硫化物负载ZnO/ZnAl2O4复合空心球及其光催化还原CO2

doi:10.15541/jim20150567

摘要/Abstract

摘要：

采用一步水热法制备了ZnO/ZnAl₂O₄纳米复合物, 通过浸渍法负载CuS、CdS和Bi₂S₃对其进行修饰, 并在模拟太阳光照射下研究负载样品的光催化活性。用XRD、SEM、TEM、BET和FL等技术对所得样品进行表征, 以NaOH 和Na₂SO₃作为光催化还原二氧化碳过程的牺牲剂, 考察了硫化物种类及其负载量对ZnO/ZnAl₂O₄光催化还原活性的影响。结果表明, 负载CuS和CdS均可提高ZnO/ZnAl₂O₄光催化还原活性, 而负载Bi₂S₃却有所降低。当CuS负载量为1wt%时, 样品光催化还原活性最佳, 反应6 h后所得还原产物甲醇的生成量为8.21 mmol/g_cat, 在相同条件下较原样提高了约3.2倍。对CuS/ZnO/ZnAl₂O₄的光催化机理进行了初步探讨。

关键词: ZnO/ZnAl2O4, 硫化物, 光催化还原CO2

Abstract:

ZnO/ZnAl₂O₄ nanocomposites were successfully synthetized by a facile one-pot hydrothermal process. CuS, CdS and Bi₂S₃ were loaded on the ZnO/ZnAl₂O₄by an impregnation process to investigate their photocatalytic activities under simulated sunlight irradiation. The as-prepared samples were characterized by XRD, SEM, TEM, BET and FL techniques. Meanwhile, photocatalytic reduction of CO₂ from water over the samples was explored using NaOH and Na₂SO₃ as sacrificial reagents. The effects of the type and the amount of sulfides on photocatalytic reduction efficiency were investigated. The results indicated that Bi₂S₃-loading lowered down the photocatalytic activity of ZnO/ZnAl₂O₄, while CuS or CdS loading enhanced the photocatalytic activity. After ZnO/ZnAl₂O₄ loaded with 1wt% CuS, the maximum yield of 8.21 mmol/g_cat methanol within 6 h was obtained, which increased by up to 3.2 times as compared to ZnO/ZnAl₂O₄under the same conditions. The photocatalytic mechanism of the as-prepared CuS/ZnO/ZnAl₂O₄were preliminarily discussed.

Key words: ZnO/ZnAl2O4, sulfide, photocatalytic reduction of CO2

中图分类号:

O614

张丽, 张秀秀, 戴超华1, 欧阳杰, 阎建辉. 硫化物负载ZnO/ZnAl₂O₄复合空心球及其光催化还原CO₂[J]. 无机材料学报, 2016, 31(7): 731-738.

ZHANG Li, ZHANG Xiu-Xiu, DAI Chao-Hua, OUYANG Jie, YAN Jian-Hui. Photocatalytic Reduction of CO₂ over Sulfied-Loaded ZnO/ZnAl₂O₄ Composite Hollow Sphere[J]. Journal of Inorganic Materials, 2016, 31(7): 731-738.

图/表 11

图1 不同硫化物负载所得样品的XRD图谱

Fig. 1 XRD patterns of samples loaded with different sulfides (a) ZnO/ZnAl2O4; (b) ZnO/ZnAl2O4/CdS; (c) ZnO/ZnAl2O4/CuS; (d) ZnO/ZnAl2O4/Bi2S3

图2 负载不同量CuS所得样品的XRD图谱

Fig. 2 XRD patterns of samples loaded with different amount of CuS (a) ZnO/ZnAl2O4; (b) CuS (0.5wt%) /ZnO/ZnAl2O4; (c) CuS (1wt%)/ ZnO/ZnAl2O4; (d) CuS (1.5wt%)/ ZnO/ZnAl2O4

图3 ZnO/ZnAl2O4和负载1wt%CuS样品的SEM照片

Fig. 3 SEM images of (a) ZnO/ZnAl2O4 and (b) CuS (1wt%)/ ZnO/ZnAl2O4

图4 ZnO/ZnAl2O4负载1wt%CuS样品的TEM(a)和HRTEM (b)照片及其EDS图谱(c)

Fig. 4 TEM (a), HRTEM (b) images and EDS pattern (c) of CuS (1wt%)/ZnO/ZnAl2O4

表1 负载不同硫化物所得样品的比表面和孔结构参数

Table 1 BET and pore-structure data of samples loaded with different sulfides

Samples	S_BET/(m²·g^-1)	BJH desorption average pore width/nm	Pore volume /(cm³·g^-1)
1wt% CdS loaded 1wt% CuS loaded 1wt% Bi₂S₃ loaded ZnO/ZnAl₂O₄	206.65 239.40 203.69 227.14	4.40 4.24 4.37 4.20	0.28 0.30 0.27 0.29

表2 负载不同量CuS所得样品的比表面和孔结构参数

Table 2 BET and pore-structure data of samples loaded with different amounts of CuS

Amount of CuS /wt%	S_BET/(m²·g^-1)	BJH desorption average pore width/nm	Pore volume /(cm³·g^-1)
0 0.5 1.0 1.5	227.14 221.16 239.40 211.71	4.20 4.36 4.24 4.30	0.29 0.28 0.30 0.27

图5 不同量CuS负载所得样品的N2吸附、脱附及孔径分布曲线

Fig. 5 Nitrogen adsorption-desorption isotherms and pore size distribution curves of samples loaded with different amounts of CuS (a) ZnO/ZnAl2O4; (b) CuS (0.5wt%) /ZnO/ZnAl2O4; (c) CuS (1wt%)/ ZnO/ZnAl2O4; (d) CuS (1.5wt%)/ ZnO/ZnAl2O4

图6 样品的荧光分析光谱图

Fig. 6 Fluorescence spectra of samples (a) ZnO/ZnAl2O4; (b) Bi2S3 (1wt%)/ZnO/ZnAl2O4; (c) CdS (1wt%)/ ZnO/ZnAl2O4; (d) CuS (1wt%)/ZnO/ZnAl2O4

图7 不同硫化物负载对甲醇生成量的影响

Fig. 7 Influence of different sulfides loading on methanol production

图8 不同CuS负载量对甲醇生成量的影响

Fig. 8 Effects of different loading amount of CuS on methanol production

图9 光催化还原CO2机理示意图

Fig. 9 Illustration on mechanism of photocatalytic reduction of CO2 (a) Schematic illustration of photo-generated charge-transfer process; (b) Band energy diagram of CuS/ZnO/ZnAl2O4

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硫化物负载ZnO/ZnAl₂O₄复合空心球及其光催化还原CO₂

Photocatalytic Reduction of CO₂ over Sulfied-Loaded ZnO/ZnAl₂O₄ Composite Hollow Sphere

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