Al掺杂SrTiO3的合成调控及其光催化全分解水性能

doi:10.6023/A25050148

摘要/Abstract

Al掺杂钛酸锶(SrTiO₃:Al)是目前唯一表观量子效率可接近100%的粉末光催化全分解水体系. 深入研究其高效光生电荷分离与表面反应效率的作用机制, 对于合理设计高性能光催化剂、推进规模化太阳能制氢具有重要意义. 可控合成光催化全分解水性能优异的SrTiO₃:Al模型体系, 是揭示其高效光生电荷利用机制的基础. 本研究系统地探讨了熔盐法制备SrTiO₃:Al过程中合成温度、Al₂O₃种类与添加量以及前驱体SrTiO₃的性质对样品光催化全分解水性能的影响. 研究结果表明, SrTiO₃:Al的最优合成温度为1423 K; 适宜的Al₂O₃源为γ-Al₂O₃和含有80% α相的Al₂O₃; 对于水热合成的SrTiO₃前驱体, 最优Al₂O₃添加量为1 mol%(相对于SrTiO₃); 而对于固相合成的SrTiO₃, 最优Al₂O₃添加量为1~2 mol%. 其中, 结晶性较高的固相法合成的SrTiO₃是制备最优光催化性能的2%-SrTiO₃:Al的理想前驱体.

关键词: 铝掺杂钛酸锶, 光催化全分解水, 熔盐法, 粉末光催化剂

Al-doped SrTiO₃ (SrTiO₃:Al) is currently the only known particulate photocatalyst that achieves near-unity apparent quantum efficiency (AQE) for overall water splitting. The underlying mechanism by which Al doping enhances photocatalytic performance has attracted widespread attention, as uncovering how photogenerated charges are efficiently utilized is critical for the rational design of high-performance photocatalysts. Such insights are essential for advancing scalable solar-to-hydrogen conversion technologies. Developing SrTiO₃:Al model photocatalysts with well-defined structures and high activity is therefore fundamental to elucidating the mechanisms behind their exceptional charge separation and surface reaction efficiencies. In this work, we systematically investigate the effects of various synthesis parameters on the photocatalytic performance of SrTiO₃:Al prepared via a flux method. The parameters studied include the temperature, the phase and amount of Al₂O₃ dopant, and the morphology and crystallinity of the SrTiO₃ precursor. The photocatalytic activity of SrTiO₃:Al exhibits a volcano-type dependence on the synthesis temperature, with the highest activity achieved at 1423 K. The crystal structure of the Al₂O₃ dopant also plays a critical role: γ-Al₂O₃ and partially crystalline α-Al₂O₃ (with 80% α-phase) lead to markedly improved performance. The optimal amount of Al₂O₃ added depends strongly on the type of precursor, 1 mol% for hydrothermally synthesized precursors and 1~2 mol% for those prepared via solid-state synthesis. At a fixed Al₂O₃ content of 2 mol%, the properties of the precursor significantly affect the final particle morphology, size distribution, and crystallinity. The best-performing sample exhibits high crystallinity and a narrow particle size distribution centered around 200 nm. Al doping in SrTiO₃:Al not only repairs lattice defects and suppresses excessive grain growth but also promotes the exposure of high-index facets. These findings suggest that multiple synthesis parameters synergistically govern the doping concentration and spatial distribution of Al, ultimately modulating lattice quality, particle structure, and charge separation efficiency—thereby determining the overall water splitting activity of SrTiO₃:Al.

Key words: Al doped SrTiO₃, photocatalytic overall water splitting, flux method, particulate photocatalyst

引用此文

罗雅玲, 庄展洋, 范峰滔, 李灿. Al掺杂SrTiO₃的合成调控及其光催化全分解水性能[J]. 化学学报, 2025, 83(6): 608-615.

Yaling Luo, Zhanyang Zhuang, Fengtao Fan, Can Li. Synthesis Control of Al-Doped SrTiO₃ and Its Photocatalytic Performance for Overall Water Splitting[J]. Acta Chimica Sinica, 2025, 83(6): 608-615.

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图/表 7

图1. (a)未添加Al2O3时不同温度下熔盐制备SrTiO3:Al的光催化活性图; (b)对应样品的XRD图; (c)是(b)中部分区域的放大XRD图; (d~g)是该组SrTiO3:Al样品对应的SEM图; 光催化活性测试条件: 100 mg光催化剂分散于100 mL去离子水中, 助催化剂的负载为0.1% (w) Rh-0.05% (w) Cr2O3-0.05% (w) CoOOH

Figure 1. (a) Photocatalytic overall water splitting activities of SrTiO3:Al synthesized via the flux method at various temperatures without Al2O3 addition. (b) XRD patterns of the corresponding samples. (c) Enlarged XRD patterns in (b). (d~g) SEM images of the corresponding SrTiO3:Al samples. Photocatalytic reaction conditions: 100 mg of photocatalyst loaded with 0.1% (w) Rh, 0.05% (w) Cr2O3, 0.05% (w) CoOOH, dispersed in 100 mL deionized water

图2. (a)添加1 mol%的γ-Al2O3时不同温度下熔盐制备1%-SrTiO3:Al的光催化全分解水活性(a)和对应的XRD衍射图(b); (c)是图(b)部分区域的放大XRD图; (d~i)不同熔盐温度下制备1%-SrTiO3:Al的SEM图; 光催化活性测试条件: 100 mg光催化剂分散于100 mL去离子水中, 助催化剂的负载为0.1% (w) Rh-0.05% (w) Cr2O3-0.05% (w) CoOOH

Figure 2. (a) Photocatalytic overall water splitting activities of 1%-SrTiO3:Al synthesized via the flux method at various temperatures with the addition of 1 mol% γ-Al2O3. (b) XRD patterns of the corresponding samples in (a). (c) Enlarged XRD patterns in (b). (d~i) SEM images of 1%-SrTiO3:Al synthesized via the flux method at various temperatures with the addition of 1 mol% γ-Al2O3. Photocatalytic reaction conditions: 100 mg of photocatalyst loaded with 0.1% (w) Rh, 0.05% (w) Cr2O3, 0.05% (w) CoOOH, dispersed in 100 mL deionized water

图3. 添加量为1 mol%, Al源分别为γ-Al2O3、α-Al2O3(0.8)和α-Al2O3合成1%-SrTiO3:Al的光催化活性(a)与对应的XRD衍射图(b); (c)是图(b)部分区域的放大XRD图; (d~f)是对应1%-SrTiO3:Al的SEM图; 光催化活性测试条件: 100 mg光催化剂分散于100 mL去离子水中, 助催化剂的负载为0.1% (w) Rh-0.05% (w) Cr2O3-0.05% (w) CoOOH

Figure 3. (a) Photocatalytic overall water splitting activities of 1%-SrTiO3:Al synthesized via the flux method with the addition of 1 mol% γ-Al2O3, α-Al2O3(0.8) and α-Al2O3, respectively. (b) XRD patterns of the 1%-SrTiO3:Al in (a). (c) Enlarged XRD patterns in (b). (d~f) SEM images of the corresponding 1%-SrTiO3:Al samples. Photocatalytic reaction conditions: 100 mg of photocatalyst loaded with 0.1% (w) Rh, 0.05% (w) Cr2O3, 0.05% (w) CoOOH, dispersed in 100 mL deionized water

图4. 以十八面体SrTiO3为前驱体调节γ-Al2O3的添加量合成SrTiO3:Al的光催化活性(a)与XRD衍射图(b); (c)是图(b)部分区域的放大XRD图; (a)中的光催化活性测试条件: 100 mg光催化剂分散于100 mL去离子水中, 助催化剂的负载为0.1% (w) Rh-0.05% (w) Cr2O3-0.05% (w) CoOOH; 以固相合成的SrTiO3为前驱体调节γ-Al2O3的添加量合成SrTiO3:Al的光催化活性(d)与XRD衍射图(e); (f)是图(e)部分区域的放大XRD图; (d)中的光催化活性测试条件: 130 mg光催化剂分散于100 mL去离子水中, 助催化剂的负载为0.1% (w) Rh-0.05% (w) Cr2O3-0.05% (w) CoOOH

Figure 4. (a) Photocatalytic overall water splitting activities of SrTiO3:Al synthesized via the flux method with varying addition amounts of γ-Al2O3 using 18-facet SrTiO3 as the precursor. (b) XRD patterns of SrTiO3:Al samples in (a). (c) Enlarged XRD patterns in (b). Photocatalytic reaction conditions in (a): 100 mg of photocatalyst loaded with 0.1% (w) Rh, 0.05% (w) Cr2O3, 0.05% (w) CoOOH, dispersed in 100 mL deionized water. (d) Photocatalytic overall water splitting activities of SrTiO3:Al synthesized via the flux method with varying addition amounts of γ-Al2O3 using solid-state-derived SrTiO3 as the precursor. (e) XRD patterns of SrTiO3:Al samples in (d). (f) Enlarged XRD patterns in (e). Photocatalytic reaction conditions in (d): 130 mg of photocatalyst loaded with 0.1% (w) Rh, 0.05% (w) Cr2O3, 0.05% (w) CoOOH, dispersed in 100 mL deionized water

图5. (a~e)十八面体SrTiO3与以其为前驱体在对应Al2O3添加量下合成的SrTiO3:Al的SEM图; (f~j)固相合成的SrTiO3与以其为前驱体在对应Al2O3添加量下合成的SrTiO3:Al的SEM图

Figure 5. (a~e) SEM images of 18-facet SrTiO3 and the corresponding SrTiO3:Al samples with various Al2O3 additions. (f~j) SEM images of SrTiO3 prepared via solid-state reaction and the corresponding SrTiO3:Al samples synthesized with various Al2O3 additions

图6. 前驱体SrTiO3的SEM图(a~e)和对应2%-SrTiO3:Al的SEM图(f~j)

Figure 6. SEM images of SrTiO3 precursors (a~e) and the corresponding 2%-SrTiO3:Al samples (f~j)

图7. 前驱体SrTiO3的XRD衍射图(a); (b)是图(a)部分区域的放大XRD图; 各类2%-SrTiO3:Al的XRD衍射图(c)和光催化全分解水活性(e); (d)是图(c)部分区域的放大XRD图; 光催化活性测试条件: 130 mg光催化剂分散于100 mL去离子水中, 助催化剂的负载为0.1% (w) Rh-0.05% (w) Cr2O3-0.05% (w) CoOOH

Figure 7. (a) XRD patterns of the SrTiO3 precursors. (b) Enlarged XRD patterns in (a). XRD patterns (c) and photocatalytic overall water splitting activities (e) of the corresponding 2%-SrTiO3:Al samples. (d) Enlarged XRD patterns in (c). Photocatalytic reaction conditions: 130 mg of photocatalyst loaded with 0.1% (w) Rh, 0.05% (w) Cr2O3, 0.05% (w) CoOOH, dispersed in 100 mL deionized water

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Al掺杂SrTiO₃的合成调控及其光催化全分解水性能

Synthesis Control of Al-Doped SrTiO₃ and Its Photocatalytic Performance for Overall Water Splitting

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