New Journal of Chemistry

- Electronic supplementary information -

Synthesis of textured polysaccharide-silica nanocomposites: comparison between

cellulose and chitin nanorods' precursors

Laura Cardoso,a Thomas Cacciaguerra,

a Philippe Gaveau,

a Laurent Heux,

b Emmanuel

Belamiea,c,

* and Bruno Alonso a,

*

a ICGM-MACS, UMR 5253 CNRS-ENSCM-UM, Institut Charles Gerhardt de Montpellier, 8

rue de l’Ecole normale, 34296 Montpellier cedex 5, France.

b CERMAV, UPR 5301 CNRS, BP 53, 38041 Grenoble cedex 9, France.

c Ecole Pratique des Hautes Etudes, PSL Research University, 75014 Paris, France

Contents:

Fig. ESI 1 Formation of large pores at high ΦCEL.

Fig. ESI 2 Examples of X-Rays diffractogram deconvolutions for spray-dried cellulose-

silica nano-composites.

Fig. ESI 3 Variation of d020 and d110 inter-reticular distances of α-chitin monocrystals.

Fig. ESI 4 13

C{1H} solid-state NMR CP-MAS spectra of spray-dried cellulose-silica

nanocomposites for various cellulose volume fractions φCEL.

Fig. ESI 5 29

Si NMR spectroscopy of chitin containing suspensions and solids.

Fig. ESI 6 Scanning Electron Micrographs of spray-dried polysaccharides and cellulose-

silica nanocomposites before and after post-synthesis treatments.

Fig. ESI 7 Transmission Electron Micrographs of spray-dried cellulose-silica

nanocomposites.

Fig. ESI 8 Transmission Electron Micrographs of spray-dried polysaccharide nanorods.

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017

Fig. ESI 1.

Formation of large pores at high ΦCEL. (a) N2 sorption isotherms (77 K) of spray-dried

cellulose-silica nanocomposites (φCEL = 0.64), before (dashed lines) and after (continuous

lines) calcination. (b) External surface of a spray-dried cellulose-silica microparticle (φCEL =

0.64) observed by SEM. (c) Size distribution of voids measured on the image in (b).

0

50

100

150

200

250

300

350

400

450

0 0.2 0.4 0.6 0.8 1

600 nm

(a) (b)

20 30 40 50 60 70 80 900

5

10

15

20

25

Fre

qu

ency

(%)

Diameter (nm)

(c)

p / p0

Vad

s.(m

L.g

-1S

TP

)

Fig. ESI 2.

Examples of X-Rays diffractogram deconvolutions for spray-dried cellulose-silica nano-

composites. The silica scattering and cellulose diffracting peaks are fitted using Gaussian

functions. Slight variations in the width and position considered for the silica scattering peak

do not affect the trends observed for the cellulose diffracting peaks.

φCEL = 0.30

2θθθθ (°)

φCEL = 0.55

2θθθθ (°)

Fig. ESI 3.

Variation of d020 and d110 inter-reticular distances of α-chitin monocrystals as a function of the

chitin volume fraction φCHI for spray-dried chitin-silica nanocomposites.

4.55

4.60

4.65

4.70

0 0.2 0.4 0.6 0.8 1

9.35

9.40

9.45

9.50

9.55

9.60

0 0.2 0.4 0.6 0.8 1

ΦΦΦΦCHI ΦΦΦΦCHI

d020 (Å

)

d110 (Å

)

Fig. ESI 4.

13C{

1H} solid-state NMR CP-MAS spectra of spray-dried cellulose-silica nanocomposites for

various cellulose volume fractions φCEL.

13C chemical shift (ppm)

10 20 30 40 50 60 70 80 90 100 110 120

φCEL = 1.00

φCEL = 0.65

φCEL = 0.40

φCEL = 0.30

φCEL = 0.29

φCEL = 0.20

φCEL = 0.14

Fig. ESI 5.

29Si NMR spectroscopy of chitin containing suspensions and solids. (a)

29Si liquid-state NMR

spectrum of initial siloxane oligomers sols ([Si] ~ 2.5 mmol.g-1

, 1615 scans). (b) 29

Si liquid-

state NMR spectrum of hybrid chitin-siloxane suspension analyzed 24 H after mixing the

siloxane oligomers sol (a) and the chitin suspension (φCHI = 0.3, [Si] ~ 0.25 mmol.g-1

, 18432

scans). (c) 29

Si solid-state NMR spectrum of spray-dried chitin-silica nanocomposites

obtained from hybrid suspensions (b) (φCHI = 0.3).

Q2

29Si chemical shift (ppm)

-140-120 -100 -80 -60

Q3 Q4

(b)

(a)

(c)

Fig. ESI 6.

Spray-dried cellulose-silica nanocomposites before and after post-synthesis treatments.

Cellulose volume fraction φCEL = 0.29

The micrographs correspond to: (a) hybrid nanocomposite; (b) calcined porous silica; (c)

ammonia treated nanocomposite. The scale bars is 2 µm.

Cellulose volume fraction φCEL = 0.64

The micrographs correspond to: (a) hybrid nanocomposite; (b) calcined porous silica; (c)

ammonia treated nanocomposite. The scale bars is 2 µm.

Spray-dried polysaccharide nanorods.

The micrographs correspond to: (a) cellulose; (b) chitin. The scale bars is 2 µm.

a b c

b ca

ba

Fig. ESI 7.

TEM micrographs of spray-dried hybrid cellulose

cellulose volume fraction φCEL

to 100 nm.

a

dried hybrid cellulose-silica nanocomposites with increasing initial

CEL = 0.14, 0.29 and 0.48 (in a, b, c resp.). The scale bar

c b

with increasing initial

. The scale bars correspond

Fig. ESI 8.

TEM micrographs of the spray

1); (c, d), cellulose (φCEL = 1). The scale bar is 1 µm in (a) and (c), and 100 nm in (b) and (d).

a

c

TEM micrographs of the spray-dried polysaccharide nanorods' suspensions: (a, b), chitin (

= 1). The scale bar is 1 µm in (a) and (c), and 100 nm in (b) and (d).

b

d

suspensions: (a, b), chitin (φCHI =

= 1). The scale bar is 1 µm in (a) and (c), and 100 nm in (b) and (d).