Research progress on photocatalytic reduction of carbon dioxide in direct Z-scheme heterojunctions system

doi:10.11949/0438-1157.20240245

Abstract

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 heterojunctions (including photocatalytic reduction experiments, radical identification experiments, in situ X-ray photoelectron spectroscopy, metal loading, and theoretical calculations) are reviewed. 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. Finally, the challenges and opportunities faced by the development of this field are summarized and prospects are given.

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

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径。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，总结了直接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。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

CLC Number:

O 643.3

Ruobing PI, Yunlong ZHOU. Research progress on photocatalytic reduction of carbon dioxide in direct Z-scheme heterojunctions system[J]. CIESC Journal, 2024, 75(10): 3379-3400.

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, 2024, 75(10): 3379-3400.

Figures/Tables 19

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

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

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

Fig.2 Schematic illustration of photocatalysis mechanism in different systems

Fig.3 ESR analysis of g-C3N4、NiTiO3 and NT/GCN40 after irradiation and schematic illustration of reaction mechanism for Z-scheme heterojunction[54]

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

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

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

Fig.7 Photocatalytic mechanism of different composite materials

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]

Fig.9 Mechanism of photocatalytic CO2 reduction in different systems

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]

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

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

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

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

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

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

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

Fig.18 Mechanism of CO2 reduction in different photocatalytic systems

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