL, Japan) fitted with energy dispersive X-ray (EDX). BET
(Brunauer-Emmett-Teller) surface area, BJH pore size and volume were
measured with nitrogen physisorption (JW-BK132, JWGB Sci & Tech Co.
Ltd., Beijing) at liquid nitrogen temperature. TG (thermogravimetry)
analysis was taken with a DTG-60AH instrument (Shimadzu, Japan)
under N2 atmosphere (40 mL/L) at a temperature range of 25-600 °C in a
heating ramp of 5 °C/min. XPS (X-ray photoelectron spectroscopy) was
operated using a K-Alpha instrument (Thermo Fisher Scientific, US). The
contact angle of a water droplet on the solid sample surface was
determined at room temperature by using a DSA30 instrument (Kruss,
Germany). NH3- and CO2-TPD (temperature programmed desorption)
patterns were recorded with an AutoChem II 2920 chemisorption
analyzer (Micromeritics, US) to evaluate the surface acidity and basicity
of catalytic materials, respectively. Before analyzing the gas (i.e., NH3 or
CO2) desorption with a thermal conductivity detector (TCD) every one
second at programmed temperature from 50 to 300 °C in He (with a
heating ramp of 10 °C min−1 and keeping at 300 °C for 60 min), the solid
sample in a quartz reactor was initially degassed at 150 °C for 60 min,
and then flushed with 10% NH3 or CO2 in 90% He (60 mL/min) for 60 min
to enable the complete adsorption of NH3 or CO2 at 50 °C, followed by
flushing with pure He (60 mL min−1) for another 60 min to elute the gas
physically adsorbed to the solid material.
Sample analysis
To identify the products after reactions, the resulting mixtures were
diluted with methanol and analyzed by GC-MS (Agilent 6890N GC/5973
MS, US). FUR, FFA, and other reagents and products involved in CTH
reactions were quantitatively analyzed on GC (Agilent 7890B) with a
flame ionization detector (FID) and a HP-5 column (30 m × 0.320 mm ×
0.25 μm) by using naphthalene as internal standard. The substrate
conversions and product yields were calculated on the basis of the
standard curves of commercial or isolated (i.e., IPMA and IPL) samples.
For quantitative analysis of products in aqueous solution, HPLC (LC-20A,
Shimadzu, Kyoto) was used instead, which was fitted with an Aminex
HPX-87H column, and ultraviolet and refractive index detectors.
Acknowledgements
We wish to thank the financial supports from the National
Natural Science Foundation of China (21576059 & 21666008),
and the National Key Technologies R&D Program of China
(2014BAD23B01).
Keywords: Renewable materials • biofuranic compounds •
heterogeneous catalysis • acid-base bifunctionality • biomass
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Table of Contents
FULL PAPER
All from Biomass: Bio-based 2,5-
furandicarboxylic acid (FDCA)
assembled with zirconium under
solvothermal conditions can give
mesoporous Zr-FDCA microspheres
functionalized with enhancive Lewis
acid-base centers, which are
H. Li, X. Liu, T. Yang, W. Zhao, S.
Saravanamurugan, S. Yang*
Page No. – Page No.
Porous zirconium-furandicarboxylate
microspheres for efficient redox
conversion of biofuranics
demonstrated to be highly active and
selective for catalytic transfer
hydrogenation and oxidation of
biofuranics to corresponding alcohols
and C4 products (see image),
respectively. The robust and
sustainable catalytic system shows
great potential for efficient valorization
of biofuranics.
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