Article(id=1320099047122260540, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320099031116792469, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20240391, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1717516800000, receivedDateStr=2024-06-05, revisedDate=1718380800000, revisedDateStr=2024-06-15, acceptedDate=null, acceptedDateStr=null, onlineDate=1792665739087, onlineDateStr=2026-10-22, pubDate=1734624000000, pubDateStr=2024-12-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792665739087, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792665739087, creator=13701087609, updateTime=1792665739087, updator=13701087609, issue=Issue{id=1320099031116792469, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='12', pageStart='3663', pageEnd='3904', issueExtLink='null', onlineDate='null', pubDate='1734624000000', pubDateStr='2024-12-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792665735272, creator='13701087609', updateTime=1792666214857, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320101042704994698, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320099031116792469, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320101042704994699, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320099031116792469, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=3737, endPage=3747, ext={EN=ArticleExt(id=1320099047302615613, articleId=1320099047122260540, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Preparation and Photocatalytic Properties of ZnO/Ag2MoO4 Composites, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

With the increasing environmental protection and sustainable development, conventional water pollution treatment methods have some challenges in practical applications. Photocatalytic technology has potential advantages such as energy conservation and environmental protection, providing an effective and sustainable method for wastewater treatment. The design and synthesis of photocatalysts are crucial in photocatalytic reactions. Silver molybdate material has some advantages of controllable morphology, unique physicochemical properties, having potential application prospects. However, the narrow photoresponse range and the high recombination efficiency of photo generated charge carriers restrict its application in the field of photocatalysis. In this study, a ZnO/Ag2MoO4 composite photocatalyst was prepared by a hydrothermal method with ZnO. The purpose was to improve the photocatalytic activity of silver molybdate via constructing heterojunctions. The photocatalytic performance of different proportions of composite materials for the degradation of organic pollutants was investigated. In addition, the optical stability of the catalyst and the active free radicals involved in the reaction were also analyzed.

Methods

ZnO/Ag2MoO4 composite catalysts with different mass fractions of 10%, 50%, and 90% ZnO were synthesized by a hydrothermal method with ZnO, AgNO3, and Na2MoO4·2H2O, respectively.

The photocatalytic degradation of organic pollutants was carried out in a photocatalytic reactor. 50 mg of photocatalyst was dispersed in 50 mL of Rhodamine B (RhB) or meloxicam (MLX) solution in each experiment. Prior to photocatalytic reaction, the suspension was stirred in the darkness for 30 min to obtain the absorption-desorption equilibrium. Afterwards, the suspension was placed under a xenon lamp (300 W) for photocatalytic degradation. At each interval, RhB or MLX solution with catalyst was sampled and centrifuged to remove the solid catalyst. The concentration of RhB or MLX was determined by a UV-Vis spectrophotometer. The similar experimental steps were used for the cyclic experiments. After each cyclic experiment, the solid catalyst was separated and washed with water and ethanol to continue the next cyclic experiment.

To determine the main active species involved in the degradation of RhB, free radical capture experiments were conducted. The free radical capture experiment followed the same steps as the normal degradation experiment. Benzoquinone, ethanol, silver nitrate, and tert-butanol were added as a scavenger for superoxide radicals, holes, electrons, and hydroxyl radicals during the reaction.

Results and discussion

ZnO/Ag2MoO4 composite catalysts with different ratios were prepared by a hydrothermal method. The results indicate the effective preparation of ZnO/Ag2MoO4 without other impurity elements. Based on the XRD patterns, the sharp diffraction peaks of ZnO/Ag2MoO4 composites indicate a good crystallinity. The SEM images show that ZAM-7 is a block shaped structure with uneven size, and ZnO is deposited in a columnar form on the surface of ZnO/Ag2MoO4. The minimum size of ZAM-7 is approximately 100-200 nm. The specific surface areas of ZnO, ZnO/Ag2MoO4, and ZAM-7 are 4.5795 m2/g, 0.0921 m2/g, and 2.6339 m2/g, respectively. The specific surface area of ZAM-7 is 28 times greater than that of ZnO/Ag2MoO4, indicating that the composition of Ag2MoO4 and ZnO is beneficial for increasing the specific surface area of the catalyst, thus providing more active sites for photocatalytic reactions.

The photocatalytic performance of ZnO/Ag2MoO4 composite materials is investigated using RhB and MLX as simulated organic pollutants. After 90-min illumination, the removal rates of RhB by ZnO, Ag2MoO4, and ZAM-7 are 40.1%, 13.8%, and 89.6%, respectively. The rate constants of ZnO, Ag2MoO4, and ZAM-7 are 1.19×10-2 min-1, 0.22×10-2 min-1, and 3.60×10-2 min-1, respectively. The degradation of meloxicam is also carried out with ZAM-7. When the catalyst dosage is 50 mg, the MLX concentration is 100 mg/L, the degradation rate of MLX by the catalyst can reach 80.6% after 270 min visible light irradiation.

Conclusions

ZnO/Ag2MoO4 composite photocatalysts were prepared by a hydrothermal method. The minimum size of ZnO/Ag2MoO4 composite catalysts was 100-200 nm. ZnO was deposited in a prismatic shape on the surface of Ag2MoO4. ZnO/Ag2MoO4 composite catalyst exhibited a superior photocatalytic degradation activity for both organic dyes and drugs. Under the optimal reaction conditions, the degradation rate of RhB by the composite catalyst could reach 95.0%, and the degradation rate of the drug MLX could reach 80.6%. The maximum reaction rate constants for the degradation of RhB by composite catalysts were 3 times and 16 times greater than those of ZnO and Ag2MoO4, respectively. The improvement of photocatalytic activity after the composition of Ag2MoO4 and ZnO was attributed to the improvement of photogenerated carrier separation efficiency, the increase of visible light absorption intensity, the reduction of band gap width, and the increase of active sites. The cyclic experiment of the catalyst showed that ZnO/Ag2MoO4 composite catalyst had a good optical stability. The results could provide a useful reference for the development and design of photocatalysts for water pollution treatment.

, authors=Yuting YANG, Yingying ZHANG, Qingtong DONG, Quanliang CHEN, authorsList=Yuting YANG, Yingying ZHANG, Qingtong DONG, Quanliang CHEN, authorCompany=null, correspAuthors=Quanliang CHEN, authorNote=

YANG Yuting (2002-), female, Master candidate. E-mail:

, correspAuthorsNote=
CHEN Quanliang (1985-), male, Ph.D., Lecturer. E-mail:
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污水中的有机染料罗丹明B和非甾体类药物美洛昔康对生物体具有较大危害,采用光催化技术处理有机污染物具有节能环保等潜在优势。通过水热法制备了新型ZnO/Ag2MoO4复合光催化剂,并利用红外光谱、X射线粉末衍射、扫描电子显微镜、X射线光电子能谱等技术对催化剂的组成、结构和形貌进行表征。结果表明:ZnO/Ag2MoO4复合催化剂最小尺寸为100~200 nm,ZnO以棱柱状沉积在Ag2MoO4表面。ZnO/Ag2MoO4复合催化剂对有机染料和药物都具有良好的光催化降解活性。在最优反应条件下,复合催化剂对罗丹明B的降解率可达95.0%,对药物美洛昔康的降解率达80.6%。复合催化剂降解罗丹明B的最大反应速率常数分别是ZnO和Ag2MoO4速率常数的3倍和16倍。Ag2MoO4和ZnO复合后光催化活性的提高归因于复合后光生载流子分离效率的提高,可见光吸收强度的增加,带隙宽度的缩小和活性位点的增加。催化剂的循环实验表明ZnO/Ag2MoO4复合催化剂具有良好的光学稳定性。研究结果为水污染治理光催化剂的开发设计提供了有益的参考。

, authors=杨玉婷, 张莹莹, 董庆桐, 陈全亮, authorsList=杨玉婷, 张莹莹, 董庆桐, 陈全亮, authorCompany=null, correspAuthors=陈全亮, authorNote=

杨玉婷(2002—),女,硕士研究生。

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陈全亮(1985—),男,博士,讲师。
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ZnO/Ag2MoO4复合材料的制备及其光催化性能
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杨玉婷 , 张莹莹 , 董庆桐 , 陈全亮
硅酸盐学报 | 研究论文 2024,52(12): 3737-3747
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硅酸盐学报 |研究论文 2024 , 52 (12) : 3737 -3747
ZnO/Ag2MoO4复合材料的制备及其光催化性能
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杨玉婷 , 张莹莹, 董庆桐, 陈全亮
作者信息
  • 西南民族大学化学与环境学院,青藏高原污染控制化学与环境功能材料国家民委重点实验室,四川 成都 610041
通讯作者:
陈全亮(1985—),男,博士,讲师。
作者简介:

杨玉婷(2002—),女,硕士研究生。

Preparation and Photocatalytic Properties of ZnO/Ag2MoO4 Composites
Yuting YANG , Yingying ZHANG, Qingtong DONG, Quanliang CHEN
Affiliations
  • State Key Laboratory of Chemical and Environmental Functional Materials for Pollution Control on Qinghai-Tibet Platea, Southwest University for Nationalities, Chengdu, Sichuan 610041
  • Corresponding Author:
    CHEN Quanliang (1985-), male, Ph.D., Lecturer. E-mail:

    YANG Yuting (2002-), female, Master candidate. E-mail:

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240391
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污水中的有机染料罗丹明B和非甾体类药物美洛昔康对生物体具有较大危害,采用光催化技术处理有机污染物具有节能环保等潜在优势。通过水热法制备了新型ZnO/Ag2MoO4复合光催化剂,并利用红外光谱、X射线粉末衍射、扫描电子显微镜、X射线光电子能谱等技术对催化剂的组成、结构和形貌进行表征。结果表明:ZnO/Ag2MoO4复合催化剂最小尺寸为100~200 nm,ZnO以棱柱状沉积在Ag2MoO4表面。ZnO/Ag2MoO4复合催化剂对有机染料和药物都具有良好的光催化降解活性。在最优反应条件下,复合催化剂对罗丹明B的降解率可达95.0%,对药物美洛昔康的降解率达80.6%。复合催化剂降解罗丹明B的最大反应速率常数分别是ZnO和Ag2MoO4速率常数的3倍和16倍。Ag2MoO4和ZnO复合后光催化活性的提高归因于复合后光生载流子分离效率的提高,可见光吸收强度的增加,带隙宽度的缩小和活性位点的增加。催化剂的循环实验表明ZnO/Ag2MoO4复合催化剂具有良好的光学稳定性。研究结果为水污染治理光催化剂的开发设计提供了有益的参考。

钼酸银  /  氧化锌  /  罗丹明B  /  美洛昔康  /  光催化
Introduction

With the increasing environmental protection and sustainable development, conventional water pollution treatment methods have some challenges in practical applications. Photocatalytic technology has potential advantages such as energy conservation and environmental protection, providing an effective and sustainable method for wastewater treatment. The design and synthesis of photocatalysts are crucial in photocatalytic reactions. Silver molybdate material has some advantages of controllable morphology, unique physicochemical properties, having potential application prospects. However, the narrow photoresponse range and the high recombination efficiency of photo generated charge carriers restrict its application in the field of photocatalysis. In this study, a ZnO/Ag2MoO4 composite photocatalyst was prepared by a hydrothermal method with ZnO. The purpose was to improve the photocatalytic activity of silver molybdate via constructing heterojunctions. The photocatalytic performance of different proportions of composite materials for the degradation of organic pollutants was investigated. In addition, the optical stability of the catalyst and the active free radicals involved in the reaction were also analyzed.

Methods

ZnO/Ag2MoO4 composite catalysts with different mass fractions of 10%, 50%, and 90% ZnO were synthesized by a hydrothermal method with ZnO, AgNO3, and Na2MoO4·2H2O, respectively.

The photocatalytic degradation of organic pollutants was carried out in a photocatalytic reactor. 50 mg of photocatalyst was dispersed in 50 mL of Rhodamine B (RhB) or meloxicam (MLX) solution in each experiment. Prior to photocatalytic reaction, the suspension was stirred in the darkness for 30 min to obtain the absorption-desorption equilibrium. Afterwards, the suspension was placed under a xenon lamp (300 W) for photocatalytic degradation. At each interval, RhB or MLX solution with catalyst was sampled and centrifuged to remove the solid catalyst. The concentration of RhB or MLX was determined by a UV-Vis spectrophotometer. The similar experimental steps were used for the cyclic experiments. After each cyclic experiment, the solid catalyst was separated and washed with water and ethanol to continue the next cyclic experiment.

To determine the main active species involved in the degradation of RhB, free radical capture experiments were conducted. The free radical capture experiment followed the same steps as the normal degradation experiment. Benzoquinone, ethanol, silver nitrate, and tert-butanol were added as a scavenger for superoxide radicals, holes, electrons, and hydroxyl radicals during the reaction.

Results and discussion

ZnO/Ag2MoO4 composite catalysts with different ratios were prepared by a hydrothermal method. The results indicate the effective preparation of ZnO/Ag2MoO4 without other impurity elements. Based on the XRD patterns, the sharp diffraction peaks of ZnO/Ag2MoO4 composites indicate a good crystallinity. The SEM images show that ZAM-7 is a block shaped structure with uneven size, and ZnO is deposited in a columnar form on the surface of ZnO/Ag2MoO4. The minimum size of ZAM-7 is approximately 100-200 nm. The specific surface areas of ZnO, ZnO/Ag2MoO4, and ZAM-7 are 4.5795 m2/g, 0.0921 m2/g, and 2.6339 m2/g, respectively. The specific surface area of ZAM-7 is 28 times greater than that of ZnO/Ag2MoO4, indicating that the composition of Ag2MoO4 and ZnO is beneficial for increasing the specific surface area of the catalyst, thus providing more active sites for photocatalytic reactions.

The photocatalytic performance of ZnO/Ag2MoO4 composite materials is investigated using RhB and MLX as simulated organic pollutants. After 90-min illumination, the removal rates of RhB by ZnO, Ag2MoO4, and ZAM-7 are 40.1%, 13.8%, and 89.6%, respectively. The rate constants of ZnO, Ag2MoO4, and ZAM-7 are 1.19×10-2 min-1, 0.22×10-2 min-1, and 3.60×10-2 min-1, respectively. The degradation of meloxicam is also carried out with ZAM-7. When the catalyst dosage is 50 mg, the MLX concentration is 100 mg/L, the degradation rate of MLX by the catalyst can reach 80.6% after 270 min visible light irradiation.

Conclusions

ZnO/Ag2MoO4 composite photocatalysts were prepared by a hydrothermal method. The minimum size of ZnO/Ag2MoO4 composite catalysts was 100-200 nm. ZnO was deposited in a prismatic shape on the surface of Ag2MoO4. ZnO/Ag2MoO4 composite catalyst exhibited a superior photocatalytic degradation activity for both organic dyes and drugs. Under the optimal reaction conditions, the degradation rate of RhB by the composite catalyst could reach 95.0%, and the degradation rate of the drug MLX could reach 80.6%. The maximum reaction rate constants for the degradation of RhB by composite catalysts were 3 times and 16 times greater than those of ZnO and Ag2MoO4, respectively. The improvement of photocatalytic activity after the composition of Ag2MoO4 and ZnO was attributed to the improvement of photogenerated carrier separation efficiency, the increase of visible light absorption intensity, the reduction of band gap width, and the increase of active sites. The cyclic experiment of the catalyst showed that ZnO/Ag2MoO4 composite catalyst had a good optical stability. The results could provide a useful reference for the development and design of photocatalysts for water pollution treatment.

silver molybdate  /  zinc oxide  /  rhodamine B  /  meloxicam  /  photocatalysis
杨玉婷, 张莹莹, 董庆桐, 陈全亮. ZnO/Ag2MoO4复合材料的制备及其光催化性能. 硅酸盐学报, 2024 , 52 (12) : 3737 -3747 . DOI: 10.14062/j.issn.0454-5648.20240391
Yuting YANG, Yingying ZHANG, Qingtong DONG, Quanliang CHEN. Preparation and Photocatalytic Properties of ZnO/Ag2MoO4 Composites[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3737 -3747 . DOI: 10.14062/j.issn.0454-5648.20240391
  • 西南民族大学中央高校基本科研业务费(ZYN2024019)
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doi: 10.14062/j.issn.0454-5648.20240391
  • 接收时间:2024-06-05
  • 首发时间:2026-10-22
  • 出版时间:2024-12-20
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  • 收稿日期:2024-06-05
  • 修回日期:2024-06-15
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西南民族大学中央高校基本科研业务费(ZYN2024019)
作者信息
    西南民族大学化学与环境学院,青藏高原污染控制化学与环境功能材料国家民委重点实验室,四川 成都 610041

通讯作者:

陈全亮(1985—),男,博士,讲师。
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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