Additive-free 1,4-butanediol mediated synthesis: a suitable route to obtain [623160]

Additive-free 1,4-butanediol mediated synthesis: a suitable route to obtain
nanostructured, mesoporous spherical zinc oxide materials with multifunctional
properties
Diana Visinescu, Mariana Scurtu, Raluca Negrea, Ruxandra Birjega,
Daniela C. Culita, Mariana Carmen Chifiriuc, Constantin Draghici,
Jose Calderon Moreno, Adina Magdalena Musuc, Ioan Balint and Oana Carp
Electronic Supplementary Information
(ESI)
Electronic
Supplementary
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(ESI)
for
RSC
Advances.
This journal is © The Royal Society of Chemistry 2015

Figure S1. Thermal curves (TG, DTG and DTA) for Zn(acac) 2·1.2 H 2O dehydration

Figure S2. FTIR spectra for ZnO BD1-ZnO BD3 series of zinc oxide samples: * – zinc oxide, * –
(C=O) acetylacetonate , and * – (C-C) BD; * – (O-H) from water and/or layered hydroxide zinc(II) acetylacetonate.

Figure S3. FTIR spectra for ZnO BD4 and ZnO BD5 samples: * – zinc oxide, * – (C=O) acetylacetonate , and * – (C-
C)BD; * – (O-H) from water and/or hydroxide zinc(II) acetylacetonate.
Figure S4. FTIR spectra for ZnO BD6 and ZnO BD7 samples: * – zinc oxide,
* – (C=O) acetylacetonate , and * – (C-C) BD; * – (O-H) from water and/or hydroxide zinc(II) acetylacetonate.

Figure S5. 1H NMR (top) and 13C NMR (bottom) spectrum for the supernatant solution obtained after the
precipitation of ZnO BD2 oxide: 1 – 1,4-butanediol specific signals, 1-e – traces of BD-ester, 2 –acetylacetonate
specific signals.

Figure S6. 1H NMR (top) and 13C NMR (bottom) spectrum for supernatant solution obtained after the ZnO BD7
precipitation: 1 – 1,4-butanediol specific signals, 1-e – traces of BD-ester, 2 –acetylacetonate specific signals.

0 200 400 600 800 10009596979899100
137.9394.9407.5
DSC
DTG
Temperature (oC)DTG DSC
mWmg-1%min-1
exoTG
-0.5-0.4-0.3-0.2-0.10.00.10.2
-4-20Mass ( %)
Figure S7. Thermal curves (TG, DTG and DSC) of ZnO BD7 sample.
Figure S8. The XRD diffractograms recorded for ZnO BD4-ZnO BD7 group of samples

Figure S9. (a) SEM panoramic micrograph; (b) TEM micrograph; (c) HRTEM image and (e) EDS analysis for
ZnO BD1 oxide.
d
a
b
c

Figure S10. (a) HRTEM image and (b) EDS analysis of ZnO BD2 product.a
b

Figure S11. (a) SEM panoramic micrograph, (b) TEM micrograph at higher magnification (c) HRTEM image
and (d) EDS analysis for ZnO BD3 product.
a
c
d
b

Figure S12. (a) SEM panoramic micrograph; (b) SEM panoramic micrograph at higher maginifcation; (c) TEM
micrograph; (d) magnified TEM image; (e) SAED pattern and (f) particles size distribution for ZnO BD5 oxide.
a
b
c
d
e
f

Figure S13. (a) SEM panoramic micrograph; (b) TEM
micrograph; (c) magnified TEM image and (d) particles
size distribution for ZnO BD6 oxide.
a
b
c
d

Figure S14. (a) SEM panoramic micrograph and (b) TEM micrograph for ZnO BD7 oxide.a
b

0.0 0.2 0.4 0.6 0.8 1.004080120160200240
ZnOBD3
ZnOBD1
ZnOBD2V (cm3g-1, STP)
P/P0
0 10 20 30 40 50 600.0000.0030.0060.0090.0120.0150.018
ZnOBD2
ZnOBD1
ZnOBD3Pore volume (cm3 g-1 nm-1)
D (nm)
Figure S15. N2 adsorption–desorption isotherms (top) and pore size distribution (bottom) of ZnO BD1 – ZnO BD3
samples

Figure S16. UV-Vis spectra for ZnO BD1-ZnO BD3 group of oxides.
Figure S17. UV-Vis spectra for ZnO BD4-ZnO BD7 group of oxides.200 300 400 5000.00.20.40.60.81.0 ZnOBD4
ZnOBD5
ZnOBD6
ZnOBD7Absorbance (a.u.)
Wavelength (nm)

Figure S18. (Ah)2 vs. h plot for determining absorption onset for ZnO BD1-ZnO BD3 group of oxides.
Figure S19. (Ah)2 vs. h plot for determining absorption onset for ZnO BD4-ZnO BD7 group of oxides.

Figure S20. Room-temperature emission PL spectra for ZnO BD4-ZnO BD7 samples
Figure S21 . Room-temperature emission PL spectra for ZnO BD1-ZnO BD3 samples, calcined at 500oC for 1h.

Figure S22 . Room-temperature emission PL spectra for ZnO BD1-ZnO BD3 samples, calcined at 500oC for 1h.

Scheme S1. Proposed reaction pathway for the formation of zinc oxide in BD-assisted synthesis.

Figure S23. TEM image at low
magnification
a
b
c
I
d
f
e
II
g
h
i
III

(a, d, g), xHRTEM micrographs centered on a particle of ZnO formed by small crystallites (b, e, h) and SAED
patterns (c, f, i) for samples obtained at 0.25 M zinc cations concentration, at 140oC after 45 (I), 90 (II) and 180
minutes (III ).

Figure S24. Graphic representation of the level of Gram-positive microbial strains growth quantified by
measuring the absorbance of liquid cultures at 600 nm in the presence of two-fold serial dilutions of the tested
compound. MIC values are indicated by red arows.

Figure S25. Graphic representation of the level of Gram-negative microbial strains growth quantified by
measuring the absorbance of liquid cultures at 600 nm in the presence of two-fold serial dilutions of the tested
compound. MIC values are indicated by red arows.

Figure S26. Graphic representation of the degree of microbial biofilms formed by the Gram-negative tested
strains development in the presence of binary concentrations of the tested compound.
Positive control50025012562,531,2515,627,813,91,950,9700.20.40.60.811.21.41.61.8
P. aeruginosa ATCC 2785
P. aeruginosa 719
E. coli ATCC 13202
E. coli 634A 492 nm
Figure S27. Graphic representation of the degree of microbial biofilms formed by the Gram-negative tested
strains development in the presence of binary concentrations of the tested compound.

Figure S28. SEM panoramic micrograph for ZnO product obtained in 1,2-propanediol for 0.25 M zinc source
concentration (140oC for 2h).