Supporting Information

Fluorinated conjugated poly(benzotriazole)/g-C3N4 heterojunctions

for significantly enhancing photocatalytic H2 evolution

Haonan Ye,a† Zhiqiang Wang,b† Fengtao Yu,a Shicong Zhang,a Kangyi Kong, a

Xueqing Gongb* Jianli Hua a* and He Tian a

aKey Laboratory for Advanced Materials, Institute of Fine Chemicals and School of

Chemistry and Molecular Engineering, East China University of Science and

Technology, 130 Meilong Road, Shanghai, 200237, P. R. China.

bKey Laboratory for Advanced Materials, Centre for Computational Chemistry

and Research Institute of Industrial Catalysis, School of Chemistry and

Molecular Engineering, East China University of Science and Technology,

Shanghai 200237, P. R. China.

† Authors are equal to contribution.

* Corresponding authors

E-mails addresses: jlhua@ecust.edu.cn ; xgong@ecust.edu.cn . Fax: +86-21-

64252756; Tel: +86-21-64250940

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List of Tables and Figures

Fig. S1. TEM image of (a) Flu-BZ polymer; (b) Flu-BZ/g-C3N4 heterojunction; (c) Flu-FBZ polymer and (d) Flu-FBZ/g-C3N4 heterojunction. Scale bar: 100 nm.

Fig. S2. Cyclic voltammetry measurements of ferrocene/ferrocenium (Fc/Fc+) in dichloromethane solution.

Fig. S3. The control experiment of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-

DFBZ/g-C3N4 PHJs. Reaction conditions: 50 mL water, 50 mg photocatalyst under

visible-light (420 nm ≤ λ ≤ 780 nm).

Fig. S4. FT-IR of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs after reaction.

Fig. S5. DRS of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs after reaction.

Fig. S6. PXRD of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs after reaction.

Fig. S7. wavelength-dependent AQY and DRS spectrum of g-C3N4, Flu-BZ/g-C3N4

and Flu-FBZ/g-C3N4 (λ = 420, 435, 475, 500, 550, 630 nm. Reaction conditions: 50

mL water, 10 mL TEOA, 50 mg photocatalyst under visible-light (420 nm ≤ λ ≤ 780

nm).

Fig. S8. Water contact angle measurements of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs

Fig. S9. F atoms on polymers assist for H2 release.

Fig. S10. 1H NMR spectrum of compound 4,7-dibromo-2-octyl-2H-benzo[d][1,2,3]triazole in CDCl3

Fig. S11. 13C NMR spectrum of compound 4,7-dibromo-2-octyl-2H-benzo[d][1,2,3]triazole in CDCl3

Fig. S12. HRMS of compound 4,7-dibromo-2-octyl-2H-benzo[d][1,2,3]triazole.

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Fig. S13. 1H NMR spectrum of compound c in CDCl3.

Fig. S14. HRMS of compound c

Fig. S15. 1H NMR spectrum of compound 4,7-dibromo-5-fluoro-2-octyl-2H-benzo[d][1,2,3]triazole in CDCl3

Fig. S16. 13C NMR spectrum of compound 4,7-dibromo-5-fluoro-2-octyl-2H-benzo[d][1,2,3]triazole in CDCl3

Fig. S17. HRMS of compound 4,7-dibromo-5-fluoro-2-octyl-2H-benzo[d][1,2,3]triazole

Fig. S18. 1H NMR spectrum of compound 4,7-dibromo-5,6-difluoro-2-octyl-2H-benzo[d][1,2,3]triazole in CDCl3

Fig. S19. 13C NMR spectrum of compound 4,7-dibromo-5,6-difluoro-2-octyl-2H-benzo[d][1,2,3]triazole in CDCl3

Fig. S20. 1H NMR spectrum of compound 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluorene in CDCl3.

Fig. S21. 13C NMR spectrum of compound 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluorene in CDCl3.

Fig. S22. HRMS of compound 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluorene.

Fig. S23. The 1H NMR spectras of (a) Flu-BZ, (b) Flu-FBZ and (c) Flu-DFBZ.

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Table S1. Elemental composition (atom ratios) of samples according to XPS analysis

Sample C/at% N/at% O/at% F/at% Pt/at% C/N

g-C3N4 31.8 64.2 3.6 0 0.8 0.52

Flu-BZ/g-C3N4 51.9 42.5 5.4 0 0.8 1.22

Flu-FBZ /g-C3N4 42.3 46.5 4.9 5.7 0.8 0.91

Flu-DFBZ /g-C3N4 50.6 35.0 5.9 8.1 0.8 1.44

Table S2. Relative ratios of two carbon species determined by C 1s spectra for samples

C=C C-(N)3

Sample

BindingEnerg

y（eV） area %Binding

Energy（eV） area %

g-C3N4 284.60 5334.55 14.00 288.04 32770.66 86.00

Flu-BZ/g-C3N4 284.60 13080.00 63.71 288.17 7450.00 36.29

Flu-FBZ /g-C3N4 284.60 19737.63 50.83 288.05 19091.14 49.17

Flu-DFBZ /g-C3N4 284.60 16865.17 70.87 288.14 6931.87 29.13

Table S3. Relative ratios of four nitrogen species determined by N 1s spectra for samples

C=N-C N-(C)3 N-H π excitation

Sample

Binding

Energy（eV）

area %

Binding

Energy（eV）

area %

Binding

Energy（eV）

area %

Binding

Energy（eV）

area %

g-C3N4 398.4659667.8

967.9

5399.70

20851.89

23.75

401.054085.4

74.65 404.28

3204.69

3.65

Flu-BZ/g-C3N4 398.3513795.1

766.5

6399.35 4632.40

22.35

400.901700.3

48.20 404.10 599.02

2.89

Flu-FBZ /g-C3N4

398.4034032.7

665.2

3399.60 9942.96

19.06

400.906889.4

313.2

0404.00

1307.86

2.51

Flu-DFBZ /g-C3N4

398.4013604.8

765.8

7399.47 5031.52

24.36

401.001520.0

27.36 404.10 499.26

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Table S4. The fitted fluorescence lifetimes and corresponding amplitudes of photoinduced charge carriers in g-C3N4, Flu-BZ, Flu-BZ/g-C3N4, Flu-FBZ, Flu-FBZ/g-C3N4, Flu-DFBZ and Flu-DFBZ/g-C3N4 PHJs

Sampleτ1 [ns] （Rel.

%）τ2 [ns] （Rel.

%）τ3 [ns] （Rel.

%）τ [ns] χ2

Flu-BZ 1.30（28.34） 3.04（71.66） 2.55 1.155

Flu-FBZ 1.31（69.30） 2.58（30.70） 1.70 1.164

Flu-DFBZ 0.74（96.80） 4.12（3.20） 0.85 1.281

Flu-BZ/g-C3N4 2.39（83.92） 7.58（11.82） 42.54（4.25） 4.71 1.261

Flu-FBZ/g-C3N4 1.47（76.32） 4.79（17.19） 32.59（6.49） 4.06 1.222

Flu-DFBZ/g-C3N4 0.95（83.26） 11.98（16.74） 2.80 1.175

g-C3N4 1.21（43.05） 5.04 （40.32） 25.51（16.63） 6.79 1.169

Table S5. Recent representative photocatalytic H2 evolution activities of D-A type PHJs

Materials light source CocatalystH2 Production(mmol g -1 h -1 )

AQY Ref

PCzF/g-C3N4 λ > 420 nm 1 wt% Pt 0.628 27% (440 nm) [S1]

PFBT/g-C3N4 λ > 420 nm 1 wt% Pt 0.722 13% (500 nm) [S1]

P3/g-C3N4 λ > 420 nm 1 wt% Pt 13.0 27.32% (520 nm) [S2]

PyP2/g-C3N4 λ > 420 nm Without cocatalyst 0.03 Not mentioned [S3]

Flu-DFBZ/g-C3N4 λ > 420 nm 1 wt% Pt 14.85 33.49% (450 nm) This work

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Fig. S1. TEM images of Flu-BZ (a) ; Flu-BZ/g-C3N4 heterojunction (b); Flu-FBZ (c)

and Flu-FBZ/g-C3N4 heterojunction (d). Scale bar: 100 nm; SEM images of Flu-BZ

(e); Flu-BZ/g-C3N4 heterojunction (f); Flu-FBZ (g) and Flu-FBZ/g-C3N4

heterojunction (h). Scale bar: 2 μm.

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Fig. S2. Cyclic voltammetry measurements of ferrocene/ferrocenium (Fc/Fc+) in

dichloromethane solution.

Fig. S3. The control experiment of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-

DFBZ/g-C3N4 PHJs. Reaction conditions: 50 mL water, 50 mg photocatalyst under

visible-light (420 nm ≤ λ ≤ 780 nm).

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Fig. S4. FT-IR of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs after

reaction.

Fig. S5. DRS of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs after

reaction.

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Fig. S6. PXRD of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and Flu-DFBZ/g-C3N4 PHJs after reaction.

Fig. S7. Wavelength-dependent AQY and DRS spectrum of g-C3N4, Flu-BZ/g-C3N4

and Flu-FBZ/g-C3N4 (λ = 420, 435, 475, 500, 550, 630 nm. Reaction conditions: 50

mL water, 10 mL TEOA, 50 mg photocatalyst under visible-light (420 nm ≤ λ ≤ 780

nm).

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Fig. S8. Water contact angle measurements of Flu-BZ/g-C3N4, Flu-FBZ/g-C3N4 and

Flu-DFBZ/g-C3N4 PHJs

Fig. S9. F atoms on polymers assist for H2 release.

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Fig. S10. 1H NMR spectrum of compound 4,7-dibromo-2-octyl-2H-benzo[d] [1,2,3]-

triazole in CDCl3

Fig. S11. 13C NMR spectrum of compound 4,7-dibromo-2-octyl-2H- benzo[d][1,2,3]-

triazole in CDCl3

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Fig. S12. HRMS of compound 4,7-dibromo-2-octyl-2H-benzo[d][1,2,3]triazole.

Fig. S13. 1H NMR spectrum of compound c in CDCl3.

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Fig. S14. HRMS of compound c

Fig. S15. 1H NMR spectrum of compound 4,7-dibromo-5-fluoro-2-octyl-2H-benzo[d]

[1,2,3]triazole in CDCl3

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Fig. S16. 13C NMR spectrum of compound 4,7-dibromo-5-fluoro-2-octyl-2H-

benzo[d][1,2,3]triazole in CDCl3

Fig. S17. HRMS of compound 4,7-dibromo-5-fluoro-2-octyl-2H-benzo[d]

[1,2,3]triazole

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Fig. S18. 1H NMR spectrum of compound 4,7-dibromo-5,6-difluoro-2-octyl-2H-

benzo[d][1,2,3]triazole in CDCl3

Fig. S19. 13C NMR spectrum of compound 4,7-dibromo-5,6-difluoro-2-octyl-2H-

benzo[d][1,2,3]triazole in CDCl3

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Fig. S20. 1H NMR spectrum of compound 2,7-bis(4,4,5,5-tetramethyl-1,3,2-

dioxaborolan-2-yl)-9H-fluorene in CDCl3.

Fig. S21. 13C NMR spectrum of compound 2,7-bis(4,4,5,5-tetramethyl-1,3,2-

dioxaborolan-2-yl)-9H-fluorene in CDCl3.

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Fig. S22. HRMS of compound 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-

9H-fluorene.

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Fig. S23. The 1H NMR spectras of Flu-BZ (a), Flu-FBZ (b) and Flu-DFBZ (c).

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References

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Shearer, S. Shen, L. Guo, Adv. Mater., 29 (2017) 1606198.

[S2] F. Yu, Z. Wang, S. Zhang, H. Ye, K. Kong, X. Gong, J. Hua, H. Tian, Adv. Funct.

Mater, 28 (2018) 1804512.

[S3] S. Zang, G. Zhang, P. Yang, D. Zheng, X. Wang, Chem. Eur. J. 25 (2019) 6102-

6107.

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