双空位诱导极化场与内建电场增强的S型异质结用于去除抗生素及六价铬

doi:10.1016/S1872-2067(25)64754-1

摘要/Abstract

摘要：

废水中抗生素和重金属通常共存, 形成难以去除的复合污染物, 对环境造成严重危害. 光驱动半导体光催化技术是解决上述问题的有效途径之一, 然而光生电子空穴对的快速复合阻碍了光催化性能的提升. S型异质结作为一种创新型的异质结, 组分中的还原型光催化材料(RP)与氧化型光催化材料(OP)具有交错能带结构、强氧化还原能力和界面间电荷分离能力, 近年来受到了广泛的关注. 目前对S型异质结的研究大多集中在寻找适合的RP和OP上, 而对于S型异质结的界面电荷转移驱动力不足的问题关注较少. 因此, 本文在适配的RP和OP基础上, 创新性地通过可再生氧空位-阳离子空位对的构建形成极化电场, 同步调控双组分费米能级以强化内建电场强度从而获得更强的电荷驱动力.

本文通过静电组装方法构建了一系列具有双空位(Mo空位和光激发O空位)的V_Mo-BMO/O_v-BOB S型异质结, 可在驱动载流子定向分离的极化电场和增强的内建电场的协同作用下实现了电荷的高效分离和污染物的有效去除. 通过X射线衍射、红外光谱、X射线光电子能谱、紫外-可见漫反射光谱和透射电镜等表征结果证实S型异质结的成功构建和双空位的有效引入. 得益于双空位对S型异质结电子结构的调制, V_Mo-BMO/O_v-BOB-0.3样品对Cr (VI)和四环素(TC)的去除率分别是单一体系的2.47倍和1.13倍, 这归因于TC和Cr (VI)共存加速了光生电子-空穴对的消耗, 从而抑制其复合. 样品在太阳光下对TC与Cr (VI)的降解速率常数分别达到0.047和0.046 min^-1, 展现出良好的实际应用潜力. 原位X射线光电子能谱证实了V_Mo-BMO/O_v-BOB异质结电子转移遵循S型电荷转移机制. 原位电子顺磁共振(EPR)图谱表明, 在LED光的照射下, 可以产生表面O空位. 这种光激发O空位(P-O_v)使V_Mo-BMO/O_v-BOB复合材料在连续5次循环反应后仍然表现出稳定的活性. 此外, 密度泛函理论计算结果表明, 双空位的引入增大了偶极矩和异质结费米能级间隙, 从而可以产生更强的内建电场, 促进界面电荷迁移. 光致发光光谱、时间分辨光致发光光谱及电化学分析表明, S型异质结和双空位的构建促进了载流子的电荷转移, 延长了载流子的寿命. 自由基猝灭实验和EPR测试发现, •OH, h⁺和•O₂⁻活性物种共同参与了光催化降解TC的反应. 通过高效液相色谱-质谱联用仪和毒性分析软件对TC的降解路径和中间体毒性进行了评估, 并通过绿豆种子培育实验研究了光催化处理后溶液的毒性. 最后, 系统阐明了V_Mo-BMO/O_v-BOB协同去除TC和Cr (VI)的反应机理.

综上所述, 本文通过在S型异质结中引入阴阳离子空位, 解决了S型异质结界面电荷传输驱动力不足的问题, 为设计高活性S型异质结催化剂进行废水净化提供了新见解.

关键词: 光催化, S型异质结, 双空位, 极化, 费米能级

Abstract:

Antibiotics and heavy metals usually co-exist in wastewater and pose serious environmental hazards. Herein, a series of V_Mo-BMO/O_v-BOB S-scheme heterojunctions with double vacancy (Mo vacancy and photoexcited O vacancy) were constructed via an electrostatic assembly method. The removal efficiency of Cr (VI) and tetracycline (TC) over V_Mo-BMO/O_v-BOB-0.3 was 2.47 and 1.13 times than that of a single system, respectively. In-situ EPR demonstrated that the surface O vacancies could be generated under LED light irradiation. These photoexcited O vacancies (P-O_v) enabled V_Mo-BMO/O_v-BOB composites still exhibit satisfactory activity after five successive cycles and an amplified Fermi level gap. The enhancement could be attributed to the enhanced internal electric field and double-vacancy-induced polarization. Additionally, the density functional theory calculation results suggested that double vacancy induced polarization electric field increases the dipole moment, which was conducive to rapid electron transport. Photoluminescence and time-resolved photoluminescence analysis demonstrated that the introduction of S-scheme heterojunction and double vacancy promoted charge transfer and prolonged the lifetime of carriers. Degradation intermediates and toxicity of products were evaluated. In conclusion, a possible mechanism based on V_Mo-BMO/O_v-BOB S-scheme heterojunction in the simultaneous removal of Cr (VI) and TC was proposed.

Key words: Photocatalysis, S-scheme heterojunction, Double vacancy, Polarization, Fermi level

郑相阳, 吴金往, 史海峰. 双空位诱导极化场与内建电场增强的S型异质结用于去除抗生素及六价铬[J]. 催化学报, 2025, 76: 50-64.

Xiangyang Zheng, Jinwang Wu, Haifeng Shi. Double-vacancy-induced polarization and intensified built-in electric field in S-Scheme heterojunction for removal of antibiotics and Cr (VI)[J]. Chinese Journal of Catalysis, 2025, 76: 50-64.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64754-1

https://www.cjcatal.com/CN/Y2025/V76/I9/50

图/表 11

Fig. 1. (a) Schematic of the procedure for the preparation of VMo-BMO/Ov-BOB samples. XRD patterns (b) and FTIR spectra (c) of Ov-BOB, VMo-BMO, and VMo-BMO/Ov-BOB-X (X = 0.2, 0.3, 0.4).

Fig. 2. SEM images of Ov-BOB (a), VMo-BMO (b), and VMo-BMO/Ov-BOB-0.3 (c). TEM (d) and HRTEM (e) images of VMo-BMO/Ov-BOB-0.3. In-situ Bi 4f (f), O 1s (g), Br 3d (h), and Mo 3d (i) XPS spectra of Ov-BOB, VMo-BMO, and VMo-BMO/Ov-BOB-0.3.

Fig. 3. (a) UV-vis DRS of Ov-BOB, VMo-BMO, and VMo-BMO/Ov-BOB-X (X = 0.2, 0.3, 0.4). (b) Tauc’s plots of Ov-BOB and VMo-BMO. (c) UV-vis DRS of VMo-BMO and BMO. (d) VB-XPS spectra of Ov-BOB and VMo-BMO.

Fig. 4. (a) EPR signals of VMo-BMO/Ov-BOB-0.3 upon visible light illumination and maintaining at ambient air with different time. (b) UV-vis DRS spectra of VMo-BMO/Ov-BOB-0.3 under dark and visible light irradiation conditions. (c) Schematic of the Ov looping on VMo-BMO/Ov-BOB-0.3. (d) Digital photographs of as-prepared samples in the initial and colored states.

Fig. 5. (a) The photocatalytic performance of VMo-BMO, Ov-BOB, BMO/Ov-BOB-0.3, VMo-BMO/Ov-BOB-0.3(MM), and VMo-BMO/Ov-BOB-X (X = 0.2, 0.3, 0.4) in TC degradation. (b) The photocatalytic performance of VMo-BMO, Ov-BOB, BMO/Ov-BOB-0.3, VMo-BMO/Ov-BOB-0.3(MM), and VMo-BMO/Ov-BOB-X (X = 0.2, 0.3, 0.4) in Cr (VI) reduction. (c) The simultaneous removal of TC and Cr (VI) over VMo-BMO/Ov-BOB-0.3. The corresponding reaction kinetics constants of TC degradation (d), Cr (VI) reduction (e), and the simultaneous removal of TC and Cr (VI) (f). Conditions: [TC] = 15 mg·L-1, [Cr (VI)] = 10 mg·L-1, [catalyst] = 0.03 g, [pH] = 7.

Fig. 6. The photocatalytic performance of simultaneous removal of TC and Cr (VI) under solar light irradiation over VMo-BMO/Ov-BOB-0.3 (a) and the corresponding reaction kinetics constants (b). (c) Recycling performance of VMo-BMO/Ov-BOB-0.3. (d) XRD patterns for fresh and used VMo-BMO/Ov-BOB-0.3. (e,f) Free radical trap experiments of VMo-BMO/Ov-BOB-0.3. EPR spectra of DMPO-·O2− (g) and DMPO-·OH (h) of VMo-BMO/Ov-BOB-0.3. Conditions: [TC] = 15 mg·L-1, [Cr (Ⅵ)] = 10 mg·L-1, [EDTA] = 1.0 mmol L-1, [IPA] = 1.0 mmol L-1, [BQ] = 0.33 mmol L-1, [Catalyst] = 0.03 g, pH = 7.

Fig. 7. (a) Proposed pathways of TC degradation over VMo-BMO/Ov-BOB-0.3. Toxicity assessment of TC and its intermediate substance: acute toxicity (b), developmental toxicity (c), and mutagenicity (d). (e) Digital photograph of mung bean seed cultured in different solutions.

Table 1 The τavg of the samples were obtained by double exponential fitting.

Sample	τ₁ (ns)	A₁ (%)	τ₂ (ns)	A₂ (%)	τ_avg (ns)
V_Mo-BMO	2.46	0.68	2.67	0.32	2.53
O_v-BOB	1.93	0.51	1.59	0.49	1.65
BMO/O_v-BOB-0.3	2.03	0.44	2.64	0.56	2.41
V_Mo-BMO/O_v-BOB-0.3 (dark)	2.71	0.64	3.04	0.36	2.84
V_Mo-BMO/O_v-BOB-0.3 (light)	2.75	0.32	3.12	0.78	3.02

Fig. 8. PL spectra (a), TR-PL decay spectra (b), EIS (c), and transient photocurrent response spectra (d) of the Ov-BOB, VMo-BMO, BMO/Ov-BOB-0.3, and VMo-BMO/Ov-BOB-0.3 samples.

Fig. 9. The crystal structures of Ov-BOB (a), VMo-BMO (b), and VMo-BMO/Ov-BOB heterojunction (c). Work function of VMo-BMO (d), BMO (e), Ov-BOB (f), and BOB (g). Modulation of Fermi level between VMo-BMO, Ov-BOB, BMO and BOB. The band structures of VMo-BMO and Ov-BOB: before contact (h), after contact (i), and the photoinduced carriers transfer mechanism (j). (k) Modulation of Fermi level between VMo-BMO, Ov-BOB, BMO and BOB.

Fig. 10. Diagram of the electrostatic potential of Ov-BOB (a), VMo-BMO (b), VMo-BMO/Ov-BOB-0.3 (c), and the value of dipole moment fitted by the electrostatic potential diagram (d). (e) The possible simultaneous removal mechanism of Cr (VI) and TC over the VMo-BMO/Ov-BOB-0.3 composite.

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