Construction of Bi2O2CO3/g-C3N4 heterojunction photocatalytic complete oxidation of benzyl alcohol to benzaldehyde

doi:10.11949/0438-1157.20210172

Abstract

Abstract:

Under the premise of ensuring selectivity, high-efficiency photocatalytic oxidation of benzyl alcohol to benzaldehyde is still a huge challenge. g-C₃N₄ has a moderate valence band position and mild oxidation ability. It has been developed for photocatalytic oxidation of benzyl alcohol to ensure the selectivity of the reaction, but the high electron-hole recombination rate makes it difficult to increase the conversion rate of the reaction. In this work, alternate $B i 2 O 2 2 +$ and $C O 3 2 -$ orthogonal symbiotic layer within Bi₂O₂CO₃ can not only increase the specific surface area of catalyst to form more active center, but also can construct local electric field to separate electronic-hole pair more efficiently. Therefore, we build the Bi₂O₂CO₃/g-C₃N₄heterojunction structure to speed up the carrier separation to enhance the reaction rate. The best photocatalyst can achieve both 100% selectivity and conversion after 9 h reaction, which reduces the cost of separation and has a huge development prospect. In this paper, the in-situ construction of the heterojunction accelerates the charge separation to promote the reaction. Its preparation method, reaction mechanism, energy level structure, etc., all have a certain guiding role in organic conversion reactions.

Key words: heterojunction, oxidation, photochemistry, alcohol, benzaldehyde

摘要：

在保证选择性的前提下高效光催化氧化苯甲醇为苯甲醛仍然是当下面临的一个巨大挑战。g-C₃N₄的价带位置适中，具有温和的氧化能力，已被开发用来光催化氧化苯甲醇以保证反应的选择性，但由于其电子空穴复合率高导致反应的转化率难以提升。由于Bi₂O₂CO₃的超薄片层结构不仅可以增加催化剂的比表面积形成更多的活性中心，同时可以形成局部电场，更有效地分离光生电子-空穴对，因此通过构建Bi₂O₂CO₃/g-C₃N₄异质结来加快光生载流子分离进而提升反应速率。其中最优的催化剂可以在反应9 h后使苯甲醇完全氧化为苯甲醛，降低了分离成本。

关键词: 异质结, 氧化, 光化学, 醇, 苯甲醛

CLC Number:

O 643

Yan LI, Liang JIAN, Qinyi MAO, Chengsi PAN, Pingping JIANG, Yongfa ZHU, Yuming DONG. Construction of Bi₂O₂CO₃/g-C₃N₄ heterojunction photocatalytic complete oxidation of benzyl alcohol to benzaldehyde[J]. CIESC Journal, 2021, 72(8): 4166-4176.

李燕, 蹇亮, 茅沁怡, 潘成思, 蒋平平, 朱永法, 董玉明. 构建Bi₂O₂CO₃/g-C₃N₄异质结光催化完全氧化苯甲醇至苯甲醛[J]. 化工学报, 2021, 72(8): 4166-4176.

Figures/Tables 9

Fig.1 Morphology of catalysts

Fig.2 N2 adsorption-desorption isotherms (a) and BJH pore size distribution (b) of g-C3N4 and 1.5-Bi2O2CO3/g-C3N4

Fig.3 XRD patterns of g-C3N4,Bi2O2CO3,x-Bi2O2CO3/g-C3N4 (x=0.5, 1.5, 2.5, 3.5)

Fig.4 XPS spectra of C 1s (a), N 1s (b), O 1s (c), Bi 4f (d) in 1.5-Bi2O2CO3/g-C3N4

Fig.5 UV-Vis diffuse reflection spectra of Bi2O2CO3, g-C3N4 and 1.5-Bi2O2CO3/g-C3N4 (a); Tauc curves of Bi2O2CO3 and g-C3N4 (b); Mott-Schottky diagram of g-C3N4 (c) and Bi2O2CO3 (d)

Fig.6 Comparison of reaction activity of g-C3N4, Bi2O2CO3, x-Bi2O2CO3/g-C3N4 (x=0.5, 1.5, 2.5, 3.5) [test conditions: 30 mg catalysts, 300 W xenon lamp (AM 1.5G), illumination time 4 h](a); The conversion of benzyl alcohol on 1.5-Bi2O2CO3/g-C3N4 in 9 h under the same conditions (b); Stability test of 1.5-Bi2O2CO3/g-C3N4 30 mg catalyst [test conditions: 30 mg catalysts, 300 W xenon lamp (AM 1.5G), illumination time 4 h] (c); The conversion of benzyl alcohol after radical capture experiment on 1.5-Bi2O2CO3/g-C3N4 (d)

Table 1 Overview of the literature on selective photocatalytic oxidation of benzyl alcohol

序号	催化剂	反应条件	选择性/%	转化率/%	文献
1	TiO₂@COF	white light LED, 30 h	99.9	92.5	[12]
2	Au-Pd/ZnIn₂S₄	λ> 420 nm, 10 h	>99	90.6	[45]
3	NH₂-MIL-125(Ti)	white light LED, 40 h	>99	88	[46]
4	N-vacancy-g-C₃N₄	AM 1.5, 9 h	>99	68.3	[20]
5	CdS@SnO₂;	λ> 420 nm, 8 h	98	78	[47]
6	Au-BiOCl-OV	λ> 420 nm, 8 h	>99	75.6	[19]
7	Bi₄O₅Br₂	blue LED, 24 h	>99	99.1	[48]
8	Bi₂O₂CO₃/g-C₃N₄	AM 1.5, 9 h	>99.9	>99.9	本工作

Fig.7 Steady-state fluorescence spectra (a), time-resolved PL decay spectra (b), transient photocurrent spectra (c), the EIS Nyquist plots (d) of photocatalysts for g-C3N4, Bi2O2CO3 and 1.5-Bi2O2CO3/g-C3N4

Fig.8 Reaction mechanism of photocatalytic oxidation of benzyl alcohol

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Construction of Bi₂O₂CO₃/g-C₃N₄ heterojunction photocatalytic complete oxidation of benzyl alcohol to benzaldehyde

构建Bi₂O₂CO₃/g-C₃N₄异质结光催化完全氧化苯甲醇至苯甲醛

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