原子分散的Ba位点作为电子促进剂增强Cu助催化剂的光还原CO2性能

doi:10.1016/S1872-2067(24)60226-3

摘要/Abstract

摘要：

化石能源的燃烧导致大气中CO₂浓度持续上升, 由此引发的温室效应严重影响人类生存环境. 因此, 降低大气中的CO₂浓度是一个全球性的挑战. 为了应对这一问题, 研究者们致力于加速CO₂的转化, 特别是通过光还原技术将CO₂转化为CO和碳氢化合物. 该技术不仅能够缓解温室效应, 还为解决能源危机提供了新的途径. 目前, 应用于光催化还原CO₂的半导体光催化剂有很多, 其中缺陷态TiO₂(TiO₂)由于其优异的光电化学性质和电子结构而备受关注. 然而, 单一的缺陷态TiO₂缺乏CO₂吸附和活化位点, 导致光还原CO₂活性较低. 因此, 设计一种高效的缺陷态TiO₂光催化剂用来提升CO₂还原性能是至关重要的.

本文通过光沉积的方法合成了Cu, Ba和CuBa修饰的TiO₂-SBO光催化剂(Cu/TiO₂-SBO, Ba/TiO₂-SBO和CuBa/TiO₂-SBO). X射线吸收谱和高分辨透射电镜结果表明, Cu和Ba物种是以原子分散的形式存在于缺陷态TiO₂表面上. 原位X射线光电子能谱、CO原位红外光谱和光电性能测试结果表明, 氧空位和CuBa双金属活性位协同促进了光诱导载流子的分离能力. 此外, 引入金属Ba作为电子供体可调节Cu位点的电子结构, 使光生电子从Ba原子转移到Cu原子上, 从而提高了Cu位点的电子密度并形成了富电子的Cu活性位点, 进而促进CO₂分子的活化. 结合原位红外光谱和理论计算表明, Cu₁Ba₃/TiO₂-SBO样品所产生的中间产物强度高于单金属修饰的TiO₂-SBO, 证实了CuBa双金属位点更有利于CO₂的活化, 从而提高了光催化还原CO₂的产率. 同时, Cu/TiO₂-SBO和Cu₁Ba₃/TiO₂-SBO对CO₂的吸附能分别为0.11和-1.59 eV, 表明Ba的存在显著地增强CO₂的吸附能力, 并促进其转化为CO和CH₄产物. 此外, 增强的*COOH结合力以及显著降低的CO和*CO中间体的形成能有利于COOH向CO的转化, 有助于CO₂高选择性地还原为CO产物. 其中Cu/TiO₂-SBO样品光还原CO₂的性能和选择性较差, 当担载碱土金属Ba之后, 有效地提高了光催化还原CO₂的活性和选择性. 最佳Cu₁Ba₃/TiO₂-SBO将CO₂还原为CO和CH₄的产率分别为32.0和7.0 µmol g^-1 h^-1, 分别是单一TiO₂-SBO产率的8倍和6倍, 其中CO产物的选择性高达53%.

综上, 本文以光沉积的方法合成了CuBa双金属修饰的TiO₂-SBO, 最优的Cu₁Ba₃/TiO₂-SBO样品在光催化还原CO₂反应中表现出了优异的活性和选择性. 此外，本文详细阐明了光催化还原CO₂的反应机理, 为将CO₂高效转化为高附加值产品提供了新思路.

关键词: 缺陷态二氧化钛, CuBa双金属, Cu助催化剂, 光还原CO₂, 光催化机理

Abstract:

The highly photocatalytic conversion of CO₂ into valuable products is a promising method for mitigating the global greenhouse effect and increasing the energy supply. However, the utilization of electron-deficient active sites to activate CO₂ leads to lower photocatalytic efficiency and selectivity. One effective strategy to improve CO₂ photoreduction performance is making precise adjustments to the electronic structure of the photocatalyst. Herein, the defective TiO₂ modified with Cu, Ba, and CuBa metal sites is synthesized via a simple photo-deposition method and applied for photoreduction of CO₂. Among the prepared catalysts, Cu₁Ba₃/TiO₂-SBO (TiO₂-SBO: TiO₂ with surface and bulk oxygen vacancies) has been demonstrated to possess excellent photocatalytic conversion of CO₂, with the activity levels of the CO and CH₄ that are 8 and 6 times higher than the bare TiO₂-SBO, and the electron selectivity of CO is up to 53%. The results reveal that oxygen vacancies and CuBa bimetallic sites have a synergistic ability to facilitate the separation of photogenerated carriers. Furthermore, the electron-donor Ba metal enables modulation of the electronic structure of Cu co-catalysts, generating electron-rich Cu metal sites that accelerate the activation of CO₂. Meanwhile, the theoretical calculations prove that the Cu₁Ba₃/TiO₂-SBO has the stronger CO₂ adsorption energy, and its strengthened binding of *COOH and the markedly reduced formation energy of CO and *CO intermediates boost the conversion of COOH to CO and enhance the selectivity of CO. Thereby, the defective TiO₂ modified with CuBa bimetal represents a more effective measure for CO₂ reduction into valuable products.

Key words: Defective TiO₂, CuBa bimetal, Cu co-catalyst, Photoreduction of CO₂, Photocatalytic mechanism

张丽娜, 刘国威, 邓欣妍, 李秋叶, 杨建军. 原子分散的Ba位点作为电子促进剂增强Cu助催化剂的光还原CO₂性能[J]. 催化学报, 2025, 70: 341-352.

Lina Zhang, Guowei Liu, Xinyan Deng, Qiuye Li, Jianjun Yang. Atomically dispersed Ba sites as electron promoters to enhance the performance for photoreduction of CO₂[J]. Chinese Journal of Catalysis, 2025, 70: 341-352.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60226-3

https://www.cjcatal.com/CN/Y2025/V70/I3/341

图/表 12

Fig. 1. TEM and HRTEM images of TiO2-SBO (a,c), Cu1Ba3/TiO2-SBO (b,d) as well as mapping diagram of Cu1Ba3/TiO2-SBO (e).

Fig. 2. XRD (a) and Raman (b) plots of TiO2-SBO, Cu/TiO2-SBO, Ba/TiO2-SBO and Cu1Ba3/TiO2-SBO samples.

Fig. 3. XANES spectra at the Cu K-edge of Cu1Ba3/TiO2-SBO, Cu foil, Cu2O and CuO (a) as well as Ba L3-edge of Cu1Ba3/TiO2-SBO and BaO (c). EXAFS spectra at Cu K-edge of Cu1Ba3/TiO2-SBO, Cu foil, Cu2O and CuO (b) as well as Ba L3-edge of Cu1Ba3/TiO2-SBO and BaO (d).

Fig. 4. XPS spectra of as synthesised samples. Ti 2p (a,c) and O 1s (b,d) of TiO2-SBO and Cu1Ba3/TiO2-SBO samples. (e) Cu 2p of Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO. (f) Ba 3d of Ba/TiO2-SBO and Cu1Ba3/TiO2-SBO.

Fig. 5. (a) CO-DRIFTS spectra of Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO. Differential charge density for Cu/TiO2-SBO (b) and Cu1Ba3/TiO2-SBO (c).

Fig. 6. (a) Photocatalytic CO2 reduction performance of all samples: (1) TiO2-SBO; (2) Cu/TiO2-SBO; (3) Ba/TiO2-SBO; (4) Cu1Ba1/TiO2-SBO; (5) Cu1Ba3/TiO2-SBO; (6) Cu0.5Ba3.5/TiO2-SBO. (b) Comparative activity of Cu1Ba3/A-TiO2 and Cu1Ba3/TiO2-SBO. (c) Cyclic stabilization tests of Cu1Ba3/TiO2-SBO. (d) The activity comparison of Cu1Ba3/Al2O3, Cu1Ba3/SiO2, and Cu1Ba3/TiO2-SBO in different atmospheres (under CO2 and without CO2).

Fig. 7. UV-vis absorption spectra (a), photocurrent (I-t) plots (b), PL (c) and electrochemical impedance spectra (d) of TiO2-SBO, Cu/TiO2-SBO, Ba/TiO2-SBO, and Cu1Ba3/TiO2-SBO samples.

Fig. 8. The CO2 Physisorption isotherms (a) and CO2-TPD plots (b) of the prepared samples. The details of the synthesized photocatalysts are available in Fig. 6(a).

Fig. 9. In situ XPS of Ti 2p (a), Cu 2p (b), and Ba 3d (c) for Cu1Ba3/TiO2-SBO.

Fig. 10. In situ DRIFTS plots of TiO2-SBO (a), Cu/TiO2-SBO (b), Ba/TiO2-SBO (c), and Cu1Ba3/TiO2-SBO (d).

Fig. 11. First-principles calculations of the CO step (a) and*CO step (c) over Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO. (b) The adsorption energy of *COOH on Cu/TiO2-SBO and Cu1Ba3/TiO2-SBO, where the cyan, pink, gray, blue and green balls represent the Ti, O, C, Cu, and Ba atoms, respectively.

Scheme 1. The mechanism and reaction pathways of photocatalytic CO2 conversion for Cu1Ba3/TiO2-SBO.

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原子分散的Ba位点作为电子促进剂增强Cu助催化剂的光还原CO₂性能

Atomically dispersed Ba sites as electron promoters to enhance the performance for photoreduction of CO₂

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