富Bi型Bi4O5Br2/TiO2复合纤维的高效光催化CO2还原

李跃军; 曹铁平; 孙大伟

doi:10.13801/j.cnki.fhclxb.20230222.004

富Bi型Bi₄O₅Br₂/TiO₂复合纤维的高效光催化CO₂还原

doi: 10.13801/j.cnki.fhclxb.20230222.004

白城师范学院　纳米光催化材料研究中心，白城 137000

基金项目: 国家自然科学基金项目(21573003)；吉林省自然科学基金项目(20140101118JC)

详细信息

通讯作者:
曹铁平，博士，教授，硕士生导师，研究方向为功能纳米材料　E-mail: bcctp2008@163.com

中图分类号: O614.32；TB33
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出版历程
- 收稿日期: 2022-12-13
- 修回日期: 2023-02-06
- 录用日期: 2023-02-10
- 网络出版日期: 2023-02-22
- 刊出日期: 2023-11-01

A bismuth-rich Bi₄O₅Br₂/TiO₂composites fibers photocatalyst enables dramatic CO₂ reduction activity

Baicheng Normal University, Research Centre of Nano-Photocatalyst, Baicheng 137000, China

Funds: National Natural Science Foundation of China (21573003); Natural Science Foundation of Jilin Province (20140101118JC)

摘要

摘要: 光催化CO₂还原技术既能实现节能减排，又能缓解能源短缺，符合当今绿色可持续发展的理念。本工作以静电纺丝技术制备的TiO₂纳米纤维为基质，结合水热还原法制备Bi@Bi₄O₅Br₂/TiO₂复合纤维。利用XRD、SEM、HRTEM、XPS、UV-Vis和碳吸附等方法对其微观结构、形貌和光学性能进行表征。结果表明：TiO₂ 纳米纤维经Bi₄O₅Br₂复合后，光谱响应范围拓展到可见光区，光生电子还原能力增强，可以将CO₂还原成CH₄和CO；金属Bi的富集不仅能提高催化剂对酸性CO₂分子的吸附能力，增强CO₂转化效率，而且能改变光催化反应路径，并有醇类物质(CH₃OH)的生成。模拟太阳光照射3 h，Bi@Bi₄O₅Br₂/TiO₂光催化CO₂还原生成CH₄、CO和CH₃OH的速率分别达到3.87、1.06和0.32 μmol·h⁻¹·g⁻¹。本文为探索高效二氧化碳光还原催化剂提供了新的机会。
- 富Bi /
- Bi₄O₅Br₂/TiO₂复合纤维 /
- 光催化 /
- CO₂还原 /
- 静电纺丝
Abstract: Photocatalytic reduction technology of CO₂ can not only achieve energy saving and emission reduction, but also alleviate energy shortage, which is in line with today's concept of green and sustainable development. By employing electrospun TiO₂ nanofibers as substrate, bismuth-rich Bi₄O₅Br₂/TiO₂ composite fibers were prepared combining with in-situ hydrothermal reduction method. The composition, morphology and photoelectric properties were characterized by XRD, SEM, HRTEM, XPS, UV-Vis and carbon adsorption. The results show that the band gap of Bi₄O₅Br₂/TiO₂ composite fibers becomes width, there is obvious absorption in the visible light band, and the reduction ability of photogenerated electrons is enhanced. Bi₄O₅Br₂/TiO₂ composite fibers can reduce CO₂ to CH₄ and CO, while the enrichment of the metal Bi can not only improve the adsorption capacity of the catalyst for acidic CO₂ molecules and enhance the conversion efficiency, but also change the photocatalytic reaction path and generate alcohol products such as CH₃OH. The CH₄, CO and CH₃OH yields of the optimized photocatalyst Bi@Bi₄O₅Br₂/TiO₂ composite fibers were 3.87, 1.06 and 0.32 μmol·h⁻¹·g⁻¹, respectively, after simulated sunlight irradiation 3 h. This work provides new opportunities for exploring high-efficiency CO₂ photoreduction catalysts.
- bismuth-rich /
- Bi₄O₅Br₂/TiO₂ composite fibers /
- photocatalytic /
- CO₂ reduction /
- electrospinning

HTML全文

图 1 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂的XRD图谱 (a) 和局部放大XRD图谱 (b)

Figure 1. XRD patterns (a) and the expanded view of XRD patterns (b) of TiO₂, Bi₄O₅Br₂, Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ samples

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图 2 样品TiO₂(a)、Bi₄O₅Br₂(b)、Bi₄O₅Br₂/TiO₂(c)_、Bi@Bi₄O₅Br₂/TiO₂(d)的SEM图像和Bi@Bi₄O₅Br₂/TiO₂ ((e), (f)) 的HRTEM图像

Figure 2. SEM images of samples TiO₂ (a), Bi₄O₅Br₂ (b), Bi₄O₅Br₂/TiO₂ (c), Bi@Bi₄O₅Br₂/TiO₂ (d) and HRTEM images of Bi@Bi₄O₅Br₂/TiO₂ ((e), (f))

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图 3 不同样品的N₂吸附-脱附等温线和孔径分布曲线

dV/dD—Differential pore volume versus diameter

Figure 3. N₂ adsorption-desorption isotherms and pore-size of different samples

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图 4 不同样品的CO₂吸附等温线 (a) 和CO₂程序升温脱附 (b)

Figure 4. CO₂ adsorption isotherms (a) and temperature programmed desorption spectrum of CO₂ (b) for the different samples

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图 5 样品Bi@Bi₄O₅Br₂/TiO₂的XPS图谱：(a) 全谱；(b) Ti2p；(c) Bi4f；(d) Br3d；(e) O1s

Figure 5. XPS spectra of the Bi@Bi₄O₅Br₂/TiO₂ sample: (a) Full spectrum; (b) Ti2p; (c) Bi4f; (d) Br3d; (e) O1s

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图 6 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂：(a) 紫外-可见漫反射；(b) 光致发光；(c) 瞬态光电流；(d) Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂的瞬态荧光衰减寿命；(e) TiO₂和Bi₄O₅Br₂的莫特肖特基曲线

τ—Fitting life; A—Corresponding proportion; C—Capacitance

Figure 6. TiO₂, Bi₄O₅Br₂, Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ samples: (a) UV-Vis DRS; (b) PL spectra; (c) Transient photocurrent responses; (d) Transient fluorescence decay lifetime of Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ samples; (e) Mott-Schottky curves of TiO₂ and Bi₄O₅Br₂ samples

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图 7 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂光催化CO₂还原3 h后CH₄、CO和CH₃OH的生成速率 (a) 及样品Bi@Bi₄O₅Br₂/TiO₂光催化产物的生成量随时间变化 (b)

Figure 7. Yields of CH₄, CO and CH₃OH for photocatalytic CO₂ reduction over TiO₂, Bi₄O₅Br₂, Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ samples after 3 hours irradiation (a) and time course of the products in the photocatalytic conversion of CO₂ over Bi@Bi₄O₅Br₂/TiO₂ sample (b)

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图 8 Bi@Bi₄O₅Br₂/TiO₂光催化CO₂还原反应机制示意图

CB—Conduction band; VB—Valence band; E_g—Band gap; E—Energy

Figure 8. Schematic mechanism of photocatalytic CO₂ reduction of Bi@Bi₄O₅Br₂/TiO₂ sample

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表 1 不同样品的比表面积、孔径和孔容大小

Table 1. Specific surface area, pore size, pore volume size of different samples

Sample	Specific surface area/ (m²·g⁻¹)	Average pore diameter/nm	Total pore volume/ (cm²·g⁻¹)
TiO₂	30	14.6	0.15
Bi₄O₅Br₂	128	20.4	0.24
Bi₄O₅Br₂/TiO₂	144	24.9	0.26
Bi@Bi₄O₅Br₂/TiO₂	132	21.6	0.25

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表 2 CO₂光催化还原产物生成速率比较

Table 2. Comparison of products generation rate for CO₂ photocatalytic reduction

Photocatalyst	Illumination period/h	Reaction condition	Product	Yield/ (μmol·g⁻¹·h⁻¹)	Reference
Pt/D-TiO_2–x	5	300 W Xe lamp 120℃, water	CH₄	0.34	[29]
Fe-TiO₂	12	Visible light (λ>400 nm)	CH₄	7.73	[30]
TiO₂-G	5	300 W Xe lamp NaHCO₃+H₂SO₄	CO CH₄	5.20 26.70	[31]
Fe/TiO₂/rGO	5	300 W Xe lamp (λ>420 nm)	CH₄ O₂	4.08 4.32	[32]
Bi₂Al₄O₉/β-Bi₂O₃	10	300 W Xe lamp H₂O	CO	13.50	[33]
Bi/Bi₄O₅Br₂	2	300 W high pressure Xenon lamp	CO CH₄	3.16 0.50	[18]
g-C₃N₄/α-Fe₂O₃		300 W Xenon lamp	CH₃OH	5.63	[34]
TiO₂/Ni(OH)₂	3	300 W Xe lamp 40 mW·cm⁻²	CO CH₄ CH₃OH CH₃CH₂OH	0.71 2.20 0.58 0.37	[8]
Notes: D—Diameter; G—Graphene; rGO—Reduced graphene oxide; λ—Wavelength.

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