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

富Bi型Bi₄O₅Br₂/TiO₂复合纤维的高效光催化CO₂还原

白城师范学院　纳米光催化材料研究中心吉林白城 13700

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
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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: 2023-02-28
- 刊出日期: 2023-11-15

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

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

Funds: National Natural Science Foundation of China, No.21573003; Natural Science Foundation of Jilin Province, No.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X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见吸收光谱(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。本研究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 X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electronmicroscopy (HRTEM), X-ray photoelectric spectroscopy (XPS), ultraviolet-visible absorption spectrum (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 paves new opportunities for exploring high-efficiency CO₂ photoreduction catalysts.
- Bismuth-rich /
- Bi₄O₅Br₂/TiO₂ composite fibers /
- Photocatalytic /
- CO₂ reduction /
- Electrospinning

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

Figure 1. XRD patterns(a) and the expanded view of XRD pattens(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图和Bi@Bi₄O₅Br₂/TiO₂ (e,f)的HRTEM图

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 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂ 的N₂吸附-脱附等温线和孔径分布曲线(插图)

Figure 3. N₂ adsorption-desorption isotherms and pore-size of TiO₂, Bi₄O₅Br₂, Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ samples

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图 4 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂的 CO₂ 吸附等温线(a)和样品Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂的CO₂程序升温脱附(b)

Figure 4. CO₂ adsorption isotherms of TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂for the samples (a) and temperature programmed desorption spectrum of CO₂ for the samples Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ (b)

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图 5 样品Bi@Bi₄O₅Br₂/TiO₂的XPS光谱图

Figure 5. XPS spectra of the Bi@Bi₄O₅Br₂/TiO₂ sample

(a) XPS survey spectra, (b) Ti 2 p, (c) Bi 4 f, (d) Br 3 d, (e )O 1 s

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图 6 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂的：(a)紫外-可见漫反射，(b)光致发光和(c)瞬态光电流；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(f)

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

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

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表 1 样品TiO₂、Bi₄O₅Br₂、Bi₄O₅Br₂/TiO₂和Bi@Bi₄O₅Br₂/TiO₂的比表面积、孔径和孔容大小

Table 1. Specific surface area, pore size, pore volume size of TiO₂, Bi₄O₅Br₂, Bi₄O₅Br₂/TiO₂ and Bi@Bi₄O₅Br₂/TiO₂ 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	Nanoscale 2020 Ref.[29]
Fe–TiO₂	12	Visible light (λ>400 nm)	CH₄	7.73	Micropor Mesopor Mat 2020 Ref.[30]
TiO₂–G	5	300 W Xe lamp NaHCO₃+H₂SO₄	CO CH₄	5.20 26.7	J Catal 2019 Ref.[31]
Fe/TiO₂/rRGO	5	300 W Xe lamp (λ>420 nm)	CH₄ O₂	4.08 4.32	Earth Env Sci 2020 Ref.[32]
Bi₂Al₄O₉/β–Bi₂O₃	10	300 W Xe lamp H₂O	CO	13.5	Green Energy Environ 2021 Ref.[33]
Bi/Bi₄O₅Br₂	2	300 W high pressure xenon lamp	CO CH₄	3.16 0.50	Nano Energy 2019 Ref.[34]
g-C₃N₄/α-Fe₂O₃		300 W Xenon lamp	CH₃OH	5.63	J CO₂ Util 2019 Ref.[35]
TiO₂/(NiOH)₂	3	300 W Xe lamp 40 mW cm⁻²	CO CH₄ CH₃OH CH₃CH₂OH	0.71 2.20 0.58 0.37	J. Mater. Chem. A 2018 Ref.[8]
Notes: D—diameter; G—graphene; rGO—reduced graphene oxide

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