Synthesis and Photocatalytic Degradation of Cu1.94S-SnS Nano-heterojunction

doi:10.6023/A23030090

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (7): 725-734.DOI: 10.6023/A23030090 Previous Articles Next Articles

Article

Cu_1.94S-SnS纳米异质结的合成及其光催化降解研究

刘嘉文^a^,^b^,^c, 林玮璜^a^,^b^,^c, 王惟嘉^c^,^d, 郭学益^a^,^b^,^c^,^*(), 杨英^a^,^b^,^c^,^*()

a 中南大学冶金与环境学院长沙 410083
b 中南大学有色金属资源循环利用湖南省重点实验室长沙 410083
c 中南大学有色金属资源循环利用国家地方联合工程中心长沙 410083
d 海南医学院第二附属医院临床医学研究所海口 570311

投稿日期:2023-03-27 发布日期:2023-05-23
基金资助:
湖南省自然科学基金(2022JJ30757); 清远市创新创业科研团队项目(2018001); 广东省科技计划(2018B030323010); 国家自然科学基金(52262040); 海南省自然科学基金(821QN411)

Synthesis and Photocatalytic Degradation of Cu_1.94S-SnS Nano-heterojunction

Jiawen Liu^a^,^b^,^c, Weihuang Lin^a^,^b^,^c, Weijia Wang^c^,^d, Xueyi Guo^a^,^b^,^c(), Ying Yang^a^,^b^,^c()

a School of Metallurgy and Environment, Central South University, Changsha 410083
b Hunan Key Laboratory of Nonferrous Metal Resources Recycling, Central South University, Changsha 410083
c National & Regional Joint Engineering Research Center of Nonferrous Metal Resources Recycling, Changsha 410083
d Institute of Clinical Medicine (ICM), the Second Affiliated Hospital of Hainan Medical University, Haikou 570311

Received:2023-03-27 Published:2023-05-23
Contact: *E-mail: xyguo@csu.edu.cn; muyicaoyang@csu.edu.cn
Supported by:
Natural Science Foundation of Hunan Province(2022JJ30757); Qingyuan Innovation and Entrepreneurship Research Team Project(2018001); Science and Technology Program of Guangdong Province(2018B030323010); National Natural Science Foundation of China(52262040); Natural Science Foundation of Hainan Province, China(821QN411)

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Abstract

In this study, Cu_1.94S-SnS nano-heterostructures were synthesized using the methods of thermal injection-cation exchange to enhance the activity of photocatalytic degradation of hazardous dyes. First, we stirred and mixed octadecene, oleylamine and copper chloride under argon atmosphere and raised the temperature to 180 ℃ for 15 min. The precursor of Cu_1.94S was cooled to 140 ℃, and then tert-dodecanethiol (t-DDT) was added. This solution was rapidly raised to 180 ℃ for 30 min, and then cooled in ice water to obtain the product of Cu_1.94S. Similarly, tin chloride and oleylamine were mixed under argon atmosphere and raised to 160 ℃ for 30 min, then cooled to 80, 120 and 160 ℃, respectively. The Cu_1.94S and tri-n-octylphosphine suspensions were injected into the precursor solution to react for 30 min. The samples were characterized using various analytical techniques, including high-resolution transmission electron microscopy (HRTEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images, STEM energy-dispersive spectroscopy (STEM-EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS). At lower temperatures (80 and 120 ℃), sheet-like Cu_1.94S-SnS single-particle nano-heterojunctions were obtained with size of about 57 nm. In contrast, regular shaped heterojunctions could not be obtained at a high temperature (160 ℃). The Uv-visible near infrared spectrophotometer (UV-Vis-NIR) absorption spectra revealed that the synthesized Cu_1.94S-SnS nano-heterostructures exhibited higher light absorption in the visible range. Photocatalytic degradation of methylene blue and tetracycline was used to evaluate the photocatalytic performance of the products. The results showed that the heterostructure effectively improved the photocatalytic activity of the parent material. Specifically, the photodegradation rate of methylene blue (MB) increased from 56% (parent material Cu_1.94S) to 98% (Cu_1.94S-SnS nano-heterojunction), indicating a significant enhancement in photocatalytic activity. And the photodegradation rate of tetracycline (TC) was also increased by about 5 times. Overall, the synthesized Cu_1.94S-SnS heterostructures possessed superior photocatalytic activity, which could be attributed to the effective charge sep-aration and improved light absorption properties. This study provided a new approach to the design and fabrication of efficient photocatalytic materials for environmental remediation.

Key words: Cu_1.94S, SnS, nano-heterojunction, methylene blue, photocatalysis

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Jiawen Liu, Weihuang Lin, Weijia Wang, Xueyi Guo, Ying Yang. Synthesis and Photocatalytic Degradation of Cu_1.94S-SnS Nano-heterojunction[J]. Acta Chimica Sinica, 2023, 81(7): 725-734.

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Fig. & Tab. 13

Figure 1. X-ray diffraction patterns of Cu1.94S and nanoparticles of Sn2＋cation half-exchange at 80, 120 and 160 ℃

Figure 2. TEM images of (a1) Cu1.94S and products with semi-exchange at (b1) 80, (c1) 120, (d1) 160 ℃; HRTEM images of (a2) Cu1.94S and products with semi-exchange at (b2) 80, (c2) 120, (d2) 160 ℃; FFT mode of (a3) Cu1.94S and products with semi-exchange at (b3) 80, (c3) 120, (d3) 160 ℃ and grain size distribution of (a4) Cu1.94S and products with semi-exchange at (b4) 80, (c4) 120, (d4) 160 ℃

Figure 3. (a) Crystal structure of hexagonal dense stacked Cu1.94S; (b) anion alignment for (080) crystal plane of Cu1.94S; (c) crystal structure of orthogonal SnS and (d) anion alignment for (021) crystal plane of SnS

Figure 4. HAADF-STEM images, STEM-EDS images and EDS of products by partial cation exchange at (a) 80, (b) 120 and (c) 160 ℃

Figure 5. Diagram of Cu1.94S-SnS formed by partial exchange of cations at 80 and 120 ℃

Figure 6. (a) XPS survey spectra of Cu1.94S and products by partial exchange at different temperatures; (b~d) HR-XPS of Cu 2p, Sn 3d and S 2p

Figure 7. (a) UV-Vis-NIR absorption spectra and (b) TAUC of Cu1.94S and products with semi-exchange at 80, 120, 160 ℃

Figure 8. UV-Vis absorption spectra of aqueous solutions of different materials for the photocatalytic degradation of MB under irradiation with a xenon lamp (simulated sunlight) at (25±1) ℃. (a) 20 mg Cu1.94S-SnS catalyst and 2 mL of H2O2 at 120 ℃; (b) 20 mg Cu1.94S catalyst and 2 mL of H2O2; (c) 2 mL of H2O2 only; (d) 20 mg Cu1.94S-SnS catalyst and 2 mL of H2O2 at 80 ℃; (e) 20 mg SnS catalyst and 2 mL of H2O2 at 160 ℃; (f) 20 mg Cu1.94S catalyst without H2O2

Figure 9. (a) Plot of MB normalized concentration (from absorbance measurements at 664 nm) versus time in solution for the different catalysts under simulated sunlight at (25±1) ℃; (b) schematic diagram of the photogenerated charge transfer mechanism and photocatalytic mechanism of the Cu1.94S-SnS catalyst under xenon lamp (simulated sunlight) radiation

材料	χ	E_g/eV	E_CB/eV	E_VB/eV
Cu_1.94S	5.01	2.52	－0.76	1.76
SnS	5.17	1.44	－0.05	1.39

Table 1. Calculation of the CB and VB potentials of Cu1.94S and SnS

Figure 10. Under irradiation with a xenon lamp (simulated sunlight) at (25±1) ℃. (a) stability test of 120 ℃ Cu1.94S-SnS catalyst for photocatalytic degradation of MB; (b) degradation of TC over the prepared photocatalyst; (c) plot of TC-normalized concentration versus time in solutions with different catalysts; (d) recycle of 120 ℃ Cu1.94S-SnS catalyst for photocatalytic degradation of TC

Figure 11. EIS spectra of Cu1.94S, Cu1.94S-SnS and SnS catalysts

材料	光源	辐照时间/min		参考文献
Cu_1.94S-SnS	300 W氙灯(AM 1.5G)	60	98	当前工作
Cu掺杂ZnO/SnS	150 W氙灯(AM 1.5G)	120	97.2	[46]
ZTPG	紫外光(60 W, 365 nm)	90	98.1	[42]
Cu_2-_xS-DE复合物	500 W氙灯	40	99.1	[39]
Cu@CuS	300 W氙灯	200	90.6	[7]
UiO-66/g-C₃N₄	350 W氙灯	240	100	[47]

Table 2. Comparison of the photocatalytic efficiency of different materials for the degradation of MB

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Cu_1.94S-SnS纳米异质结的合成及其光催化降解研究

Synthesis and Photocatalytic Degradation of Cu_1.94S-SnS Nano-heterojunction

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Cu1.94S-SnS纳米异质结的合成及其光催化降解研究

Synthesis and Photocatalytic Degradation of Cu1.94S-SnS Nano-heterojunction

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Supporting Info.

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Abstract

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References 47

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Cu_1.94S-SnS纳米异质结的合成及其光催化降解研究

Synthesis and Photocatalytic Degradation of Cu_1.94S-SnS Nano-heterojunction