Supporting Information

Mechanochemical Synthesis of a New Triptycene-Based Imine-Linked

Covalent Organic Polymer for Degradation of Organic Dye

Kawal Preet†, Girish Gupta‡, Moumita Kotal§, Sushil Kumar Kansal‡, Deepak B Salunke†, Harish K
Sharma§, Subash Chandra Sahoo*†, Pascal Van Der Voort ‖‖, and Sandipan Roy* §
†
Department of Chemistry, Panjab University, Chandigarh 160014, India
‡
Dr. S.S. Bhatnagar University Institute of Chemical Engineering & Technology, Panjab University,
Chandigarh 160014, India
§
Department of Chemistry, Maharishi Markandeshwar (Deemed to be University), Mullana (Ambala),
Haryana 133207, India
‖‖
Department of Inorganic and Physical Chemistry, Ghent University, Gent 9000, Belgium

*Corresponding Author. E-mail: sandipanroy06@gmail.com; subash.chem@gmail.com

EXPERIMENTAL SECTION

Materials and Methods. All reagents and solvents were purchased from Sigma-Aldrich/Alfa

Aesar and were used as received. The solid-state CP/MAS (cross-polarization with magic

angle spinning) 13C NMR spectrum was carried out on a Bruker Avance 400 spectrometer,

operating at 100.6 MHz. The IR spectra were recorded on Thermo Scientific (NICOLET

IS50) FT-IR spectrophotometer in the range 4000-400 cm -1. Powder X-ray was done on

X’Pert Pro Panalytical’s instrument with Cu Kα radiation (λ =1.54178 Å). To study the

thermal decomposition of synthesized material, thermal analysis was carried out using TGA

instrument with an SDTA sensor from Mettler Toledo upon loading over an alumina pan and

heating from 30 °C to 1000 °C at a heating rate of 10 °C min -1 under N 2 atmosphere. The

Diffuse reflectance spectra (DRS) were recorded with a Cary Model 5000 UV−visible−NIR

spectrophotometer. N 2 adsorption−desorption measurements were performed at 77 K using a

Quantacrome autosorb iQ automated gas sorption analyzer. The morphologies of the

synthesized materials were characterized by field emission scanning electron microscope

(FESEM, Zeiss, Supra-40) and high-resolution transmission electron microscope (HRTEM,

FEI-TECNAI G2 20S-TWIN, Type-5022/22), respectively.

Synthesis of Triaminotriptycene (TP-NH 2)

The synthesis of TP-NH 2 was carried out from trinitrotriptycene (TP-NO 2) precursor via

modified literature procedure. 1

Synthesis of Trinitrotriptycene (TP-NO 2)

Concentrated HNO 3 (40 mL) was added to triptycene (1 g, 4 mmol) followed by heating at 75

°C for 24 hours. The yellow colour solution was cooled to room temperature, then poured

into H 2O (400 mL) and stirred for 30 min. The precipitate was collected, washed with cold

water and then dried in air. The final pure product (white solid) was obtained by column

chromatography on silica gel with ethylacetate/hexane solvent system. The yield was about

20%.

Synthesis of Triaminotriptycene (TP-NH 2)

To a solution of trinitrotriptycene (TP-NO 2) (0.2 g, 0.5 mmol) in THF (10 mL) was added

hydrazine monohydrate (0.5 mL) and Raney Ni (0.2 g). After heating at 60 °C for 2 hr, the

mixture was cooled to room temperature and then filtered. The filtrate was concentrated by

rotary evaporation to obtain light brown solid product. The yield was about 75%.

Synthesis of TP-COP

In a typical mechanochemical synthesis, triaminotriptycene (TP-NH 2) (300 mg, 1 mmol) and

terephthaldehyde (205 mg, 1.5 mmol) were placed in a mortar and ground using a pestle at

room temperature; after 15 min, a light-yellow powder (a mixture of oligomers and starting

materials) was obtained. Over the next 30 min of grinding, a powdered material with a yellow

color was obtained, indicating the complete TP-COP formation as there has not been changed
in color upon further grinding. The yellow powder formed was collected and washed with

several times by methanol and acetone to remove some unreacted starting materials, then

dried at 120 °C under vacuum for 16 hours to obtain pure yellow powder material (TP-COP)

in ~75% isolated yield.

Photocatalytic Investigations

The photocatalytic degradation of aqueous solution of rhodamine B (RhB) dye (10 mg/L)

was performed under sunlight illumination with average intensity of 73 Klux. 100 mL of the

dye solution was introduced into a cylindrical slurry batch reactor. The dye solution along

with certain amount of catalyst was stirred under dark for 30 minutes for the achievement of

adsorption-desorption equilibrium prior to the introduction of light source. Then the reaction

was subjected to sunlight. Aliquots were drawn from the reaction at specific set of intervals

through Chromafil syringe filter (0.45 µm). The degradation efficiency (%) can be calculated

from equation stated below:

Degradation efficiency (%) =

where C 0 and C t are the concentrations of RhB dye at t=0 and t minutes of photocataytic

reaction.

After completion of each photocatalytic cycle, the aqueous solution was centri fuged to

recycle the TP-COP powder which was then dried at 60°C. For reusability measurements, the

as-prepared TP-COP material was recycled and reused in the decomposition of RhB under

same conditions.
 C=N C-N
Intensity (a. u.)
C=C

CH=O
C=O

N-H
TP-COP
Terephthaldehyde
C=C
TP-NH2

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)
Figure S1. FTIR spectra of TP-COP and the precursor monomers: terephthaldehyde and TP-
NH 2.

200 nm

Figure S2. FESEM image of TP-COP.

 (a) (b)

100 nm 5 nm

Figure S3. (a) Low resolution TEM image and (b) High resolution TEM image of TP-COP.

(a) 100
(b)
0.20
N2 Uptake (cm3 g-1)

80
dV/dlog(w) (cm3 g-1)

0.16

60
0.12

40 0.08

20 0.04

0 0.00
0.0 0.2 0.4 0.6 0.8 1.0 0 5 10 15 20 25
Relative Pressure (P/Po) Pore Width (nm)

Figure S4. (a) N 2 adsorption–desorption isotherm and (b) corresponding pore-size

distributions of HPNC-700 and HPNC-900.
 100

Residual Weight (%)

90

80

70

60

50

100 200 300 400 500 600 700 800 900

Temperature (oC)

Figure S5. TGA curve of TP-COP under N 2 atmosphere.

Table S1. Comparative studies of our designed TP-COP with the reported COPs in terms of
photocatalytic dye degradation.

TP-COP PDA-COP1 COP-NT POP-1

Band gap 2.49 2.10 2.02 2.03
(eV)
Organic Rhodamine Methyl orange Methyl orange Rhodamine B
pollutant B (MO), Rhodamine
used B (RhB) and
Methylene blue
(MB)
Source of Solar Light Visible light Visible light LED light
irradiation
pH 4.6 - 7 (MO), 4 (Rh B), 4
10 (MB)
Degradation 160 120 600 (MO), 240 (Rh 180
time B), 100 (MB)
(minutes)
% 95% 92% 67%, 78%, 57% 93%
Degradation
Recyclability 91% at Not reported Not reported 93% at third cycle
third cycle
References Our Work 2 3 4
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