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UCI Aerosol Photochemistry Group::Sergey Nizkorodov...
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S1 Supporting Information Efficient formation of light-absorbing polymeric nanoparticles from the reaction of soluble Fe(III) with C4 and C6 dicarboxylic acids Ashley Tran, † Geoffrey Williams, † Shagufta Younus, † Nujhat N. Ali, ‡ Sandra L. Blair, ‡ Sergey A. Nizkorodov, ‡ and Hind A. Al-Abadleh † * † Department of Chemistry and Biochemistry, Wilfrid Laurier University, Waterloo, ON N2L 3C5, Canada ‡ Department of Chemistry, University of California, Irvine, California 92697, United States Journal: Environmental Science and Technology Prepared: July 19, 2017 Supplementary Data (12 pages) Additional Experimental Details................................................................................................... S2 Figure S1 ....................................................................................................................................... S3 Figure S2 ....................................................................................................................................... S4 Figure S3 ....................................................................................................................................... S5 Figure S4 ....................................................................................................................................... S6 Figure S5 ....................................................................................................................................... S7 Figure S6 ....................................................................................................................................... S8 Table S1 ........................................................................................................................................ S8 Figure S7 ....................................................................................................................................... S9 Figure S8 ..................................................................................................................................... S10 Figure S9 ..................................................................................................................................... S11 References ................................................................................................................................... S12
Transcript of UCI Aerosol Photochemistry Group::Sergey Nizkorodov...
S1
Supporting Information
Efficient formation of light-absorbing polymeric nanoparticles from the
reaction of soluble Fe(III) with C4 and C6 dicarboxylic acids
Ashley Tran,† Geoffrey Williams,† Shagufta Younus,† Nujhat N. Ali,‡ Sandra L.
Blair,‡ Sergey A. Nizkorodov,‡ and Hind A. Al-Abadleh†*
†Department of Chemistry and Biochemistry, Wilfrid Laurier University, Waterloo, ON N2L 3C5, Canada ‡Department of Chemistry, University of California, Irvine, California 92697, United States
Journal: Environmental Science and Technology
Prepared: July 19, 2017
Supplementary Data (12 pages) Additional Experimental Details ................................................................................................... S2 Figure S1 ....................................................................................................................................... S3 Figure S2 ....................................................................................................................................... S4 Figure S3 ....................................................................................................................................... S5 Figure S4 ....................................................................................................................................... S6 Figure S5 ....................................................................................................................................... S7 Figure S6 ....................................................................................................................................... S8 Table S1 ........................................................................................................................................ S8 Figure S7 ....................................................................................................................................... S9 Figure S8 ..................................................................................................................................... S10 Figure S9 ..................................................................................................................................... S11 References ................................................................................................................................... S12
S2
Additional Experimental Details For ATR-FTIR measurements, the particles were deposited onto a ZnSe crystal from a
water/ethanol slurry followed by drying overnight. Absorption spectra of these particles were
obtained by referencing to the clean and dry ZnSe crystal.
The TGA analysis was completed on a TGA Q50 V20.8 Build 34 instrument while
flowing nitrogen gas at 40 and 60 mL/min for balance and samples, respectively. The sample
was thermally equilibrated at 40ºC, followed by a temperature ramp at a rate of 10ºC min-1 up to
800ºC.
The TEM, SEM-EDS and EELS measurements were done at the Canadian Centre for
Electron Microscopy, McMaster University. The samples were ground using a mortar and
pestle. The powder was mixed with a solution of 50%/50% ethanol/DI water and sonicated for
10 min. TEM analysis was performed in a JEOL 2010F TEM/STEM operated at 200 kV. The
electron microscope was equipped with a Gatan imaging filtering (GIF) system for the
acquisition of the electron energy loss spectra (EELS).
The oxidation state composition of iron was analyzed by XPS in a Thermo-VG Scientific
ESCALab 250 microprobe with a monochromatic Al Ka X-ray source (1486.6 eV), operated
with a typical energy resolution of 0.4 - 0.5 eV full width at half-maximum. To correct for extra
charging, the binding energy curve in the Fe 2p region for each compound was calibrated against
the C 1s peak in the survey spectrum, which has a value of 284.8 eV per reference1.
S3
Figure S1. Difference spectra obtained by subtracting the absorbance of FeCl3 reactant standard solution (after accounting for dilution) from that collected for the unfiltered reaction solution after 120 min of reaction, as shown in Figure 2 in the main manuscript. The subtraction factor, s, was 1.1 for (a) and 1.2 for (b) according to this formula: D Absorbance = Absorbance of mixture – s × Absorbance of control FeCl3 solution shown in Figure 2.
0.20
0.15
0.10
0.05
0
Δ A
bsor
banc
e
600500400300200Wavelength (nm)
370
(a) Fe-polyfumarate slurry
0.20
0.15
0.10
0.05
0
Δ A
bsor
banc
e
600500400300200Wavelength (nm)
370
(b) Fe-polymuconate slurry
S4
(a)
(b)
(c)
(d)
Figure S2: Reported structures for polymers formed from (a) the reaction of aqueous phase FA with FeCl3 as patented by Apblett,2 (b) the reaction of aqueous phase FA with FeCl3 at 85°C forming MOF MIL-88A,3 (c) the reaction of cis,cis-muconic acid with excess dialcohol in the presence of Ti(IV) butoxide,4 (this structure shows an example of metal-catalyzed polymerization of muconic acid),4 and (d) Fe(II) fumarate reported in references.5,6
OO Fe O
OOO Fe O
O
x
O
O O
O
Fe-O clusters
OOH
O
OO
OO
OO
H
mn
OO Fe
OH2
OH
OO
OO Fe
OH2
OH
OO
x
S5
Figure S3. Digital images of unfiltered solutions following 1 h and 24 h reaction times between maleic and succinic acids with FeCl3 at pH 2.4, followed by filtration.
HOOH
O
O
Succinic acid (SA) C4H6O4
Maleic acid (MaA) cis-C4H4O4
pKa = 4.2, 5.6 pKa = 1.9, 6.2
Control Experiments
MaA 2.1 mM pH 7 (no Fe)
MaA:Fe (1:2) pH 2.4 (1 min)
O OOHHO
pH 2.4 (60 min)
pH 2.4 (24 h)
SA 2.1 mM pH 6 (no Fe)
SA:Fe (1:2) pH 2.4 (1 min)
pH 2.4 (60 min)
pH 2.4 (24 h)
S6
(a) Fe-polyfumarate
(b) Fe-polymuconate
Figure S4. Proposed chemical structure of (a) Fe-polyfumarate and (b) polymuconate formed in our studies based on the results of dry particle characterization detailed in the main text.
O
OFe
H2O
OH2
OO
Ox
OOH
O
O O
O
K+
OH2
Fe
H2O
OH2
O
OOH
O
O
K+
OH2
O
OFe
OH2O OH2
OHO
O
O
x
Fe
H2O OH2
OH
O
O
S7
Figure S5. Representative STEM-EDS images and elemental mapping (C, O, Cl, and Fe) of (a) Fe-polyfumarate, and (b) Fe-polymuconate particles.
700 nm
C Kα1,2 O Kα1
Fe Kα1 Cl Kα1
(a) Fe-polyfumarate
(b) Fe-polymuconate
300 nm
C Kα1,2 O Kα1
Fe Kα1 Cl Kα1
S8
Figure S6. TGA curves showing % weight loss due to thermal decomposition of standard reactant compounds (FA, MA, and FeCl3×6H2O) and Fe(II) fumarate in relation to Fe-polyfumarate and Fe-polymuconate. Table S1: Analysis of the TGA data (n.a. = not available) Reaction for thermal decomposition
% mass residual, (c1)
% Fe calculated from c1, (c2)
Calculated molar weight (g mol-1) from c2
Molar weight based on chemical formula (g mol-1)
FeCl3·6H2O(s) ® 0.5 Fe2O3 (s) + 4.5H2O (g) + 3HCl (g) (see ref. 7)
29.7
20.7
270.5
270.5
Fe(II)C4H2O4 ® 0.5 Fe2O3 (s) + C2H2 (g) + 2 CO(g) + 0.25 O2 (g) (see ref. 8)
46.9
32.8
170.7
169.9
Fe-fumarate (FeCxOyHz)® 0.5x Fe2O3 + gases
38.2 26.7 209.7 n.a.
Fe-muconate (FeCxOyHz)® 0.5x Fe2O3 + gases
35.4 24.8 225.8 n.a.
120
100
80
60
40
20
0
Wei
ght (
%)
800700600500400300200100Temperature (ºC)
29.7%35.4%38.2%46.9%
Fumaric acid (s) "standard" Muconic acid (s) "standard" FeCl3·6H2O (s) "standard" Fe(II)C4H2O4 (s) "standard"
Fe-polyfumarate (s) Fe-polymuconate (s)
S9
Figure S7. XPS spectra of the Fe 2p region for Fe-polyfumarate and Fe-polymuconate particles in relation to the standard compound, Fe(II) fumarate. Each binding energy curve was calibrated against the C 1s peak which has a fixed value of 284.8 eV per Ref. 1 to correct for charging. Spectra are offset for clarity.
5000
4000
3000
2000
1000
0
Cou
nts
(a.u
.)
735730725720715710705700Binding Energy (eV)
Fe-polyfumarate
Fe-polymuconate
Fe(II) fumarate
710.6 724.2
710.5 724.2
710.0 723.0713.9
(Alfa Aesar)
Fe 2p
S10
Figure S8. Representative EELS spectra (Background subtracted) for the oxygen K-edge of (a) standard Fe(II) fumarate, Fe-polyfumarate and Fe-polymuconate particles, and (b) standard fumaric and muconic acids particles.
36x103
30
24
18
12
6
0
Cou
nts
(a.u
.)
615600585570555540525Energy Loss (eV)
Fe-polyfumarate
Fe-polymuconate
Fe(II) fumarate(Alfa Aesar)
559.2
537
526.6
545.2
537
540
530 564.6
(a)O K-edge 8 x103
6
4
2
0
Cou
nts
(a.u
.)
615600585570555540525Energy Loss (eV)
Fumaric acid
Muconic acid
537
540
530 (reactant)
(reactant)
(b)O K-edge
S11
Figure S9: Mass-normalized absorption coefficient (MAC) plot for the reaction of 0.1 mM of (a) fumaric acid (FA), and (b) muconic acid (MA) with FeCl3 after 1, 60 and 120 min dark reaction at pH 3 (unfiltered solution). The final reaction mixture contain 1:2 molar ratio organic reactant:Fe. MAC values were calculated from Eq. (1) and were not corrected for the contribution from scattering by particles in solution.
10
8
6
4
2
0
MA
C (m
2 g-1
)
600550500450400350300Wavelength (nm)
(a)
Fe-polyfumarate 1 min 60 min 120 min
10
8
6
4
2
0
MA
C (m
2 g-1
)
600550500450400350300Wavelength (nm)
(b)
Fe-polymuconate 1 min 60 min 120 min
S12
References: (1) Grosvenor, A.P.; Kobe, B.A.; Biesinger, M.C.; McIntyre, N.S., Investigation of multiplet
splitting of Fe 2p XPS spectra and bonding in iron compounds. Surf. Interface Anal. 2004, 36, 1564-1574.
(2) Apblett, A.W., Iron coordination polymers for adsorption of arsenate and phosphate. The Board of Regents for Oklahoma State University, Patent, US 2013/0292338 A1, 2013; pp. 1-8
(3) Lin, K.-Y.A.; Chang, H.-A.; Hus, C.-J., Iron-based metal organic framework, MIL-88A, as a heterogeneous persulfate catalyst for decolorization of Rhodamine b in water. RSC Adv. 2015, 5, 32520-32530.
(4) Rorrer, N.A.; Dorgan, J.R.; Vardon, D.R.; Martinez, C.R.; Yang, Y.; Beckham, G.T., Renewable unsaturated polyesters from muconic acid. ACS Sustainable Chem. Eng. 2016, 4, 6867-6876.
(5) Kapor, A.J.; Nikolic, L.B.; Nikolic, V.D.; Stankovic, M.Z.; Cakic, M.D.; Ilic, D.P.; Mladenovic-Ranisavljevic, I.I.; Ristic, I.S., The synthesis and characterization of iron(II) fumarate and its inclusion complexes with cyclodextrins. Adv. Technol. 2012, 1, 7-15.
(6) Skuban, S.; Dzomic, T.; Kapor, A.; Cvejic, Z.; Rakic, S., Dielectric and structural properties of iron- and sodium-fumarates. J. Res. Phys. 2012, 36, 21-29.
(7) Kanungo, S.B.; Mishra, S.K., Thermal dehydration and decomposition of FeCl3.xH2O. J. Thermal Anal. 1996, 46, 1487-1500.
(8) Nikumbh, A.K.; Phadke, M.M.; Date, S.K.; Bakare, P.P., Missbauer spectroscopic and D.C. electrical conductivity study of the thermal decomposition of some iron(II) dicarboxylates. Thermochimica Acta 1994, 239, 253-268.
