Cr-WO<sub>3</sub>超细纳米线用于苯乙烯选择性氧化制苯甲醛

王会香; 李鹏慧; 吕宝亮

doi:10.19906/j.cnki.JFCT.2023038

Cr-WO₃超细纳米线用于苯乙烯选择性氧化制苯甲醛

doi: 10.19906/j.cnki.JFCT.2023038

1.
山西师范大学化学与材料科学学院, 山西太原 030031
2.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001

基金项目: 国家自然科学基金（21972158），中国科学院洁净能源创新研究院-榆林学院联合基金（2021017），煤炭与绿色化工高效利用国家重点实验室基金（2021-K10），山西省优秀博士科研启动基金（SQ2019006）和专利转化专项基金（202202093）资助。

详细信息

通讯作者:
E-mail: lvbl@sxnu.edu.cn

中图分类号: O643
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出版历程
- 收稿日期: 2023-04-06
- 修回日期: 2023-04-26
- 录用日期: 2023-04-26
- 网络出版日期: 2023-05-06
- 刊出日期: 2023-12-05

Selective oxidation of styrene to benzaldehyde with Cr-WO₃ ultrafine nanowires

1.
School of Chemistry and Materials Science, Shanxi Normal University, Taiyuan 030031, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by the National Natural Science Foundation of China (21972158), Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (2021017), Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2021-K10), Doctoral Research Initiation Fund of Shanxi Province (SQ2019006) and Patent Conversion Foundation of Shanxi Province (202202093)

摘要

摘要: 本工作在水热法制备WO₃过程中直接引入Cr^{3 +}作为改性剂，其在非（001）晶面的选择性吸附，实现了WO₃形貌从纳米棒到[001]取向超细纳米线（UNWs）的转变，最终所得Cr-WO₃ UNWs催化剂的比表面积可达297 m²/g。此外，Cr^{3 +}的晶格掺杂和减缓结晶作用有效增加了WO₃表面氧空位（L酸位点）浓度。在苯乙烯选择性氧化制苯甲醛反应中，最佳条件下（70 ℃、r(n_H₂O₂/n_苯乙烯)=2.0、6 h、m=30 mg），Cr-WO₃ UNWs分别将苯乙烯转化率和苯甲醛选择性从单一WO₃纳米棒的19.0%和49.6%提升到72.0%和84.6%，其催化性能的提升归结于以下两点：第一，超大比表面积可提供充足的反应活性位点；第二，L酸位点可将H₂O₂活化为W-OOH活性物种，L酸位点浓度的增加有利于更多活性物种的产生。
- WO₃改性 /
- 氧空位 /
- 比表面积 /
- 苯乙烯氧化 /
- 苯甲醛
Abstract: The oxidation of styrene to benzaldehyde has advantages of mild conditions and no chlorine impurities in the product, and the design of highly active catalyst is the core. As a solid acid catalyst, WO₃ has excellent performance in thermal oxidation reaction, but its activity is limited by small specific surface area and high B acid content. In this work, the Cr^{3 +} cation was introduced as a modifier during the preparation of WO₃. The adsorption of Cr^{3 +} cations on non-(001) crystal plane realized the transformation of WO₃ from nanorods to ultrafine nanowires (UNWs), and the specific surface area of obtained Cr-WO₃ UNWs increased to 297 m²/g. In addition, Cr^{3 +} cation could dope into the lattice of WO₃ and slow down its crystallization, both of which effectively enriched the surface oxygen vacancies (L acid sites) of WO₃. In the reaction of selective oxidation of styrene to benzaldehyde, Cr-WO₃ UNWs effectively increased the conversion of styrene and the selectivity of benzaldehyde from 19.0% and 49.6% of pure WO₃ nanorod to 72.0% and 84.6% respectively under the optimized condition of 70 ℃, r(n_H₂O₂/n_styrene)=2.0, 6 h and m=30 mg. The improvement of catalytic performance can be attributed to the following two reasons:(1) the large specific surface area can provide sufficient active site for reaction; (2) the L acid site can activate H₂O₂ into active W-OOH, and an increase in the concentration of L acid site is beneficial for the production of more active species.
- WO₃ modification /
- oxygen vacancy /
- specific surface area /
- styrene oxidation /
- benzaldehyde

HTML全文

FIG. 2808. FIG. 2808.

FIG. 2808. FIG. 2808.

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图 1 Cr-WO₃和纯WO₃样品的SEM照片

Figure 1 SEM images of ((a), (b)) Cr-WO₃ and ((c), (d)) pure WO₃ samples

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图 2 Cr-WO₃和纯WO₃的XRD谱图

Figure 2 XRD patterns of Cr-WO₃ UNWs and WO₃ NRs

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图 3 Cr-WO₃和WO₃样品的TEM、HRTEM和SAED照片以及Cr-WO₃的EDX mapping图

Figure 3 TEM, HRTEM images and SAED patterns of ((a)−(c)) Cr-WO₃ UNWs and ((d)−(f)) WO₃ NRs; ((g)−(j)) EDX mapping images of Cr-WO₃ UNWs

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图 4 样品的Raman谱图

Figure 4 Raman spectra of Cr-WO₃ UNWs and WO₃ NRs

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图 5 Cr-WO₃和WO₃的XPS全谱、Cr 2p、W 4f和O 1s谱图

Figure 5 (a) Full XPS spectra of samples; (b) Cr 2p of Cr-WO₃ UNWs; (c) W 4f and (d) O 1s of Cr-WO₃ UNWs and WO₃ NRs

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图 6 样品在70 ℃下的Py-FTIR吸收光谱谱图

Figure 6 Py-FTIR spectra of Cr-WO₃ UNWs, WO₃ NRs and Cr₂WO₆ NPs at 70 ℃

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图 7 样品的N₂吸附-脱附曲线及孔分布

Figure 7 N₂ adsorption/desorption isotherms and corresponding pore size distributions (inset e) of (a) Cr-WO₃ UNWs, (b) WO₃ NRs and (c) Cr₂WO₆ NPs

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图 8 Cr-WO₃ UNWs催化苯乙烯制苯甲醛反应的影响因素

Figure 8 Influence factors of styrene to benzaldehyde on Cr-WO₃ UNWs (a): molar ratio r of H₂O₂ to styrene; (b): reaction temperature; (c): reaction time; (d): catalyst dosage

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图 9 H₂O₂效率和不同H₂O₂用量下的转化率

Figure 9 (a) H₂O₂ efficiency and (b) conversion increment of styrene under different H₂O₂ dosage

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图 10 不同样品作用下的苯乙烯转化率和苯甲醛选择性

Figure 10 (a) Conversion of styrene and (b) selectivity of benzaldehyde under different catalysts

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图 11 10 mg用量时WO₃和Cr-WO₃的性能比较

Figure 11 (a) Conversion, selectivity and (b) BD yield of WO₃ NRs and Cr-WO₃ UNWs with 10 mg dosage

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图 12 催化剂的循环性能

Figure 12 The cycling performance of Cr-WO₃ UNWs

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图 13 苯乙烯在催化剂上可能的反应过程

Figure 13 The possible oxidation reaction process of styrene on the Cr-WO₃ UNWs

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