煤矸石/BiVO<sub>4</sub>复合光催化剂的制备及其对黄药废水的降解

唐双; 张雪乔; 蒋莉萍; 钟晓娟; 肖利; 魏于凡

doi:10.13801/j.cnki.fhclxb.20230505.001

煤矸石/BiVO₄复合光催化剂的制备及其对黄药废水的降解

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: TB33;TQ426;O643.3;X703
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出版历程
- 收稿日期: 2023-02-01
- 修回日期: 2023-04-20
- 录用日期: 2023-04-22
- 网络出版日期: 2023-05-05
- 刊出日期: 2023-11-30

Preparation of coal gangue/BiVO₄ composite photocatalyst and its degradation of xanthate wastewater

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: 选矿废水中的黄药会严重危害环境，钒酸铋能在可见光条件下实现黄药的降解，但其严重的电子-空穴复合影响其实用性，鉴于煤矸石丰富的孔隙结构及成分组成，本文采用水热法合成了煤矸石负载型光催化剂(CG/BiVO₄)，运用XRD、FTIR、SEM、UV-Vis DRS、PL等手段对催化剂进行表征，以黄药为目标污染物，在可见光作用下考察黄药的光催化降解性能及煤矸石改性钒酸铋的作用机制。结果表明，与纯BiVO₄相比，负载型CG/BiVO₄的光催化性能显著提高，在煤矸石负载量20wt%，pH=7、催化剂投加量为1.5 g/L、黄药初始浓度C₀=10 mg/L的条件下，CG/BiVO₄在540 min时对黄药的降解率达到最大，为93%，黄药的光降解过程符合一级动力学模型，处理后化学需氧量浓度C_COD为11.47 mg/L，符合排放标准要求。响应面分析得到的最优反应条件下的预测值与实际降解率仅相差0.96%，可见该模型可较好地预测20%-CG/BiVO₄对黄药废水的降解率。结合各项表征分析可知，CG的负载可显著增加催化剂的比表面积，提高其对可见光的响应，改善光催化体系中电子和空穴的分离效率的同时降低光生电子-空穴对复合几率，这是复合光催化剂性能提高的重要原因；机制分析得知，黄药光降解的主要自由基为h⁺，•O₂⁻ 和•OH次之，黄药中的烷基、C=S在自由基作用下首先发生断裂，形成中间产物过黄药(ROCSSO⁻)，随后矿化生成SO₄²⁻等小分子，光反应7 h，S的转化率与黄药降解率接近，且循环5次，降解率不低于90%，可见该催化剂具有较好的光催化性能，这为煤矸石在光催化领域的资源化利用奠定了理论基础。
- 煤矸石 /
- BiVO₄ /
- 光催化 /
- 黄药 /
- 可见光 /
- 降解 /
- 废水处理
Abstract: Xanthate in mineral processing wastewater can do serious harm to environment. Bismuth vanadate can degrade xanthate under visible light, but its serious electron-hole complex affects its practicability, in view of the abundant pore structure and composition of coal gangue, the coal gangue supported photocatalyst (CG/BiVO₄) was synthesized by hydrothermal method. The catalysts were characterized by XRD, FTIR, SEM, UV-Vis DRS, PL, the photocatalytic degradation of xanthate and the mechanism of coal gangue modified bismuth vanadate were investigated under visible light. The results showed that the photocatalytic activity of the supported CG/BiVO₄ is significantly higher than that of the pure BiVO₄. Under the conditions of 20wt% coal gangue loading, pH=7, catalyst dosage is 1.5 g/L, initial concentration of xanthate C₀=10 mg/L, the degradation rate of xanthate over CG/BiVO₄ reached the maximum at 540 min, which was 93% . The photodegradation process of xanthate complied with the first-order kinetic model. After treatment, the concentration of chemical oxygen demand C_COD was 11.47 mg/L, which met the emission standard. The predicted degradation rate of 20%-CG/BiVO₄ was only 0.96% different from the actual degradation rate, which indicated that the model could predict the degradation rate of 20%-CG/BiVO₄. The results show that the loading of CG can significantly increase the specific surface area of the catalyst, improve its response to visible light, increase the separation efficiency of electrons and holes in the photocatalytic system, and decrease the recombination probability of photogenerated electrons and holes, this is an important reason for the improvement of the performance of the composite photocatalyst, the mechanism analysis showed that h⁺ was the main free radical in xanthate photodegradation, while •O₂ ⁻ and •OH were secondary, under the action of free radical, the alkyl group and C=S in the xanthate were firstly broken, and formed the intermediate product, peroxy xanthate (ROCSSO⁻) , then mineralized to form small molecules such as SO₄²⁻. After 7 h of photoreaction, the conversion of Sulfur was close to the degradation rate of xanthate, and the degradation rate was not less than 90% after 5 cycles, it can be seen that the catalyst has good photocatalytic performance, which lays a theoretical foundation for the resource utilization of coal gangue in the photocatalytic field.
- coal gangue /
- BiVO₄ /
- photocatalysis /
- xanthate /
- visible light /
- degradation /
- wastewater

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图 1 BiVO₄与CG/BiVO₄的XRD图谱

Figure 1. XRD patterns of BiVO₄ and CG/BiVO₄

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图 2 BiVO₄与CG/BiVO₄的FTIR图谱

Figure 2. FTIR spectra of BiVO₄ and CG/BiVO₄

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图 3 BiVO₄(a)、10%-CG/BiVO₄(b)、20%-CG/BiVO₄ (c)、30%-CG/BiVO₄(d) 材料的SEM图像

Figure 3. SEM images of BiVO₄ (a), 10%-CG/BiVO₄(b), 20%-CG/BiVO₄ (c), 30%-CG/BiVO₄ (d) composite

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图 4 ((a)~(c)) 20%-CG/BiVO₄不同放大倍率的SEM图像；(d) 20%-CG/BiVO₄的EDS能谱图

Figure 4. ((a)-(c)) SEM images of 20%-CG/BiVO₄ at different magnification; (d) EDS mapping of 20%-CG/BiVO₄

d—Particle size

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图 5 (a) BiVO₄与CG/BiVO₄的UV-Vis吸收光谱图；(b) 带隙计算图

Figure 5. (a) UV-Vis absorption spectra of BiVO₄ and CG/BiVO₄; (b) Calculation diagram of band gaps

α—Absorptivity index; h—Planck constant; v—Frequency

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图 6 BiVO₄与CG/BiVO₄的PL图谱

Figure 6. PL spectra of BiVO₄ and CG/BiVO₄

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图 7 (a) BiVO₄与CG/BiVO₄的电流-时间(I-t)曲线；(b) BiVO₄与CG/BiVO₄的EIS图

Figure 7. (a) Photocurrent-time (I-t) curves of BiVO₄ and CG/BiVO₄; (b) EIS diagram of BiVO₄ and CG/BiVO₄

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图 8 (a) CG、BiVO₄与CG/BiVO₄对黄药的吸附平衡图；(b) CG、BiVO₄与CG/BiVO₄对黄药的降解效果图；(c) 一级动力学模型

Figure 8. (a) Adsorption equilibrium diagram of CG, BiVO₄ and CG/BiVO₄ composite on xanthate; (b) Degradation effect of CG, BiVO₄ and CG/BiVO₄ composite on xanthate; (c) The first-order kinetic model

k—First-order kinetics constant; C₀—Initial concentration of xanthate solution (25 mg/L); C—Xanthate concentration in solution

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图 9 20%-CG/BiVO₄对化学需氧量(COD)的降解曲线

Figure 9. Chemical oxygen demand (COD) degradation curve of 20%-CG/BiVO₄

C_COD—Concentration of COD

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图 10 (a) pH对黄药的降解影响图；(b) 催化剂投加量对黄药的降解效果影响图；(c) 初始浓度对黄药的降解效果影响图

Figure 10. (a) pH effect diagram on degradation of xanthate; (b) Influence of catalyst dosage on the degradation of xanthate; (c) Effect of initial concentration on the degradation of xanthate

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图 11 (a) 因素A和B的响应面；(b) 因素A和C的响应面；(c) 因素B和C的响应面

Figure 11. (a) Response surface of factors A and B; (b) Contour and response surface of factors A and C; (c) Contour and response surface of factors B and C

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图 12 20%-CG/BiVO₄的循环反应图

Figure 12. Cyclic reaction diagram of 20%-CG/BiVO₄

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图 13 黄药的紫外全谱扫描图

Figure 13. UV full spectra scan of xanthate

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图 14 光反应过程中黄药溶液的FTIR图谱

Figure 14. FTIR spectra of xanthate solution in the process of photoreaction

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图 15 反应过程中黄药、SO₄²⁻浓度与S转化率的变化规律

Figure 15. Change rule of xanthate, SO₄²⁻ concentration and S conversion rate during the reaction

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图 16 自由基猝灭剂对CG/BiVO₄降解黄药的影响

Figure 16. Effect of free radical quenching agent on degradation of xanthate by CG/BiVO₄

IPA—Isopropanol; BQ—Benzoquinone

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图 17 CG/BiVO₄对黄药的光降解机制示意图

Figure 17. Schematic diagram of photodegradation mechanism of CG/BiVO₄ on xanthate

CB—Conduction band; VB—Valence band

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表 1 BiVO₄与煤矸石(CG)/BiVO₄的命名与比表面积

Table 1 Naming and specific surface area of BiVO₄ and coal gangue (CG)/BiVO₄

Sample	Specific surface area/(m²∙g⁻¹)	Mass fraction of CG/wt%
BiVO₄	2.5	—
5%-CG/BiVO₄	7.5	5
10%-CG/BiVO₄	8.0	10
20%-CG/BiVO₄	8.2	20
30%-CG/BiVO₄	8.7	30

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表 2 影响CG/BiVO₄光降解黄药的因素及水平

Table 2 Factors and levels affecting CG/BiVO₄ photodegradation of xanthate

Factor	Lever
Factor	−1	0	+1
pH	7	9	11
Dosage of catalyst/(g∙L⁻¹)	3	3.5	4
C₀/(mg∙L⁻¹)	10	25	50
Note: C₀—Xanthate initial concentration.

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表 3 优化CG/BiVO₄光降解黄药实验中回归模型的方差分析1

Table 3 Variance analysis of regression model 1 in optimizing CG/BiVO₄ photodegradation of xanthate

Source	SS	DF	Mean square	F value	p value prob>F	Coefficient
Model	118.69	9	13.19	49.93	<0.0001		Significant
A	43.88	1	43.88	166.11	<0.0001	−2.38
B	0.26	1	0.26	1.00	0.3505	−0.18
C	32.36	1	32.36	122.52	<0.0001	−2.01
AB	0.56	1	0.56	2.13	0.1878	0.37
AC	14.63	1	14.63	55.37	0.0001	1.88
BC	0.36	1	0.36	1.35	0.2830	0.29
A²	12.23	1	12.23	46.30	0.0003	1.70
B²	2.77	1	2.77	10.50	0.0142	0.81
C²	1.19	1	1.19	4.49	0.0718	0.58
Residual	1.85	7	0.26
Lack of fit	1.30	3	0.43	3.19	0.1460		Not significant
Pure error	0.55	4	0.14
Cor total	120.54	16
Notes: A—Initial pH of the reaction; B—Catalyst dosage; C—Initial concentration of xanthate; SS—Sum of squares; DF—Degree of freedom.

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表 4 优化CG/BiVO₄光降解黄药实验中回归模型的方差分析2

Table 4 Variance analysis of regression model 2 in optimizing CG/BiVO₄ photodegradation of xanthate

Project	Value	Project	Value
Std.Dev	0.51	R²	0.9847
Mean	87.49	Adj R-Squared	0.9649
CV/%	0.59	Pred R-Squared	0.8166
PRESS	22.10	Adeq precisior	23.555
Notes: Std.Dev—Standard deviation; CV—Coefficient of variation; PRESS—Predicted residual error sum of square; R²—Coefficient of determination; Adj—Adjusted multiple correlation cofficient; Pred—Predictive correlation coefficient; Adeq—Adeq precision.

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表 5 CG/BiVO₄光降解黄药过程中的SO₄²⁻浓度与S转化率

Table 5 SO₄²⁻ concentration and sulfur conversion in photodegradation of xanthate by CG/BiVO₄

Light time/h	Concentration of SO₄²⁻/(mg·L⁻¹)	Conversion of sulfur/%
1	12.86	25.72
2	22.25	44.50
3	27.48	54.96
4	28.75	57.50
5	31.29	62.58
6	38.24	76.48
7	45.34	90.68

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期刊类型引用(4)

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3.	何占伟，何帅，王贵帅，李世豪，陈广玉，高忙忙，李会标. “双碳”战略下我国煤矸石的综合利用技术研究进展. 矿产保护与利用. 2024(06): 1-14 . 百度学术
4.	原新宇，刘树龙，余青龙，张敏哲，王贻明，许宏图，苏凤波，李敏. 煤矸石基胶结充填体力学性能及微观结构演化研究. 现代矿业. 2023(12): 207-212 . 百度学术

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长摘要

目的
选矿废水中的黄药会严重危害环境，钒酸铋能在可见光条件下实现黄药的降解，但其严重的电子-空穴复合影响其实用性，鉴于煤矸石丰富的孔隙结构及成分组成，本文将煤矸石负载至钒酸铋，制成一种新型光催化剂，考察其对黄药的光催化降解作用，并分析煤矸石改性钒酸铋的作用机理。
方法
①采用水热法制备煤矸石负载型光催化剂(CG/BiVO)，运用X射线衍射(XRD)、傅里叶变换红外(FTIR)、扫描电子显微镜(SEM)表征手段分析CG/BiVO的微观形貌和化学组成，通过紫外-可见漫反射(UV-Vis DRS)、光致发光光谱(PL)、电化学表征手段研究煤矸石的负载能够提高光催化剂活性的原因。②以黄药为目标污染物，在可见光作用下对CG/BiVO进行光催化活性评价，通过单因素实验分别考察pH值、催化剂投加量和黄药初始浓度对光催化降解黄药的影响。③分析水样在不同反应时间段的紫外全谱扫描和红外光谱，判断黄药降解过程中，中间产物的生成与变化，通过荧光光谱以及离子色谱分析探索分析了光催化降解黄药的最终产物，最后通过自由基猝灭实验考察光催化剂在反应体系中的主要活性物质，分析总结黄药的降解机理。
结果
①与纯BiVO相比，负载型CG/BiVO的光催化性能显著提高，其中煤矸石的最佳负载量为20%。在煤矸石负载量20%，pH=7、催化剂投加量=1.5 g/L、黄药初始浓度=10 mg/L的条件下，CG/BiVO在540 min时对黄药的降解率达到最大，为93%，是纯BiVO的2.0倍。②在20%-CG/BiVO作用下，黄药降解率随pH值的升高而降低，但由于黄药化学性质不稳定，在酸性条件下易分解，此时黄药的降解不完全是由光催化剂作用引起的；黄药降解率随催化剂投加量的增加而增加，这是因为催化剂投加量越多，光催化反应的活性位点就越多；黄药降解率随初始浓度的增加而逐渐降低，主要是因为催化剂的有效吸附位是一定的，当黄药浓度过高，会延长反应时间。黄药的光降解过程符合一级动力学模型，处理后为11.47 mg/L，符合排放标准要求。③利用响应面分析得到的最优反应条件，pH= 7.0、=3.8 g/L、=10.1 mg/L时，预测黄药降解率达到最大，为94.14%，该预测值与实际降解率仅相差0.96%，可见该模型可较好地预测20%-CG/BiVO对黄药废水的降解率。
结论
①结合各项表征分析可知，CG的负载可显著增加催化剂的比表面积，提高其对可见光的响应，改善光催化体系中电子和空穴的分离效率的同时降低光生电子-空穴对复合机率，这是复合光催化剂性能提高的重要原因。②通过机理分析得知，黄药光降解的主要自由基为h，•O 和•OH次之，黄药中的烷基、C═S在自由基作用下首先发生断裂，形成中间产物过黄药(ROCSSO)，随后矿化生成SO 等小分子，光反应7 h，S的转化率与黄药降解率接近，且循环5次，降解率不低于90%，可见该催化剂不仅具有较好的光催化性能，还具有较好的稳定性，这为煤矸石在光催化领域的资源化利用奠定了理论基础。

创新点

煤矸石是采煤和洗煤过程中排放的固体废物，也是一类具有附加价值的潜在资源。本文对天然煤矸石进行热改性，后通过水热合成法制成煤矸石/BiVO₄负载型光催化剂。适量煤矸石的负载可增大BiVO₄的比表面积，提高其对可见光的响应，同时还可明显改善光生电子-空穴的分离效率，降低光生电子-空穴对的复合机率，延长电子空穴对的寿命，进而显著提高BiVO₄的光催化性能。在黄药废水的降解实验中，促使黄药光降解效率显著提高；在可见光作用下，黄药可光催化降解为无机小分子物质，实现了“以废治废”，达到社会、经济、环境三效合一的效果，具有深远的应用价值。
(a)CG、BiVO₄与CG/BiVO₄对黄药的光催化剂降解曲线和(b)光催化降解机制示意图