直接Z型异质结体系光催化还原二氧化碳研究进展

doi:10.11949/0438-1157.20240245

摘要/Abstract

摘要：

全球变暖与能源不足是世界性难题，利用太阳能通过光催化还原二氧化碳为高附加值的含碳化学品有望成为解决以上问题的重要途经。因此，制备高效且低成本的光催化材料至关重要。已知的双组分催化剂中，直接Z型异质结光催化剂因其较低的光生电子空穴复合率、强氧化及还原能力和较高的光催化反应效率得到广泛关注。综述了光催化还原二氧化碳的原理，直接Z型异质结的确认方法（包括光催化还原实验、自由基鉴别实验、原位辐照X射线光电子能谱、金属负载及理论计算等方法），明确了直接Z型异质结的光催化机理。此外，对直接Z型异质结结构中承担氧化或还原作用的常见催化剂的现阶段研究现状进行总结。最后，对于该领域发展所面临的挑战和机遇进行了总结和展望。

关键词: 光催化, 复合材料, 催化剂, 直接Z型异质结, 二氧化碳, 还原

Abstract:

Global warming and energy shortage is a worldwide problem, the use of solar energy photocatalytic reduction of carbon dioxide into high value-added carbon chemicals is expected to become an important way to solve the above problems. Therefore, it is crucial to develop efficient and low-cost photocatalytic materials. Among the known two-component catalysts, direct Z-scheme heterojunctions photocatalysts have attracted wide attention due to their lower rate of photo-generated electron-hole recombination, strong oxidizing and reducing capabilities, and higher photocatalytic reaction efficiency. The principle of photocatalytic reduction of carbon dioxide and the identification of direct Z-scheme heterojunction are reviewed (including photocatalytic reduction experiments, radical identification experiments, in situ X-ray photoelectron spectroscopy, metal loading, and theoretical calculations). The photocatalytic mechanism of direct Z-scheme heterojunctions is clarified. In addition, the current research status of common catalysts for oxidation or reduction in direct Z-heterostructure is summarized. Lastly, a summary and outlook on the challenges and opportunities facing the development in this field are provided.

Key words: photocatalysis, composites, catalyst, direct Z-scheme heterojunction, carbon dioxide, reduction

中图分类号:

O 643.3

皮若冰, 周云龙. 直接Z型异质结体系光催化还原二氧化碳研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20240245.

Roubing PI, Yunlong ZHOU. Research progress of direct Z-scheme heterojunctions system photocatalytic reduction of carbon dioxide[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240245.

图/表 19

图1 (a) Ⅱ型异质结和 (b) 直接Z型异质结光催化机理示意图

Fig.1 Diagram of photocatalytic mechanism of (a) Ⅱ- scheme heterojunction and (b) direct Z-scheme heterojunction

表1 光催化还原二氧化碳反应式及氧化还原电位（H2O存在条件下）

Table 1 Photocatalytic reduction of CO2 reaction formula and redox potential （with water）

反应方程	氧化还原电位E₀/(V vs NHE，pH=7.0))
2H₂O + 4h⁺→ O₂ + 4H⁺	+0.81V
2H⁺ + 2e^- → H₂	－0.42V
CO₂ + 2H⁺ +2e^- → CO + H₂O	-0.53V
CO₂ + 2H⁺ + 2e^- → HCOOH	-0.61V
CO₂ + 4H⁺ + 4e^- → HCHO + H₂O	-0.48V
CO₂ + 6H⁺ + 6e^- → CH₃OH + H₂O	-0.39V
CO₂ + 8H⁺ + 8e^- → CH₄ + 2H₂O	-0.24V
2CO₂ + 8H⁺ + 8e^- → CH₃COOH + 2H₂O	-0.31V
2CO₂ + 10H⁺ + 10e^- → CH₃CHO + 3H₂O	-0.36V
2CO₂ + 12H⁺ + 12e^- → C₂H₅OH + 3H₂O	-0.33V
2CO₂ + 14H⁺ + 14e^- → C₂H₆ + 4H₂O	-0.27V

图2 不同体系光催化机理示意图

Fig.2 Schematic illustration of mechanism photocatalysis in different systems

图3 光照后g-C3N4、NiTiO3和NT/GCN4的ESR分析图及Z型异质结反应机理示意图[54]

Fig.3 ESR analysis of g-C3N4、NiTiO3 and NT/GCN4 after irradiation and schematic illustration of reaction mechanism for Z-scheme heterojunction[54]

图4 光催化体系中•OH的检测及复合体系光催化机理[55]

Fig.4 Detection of •OH in photocatalytic systems and photocatalytic mechanism of composite system[55]

图5 ZnO/2%d的ISI-XPS高分辨率光谱和直接Z型电荷转移机制[58]

Fig.5 ISI-XPS high-resolution spectrum of ZnO/2%d and the direct Z-scheme charge transfer mechanism[58]

图6 通过在CPB/BWO异质结上光沉积Pt纳米粒子(NPs)跟踪电子转移路线:(a) TEM (b) HRTEM图像[61]

Fig.6 Tracking the electron transfer route by photodeposition of Pt nanoparticles (NPs) on the CPB/BWO heterojunction: (a) TEM (b)HRTEM images[61]

图7 不同复合材料的光催化机理图

Fig.7 Diagram of photocatalytic mechanism of different composite materials

图8 (a) (b) 不同材料在紫外可见光及可见光下的电流密度[80] (c) TiO2/ZnIn2S4形成的Z型体系示意图[80](d) Zn3In2S6/TiO2的光催化还原机理图[81]

Fig.8 (a) (b) Current density of different materials in UV-visible light and visible light[80] (c) Schematic diagrams for energy bands of TiO2 nanobelt and ZnIn2S4 nanosheet and the transfer of photogenerated electrons from TiO2 to ZnIn2S4 forming Z-scheme system under UV–vis light irradiation [80] (d) The CO2 photocatalytic reduction right mechanism of ZIS/TiO2[81]

图9 不同体系的光催化还原CO2反应机理图

Fig.9 Mechanism diagram of photocatalytic CO2 reduction in different systems

图10 (a) 不同还原剂对WO3/g-C3N4光催化CO2还原的影响 (b) Z型WO3/g-C3N4异质结示意图[88]

Fig.10 (a) Effect of reducing agent on the photoactivity of WO3/g-C3N4 for photocatalytic CO2 reduction (b) Schematic illustration of direct Z-scheme WO3/g-C3N4 heterojunction[88]

图11 WO3与LTON的费米能级，复合材料的内置电子场及Z型电荷转移机理[90]

Fig.11 Fermi levels of WO3 and LTON, internal electron fields of composites and Z-scheme charge transfer mechanism[90]

图12 Octa-SnFe2O4/α-Fe2O3的HRTEM图及光催化机理图[93]

Fig.12 HRTEM diagram and photocatalytic mechanism diagram of Octa-SnFe2O4/α-Fe2O3[93]

图13 不同体系的光催化还原CO2反应机理图

Fig.13 Mechanism diagram of photocatalytic CO2 reduction in different systems

图14 复合材料的高分辨率TEM图像、还原产物的GC-MS谱图及CO2产生碳氢化合物燃料的机理[101]

Fig.14 HRTEM images of composites, GC-MS spectra of reduction products and mechanistic representation of the production of hydrocarbon fuels from CO2[101]

图15 不同构型的异质结构的光催化剂的光催化性能及光催化机理[102]

Fig.15 Photocatalytic performance and photocatalytic mechanism of heterogeneous photocatalysts with different configurations[102]

图16 不同光催化体系能带位置及光催化还原二氧化碳机理图

Fig.16 Diagram of energy band position and mechanism of photocatalytic CO2 reduction in different photocatalytic systems

图17 Ⅱ型及Z型异质结示意图及C50、Pt/C50的TEM图像[112]

Fig.17 Diagram of Ⅱ-scheme and Z-scheme heterojunction and TEM image of C50, Pt/C50[112]

图18 不同光催化体系还原CO2反应机理图

Fig.18 Mechanism of CO2 reduction in different photocatalytic systems

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