Coupling photocatalytic fuel cell based on S-scheme g-C3N4/TNAs

photoanode with H2O2 activation for p-Chloronitrobenzene

degradation and simultaneous electricity generation under visible light

Wenjie Liua,c, Siyue Huoa,c, Xingchen Liua,c, Yanhao Wanga,c, Shuaishuai Xina, b *, Wenxian Fua,c,

Mengchun Gaoa, c *, Haijiao Xied

a
Key Lab of Marine Environment and Ecology, Ministry of Education, Ocean University of China,

Qingdao 266100, China

b
Qingdao Engineering Research Center for Rural Environment, College of Resources and

Environment, Qingdao Agricultural University, Qingdao 266109, China

c
Shandong Provincial Key Laboratory of Marine Environment and Geological Engineering, Ocean

University of China, Qingdao 266100, China

d
Hangzhou Yanqu Information Technology Co., Ltd., Hangzhou, 310003, China

*Corresponding author.

E-mail: xinshuaishuai90@outlook.com (Shuaishuai Xin)

E-mail: mengchungao@outlook.com (Mengchun Gao)

Text S1 Fabrication procedure of TNAs photoanode

The TNAs photoanode was fabricated through anodization method with titanium sheet (99.9%

purity) and platinum sheet as the anode and cathode, respectively. Prior to anodization, titanium plate

was soaked in an acid solution (HF: H2O = 1:1, in volume) for 10 s, and then rinsed with deionized

water to remove surface impurities. The treated titanium sheet with an effective size of 4 cm × 1 cm

was anodized at 30 V for 30 min with a mixed solution (ethylene glycol, 0.5 wt% ammonium

fluoride and 10 vol% water) as the electrolyte. Subsequently, the anodized titanium sheet was

washed with deionized water, dried at 80 ℃ and annealed in a muffle furnace at 450 ℃ for 2 h to

obtain the TNAs photoanode.

Text S2 Preparation of g-C3N4

Firstly, 4 g melamine powder placed in a crucible was calcined at 550 ℃ for 2 h in muffle furnace,

and the bulk yellow product was ground in an agate mortar and screened with 200 mesh sieves to

obtain g-C3N4 powder. Secondly, the g-C3N4 power was stripped at concentrated H2SO4 solution with

ultrasonic treatment for 8 h, and then washed to neutral with distilled water. Finally, the 300 mg

stripped g-C3N4 power was added into 1 L water and broken into smaller particles through an

ultrasonic crusher to acquire g-C3N4 dispersion.

Text S3 Detail of gas chromatography mass spectrometry analysis

The degradation products of p-Chloronitrobenzene (p-CNB) were identified by gas chromatography

mass spectrometry (Shimadzu LC-20AD) analysis with an Ultimate Plus-C18 column (5 μm, 4.6 ×

150 mm). Column temperature was set at 30°C, and the mobile phase was a mixture of acetonitrile
and water (60 : 40, V : V) with a flow rate of 1.0 mL min-1. Emission and excitation wavelengths

were 260 nm, with an injection volume of 10 μL.

Text S4 Parameters of density functional theory calculation

The DFT calculations were performed using Gaussian16 [1] at the B3LYP [2] /def2-TZVP [3, 4]

level with the D3(BJ) empirical dispersion correction [5]. The Fukui index was obtained with the

Multiwfn program to predict the possible reactive sites of radical attack for p-CNB molecule.

Reference

[1] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.

Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, et al, Gaussian 16, Revision A.03;

Gaussian, Inc.: Wallingford, CT, 2016.

[2] Becke, A. D. Density-Functional Thermochemistry. III. The Role of Exact Exchange. J. Chem.

Phys. 98 (1993) 5648−5652. https://doi.org/10.1063/1.464913

[3] F. Weigend and R. Ahlrichs. Balanced basis sets of split valences, triple zeta valence and

quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. In: Phys. Chem.

Chem. Phys. 7 (2005) 3297–3305. https://doi.org/10.1039/B508541A

[4] F. Weigend. Accurate Coulomb-fitting basis sets for H to Rn. In: Phys. Chem. Chem. Phys. 8

(2006) 1057–1065. https://doi.org/10.1039/b515623h.

[5] S. Grimme, S. Ehrlich and L. Goerigk, Effect of the damping function in dispersion corrected

density functional theory, J. Comp. Chem. 32 (2011) 1456-65.

https://doi.org/10.1002/jcc.21759.
Text S5 The economic analysis

The electrical energy per order (EE/O) and the total cost for p-CNB degradation in the present

work were determined by Eq. S1-2, respectively [1-2].

C0
EE/O =(P × t )/(V×60×log ) (1)
C

Cost total = (EE/O) × eletricity cost +Cost H2O2 + Cost photoanode (2)

where P is the input power of light (kW); t is the degradation time (min); V is the reaction volume

(L); C0 and Ct are the initial and final p-CNB concentration (mg L-1), respectively. Cost H2O2 , Cost TNAs

and Cost g-C3N4/TNAs were calculated into 8.64 yuan∙mol-1, 2.0 yuan and 2.2 yuan, respectively. The

industrial electricity price was 0.86-1.80 yuan∙kW h-1 in China, the data are from

http://news.ddcjw.cn/news/202208/374851.html.

Reference

[1] B. Xia, F. Deng, S. Zhang, L. Hua, X. Luo, M. Ao. Design and synthesis of robust Z-scheme

ZnS-SnS2 n-n heterojunctions for highly efficient degradation of pharmaceutical pollutants:

Performance, valence/conduction band offset photocatalytic mechanisms and toxicity

evaluation. J. Hazard. Mater. 392 (2020) 122345.

https://doi.org/10.1016/j.jhazmat.2020.122345.

[2] X. Zhang, M. Kamali, T. Uleners, J. Symus, S. Zhang, Z. Liu, M. E. V. Costa, L. Appels, D.

Cabooter, R.Dewil. UV/TiO2/periodate system for the degradation of organic pollutants–

Kinetics, mechanisms and toxicity study. Chem. Eng. J. 449 (2022) 137680.

https://doi.org/10.1016/j.cej.2022.137680.
Fig. S1. Adsorption removal efficiency of p-CNB by TNAs and g-C3N4/TNAs.

Fig. S2. EDX spectrum of g-C3N4/TNAs.

 Fig. S3. Consumption of H2O2 in various systems.

Fig. S4. Photodegradation efficiency and the corresponding kinetic curves (the inset) of p-CNB by
TNAs and g-C3N4/TNAs.

Fig. S5. The kinetic curves for p-CNB degradation in various system.
Fig. S6. Output voltage in H2O2-PFC system with g-C3N4/TNAs photoanode during the p-CNB

degradation process

Fig. S7. Effect of H2O2 concentration on the kinetic curves for p-CNB degradation

a
b

Fig. S8. Effect of solution pH on the kinetic curves for p-CNB degradation (a) and H2O2
 consumption (b).

Fig. S9. J-V and P-V curves under different atmospheres in H2O2-PFC system.

Fig. S10. Effect of solution pH on output voltage in H2O2-PFC system

 Fig. S11. Mott-Schottky plots of TNAs and g-C3N4.

Fig. S12. J-V and P-V curves for control experiment and addition of AgNO3 in H2O2-PFC system

a b

c d

Fig. S13. GC/MS spectra of solution before (a) and after reaction (b-d)
 Table S1 The fitted parameters of electrochemical impedance spectroscopy

Samples Rs (Ω) Rct (Ω)

TNAs 2.13 205.3
g-C3N4/TNAs 1.16 54.5

Table S2 The economic analysis in various system

EE/O Costphotoanode CostH2O2 Costtotal
Systems
(kWh∙L-1) (yuan ∙L-1) (yuan ∙L-1) (yuan ∙L-1)
photolysis 50 0 0 43.00-90.00
H2O2 + photolysis 44 0 0.09 37.93-79.29
PFC with TNAs 27 2.00 0 25.22-50.60
PFC with g-C3N4/TNAs 12 2.20 0 12.52-23.80
H2O2-PFC with TNAs 22 2.00 0.09 21.01-41.69
H2O2-PFC with g-C3N4/TNAs 8 2.20 0.09 9.17-16.69

Table S3 Comparison of electricity energy output in various PFC systems.

Systems JSC (μA·cm−2) Voc (V) Pmax(μW⋅cm -2)
PFC with TNAs 2.0 0.278 0.107
PFC with g-C3N4/TNAs 6.0 0.357 0.296
H2O2-PFC with TNAs 15.0 0.313 1.113
H2O2-PFC with g-C3N4/TNAs 55.0 0.422 5.520