Cr(VI)对黄药光降解性能影响及其协同作用机制

张雪乔; 钟晓娟; 唐双; 蒋莉萍; 魏于凡; 肖利

doi:10.13801/j.cnki.fhclxb.20230814.001

Cr(VI)对黄药光降解性能影响及其协同作用机制

doi: 10.13801/j.cnki.fhclxb.20230814.001

成都信息工程大学　资源环境学院，成都 610225

基金项目: 四川省科技计划项目(2021YFG0267)；煤炭精细勘探与智能开发全国重点实验室开放基金资助项目(SKLCRSM21KF001)

详细信息

通讯作者:
张雪乔，博士，副教授，硕士生导师，研究方向为环境材料与水污染防治　E-mail: zxq@cuit.edu.cn

中图分类号: TQ426.1；TB332
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出版历程
- 收稿日期: 2023-05-25
- 修回日期: 2023-07-12
- 录用日期: 2023-07-29
- 网络出版日期: 2023-08-14
- 刊出日期: 2024-03-01

Effect of Cr(VI) on photocatalytic of xanthate and synergistic mechanism

School of Resources and Environment, Chengdu University of Information Technology, Chengdu 610225, China

Funds: Science and Technology Project of Sichuan Province (2021YFG0267); Project Supported by Open Fund of National Key Laboratory of Coal Fine Exploration and Intelligent Development (SKLCRSM21KF001)

摘要

摘要: 为进一步研究黄药和Cr(VI)共存体系中，Cr(VI)对黄药光降解性能的影响以及两者协同作用机制，本文以煤矸石/钒酸铋(CG/BiVO₄)为光催化剂，黄药和Cr(VI)共存体系为研究对象，通过光催化活性测试以及紫外光谱、红外光谱、离子色谱和猝灭实验等技术手段，深入研究黄药光氧化和Cr(VI)光还原过程以及两者之间的协同作用机制。结果表明，在黄药和Cr(VI)的共存体系中，两者之间存在显著的协同效应，当黄药浓度为25 mg/L、pH=7、催化剂投加量为1.5 g/L、Cr(VI)浓度为2.0 mg/L、反应480 min时，CG/BiVO₄对黄药和Cr(VI)的去除率均达最佳，分别是98.81%和88.80%；基于响应面法预测得到共存体系中黄药的降解率为94.79%，与实际降解率相差 3.82%，该响应面模型可预测共存体系下黄药的降解过程；共存体系中黄药的C=S振动优先发生变化，其次为C—O—C、S—H、S—C—S和丁基，光反应3 h形成中间产物过黄药(ROCSSO⁻)，7 h的转化率最高为97.94%；协同作用机制研究发现，Cr(VI)光还原会迅速捕捉光生e⁻，黄药光降解会大量消耗h⁺，两者在光反应过程中不断消耗光生电子和空穴，一方面可抑制光生电子和空穴对的复合，延长光生电子空穴对的寿命；另一方面光生电子-空穴对的快速消耗，加速了光能向化学能的转化，提高了可见光利用率的同时生成大量光生电子空穴对，进而促使黄药和Cr(VI)的协同去除。
- Cr (VI) /
- 黄药 /
- 光催化 /
- 协同机制 /
- 降解 /
- 去除
Abstract: In order to further study the effect of Cr(VI) on the photodegradation of xanthate and its synergistic mechanism in the co-existing system of xanthate and Cr(VI), the photocatalyst of coal gangue/bismuth vanadate (CG/BiVO₄) was used, xanthate and Cr(VI) coexisting systems were studied by photocatalytic activity test, UV, FTIR, ion chromatography and quenching experiments, the photooxidation of xanthate and photoreduction of Cr(VI) and their synergistic mechanism were explored. The results show that there is a significant synergistic effect between the photo-oxidation of xanthate and photo-reduction of Cr(VI) in the co-existence system of xanthate and Cr(VI). Then, at the xanthate of 25 mg/L and the pH value of 7, with the dosage of catalyst being 1. 5 g/L, at the Cr(VI) of 2.0 mg/L, the removal rate of xanthate and Cr(VI) by CG/BiVO₄ are the best during a period of 480 min, reaching 98.81% and 88.80% respectively. The predicted degradation rate of xanthate is 94.79% by response surface methodology, lower 3.82% than the actual degradation rate, which indicates that the model can be used to predict the degradation of xanthate in the co-existing system. In the co-existing system, the vibration of C=S is changed first, followed by C—O—C, S—H, S—C—S, butyl, and the intermediate product peroxy xanthate (ROCSSO⁻) is formed after the visible light illumination 3 h , the highest conversion of sulfur is reached 97.94% after the visible light illumination 7 h. The synergistic mechanism analysis shows that the photogenerated e⁻ are rapidly captured in the photo-reduction of Cr(VI) and photogenerated h⁺ are consumed by xanthate photodegradation. The photogenic electron and hole pairs are consumed, on the one hand, due to the inhibition of photogenerated electrons and holes recombination, the lifetime of photogenerated electron and hole pairs are prolonged, on the other hand, the rapid consumption of photogenerated electron-hole pairs accelerates the conversion of light energy to chemical energy, generating a large number of photogenerated electron-hole pairs, therefor promoting the synergistic removal of xanthate and Cr(VI) .
- Cr(VI) /
- xanthatet /
- photocatalysis /
- synergistic mechanism /
- degradation /
- removal

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图 1 Cr(VI)对煤矸石/钒酸铋(CG/BiVO₄)光降解黄药反应进程的影响

Figure 1. Effect of Cr(VI) on photodegradation of xanthate by coal gangue/bismuth vanadate (CG/BiVO₄)

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图 2 CG/BiVO₄对Cr(VI)的还原曲线图

Figure 2. Cr(VI) reduction curves of CG/BiVO₄

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图 3 黄药降解率各因素的响应面：(a) A和B；(b) A和C；(c) A和D；(d) B和C；(e) B和D；(f) C和D

Figure 3. Response surface of factors for degradation rate of xanthate: (a) A and B; (b) A and C; (c) A and D; (d) B and C; (e) B and D; (f) C and D

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图 4 废水Ⅰ (a)、废水Ⅱ (b)的紫外全谱扫描图及在226 nm处的局部放大图

Figure 4. UV full spectra scan and local magnification at 226 nm of wastewater Ⅰ (a) and wastewater Ⅱ (b)

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图 5 体系Ⅰ的红外同步光谱图(a)和异步图(b)；体系Ⅱ的红外同步光谱图(c)和异步图(d)

Figure 5. Infrared synchronous spectra (a) and asynchronous spectra (b) of system Ⅰ; Infrared synchronous spectra (c) and asynchronous spectra (d) of system Ⅱ

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图 6 CG/BiVO₄在不同猝灭剂下对黄药的降解图(a)和对Cr(VI)的降解图(b)

Figure 6. Degradation diagrams of CG/BiVO₄ on xanthate (a) and Cr(VI) (b) under different quenching agents

C/C₀—Ratio of the concentration of Cr(VI) at different time to the initial concentration of Cr(VI); IPA—Isopropyl alchohol; BQ—Benzoquinone

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图 7 黄药降解率与S转化率的变化规律

Figure 7. Change rule of degradation rate of xanthate and sulfur conversion rate

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图 8 Cr(VI)和黄药共存体系中CG/BiVO₄对黄药的光降解机制示意图

Figure 8. Mechanism of photodegradation of xanthate by CG/BiVO₄ in the co-existence system of Cr(VI) and xanthate

CB—Conduction band; VB—Valence band

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表 1 影响CG/BiVO₄光降解黄药的因素及水平

Table 1. Factors and levels affecting CG/BiVO₄ photodegradation of xanthate

Factor	Lever
Factor	−1	0	+1
pH	7	9	11
m/(g·L^-1)	1	2	3
C₀/(mg·L⁻¹)	6	8	10
C_Cr/(mg·L⁻¹)	0.5	1.5	2.5
Notes: m—Catalyst dosage; C₀—Initial concentration of xanthate; C_Cr—Concentration of Cr(VI).

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表 2 共存体系中优化CG/BiVO₄光降解黄药实验回归模型的方差分析

Table 2. Variance analysis of regression model in optimizing CG/BiVO₄ photodegradation of xanthate in co-existing system

Source	SS	DF	Mean square	F value	P value prob>F
Model	22.73	14	1.62	236.55	<0.0001
A	9.36	1	9.36	1364.23	<0.0001
B	3.47	1	3.47	505.12	<0.0001
C	4.38	1	4.38	638.19	<0.0001
D	0.12	1	0.12	16.91	0.0011
AB	6.75	1	6.75	9.87	0.9527
AC	0	1	0	0	1.0000
AD	6.75	1	6.75	9.87	0.9527
BC	0	1	0	0	1.0000
BD	0	1	0	0	1.0000
CD	6.75	1	6.75	9.87	0.9527
A²	2.12	1	2.12	309.12	<0.0001
B²	2.12	1	2.12	309.03	<0.0001
C²	0.072	1	0.072	10.55	0.0058
D²	0.066	1	0.066	9.56	0.0080
Residual	0.096	14	18.63
Lack of fit	0.089	10	24.06	4.74	0.0736
Pure error	20.3	4	5.05
Cor total	22.83	28
Notes: A—Initial pH of the reaction; B—Catalyst dosage; C—Initial concentration of xanthate; D—Cr(VI) concentration; SS—Sum of squares; DF—Degree of freedom; F value—Ratio of the mean square to the residual term; P value prob—Influence degree value of each factor.

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