Octacarboxylated cobalt phthalocyanine (CoPc) was covalently conjugated to cellulose nanocrystals (CNCs) by employing an esterification protocol. Solid-state NMR, X-ray photoelectron spectroscopy (XPS), Raman, and infrared spectra were used to verify and study the nature of covalent attachment responsible for the immobilization of CoPc on the CNC surface. The covalent attachment was investigated from a theoretical simulation perspective using dispersion-corrected density functional theory (DFT) calculations, which verified the stable bond formation between CNC and CoPc. CoPc is an organic semiconductor with a high exciton binding energy, and CNCs are known to be insulating. Yet, Kelvin probe force microscopy (KPFM) indicated charge carrier generation and long-lived charge separation in the CNC–CoPc conjugate compared to pristine CoPc under visible light illumination. Such behavior is more typical of a semiconductor nanocomposite. The CNC–CoPc conjugate exhibited superior performance in the visible-light-driven surface photocatalytic reduction of 4-nitrobenzenethiol (4-NBT) to p,p′-dimercaptoazobenzene (DMAB) and photodegradation of rhodamine B.

1. S1
Supporting Information
Unusual Electronic Properties of Cellulose Nanocrystals
Conjugated to Cobalt Phthalocyanine: Long-Lived Charge
Separation and Visible Light Driven Photocatalytic Activity
Kazi M. Alam,1, 2
Pawan Kumar,1
Narendra Chaulagain,1
Sheng Zeng,1
Ankur Goswami,1, 3
John
Garcia,1
Ehsan Vahidzadeh,1
Manish L. Bhaiyya,5
Guy M. Bernard,4
Sanket Goel,5
Vladimir K.
Michaelis,4
Alexander E. Kobryn,2
Sergey Gusarov2
and Karthik Shankar1∗
1
Department of Electrical and Computer Engineering, University of Alberta, 9211-116 St., Edmonton, AB T6G 1H9,
Canada
2
Nanotechnology Research Centre, National Research Council Canada, 11421 Saskatchewan Drive, Edmonton, AB
T6G 2M9, Canada
3
Department of Materials Science and Engineering, Indian Institute of Technology Delhi, New Delhi 11016, India
4
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
5
MEMS, Microfluidics and Nanoelectronics (MMNE) Lab, Department of Electrical and Electronics Engineering,
Birla Institute of Technology and Science – Pilani, Hyderabad campus, Hyderabad 500078, India
*corresponding authors’ email addresses: kmalam@ualberta.ca, kshankar@ualberta.ca
∗
Tel: 780-492-1354; email: kshankar@ualberta.ca

2. S2
Methodology
Synthesis of octacarboxylated cobalt phthalocyanine, CoPc-(COOH)8
A microwave assisted solid state reaction was used for the synthesis of cobalt octacarboxylated
phthalocyanine. For the synthesis finally grounded pyromellitic dianhydride, PMDA (2.0 g, 9.15
mmol), urea (10.4 g, 0.17 mol), cobalt chloride hexahydrate CoCl2.6H2O (4.37 g, 36.9 mmol), and
catalytic amount of ammonium heptamolybdate tetrahydrate (0.1 g) were taken in a beaker and
mixed well. The beaker was loosely covered with a glass lid and irradiated under microwave using
a household microwave oven operating at 480 W for 10 min. The color of solid changed from
purple to green to black. The solid-state reaction under microwave promotes cyclic polymerization
of PMDA, in the presence of urea and metal producing metal phthalocyanine cyclic imide. The
afforded solid was grounded well and washed with water and acetone several times to remove
unreacted PMDA and urea and finally dried. To remove the unreacted excess of cobalt salt the
dried solid was mixed with 6M HCl and stirred followed by decantation of liquid. This step was
repeated several times to completely remove metal salt. To hydrolyze the cobalt phthalocyanine
cyclic imide the obtained solid was digested in a 10% KOH (125 mL) aqueous solution at 85 °C
with stirring for 8h. The color of solution was changed to blue green. To this solution 50 mL water
added and solution was filtered. The filtrate was acidified with concentrated HCl to get a pH value
3. This step converts potassium salt of phthalocyanine carboxylic acid into free carboxylic acid.
The precipitated octacarboxylated cobalt phthalocyanine CoPc-(COOH)8 was washed several
times with water until it starts to dissolve in water and finally washed with acetone and dried under
vacuum at room temperature.

3. S3
Synthesis of octacarbonylchloride phthalocyanine cobalt, CoPc-(COCl)8
Carboxylic acid groups in CoPc-(COOH)8 have limited reactivity towards the -OH group. So, -
COOH present on zinc octacarboxyphthalocyanine groups were transformed into activated acyl
chloride group by treatment with thionyl chloride (SOCl2). Briefly, CoPc-(COOH)8 was grounded
well in mortar and the obtained powder was treated with excess of SOCl2, 1 M solution in CH2Cl2
with stirring for 1 h at room temperature. Subsequently, the obtained cobalt octacarbonylchloride
phthalocyanine, CoPc-(COCl)8 was separated from solution by decantation dried under vacuum
and used immediately for the further steps or stored under desiccator for later use.
Synthesis of CoPc conjugated cellulose nanocrystals (CNC-CoPc)
The covalent functionalization of CNCs with CoPc was achieved by taking advantage of the
abundant -OH functional groups on CNCs and activated -COCl group on CoPc-(COCl)8 which
react together to form ester linkage (-COO-). In general, a calculated amount of CNCs were
dispersed in anhydrous DMF by using probe sonication for 6h. The obtained suspension was
transferred in a round bottom flask and 20 wt% CoPc-(COCl)8 and 1 mL of triethyl amines (to
extract formed HCl from the reaction) was added. The content of RB flask was stirred at 130 °C
for 12 h under nitrogen atmosphere. After cooling to room temperature, afforded CoPc-CNCs
suspension was centrifuged and washed with DMF to remove unreacted CoPc, followed by
washing with methanol and drying under vacuum conditions.
Synthesis of silver nanoparticles
A polyol synthesis protocol was employed to synthesize Ag nanoparticles.1-2
Silver nitrate
(AgNO3) and sodium sulfide (Na2S) were used as the Ag precursor and the reducing agents
respectively, while poly(vinyl pyrrolidone) (PVP) played the role for the capping agent. AgNO3,

4. S4
PVP and Na2S were added into preheated ethylene glycol (EG) at 160°C. The formation of Ag
nanoparticles was indicated through a color change of the reaction media into reddish brown. The
size of the nanoparticles is a function of reaction time, which was chosen to be seven minutes, in
order to obtain an approximately rounded nanocube shape of average edge dimension of ~ 45 nm.
The presence of Na2S promotes the formation of Ag2S at the initial stage, which acts
simultaneously, as a seed and a reduction catalyst for the formation of Ag nanoparticles later.2
Structural and physicochemical characterizations
Atomic absorption spectroscopy (AAS). AGILENT 240 FS AAS instrument was employed for the
Co analysis. A hollow cathode lamp (HCL) was used as a source of Co wavelength light with air
acetylene flame. A calibration plot of absorbance vs. standard solutions was first obtained then the
samples were introduced into the instrument. Absorbance values obtained for the samples were
then used to determine concentration values for the samples using the calibration plot.
X-ray photoelectron spectroscopy (XPS). The surface chemical composition, oxidation state and
binding energy of various elements present in materials were determined with X-ray photoelectron
spectroscopy (XPS) using Axis-Ultra, Kratos Analytical instrument equipped with monochromatic
Al-Kα source (15 kV, 50 W) and photon energy of 1486.7 eV under ultrahigh vacuum (∼10−8
Torr). The binding energy of all elements were assigned relative to the binding energy of C1s core
level (BE ≈ 284.8 eV) of adventitious hydrocarbon. The obtained raw data was deconvoluted in
various peak component by using CasaXPS and later plotted in origin 8.5.
Solids state nuclear magnetic resonance spectroscopy (NMR). NMR spectra were acquired on a
Bruker Avance 300 NMR (B0 = 7.05 T) spectrometer equipped with a 4 mm double resonance
magic angle spinning (MAS) NMR probe. The 13
C NMR spectra of natural abundance samples

5. S5
were acquired using the cross polarization3
technique, with contact times of 3 ms, a 4.0 µs 1
H π/2
pulse (ƔB1/2π = 62.5 kHz) and a recycle delay of 3.0 s. All data were acquired using broadband
proton decoupling (ƔB1/2π = 62.5 kHz) via two-pulse phase modulation (TPPM). Powdered
samples were packed into 4 mm zirconia rotors and all spectra were acquired under MAS
conditions using a spinning frequency of 14 kHz to ensure that spinning sidebands did not overlap
with isotropic peaks. Spectra were referenced to TMS (δ(13
C) = 0.00 ppm) by setting the high
frequency 13
C peak of solid adamantane to 38.56 ppm.
X-ray diffractometry (XRD). X-ray powder diffraction spectra of pristine materials and the
conjugate were acquired on a Bruker D8 advance diffractometer that is equipped with a 2D
detector (VANTEC-500). The radiation source is a Cu X-ray tube (Cu-Kα, IμSμ, λ = 0.15418 nm)
operating at 50 W at room temperature.
Field emission scanning electron microscopy (FESEM) imaging. The morphological features of
lab-grown Ag nanoparticle coated CoPc and CNC-CoPc samples were characterized using a field
emission scanning electron microscope (Hitachi S-4800 FESEM) operating at an accelerating
voltage of 3 kV.
Transmission electron microscopy (TEM) imaging and elemental analysis (EDX). JEOL 2200 FS
transmission electron microscope (TEM), equipped with a field emission gun was used for
analyzing the fine structural features and elemental mapping of lab-grown Ag nanoparticles. The
accelerating voltage was 200 kV. Scanning TEM (STEM) mode with a nominal probe size of 1
nm was used for EDX elemental analysis. JEOL JEM-ARM200CF, which has a better resolution
than JEOL 2200 FS, was used for the CNC-CoPc samples for obtaining the high-resolution TEM
(HRTEM) images and elemental mapping. This tool is equipped with a cold Field-Emission Gun,
a probe Cs corrector, and a Silicon Drift EDX detector. Same acceleration voltage (200 kV) was

6. S6
used in this measurement. STEM mode was employed for elemental analysis based on energy
dispersive X-ray (EDX) imaging. HRTEM files from both machines were processed with Gatan
micrograph for obtaining lattice spacings.
Raman spectroscopy. The vibrational properties were studied using a Raman spectrometer
(Nd:YAG laser Raman Microscope, Nicolet Omega XR). The excitation wavelength of the Raman
laser was 532nm; the incident power was 10 mW and a 50X objective was employed. The
fluorescence correction factor was set to as high as 6. The other experimental parameters were an
aperture size of 50 µm and 900 lines/mm grating.
Fourier transform infrared spectroscopy (FTIR). Fourier transform infrared spectra of pristine
CNC, pristine CoPc and CNC-CoPc were collected using an Agilent FTS7000 FTIR Imaging
System. This tool is equipped with a diamond ATR (attenuated total reflection). Prior to the
collection of the spectra, powder samples were placed on the clean diamond crystal. A moderate
nitrogen gas flow was maintained through the ATR assembly during data collection. FTIR
transmittance data were recorded in the frequency range of 400–4000 cm-1
.
Ultraviolet−Visible Spectroscopy (UV−Vis). The optical properties of the pristine CoPc and the
conjugate were obtained through UV−Vis-NIR spectrometry on a Perkin Elmer Lambda-1050
UV–Vis-NIR spectrophotometer operating in the transmission mode. Pristine CoPc and CNC-
CoPc were dispersed in DMF and the diluted solutions were kept in a quartz cuvette prior to data
collection.
Photoluminescence spectroscopy (PL). Steady state photoluminescence spectra of samples were
collected on a Varian Cary Eclipse fluorimeter that uses a xenon lamp excitation source. The slit
width was kept 5 nm and the excitation wavelength was variable.

7. S7
Kelvin probe force microscopy (KPFM). Kelvin probe force microscopy was employed to measure
the surface potential (contact potential difference) in order to elucidate the nature of charge carrier
generation/transport mechanism in CoPc and CNC-CoPc both in dark and illumination. A
Dimension fast scan atomic force microscope (Bruker Nanoscience Division, Santa Barbara, CA,
USA) was used in the presence and absence of a 635 nm diode laser. The irradiation was
orthogonal to the samples on a custom-made optical setup. A SCM-PIT cantilever with 4.4N m-1
stiffness and lift height of 75 nm, operated at 2kHz lock-in bandwidth while maintaining a scan
speed of 1 Hz. Sample grounding with the AFM chuck was achieved through a conducting copper
tape. Sample routing at zero tip bias condition was set during the surface potential mapping. In
order to achieve steady state condition, dark and illumination conditions were maintained for at
least 5 min prior to each data collection. The Pt-Ir tip work function was calibrated by measuring
the contact potential difference of HOPG and the tip.
Cyclic voltammetry (CV). Cyclic voltammograms of the samples (bare CoPc and CNC-CoPc) in
aqueous solvents were obtained using a Zahner PP211 (Zennium) potentiostat. Powder samples
were first dissolved in 0.1M Na2SO4 solution and placed in a home-made 3D printed graphene
filament based fluidic device having two electrodes for electrical connections. The experiment was
conducted at room temperature and the potentiostat slew rate was 100 mV/s.
Photocatalytic reaction test
Raman surface photocatalytic transformation of 4-NBT to DMAB. Thin films of CoPc and CNC-
CoPc were coated on glass substrate by spin casting 25 mg/mL solution in DMF at 600 rpm
followed by heating on a hot plate at 70 °C to ensure complete evaporation of residual solvent. A
dilute aqueous solution of lab-grown Ag nanoparticles was spin-cast at 1000 rpm onto these
samples (CoPc and CNC-CoPc) followed by 30 min of baking at 100 °C. A bare Ag sample (on

8. S8
glass) was also prepared for a reference, using same experimental conditions. The prepared CoPc-
Ag, CNC-CoPc-Ag and the bare Ag samples were tested for Raman surface catalytic
photoreduction test of 4-NBT to DMAB. Prior to the test, a methanolic solution of 4-NBT (5 × 10-
5
m) was drop-casted on these samples followed by drying in a vacuum oven at room temperature.
For this experiment, we used the same Raman spectrometer (Nd:YAG laser Raman Microscope,
Nicolet Omega XR) mentioned earlier. The laser was 532 nm with variable power from 0.1 mW
to 10 mW with a 10 × objective. The other parameters were aperture size of 50 μm pinhole, spot
size of 2 μm, fluorescence correction factor of 6, and 2 cm−1/CCD pixel element with 900 lines/mm
spectral dispersion grating. Raman spectra were collected for 5 × 20 s exposure time at room
temperature in air. The Raman spectrum of DMAB was obtained by digitizing previously
published data.4
Photocatalytic degradation of rhodamine B. The photocatalytic performance of pristine CoPc and
CNC-CoPc were also tested through degradation of rhodamine B (RhB). Certain amount of
photocatalysts were mixed with 50 mL dilute RhB solution (0.01 mM) in a glass vial. In order to
achieve an adsorption-desorption equilibrium between the catalysts and the dye, the suspension
was kept in dark under magnetic stirring for 60 minutes, while a small portion of solution was
collected in a cuvette in 30 minutes interval. For the photocatalytic activity test, the solution was
kept underneath a solar simulator (AM1.5 G illumination at 100 mW/cm2
) under constant
magnetic stirring condition. The solutions were collected after every 20 minutes of irradiation time
followed by high-speed centrifugation to remove any unreacted particles. The clean and
transparent solutions were characterized immediately using transmission mode UV-Vis
spectroscopy.
Modeling and computation

9. S9
The electronic properties of CoPc and CNC-CoPc photocatalysts were studied through quantum
chemical calculations performed by density functional theory (DFT). Prior to DFT-based geometry
optimization and electronic properties calculation, we optimized a large segment of the pristine
CNC by employing classical molecular dynamics (MD) protocol for the purpose of imparting
physical stability. A small portion of the MD-optimized system was considered for further DFT
calculation steps. Bellow, the two computational schemes have been briefly described.
Calculations using molecular dynamics. At the first step, we generated a large CNC-segment
consisting cellulose nanofibrils of type I, β phase in Materials studio. We have built 36 cellulose
chains in a hexagonal arrangement (Fig. S12d). Each chain contains 6 repetitive D-glucose units
(Fig. S12c). Therefore, the degree of polymerization was kept as 6. The CNC system comprising
these 36 microfibrils in the transverse section results in a structure of ~ 4 nm diameter, which can
be a representative model for computation. Moreover, such systems are analogous to
experimentally observed CNCs in the typical plant derived CNCs.5
The computations were
performed in LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator) with
COMPASS (Condensed-phase Optimized Molecular Potential for Atomistic Simulation Studies)
force field.5-7
Periodic boundary conditions were employed in this computational scheme along
the CNC axis.
Calculations using density functional theory. The MD optimized system of CNC was considered
for the next DFT based computational steps. Two relevant planes of CNC, hydrophilic plane (110)
and hydrophobic plane (200)5
were taken for further calculations (Fig. S12). It is to be noted that,
these two dominant surfaces have different surface chemistries, such as the former has higher
number of hydroxyl groups, that leads to anisotrpy in CNCs.8
These two representative
hydrophilic and hydrophobic planes were kept intact so as to simulate an environment where the

10. S10
large MD-optimized background would be present. However, the O atom of CNC surface (from -
OH) involved in the covalent bond formation and few more neighboring atoms of this O atom of
the CNC surface plane were relaxed. CoPc molecules were attached both horizontally and
vertically on these two planes of the CNC. The surface -SO3 group of CNC, which is a by-product
of H2SO4 hydrolysis,9
and the entire CoPc molecule were fully relaxed during optimization.
Spin polarized DFT realized in OpenMX 3.8 (Open source package for Material eXplorer)
package, was used for all the calculations for the pristine Cobalt phthalocyanine and CoPc
conjugated CNC.10
Pseudo-atomic localized basis functions10
and norm-conserving
pseudopotentials,11
implemented in this package, were employed in all the calculations. Perdew–
Burke–Ernzerhof (PBE) exchange-correlation functional with the general gradient approximation
(GGA) was considered in the computational model.12
CNCs are characterized by long range
interactions, such as van der Walls interactions and hydrogen bonds.8, 13
Thus, we opted for
dispersion-corrected functional that takes into account the long-range electron correlations.14
DFT-
D2 method as implemented in OpenMX, has been incorporated in all the calculations. Gaussian
broadening method was employed for the construction of projected density of states (PDOS) plots,
with broadening function’s half-width, S to be 0.02 eV. Molecular orbitals (HOMO and LUMO)
and electron density difference isosurfaces were constructed using VMD (visual molecular
dynamics) visualization software. The value of the isosurfaces for the electron density difference
plots were taken as 0.01 eV Å-3
. In all the computations, energy cut-off value was used as 220 eV
and the threshold for convergence criterion for self-consistent loop was set to 5 × 10-5
.

11. S11
Figure S1. Conjugating CoPc onto CNC surface. Molecular structure of octacarboxylated CoPc
(top), −OH groups on CNC surface (bottom left), octacarbonylchloride phthalocyanine cobalt
(bottom middle) and CNC-CoPc (bottom right).

12. S12
Figure S2. XPS elemental survey scan of CoPc (black), CNC (blue) and CNC-CoPc (red) and HR-
XPS spectra of (b) CNC in N1s region, (c) CNCs in S2p region and (d) CNC-CoPc in S2p region.

13. S13
Figure S3. (a) CPMAS 13
C NMR spectra of CoPc (bottom), CNC (middle) and CNC-CoPc (top).
(b) X-ray diffraction patterns of CoPc (bottom), CNC (middle) and CNC-CoPc (top).

14. S14
Figure S4. (a) Raman spectra of CoPc (bottom), CNC (middle) and CNC-CoPc (top). The
excitation wavelength was 532 nm. (b) FTIR spectra of CoPc (bottom), CNC (middle) and CNC-
CoPc (top).

15. S15
Figure S5. Excitation dependent Soret band emission spectra of (a) CoPc and (b) CNC-CoPc
respectively. All the photoluminescence data were collected in DMF.

16. S16
Figure S6. Surface topographic AFM (a) height and (b) phase images of CNC-CoPc on FTO.

17. S17
Figure S7. Cyclic voltammogram of (a) bare octacarboxylated CoPc and (b) CNC-CoPc in
aqueous solvent.

18. S18
Figure S8. (a) FESEM image of a sub-monolayer Ag nanoparticles on CNC-CoPc film. (b)
FESEM image of a sub-monolayer Ag nanoparticles on CoPc film. (c) HRTEM image of Ag
nanoparticle. (d) Selected magnified region of (c) showing lattice plane (1 1 1) of Ag. (e) Bright
field STEM-EDX image of a small cluster of Ag nanoparticles. STEM-EDX elemental mapping
for (f) silver and (h) oxygen. (g) X-ray diffractograms of the lab-grown Ag nanoparticles drop-cast
on glass.

19. S19
Figure S9. Photocatalytic performance test by a RhB degradation experiment for bare
octacarboxylated CoPc and CNC-CoPc conjugated systems under AM1.5G one-sun simulated
sunlight. (a) Bare CoPc without any added scavenger and CNC-CoPc conjugate without and with
added scavenger. (b) CNC-CoPc conjugate without any scavenger under continuous dark and
under partial dark and AM1.5G one-sun simulated sunlight. The inset of (b) is showing the two
possible photocatalytic pathways, namely chromophore cleavage (cycloreversion) and N-
deethylation.

20. S20
Figure S10. UV-Vis absorption spectra in RhB degradation experiment for bare octacarboxylated
CoPc and CNC-CoPc conjugated systems under AM1.5G one-sun simulated sunlight. (a) Bare
CoPc without any added scavenger. (b) & (c) CNC-CoPc conjugate without any scavenger under
continuous dark and under partial dark and AM1.5G one-sun simulated sunlight respectively. (d)
& (e) CNC-CoPc conjugate with AgNO3 and EDTA scavengers respectively.

21. S21
Figure S11. Photocatalytic performance test by a RhB degradation experiment for two different
amounts of bare octacarboxylated CoPc under AM1.5G one-sun simulated sunlight.

22. S22
Figure S12. Steady state photoluminescence spectra of bare RhB (pink), bare CoPc emerged in
aqueous RhB solution (brown) and CNC-CoPc conjugate emerged in aqueous RhB solution
(cyan). The excitation wavelength was 470 nm.

23. S23
Figure S13. CNC-segment considered for large scale molecular dynamics simulation; (a)
Schematic perspective view, (b) top view, (c) side view, and (d) cross-sectional view of the
generated structure. The hydrophilic and hydrophobic planes (110) and (200) respectively, were
taken from the optimized structure for further quantum chemical calculations using DFT. C, O and
H atoms are in grey, red and white colours respectively. The green arrow is along CNC axis (z-
direction).

24. S24
Figure S14. Projected density of states (PDOS) of atoms involved in covalent bond formation
between CoPc (C) and CNC (O). Metallophthalocyanine rings orient vertical to the CNC surface,
(a) hydrophilic plane (110) and (b) hydrophobic plane (200). Metallophthalocyanine rings orient
horizontal to the CNC surface, (c) hydrophilic plane (110) and (b) hydrophobic plane (200).

25. S25
Figure S15. Isosurfaces of electron density difference for CNC-CoPc. Metallophthalocyanine
rings orient vertically to the CNC surface, (a) hydrophilic plane (110) and (b) hydrophobic plane
(200). Metallophthalocyanine rings orient horizontal to the CNC surface, (c) hydrophilic plane
(110) and (b) hydrophobic plane (200). The pink and tan colored surfaces represent charge
depletion and accumulation regions respectively. The isosurface value is set to 0.01 eV Å-3
. The
colors for C, O, H, S, N and Co atoms are cyan, orange, white, yellow, gray and green respectively.

26. S26
Figure S16. Total density of states (DOS) and density of states projected on Co atom (d-orbital
only) for (a) pristine CoPc and (b)-(e) CNC-CoPc conjugated systems. Metallophthalocyanine
rings oriented vertically to the CNC surface, for the (b) hydrophilic plane (110) and (c)
hydrophobic plane (200). Metallophthalocyanine rings oriented horizontally to the CNC surface,
for the (d) hydrophilic plane (110) and (e) hydrophobic plane (200).

27. S27
Table S1. Summary of RhB degradation results.
Catalyst/
adsorbent
name
Catalyst/
adsorbent
amount
(mg)
Added
scavenger
Dwelling
time in dark
(min.)
C/Co
Dwelling
time in light
(min.)
C/Co
CoPc 5 None 60 0.13 80 0.13
CoPc 10 None 60 0.10 80 0.13
CNC-CoPc 10 None 180 0.44 0 N/A
CNC-CoPc 10 None 60 0.55 80 0.27
CNC-CoPc 10 None 60 0.55 120 0.2
CNC-CoPc 10 AgNO3 60 0.57 80 0.06
CNC-CoPc 10 EDTA 60 0.50 80 0.51

28. S28
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