g-C3N4-CdS-NiS2 composite nanotube: synthesis and its photocatalytic activity for H2 generation under visible light

doi:10.11949/0438-1157.20191249

Abstract

Abstract:

Rapid recombination of photogenerated electron-hole pairs is one of important factors leading to poor performance of semiconductor photocatalysts. Constructing a heterojunction is an effective method for separation of photogenerated electron-hole pairs. In the present work, g-C₃N₄-CdS-NiS₂ composite nanotube was synthesized via thermal condensation using urea and thiourea as precursors, and subsequent two-step hydrothermal reactions. The photocatalytic activity of g-C₃N₄-CdS-NiS₂ composite was investigated for H₂ generation from water using triethanolamine as sacrificial agent under visible light irradiation. The optimal g-C₃N₄-CdS-NiS₂ composite with the content of CdS 10%(mass) produced H₂ at a rate of 50.9 μmol·h^-1, which is 25 times and 11 times of that of pure g-C₃N₄ nanotube and g-C₃N₄-CdS (NiS₂) binary composite, respectively. Moreover, cyclic photocatalytic experiments demonstrated the high stability of g-C₃N₄-CdS-NiS₂ composite. The improvement in the photocatalytic performance for H₂ production can be mainly attributed to the formation of heterojunction between CdS, NiS₂ and g-C₃N₄ nanotubes, which is beneficial to the separation of photogenerated electron-hole pairs.

Key words: hydrogen production, catalysis, photochemistry, heterojunction, cadmium sulfide, nickel sulfide, nanotube, visible light catalysis, g-C₃N₄

摘要：

光生电子-空穴对的快速复合是导致半导体光催化剂性能不佳的重要因素之一，构建异质结是分离光生电子-空穴对的有效方法。结合热缩合和两步水热反应构建了g-C₃N₄-CdS-NiS₂复合纳米管，并进一步研究了在可见光照射下不同CdS含量的g-C₃N₄-CdS-NiS₂分解水制氢的光催化性能。结果表明，当CdS含量为10%(质量)时，三元复合物的产氢速率最高(50.9 μmol·h^-1)，是纯g-C₃N₄纳米管的25倍，是g-C₃N₄-CdS和g-C₃N₄-NiS₂二元复合物的11倍。而且，经过五次循环光催化反应后，产氢速率保持不变。光催化制氢性能的提高主要源于g-C₃N₄、CdS与NiS₂形成的异质结促进光生电子和空穴的迁移及电子-空穴对的分离。

关键词: 制氢, 催化, 光化学, 异质结, 硫化镉, 硫化镍, 纳米管, 可见光催化, g-C₃N₄

CLC Number:

O 643.36

Kelong CHEN, Jianhua HUANG. g-C₃N₄-CdS-NiS₂ composite nanotube: synthesis and its photocatalytic activity for H₂ generation under visible light[J]. CIESC Journal, 2020, 71(1): 397-408.

陈克龙, 黄建花. g-C₃N₄-CdS-NiS₂复合纳米管的制备及可见光催化分解水制氢[J]. 化工学报, 2020, 71(1): 397-408.

Figures/Tables 15

Fig.1 Schematic diagram of synthesis of g-C3N4-CdS-NiS2 ternary composite

Fig.2 XRD patterns of as-prepared CdS, g-C3N4, g-C3N4-0.1CdS, g-C3N4-NiS2 and g-C3N4-xCdS-NiS2 composites

Fig.3 SEM images of g-C3N4 (a), CdS (b) and g-C3N4-0.1CdS-NiS2 (c); EDS (d) and elemental mapping (e) image of g-C3N4-0.1CdS-NiS2

Fig.4 TEM (a) and HR-TEM (b) images of g-C3N4-0.1CdS-NiS2

Fig.5 XPS spectra of g-C3N4-0.1CdS-NiS2 composite: survey (a); C 1s (b); N 1s (c); Cd 3d (d); Ni 2p (e); and S 2p (f)

Fig.6 N2 adsorption-desorption isotherms of g-C3N4, g-C3N4-0.1CdS and g-C3N4-0.1CdS-NiS2 (inset: distribution of pore size)

Table 1 Pore structure parameters of g-C3N4, g-C3N4-0.1CdS and g-C3N4-0.1CdS-NiS2

光催化剂	S_BET/(m²·g^-1)	平均孔径/nm	孔体积/(cm³·g^-1)
g-C₃N₄	77.9	19.5	0.397
g-C₃N₄-0.1CdS	73.8	18.8	0.368
g-C₃N₄-0.1CdS-NiS₂	47.1	16.8	0.247

Fig.7 UV-vis DRS of g-C3N4, CdS, NiS2, g-C3N4-0.1CdS, g-C3N4-NiS2 and g-C3N4-0.1CdS-NiS2 (a); Tauc plots of (αhν)2-hν for g-C3N4 and CdS (b)

Fig.8 Time course (a) and average rate (b) of H2 evolution over various photocatalysts

Table 2 Comparison of H2 production rate between g-C3N4-0.1CdS-NiS2 and some reported composite photocatalysts

光催化剂	助催化剂	氙灯功率，波长	催化剂用量/mg	性能/(μmol·h^-1)	稳定性	Ref.
g-C₃N₄纳米管/CdS	NiS₂	300 W，λ>420 nm	50	50.9	25 h/100%	this work
CdS 纳米棒/g-C₃N₄ 纳米片	NiS	300W，λ>420 nm	50	128	12 h/80%	[20]
CdS 纳米棒/g-C₃N₄ 纳米片	CoP	300 W，λ>400 nm	5	118	20 h/100%	[19]
块体g-C₃N₄/CdS量子点	Pt	300 W，λ>400 nm	100	17.3	30 h/100%	[23]
CdS/g-C₃N₄	CuS	350 W，λ>400 nm	50	57.6	－	[24]
g-C₃N₄纳米片/CdS量子点	WS₂	300 W，λ>420 nm	10	11.7	20 h/90%	[35]
g-C₃N₄纳米片/炭黑	NiS	300 W，λ>420 nm	50	18.3	12 h/90%	[25]
CdS/碳量子点	NiS	350 W，λ>420 nm	100	144.5	15 h/100%	[44]

Fig.9 Cyclic photocatalytic H2 evolution over g-C3N4-0.1CdS-NiS2 (a), XRD patterns (b) and SEM images (c, d) of g-C3N4-0.1CdS-NiS2 before and after cyclic H2 generation

Fig.10 PL spectra of g-C3N4, g-C3N4-0.1CdS, g-C3N4-NiS2 and g-C3N4-0.1CdS-NiS2

Fig.11 Transient photocurrent response (a) and EIS Nyquist plot (b) of pure g-C3N4, g-C3N4-0.1CdS, g-C3N4-NiS2 and g-C3N4-0.1CdS-NiS2

Fig.12 Mott-Schottky plot for g-C3N4 (a) and CdS (b) (inset: energy diagram of CB and VB levels)

Fig.13 Proposed mechanism of H2 evolution over g-C3N4-CdS-NiS2 under visible light irradiation

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g-C₃N₄-CdS-NiS₂ composite nanotube: synthesis and its photocatalytic activity for H₂ generation under visible light

g-C₃N₄-CdS-NiS₂复合纳米管的制备及可见光催化分解水制氢

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