改性氮化碳光催化剂在生物质氧化反应中的应用

doi:10.15541/jim20210262

无机材料学报 ›› 2022, Vol. 37 ›› Issue (1): 38-44.DOI: 10.15541/jim20210262

• 专栏: CO ₂ 绿色转化(特邀编辑: 欧阳述昕, 王文中) • 上一篇下一篇

改性氮化碳光催化剂在生物质氧化反应中的应用

刘雪晨¹(), 曾滴¹^,², 周沅逸¹^,², 王海鹏¹^,², 张玲¹^,²(), 王文中¹^,²^,³()

1.中国科学院上海硅酸盐研究所, 上海 200050
2.中国科学院大学, 北京 100049
3.中国科学院大学杭州高等研究院, 杭州 310024

收稿日期:2021-04-20 修回日期:2021-06-23 出版日期:2022-01-20 网络出版日期:2021-06-30
通讯作者: 张玲, 副教授. E-mail: lingzhang@mail.sic.ac.cn; 王文中, 教授. E-mail: wzwang@mail.sic.ac.cn
作者简介:刘雪晨(1996-), 女, 硕士研究生. E-mail: xuechen1215@shu.edu.cn
基金资助:
国家自然科学基金(51972325);国家自然科学基金(51972327)

Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts

LIU Xuechen¹(), ZENG Di¹^,², ZHOU Yuanyi¹^,², WANG Haipeng¹^,², ZHANG Ling¹^,²(), WANG Wenzhong¹^,²^,³()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China

Received:2021-04-20 Revised:2021-06-23 Published:2022-01-20 Online:2021-06-30
Contact: ZHANG Ling, associate professor. E-mail: lingzhang@mail.sic.ac.cn; WANG Wenzhong, professor. E-mail: wzwang@mail.sic.ac.cn
About author:LIU Xuechen(1996-), female, Master candidate. E-mail: xuechen1215@shu.edu.cn
Supported by:
National Natural Science Foundation of China(51972325);National Natural Science Foundation of China(51972327)

摘要/Abstract

摘要：

利用氮化碳光催化剂催化生物质选择性转化, 不仅扩展了非金属催化剂的应用领域, 而且能够缓解化工产品过度依赖于化石能源的现状。2,5-二甲酰基呋喃是生产多种化工产品的关键中间体, 本研究将均苯四甲酸二酐引入氮化碳骨架, 并利用H₂O₂进行处理, 制备了含有氮羟基的改性氮化碳光催化剂, 并探究其在可见光激发下将生物质平台分子5-羟甲基糠醛通过绿色化学的方法选择性地氧化为2,5-二甲酰基呋喃的性能。结果表明：经过H₂O₂改性的催化剂, 在可见光激发下可以产生氮氧自由基, 使得底物分子侧链上的羟基选择性地氧化为醛基, 避免了在水相光催化条件下可能产生的多种活性氧物种引起的开环、矿化反应等副反应。特别是, 当光催化剂前驱体中蜜勒胺与均苯四甲酸二酐的比例为1 : 2时, 在400 nm LED光源激发下, 目标产物的选择性可达到96.2%。

关键词: 光催化, 5-羟甲基糠醛, 2,5-二甲酰基呋喃, 氮氧自由基, 氮化碳

Abstract:

Using carbon nitride photocatalysts to catalyze the selective conversion of biomass platform molecules could not only expand the application fields of non-metallic catalysts but also alleviate the dependence on fossil energy in chemical manufacturing. 2,5-diformylfuran is an indispensable intermediate for the production of value-added chemicals. In this study, pyromellitic dianhydride and melem were used as the precursors. The pyromellitic dianhydride monomer was incorporated into the carbon nitride skeleton by high-temperature heat-treatment, and the catalysts were further treated with H₂O₂. Finally non-metallic carbon nitride photocatalysts containing nitrogen hydroxyl groups were prepared. Moreover, its performance in the selective oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran under visible light excitation was investigated. The results showed that H₂O₂-treated samples could generate nitroxide radicals under light irradiation, resulting in the selective oxidation of hydroxyl groups on the side chains of 5-hydroxymethylfurfural molecules into aldehyde groups, avoiding undesired side-reactions (ring-opening, mineralization reactions, etc.) caused by various reactive oxygen species that may be generated in aqueous solutions. In particular, under the excitation of an LED light source with a specific wavelength (400 nm), when the ratio of melem to PMDA precursor was 1 : 2, the selectivity of 2,5-diformylfuran over the photocatalyst could reach 96.2%.

Key words: photocatalysis, 5-hydroxymethylfurfural, 2,5-diformylfuran, nitroxide radical, carbon nitrde

中图分类号:

O643

刘雪晨, 曾滴, 周沅逸, 王海鹏, 张玲, 王文中. 改性氮化碳光催化剂在生物质氧化反应中的应用[J]. 无机材料学报, 2022, 37(1): 38-44.

LIU Xuechen, ZENG Di, ZHOU Yuanyi, WANG Haipeng, ZHANG Ling, WANG Wenzhong. Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts[J]. Journal of Inorganic Materials, 2022, 37(1): 38-44.

图/表 11

图1 不同制备条件下获得样品的XRD谱图

Fig. 1 XRD patterns of samples prepared at different conditions (a) Sample PI (1:1) and its precursor PMDA and melem; (b) Samples PI (1:1), PI (2:1), PI (1:2), and PI (1:2)-120

图2 样品PI(1:2)(a, b)和样品PI(1:2)-120(c, d)的TEM照片

Fig. 2 TEM images of sample PI (1:2) (a, b) and sample PI (1:2)-120 (c, d)

图3 不同样品的XPS谱图(C1s)(a~d)和PI样品的结构简图(e)(不同颜色的C原子与XPS谱图对应)

Fig. 3 XPS spectra of different samples (C1s)(a-d), and structural illustration of PI sample (e) (different colors of C atoms correspond to XPS spectra) (a) PI (1:1); (b) PI (1:1)-120; (c) PI (1:2); (d) PI (1:2)-120; Colorful figures are available on website

图4 不同样品的O2-TPD图(a), 紫外-可见漫反射图(b)及光电流图谱(c)

Fig. 4 O2-TPD (a), UV-Vis diffuse reflectance spectra (b) and photocurrent profiles (c) of different samples Colorful figures are available on website

表1 不同催化剂对HMF催化氧化的实验结果

Table 1 Experimental results of catalytic oxidation of HMF by different catalysts

Entry	Catalyst	Con./%	Sel./%
1^[a]	C₃N₄	62.8	13.5
2^[a]	Melem	69.9	12.4
3^[a]	PI (1:1)	72.4	16.4
4^[a]	PI (2:1)	94.6	3.4
5^[a]	PI (1:2)	72.0	19.3
6^[a]	PI (1:1)-120	14.7	57.3
7^[a]	PI (1:2)-120	22.3	67.8
8^[b]	PI (1:2)-120	53.3	96.2
9^[c]	PI (1:2)	85.9	9.7

图5 氮氧自由基的检测及催化机理分析

Fig. 5 Nitrogen oxide radical detection and catalytic mechanism analysis (a) FT-IR spectra of PI (1:2) and PI (1:2)-120; (b) In situ FT-IR spectra of PI (1:2)-120 illuminated in air; (c) Absorption intensity versus time for catalyst suspensions with 4 mmol/L HMF added

图6 PI催化剂在H2O2处理前后可能的结构变化及其催化氧化HMF可能的机制

Fig. 6 Possible structural changes in PI catalysts before and after H2O2 treatment and their possible mechanism for catalytic oxidation of HMF

图S1 PI(1:2)、PI(1:2)-120的瞬时光电流衰减的归一化曲线

Fig. S1 Normalized decay of the transient photocurrent of PI (1:2) and PI (1:2)-120 samples

图S2 不同样品的Mott-Schottky图(a, b), 基于紫外-可见漫反射的带隙估算图(c), 基于VB XPS的价带位置估算图(d)以及催化剂能带位置示意图(e)

Fig. S2 Mott-Schottky spectra (a, b), estimated bandgap based on UV-Vis diffuse reflectance (c), valence band position estimation based on VB XPS (d), schematic diagram of catalyst energy band position (e) of different samples

图S3 (a)测试反应后甲臜的吸光度对比超氧自由基产量; (b)羟基自由基产量对比; (c)H2O2的产量对比

Fig. S3 (a) Comparison of absorbance of methanone after testing the superoxide radical reaction; (b) Comparison of the yields of OH; (c) Comparison of the yields of H2O2 Experimental condition: 50 mg Catalyst, 30 mL deionized water, atmospheric pressure: air atmosphere, 15 ℃, reaction time: 1 h (Fig. S3(a) concentration of NBT solution=0.2 mmol/L)

图S4 PI(1 : 2)-120催化剂的循环实验

Fig. S4 Cycling experiments of PI(1 : 2)-120 catalyst Experimental conditions: 50 mg PI(1:2)-120 catalyst, 400 nm LED lamp, 30 mL 0.67 mmol/L HMF aqueous solution, atmospheric pressure air, reaction for 12 h at 15 ℃

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改性氮化碳光催化剂在生物质氧化反应中的应用

Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts

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