Article(id=1320090058770723276, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320090049606172775, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20240674, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1729785600000, receivedDateStr=2024-10-25, revisedDate=1731340800000, revisedDateStr=2024-11-12, acceptedDate=null, acceptedDateStr=null, onlineDate=1792663596098, onlineDateStr=2026-10-22, pubDate=1747670400000, pubDateStr=2025-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792663596098, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792663596098, creator=13701087609, updateTime=1792663596098, updator=13701087609, issue=Issue{id=1320090049606172775, tenantId=1146029695717560320, journalId=1263187385517883426, year='2025', volume='53', issue='5', pageStart='1031', pageEnd='1402', issueExtLink='null', onlineDate='null', pubDate='1747670400000', pubDateStr='2025-05-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792663593913, creator='13701087609', updateTime=1792663765419, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320090769013190788, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320090049606172775, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320090769013190789, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320090049606172775, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1057, endPage=1065, ext={EN=ArticleExt(id=1320090059022381517, articleId=1320090058770723276, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Synthesis of Sm-doped Ceria Photocatalyst and Its Purification Mechanism of Bisphenol A Pollutant, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

Ceria (CeO2) is an important rare earth metal oxide abundant in nature. Due to the easy conversion of the oxidation valence between cerium ions, CeO2 has a high oxygen storage capacity. The band gap value of ceria is similar to that of other traditional semiconductor photocatalyst of TiO2, so it has the potential to be a suitable and efficient photocatalyst. Specifically, ion doping can introduce new energy levels into the band structure of ceria, reduce its band gap width, and enable more visible light to be absorbed, thereby ultimately improving the photocatalytic efficiency. Secondly, when other cations enter the CeO2 lattice, they form oxygen vacancies (oxygen defects) under structural deformation and charge compensation mechanisms. The oxygen vacancy formed in this process can act as an effective trapping point for photogenerated electrons, effectively reduce the recombination rate of electrons and holes, and significantly improve the photocatalytic efficiency of the material. In addition, ion doping can also change the electronic structure of cerium oxide, making it have better conductivity and charge transport performance, which is conducive to the separation and transport of photogenic carriers. Generally speaking, it is very difficult to introduce ions into the CeO2 lattice. The author focuses on designing the synthesis system of CeO2 photocatalyst doped with Sm ions and systematically studying and summarizing the reaction ratio relationship of raw materials, so as to elucidate the influence of ion doping on photocatalytic performance from the perspective of photocatalytic mechanism.

Methods

Firstly, 5.88 g C6H5Na3O7·2H2O and 60 mL deionized water were stirred magnetically together at room temperature for 30 min. Then, 2.40 g urea was added and mixed for 30 min continually (solution 1). At the same time, 1.00 g Ce(NO3)3·6H2O and different molar ratios of Sm(NO3)3·6H2O were dissolved in 20 mL deionized water and stirred for 30 min, respectively (solution 2). Next, solution 2 was added into solution 1 and continue to stir for 30 min until the solution shows a light-yellow color. Then, the mixed reaction liquid was transferred to a 100 mL hydrothermal reactor, and cooled naturally after the hydrothermal reaction at 120 ℃ for 36 h. After used deionized water and ethanol to clean at least three times, and finally dried for 12 h at 70 ℃ and calcined at 500 ℃ for 4 h to obtain the target product. At the same time, CeO2 product without adding Sm(NO3)3·6H2O precursor were used as a comparison sample.

Results and discussion

The influence of different doping concentrations on the photocatalytic performance of ceria was studied in detail, and the optimal doping ratio of Ce and Sm was determined to be 1.00∶0.15 (0.15-SC). SEM images indicated that Sm-doped material still maintained a broom-like morphology, but the surface smoothness, average diameter and length of the nanorods showed slight changes. From XRD analysis, all the samples exhibited sharp diffraction peaks, indicating high crystallinity, and no impurity peaks are detected, meaning that the doping process does not affect the crystal purity of the final product. UV-Vis absorption spectrum shows that the bandgap value (Eg) of these Sm-doped samples is significantly reduced compared to that of pure CeO2, and the Eg of the 0.15-SC sample is the smallest at only 2.88 eV. The factors that lead to the reduction of the band gap can be attributed to two points: First, the nanoscale CeO2 composed grains can induce the quantum limiting effect, which leads to the spectral redshift; Second, the decrease of particle size will increase the Ce3+ content at the edge of CeO2. With the decrease of Ce3+ content, the UV-Vis spectra will also show a redshift phenomenon.

Compared with other Sm-CeO2 samples, pure phase CeO2 showed the strongest characteristic peak strength and the lowest peak strength when the doping ratio was 1.00∶0.15, indicating that Sm-CeO2 samples had the best effect on promoting the separation of photogenerated holes and electron pairs and photocatalytic performance at this ratio. The environmental pollutant bisphenol A (BPA) was used as a photocatalytic degradation model, and it was found that the efficiency of all the Sm-doped CeO2 samples was improved, and the degradation efficiency of the 0.15-SC sample was the highest, reaching 99.83%, which was 3.52-times superior than that of the pure CeO2 (28.31%). The capture experiment of the active substances can be judged that both hydroxyl radicals (·OH) and holes (h+) played very important roles in the photocatalytic degradation of BPA on the 0.15-SC sample. And after four performance cycling experiments, the degradation rate of the 0.15-SC sample was still maintained 89.53%, indicating that it has good recyclability.

Conclusions

In summary, Sm-doped ceria material exhibits high photocatalytic purification activity for environmental pollutants, fully proving that ion's doping can act as an effective method to efficiently improve photocatalytic performance, and can further provide effective ideas for designing ion-doping systems for similar metal oxide materials in the future.

, authors=Yifan WANG, Wenxuan QIAN, Dong XU, Jianhua HOU, Hui YANG, authorsList=Yifan WANG, Wenxuan QIAN, Dong XU, Jianhua HOU, Hui YANG, authorCompany=null, correspAuthors=Hui YANG, authorNote=

WANG Yifan (2005-), female, undergraduate. E-mail:

, correspAuthorsNote=
YANG Hui (1994-), female, Ph.D., Lecturer. E-mail:
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二氧化铈(CeO2)材料因其独特的光、磁、电性能而备受关注,尤其在光催化降解环境污染物方面展现出了高效、无毒、低成本的显著优势。以硝酸铈和硝酸钐为原料,采用无模板一步水热法成功制备了具有类扫帚状形貌的钐离子掺杂二氧化铈(Sm-CeO2)光催化剂,详细研究了不同掺杂浓度对其光催化性能的影响,同时确定了最佳掺杂比为Ce/Sm摩尔比= 1.00∶0.15(0.15-SC)。紫外-可见吸收光谱表明Sm掺杂后的样品与未掺杂CeO2相比带隙值(Eg)明显减小,最佳掺杂比时0.15-SC样品的Eg最小仅为2.88 eV。以环境污染物双酚A(BPA)为降解实验的模型,发现Sm掺杂后的CeO2样品光催化降解效率均有一定程度的提升,且0.15-SC样品降解效率最高达99.83%,是未掺杂CeO2(28.31%)的3.52倍。活性物质的猝灭实验可以判断出,羟基自由基(·OH)和空穴(h+)在0.15-SC样品光催化降解BPA过程中起到很大的作用。且在4次的性能循环性实验后,0.15-SC样品仍保持89.53%的降解率,表明其可循环利用性良好。本工作中钐离子掺杂后二氧化铈材料展现出较高的光催化净化环境污染物活性,充分证实了离子掺杂是一种有效提高光催化性能的方法,可为以后同类金属氧化物材料设计离子掺杂体系提供有效的思路。

, authors=王一帆, 钱文轩, 徐冬, 侯建华, 杨慧, authorsList=王一帆, 钱文轩, 徐冬, 侯建华, 杨慧, authorCompany=null, correspAuthors=杨慧, authorNote=

王一帆(2005—),女,本科。

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杨慧(1994—),女,博士,讲师。
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钐离子掺杂二氧化铈光催化剂的制备及其净化双酚A污染物的机理
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王一帆 , 钱文轩 , 徐冬 , 侯建华 , 杨慧
硅酸盐学报 | 研究论文 2025,53(5): 1057-1065
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硅酸盐学报 |研究论文 2025 , 53 (5) : 1057 -1065
钐离子掺杂二氧化铈光催化剂的制备及其净化双酚A污染物的机理
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王一帆 , 钱文轩, 徐冬, 侯建华, 杨慧
作者信息
  • 扬州大学环境科学与工程学院,江苏 扬州 225127
通讯作者:
杨慧(1994—),女,博士,讲师。
作者简介:

王一帆(2005—),女,本科。

Synthesis of Sm-doped Ceria Photocatalyst and Its Purification Mechanism of Bisphenol A Pollutant
Yifan WANG , Wenxuan QIAN, Dong XU, Jianhua HOU, Hui YANG
Affiliations
  • College of Environmental Science and Engineering, Yangzhou University, Yangzhou 225127, Jiangsu, China
  • Corresponding Author:
    YANG Hui (1994-), female, Ph.D., Lecturer. E-mail:

    WANG Yifan (2005-), female, undergraduate. E-mail:

出版时间: 2025-05-20 doi: 10.14062/j.issn.0454-5648.20240674
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二氧化铈(CeO2)材料因其独特的光、磁、电性能而备受关注,尤其在光催化降解环境污染物方面展现出了高效、无毒、低成本的显著优势。以硝酸铈和硝酸钐为原料,采用无模板一步水热法成功制备了具有类扫帚状形貌的钐离子掺杂二氧化铈(Sm-CeO2)光催化剂,详细研究了不同掺杂浓度对其光催化性能的影响,同时确定了最佳掺杂比为Ce/Sm摩尔比= 1.00∶0.15(0.15-SC)。紫外-可见吸收光谱表明Sm掺杂后的样品与未掺杂CeO2相比带隙值(Eg)明显减小,最佳掺杂比时0.15-SC样品的Eg最小仅为2.88 eV。以环境污染物双酚A(BPA)为降解实验的模型,发现Sm掺杂后的CeO2样品光催化降解效率均有一定程度的提升,且0.15-SC样品降解效率最高达99.83%,是未掺杂CeO2(28.31%)的3.52倍。活性物质的猝灭实验可以判断出,羟基自由基(·OH)和空穴(h+)在0.15-SC样品光催化降解BPA过程中起到很大的作用。且在4次的性能循环性实验后,0.15-SC样品仍保持89.53%的降解率,表明其可循环利用性良好。本工作中钐离子掺杂后二氧化铈材料展现出较高的光催化净化环境污染物活性,充分证实了离子掺杂是一种有效提高光催化性能的方法,可为以后同类金属氧化物材料设计离子掺杂体系提供有效的思路。

二氧化铈  /  离子掺杂  /  光催化降解  /  双酚A
Introduction

Ceria (CeO2) is an important rare earth metal oxide abundant in nature. Due to the easy conversion of the oxidation valence between cerium ions, CeO2 has a high oxygen storage capacity. The band gap value of ceria is similar to that of other traditional semiconductor photocatalyst of TiO2, so it has the potential to be a suitable and efficient photocatalyst. Specifically, ion doping can introduce new energy levels into the band structure of ceria, reduce its band gap width, and enable more visible light to be absorbed, thereby ultimately improving the photocatalytic efficiency. Secondly, when other cations enter the CeO2 lattice, they form oxygen vacancies (oxygen defects) under structural deformation and charge compensation mechanisms. The oxygen vacancy formed in this process can act as an effective trapping point for photogenerated electrons, effectively reduce the recombination rate of electrons and holes, and significantly improve the photocatalytic efficiency of the material. In addition, ion doping can also change the electronic structure of cerium oxide, making it have better conductivity and charge transport performance, which is conducive to the separation and transport of photogenic carriers. Generally speaking, it is very difficult to introduce ions into the CeO2 lattice. The author focuses on designing the synthesis system of CeO2 photocatalyst doped with Sm ions and systematically studying and summarizing the reaction ratio relationship of raw materials, so as to elucidate the influence of ion doping on photocatalytic performance from the perspective of photocatalytic mechanism.

Methods

Firstly, 5.88 g C6H5Na3O7·2H2O and 60 mL deionized water were stirred magnetically together at room temperature for 30 min. Then, 2.40 g urea was added and mixed for 30 min continually (solution 1). At the same time, 1.00 g Ce(NO3)3·6H2O and different molar ratios of Sm(NO3)3·6H2O were dissolved in 20 mL deionized water and stirred for 30 min, respectively (solution 2). Next, solution 2 was added into solution 1 and continue to stir for 30 min until the solution shows a light-yellow color. Then, the mixed reaction liquid was transferred to a 100 mL hydrothermal reactor, and cooled naturally after the hydrothermal reaction at 120 ℃ for 36 h. After used deionized water and ethanol to clean at least three times, and finally dried for 12 h at 70 ℃ and calcined at 500 ℃ for 4 h to obtain the target product. At the same time, CeO2 product without adding Sm(NO3)3·6H2O precursor were used as a comparison sample.

Results and discussion

The influence of different doping concentrations on the photocatalytic performance of ceria was studied in detail, and the optimal doping ratio of Ce and Sm was determined to be 1.00∶0.15 (0.15-SC). SEM images indicated that Sm-doped material still maintained a broom-like morphology, but the surface smoothness, average diameter and length of the nanorods showed slight changes. From XRD analysis, all the samples exhibited sharp diffraction peaks, indicating high crystallinity, and no impurity peaks are detected, meaning that the doping process does not affect the crystal purity of the final product. UV-Vis absorption spectrum shows that the bandgap value (Eg) of these Sm-doped samples is significantly reduced compared to that of pure CeO2, and the Eg of the 0.15-SC sample is the smallest at only 2.88 eV. The factors that lead to the reduction of the band gap can be attributed to two points: First, the nanoscale CeO2 composed grains can induce the quantum limiting effect, which leads to the spectral redshift; Second, the decrease of particle size will increase the Ce3+ content at the edge of CeO2. With the decrease of Ce3+ content, the UV-Vis spectra will also show a redshift phenomenon.

Compared with other Sm-CeO2 samples, pure phase CeO2 showed the strongest characteristic peak strength and the lowest peak strength when the doping ratio was 1.00∶0.15, indicating that Sm-CeO2 samples had the best effect on promoting the separation of photogenerated holes and electron pairs and photocatalytic performance at this ratio. The environmental pollutant bisphenol A (BPA) was used as a photocatalytic degradation model, and it was found that the efficiency of all the Sm-doped CeO2 samples was improved, and the degradation efficiency of the 0.15-SC sample was the highest, reaching 99.83%, which was 3.52-times superior than that of the pure CeO2 (28.31%). The capture experiment of the active substances can be judged that both hydroxyl radicals (·OH) and holes (h+) played very important roles in the photocatalytic degradation of BPA on the 0.15-SC sample. And after four performance cycling experiments, the degradation rate of the 0.15-SC sample was still maintained 89.53%, indicating that it has good recyclability.

Conclusions

In summary, Sm-doped ceria material exhibits high photocatalytic purification activity for environmental pollutants, fully proving that ion's doping can act as an effective method to efficiently improve photocatalytic performance, and can further provide effective ideas for designing ion-doping systems for similar metal oxide materials in the future.

ceria  /  ion's doping  /  photocatalytic degradation  /  bisphenol A
王一帆, 钱文轩, 徐冬, 侯建华, 杨慧. 钐离子掺杂二氧化铈光催化剂的制备及其净化双酚A污染物的机理. 硅酸盐学报, 2025 , 53 (5) : 1057 -1065 . DOI: 10.14062/j.issn.0454-5648.20240674
Yifan WANG, Wenxuan QIAN, Dong XU, Jianhua HOU, Hui YANG. Synthesis of Sm-doped Ceria Photocatalyst and Its Purification Mechanism of Bisphenol A Pollutant[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (5) : 1057 -1065 . DOI: 10.14062/j.issn.0454-5648.20240674
  • 国家自然科学基金青年项目(22406161)
  • 扬州市“绿杨金凤”优秀博士项目(137013435)
  • 扬州大学“高端人才支持计划”
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doi: 10.14062/j.issn.0454-5648.20240674
  • 接收时间:2024-10-25
  • 首发时间:2026-10-22
  • 出版时间:2025-05-20
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  • 收稿日期:2024-10-25
  • 修回日期:2024-11-12
基金
国家自然科学基金青年项目(22406161)
扬州市“绿杨金凤”优秀博士项目(137013435)
扬州大学“高端人才支持计划”
作者信息
    扬州大学环境科学与工程学院,江苏 扬州 225127

通讯作者:

杨慧(1994—),女,博士,讲师。
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2种不同金属材料的力学参数
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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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