| 第 52 卷第 5 期 |  | Vol. 52 No. 5 | | 2022 年 10 月 | Oct 2022 |
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所屬欄目：功能材料
P摻雜C3N4的制備及其在堿催化反應中的應用 |
| 陳 琨，肖 廣，蘭東輝*，沈 靜*，區澤堂，易 兵*
（湖南工程學(xué)院 材料與化工學(xué)院，環(huán)境催化與廢棄物再生化湖南省重點(diǎn)實(shí)驗室，湖南 湘潭 411104） |
| 摘 要：基于酸堿協(xié)同催化設計思想，以結構類(lèi)似的三聚氰胺和六氯環(huán)三磷腈熱縮聚制備了P摻雜的C3N4材料。利用SEM和BET分析P摻入前后材料的結構，發(fā)現P摻入后材料變?yōu)橹睆郊s為5 μm的球狀結構，比表面積由8.2 m2/g增加至11.9 m2/g。采用XPS和31P MAS NMR證明P以P-OH和P=O鍵形式進(jìn)入三嗪結構骨架中。將P摻雜的C3N4材料作為無(wú)金屬多相催化劑應用于堿催化反應中。采用硝酸將部分P-OH氧化為P=O，探討了P種類(lèi)和數量對環(huán)氧丙烷與CO2環(huán)加成反應、碳酸丙烯酯與甲醇酯交換反應以及苯甲醛與丙二腈Knoevenagel反應的影響，結合XPS和31P MAS NMR表征結果發(fā)現P-OH的引入有利于CO2環(huán)加成反應、酯交換反應和Knoevenagel反應的進(jìn)行。 |
| 關(guān)鍵詞：多相催化劑；碳三氮四；堿催化；CO2環(huán)加成反應；酯交換反應；Knoevenagel反應 |
| 中圖分類(lèi)號：O530.24 文獻標識碼：A 文章編號：1009-9212（2022）05-0050-07 |
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| Facile Synthesis of P-doped C3N4 for Base-catalyzed Reactions |
| CHEN Kun, XIAO Guang, LAN Dong-hui*, SHEN Jing*, AU Chak-tong, YI Bing*
(Hunan Provincial Key Laboratory of Environmental Catalysis and Waste Rechemistry, College of Materials and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, China) |
| Abstract：Based on the synergic catalytic effects between Base and Acid, P doped carbon nitride were facilely synthesized by thermal polycondensation of hexachlorotriphosphazene and melamine. Based on the results of SEM and BET analyses, P-C3N4 show a spheroidal structure with 11.9 m2/g. As characterized by XPS and 31P MAS NMR analyses, there is substitution of P atoms for C atoms which located at the bay and edge terminal positions. Partial P-OH bonds of P doped carbon nitride were oxidized to P=O by HNO3. The P doped carbon nitride was used as easy-to-handle and metal-free heterogeneous catalyst for base-catalyzed reactions such as cycloaddition of CO2 with propylene oxide, transesterification of propylene carbonate with methanol, Knoevenagel reaction between benzaldehyde and malononitrile. The relation between catalytic performance and the type and amount of P were investigated. The excellent performance of P-C3N4 for CO2 cycloaddition, transesterification and Knoevenagel reaction is owing to the synergetic effect of P-OH and uncondensed amino groups. |
| Key words：heterogeneous catalysts; C3N4; base-catalyzed reaction; CO2 cycloaddition; transesterification; Knoevenagel reaction |
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基金項目：湖南省教育廳優(yōu)秀青年項目（18B379），湖南省自然科學(xué)基金項目（2018JJ3099），大學(xué)生創(chuàng )新創(chuàng )業(yè)項目（202211342015），湖南省研究生科技創(chuàng )新項目（CX20221295）。
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作者簡(jiǎn)介：陳 琨（1999—），男，湖南岳陽(yáng)人，碩士，研究方向：多相催化（E-mail：756932363@qq.com）。
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聯(lián) 系 人：蘭東輝，副教授，博士，研究方向：多相催化、CO2資源化、碳酸酯合成（E-mail：donghuilan@hnu.edu.cn）；沈 靜，講師，博士，研究方向：功能材料；易 兵，教授，博士，研究方向：綠色合成，催化與不對稱(chēng)合成。
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收稿日期：2022-08-14
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