十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛

引用本文: 邓长顺, 许孟霞, 董珍, 李磊, 杨金月, 郭学峰, 彭路明, 薛念华, 祝艳, 丁维平. 十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛[J]. 催化学报, 2020, 41(2): 341-349. doi: S1872-2067(19)63417-0 shu

Citation: Changshun Deng, Mengxia Xu, Zhen Dong, Lei Li, Jinyue Yang, Xuefeng Guo, Luming Peng, Nianhua Xue, Yan Zhu, Weiping Ding. Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles[J]. Chinese Journal of Catalysis, 2020, 41(2): 341-349. doi: S1872-2067(19)63417-0 shu

十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛

邓长顺 ^a, ,
许孟霞 ^a, ,
董珍 ^a, ,
李磊 ^a,b, ,
杨金月 ^a, ,
郭学峰 ^a, ,
彭路明 ^a, ,
薛念华 ^a, ,
祝艳 ^a, ,
丁维平 ^a,

a 南京大学化学化工学院介观化学教育部重点实验室, 江苏南京 210093;
b 中石化炼化工程(集团)股份有限公司洛阳技术研发中心, 河南洛阳 471003
基金项目:
国家自然科学基金（91434101，91745108）；国家重点研发计划（2017YFB0702900）.

摘要: 苯甲醛是一种用途广泛的重要化学品，通过O₂氧化甲苯制取苯甲醛是最佳生产途径，也是近几十年来工业界迫切需要的反应之一.虽然该反应在苄基上结合一个氧再脱除两个氢即可，对该反应的多相催化过程也已经研究了几十年，但其性能仍远远低于工业要求.当前的工业过程主要有甲苯氯化水解法和甲苯均相氧化法两种，但都存在严重的环境污染和腐蚀问题，且产品中含有少量卤素，阻碍了其在诸如香水或食品中的高端应用.近年来，以O₂作为氧化剂及Pd，Au，Pt，Ag，Ru等贵金属或它们间的合金为催化剂的甲苯液相氧化反应研究取得了一些很好的进展，但仍然不能在高甲苯转化率下高选择性地得到苯甲醛.本课题组曾报道了一种高效的混相催化体系，以O₂作为氧化剂将甲苯专一地催化氧化为苯甲醛，其中十六烷基膦酸-氧化铁（HDPA-FeO_x）纳米颗粒处在甲苯和水的界面上，稳定了该O/W类皮克林乳液（Pickering）.为了进一步提高催化剂晶格氧的移动性以提升催化活性，本文采用Mn，Co，Ni，Cu，Cr，Mo，V和Ti等一系列金属氧化物对催化剂HDPA-FeO_x进行掺杂，同时使用一种特殊的纳米Al₂O₃作为载体，大大地增加了催化剂制备的便捷性和保证了催化剂在实际应用中的稳定性.
TEM和XRD结果表明，Al₂O₃负载了金属氧化物后，其形貌仍为纳米棒状结构，并只能观察到Al₂O₃的晶相衍射峰，表明金属氧化物均匀地负载在其表面.BET结果表明，负载后的催化剂的孔结构与载体Al₂O₃类似.FT-IR结果表明，HDPA很好地吸附在了催化剂表面.TG结果表明，催化剂中HDPA含量与加入量相符，质量分数为~5%.结合前期工作可知，HDPA能够调整FeM纳米棒表面催化性质，且以1 HDPA/nm²的密度为最佳，此时，甲苯液相氧化为苯甲醛的催化性能最佳.
催化性能测试结果表明，催化剂吸附了HDPA后，甲苯的转化率显著增加，且只生成苯甲醛.在所考察的第二种掺杂金属中，以Ni的效果为最好.该催化剂在最佳反应条件下，甲苯转化率为83%（TOF=0.027 nm^-2·s^-1），苯甲醛选择性为~100%.而Cr，Mo，V和Ti等高价金属则抑制了该反应，这也说明通过掺杂第二种金属调变晶格氧的活动性可影响反应性能.经过优化后，最佳反应条件为：pH值为2.5，反应温度为180℃.原位FT-IR结果表明，180℃下，甲苯在吸附有HDPA的催化剂表面能够发生化学吸附，苄基C-H键解离并与晶格氧产生结合，形成了C₆H₅-CH₂-O-Fe中间物种，该物种脱附即得苯甲醛.该温度下，表面HDPA对甲苯的化学吸附不可缺.

关键词:

English

Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles

a Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, Jiangsu, China;
b Luoyang R&D Center of Technology, Sinopec Engineering (Group) Co., Ltd., Luoyang 471003, Henan, China
Received Date: 08 May 2019
Revised Date: 30 May 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (91434101, 91745108), the Ministry of Science and Technology of the People's Republic of China (2017YFB0702900).

Abstract: A series of hexadecylphosphate acid (HDPA) terminated mixed-oxide nanoparticles have been investigated to catalyze the oxidation of toluene exclusive to benzaldehyde under mild conditions in an emulsion of toluene/water with the catalysts as stabilizers. With the HDPA-Fe₂O₃/Al₂O₃ as the basic catalyst, a series of transition metals, such as Mn, Co, Ni, Cu, Cr, Mo, V, and Ti, was respectively doped to the basic catalyst to modify the performance of the catalytic system, in expectation of influencing the mobility of the lattice oxygen species in the oxide catalysts. Under normally working conditions of the catalytic system, the nanoparticles of catalysts located themselves at the interface between the oil and water phases, constituting the Pickering emulsion. Both the doped iron oxide and its surface adsorbed hexadecylphosphate molecules were essential to the catalytic system for excellent performances with high toluene conversions as well as the exclusive selectivity to benzaldehyde. Under optimal conditions,~83% of toluene conversion and >99% selectivity to benzaldehyde were obtained, using molecular oxygen as oxidant and HDPA-(Fe₂O₃-NiO)/Al₂O₃ as the catalyst. This process is green and low cost to produce high quality benzaldehyde from O₂ oxidation of toluene.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛

English

Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛

English

Exclusively catalytic oxidation of toluene to benzaldehyde in an O/W emulsion stabilized by hexadecylphosphate acid terminated mixed-oxide nanoparticles

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs