类金属WO2/g-C3N4复合光催化剂的构造及其优异的光催化性能

doi:10.1016/S1872-2067(22)64210-4

催化学报 ›› 2023, Vol. 47: 161-170.DOI: 10.1016/S1872-2067(22)64210-4

类金属WO₂/g-C₃N₄复合光催化剂的构造及其优异的光催化性能

李宁^a^,^b,*(), 高雪云^b, 苏俊珲^b, 高旸钦^b, 戈磊^a^,^b,*()

^a中国石油大学(北京)重质油加工国家重点实验室, 北京102249
^b中国石油大学(北京)新能源与材料学院, 材料科学与工程系, 北京102249

收稿日期:2022-08-23 接受日期:2022-12-13 出版日期:2023-04-18 发布日期:2023-03-20
通讯作者: *电子信箱: wubian.good@163.com (李宁),gelei08@sina.com (戈磊).
基金资助:
中国石油大学(北京)科学基金(2462017YJRC048);中国石油大学(北京)科学基金(2462018BJC005);国家自然科学基金(51802351)

Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis

Ning Li^a^,^b,*(), Xueyun Gao^b, Junhui Su^b, Yangqin Gao^b, Lei Ge^a^,^b,*()

^aState Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, Beijing 102249, China
^bDepartment of Materials Science and Engineering, College of New energy and Material, China University of Petroleum Beijing, Beijing 102249, China

Received:2022-08-23 Accepted:2022-12-13 Online:2023-04-18 Published:2023-03-20
Contact: *E-mail: wubian.good@163.com (N. Li),gelei08@sina.com (L. Ge).
Supported by:
Science Foundation of China University of Petroleum Beijing(2462017YJRC048);Science Foundation of China University of Petroleum Beijing(2462018BJC005);National Natural Science Foundation of China(51802351)

摘要/Abstract

摘要：

随着化石燃料快速消耗和环境污染日益严峻, 高效光催化产氢技术作为最有前景的绿色能源技术之一而备受关注. 作为典型的2D纳米片, g-C₃N₄具有很多适合应用在光催化领域的特性, 如可见光效应、大比表面积和环境友好等, 但单一g-C₃N₄的载流子复合率高, 光催化性能不佳. 研究者尝试负载贵金属(如Pt, Ag, Au等), 利用贵金属功函数较高, 可以快速捕获g-C₃N₄表面的光生电子, 从而有效抑制光生载流子的复合; 但其成本较高, 限制了该技术的产业化. 目前类金属材料(MoO₂, NbO₂, WO₂等)不仅表现出类似贵金属的特性, 且价格低廉, 有望替代贵金属. 因此, 引入类金属助催化剂是实现高载流子浓度和宽光谱照射下强光子吸收的好方法.

本文设计并制备了类金属WO₂/g-C₃N₄纳米复合物, 其表现出了较好的光催化性能: 在可见光照射2 h, 4 wt% WO₂/g-C₃N₄的光催化降解效率高达96%; 同时, 4 wt% WO₂/g-C₃N₄/Pt产氢效率高达2436.9 μmol g^‒1h^‒1, 是未改性样品3 wt% Pt/g-C₃N₄的2.55倍和非贵金属样品WO₂/g-C₃N₄的6.18倍, 且表现出很好的循环稳定性. 紫外可见漫反射光谱和态密度计算结果表明, WO₂具有非常窄的带隙, 可吸收200‒800 nm的宽范围可见光. 实验测试和理论计算结果表明, WO₂因带隙较窄而表现出类金属特性, 即在WO₂/g-C₃N₄界面, WO₂快速捕获电子, 从而抑制光生载流子的复合. 类金属WO₂因具有较低的功函数而表现出比贵金属Pt低的捕获光生电子活性. 综上, 本文为合理设计助催化剂/半导体, 实现高效的光催化性能提供了新视角.

关键词: g-C₃N₄, 类金属WO₂, 光催化产氢性能, 光催化降解, 非贵金属光催化剂

Abstract:

The introduction of a metallic cocatalyst is a good strategy for achieving a high carrier density and absorbing photons under wide-spectrum illumination. Herein, metallic WO₂/g-C₃N₄ nanocomposites were designed and synthesized for the first time using a simple calcination method to enhance the photocatalytic performance. WO₂/g-C₃N₄ exhibited significant photocatalytic properties: under visible light irradiation, 4 wt% WO₂/g-C₃N₄ exhibited an RhB photocatalytic degradation of 96% in 120 min. Meanwhile, the H₂ production rate of 4 wt% WO₂/g-C₃N₄/3 wt% Pt was 2436.9 μmol g^-1 h^-1, which was 2.55 and 6.18 times higher than that of 3 wt% Pt/g-C₃N₄ (956.35 μmol g^-1 h^-1) and WO₂/g-C₃N₄, respectively. Experimental tests and density functional theory calculations reveal that WO₂ exhibits a metal-like performance with a narrow bandgap to capture electrons and hinders the recombination of photogenerated charge carriers at the interface of WO₂/g-C₃N₄. Our study provides a new perspective for the rational design of metallic cocatalysts/semiconductors with highly efficient photocatalytic properties.

Key words: g-C₃N₄, Metallic WO₂, Photocatalytic hydrogen production, Photocatalytic degradation, Noble-metal-free photocatalyst

李宁, 高雪云, 苏俊珲, 高旸钦, 戈磊. 类金属WO₂/g-C₃N₄复合光催化剂的构造及其优异的光催化性能[J]. 催化学报, 2023, 47: 161-170.

Ning Li, Xueyun Gao, Junhui Su, Yangqin Gao, Lei Ge. Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis[J]. Chinese Journal of Catalysis, 2023, 47: 161-170.

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图/表 9

Fig. 1. (a) XRD patterns of g-C3N4, WO2, and WO2/g-C3N4 nanoparticles. (b) TEM image of 4 wt% WO2/g-C3N4. (c) HRTEM image of 4 wt% WO2/g-C3N4. (d) Mapping image of 4 wt% WO2/g-C3N4/3 wt% Pt.

Fig. 2. XPS spectra of g-C3N4, WO2, and 4 wt% WO2/g-C3N4 nanocomposites. (a) C 1s; (b) N 1s; (c) W 4f; (d) O 1s.

Fig. 3. Photocatalytic properties of the samples under visible irradiation. (a) Photocatalytic degradation activity of RhB. (b) Relationship between ?ln(C/C0) and irradiation time. (c,d) Photocatalytic H2 production performance with 3 wt% Pt as cocatalyst. (e) Cycle experiments of 4 wt% WO2/g-C3N4 for the photodegradation of RhB. (f) Cycle experiment data of the photocatalytic H2 production activity of the 4 wt% WO2/g-C3N4/3 wt% Pt photocatalyst.

Fig. 4. Transient photocurrent response curves (a), EIS spectra (b), PL spectra (c), and TRPL spectra (d) of g-C3N4, WO2, and 4 wt% WO2/g-C3N4 samples.

Fig. 5. (a) UV-vis diffuse reflectance spectra. (b) DRS band gap and UV-Vis-near-infrared absorption spectra (inset image). (c) Mott-Schottky plots of g-C3N4, WO2, and 4 wt% WO2/g-C3N4. (d) Band structures of g-C3N4 and WO2.

Fig. 6. Energy band structure (a) and DOS mapping (b) of g-C3N4; energy band structure (c) and DOS mapping (d) of WO2.

Fig. 7. ESR spectra of the 4 wt% WO2/g-C3N4 photocatalyst at room temperature. (a) e?; (b) H+; (c) ?O2-; (d) ?OH.

Fig. 8. Electrostatic potentials of g-C3N4 (a) and WO2 (111) surfaces (b).

Scheme 1. Possible photocatalytic mechanism under visible light illumination. (a) Photodegradation mechanism; the middle part represents the work functions of g-C3N4 and WO2 before contact. (b) Photocatalytic H2 production process.

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类金属WO₂/g-C₃N₄复合光催化剂的构造及其优异的光催化性能

Metallic WO₂-decorated g-C₃N₄ nanosheets as noble-metal-free photocatalysts for efficient photocatalysis

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