Recent progress in the biomass-mediated synthesis of porous materials

Article abstract of DOI:10.1016/j.ica.2018.12.045

The aim of this Account article is to demonstrate the versatility of using biomass residues or their extracted molecules in the synthesis of different families of porous materials. While our former studies mainly focused on zeolites, the present contribution gives more space to polyoxometalates (POMs), layered-doubled hydroxides (LDHs) as well as transitional mesoporous aluminas. The Bio-Sourced Secondary Template (BSST) strategy presented herein should serve as a basis for rationally preparing porous materials (micro-, meso- or macro- or combination of those) for sorption or catalytic applications.

Full text of DOI:10.1016/j.ica.2018.12.045

Inorganica Chimica Acta 487 (2019) 379–386
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Research paper
☆
Recent progress in the biomass-mediated synthesis of porous materials
a
a
a,b
a,c
c
Rogeria Bingre , Cristina Megias Sayago , Pit Losch , Liang Huang , Qiang Wang ,
d
a,⁎
Marcelo M. Pereira , Benoît Louis
a
b
c
ICPEES, UMR 7515 CNRS, Université de Strasbourg, ECPM, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France
Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany
Environmental Functional Nanomaterials (EFN) Laboratory, College of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China
d
LACES, Universidade Federal do Rio de Janeiro, Centro de Tecnologia, Departamento de Química Inorgânica, Avenida Athos da Silveira Ramos, 149, Ilha do Fundão, Rio
de Janeiro, RJ 21941-909, Brazil
A B S T R A C T
The aim of this Account article is to demonstrate the versatility of using biomass residues or their extracted molecules in the synthesis of different families of porous
materials. While our former studies mainly focused on zeolites, the present contribution gives more space to polyoxometalates (POMs), layered-doubled hydroxides
(
LDHs) as well as transitional mesoporous aluminas. The Bio-Sourced Secondary Template (BSST) strategy presented herein should serve as a basis for rationally
preparing porous materials (micro-, meso- or macro- or combination of those) for sorption or catalytic applications.
1
. Introduction
structures by a sound engineering of OSDA [12,13]. Interestingly, cal-
culations based on sophisticated algorithms became an unavoidable
tool to predict the stability of new structures [14,15].
Chemistry relies on the design and control of systems over multiple-
length scales ranging from the molecule to the crystal [1]. The assembly at
the molecular level involves at least two species, based on non-covalent
interactions (hydrogen bonding, electrostatic forces, van der Waals forces,
metal-ion coordination), being the cornerstone of long-range organization
Recently, the Rimer group demonstrated how zeolite growth
modifiers (polyamines, proteins and sugars) impact the assembly of
crystal sub-units and then alter the final size and morphology of the
crystals [16–20]. In parallel, Morris et al. have developed a smart As-
sembly-Disassembly-Organisation-Reassembly (ADOR) strategy to or-
ganize zeolite precursors in different ways [21,22].
[
2–6]. Precious insights have been gained by the definition and under-
standing of supramolecular chemistry by Jean-Marie Lehn [7].
Though covalent bonding prevails in inorganic porous solids, the latter
materials are often meta-stable, being even produced after successive
meta-stable steps [8,9]. For instance, crystalline microporous aluminosi-
licates are typically produced (under hydrothermal conditions) via a sol-
gel process using: a silica and an alumina-source (called T-atom source), a
mineralising agent (either hydroxides or fluorides) and an organic struc-
ture directing agent (OSDA). These ingredients are allowed to dissolve in
water, then placed under autogenous pressure at temperatures higher than
In the present account, we aim to present our recent findings on
zeolite synthesis in the presence of biomass or its extracted main
building blocks. Besides, we report also the successful application of so-
called BSST approach to the design of alumina, POMs and LDHs porous
materials, being then called ‘Bio-Sourced Template’ (BST) strategy.
Structure-activity relationships were tentatively established be-
tween textural/structural properties of those as-obtained biomass-
mediated porous materials and their behaviour in C chemistry. Two
1
1
00 °C. The formation of the zeolite crystalline structures is governed by
examples were chosen: (i) CO capture; (ii) conversion of methanol into
2
electrostatic, van der Waals and hydrophobic forces known as supramo-
lecular interactions. The understanding of those supramolecular assem-
blies involved in zeolite syntheses is therefore mandatory to rationally
conceive new zeolite structures [10].
hydrocarbons. Finally, the possibility of designing materials with
hierarchical porosity was also highlighted.
2. Bio-sourced secondary templates in zeolite synthesis
2.1. BSST as an efficient crystal growth modifier
In spite of being considered as ‘hard matter’ themselves, internal
voids present in zeolites remain ‘soft matter’ and a parallel can there-
fore be drawn with enzymes found in Nature [11]. Indeed, high-energy
frameworks could be obtained as thermodynamically favoured
The organic structure directing agent (OSDA) acts as the template,
☆
Special Contribution in honour of Prof. M.L.H. Green for his outstanding contributions to chemistry and inspiration given to young scientists.
⁎
Corresponding author.
E-mail address: blouis@unistra.fr (B. Louis).
https://doi.org/10.1016/j.ica.2018.12.045
Received 3 October 2018; Received in revised form 17 December 2018; Accepted 24 December 2018
Available online 26 December 2018
0020-1693/ © 2018 Published by Elsevier B.V.

R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
usually possessing a positive charge thus interacting through electro-
static forces with negatively charged T-atom tetrahedron monomers.
Aluminates and silicates self-assemble around the OSDA and con-
densate to nuclei and then crystallites under high temperature and
autogenous pressure. Though different kinds of sophisticated organic
cations can be used as OSDA [23,24], templates may also originate from
cheap and naturally occurring (alkali-) metal cations.
in the presence of biomass fibres (Fig. 1c and d), subjected to alkaline
hydrolysis or not, readily form aggregates of nano-French fries. This
suggests that crystallization phenomenon was hindered in the presence
of biomass residues. These observations are in line with former studies
which demonstrated an induction of different effects to the final zeolite
crystal, depending on either the presence of biopolymers or oligomers
and monosaccharides as BSST [15,26]. The samples were also analysed
by XRD and all the patterns confirmed the sole presence of the MFI
structure (Fig. 2).
According to Ostwald ripening, the primary product formed in a
zeolite synthesis is barely the most stable [25]. Indeed, series of kinetic
products may form as transient meta-stable phases prior to the forma-
tion of stable thermodynamic product. The consequence is that any
single modification in the gel may allow shifting from one structure to
another.
Nitrogen adsorption–desorption isotherms confirmed the micro-
porous nature of all MFI samples, although presenting a smaller surface
area (Table 2) when compared to well-established ZSM-5 zeolites. The
differences observed in SBET values could either be explained by the
presence of defects within the zeolite pores (like debris) or by the non-
complete crystallisation of the material. Fig. 3 presents the isotherms of
micron-sized ZSM5-BH, ZSM5-BT and ZSM-5-FH samples. Textural
properties referring to ZSM5-ref and ZSM5-B were already discussed in
our earlier contribution [36].
One can therefore easily imagine that the addition of any “extra-
agent” to the gel may obviously induce severe modifications to the
textural or structural properties of the final material [26]. Among extra-
agents, usually called crystal growth modifiers (CGMs), used in the
synthesis of zeolites, one can cite the following (non-exhaustive) list:
chitosan [27], proteins [28], cotton fibres [29], cellulose [30], amino
acids [16–20], crown ether [31], vanillin and lignin [32].
The materials synthesized in the presence of biomass fibres grew in
micron-sized assemblies formed by smaller and rather elongated crys-
tals. The widths of those rectangular crystals were few hundreds of
nanometres in size. The presence of intercrystalline mesoporosity could
be ascertained by TEM analysis of ZSM5-FH sample (Fig. 4).
The existence of special affinities between sugars and (alumino)si-
licates has been elegantly confirmed by Jaber et al. [33]. While ribose
chemical stabilization could be evidenced on a silica surface, the ratio
between furanose and pyranose isomers was shown to be dependent on
inorganic solid surface composition [33].
Table 2 summarizes the textural and acidic properties of all as-
synthesized samples. Whilst specific surface areas and pore volumes are
similar among the samples, it turns out that the total number of OeH
groups measured by H/D isotope exchange strongly differ among the
samples. Indeed, ZSM5-ref and ZSM5-BT led to roughly 0.3–0.4 mmol
OeH groups per gram of zeolite, corresponding to usual values found
for strong BrØnsted acid sites density in MFI zeolite having 20 < Si/
Al < 25 [37]. In stark contrast, the two samples obtained using solid
BSST, pristine or alkaline hydrolysed bagasse fibres, exhibit a larger
number of OeH groups, as already observed in the study from Ocampo
et al. [36]. Surprisingly, ZSM5-FH possesses 1.70 mmol OeH groups per
gram of catalyst which strongly suggests the presence of numerous
Based on preliminary results obtained with biomass residues
[
26,32] as CGMs, the effect of either sugar cane bagasse, or compounds
obtained from its alkaline hydrolysis for the preparation of MFI zeolites
was investigated. In addition, this BSST strategy was also applied to
other classes of porous solids: LDHs, POMs and transitional aluminas.
2.2. BSST in MFI zeolite synthesis and acid catalysis
Inspired by the biomineralization process described by Valtchev
et al. during the replication of Equisetum Arvense plant [34] and by the
specific interactions created between (alumino)silicates and sugars or
amino acids [15,35], we have investigated how these small molecules
could impact the zeolite crystallization, mediate the creation of hier-
archical porosity (micro-meso or micro-macro) and also induce specta-
cular crystal assemblies.
(
weakly) acidic silanol groups (SieOH) besides strong BrØnsted acid
sites. One may therefore expect a different behaviour of the later
sample in acid catalysis.
The catalytic activity of ZSM-5 samples was evaluated in the con-
version of methanol to hydrocarbons, either to C
2
-C olefins or C5+
4
gasoline fraction (Fig. 5). The highest selectivity towards light olefins
MFI zeolites were prepared after different treatments made to the
biomass as summarized in Table 1. In addition betaine as a mimicking
compound to bio-sourced polymers was also used. SEM images of as-
synthesized samples are shown in Fig. 1. As reported in our former
studies [26,32,36], the use of bagasse led to a great impact on the
morphology and size of MFI zeolite crystals.
fraction (MTO behaviour) was achieved over ZSM5-FH catalyst, being
5
2%. Likewise, this catalyst exhibited the highest resistance to deacti-
vation, i.e.; time for reaching complete conversion loss, 28 h when com-
pared to ZSM5-ref (13 h). This might be explained by the presence of
weak acidity at the zeolite surface, hindering the formation of con-
secutive products (C5+ alkanes and aromatics) as well as the occurrence
of an extensive coking process. It is worthy to note that except ZSM5-
BH, all samples demonstrated higher yields towards olefins (above
Prismatic morphology of roughly 2 µm in length could be observed
for ZSM5-ref material, i.e., in the absence of any BSST species. Likewise,
sharp prismatic MFI crystals are well evidenced in the samples prepared
with bagasse hydrolysate (ZSM5-BH) and betaine (ZSM5-BT) as shown
on Fig. 1b and 1e, respectively. However, the sizes of the latter two
materials appear larger than ZSM5-ref, being close to 10 µm. It seems
therefore that betaine and extracted molecules from the biomass favour
the crystallization of larger MFI crystals. In contrast, zeolites prepared
3
0%) as well as enhanced catalyst stability than ZSM5-ref (Fig. 5).
To sum-up the impact of BSST species involved in ZSM-5 zeolite
syntheses, it is important to mention that MFI crystals grew mainly
according to c-elongated mode, suggesting the creation of peculiar in-
teractions between silicates/aluminates and bio-sourced species. Hence
this BSST strategy is therefore able to guide the zeolite crystal growth
[
26].
Table 1
BSST nature and quantity used during the synthesis of MFI zeolites.
3
. BST synthesis of layered double hydroxides (LDHs)
Biomass
Mass added (mg)
Sample
None
–
ZSM5-ref
ZSM5-BH
ZSM5-B
Layered Double Hydroxides (LDHs) are promising materials, which
*
Hydrolysis of bagasse
Pristine bagasse
Fibres from hydrolysis
Betaine
30
can be used as a catalyst or as a support for numerous reactions, or as a
sorbent material [38–40]. LDHs, known as hydrotalcite-like com-
pounds, are members of layered materials family, which comprise
mono- or di- and trivalent cations represented by the formula
100
100
100
ZSM5-FH
ZSM5-BT
z+
3+
x
m+
z+
*
The quantity of hydrolysed bagasse is given in mL (for a 60 mL reactor
[M1−x
M
(OH)
2
]
X
n−m/n·yH O. In an overwhelming majority of
2
2+ 2+ 2+ 3+ 3+, 3+,
volume).
cases z = 2 and M = Mg , Zn , Ni etc, and M = Al
Mn
380

R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
Fig. 1. SEM images of as-synthesized MFI zeolites: a) ZSM5-ref, b) ZSM5-BH, c) ZSM5-B, d) ZSM5-FH, and e) ZSM5-BT.
Table 2
Textural and acidic properties of all-prepared samples.
Sample
S
BET
m /g)
S
micro
2
V
pore
3
V
micro
3
BrØnsted acidity
2
(
(m /g)
(cm /g)
(cm /g)
(mmol OeH/gcat)
ZSM5-ref
–
–
–
–
0.44
–
ZSM5-BH 266
181
–
0.13
–
0.09
–
ZSM5-B
–
1.06
1.70
0.29
ZSM5-FH 250
ZSM5-BT 209
164
125
0.14
0.11
0.08
0.06
3
+
Fe
etc. The structure of LDHs has been well solved and related to
brucite, Mg(OH)
2
, consisting of positively charged brucite-like layers,
with interlayer spaces containing charge compensating anions and
water molecules. Since the chemical composition of both charged layers
and interlayer anions can be exactly controlled, LDHs possess high
potential in a wide range of applications such as fire retardant [41],
catalysts [42], high-temperature CO capture [43], etc.
2
LDH with Mg/Al = 3 were synthesized using a co-precipitation
method. A reference sample named LDH was prepared as well as 2
BSST-mediated samples: (i) using lignin; (ii) or using bagasse. Both
solids were added during the co-precipitation step.
Fig. 2. XRD patterns of the as-prepared zeolite samples.
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R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
Fig. 3. Nitrogen adsorption-desorption isotherms for ZSM5-BH, ZSM5-BT and
ZSM5-FH.
Fig. 6. XRD patterns of LDH prepared in the presence of sugar cane bagasse or
lignin.
SEM analysis confirms the presence of nanolayers in the materials
(
Fig. 7). As a reference sample, LDH exhibits a typical nano-flower
morphology with a thickness of 15 nm for the petals (Fig. 7a). The same
morphology could be observed for the LDH/bagasse sample (Fig. 7b),
suggesting that its presence did not impact the LDH crystal growth.
From the micrographs (Fig. 7a and b), it is worthy to mention that the
‘
flower-like’ particle size is in a 400–500 nm range, with approximately
1
00 nm for individual petals. After calcination the particle size did not
change as already shown by DLS experiments from Wang et al. [44].
The presence of large and non-soluble biomass fibres may hardly
influence the nucleation process. In stark contrast, the presence of so-
luble oxidized lignin species hindered the formation of nano-flowers
Fig. 4. TEM image of ZSM5-FH confirming the presence of intercrystalline
mesoporosity.
(
Fig. 7c), hence leading to the formation of a lamellar structure with
lower crystallinity (Fig. 6).
The latter materials were tested as CO sorbent to evaluate the
2
impact of BSST species during the co-precipitation synthesis of porous
solids. As expected, fresh LDH did not exhibit CO capture capacity. A
2
thermal treatment at 673 K was therefore applied, leading to LDHs
gradual loss of their layered structures. LDHs suffer from extensive
dehydroxylation and decarbonation, thus leading to the formation of
mixed metal oxide structure [45]. The latter is known to possess a high
affinity for CO capture. Fig. 8 shows the XRD patterns of LDHs, after
2
calcination at 673 K. It can clearly been observed that (00l) diffractions
vanished, indicating the complete transformation of LDHs into amor-
phous mixed oxides (MgAlO ), possessing MgO periclase phase features
x
(
Fig. 8).
CO
at 473 K by a thermogravimetric sorption method using a Q500 TGA
2
capture capacities of each LDH derived sorbents were measured
analyzer. Conventional MgAl LDH led to a CO
2
capture capacity of
which is consistent with literature reports. It appeared
promoted CO capture capacity to
within 30 min, corresponding to a 16% relative in-
crease. Usually, less crystalline material (even amorphous) is favorable
for CO capture, thus rendering LDH/lignin a good potential CO ad-
sorbent.
−
1
0
.50 mmol g
,
that LDH/lignin led to
a
2
Fig. 5. Catalytic data acquired for Methanol-To-Hydrocarbons reaction. Yields
−1
0
.58 mmol g
towards olefins (ethylene, propylene and butylenes) and gasoline fraction (C4+
)
as well as the time to complete deactivation are presented.
2
2
According to XRD patterns, LDH structure can be assessed for the
two biomass-synthesized samples (Fig. 6). Indeed, all three samples
were obtained in pure layered double hydroxide structure with char-
acteristic diffractions corresponding to (0 0 3), (0 0 6), (0 0 9), (0 1 5),
Unfortunately, the same trend could not be observed over LDH/
−1
sugar cane bagasse, with only 0.18 mmol g
CO captured under the
2
same conditions. Those sorption capacities may be explained (at least
partially) by the differences observed in crystallinity/sizes among
(
0 1 8), (1 1 0) and (1 1 3) planes [44]. After the addition of biomass, it
MgO/MgAl O sorbents, derived from LDHs (Fig. 8). Calcined LDH and
x
appears that as-prepared LDHs exhibit weaker and broader reflection
peaks, corresponding to smaller crystalline domains. Pristine LDH,
obtained without any BSST addition, led to the sharpest diffractions,
indicating well-crystallized particles.
calcined LDH/lignin exhibit weaker intensities than calcined LDH/su-
garcane bagasse, which suggest a lower degree of crystallinity and
smaller particle size, being beneficial for CO capture.
2
382

R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
Fig. 7. SEM images of (a) LDH; (b) LDH/bagasse; (c) LDH/lignin.
Fig. 8. XRD patterns of calcined LDH samples. (★) periclase MgO.
. BST synthesis of polyoxometalates (POMs)
Fig. 9. XRD patterns of calcined POM: PMoA, CsPMo and CsPMo + L.
4
decrease in the average pore diameter with respect to pristine alumina.
In order to further expand the BST strategy to other valuable inorganic
In contrast, Al
2
O
3
-BH and Al
2
O -FH led even to reduced specific surface
3
materials, we have decided to evaluate the impact of lignin presence during
the assembly processes involved in the synthesis of polyoxometalates
areas as well as slightly lower pore volumes. The samples prepared by
this hydrothermal method exhibited a type IV isotherm, thus con-
firming the presence of mesopores [48]. According to the latter study, it
(
POMs). In a former study, we have shown how Keggin-type units self-as-
sembled into nanoparticles, ending up with large micron-sized crystals [4].
XRD pattern (Fig. 9) of pristine PMoA acid exhibits the typical dif-
fractions of Keggin structure, corresponding in this case to hydrated
was shown that Al
2
O -B alumina possesses a rather different pore or-
3
ganization with higher interconnectivity with respect to the one pre-
pared without BST [48]. Fig. 11 presents a high-resolution TEM image
which further assesses the lamellar arrangement of the mesopores.
H
3
PMo12
O
40·xH O form (ICSD # 00-050-0304). It is worthy to remind
2
that depending on the degree of hydration, Keggin-type POM with
different space groups can be produced. For instance, the two Cs-salt
samples exhibit similar diffraction lines accounting for the formation of
These improved textural properties exhibited by Al
2
O -B as well as
3
its special arrangement of alumina planes into a lamellar structure
suggests that different kinds of interactions are involved between bio-
mass-derived compounds, produced under ‘in situ’ conditions, and
alumina-hydrate precursor, thus affecting the structure by probably
acting on aluminate ions in tetrahedral positions of η-alumina [50].
Similarly to zeolite syntheses, it appears reasonable that supramole-
cular interactions between oligomers originated from biomass and
aluminate species occur. Hydrogen bonding for instance might direct
such transformation as already suggested for cyclodextrin-mediated
alumina preparation [51].
the acidic cesium salt Cs
x
H3−xPMo12O40 [46,47], named CsPMo and
CsPMo + L, respectively. It is worthy to note that BST-containing POM
exhibits broader peaks in comparison to lignin-free sample. The latter
can be attributed to the formation of smaller particles in the presence of
lignin, as evidenced by SEM (Fig. 10).
The difference in particle sizes can be ascribed to the presence/
absence of lignin during the synthesis and its possible interaction with
POM heteropolyanions which controls somehow their ionic assembly
+
with Cs cations.
Opposing to classical mesoporous alumina syntheses with mainly
Pluronic® P123, the BST approach appears extremely attractive as it
allows a drastic reduction in the cost of synthesis. Since mesoporous
aluminas are abundantly used in industry as catalyst or as catalyst
support, new methodologies for decreasing its production cost are
therefore warranted. M.L.H. Green also inspired our researches while
investigating the effect of glucose as a template [52].
5
. BST synthesis of mesoporous aluminas
The preparation of transitional aluminas using sugar cane bagasse has
been reported by Cardoso et al. [48]. The textural properties of γ-Al
O
2 3
obtained using BSTs are given in Table 3. BET surface area remained lower
2
−1
for γ-Al
2
O reference material, i.e.; 206 m g in the absence of biomass
3
[
49]. The use of sugar cane bagasse as BST led to achieve roughly a 30%
6. Outlook
2
−1
increase in the BET area (267 m g ).
However, pore volume and mesopore diameter did not change sig-
Inspired by anti-freeze proteins behaviour, known to inhibit the
crystalline growth of ice, we were recently able to shed light on the
nificantly, except for Al
2
O -B sample which demonstrated roughly 25%
3
383

R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
Fig. 11. HRTEM image of alumina prepared in the presence of bagasse.
complex mechanisms involved in BSST-mediated zeolite syntheses
[
15,26]. The presence of either biomass residues or molecules extracted
in their hydrolysates, amphiphilic in nature, guided the crystalline
growth of ice in a peculiar way [26]. Mimicking Nature is a timely
strategy to design porous materials with tailored properties. Buehler
et al. have recently given a bright overview of hierarchical materials
found in Nature (spider silk, crustaceous exoskeletons, nanocellulose
from wood, collagen protein) along with insights to adapt such
knowledge to the development of smart nanomaterials [53].
An important outcome for our studies remains that biomass (or its
extracted compounds: C
5
or C sugars, lignin building blocks) act as a
6
Bio-Sourced Secondary Template, named BSST [26]. Though the self-
assembly mechanism of organic moieties in solution is still unknown,
H-bonding interactions between BSST and (alumino)silicate monomers
might be reasonably expected. The final inorganic material, mainly
zeolite studied to date, can take benefits from BSST complex hydro-
philic and hydrophobic zones, leading to well-controlled non covalent
interactions and chelating properties. Hence, zeolites possessing hier-
archical porosity, i.e.; micro-meso [36] or micro-macro [32] could be
designed.
Finally, we were also able to use this unprecedented methodology to
insert 20% more Al atoms, as T-positions, in the MFI framework, thus
achieving a Si/Al = 8 never reached before [15]. Again, mother Nature
allowed to grow a natural analog to the MFI structure, called mutinaite
Fig. 10. SEM images of POM samples. (a) PMoA, (b) CsPMo and (c) CsPMo + L.
[
54] a long time ago. One can therefore be optimistic that the BSST
approach may allow crossing the bridge of metastability structures,
diminishing further Si/Al limits and probably guiding the growth to-
wards novel zeolite structures.
Table 3
Textural properties of γ-aluminas prepared from boehmite.
The present contribution brings an added-value to the use of bio-
mass for the design of porous materials. Indeed, The BSST concept
developed for zeolites has now been expanded as BST concept for LDHs,
POMs and alumina, which are also extremely important classes of
porous solids. Moreover, it turns out that not sole hydrothermal
synthesis is warranted to get system perturbations during the crystal-
lites formation, but also (co)-precipitation technique.
a
b
c
Samples
BETSurface area
Pore volume
Average Pore
2
−1
3 −1
(
m ·g
)
(cm ·g
)
Diameter (nm)
2
Al O
2
Al O
2
Al O
2
Al O
3
3
3
3
-ref
206
267
149
193
0.53
0.51
0.46
0.45
10.3
7.7
-B
-BH
-FH
12.1
9.3
a
b
c
BET surface area.
To conclude, this BSST concept for tailoring different class of porous
solids fits perfectly within the supramolecular chemistry (found so often
in Nature) developed by J.M. Lehn [7]. Supramolecular assemblies
consist of the spontaneous association of numerous components into a
specific phase having a well-defined microscopic organization.
Calculated by BJH desorption.
Average pore diameter (4 V/A from the desorption branch).
384

R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
This account was written to honor the outstanding contributions
(Sigma Aldrich, 0.27 g) were dissolved separately in distilled water
from M.L.H. Green to chemistry. Malcolm himself, in his earliest studies
played with the ‘reversibility’ found in self-assembly processes while
studying β-hydrogen abstraction from a metal-alkyl system [55]. We
hope that he enjoys our contribution, finding it tasty like whisky; si-
milarly to what we feel reading his papers which were always on the
sidelines before becoming timely!
according to the literature [56]. After that, Cs
2
CO solution was added
3
dropwise to the acid solution under vigorous stirring, leading to the
formation of insoluble salt. The mixture was then aged overnight and
the solvent removed by heating. CsPMo is the adopted nomenclature for
this compound.
Alkali lignin (Aldrich) was used as possible template during the
second caesium salt preparation. Targeting synthesis steps reduction,
lignin hydrolysis was performed under acidic conditions, using the
same PMoA solution needed to form the insoluble salt. In this way,
lignin (300 mg) was added to a 0.1 M PMoA solution and the mixture
stirred during 24 h. Once lignin was hydrolyzed (completely soluble in
7
. Experimental
7
.1. BSST synthesis of MFI zeolite
7
.1.1. Materials
the acid solution), a Cs
2
CO solution was added dropwise to the mix-
3
Sodium chloride (NaCl, ACS reagent) was purchased from NORM-
ture, appearing as milky precipitate. After ageing during 24 h, solvent
was removed by heating. This sample is named as CsPMo + L. All
samples were calcined at 573 K in static air during 2 h.
APUR. Sodium aluminate anhydrous (NaAlO , technical grade) was
2
purchased from Riedel-de Haën. Sodium hydroxide (pearl 97%) was
purchased from Alfa Aesar. Tetrapropylammonium hydroxide (TPAOH,
2
0–25% in water) and trimethyl glycerine (betaine, 97%) were pur-
7.4. Synthesis of transitional aluminas
chased from TCI Chemicals. Tetraethyl orthosilicate (TEOS, 99%) was
purchased from Sigma-Aldrich. Ammonium nitrate (NH
4
NO
3
, ACS re-
Transitional aluminas were prepared by sol-gel method using
boehmite as a precursor in a similar procedure reported elsewhere [48].
agent, 98%) was purchased from Acros Organics. Sugar cane bagasse
was provided by Petrobras SA (Cenpes, RJ, Brazil). Details regarding its
chemical composition were reported elsewhere [36].
The reference sample (named Al
2
O -ref) was prepared by adding
3
7.5 mL of deionized water to 3 g of bayerite. These components were
mixed manually in a beaker, then transferred to an autoclave and kept
for 16 h at 423 K under autogenous pressure. The resulted white gel was
subsequently dried overnight at 373 K, then calcined in a muffle fur-
nace in air at 873 K for 2 h (at a heating rate of 10 °C/min). The same
protocol was undertaken with an addition of 1.1 g sugar cane biomass
7
.1.2. Synthesis protocol
A gel with a typical molar composition of 1 NaAlO : 10 TEOS: 13
2
TPAOH, 4.4 NaCl: 3000 H O was prepared in a 500 mL Erlenmeyer
2
flask and aged for 2 h under stirring at room temperature. The gel was
then transferred to a Teflon-lined stainless steel autoclave (60 mL ef-
fective volume) and placed in an oven at 443 K for 48 h. After hydro-
thermal treatment, the solution was filtered and washed with distilled
water until pH 7. The solid was dried overnight at 378 K and calcined at
to produce Al
2
O -B sample; or addition of 6 mL of hydrolysis of bagasse
3
(sample Al
2
3
O -BH); or addition of 1.1 g of remaining fibres from the
hydrolysis (sample Al
2
O -FH).
3
8
23 K for 15 h. The solid, obtained in its sodium form, was ion-ex-
7.5. Characterization
changed three times with 30 mL NH
4
NO aqueous solution (1 M) per
3
0
.2 g of zeolite at 353 K under stirring for 1 h, followed by filtration and
Powder X-ray diffraction (XRD) patterns of zeolites were acquired
using a Bruker D8 (Cu Kα) diffractometer operated at 40 kV and 40 mA.
XRD patterns were recorded in the 2θ = 5–60° range with a step size of
0.05°. LDHs XRD patterns were acquired over a Rigaku Ultima IV ap-
paratus using CuKα radiation (λ = 0.15418 nm), operated at 40 kV and
drying. The ammonium zeolite-form was calcined at 823 K for 15 h to
leave acidic H-ZSM-5 zeolite.
The hydrolysis of bagasse fibres was performed with an aqueous
solution of 1 M NaOH at pH 11 during 24 h. After filtration, both the
fibres remaining from the hydrolysis, and the aqueous solution were
added separately during ageing step (if applied) in different weight
percentages (Table 1).
−
1
20 mA. Scans were performed at 2° min
in the 3–70° range.
The zeolites were also analysed by scanning electron microscopy
(SEM) using a JEOL JSM-6700F microscope working at a 9 kV accel-
erating voltage. Bulk elemental analyses were determined by X-ray
fluorescence using a XEPOS spectrometer equipped with a 50-Watt end-
window X-ray tube to excite the samples.
7
.2. Synthesis of LDHs
LDH with Mg/Al = 3 were synthesized using co-precipitation
The textural characterisation of as-prepared materials using ni-
trogen physisorption was made using Micromeritics ASAP 2010C
equipment. Samples were pre-treated in-situ at 473 K under vacuum
before the analyses. Surface areas were determined using the BET
method and pore size distributions were obtained using the BJH
method from the adsorption branch of the isotherms.
method. All chemicals were purchased from Acros Organics, VWR and
Sigma-Aldrich. In brief, a salt solution containing a mixture of Mg
(
NO
3
)
2
·H
2
O and Al(NO
3
)
3
9H O was added dropwise into a base solu-
2
tion (100 mL) containing Na
2
CO and additives. The pH of the pre-
3
cipitation solution was kept constant at a value of 10 by addition of
NaOH (4 M) solution. The resulting mixture was aged at room tem-
perature over night with continuous stirring. The aged mixture was
then filtered and washed with deionized water until pH = 7, followed
by drying at 100 °C in an oven. Concerning the preparation with the
addition of BSST, lignin and bagasse fibres were added (0.47 g) to
Thermogravimetric sorption of CO
2
on MgAl LDH derived ad-
sorbents were measured using a TGA analyzer (Q5000 TA Instrument).
LDHs were first calcined in a furnace at 673 K for 5 h before transferring
to the TGA analyzer. To avoid an error caused by the memory effect, the
test was done immediately after the first calcination. Finally, the sam-
1
00 mL Na
2
CO
3
solution.
ples were calcined in situ at 673 K for 1 h in N
2
before adsorption. CO
2
adsorption experiments were carried out at 1 atm with a constant flow
−1
7
.3. Synthesis of POMs
of CO (40 mL min ) at 473 K.
2
Home-made H/D exchange isotope technique was used to determine
the total number of OeH groups present in different solids. The catalyst
(200 mg) was first activated at 723 K for 60 min under dry nitrogen flow
(40 mL/min). The deuteration of the catalyst was performed at 473 K by
flowing, through the catalyst, nitrogen saturated by water vapour (U-
Commercial phosphomolybdic acid (H
3
PMo12
O
40·14H O, Johnson
2
Matthey) was used as-received both as reference and reagent for cae-
sium based salts synthesis. The adopted nomenclature is PMoA. In order
to study the effect of biomass addition during salt formation two dif-
ferent synthesis were carried out, one excluding the use of any re-
shaped stripper containing D
2
O) during 1 h. Then, the sample was
O.
newable material. For this first synthesis, PMoA (1 g) and Cs
2
CO
3
purged in dry nitrogen for 1 h to remove the excess of physisorbed D
2
385

R. Bingre et al.
Inorganica Chimica Acta 487 (2019) 379–386
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2
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2
641.
x
y
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3
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1
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4
−
1
WHSV = 1.20 gMEOH/gcat.h . The reactant was subsequently fed to the
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Brazil (N° 203405/2015-3) and to the Chinese Science Council and the
French Ministry for Foreign Affairs for funding their Cai Yuanpei pro-
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