SrBiB微晶玻璃制备及其性能调控研究

doi:10.16552/j.cnki.issn1001-1625.2025.1122

摘要/Abstract

摘要：

本文系统研究了不同热处理条件下SrO-Bi₂O₃-B₂O₃（SrBiB）微晶玻璃及其稀土掺杂上转换体系的光催化性能。结果表明，35SrO-25Bi₂O₃-40B₂O₃经两步热处理后在180 min表现出最优的亚甲基蓝（MB）降解效率（93%）与反应速率常数（0.008 63 min^-1），这主要归因于其较窄的带隙及玻璃基质中Bi₆B₁₀O₂₄晶体的均匀分布。进一步在 SrBiB 微晶玻璃中引入 Yb³⁺/Tm³⁺，并通过两步热处理结合 HCl 化学刻蚀，成功构建了具有核壳结构的微晶玻璃。XRD、SEM、TEM 等表征结果表明，刻蚀后样品表面形成片层花状结构，且随着刻蚀时间延长，上转换发光强度逐渐增强，比表面积显著提高。光催化性能测试表明，HCl刻蚀30 min后的样品在全光谱与近红外光照下均表现出最优异的降解性能（210 min 降解率分别为 80%与 63%），这主要得益于其增强的可见-近红外光吸收能力、有效的载流子分离及核壳结构与表面缺陷共同促进的活性位点暴露。本研究为设计具有宽光谱响应的高效上转换光催化剂提供了新思路，并在近红外光驱动的废水处理等领域展现出良好的应用潜力。

关键词: 微晶玻璃, 稀土离子, 光催化, 上转换发光, 两步热处理

Abstract:

This study systematically investigated the photocatalytic performance of SrO-Bi₂O₃-B₂O₃（SrBiB） glass-ceramics and their rare-earth-doped upconversion systems under different heat treatment conditions. The results show that 35SrO-25Bi₂O₃-40B₂O₃ after two-step heat treatment exhibit the optimal methylene blue （MB） degradation efficiency （93%） and reaction rate constant （0.008 63 min^-1） within 180 min， which is mainly attributed to its smaller band gap and uniform distribution Bi₆B₁₀O₂₄crystals in the glass matrix. Furthermore， Yb³⁺/Tm³⁺is introduced into the SrBiB glass-ceramics， and a core-shell structured glass-ceramics is successfully constructed through two-step heat treatment combined with HCl chemical etching. XRD， SEM， TEM and other characterizations results confirm that a layered flower-like structure formed on the surface of the etched samples， and the upconversion luminescence intensity gradually increase and the specific surface area significantly increase with the extension of etching time. Photocatalytic performance tests show that sample after HCl etching for 30 min display the best degradation performance under both full-spectrum and near-infrared light （degradation rates of 80% and 63% after 210 min， respectively）， which is attributed to its enhanced visible-near-infrared light absorption， effective carrier separation， and the exposure of active sites promoted by the combined effects of core-shell structure and surface defects. This study provides a new strategy for the design of efficient upconversion photocatalysts with broad-spectrum response and demonstrates promising application potential in fields such as wastewater treatment driven by near-infrared light.

Key words: glass-ceramics, rare earth ion, photocatalytic, upconversion luminescence, two-step heat treatment

中图分类号:

TQ171

龚非凡, 王君, 吴渊, 高盛楠, 王觅堂. SrBiB微晶玻璃制备及其性能调控研究[J]. 硅酸盐通报, 2026, 45(3): 1018-1030.

GONG Feifan, WANG Jun, WU Yuan, GAO Shengnan, WANG Mitang. Preparation and Performance Regulation of SrBiB Glass-Ceramics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(3): 1018-1030.

图/表 14

表1 SrBiB微晶玻璃样品的制备

Table 1 Preparation of SrBiB glass-ceramics samples

Sample	Chemical formula	T_g/℃	T_c/℃	Preparation method
SBBO-1-Asq	28SrO-30Bi₂O₃-42B₂O₃	420	535	Quenching
SBBO-1-1	28SrO-30Bi₂O₃-42B₂O₃	420	535	One-step heat treatment
SBBO-1-2	28SrO-30Bi₂O₃-42B₂O₃	420	535	Two-step heat treatment
SBBO-2-Asq	32SrO-21Bi₂O₃-47B₂O₃	424	537	Quenching
SBBO-2-1	32SrO-21Bi₂O₃-47B₂O₃	424	537	One-step heat treatment
SBBO-2-2	32SrO-21Bi₂O₃-47B₂O₃	424	537	Two-step heat treatment
SBBO-3-Asq	35SrO-25Bi₂O₃-40B₂O₃	440	550	Quenching
SBBO-3-1	35SrO-25Bi₂O₃-40B₂O₃	440	550	One-step heat treatment
SBBO-3-2	35SrO-25Bi₂O₃-40B₂O₃	440	550	Two-step heat treatment

表2 上转换SrBiB微晶玻璃样品的制备

Table 2 Preparation of upconversion SrBiB glass-ceramic samples

Sample	Chemical formula	Preparation method
SBBO-5Yb-Asq	31.6SrF₂-31.6Bi₂O₃-31.6B₂O₃-5Yb₂O₃-0.2Tm₂O₃	Quenching
SBBO-5Yb-HT	31.6SrF₂-31.6Bi₂O₃-31.6B₂O₃-5Yb₂O₃-0.2Tm₂O₃	480 ℃ 6 h+580 ℃ 3 h
SBBO-10Yb-Asq	30SrF₂-30Bi₂O₃-29.8B₂O₃-10Yb₂O₃-0.2Tm₂O₃	Quenching
SBBO-10Yb-HT	30SrF₂-30Bi₂O₃-29.8B₂O₃-10Yb₂O₃-0.2Tm₂O₃	480 ℃ 6 h+580 ℃ 3 h
SBBO-HCl-5	31.6SrF₂-31.6Bi₂O₃-31.6B₂O₃-5Yb₂O₃-0.2Tm₂O₃	0.1 mol/L HCl etching 5 min
SBBO-HCl-15	31.6SrF₂-31.6Bi₂O₃-31.6B₂O₃-5Yb₂O₃-0.2Tm₂O₃	0.1 mol/L HCl etching 15 min
SBBO-HCl-30	31.6SrF₂-31.6Bi₂O₃-31.6B₂O₃-5Yb₂O₃-0.2Tm₂O₃	0.1 mol/L HCl etching 30 min
SBBO-HCl-60	31.6SrF₂-31.6Bi₂O₃-31.6B₂O₃-5Yb₂O₃-0.2Tm₂O₃	0.1 mol/L HCl etching 60 min

图1 SrBiB基质玻璃的DSC曲线，以及三种组分SrBiB玻璃淬火和热处理样品的XRD谱

Fig.1 DSC curves of SrBiB matrix glass， XRD patterns of quenched and heat-treated samples of three-component SrBiB glasses

图2 SBBO-1-Asq、SBBO-1-1、SBBO-1-2、SBBO-2-Asq、SBBO-2-1、SBBO-2-2、SBBO-3-Asq、SBBO-3-1和SBBO-3-2样品的SEM照片

Fig.2 SEM images of samples SBBO-1-Asq， SBBO-1-1， SBBO-1-2， SBBO-2-Asq， SBBO-2-1， SBBO-2-2， SBBO-3-Asq， SBBO-3-1， and SBBO-3-2

图3 SrBiB热处理样品的C/C0曲线和ln（C/C0）与时间图

Fig.3 C/C0 curves and ln（C/C0） versus time plots of SrBiB heat-treated samples

图4 上转换SrBiB基质玻璃的DSC曲线

Fig.4 DSC curves of upconversion SrBiB matrix glass

图5 稀土掺杂的淬火玻璃和热处理玻璃和0.1 mol/L的HCl刻蚀5、15、30、60 min SBBO-5Yb-HT GCs的样品的XRD谱

Fig.5 XRD patterns of rare earth doped quenched glass and heat-treated glass， and SBBO-5Yb-HT GCs samples etched with 0.1 mol/L HCl for 5， 15， 30， and 60 min

图6 稀土掺杂的上转换玻璃热处理样品和0.1 mol/L的HCl刻蚀5、15、30、60 min SBBO-5Yb-HT GCs样品的PL谱

Fig.6 PL spectra of heat-treated samples of rare-earth-doped upconversion glass and SBBO-5Yb-HT GCs samples etched with 0.1 mol/L HCl for 5， 15， 30， and 60 min.

图7 SBBO-5Yb-HT、SBBO-HCl-5、SBBO-HCl-15、SBBO-HCl-30和SBBO-HCl-60样品的SEM照片

Fig.7 SEM images of SBBO-5Yb-HT， SBBO-HCl-5， SBBO-HCl-15， SBBO-HCl-30， and SBBO-HCl-60

图8 SBBO-HCl-30样品的TEM、HRTEM照片及元素分布图

Fig.8 TEM， HRTEM images， and element distribution mappings of SBBO-HCl-30 sample

图9 SBBO-5Yb-HT和SBBO-HCl-30样品氮气吸脱附曲线

Fig.9 Nitrogen adsorption-desorption curves of SBBO-5Yb-HT and SBBO-HCl-30 samples

图10 SBBO-5Yb-HT和0.1 mol/L的HCl刻蚀5、15、30、60 min GCs的样品的紫外-可见-近红外吸收光谱图和经典Tauc图

Fig.10 UV-Vis-NIR absorption spectra and Tauc spectra of SBBO-5Yb-HT and 0.1 mol/L HCl etched GCs for 5， 15， 30， and 60 min

图11 全光谱下SBBO-5Yb-HT和0.1 mol/L的HCl刻蚀5、15、30、60 min GCs的样品的C/C0曲线和ln（C/C0）与时间图，以及近红外光照下SBBO-5Yb-HT和0.1 mol/L的HCl刻蚀5、15、30、60 min GCs的样品的C/C0曲线和ln（C/C0）与时间图

Fig.11 C/C0 curves and ln（C/C0） versus time plots of SBBO-5Yb-HT and 0.1 mol/L HCl etched GCs for 5， 15， 30， and 60 min under full-spectrum light， and C/C0 curves and ln（C/C0） versus time plots of SBBO-5Yb-HT and 0.1 mol/L HCl etched GCs for 5， 15， 30， and 60 min under near-infrared light

图12 SBBO-HCl-30样品在近红外下与全光谱下的降解率

Fig.12 Degradation rate of SBBO-HCl-30 sample under near-infrared and full-spectrum light

参考文献 30

[1]	BEALL G H. Dr. S. donald （don） Stookey （1915-2014）： pioneering researcher and adventurer［J］. Frontiers in Materials， 2016， 3： 37.
[2]	DYE L. A bright future for JMT［J］. Journal of Medical Toxicology， 2011， 7（4）： 255.
[3]	KARPUKHINA N， HILL R G， LAW R V. Crystallisation in oxide glasses-a tutorial review［J］. Chemical Society Reviews， 2014， 43（7）： 2174-2186.
[4]	DE PABLOS-MARTIN A， FERRARI M， PASCUAL M J， et al. Glass-ceramics： a class of nanostructured materials for photonics［J］. La Rivista Del Nuovo Cimento， 2015， 38（7）： 311-369.
[5]	HOLAND W， Beall G H. Glass ceramic technology［M］.2nd Edition，Hoboken， New Jersey： John Wiley & Sons， 2012：59-72.
[6]	KOMATSU T. Design and control of crystallization in oxide glasses［J］. Journal of Non-Crystalline Solids， 2015， 428： 156-175.
[7]	EDGAR D Z. A bright future for glass-ceramics［J］. American Ceramic Society Bulletin，2010，89（8）：19-27.
[8]	BROW R K， SCHMITT M L. A survey of energy and environmental applications of glass［J］. Journal of the European Ceramic Society， 2009， 29（7）： 1193-1201.
[9]	LEBULLENGER R， CHENU S， ROCHERULLÉ J， et al. Glass foams for environmental applications［J］. Journal of Non-Crystalline Solids， 2010， 356（44/45/46/47/48/49）： 2562-2568.
[10]	KUMAR S， KUSHWAHA H S， SINGH V P， et al. Solar light induced antibacterial performance of TiO₂ crystallized glass ceramics［J］. International Journal of Applied Glass Science， 2018， 9（4）： 480-486.
[11]	IIDA Y， AKIYAMA K， KOBZI B， et al. Structural analysis and visible light-activated photocatalytic activity of iron-containing soda lime aluminosilicate glass［J］. Journal of Alloys and Compounds， 2015， 645： 1-6.
[12]	KUSHWAHA H S， THOMAS P， VAISH R. Visible light driven multifunctional photocatalysis in TeO₂-based semiconductor glass ceramics［J］. Journal of Photonics for Energy， 2017， 7（1）： 016502.
[13]	KADAM S R， PANMAND R P， SONAWANE R S， et al. A stable Bi₂S₃ quantum dot-glass nanosystem： size tuneable photocatalytic hydrogen production under solar light［J］. RSC Advances， 2015， 5（72）： 58485-58490.
[14]	MARGHA F H， RADWAN E K， BADAWY M I， et al. Bi₂O₃-BiFeO₃ glass-ceramic： controllable β-/γ-Bi₂O₃ transformation and application as magnetic solar-driven photocatalyst for water decontamination［J］. ACS Omega， 2020， 5（24）： 14625-14634.
[15]	DJURIŠIĆ A B， HE Y L， NG A M C. Visible-light photocatalysts： prospects and challenges［J］. APL Materials， 2020， 8（3）： 030903.
[16]	SHARMA S K， SINGH V P， CHAUHAN V S， et al. Photocatalytic active bismuth fluoride/oxyfluoride surface crystallized 2Bi₂O₃-B₂O₃ glass-ceramics［J］. Journal of Electronic Materials， 2018， 47（7）： 3490-3496.
[17]	YOSHIDA K， TAKAHASHI Y， IHARA R， et al. Large enhancement of photocatalytic activity by chemical etching of TiO₂ crystallized glass［J］. APL Materials， 2014， 2（10）： 106103.
[18]	LI G B， HUANG S Q， SHEN Y W， et al. Synthesis of an efficient lanthanide doped glass-ceramic based near-infrared photocatalyst by a completely waterless solid-state reaction method［J］. Dalton Transactions， 2019， 48（27）： 9925-9929.
[19]	LI G B， HUANG S Q， LI K， et al. Near-infrared responsive Z-scheme heterojunction with strong stability and ultra-high quantum efficiency constructed by lanthanide-doped glass［J］. Applied Catalysis B： Environmental， 2022， 311： 121363.
[20]	BUTLER M A. Photoelectrolysis and physical properties of the semiconducting electrode WO₂ ［J］. Journal of Applied Physics， 1977， 48（5）： 1914-1920.
[21]	CHEN S G， LI Y H， WU Z X， et al. Enhanced photocatalytic activity of Te-doped Bi₂MoO₆ under visible light irradiation： effective separation of photogenerated carriers resulted from inhomogeneous lattice distortion and improved electron capturing ability［J］. Journal of Solid State Chemistry， 2017， 249： 124-130.
[22]	SUBHADRA M， KISTAIAH P. Effect of Bi₂O₃ content on physical and optical properties of 15Li₂O-15K₂O-xBi₂O₃-（65-x） B₂O₃∶5V₂O₅ glass system［J］. Physica B： Condensed Matter， 2011， 406（8）： 1501-1505.
[23]	DEVARAJULU G， RAVI O， REDDY C M， et al. Spectroscopic properties and upconversion studies of Er³⁺-doped SiO₂-Al₂O₃-Na₂CO₃-SrF₂-CaF₂ oxyfluoride glasses for optical amplifier applications［J］. Journal of Luminescence， 2018， 194： 499-506.
[24]	GUO X Y， SONG W Y， CHEN C F， et al. Near-infrared photocatalysis of β-NaYF₄∶Yb³⁺， Tm³⁺@ZnO composites［J］. Physical Chemistry Chemical Physics， 2013， 15（35）： 14681-14688.
[25]	LI C H， WANG F， ZHU J， et al. NaYF₄： Yb， Tm/CdS composite as a novel near-infrared-driven photocatalyst［J］. Applied Catalysis B： Environmental， 2010， 100（3/4）： 433-439.
[26]	DI J， CHEN C， YANG S Z， et al. Defect engineering in atomically-thin bismuth oxychloride towards photocatalytic oxygen evolution［J］. Journal of Materials Chemistry A， 2017， 5（27）： 14144-14151.
[27]	YANG X Y， LIU H X， LI T D， et al. Preparation of flower-like ZnO@ZnS core-shell structure enhances photocatalytic hydrogen production［J］. International Journal of Hydrogen Energy， 2020， 45（51）： 26967-26978.
[28]	HUANG X Q， NIU Y L， PENG Z P， et al. Core-shell structured BiOCl@polydopamine hierarchical hollow microsphere for highly efficient photocatalysis［J］. Colloids and Surfaces A： Physicochemical and Engineering Aspects， 2019， 580： 123747.
[29]	SHAN L W， DING J， SUN W L， et al. Core-shell heterostructured BiVO₄/BiVO₄∶Eu³⁺ with improved photocatalytic activity［J］. Journal of Inorganic and Organometallic Polymers and Materials， 2017， 27（6）： 1750-1759.
[30]	LI J H， HAN M S， GUO Y， et al. Fabrication of FeVO₄/Fe₂TiO₅ composite catalyst and photocatalytic removal of norfloxacin［J］. Chemical Engineering Journal， 2016， 298： 300-308.