Supporting Information for

Sodium Doping and 3D Honeycomb Nanoarchitecture: Key

Features of Covalent Triazine-Based Frameworks (CTF)

Organocatalyst for Enhanced Solar-Driven Advanced Oxidation

Processes

Tao Zeng1,2, Shuqi Li1,Yi Shen1, Haiyan Zhang1, Hongru Feng3, Xiaole Zhang4,

Lingxiangyu Li5, Zongwei Cai2*, and Shuang Song1*

1. Key Laboratory of Microbial Technology for Industrial Pollution Control of

Zhejiang Province, College of Environment, Zhejiang University of Technology,

Hangzhou, Zhejiang, 310032, PR China

2. State Key Laboratory of Environmental and Biological Analysis, Department

of Chemistry, Hong Kong Baptist University, Hong Kong SAR, PR China

3. State Key Laboratory of Environmental Chemistry and Ecotoxicology,

Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences,

Beijing, 100085, PR China

4. College of Life Science, North China University of Science and Technology,

Tangshan, Hebei, 063000, PR China

5. Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University,

Hangzhou 310018, PR China

* Corresponding Author

Tel.: +86-571-88320726, E-mail: ss@zjut.edu.cn

Tel.: +852-34117070, E-mail: zwcai@hkbu.edu.hk;

Characterization

The crystallographic phases of the prepared catalysts were identified by XRD

(SCINTAG X’TRA X-ray diffractometer, Thermo ARL) using Cu-Kα radiation

operating at 45 kV and 40 mA in the 2θ range of 10–80°. The optical properties of the

catalyst particles were examined using a UV/Vis spectrophotometer (TU-1901,

Pgeneral) in the range of 200–800 nm with BaSO4 as the background. The surface

areas of the prepared samples were measured by nitrogen adsorption at 77 K and

calculated using the BET method (ASAP-2010 Analyzer, Micromeritics). The

functional groups were characterized by fourier transform infrared spectroscopy

(FTIR, Nexus 670, USA). The morphology was characterized with scanning electron

microscope (SEM) (S-4800, Hitachi) and transmission electron microscopy (TEM,

Tecnai G2 F30 S-Twin, Netherlands) equipped with an EDX system (Genesis 4000,

EDAX). 1H NMR measurements were recorded on Bruker Bruker AVANCE 300

system. Solid State 13C CP MAS NMR measurements were carried out using Bruker

Avance II solid state NMR spectrometer operating at 300 MHz Larmor frequency

equipped with a standard 4 mm magic angle spinning (MAS) double resonance probe

head. The chemical compositions and electronic states of the prepared particles were

determined by XPS (PHI 5000 C, PerkinElmer) using Mg-Kα radiation (1253.6 eV).

Photoelectrochemical measurements

The transient photocurrent response, liner sweep voltammetry (LSV), electrochemical

impedance measurements and Mott–Schottky measurement were performed using a

CHI660E electrochemical workstation (Chenhua Instrument Co. Ltd., Shanghai,

China) with a standard three-electrode system. The working electrode was prepared as

follows: 20 mg photocatalyst was dispersed in a mixture of 5 % Nafion solution (50

μL) and isopropanol (300 μL) and ultrasonicated for 120 min to form a uniform

suspension. Then, 90 μL of suspension was dip-coated on the 1 cm × 1 cm ITO and

FTO glass and dried overnight at room temperature. The as-prepared electrode,

saturated calomel electrode (SCE) and Pt wire were acted as working electrode,

counter electrode and reference electrode, respectively. The working electrode was

irradiated from the opposite side of the as-prepared film under a 300 W Xe lamp. An

aqueous solution of Na2SO4 (0.1 M) was used as the electrolyte.

Theoretical computation

All the density functional theory (DFT) calculations were performed using the Dmol3

module in Materials Studio software (Accelrys Inc., San Diego, version 6.1). The

double numerical plus polarization (DNP) basis set was used. The exchange-

correlation energy was calculated using the Perdew-Burke-Ernzerhof (PBE) function

of generalized gradient approximation (GGA). The k-points were sampled in a 1 × 2 ×

1 Monkhorst-Pack grid in all calculations. The convergence criteria of self-consistent

field tolerance, energy tolerance, maximum force tolerance and maximum

displacement tolerance during the calculations were 1.0 × 10-6 Ha/atom, 1.0 × 10-5 Ha,

0.002 Ha/Å and 0.005 Å, respectively.

Analytical methods

In order to determine the PMS concentration, samples were prepared by placing 1 mL

of reaction solution in a 4 mL cuvette. Then 1 mL of 10 mM FeSO4·7H2O solution

acidified by 1 M H2SO4 was added. Finally, 0.2 mL of 0.3 M KSCN solution was

added after 5 min. The absorbance was immediately read with a spectrophotometer at

a wavelength of 460 nm. The bisphenol A concentrations were measured by high-

performance liquid chromatography HPLC system (Waters 1525 with a C18 column

4.6 mm × 150 mm, 5 μm) at the wavelength of 225 nm. The mobile phase was

methanol: ultrapure water (60:40), and the flow rate was set to 1 mL min -1. The

phenol concentrations were measured by high-performance liquid chromatography

HPLC system (Waters 1525 with a C18 column 4.6 mm × 150 mm, 5 μm) at the

wavelength of 270 nm. The mobile phase was methanol: ultrapure water (70:30), and

the flow rate was set to 1 mL min-1. The 4-chlorophenol concentrations were

measured by high-performance liquid chromatography HPLC system (Waters 1525

with a C18 column 4.6 mm × 150 mm, 5 μm) at the wavelength of 210 nm. The

typical eluent comprised a binary mixture of 0.1% phosphoric acid aqueous solution

and methanol (typically 30:70), and the flow rate was set to 1 mL min-1. The Acid

Orange 7 concentration was measured by a UV–Vis spectrophotometer (Tu-1810) at a

wavelength of 486 nm. The Acid Orange 7 concentration was measured by a UV–Vis

spectrophotometer (Tu-1810) at a wavelength of 486 nm. The concentration of

Rhodamine B in the system was analyzed by measuring the absorbance at 554 nm

with a Tu-1810 spectrophotometer.

Figure S1. Photographs of various samples.

Figure S2. 1H NMR spectra of various samples.

Figure S3. XPS spectrum of core-level O 1s.

Figure S4. Influencing factors on the CBZ removal efficiency in H-CTFs-

Na/vis/PMS system: (a) catalyst dosage, (b) PMS concentration, (c) CBZ

concentration, and (d) initial pH.

Figure S4a illustrates the removal of CBZ over time at different catalyst dosages in

solution. As expected, an enhancement in CBZ degradation was observed with an

increase in the H-CTF-Na dosage from 0.0 to 0.4 g·L-1. This increase is clearly

attributed to the increased availability of active sites in the catalyst for the generation

of photogenerated charge carriers and PMS activation, and approximately 96%

removal of CBZ could be attained within 100 min at 0.4 g·L -1 of H-CTF-Na loading.

However, further increasing the catalyst dosage to 0.8 g·L-1 did not greatly improve

CBZ degradation. The PMS concentration showed a similar effect on CBZ

degradation. As shown in Figure S4b, ~97% removal of CBZ could be attained within

100 min at a PMS concentration of 1.3 mM, and the degradation efficiency gradually

decreased with decreasing PMS concentration, likely due to the lack of sufficient

oxidant to produce active radicals. A PMS concentration greater than 1.3 mM did not

result in increased degradation efficiency but led to a slight inhibition, perhaps

because of the self-quenching of radicals by excess PMS. The influence of the initial

CBZ concentration on the degradation rate is presented in Figure S4c. It was found

that the degradation efficiency decreased with increasing CBZ concentration, which

might be explained by the fact that more time is needed for a higher initial CBZ

concentration to achieve the same removal rate at fixed dosages of H-CTF-Na and

PMS. As illustrated in Figure S4d, the H-CTF-Na/vis/PMS system showed effective

photocatalytic activity toward CBZ degradation over a broad initial pH range, and the

removal efficiency of CBZ was accelerated at higher initial pH. The reason may be

originated from the enhancement of base-activation.

Figure S5. Mineralization of CBZ in H-CTFs-Na/vis and H-CTFs-Na/vis/PMS

systems.

Figure S6. Side view of optimized geometries of pristine CTFs and H-CTFs-Na with

different Na position.

Figure S7. Calculated charge distribution of optimized geometries of pristine CTFs

and H-CTFs-Na with different Na position.

Figure S10. (a) CBZ oxidation by H-CTFs-Na/vis/PMS system in H2O and D2O, and

(b) effects of NaN3 on PMS decomposition.

Figure S11. Effects of various electron acceptors on CBZ degradation in

H-CTF-Na/vis system.

Figure S12. The effect of nitrogen purging on CBZ removal in H-CTF-Na/vis system.

Figure S13. EPR spectroscopy analysis using TEMP as the trapping agent.

Figure S14. The variation of PMS concentration with reaction time in

H-CTF-Na/PMS/vis systems.

Figure S15. The removal of CBZ in real water bodies based on H-CTF-Na/PMS/vis

system.

Figure S16. XRD (a), XPS survey (b), XPS C 1s core-level (c), N 1s core-level (d),

Na 1s core-level (e), and O 1s core-level (f) spectra of fresh and recycled H-CTFs-Na

catalyst.

Figure S17. FTIR (a) and diffuse reflectance UV–vis (b) spectra of fresh and recycled

H-CTFs-Na catalyst; TEM image of recycled H-CTFs-Na (c).

Table S1 BET surface area and pore characters of various samples.

Sample BET SurfaceArea (m²g-1)

Pore Diameter(nm)

Pore Volume(m3g-1)

CTFs 1.7 72.9 0.03CTFs-Na 2.8 50.4 0.03

H-CTFs-Na 18.6 32.7 0.15SiO2@ CTFs 4.3 30.4 0.03

Table S2. Rate constants for the reaction of quenchers with reactive oxygen species

Reaction rate constant (M-1s-1)

Compounds •OH SO4•- 1O2 Ref.

Methanol 9.7×108 2.5×107 3.0×103 1

NaN3 1.2×1010 2.52×109 1.0×109 2

Table S3. The catalytic performance comparison of recently reported photocatalysts

for PMS activation.

PhotocatalystCatalyst loading(g L-1)

PMS(mM)

PollutantsTargetsConc. (mM)

Removal Efficiency% (min)

Ref.

Ag/mpg-C3N4 0.1 1 Bisphenol A 0.087 ~99 (60) 3

5 wt% PI-g-C3N4 1   5  Bisphenol A 0.043 ~92 (60) 4

FeOCl 0.5 12 Bisphenol A 0.219 ~100 (30) 5

g-C3N4 nanosheet 0.5 1.2(PS) Bisphenol A 0.02 ~100 (90) 6

Pd/g-C3N4 0.1 1 Bisphenol A 0.08 ~91 (60) 7

S-doped C3N4 0.3 0.49 Bisphenol A 0.2 ~50 (120) 8

This work 0.1 0.65 Bisphenol A 0.1 ~90 (50)Co3O4-300 0.2 1.6 Phenol 0.21 ~100 (120) 9

ZnO/UV 0.6 0.6 Phenol 0.26 ~100 (300) 10

 Co-ZnTiO3 0.5 3.2 Phenol 0.26 ~100 (120) 11

This work 0.1 0.65 Phenol 0.1 ~93 (50)RGO-CoFe2O4 0.4 0.1 4-Chlorophenol 0.077 ~100 (60) 12

Pt/WO3 0.5 1 4-Chlorophenol 0.1 ~86 (100) 13

TiO2 0.5 0.5 4-Chlorophenol 0.1 ~100 (240) 14

This work 0.1 0.65 4-Chlorophenol 0.1 ~96 (100)MnOx OMS-2 0.2 0.16 Acid Orange 7 0.11 ~93 (15) 15

TiO2 1 2 Acid Orange 7 0.1 ~100 (90) 16

MIL-53(Fe) 0.6 2(PS) Acid Orange 7 0.05 ~99 (90) 17

g-C3N4 0.4 0.65 Acid Orange 7 0.086 ~86 (30) 18

g-C3N4 0.4 0.65 Rhodamine B 0.042 ~90 (30) 18

BiVO4 0.5 1 Rhodamine B 0.02 ~92.4 (60) 19

1.0Co–500TiO2 1 0.4 Rhodamine B 0.2 ~100 (80) 20

α-Sulfur 0.5 0.5 Rhodamine B 0.02 ~100 (50) 21

TiMCM-41 3.0 0.125 Methyl orange 0.05 ~78 (60) 22

Fe–TiO2 1.8 0.3 Acid red 88 0.05 ~82 (540) 23

TiO2 1.142 0.5 Reactive Red 180 0.05 ~95 (40) 24

This work 0.1 0.65 Acid Orange 7 0.1 ~97 (50)

This work 0.1 0.65 Rhodamine B 0.1 ~95 (70)30%AC/g-C3N4  1  5  Atrazine 0.023 ~97 (120) 25

FeOCl 0.5 12 Carbamazepine 0.042 ~100 (30) 5

Fe3O4/BiOBr/C 1 0 Carbamazepine 0.042 ~98 (180) 26

BiOCl 0.5 0 Carbamazepine 0.01 ~96 (150) 27

BiOCl/Fe3O4 0.6 0 Carbamazepine 0.008 ~75 (60) 28

BiOCl 0.8 0 Carbamazepine 0.01 ~99 (90) 29

NaBiO3 1 0 Carbamazepine 0.02 ~99 (60) 30

Ag/AgCl/Bi4Ti3O12 1 0 Carbamazepine 0.021 ~82 (120) 31

TiO2@SiO2@Fe3O4 1 0 Carbamazepine 0.008 ~71 (540) 32

NV-g-C3N4 1.020 （ SO3

2-

）Carbamazepine 0.042 ~97 (120) 33

This work 0.4 1.3 Carbamazepine 0.021 ~97 (100)

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