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Visible-Light-Responsive Graphitic Carbon Nitride (g-C3N4):

Rational Design and Photocatalytic Applications for Water Treatment

Supporting Information

Qinmin Zheng,1 David P. Durkin,2 Justin E. Elenewski,3 Yingxue Sun,1, 4 Nathan A. Banek,3

Likun Hua,5 Hanning Chen,3 Michael J. Wagner,3 Wen Zhang,5 Danmeng Shuai,1*

1
Department of Civil and Environmental Engineering, The George Washington University,

Washington, DC 20052, United States


2
Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, United States
3
Department of Chemistry, The George Washington University, Washington, DC 20052, United

States
4
Department of Environmental Science and Engineering, Beijing Technology and Business

University, Beijing 100048, China


5
Department of Civil and Environmental Engineering, New Jersey Institute of Technology,

Newark, NJ 07102, United States

* Corresponding Author: Phone: 202-994-0506, Fax: 202-994-0127, Email:

danmengshuai@gwu.edu, Website: http://materwatersus.weebly.com/

Environmental Science and Technology

3 Tables, 16 Figures, and 38 Pages

S1
I. Materials and Methods

Reagents

All chemicals were at least reagent grade and used as received. The synthesis of g-C3N4

involved urea (Sigma-Aldrich, 98%), melamine (Acros Organic, 99+%), cyanuric acid (Sigma-

Aldrich 98%), barbituric acid (Sigma-Aldrich, 99%), etidronic acid monohydrate (Sigma-Aldrich

,95+%), and ethanol (Sigma-Aldrich, 99.5%). A buffer solution of 1 mM potassium phosphate

monobasic (Fisher Scientific, 99.3%) was adjusted to pH 7.3 and used in photocatalytic

experiments. Phenol (Sigma-Aldrich, 99+%), atrazine (Sigma-Aldrich, 98.8%), carbamazepine

(Sigma-Aldrich, 98+%), and sulfamethoxazole (Sigma-Aldrich, 99+%) were used as probe

contaminants in photocatalytic studies. Potassium nitrate (Fisher Scientific, 99.9%), humic acid

sodium salt (Sigma-Aldrich), magnesium chloride (Fisher Scientific, 99.4%), calcium chloride

dihydrate (Fisher Scientific, 74.3%), and sodium hydrosulfide hydrate (Sigma-Aldrich, NaHS

60+%) were selected as representative natural water constituents or foulants for photocatalytic

reactions. Ammonium oxalate (Sigma-Aldrich, 99+%), tert-butyl alcohol (Sigma-Aldrich,

99+%), superoxide dismutase (from bovine erythrocytes, Sigma-Aldrich, > 3,000 units mg-1 of

protein), catalase (from bovine liver, lyophilized powder, Sigma-Aldrich, 2,000-5,000 units mg-1

of protein), and L-histidine (Sigma-Aldrich, 99+%) were selected as scavengers for oxidative

species in photocatalytic reactions. The eluents for high performance liquid chromatographic

(HPLC) analyses of pollutants consisted of sodium acetate (Sigma-Aldrich, anhydrous),

potassium phosphate monobasic (Fisher Scientific, 99.3%), acetonitrile (ACN) (Fisher Scientific,

99.9%), and methanol (Sigma-Aldrich, 99.9%). All solutions were prepared in ultrapure water

(Millipore, Milli-Q, 18.2 M cm).

S2
Density Functional Theory (DFT) Simulations

Electronic structure calculations were conducted using density functional theory (DFT)1, 2 as

implemented in the CP2K suite.3 An initial cell relaxation was performed with the Perdew-

Burke-Ernzerhof (PBE) density functional,4 a moderately-sized double-zeta valence polarized

(DZVP) basis set,5 and Goedecker-Teter-Hutter (GTH) pseudopotentials (grid cutoff of 300 Ry)6,
7
in a hybrid Gaussian-plane wave (GPW) framework.8, 9 This optimized cell geometry was then

used to define subsequent relaxations for undoped and doped materials via the range-separated,

hybrid Heyd-Scuseria-Ernzerhof 06 (HSE06) functional.10, 11 Energy shifts due to solvation were

quantified by performing a reference calculation on undoped g-C3N4 using an implicit model.12

All structures with nitrogen site substitutions were assumed to be uncharged, while

interstitially doped systems and those with dopants at carbon sites were assigned a charge of +1.

The relative stability of each dopant family was determined by comparing geometries optimized

using undoped g-C3N4 cell parameters, excluding the nitrogen to carbon substitutions which used

the average of optimized cell parameters for that series of dopants.

g-C3N4 Synthesis

The conventional g-C3N4 samples (i.e., U and M) were synthesized from urea or melamine.

10 g of urea or melamine powder was put into an alumina crucible with a cover (not sealed),

heated at a rate of 2.3 C min-1 and maintained at 550 C for 4 h in a muffle furnace, and then

cooled down naturally. The supramolecule-based g-C3N4 samples without non-metal doping,

MC, were synthesized from melamine and cyanuric acid (mass ratio 1:1). Carbon-doped,

supramolecule-based g-C3N4 samples, MCBx, were synthesized from melamine, cyanuric acid,

and barbituric acid with different mass ratios (i.e., 2 g of melamine, (2-x) g of cyanuric acid, and

S3
x g of barbituric acid; x = 0-1.9). Phosphorus-doped, supramolecule-based g-C3N4 samples,

MCEy, were synthesized from melamine, cyanuric acid, and etidronic acid with different mass

ratios (i.e., 2 g of melamine, (2-y) g of cyanuric acid, and y g of etidronic acid; y = 0-0.5).

Precursors were first dispersed in 40 mL of ethanol to form suspension. The suspension was next

stirred at ambient temperature for 3 h, followed by sonication (Elamsonic P, 37 kHz, 100 W) at

room temperature for an additional 3 h. The suspension was then dried on a hot plate at 70 C

until no obvious liquid was found, and white supramolecular aggregates were formed. Finally,

the dried supramolecular aggregates were put into an alumina crucible with a cover (not sealed),

heated at a rate of 2.3 C min-1 and maintained at 550 C for 4 h in a muffle furnace, and cooled

down naturally.

g-C3N4 Characterization

The crystal phase of g-C3N4 was determined by X-ray powder diffraction (XRD) analyses on

a Rigaku Miniflex+ diffractometer with Cu K radiation.

Sample morphologies were characterized with a scanning electron microscope (SEM, JEOL

6700F) and a transmission electron microscope (TEM, Philips CM300 FEG). For SEM, g-C3N4

samples dispersed in ethanol were cast and dried on a sample stub, and SEM micrographs were

collected at 10 kV with a secondary electron detector. For TEM, g-C3N4 samples dispersed in

ethanol were also cast and dried on a Cu grid with a carbon support, and TEM images were

collected at 300 kV. The elemental distribution of MCE was characterized by SEM-energy

dispersive spectroscopy (EDS) (SEM, TESCAN MIRA3 FEI; EDS, TEAM Octane SSD) at an

accelerating voltage of 20 kV.

S4
The surface properties were investigated by X-Ray photoelectron spectroscopy (XPS). A PHI

5400 system was used for analysis under UHV conditions (pressure < 10-8 Torr). A Mg K

source (1253.6 eV) was utilized, and ejected photoelectrons were measured with a hemispherical

energy analyzer operating at 58.7 eV constant pass-energy. Peak positions were referenced to

C1s, 284.5 eV, and CasaXPS was used to determine chemical composition and atomic

concentrations at the surface (up to ca. 10 nm).

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra were collected

using a Nicolet 6700 spectrometer from 4000-525 cm-1 (32 scans at 4 cm-1 resolution). Spectra

were peak normalized by the C-N asymmetric stretch at 1231 cm-1, a region present in every

sample tested with relative invariant spectral intensity.

The Braunauer-Emmitt-Teller (BET) surface area and porosity analyses were performed by

N2 adsorption/desorption using a Micromeritics TriStar 3000. Isotherm adsorption data for P0/P

was recorded from 0.06-0.989. The volume of micropores was determined by t-plot analysis and

the volume of mesopores was determined by BJH analysis. Samples were degassed at 140 C for

12 h under dynamic vacuum (10-3 Torr) prior to analysis.

Bulk carbon, hydrogen, and nitrogen were analyzed on Model CE 440 CHN Analyzer. The

capsule containing g-C3N4 samples was injected into a high temperature (1000 C) furnace and

combusted in pure O2 under static conditions. To ensure the complete combustion, a dynamic

burst of O2 was added at the end of the combustion period. The resulting combustion product

contained CO2, H2O, and N2/NOx, and it next passed over Cu to scrub excess O2 and reduce NOx

to N2. After scrubbing, the gases entered a mixing volume chamber to ensure a homogenous

mixture at constant temperature and pressure, and were detected by high-precision thermal

conductivity detectors. A H2O trap and a CO2 trap were used between the detectors, and the

S5
differential signal before and after the trap was proportional to the H2O concentration and CO2

concentration. Finally, N2 was measured against a He reference.

The optical absorbance spectra of the photocatalysts and their band gap were determined by a

Thermo Scientific Evolution 300 UV-vis spectrophotometer with a Praying Mantis diffuse

reflectance infrared Fourier transform spectroscopy (DRIFTS) accessory. The absorbance of g-

C3N4 samples irradiated by light over a wavelength scan from 200 to 800 nm was measured, and

the value was then converted into reflectance by equation S1:

1
A log( )
R (S1)

where A is the measured absorbance and R is the reflectance. The function , representative of

optical absorption, which is equivalent to adsorption coefficient divided by scattering coefficient

for g-C3N4, was calculated from the Kubelka-Munk formula:13-15

(1 R)2

2R (S2)

The band gap was obtained by extrapolating the linear portion of (h)1/2 versus photon-energy

plots at (h)1/2 = 0, h is Plancks constant (4.1410-15 eV s), is the frequency of photons

which can be obtained by dividing c, the speed of light (3.0108 m s-1) by , the photons

wavelength.

The photoluminescence (PL) spectra were obtained from a home-made apparatus based on a

Thermo Nicolet Nexus 670 rapid scan FTIR spectrometer. The PL spectra of the samples were

obtained using a 354 nm diode pumped solid state laser from Teem Photonics as excitation

source. The intensity on the samples was 30 W focused to a spot of 100 m in diameter. The

emitted fluorescence was focused to a 300 mm path length monochromator and collected by a

thermoelectrically-cooled charge-coupled device (CCD) camera, both from Princeton

S6
Instruments. A long wavelength pass filter cutting at 420 nm was used to block the laser light

into the monochromator.

Zeta potential and hydrodynamic diameter of g-C3N4 aqueous suspension were determined

using folded capillary cells (DTS 1061, Malvern) on a Zetasizer Nano ZS instrument (Malvern,

ZEN3600). The temperature was maintained at 25 C, and the scattering angle was 173 from the

incident laser beam.

The UV-vis spectra of g-C3N4 aqueous suspension was obtained on a Thermo scientific

Evolution 201PC spectrophotometer. The absorption spectra of the catalyst suspension were

measured in the region of 200 to 800 nm with at a resolution of 2 nm. The sample cell was a

quartz cuvette (1 cm by 1 cm). The concentration of the prepared catalysts was 1 g L-1 in the

aqueous solution, and the suspension was dispersed using a bath sonicator (100 W) for 10 min.

Light Source Description and Characterization

Xenon arc lamp (1000 W) was selected as a light source in our study, similar to the one used

in other research.16 A long-pass optical filter with a cut-off wavelength of 400 nm was used to

simulate visible light irradiation at earths surface. Spectral irradiance, photon fluence, and

optical powder density of the Xenon lamp were recorded by a spectroradiometer (AvaSpec

ULS2048L). The spectral irradiance was plotted in Figure S1, and the photon fluence and the

optical powder density were 601 (mol of photons) m-2 s-1 and 16.7 mW cm-2, respectively.

S7
Figure S1. The spectral irradiance of the Xenon lamp ( > 400 nm). g-C3N4 with a band gap of

2.72 eV only absorbs photons with a wavelength up to ca. 460 nm.

Photocatalytic Activity Tests in a Phosphate Buffer

First, 15 mg of g-C3N4 was mixed with ultrapure water and dispersed via sonication

(Elamsonic P, 37 kHz, 100 W) for 15 minutes. The dispersed g-C3N4 suspension and a probe

pollutant (i.e., phenol, atrazine, carbamazepine, or sulfamethoxazole) were added to a phosphate

buffer solution in a jacketed reactor, giving a total reaction volume of 15 mL, the g-C3N4 loading

of 1 g L-1, the phosphate buffer concentration of 1 mM (pH 7.3), and the pollutant concentration

of 100 M. The reactor had a diameter of 4 cm and starting depth of suspension of 1.5 cm. The

S8
surface of the suspension was centered 20 cm below the Xenon lamp, which had a beam width of

6 cm. The reaction temperature was maintained at 25 oC. The suspension was stirred for 20

minutes in the dark in order to ensure suspension homogeneity, and a sample of 300 L was next

taken to quantify the initial pollutant concentration. Pollutant adsorption onto g-C3N4 was

negligible, based on the comparison of the measured initial concentration with the concentration

in control reactors in absence of g-C3N4. The reactor was then irradiated under the Xenon lamp

(> 400 nm, typically for 60 minutes), during which aqueous aliquots were withdrawn

periodically. The aliquots were next centrifuged at 13,000 rpm (16,060 g) for 1 hour in the dark

to allow the particles to settle down. The supernatant was transferred to a 1.5 mL amber

autosampler vial for subsequent analysis via HPLC with photodiode array detection (Shimadzu

LC-20AT Prominence HPLC-DAD). For atrazine degradation over multiple photocatalytic

cycles, g-C3N4 was harvested by centrifugation after each cycle, rinsed with ultrapure water, and

reused for the next run. The photocatalyst used after four cycles was characterized by SEM-EDS

and ATR-FTIR.

Photocatalytic Activity Tests in Simulated Complex Water Matrices and Real Water

Samples

To explore the influence of water chemistries on photocatalytic performance, particularly

water matrices representative of water treatment systems, the reactivity of MCB0.07 for atrazine

degradation was explored in simulated water samples (1 mM phosphate buffer solution with the

presence of 5 mM NaHCO3, 50 mM CaCl2, 50 mM MgCl2, 5 mg L-1 humic acid sodium salt, 5

mg L-1 NaNO3 as N, or 0.1 mM NaHS; pH 7.3 for all solutions except for NaHCO3 solution with

pH 7.5). Ca2+ and Mg2+ were selected to represent the hardness species in water, NO3-, humic

S9
acid, and HS- were selected as representative scavengers for oxidative species generated from

photocatalytic reactions, and HCO3- was selected to represent alkalinity species that could also

react with the oxidative species. Atrazine degradation was also conducted in real water samples

collected form the Griffith Water Treatment Plant (GWP) and the Broad Run Wastewater

Reclamation Facility (BRWRF) in Virginia. Samples were collected from the raw water of GWP

(GWP-1, i.e., water from Occoquan reservoir, VA), the final effluent from GWP (GWP-4), the

effluent after membrane bioreactor treatment in BRWRF (BRWRF-1), and the final effluent

from BRWRF (BRWRF-3), and filtered through a 0.45 m polyvinylidene fluoride (PVDF)

membrane before photocatalytic reactions. For the exploration of long-term effect of complex

water matrices for photocatalytic activity, MCB0.07 was also added to the water samples and

magnetically stirred in the dark for 24 hours to pre-foul the photocatalyst before the

photocatalytic reactions. Atrazine was added to the reactor 20 minutes before irradiation to

ensure suspension homogeneity, and again, there was no evidence of adsorption in any system.

The flow chart of water and wastewater treatment process in GWP and BRWRF is shown in

Figure S2. pH and alkalinity of these real water samples are listed in Table S1.

S10
Figure S2. The flow chart of (a) water treatment process in the Griffith Water Treatment Plant

(GWP) and (b) wastewater treatment process in the Broad Run Wastewater Reclamation Facility

(BRWRF).

Table S1. Characteristics of Water Samples

GWP-1 GWP-4 BRWRF-1 BRWRF-3

pH 6.7 7.2 7.5 7.0

Alkalinity (mg L-1 as CaCO3) 56 61 87 N/A

S11
HPLC Analysis

The Shimadzu LC-20AT Prominence HPLC System was equipped with a Shimadzu C18

column (4.6 50 mm, 1.8 m particle size). The HPLC analysis method for phenol was based on

the previous work and employed a mobile phase of 65:35 1 mM sodium acetate: ACN at pH 3, a

flow rate of 0.75 mL min-1, an injection volume of 20 L, and a 254 nm detection wavelength.17

The HPLC analysis method for atrazine was based on the previous work and employed a mobile

phase of 50:50 ultrapure water: ACN, a flow rate of 1 mL min-1, an injection volume of 100 L,

and a 223 nm detection wavelength.18 The HPLC analysis method for carbamazepine was based

on the previous work and had a mobile phase of 55:45 ultrapure water: ACN, a flow rate of 1 mL

min-1, an injection volume of 25 L, and a 213 nm detection wavelength.19 The HPLC analysis

method for sulfamethoxazole was based on the previous study and had a mobile phase of 70:30 5

mM potassium phosphate monobasic (pH adjusted to 5.0): methanol, a flow rate of 1 mL min-1,

an injection volume of 20 L, and a 268 nm detection wavelength.16

S12
II. Results and Discussion

Table S2. Band Gap, and the Energy Level of Conduction Band Minimum (CBM) and Valence

Band Maximum (VBM) Calculated Based on Density Functional Theory (DFT) Simulations

Band Gap (eV) CBMa (V) VBMa (V)

Undoped g-C3N4 2.75 -1.03 1.71

N1 C doped g-C3N4 2.58 -1.01 1.57

N2 C doped g-C3N4 2.08 0.05 2.13

N3 C doped g-C3N4 2.94 -0.67 2.28

N1 P doped g-C3N4 2.06 -0.71 1.36

N2 P doped g-C3N4 1.69 -0.20 1.49

N3 P doped g-C3N4 2.90 -0.70 2.20

C1 P doped g-C3N4 1.93 0.12 2.05

C2 P doped g-C3N4 1.86 0.19 2.05

Pore P doped g-C3N4 1.14 -0.06 1.08

a
vs. standard hydrogen electrode (SHE)

S13
Influence of Mass Transfer Processes on Observed Reaction Rates

The following calculations were performed to investigate the potential effects of

aqueous/solid and intraparticle mass transfer processes on the observed reaction rates. The

calculations followed a similar approach reported for N-nitrosodimethylamine (NDMA)

reduction on a Pd/Al2O3 catalyst or a Ni catalyst.20 The results show that mass transfer was not

expected to limit the observed reaction rates in our system.

Aqueous/solid mass transfer limitations

Here we estimate the lower limit for the aqueous/solid mass transfer rate constant for atrazine

degradation on MCB0.07 (kaq/s, a) and compare it with the measured reaction rate constant.

Atrazine degradation on MCB0.07 was selected because it showed the fastest degradation kinetics

compared to the other photocatalytic reactions in our study. Criteria for the evaluation of

potential influence of aqueous/solid mass transfer limitations on the observed rate constants are

following:

1. No aqueous/solid mass transfer limitations expected if calculated kaq/sa is much greater

than the largest measured kobs, MCB value.

2. Significant potential for aqueous/solid mass transfer limitations is expected if kaq/sa is

close to or less than the measured kobs, MCB value.

The slip velocity method21 is used to calculate the mass transfer coefficient (kaq/s) for

particles traveling at the slip velocity (ut) relative to the suspending liquid. Because the particle

size of MCB0.07 was much smaller than 1 mm, Stokes law is assumed to be applicable and the

particles slip velocity is calculated by:

gd p2 ( p )
ut
18 (S3)

S14
where g is the gravity constant, dp and p are the hydrodynamic diameter and density of the

photocatalyst particle, respectively, is the density of water, and is the absolute viscosity of

water.

The aqueous/solid mass transfer coefficient is then estimated by the following expression:

Dmol D
kaq / s Sh mol (2 0.6 Re0.5 Sc0.33 )
dp dp
(S4)

where Dmol is the molecular diffusion coefficient of the reacting solute (atrazine), Sh is the

Sherwood number, Re is the modified Reynolds number, and Sc is the Schmitt number. The last

two parameters are calculated by the following expressions:

d p ut
Re
H O 2
(S5)

H O
Sc 2

Dmol (S6)

where H2O is the kinematic viscosity of water. The molecular diffusion coefficient for atrazine in

water is calculated using the method in Hayduk and Laudie:21

13.26 105
Dmol
1.14 ( ' ) 0.589 (S7)

where Dmol is in the unit of cm2 s-1, is in the unit of g m-1 s-1, and is the molar volume of

atrazine, which is 250.6 cm3 mol-1, calculated using the LeBas method.22 Plugging the results

into equation S5, using = 1.002 g m-1 s-1 (at 20 C), then

13.26 105
Dmol 1.14 0.589
5.111010 m2 s 1
1.002 (250.6)

The values and other physical constants summarized in the Table S3 are then used in equations

S2-6 to determine kaq/s.

S15
Table S3. Constants Used to Calculate the Mass Transfer Coefficient

Constant Value

Dmol of atrazine 5.1110-10 m2 s-1

Gravity constant, g 9.81 m s-2

Photocatalyst particle diameter, dp 2.3910-6 m, determined by dynamic light scattering

Kinematic viscosity of water, H2O 1.003 10-6 m2 s-1 (at 20 C)

Particle density,23 p 1.34 106 g m-3

Water density, 9.98 105 g m-3 (at 20 C)

Absolute viscosity of water, 1.002 g m-1 s-1 (at 20 C)

m g g
gd p2 ( p ) (9.81 2
)(2.39 106 m) 2 (1.34 106 3 9.98 105 3 )
ut s m m 1.07 106 m s 1
18 18(1.002
g
)
ms
6 6 m
d p ut (2.39 10 m)(1.07 10 s )
Re 2.54 106
H 2O 6 m
2
1.003 10
s
2
6 m
H 2O 1.003 10 s
Sc 2
1962
Dmol 10 m
5.1110
s
m2
5.111010
D D s (2 0.6(2.54 10 6 ) 0.5 (1962) 0.33 ) 4.30 10 4 m s 1
kaq / s mol Sh mol (2 0.6 Re0.5 Sc 0.33 )
dp dp 2.39 106 m

To calculate the mass transfer rate constant, the mass transfer coefficient should be

multiplied by the geometric surface area of the catalyst per volume of solution, a:

total surface area SAp M 1


a
total volume p Vp VR
(S8)

where SAp is the geometric surface area of one MCB0.07 aggregate, which is assumed to have a

spherical structure; M is the mass of photocatalyst in the reactor; Vp is the volume of one

S16
MCB0.07 aggregate; and VR is the volume of reaction suspension. For the fastest reaction

measured, M = 0.015 g and VR = 0.015 L, so

SAp M 1 4 (2.39 106 m / 2) 2 (0.015 g ) 1


a 1871.1m1
p Vp VR 1.34 10 g / m 4 / 3 (2.39 10 m / 2) 1.5 10 m
6 3 6 3 5 3

kaq / s a 4.30 104 m s 1 1871.1m1 0.8s 1


(S9)

This value is about 3 orders-of-magnitude larger than the measured kobs,MCB value (8.010-4 s-1).

Thus the results indicate the aqueous/solid mass transfer is expected to have negligible limitation

on the measured reaction rates.

Intraparticle mass transfer limitations

The potential of intraparticle mass transfer resistance is also investigate by using the same

approach in previous studies, the criteria used are following:

2
1. No resistance to pore diffusion if < 1. (S10a)

2
2. Significant resistance to pore diffusion if > 1. (S10b)

where L is characteristic diffusion path length for the photocatalyst and De is the effective

diffusivity of the reacting solute. L and De are estimated using the following equations:24

1
L dp
6 (S11)

Dmol
De
(S12)

where is the porosity of the photocatalyst particle (typically ranging from 0.2-0.7) and is the

tortuosity factor (typically ranging from 2-10). The most conservative values from each range are

used to maximize the possibility that the criterion in equation S10a is met (i.e., we chose the

S17
smallest (0.2) and largest (10) in order to obtain the smallest possible De value), and, in turn,

the largest possible value for equations 10a and b:

1 1
L d p 2.39 106 m 3.99 107 m
6 6
2
10 m
5.1110 0.2
D s
De mol 1.02 1011 m2 s 1
10

The largest observed reaction rate constant was 8.010-4 s-1 for atrazine degradation on

MCB0.07. This rate constant and the values of L and De calculated above are then used to test the

criteria outlined in equations 10a and b:

L2 8.0 104 s 1 (3.99 107 m)2


kobs 11 2 1
1.25 105 m 1
De 1.02 10 m s

Because the value is several orders-of-magnitude less than one, intrapaticle mass transfer

resistance is negligible on the time scale over which the photocatalytic degradation was observed

in our system.

S18
Figure S3. Phenol degradation on MCBx (x = 0.01-1.9) under simulated visible sunlight

irradiation. Experimental conditions: photocatalyst loading of 1 g L-1; phenol initial

concentration of 100 M; phosphate buffer of 1 mM, pH 7.3; and Xenon lamp irradiation, >

400 nm). Error bars represent uncertainties of duplicates.

S19
(a)

S20
(b)

S21
(c)

Figure S4. Scanning electron microscopic images and elemental mapping analyses of (a)

MCE0.01, (b) MCE0.07, and (c) MCE0.5.

S22
Figure S5. (a) Phenol and (b) atrazine degradation on MCEy (y = 0.01-0.5) under simulated

visible sunlight irradiation. Experimental conditions: photocatalyst loading of 1 g L-1; phenol or

atrazine initial concentration of 100 M; phosphate buffer of 1 mM, pH 7.3; and Xenon lamp

irradiation, > 400 nm).

S23
Figure S6. XRD pattern of different g-C3N4 samples (U, M, MC, and MCB0.07). a.u. represents

arbitrary units. The peak at 13 corresponding to in-plane ordering of tri-s-triazine units was less

pronounced for supramolecule-based g-C3N4 (i.e, MC and MCB0.07) compared to M, indicating

that more defects may be generated in the growth of g-C3N4 with the addition of cyanuric acid

and/or barbituric acid.15, 25


The other peak around 27.6, representative of (002) interlayer

stacking, became broader for supramolecule-based g-C3N4 and U, suggesting their crystallinities

are lower than that of M. The results may indicate that polymer-like growth was dominated in U,

MC, and MCB0.07 compared to the growth of a graphitic structure in M.15, 25, 26

S24
Figure S7. ATR-FTIR spectra of different g-C3N4 samples (U, M, MC, and MCB0.07). Six bands

in the 1200-1650 cm-1 region (1630, 1530, 1450, 1395, 1313, and 1235 cm-1) characterize

stretching modes of C-N heterocycles,27 and one band at 805 cm-1 characterizes triazine.23

S25
Figure S8. XPS stack plots of carbon 1s (left) and nitrogen 1s (right) spectra for different g-C3N4

samples (U, M, MC, and MCB0.07). a.u. represents arbitrary units. The lower C(1s) binding

energy region (284.5 eV) was attributed to alkyl carbon (i.e. -C-C- or -C-H), most likely either

adventitious carbon adsorbed on the surface or any sp3 graphitic carbon formed during

pyrolysis.27 The peak at ca. 288 eV was attributed to sp2 carbon (i.e., -C-N=C-) present in the

backbone of g-C3N4.28 The broad region at ca. 293 eV was attributed to -* excitations between

the graphitic layers.29 Analysis of the N(1s) region revealed three primary regions characteristic

of g-C3N4. The peak at ca. 398.5 eV (0.3) represented sp2 nitrogen (i.e., -C-N=C-) in the

backbone of g-C3N4.28 The peak at 400.6 eV was attributed to nitrogen (i.e., N-C(3)) at the

structural edges of g-C3N4,30, 31 and the broad peak at ca. 404 eV resulted from -* excitations

between the stacked layers.29, 32

S26
Figure S9. SEM images of supramolecular complex (MCB0.07 precursor) prepared in different

solvents: (a) ethanol, (b) water.

S27
Figure S10. (a) N2 adsorption-desorption isotherms of different g-C3N4 samples (U, M, MC, and

MCB0.07) and (b) corresponding pore-size distribution. STP represents standard temperature (273

K) and pressure (1 atm). Isotherms and pore volumes are highlighted in the insets.

S28
Figure S11. Band gap analyses of different g-C3N4 samples (U, M, MC, and MCB0.07).

S29
Figure S12. Optical absorbance of g-C3N4 suspensions (1 g L-1 of U, M, MC, and MCB0.07 in a

phosphate buffer, 1 mM, pH 7.3).

S30
Figure S13. Photoluminescence emission spectra of g-C3N4 samples U, M, MC, and MCB0.07.

The spectra of U, MC, and MCB0.07 are highlighted in the inset. a.u. represents arbitrary units.

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Figure S14. (a) Photocatalytic rate constants of atrazine degradation on MCB0.07 under visible

light irradiation over multiple cycles. (b) ATR-FTIR spectra and (c) SEM images of fresh and

recovered MCB0.07 before and after reactions. Error bars represent 95% confidence intervals.

Experimental conditions: photocatalyst loading of 1 g L-1; atrazine initial concentration of 100

M; phosphate buffer of 1 mM, pH 7.3; and Xenon lamp irradiation, > 400 nm.

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Figure S15. (a) The reactivity inhibition of phenol and atrazine degradation on U and MCB0.07 in

the presence of scavengers (10 mM of tert-butyl alcohol as a OH scavenger, 10 mM of

ammonium oxalate as a hole scavenger, and 10 mM of L-histidine as a 1O2 scavenger). (b) The

reactivity inhibition of phenol degradation on U in the presence of various scavengers (10 mM of

tert-butyl alcohol as a OH scavenger, 10 mM of ammonium oxalate as a hole scavenger, 10 mM

of L-histidine as a 1O2 scavenger, 2 U mL-1 of superoxide dismutase as a O2- scavenger, and 200

U mL-1 of catalase as a H2O2 scavenger). The reactivity inhibition (%) was calculated by

dividing the reactivity difference without and with the scavenger by the reactivity without the

scavenger. Experimental conditions: photocatalyst loading of 1 g L-1; phenol or atrazine initial

concentration of 100 M; phosphate buffer of 1 mM, pH 7.3; and Xenon lamp irradiation, >

400 nm.

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Figure S16. Atrazine degradation by (a) freshly prepared MCB0.07 suspension in simulated water

samples, (b) 24 h-aged MCB0.07 suspension in simulated water samples, (c) freshly prepared

MCB0.07 suspension in real water samples, and (d) 24 h-aged MCB0.07 suspension in real water

samples under simulated visible sunlight irradiation (Xenon lamp, > 400 nm). The initial

concentration of atrazine was 100 M in simulated water samples and 20 M in real water

samples. Atrazine degradation was faster with the lower initial concentration of 20 M. Control

experiments were conducted under the same experimental conditions in a phosphate buffer (pH

7.3, 1 mM) prepared from ultrapure water. The foulants or natural water constituents were

amended into the phosphate buffer for simulated water tests. No phosphate buffer was used for

the real water tests. Photocatalyst loading was 1 g L-1.

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