Article(id=1319969657453400250, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20230398, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1686153600000, receivedDateStr=2023-06-08, revisedDate=1689696000000, revisedDateStr=2023-07-19, acceptedDate=null, acceptedDateStr=null, onlineDate=1792634890186, onlineDateStr=2026-10-22, pubDate=1705680000000, pubDateStr=2024-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792634890186, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792634890186, creator=13701087609, updateTime=1792634890186, updator=13701087609, issue=Issue{id=1319969627665445134, tenantId=1146029695717560320, journalId=1263187385517883426, year='2024', volume='52', issue='1', pageStart='1', pageEnd='370', issueExtLink='null', onlineDate='null', pubDate='1705680000000', pubDateStr='2024-01-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792634883085, creator='13701087609', updateTime=1792641944622, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1319999245965443838, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1319999245965443839, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1319969627665445134, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=109, endPage=121, ext={EN=ArticleExt(id=1319969657671504059, articleId=1319969657453400250, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Tunable Energy Band of Indium Tin Sulfide (InxSn5-xS8) and Visible-Light-Driven Photocatalytic H2O2 Generation, columnId=1319726165087077079, journalTitle=Journal of the Chinese Ceramic Society, columnName=Research Article, runingTitle=null, highlight=null, articleAbstract=
Introduction

Hydrogen peroxide (H2O2) is an important chemical that can be utilized as oxidant and fuel. Photocatalytic technology based on semiconductors can produce H2O2 from water and oxygen with sustainable solar energy as a sole energy input, which is a promising approach for industrial application. Nevertheless, the photoactivity of the common catalysts (i.e., graphitic carbon nitride, metal oxide, metal-organic frameworks, etc.) is low due to the poor utilization of solar light, easy recombination of electron-hole pairs, small quantity of reactive sites and weak redox ability. Developing efficient photocatalytic systems thus becomes an urgent target. Metal sulfides can be classified to single metal sulfide (i.e., CdS, In2S3, etc.), bimetallic sulfide (i.e., ZnIn2S4、CdIn2S4, etc.) and trimetallic sulfide (i.e., Cu2ZnSnS4). Sulfides exhibits the suitable band structures that can harness visible light and possess the proper redox capability. Meanwhile, the high structural symmetry enables them ultrafast charge carries transportation. The band structure of the semiconductor is a prerequisite both for optical absorption and redox ability. For photocatalytic H2O2 production, oxygen reduction reaction (ORR) and water oxidation reaction (WOR) channels can synergistically achieve the maximum activity. The ORR requires a potential that is more negative than -0.33 V vs. normal hydrogen electrode (NHE). The WOR needs a potential that is more positive than +1.78 V vs. NHE. The larger bandgap can induce the limited photon absorption. Thus, modulating the band structure of the metal sulfide through changing the metals ratio is an effective strategy to boost the photoactivity.

Methods

InxSn5-xS8 samples were prepared through a hydrothermal approach. A certain amount of InCl3·4H2O and SnCl4·5H2O were dissolved into deionized water and then added L-Cysteine into the solution. Thereafter, the suspension was treated by a hydrothermal method at 180 ℃ for 24 h. In2S3 and SnS2 were prepared by the same procedure without the addition of SnCl4·5H2O or InCl3·4H2O. The XRD patterns were characterized by X'Pert3MRD. The Raman spectra were obtained by LabRAM HR Evolution with 532 nm laser. The morphology structure was detected by a modelGemini SEM 500 scanning electron microscope and a modelJEM-2100 transmission electron microscope. The specific surface area and pore size were analyzed by a model ASAP2460BET instrument. The XPS spectra were obtained by an X-ray photoemission spectroscope with Al Kα excitation. The ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) was determined by an ultraviolet-visible absorbance spectroscope. The photoluminescence (PL) and time-resolved photoluminescence (TR-PL) spectra were collected on Horiba Fluorologat 375 nm. The transient photocurrent, electrochemical impedance spectra and Mott-Schottky plots were measured on a modelDH7000 electrochemical workstation.

Photocatalytic H2O2 production was evaluated in a sealed three-neck round bottom flask with the mixture of deionized water and isopropanol under visible light illumination (λ≥420 nm). After purging with oxygen for 30 min, the reaction system was placed under Xenon lamp and then extracted the suspension at certain time interval. The concentration of H2O2 was estimated by iodometry methods. The reaction pathway was investigated by scavengers experiment and changing the gases.

Results and discussion

The as-prepared In4SnS8 nanomaterials have a typical cubic structure with the flower-like morphology that is composed of ultrathin 2D nanosheets with the thicknesses of 5-10 nm. Apristine In2S3 presents a 3D solid sphere with the diameters of 4-7 μm, and SnS2 has a plate-like structure with a lateral size of ~1 μm. The hierarchical structure of In4SnS8 endow it with the maximum specific surface area of 648.056 m2/g, benefiting for the surface photoreaction. Nevertheless, pure In2S3 and SnS2 possess the small specific surface area of 70.631 m2/g and 30.411 m2/g. According the UV-Vis DRS, the bandgap of In2S3, In9SnS16, In4SnS8, In3Sn2S8, In2Sn3S8 and SnS2 is 2.03, 1.98, 2.16, 1.87, 1.80 and 1.78 eV, respectively. According to Mott-Schottky (MS) plots, their conductive band (CB) potential is calculated to be -0.24、-0.26、-0.39、-0.24、-0.22 and -0.31 eV, respectively. Their corresponding valance band (VB) is thus 1.79、1.72、1.77、1.63、1.58 and 1.47 eV, respectively. CB and VB both for In4SnS8 can meet the requirement of ORR and WOR channels for H2O2 evolution. While other photocatalysts can only undergo the single pathway of direct two-electron reduction reaction.

Under visible light illumination, In4SnS8 nanomaterials have the maximum photoactivity with a H2O2 production rate of 1.936 μmol·L-1·min-1, which is 5.2- and 71.7- fold greater than that of pristine In2S3 and SnS2. They also present a good stability after 4 cycles experiments. The photo-reactivity of In9SnS16, In3Sn2S8 and In2Sn3S8 dramatically decreases in N2 atmosphere, indicating that ORR is a dominant pathway in the three systems above. For In2S3 and In4SnS8, the concentration of H2O2 is decreased by 30%-50% in N2, implying that WOR pathway is also responsible for H2O2 evolution. The trapping agent experiment demonstrates that 2e- WOR, direct one-step two-electron ORR and indirect sequential two-step single-electron ORR all exist in In4SnS8 system. Among all the photocatalysts, In4SnS8 exhibits the maximum photocurrent of 0.25 mA·cm-2, the minimum interfacial electron transfer resistance, the lowest photoluminescence signal and the shortest charge carrier lifetime, indicating that the electron-hole pairs in In4SnS8 can efficiently separate and migrate to the surface, then boost the photo-reactivity.

Conclusions

A series of InxSn5-xS8 materials were prepared through a hydrothermal process. In4SnS8 nanomaterials exhibited the superior photocatalytic performance and its visible-light-driven H2O2 production rate was 1.936 μmol·L-1·min-1, which was 5.2- and 71.7- fold greater than that of pristine In2S3 and SnS2. The band structure analysis demonstratedthat the bandgap and band position of InxSn5-xS8 could be controlled by In/Sn molar ratio. In4SnS8 had the proper bandgap of 2.16 eV and its CB and VB lied at -0.39 and 1.77 eV, thus satisfying the potential of two independent pathways for H2O2 generation, i.e., oxygen reduction reaction and water oxidation reaction. In addition, the hierarchical nanoflower-like structure of bimetallic In4SnS8 nanomaterials could also provide the more reactive sites, which were responsible for the improved photocatalytic performance.

, authors=Tong ZHOU, Liang ZHAO, Shixiang XUE, Pan WU, Xinxin YANG, Ziqiang TAN, Wanying LEI, authorsList=Tong ZHOU, Liang ZHAO, Shixiang XUE, Pan WU, Xinxin YANG, Ziqiang TAN, Wanying LEI, authorCompany=null, correspAuthors=Wanying LEI, authorNote=

ZHOU Tong (1998-), male, Master. E-mail:

, correspAuthorsNote=
LEI Wanying (1991-), female, Ph.D., Associate Professor. E-mail:
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双氧水(H2O2)是一种重要的化学品,可以作为氧化剂或者燃料使用。基于半导体的光催化技术能够利用可再生的太阳能,以水和氧气为原料生产双氧水,是一种极具应用前景的工艺。因此,开发高效的半导体材料成为了急需突破的目标。通过调整原料的摩尔比,利用水热法制备出一系列硫化铟锡(InxSn5-xS8)样品,其中,In4SnS8纳米材料表现优异的光催化性能,在可见光下生成H2O2的速率为1.936 μmol/(L·min),较单独In2S3和SnS2分别提高了5.2倍和71.7倍。能带结构分析说明InxSn5-xS8的禁带宽度和能带位置可以由In/Sn摩尔比例控制,In4SnS8纳米材料具有合适的带宽(2.16 eV),其导带和价带分别位于-0.39 eV和1.77 eV,可以有效利用可见光并且能够同时满足双氧水生成过程的氧气还原路径和水氧化路径。此外,In4SnS8纳米材料的多级次纳米花状形貌可以提供更多的反应活性位点,达到提升光催化性能的目的。

, authors=周彤, 赵亮, 薛世翔, 吴攀, 杨鑫鑫, 谭自强, 雷琬莹, authorsList=周彤, 赵亮, 薛世翔, 吴攀, 杨鑫鑫, 谭自强, 雷琬莹, authorCompany=null, correspAuthors=雷琬莹, authorNote=

周彤(1998—),男,硕士。

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雷琬莹(1991—),女,博士,副教授。
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硫化铟锡(InxSn5-xS8)的能带调控及其可见光催化生成H2O2性能
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周彤 , 赵亮 , 薛世翔 , 吴攀 , 杨鑫鑫 , 谭自强 , 雷琬莹
硅酸盐学报 | 研究论文 2024,52(1): 109-121
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硅酸盐学报 |研究论文 2024 , 52 (1) : 109 -121
硫化铟锡(InxSn5-xS8)的能带调控及其可见光催化生成H2O2性能
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周彤 , 赵亮, 薛世翔, 吴攀, 杨鑫鑫, 谭自强, 雷琬莹
作者信息
  • 西安建筑科技大学材料科学与工程学院,西安 710055
通讯作者:
雷琬莹(1991—),女,博士,副教授。
作者简介:

周彤(1998—),男,硕士。

Tunable Energy Band of Indium Tin Sulfide (InxSn5-xS8) and Visible-Light-Driven Photocatalytic H2O2 Generation
Tong ZHOU , Liang ZHAO, Shixiang XUE, Pan WU, Xinxin YANG, Ziqiang TAN, Wanying LEI
Affiliations
  • College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China
  • Corresponding Author:
    LEI Wanying (1991-), female, Ph.D., Associate Professor. E-mail:

    ZHOU Tong (1998-), male, Master. E-mail:

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230398
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双氧水(H2O2)是一种重要的化学品,可以作为氧化剂或者燃料使用。基于半导体的光催化技术能够利用可再生的太阳能,以水和氧气为原料生产双氧水,是一种极具应用前景的工艺。因此,开发高效的半导体材料成为了急需突破的目标。通过调整原料的摩尔比,利用水热法制备出一系列硫化铟锡(InxSn5-xS8)样品,其中,In4SnS8纳米材料表现优异的光催化性能,在可见光下生成H2O2的速率为1.936 μmol/(L·min),较单独In2S3和SnS2分别提高了5.2倍和71.7倍。能带结构分析说明InxSn5-xS8的禁带宽度和能带位置可以由In/Sn摩尔比例控制,In4SnS8纳米材料具有合适的带宽(2.16 eV),其导带和价带分别位于-0.39 eV和1.77 eV,可以有效利用可见光并且能够同时满足双氧水生成过程的氧气还原路径和水氧化路径。此外,In4SnS8纳米材料的多级次纳米花状形貌可以提供更多的反应活性位点,达到提升光催化性能的目的。

双金属硫化物  /  能带调控  /  纳米材料  /  光催化  /  双氧水生成
Introduction

Hydrogen peroxide (H2O2) is an important chemical that can be utilized as oxidant and fuel. Photocatalytic technology based on semiconductors can produce H2O2 from water and oxygen with sustainable solar energy as a sole energy input, which is a promising approach for industrial application. Nevertheless, the photoactivity of the common catalysts (i.e., graphitic carbon nitride, metal oxide, metal-organic frameworks, etc.) is low due to the poor utilization of solar light, easy recombination of electron-hole pairs, small quantity of reactive sites and weak redox ability. Developing efficient photocatalytic systems thus becomes an urgent target. Metal sulfides can be classified to single metal sulfide (i.e., CdS, In2S3, etc.), bimetallic sulfide (i.e., ZnIn2S4、CdIn2S4, etc.) and trimetallic sulfide (i.e., Cu2ZnSnS4). Sulfides exhibits the suitable band structures that can harness visible light and possess the proper redox capability. Meanwhile, the high structural symmetry enables them ultrafast charge carries transportation. The band structure of the semiconductor is a prerequisite both for optical absorption and redox ability. For photocatalytic H2O2 production, oxygen reduction reaction (ORR) and water oxidation reaction (WOR) channels can synergistically achieve the maximum activity. The ORR requires a potential that is more negative than -0.33 V vs. normal hydrogen electrode (NHE). The WOR needs a potential that is more positive than +1.78 V vs. NHE. The larger bandgap can induce the limited photon absorption. Thus, modulating the band structure of the metal sulfide through changing the metals ratio is an effective strategy to boost the photoactivity.

Methods

InxSn5-xS8 samples were prepared through a hydrothermal approach. A certain amount of InCl3·4H2O and SnCl4·5H2O were dissolved into deionized water and then added L-Cysteine into the solution. Thereafter, the suspension was treated by a hydrothermal method at 180 ℃ for 24 h. In2S3 and SnS2 were prepared by the same procedure without the addition of SnCl4·5H2O or InCl3·4H2O. The XRD patterns were characterized by X'Pert3MRD. The Raman spectra were obtained by LabRAM HR Evolution with 532 nm laser. The morphology structure was detected by a modelGemini SEM 500 scanning electron microscope and a modelJEM-2100 transmission electron microscope. The specific surface area and pore size were analyzed by a model ASAP2460BET instrument. The XPS spectra were obtained by an X-ray photoemission spectroscope with Al Kα excitation. The ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS) was determined by an ultraviolet-visible absorbance spectroscope. The photoluminescence (PL) and time-resolved photoluminescence (TR-PL) spectra were collected on Horiba Fluorologat 375 nm. The transient photocurrent, electrochemical impedance spectra and Mott-Schottky plots were measured on a modelDH7000 electrochemical workstation.

Photocatalytic H2O2 production was evaluated in a sealed three-neck round bottom flask with the mixture of deionized water and isopropanol under visible light illumination (λ≥420 nm). After purging with oxygen for 30 min, the reaction system was placed under Xenon lamp and then extracted the suspension at certain time interval. The concentration of H2O2 was estimated by iodometry methods. The reaction pathway was investigated by scavengers experiment and changing the gases.

Results and discussion

The as-prepared In4SnS8 nanomaterials have a typical cubic structure with the flower-like morphology that is composed of ultrathin 2D nanosheets with the thicknesses of 5-10 nm. Apristine In2S3 presents a 3D solid sphere with the diameters of 4-7 μm, and SnS2 has a plate-like structure with a lateral size of ~1 μm. The hierarchical structure of In4SnS8 endow it with the maximum specific surface area of 648.056 m2/g, benefiting for the surface photoreaction. Nevertheless, pure In2S3 and SnS2 possess the small specific surface area of 70.631 m2/g and 30.411 m2/g. According the UV-Vis DRS, the bandgap of In2S3, In9SnS16, In4SnS8, In3Sn2S8, In2Sn3S8 and SnS2 is 2.03, 1.98, 2.16, 1.87, 1.80 and 1.78 eV, respectively. According to Mott-Schottky (MS) plots, their conductive band (CB) potential is calculated to be -0.24、-0.26、-0.39、-0.24、-0.22 and -0.31 eV, respectively. Their corresponding valance band (VB) is thus 1.79、1.72、1.77、1.63、1.58 and 1.47 eV, respectively. CB and VB both for In4SnS8 can meet the requirement of ORR and WOR channels for H2O2 evolution. While other photocatalysts can only undergo the single pathway of direct two-electron reduction reaction.

Under visible light illumination, In4SnS8 nanomaterials have the maximum photoactivity with a H2O2 production rate of 1.936 μmol·L-1·min-1, which is 5.2- and 71.7- fold greater than that of pristine In2S3 and SnS2. They also present a good stability after 4 cycles experiments. The photo-reactivity of In9SnS16, In3Sn2S8 and In2Sn3S8 dramatically decreases in N2 atmosphere, indicating that ORR is a dominant pathway in the three systems above. For In2S3 and In4SnS8, the concentration of H2O2 is decreased by 30%-50% in N2, implying that WOR pathway is also responsible for H2O2 evolution. The trapping agent experiment demonstrates that 2e- WOR, direct one-step two-electron ORR and indirect sequential two-step single-electron ORR all exist in In4SnS8 system. Among all the photocatalysts, In4SnS8 exhibits the maximum photocurrent of 0.25 mA·cm-2, the minimum interfacial electron transfer resistance, the lowest photoluminescence signal and the shortest charge carrier lifetime, indicating that the electron-hole pairs in In4SnS8 can efficiently separate and migrate to the surface, then boost the photo-reactivity.

Conclusions

A series of InxSn5-xS8 materials were prepared through a hydrothermal process. In4SnS8 nanomaterials exhibited the superior photocatalytic performance and its visible-light-driven H2O2 production rate was 1.936 μmol·L-1·min-1, which was 5.2- and 71.7- fold greater than that of pristine In2S3 and SnS2. The band structure analysis demonstratedthat the bandgap and band position of InxSn5-xS8 could be controlled by In/Sn molar ratio. In4SnS8 had the proper bandgap of 2.16 eV and its CB and VB lied at -0.39 and 1.77 eV, thus satisfying the potential of two independent pathways for H2O2 generation, i.e., oxygen reduction reaction and water oxidation reaction. In addition, the hierarchical nanoflower-like structure of bimetallic In4SnS8 nanomaterials could also provide the more reactive sites, which were responsible for the improved photocatalytic performance.

bimetallic sulfide  /  tunable bandgap  /  nanomaterials  /  photocatalytic  /  hydrogen peroxide evolution
周彤, 赵亮, 薛世翔, 吴攀, 杨鑫鑫, 谭自强, 雷琬莹. 硫化铟锡(InxSn5-xS8)的能带调控及其可见光催化生成H2O2性能. 硅酸盐学报, 2024 , 52 (1) : 109 -121 . DOI: 10.14062/j.issn.0454-5648.20230398
Tong ZHOU, Liang ZHAO, Shixiang XUE, Pan WU, Xinxin YANG, Ziqiang TAN, Wanying LEI. Tunable Energy Band of Indium Tin Sulfide (InxSn5-xS8) and Visible-Light-Driven Photocatalytic H2O2 Generation[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (1) : 109 -121 . DOI: 10.14062/j.issn.0454-5648.20230398
  • 国家自然科学基金项目(51902443)
  • 陕西省教育厅重点科研计划项目(22JY039)
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2024年第52卷第1期
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doi: 10.14062/j.issn.0454-5648.20230398
  • 接收时间:2023-06-08
  • 首发时间:2026-10-22
  • 出版时间:2024-01-20
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  • 收稿日期:2023-06-08
  • 修回日期:2023-07-19
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国家自然科学基金项目(51902443)
陕西省教育厅重点科研计划项目(22JY039)
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    西安建筑科技大学材料科学与工程学院,西安 710055

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雷琬莹(1991—),女,博士,副教授。
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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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