调控Cs3Bi2Br9@VO-In2O3 S型异质结的费米能级和内建电场促进光生电荷分离和二氧化碳还原

doi:10.1016/S1872-2067(23)64549-8

摘要/Abstract

摘要：

近年来, 卤化物钙钛矿材料由于具有合适的能带结构和良好的可见光捕获能力, 被广泛应用于光催化还原CO₂. 然而, 单一的卤化物钙钛矿的载流子辐射复合严重, 导致其电荷分离效率较低, 并且对CO₂的捕获能力较差, 进而限制了其在光催化领域的实际应用. 构建异质结被认为是解决单一半导体光催化剂光生载流子分离效率低等问题的有效策略. 研究表明, S型异质结不仅可以实现光生载流子的有效分离, 而且其独特的光生电荷传输路径还可以使异质结体系保留较强的氧化还原能力, 利于光催化反应进行.

本文以提高Cs₃Bi₂Br₉钙钛矿量子点的载流子分离效率和CO₂吸附能力为目标, 构建了Cs₃Bi₂Br₉@V_O-In₂O₃(CBB@V_O-In₂O₃) S型异质结, 并探究了氧空位在该异质结光催化还原CO₂中的作用. 首先, 将Cs₃Bi₂Br₉钙钛矿量子点(PQD)嵌入到介孔In₂O₃基体中, 构建了CBB@In₂O₃ S型异质结. 然后, 将氧空位(V_O)引入到异质结的还原型半导体(介孔In₂O₃)中, 增大了CBB和V_O-In₂O₃之间的费米能级(E_F)差异, 进而增强了CBB@V_O-In₂O₃ S型异质结的内建电场. 电子自旋共振谱、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-vis DRS)等结果表明, In₂O₃中成功引入了氧空位. 表面电荷密度和表面光电压测试结果表明, CBB@In₂O₃异质结的内建电场强度为单一CBB的4.07倍, 而CBB@V_O-In₂O₃异质结的内建电场强度比单一的CBB提升了11.69倍, 进一步证明在In₂O₃中引入氧空位可以增大两种材料的费米能级差异及内建电场强度. 密度泛函理论(DFT)理论计算结果表明, 氧空位的引入能够使In₂O₃的费米能级向上移动, 使In₂O₃和CBB之间的费米能级差异增大, 与实验结果相一致. 这种增强的内建电场为光生载流子的定向迁移提供了更强的驱动力, 从而有效提高了该S型异质结的电荷分离效率. 采用UV-vis DRS, Tauc曲线和莫特-肖特基图谱等分析了In₂O₃和CBB的能级结构, 发现两种材料的能级位置交错排列, 有利于形成S型异质结. 瞬态吸收光谱、光辅助开尔文力显微镜和原位XPS等结果表明, 该异质结的电荷转移模式为S型. 该S型异质结的内建电场促进了电荷的高效分离, 使得CBB@V_O-In₂O₃异质结表现出较好的光催化CO₂还原为CO的性能, 其生成CO的产率为130.96 μmol g^‒1 h^‒1. 此外, 该CBB@V_O-In₂O₃ S型异质结表现出良好的光催化稳定性, 经过10次循环实验后, 其催化CO₂还原的性能未发生明显的下降. 通过原位漫反射红外傅立叶变换光谱研究了反应中间体和CO₂光转化途径. 结合DFT计算发现, V_O-In₂O₃中的氧空位作为活性位点, 能够优化反应中间体的配位模式, 从而降低了光催化还原CO₂的活化能.

综上所述, 调控S型异质结的内建电场是提高异质结电荷分离效率、提升材料光催化性能的有效策略. 本文构建了Cs₃Bi₂Br₉@V_O-In₂O₃(CBB@V_O-In₂O₃) S型异质结, 并探究了氧空位在该异质结光催化还原CO₂中的作用, 为高效S型异质结光催化材料的设计提供了一种新思路, 也为探索氧空位在S型异质结中的作用及人工光合成催化剂的制备提供一定参考.

关键词: S型异质结, 内建电场, 氧空位, V_O-In₂O₃, Cs₃Bi₂Br₉

Abstract:

Modulating the internal electric field (IEF) represents a potential strategy to stimulate the photocatalytic activity of heterojunctions, especially S-scheme photocatalysts. Herein, a Cs₃Bi₂Br₉@V_O-In₂O₃ (CBB@V_O-In₂O₃) S-scheme heterojunction, of which Cs₃Bi₂Br₉ perovskite quantum dots (PQDs) are embedded into mesoporous V_O-In₂O₃ hosts, is rationally designed as a cornerstone for further IEF manipulation. Briefly, by introducing oxygen vacancies (V_O) into the composed reduction semiconductor (mesoporous In₂O₃), an enlarged Fermi level (E_F) gap between CBB and V_O-In₂O₃ is achieved, yielding an intensified IEF over the CBB@V_O-In₂O₃ heterojunction. Such an enhanced IEF affords a much more robust driving force for directional carrier delivery, leading to accelerated carrier transfer of CBB@V_O-In₂O₃ heterojunction. Consequently, the optimized CBB@V_O-In₂O₃ heterojunction features desirable CO₂-to-CO conversion efficiency, and its CO production rate reaches 130.96 μmol g^-1 h^-1. The reaction intermediates and CO₂ photoconversion pathway were unraveled by in-situ diffuse reflectance infrared Fourier transform spectroscopy. Combining with the DFT calculation, it was revealed that oxygen vacancies in V_O-In₂O₃ act as reactive centers, which optimize the coordination modes of the intermediates, thus reducing the activation energy for photocatalytic CO₂ reduction. Our work demonstrates that the IEF modulation of S-scheme-based heterojunction could significantly boost the charge separation and then to drive efficient catalytic reaction, achieving high-efficiency solar fuel production.

Key words: S-Scheme heterojunction, Internal electric field, Oxygen vacancy, V_O-In₂O₃, Cs₃Bi₂Br₉

张志洁, 王雪盛, 唐慧玲, 李德本, 徐家跃. 调控Cs₃Bi₂Br₉@V_O-In₂O₃ S型异质结的费米能级和内建电场促进光生电荷分离和二氧化碳还原[J]. 催化学报, 2023, 55: 227-240.

Zhijie Zhang, Xuesheng Wang, Huiling Tang, Deben Li, Jiayue Xu. Modulation of Fermi level gap and internal electric field over Cs₃Bi₂Br₉@V_O-In₂O₃S-scheme heterojunction for boosted charge separation and CO₂ photoconversion[J]. Chinese Journal of Catalysis, 2023, 55: 227-240.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64549-8

https://www.cjcatal.com/CN/Y2023/V55/I12/227

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Fig. 1. (a) Graphic representation of the synthesis procedure of CBB@VO-In2O3 heterojunction. (b) Fermi level modulation of In2O3 for intensified IEF of CBB@VO-In2O3 heterojunction.

Fig. 2. EPR spectra (a), O 1s XPS spectra (b), UV-vis DRS (c), Tauc curves (d), M-S curves (e), and CB and VB positions (f) of In2O3 and VO-In2O3.

Fig. 3. Electrostatic potentials of In2O3 (a) and VO-In2O3 (c). DOS of In2O3 (b) and VO-In2O3 (d). The side view (e) and planar-averaged (f) electron density difference of the CBB@VO-In2O3 heterojunction.

Fig. 4. SCD (a), SPV (b), and IEF intensity (c) of CBB, CBB@In2O3, and CBB@VO-In2O3. (d) Amplifying IEF intensity between VO-In2O3 and CBB by introducing oxygen vacancies in In2O3.

Fig. 5. (a) XRD patterns of samples. TEM images of CBB PQDs (b) and the CBB@VO-In2O3 heterojunction (c-e). HRTEM image (f) and elemental mapping (g) of CBB@VO-In2O3.

Fig. 6. Photocatalytic production of CO with irradiation time (a) and CO production rate (b) over CBB, In2O3, VO-In2O3, CBB@In2O3, and CBB@VO-In2O3. (c) Production of CO under various conditions. (d) GC-MS analysis of 13CO from 13CO2 isotope experiment. (e) CO production rate over the CBB@VO-In2O3 heterojunctions with different weight ratios. (f) The recycle activity of CBB@VO-In2O3 for CO2 photoreduction. (g) Comparison of CO2 reduction performances of similar photocatalytic systems presented in recent papers.

Fig. 7. (a) Full-scan XPS of CBB, In2O3, VO-In2O3, and CBB@VO-In2O3 heterojunction. In situ XPS of Cs 3d (b), Bi 4f (c), Br 3d (d), In 3d (e), and O 1s (f) in CBB@VO-In2O3.

Fig. 8. Surface potential distribution variations of VO-In2O3 (a,b) and CBB@VO-In2O3 (c,d) in dark and light (ΔCPD = CPDlight - CPDdark). (e) S-scheme carrier separation mechanism of CBB@VO-In2O3 heterojunction under visible light illumination.

Fig. 9. The transient absorption spectra of CBB (a) and experimental decay kinetics (b) monitored under 550 nm. The transient absorption spectra of CBB@VO-In2O3 (c) and experimental decay kinetics (d) fitted under 520 nm.

Fig. 10. (a) In-situ DRIFTS spectra of CBB@VO-In2O3 collected every 10 min under visible light irradiation. (b) Optimized geometric structures of Gibbs free energy (ΔG) calculation of CO2 photoreduction over CBB@VO-In2O3. (c) Calculated ΔG for major steps in CO2 photoreduction over CBB and CBB@VO-In2O3. (d) Illustration of the mechanism for enhanced photocatalytic CO2 reduction performance over the CBB@VO-In2O3 heterojunction.

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调控Cs₃Bi₂Br₉@V_O-In₂O₃ S型异质结的费米能级和内建电场促进光生电荷分离和二氧化碳还原

Modulation of Fermi level gap and internal electric field over Cs₃Bi₂Br₉@V_O-In₂O₃S-scheme heterojunction for boosted charge separation and CO₂ photoconversion

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