H2O molecule adsorption on s-triazine-based g-C3N4

doi:10.1016/S1872-2067(20)63598-7

Abstract

Abstract:

The interaction between a gas molecule and photocatalyst is vital to trigger photocatalytic reaction. The surface state of photocatalyst affects much in this interaction. Herein, adsorption of H₂O molecules on s-triazine-based g-C₃N₄ was thoroughly studied by first-principle calculation. Although various initial adsorption models with multifarious locations of H₂O molecules were built, the optimized models with strong adsorption energy pointed to the same adsorption configuration, in which the H₂O molecule hold an upright orientation above the corrugated g-C₃N₄ monolayer. An intermolecular O-H…N hydrogen bond formed via the binding of a polar O-H bond in H₂O molecule and a two-coordinated electron-rich nitrogen atom in g-C₃N₄. Under the bridging effect of this intermolecular hydrogen bond, electrons would transfer from g-C₃N₄ to the H₂O molecule, thereby lowering the Fermi level and enlarging work function of g-C₃N₄. Interestingly, regardless of the substitute, i.e. g-C₃N₄ multilayer, large supercell and nanotube, this adsorption system was highly reproducible, as its geometry structure and electronic property remained unchanged. In addition, the effect of nonmetal element doping on adsorption energy was explored. This work not only disclosed a highly preferential H₂O adsorbed g-C₃N₄ architecture established by intermolecular hydrogen bond, but also contributed to the deep understanding and optimized design in water-splitting process on g-C₃N₄-based photocatalysts.

Key words: g-C₃N₄, H₂O, Density functional theory, Hydrogen bond, Adsorption energy

Bicheng Zhu, Liuyang Zhang, Bei Cheng, Yan Yu, Jiaguo Yu. H₂O molecule adsorption on s-triazine-based g-C₃N₄[J]. Chinese Journal of Catalysis, 2021, 42(1): 115-122.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63598-7

https://www.cjcatal.com/EN/Y2021/V42/I1/115

Figures/Tables 14

Fig. 1. Top view (upper) and side view (lower) of the constructed adsorption models with different adsorption manners (taking the adsorption at N2 site as an example): the H2O molecule plane being parallel to the g-C3N4 plane (a), the H2O molecule plane being perpendicular to the g-C3N4 plane with upward (b) and downward (c) orientation of the H-O-H angle.

Fig. 2. Top views of the constructed upward vertical adsorption models with various adsorption sites and directions.

Fig. 3. Top views of the constructed parallel adsorption models with various adsorption sites and directions. The dashed line displays the symmetry axis of a H2O molecule.

Table 1 Calculated adsorption energy (eV) for H2O adsorbed g-C3N4 models.

Adsorption configuration	Vertical		Parallel
Adsorption configuration	Upward	Downward	X-n	X-n’
N1-1	-1.344	-2.288	-2.525	—
N1-2	-1.345	-2.541	-2.553	-2.351
N2-1	-2.538	-2.549	-2.543	-2.544
N2-2	-2.557	-2.565	-2.548	-2.246
N2-3	-2.544	-2.554	-2.562	-2.538
N2-4	-2.229	-2.558	-2.567	—
C-1	-2.501	-2.543	-2.501	—
C-2	-2.501	-2.566	-2.519	-2.501
C-3	-2.180	-2.539	-2.543	-2.204
C-4	-2.539	-2.540	-2.540	-2.500
B1-1	-2.541	-2.538	-2.565	—
B1-2	—^a	-2.259	-2.542	-2.512
B2-1	-2.540	-2.540	-2.542	-2.549
B2-2	-2.549	-2.513	-2.551	-2.261
I1-1	-2.046	-2.560	-2.564	—
I1-2	-2.047	-2.561	-2.542	-2.554
I2-1	-2.291	—^a	-2.320	—
I2-2	-1.353	-2.549	-2.185	-2.330

Fig. 4. Top view (a) and side view (b) of the optimized adsorption model with the most negative adsorption energy. The dashed line represents the O-H…N hydrogen bond.

Table 2 Mulliken charge and geometric parameters of single and adsorbed H2O molecules.

H₂O molecule	Mulliken charge (e)			Bond length (Å)		Bond angle (°)
H₂O molecule	H1 ^a	O	H2	O-H1	O-H2	Bond angle (°)
Single H₂O molecule	0.52	-1.05	0.53	0.976	0.976	104.6
Adsorbed H₂O molecule	0.49	-1.04	0.52	0.994	0.975	105.3

Fig. 5. Electrostatic potential of pure g-C3N4 (a) and extracted g-C3N4 (b) from the H2O adsorbed g-C3N4 model; (c) PDOS of N and H atoms in the O-H…N hydrogen bond.

Fig. 6. Adsorption energy and final distance between the g-C3N4 substrate and H2O molecule of the adsorption models with initial distances of 1-5 ?.

Fig. 7. Adsorption energy and optimized structures of H2O molecule adsorbed 2 × 2 multilayer g-C3N4 models.

Fig. 8. Adsorption energy and optimized structures of H2O molecule adsorbed monolayer g-C3N4 supercells.

Table 3 Mulliken charge and geometric parameters of the adsorbed H2O molecule on monolayer g-C3N4 supercells.

Supercell	Mulliken charge (e)			Bond length (Å)		H…N distance (Å)
Supercell	H1	O	H2	O-H1	O-H2	H…N distance (Å)
2×2	0.49	-1.04	0.52	0.994	0.975	1.92
3×3	0.48	-1.04	0.52	0.994	0.975	1.91
4×4	0.48	-1.04	0.52	0.993	0.975	1.91

Fig. 9. Optimized structures of (6,6), (8,8), (10,10) g-C3N4 nanotubes (a-c), and H2O adsorption on (6,6), (8,8), (10,10) g-C3N4 nanotubes (d-f). Parts of C and N atoms in (d-f) are shown by yellow balls in order to clearly present the location of the H2O molecule.

Table 4 Mulliken charge and geometric parameters of the adsorbed H2O molecule on (n,n) g-C3N4 nanotubes.

(n,n)	Mulliken charge (e)			Bond length (Å)		H…N distance (Å)
(n,n)	H1	O	H2	O-H1	O-H2	H…N distance (Å)
(6,6)	0.49	-1.04	0.52	0.988	0.975	2.02
(8,8)	0.50	-1.04	0.52	0.988	0.975	2.09
(10,10)	0.49	-1.04	0.52	0.991	0.975	1.96

Fig. 10. Adsorption energy for H2O adsorption on pristine and nonmetal-doped g-C3N4.

References

[1]	Y. Li, D. Zhang, X. Feng, Q. Xiang, Chin. J. Catal., 2020, 41, 21-30.
[2]	X. Li, J. Wen, J. Low, Y. Fang, J. Yu, Sci. China Mater., 2014, 57, 70-100.
[3]	M. Gałynska, P. Persson, Adv. Quantum Chem., 2014, 69, 303-332.
[4]	Z. Du, C. Zhao, J. Chen, D. Zhang, Comp. Mater. Sci., 2017, 136, 173-180.
[5]	I. Onal, S. Soyer, S. Senkan, Surf. Sci., 2006, 600, 2457-2469.
[6]	S. S. Gupta, M. A. van Huis, J. Phys. Chem. C, 2017, 121, 9815-9824.
[7]	J. Fu, B. Zhu, W. You, M. Jaroniec, J. Yu, Appl. Catal. B, 2018, 220, 148-160.
[8]	A. Al-Sunaidi, S. Goumri-Said, Chem. Phys. Lett., 2011, 507, 111-116.
[9]	L. Zhang, B. Wen, Y. Zhu, Z. Chai, X. Chen, M. Chen, Comp. Mater. Sci., 2018, 150, 484-490.
[10]	M. Oshikiri, M. Boero, A. Matsushita, J. Ye, J. Electroceram., 2009, 22, 114-119.
[11]	M. Oshikiri, M. Boero, J. Phys. Chem. B, 2006, 110, 9188-9194.
[12]	H. S. Wahab, T. Bredow, S. M. Aliwi, J. Mol. Struct.: Theochem, 2008, 868, 101-108.
[13]	A. Ignatchenko, D. G. Nealon, R. Dushane, K. Humphries, J. Mol. Catal. A, 2006, 256, 57-74.
[14]	H. Sheng, H. Zhang, W. Song, H. Ji, W. Ma, C. Chen, J. Zhao, Angew. Chem. Int. Ed., 2015, 54, 5905-5909.
[15]	S. Hosseinpour, F. Tang, F. Wang, R. A. Livingstone, S. J. Schlegel, T. Ohto, M. Bonn, Y. Nagata, E. H. G. Backus, J. Phys. Chem. Lett., 2017, 8, 2195-2199.
[16]	H. Zhang, P. Zhou, Z. Chen, W. Song, H. Ji, W. Ma, C. Chen, J. Zhao, J. Phys. Chem. C, 2017, 121, 2251-2257.
[17]	V. Quaranta, M. Hellström, J. Behler, J. Phys. Chem. Lett., 2017, 8, 1476-1483.
[18]	A. I. Gavrilyuk, Appl. Surf. Sci., 2016, 364, 498-504.
[19]	Z. Li, Y. Ma, X. Hu, E. Liu, J. Fan, Chin. J. Catal., 2019, 40, 434-445.
[20]	S. Cao, Q. Huang, B. Zhu, J. Yu, J. Power Sources, 2017, 351, 151-159.
[21]	Y. Li, Z. Jin, L. Zhang, K. Fan, Chin. J. Catal., 2019, 40, 390-402.
[22]	F. Mei, Z. Li, K. Dai, J. Zhang, C. Liang, Chin. J. Catal., 2020, 41, 41-49.
[23]	J. Fu, C. Bie, B. Cheng, C. Jiang, J. Yu, ACS Sustainable Chem. Eng., 2018, 6, 2767-2779.
[24]	K. Qi, W. Lv, I. Khan, S. Liu, Chin. J. Catal., 2020, 41, 114-121.
[25]	Y. Ren, D. Zeng, W.-J. Ong, Chin. J. Catal., 2019, 40, 289-319.
[26]	Y. Li, F. Gong, Q. Zhou, X. Feng, J. Fan, Q. Xiang, Appl. Catal. B, 2019, 118381.
[27]	B. Zhu, P. Xia, W. Ho, J. Yu, Appl. Surf. Sci., 2015, 344, 188-195.
[28]	E. X. Han, Y. Y. Li, Q. H. Wang, W. Q. Huang, L. Luo, W. Hu, G. F. Huang, J. Mater. Sci. Technol., 2019, 35, 2288-2296.
[29]	S. Cao, Y. Li, B. Zhu, M. Jaroniec, J. Yu, J. Catal., 2017, 349, 208-217.
[30]	M. Jourshabani, Z. Shariatinia, A. Badiei, J. Mater. Sci. Technol., 2018, 34, 1511-1525.
[31]	N. Xiao, S. Li, S. Liu, B. Xu, Y. Li, Y. Gao, L. Ge, G. Lu, Chin. J. Catal., 2019, 40, 352-361.
[32]	T. Tong, B. Zhu, C. Jiang, B. Cheng, J. Yu, Appl. Surf. Sci., 2018, 433, 1175-1183.
[33]	J. Liu, B. Cheng, Appl. Surf. Sci., 2018, 430, 348-354.
[34]	B. Zhu, S. Wageh, A. A. Al-Ghamdi, S. Yang, Z. Tian, J. Yu, Catal. Today, 2019, 335, 117-127.
[35]	J. Liu, B. Cheng, J. Yu, Phys. Chem. Chem. Phys., 2016, 18, 31175-31183.
[36]	B. Zhu, B. Cheng, L. Zhang, J. Yu, Carbon Energy, 2019, 1, 32-56.
[37]	S. M. Aspera, M. David, H. Kasai, Jpn. J. Appl. Phys., 2010, 49, 115703.
[38]	Y. Guo, C. Tang, X. Wang, C. Wang, L. Fu, Chin. Phys. B, 2019, 28, 048102.
[39]	Y. Ji, H. Dong, H. Lin, L. Zhang, T. Hou, Y. Li, RSC Adv., 2016, 6, 52377-52383.
[40]	S. Lin, X. Ye, X. Gao, J. Huang, J. Mol. Catal. A, 2015, 406, 137-144.
[41]	H. Wu, L. Liu, S. Zhao, Phys. Chem. Chem. Phys., 2014, 16, 3299-3304.
[42]	J. Sun, X. Li, J. Yang, Nanoscale, 2018, 10, 3738-3743.
[43]	J. Wirth, R. Neumann, M. Antonietti, P. Saalfrank, Phys. Chem. Chem. Phys., 2014, 16, 15917-15926.
[44]	Q. Xiang, F. Li, D. Zhang, Y. Liao, H. Zhou, Appl. Surf. Sci., 2019, 495, 143520.
[45]	J. Goclon, K. Winkler, Appl. Surf. Sci., 2018, 462, 134-141.
[46]	B. Zhu, L. Zhang, D. Xu, B. Cheng, J. Yu, J. CO₂ Util., 2017, 21, 327-335.
[47]	B. Zhu, J. Zhang, C. Jiang, B. Cheng, J. Yu, Appl. Catal. B, 2017, 207, 27-34.
[48]	Y. Li, J. Chen, Y. Chen, Y. Zhu, Y. Liu, J. Phys. Chem. C, 2019, 123, 3048-3057.
[49]	A. Calzolari, A. Catellani, J. Phys. Chem. C, 2009, 113, 2896-2902.
[50]	H. S. Chen, F. S. Meng, X. F. Li, S. L. Zhang, Acta Phys. Sin., 2009, 58, 887-892.
[51]	H. Kamisaka, K. Yamashita, Surf. Sci., 2007, 601, 4824-4836.
[52]	Q. Xu, B. Zhu, C. Jiang, B. Cheng, J. Yu, Sol. RRL, 2018, 2, 1800006.
[53]	J. Zhang, J. Fu, Z. Wang, B. Cheng, K. Dai, W. Ho, J. Alloys Compd., 2018, 766, 841-850.
[54]	Q. Xu, B. Zhu, B. Cheng, J. Yu, M. Zhou, W. Ho, Appl. Catal. B, 2019, 255, 117770.
[55]	L. M. Azofra, D. R. MacFarlane, C. Sun, Phys. Chem. Chem. Phys., 2016, 18, 18507-18514.
[56]	Q. Guo, Y. Xie, X. Wang, S. Zhang, T. Hou, S. Lv, Chem. Commun., 2004, 26-27.
[57]	J. Gao, Y. Zhou, Z. Li, S. Yan, N. Wang, Z. Zou, Nanoscale, 2012, 4, 3687-3692.
[58]	Y. Lee, D.-G. Kwon, G. Kim, Y.-K. Kwon, Phys. Chem. Chem. Phys., 2017, 19, 8076-8081.
[59]	M. Y. Duan, G. S. Shi, C. L. Wang, L. P. Zhou, X. R. Chen, H. P. Fang, Commun. Theor. Phys., 2012, 58, 275-279.
[60]	F. Shojaei, H. S. Kang, RSC Adv., 2015, 5, 10892-10898.
[61]	Q. Yan, G. F. Huang, D. F. Li, M. Zhang, A. L. Pan, W. Q. Huang, J. Mater. Sci. Technol., 2018, 34, 2515-2520.
[62]	X. Qu, S. Hu, J. Bai, P. Li, G. Lu, X. Kang, J. Mater. Sci. Technol., 2018, 34, 1932-1938.
[63]	J. Li, W. Zhao, J. Wang, S. Song, X. Wu, G. Zhang, Appl. Surf. Sci., 2018, 458, 59-69.
[64]	J. Liu, J. Alloys Compd., 2016, 672, 271-276.
[65]	Q. He, F. Zhou, S. Zhan, N. Huang, Y. Tian, Appl. Surf. Sci. , 2018, 430, 325-334.
[66]	G. Dong, K. Zhao, L. Zhang, Chem. Commun., 2012, 48, 6178-6180.

H₂O molecule adsorption on s-triazine-based g-C₃N₄

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 14

References

Related Articles 15

Recommended Articles

Metrics

[1]	Binbin Zhao, Wei Zhong, Feng Chen, Ping Wang, Chuanbiao Bie, Huogen Yu. High-crystalline g-C₃N₄ photocatalysts: Synthesis, structure modulation, and H₂-evolution application [J]. Chinese Journal of Catalysis, 2023, 52(9): 127-143.
[2]	Jin-Nian Hu, Ling-Chan Tian, Haiyan Wang, Yang Meng, Jin-Xia Liang, Chun Zhu, Jun Li. Theoretical screening of single-atom electrocatalysts of MXene-supported 3d-metals for efficient nitrogen reduction [J]. Chinese Journal of Catalysis, 2023, 52(9): 252-262.
[3]	Xin Liu, Maodi Wang, Yiqi Ren, Jiali Liu, Huicong Dai, Qihua Yang. Construction of modularized catalytic system for transfer hydrogenation: Promotion effect of hydrogen bonds [J]. Chinese Journal of Catalysis, 2023, 52(9): 207-216.
[4]	Lu Cheng, Xuning Chen, P. Hu, Xiao-Ming Cao. Advantages and limitations of hydrogen peroxide for direct oxidation of methane to methanol at mono-copper active sites in Cu-exchanged zeolites [J]. Chinese Journal of Catalysis, 2023, 51(8): 135-144.
[5]	Zhaochun Liu, Xue Zong, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. A computational study of electrochemical CO₂ reduction to formic acid on metal-doped SnO₂ [J]. Chinese Journal of Catalysis, 2023, 50(7): 249-259.
[6]	Liyuan Gong, Ying Wang, Jie Liu, Xian Wang, Yang Li, Shuai Hou, Zhijian Wu, Zhao Jin, Changpeng Liu, Wei Xing, Junjie Ge. Reshaping the coordination and electronic structure of single atom sites on the right branch of ORR volcano plot [J]. Chinese Journal of Catalysis, 2023, 50(7): 352-360.
[7]	Shipeng Geng, Liming Chen, Haixin Chen, Yi Wang, Zhao-Bin Ding, Dandan Cai, Shuqin Song. Revealing the electrocatalytic mechanism of layered crystalline CoMoO₄ for water splitting: A theoretical study from facet selecting to active site engineering [J]. Chinese Journal of Catalysis, 2023, 50(7): 334-342.
[8]	Xinjie Song, Shipeng Fan, Zehua Cai, Zhou Yang, Xun Chen, Xianzhi Fu, Wenxin Dai. NH₃ synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H₂O over Cu/CeO₂ [J]. Chinese Journal of Catalysis, 2023, 49(6): 168-179.
[9]	Zheng-Qing Huang, Shu-Yue He, Tao Ban, Xin Gao, Yun-Hua Xu, Chun-Ran Chang. Mechanistic and microkinetic study of nonoxidative coupling of methane on Pt-Cu alloy catalysts: From single-atom sites to single-cluster sites [J]. Chinese Journal of Catalysis, 2023, 48(5): 90-100.
[10]	Huijuan Jing, Jun Long, Huan Li, Xiaoyan Fu, Jianping Xiao. Computational insights on potential dependence of electrocatalytic synthesis of ammonia from nitrate [J]. Chinese Journal of Catalysis, 2023, 48(5): 205-213.
[11]	Zhiyue Zhao, Zhiwei Jiang, Yizhe Huang, Mebrouka Boubeche, Valentina G. Matveeva, Hector F. Garces, Huixia Luo, Kai Yan. Facile synthesis of CoSi alloy catalysts with rich vacancies for base- and solvent-free aerobic oxidation of aromatic alcohols [J]. Chinese Journal of Catalysis, 2023, 48(5): 175-184.
[12]	Sue-Faye Ng, Xingzhu Chen, Joel Jie Foo, Mo Xiong, Wee-Jun Ong. 2D carbon nitrides: Regulating non-metal boron-doped C₃N₅ for elucidating the mechanism of wide pH range photocatalytic hydrogen evolution reaction [J]. Chinese Journal of Catalysis, 2023, 47(4): 150-160.
[13]	Ning Li, Xueyun Gao, Junhui Su, Yangqin Gao, Lei Ge. Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis [J]. Chinese Journal of Catalysis, 2023, 47(4): 161-170.
[14]	Eun Hyup Kim, Min Hee Lee, Jeehye Kim, Eun Cheol Ra, Ju Hyeong Lee, Jae Sung Lee. Synergy between single atoms and nanoclusters of Pd/g-C₃N₄ catalysts for efficient base-free CO₂ hydro-genation to formic acid [J]. Chinese Journal of Catalysis, 2023, 47(4): 214-221.
[15]	Qian Li, Qijun Tang, Peiyao Xiong, Dongzhi Chen, Jianmeng Chen, Zhongbiao Wu, Haiqiang Wang. Effect of palladium chemical states on CO₂ photocatalytic reduction over g-C₃N₄: Distinct role of single-atomic state in boosting CH₄ production [J]. Chinese Journal of Catalysis, 2023, 46(3): 177-190.