BiOBr的形貌调控及其光催化CO2还原性能的研究

doi:10.11949/0438-1157.20241403

摘要/Abstract

摘要：

利用光催化技术将大气中的CO₂转化为高附加值的化学原料，是缓解能源和环境问题的有效方法。通过水热法制备了BiOBr，并采用聚乙烯吡咯烷酮（PVP）调控BiOBr的形貌。分析催化剂表征结果可知，引入PVP可成功制备得到纳米球状的BiOBr-xP（x表示引入PVP的量），相比于BiOBr，BiOBr-xP具有更大的比表面积，提高了活性位点的暴露概率。同时，PVP的引入改善了BiOBr的能带结构，BiOBr-xP的导带电势更负，有效提高了BiOBr的还原能力。光催化CO₂还原测试结果表明，BiOBr-2P具有最佳的光催化CO₂还原活性，CO的生成速率为2.74 μmol‧g^-1‧h^-1，是未引入PVP制备的BiOBr（0.81 μmol‧g^-1‧h^-1）的3.38倍。

关键词: 光催化, 二氧化碳, 一氧化碳, 形貌, BiOBr

Abstract:

The use of photocatalytic technology to convert atmospheric CO₂ into high-value-added chemical raw materials is an effective way to alleviate energy and environmental problems. In this work, BiOBr was synthesized via a hydrothermal method, and polyvinylpyrrolidone (PVP) was used to regulate the morphology of BiOBr. The catalyst characterization results show that nano-spherical BiOBr-xP (x represents the amount of PVP introduced) was successfully prepared by introducing PVP. Compared with BiOBr, BiOBr-xP has a larger specific surface area and increases the exposure probability of active sites. Meanwhile, the use of PVP improved the band structure of BiOBr, resulting in a more negative conduction band potential for BiOBr-xP, effectively improving its reduction capacity. Photocatalytic CO₂ reduction tests indicate that BiOBr-2P exhibits optimal photocatalytic activity, achieving a CO generation rate of 2.74 μmol‧g^-1‧h^-1, which is 3.38 times greater than that of BiOBr without PVP (0.81 μmol‧g^-1‧h^-1).

Key words: photocatalysis, carbon dioxide, carbon monoxide, morphology, BiOBr

中图分类号:

TQ 135.3

卢丽丽, 李晨, 陈柳云, 谢新玲, 罗轩, 苏通明, 秦祖赠, 纪红兵. BiOBr的形貌调控及其光催化CO₂还原性能的研究[J]. 化工学报, 2025, 76(6): 2687-2700.

Lili LU, Chen LI, Liuyun CHEN, Xinling XIE, Xuan LUO, Tongming SU, Zuzeng QIN, Hongbing JI. Morphology regulation of BiOBr and study on its performance of photocatalytic CO₂ reduction[J]. CIESC Journal, 2025, 76(6): 2687-2700.

图/表 11

图1 BiOBr和BiOBr-xP的XRD谱图(a)、FTIR光谱图(b)、N2吸附-脱附等温线(c)和孔径分布 (d)

Fig.1 XRD patterns (a), FTIR spectra (b), N2 adsorption-desorption isotherms (c) and pore size distribution (d) of BiOBr and BiOBr-xP

表1 BiOBr和BiOBr-xP的比表面积、孔容和平均孔径

Table 1 Specific surface area， pore volume， and average pore diameter of BiOBr and BiOBr-xP

样品	比表面积/(m²‧g^-1)	孔容/(cm³‧g^-1)	平均孔径/nm
BiOBr	6.26	0.025	14.31
BiOBr-1P	23.16	0.084	8.59
BiOBr-2P	24.56	0.072	7.84
BiOBr-5P	21.25	0.064	7.08
BiOBr-10P	12.19	0.041	7.78

图2 BiOBr(a)、BiOBr-1P(b)、BiOBr-2P(c)、BiOBr-5P(d)和BiOBr-10P(e)的SEM图

Fig.2 SEM images of BiOBr (a), BiOBr-1P (b), BiOBr-2P (c), BiOBr-5P (d), and BiOBr-10P (e)

图3 BiOBr[(a)~(c)]和BiOBr-2P[(d)~(f)]的TEM和HRTEM图，BiOBr-2P的HAADF-STEM图(g)和相应的EDS元素映射图[(h)~(j)]

Fig.3 TEM and HRTEM images of BiOBr[(a)—(c)] and BiOBr-2P[(d)—(f)], HAADF-STEM image (g) and the corresponding EDS element mappings [(h)—(j)] of BiOBr-2P

图4 BiOBr和BiOBr-2P的XPS全谱图(a)和Bi 4f(b)、Br 3d(c)、O 1s(d)和C 1s(e)的高分辨率XPS谱图，BiOBr-2P的N 1s(f)的高分辨率XPS谱图

Fig.4 XPS survey spectra of BiOBr and BiOBr-2P (a), high resolution XPS spectra of Bi 4f (b), Br 3d (c), O 1s (d), and C 1s (e) in BiOBr and BiOBr-2P, high resolution XPS spectra of N 1s (f) in BiOBr-2P

图5 BiOBr和BiOBr-xP的紫外-可见漫反射光谱(a)、禁带宽度(b)、PL光谱图(c)和瞬态光电流响应图(d)

Fig.5 UV-Vis diffuse reflectance spectra (a), band gap (b), PL spectra (c) and transient photocurrent response (d) of BiOBr and BiOBr-xP

图6 BiOBr和BiOBr-xP光催化CO2还原为CO的产量(a)和速率(b)，不同反应条件下BiOBr-2P光催化CO2还原为CO的产量(c)，BiOBr和BiOBr-2P光催化CO2还原的稳定性测试(d)

Fig.6 CO yield (a) and production rate (b) of photocatalytic CO2 reduction over BiOBr and BiOBr-xP, CO yield of photocatalytic CO2 reduction over BiOBr-2P under different reaction conditions (c), stability test of photocatalytic CO2 reduction over BiOBr and BiOBr-2P (d)

图7 BiOBr-2P反应前(a)和反应后(b)的SEM图；BiOBr-2P反应前和反应后的XRD谱图(c)和FTIR光谱图(d)

Fig.7 SEM images of BiOBr-2P before (a) and after (b) reaction, XRD patterns (c) and FTIR spectra (d) of BiOBr-2P before and after reaction

图8 黑暗下CO2和H2O在BiOBr(a)和BiOBr-2P(c)上共吸附的原位漫反射傅里叶变换红外光谱和光照下BiOBr(b)和BiOBr-2P(d)光催化CO2还原反应的原位漫反射傅里叶变换红外光谱

Fig.8 In-situ DRIFTS spectra of coadsorption of CO2 and H2O on BiOBr (a) and BiOBr-2P (c) in the dark, in-situ DRIFTS spectra of photocatalytic CO2 reduction reaction over BiOBr (b) and BiOBr-2P (d) under light irradiation

图9 BiOBr和BiOBr-2P的Mott-Schottky曲线[(a)、(b)]和XPS价带谱[(c)、(d)]

Fig.9 Mott-Schottky plots [(a), (b)] and XPS valence band spectra [（c）, (d)] of BiOBr and BiOBr-2P

图10 BiOBr-2P的能带结构

Fig.10 Energy band structure of BiOBr-2P

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BiOBr的形貌调控及其光催化CO₂还原性能的研究

Morphology regulation of BiOBr and study on its performance of photocatalytic CO₂ reduction

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