烷基膦酸键合的纳米氧化物上甲苯选择氧化制苯甲醛的类酶机理

doi:10.1016/S1872-2067(20)63758-5

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1509-1518.DOI: 10.1016/S1872-2067(20)63758-5

烷基膦酸键合的纳米氧化物上甲苯选择氧化制苯甲醛的类酶机理

邓长顺, 崔韵, 陈俊超, 陈腾, 郭学锋, 季伟捷, 彭路明, 丁维平^*()

南京大学化学化工学院, 介观化学教育部重点实验室,江苏南京210023

收稿日期:2020-11-19 接受日期:2021-01-11 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 丁维平
基金资助:
国家自然科学基金(21932004);国家自然科学基金(91745108);国家重点研发计划(2017YFB0702800)

Enzyme-like mechanism of selective toluene oxidation to benzaldehyde over organophosphoric acid-bonded nano-oxides

Changshun Deng, Yun Cui, Junchao Chen, Teng Chen, Xuefeng Guo, Weijie Ji, Luming Peng, Weiping Ding^*()

Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China

Received:2020-11-19 Accepted:2021-01-11 Online:2021-09-18 Published:2021-05-16
Contact: Weiping Ding
About author:^* Tel: +86-25-89685077; Fax: +86-25-89687761; E-mail: dingwp@nju.edu.cn
Supported by:
National Science Foundation of China(21932004);National Science Foundation of China(91745108);National Key R&D Program of China(2017YFB0702800)

摘要/Abstract

摘要：

在传统催化反应中, 分子氧催化氧化烷烃生成目标产物的选择性最低, 常产生副产物以及大量的CO_x和水, 因需要复杂的分离过程而导致流程的投资成本高. 因此, 在过去几十年里, 针对此类反应的研究以提高选择性为首要目标, 但克服这一挑战的任务依然艰巨. 在此类反应中, 甲苯经O₂选择性催化氧化是制备苯甲醛的最佳途径, 但从未实现工业化, 其中的主要难点在于苯甲醛在临氧条件下的继续氧化反应速率比甲苯氧化高4个数量级以上. 因此, 在高甲苯转化率下高选择性获得苯甲醛是绿色化学研究中一个极具挑战性的课题.
本文发现一种甲苯/水的类皮克林乳液催化体系对甲苯转化为苯甲醛有很高的活性和选择性, 其中两性纳米颗粒(十六烷基膦酸, 简写为HDPA, 键合的纳米铁基氧化物)作为催化剂并处在乳液相界面处. 在温和条件下通过O₂氧化, 苯甲醛的时空产率大于2 g·g^-1·h^-1, 整个过程没有使用H₂O₂、卤素或其它自由基引发剂. 实验发现, 用于甲苯氧化反应的相关催化剂HDPA-FeMO_x/γ-Al₂O₃ (M: V和Mo等)的作用机制类似甲烷单加氧酶. 在传统固定床反应器中和温和的条件下(70~160 °C, 常压), 催化剂能将甲苯单一氧化为苯甲醛. 催化剂的活性中心与HDPA以单齿态与氧化物表面键合有关, 并且它的另一个磷羟基与氧化物表面在非键合态和键合态之间循环变化, 分别对应甲苯反应中催化剂的氧化态和还原态, 即HDPA与氧化物表面通过单齿和双齿键合循环变化, 极大地提升了该铁基复合氧化物晶格氧的移动性而使得催化剂反应活性得到明显提升.
透射电子显微镜、X射线衍射和氮吸附测量结果表明, 铁基复合金属氧化物在γ-Al₂O₃纳米棒上具有良好的分散性和较大的比表面积. X射线光电子能谱、吡啶吸附FT-IR和³¹P NMR结果表明, 与表面键合的HDPA保留了有机膦酸属性, 没有与FeMO_x/γ-Al₂O₃生成体相磷酸盐, 其中, 以单齿状态与表面键合HDPA分子只占总数的2%左右. H₂-TPR和CO-TPR结果表明, HDPA的键合强烈影响了晶格氧的流动性或金属氧化物的活性. 反应条件下原位FT-IR结果表明, HDPA-FeVO_x/γ-Al₂O₃在70 °C下即能催化甲苯氧化成苯甲醛, 且不会过度氧化, 该催化剂的晶格氧物种可参与甲苯转化为苯甲醛. 此外, 发现HDPA-Fe₂O₃/γ-Al₂O₃对甲苯的吸附具有特殊的分子识别作用, 以苯甲醇氧化作为对照反应的研究结果也表明HDPA-Fe₂O₃/γ-Al₂O₃对甲苯氧化为苯甲醛的反应存特异催化作用. 宏观反应动力学测试结果表明, 催化剂上苯甲醛生成的表观活化能仅为~44.5 kJ/mol. 在低H₂O浓度下, 甲苯氧化速率对甲苯浓度为一级反应, 对O₂浓度为零级反应, 基元反应步骤推导出来的动力学方程与实验结果良好吻合, 说明了该催化剂上类酶反应基元步骤假设的合理性.

关键词: 选择氧化, 甲苯, 苯甲醛, 十六烷基膦酸, 类酶, 机理

Abstract:

The completely selective oxidation of toluene to benzaldehyde with dioxygen, without the need to use H₂O₂, halogens, or any radical initiators, is a reaction long desired but never previously successful. Here, we demonstrate the enzyme-like mechanism of the reaction over hexadecylphosphate acid (HDPA)-bonded nano-oxides, which appear to interact with toluene through specific recognition. The active sites of the catalyst are related to the ability of HDPA to change its bonding to the oxides between monodentate and bidentate during the reaction cycle. This greatly enhances the mobility of the crystal oxygen or the reactivity of the catalyst, specifically in toluene transformations. The catalytic cycle of the catalyst is similar to that of methane monooxygenase. In the presence of catalyst and through O₂ oxidation, the conversion of toluene to benzaldehyde is initiated at 70 °C. We envision that this novel mechanism reveals alternatives for an attractive route to design high-performance catalysts with bioinspired structures.

Key words: Selective oxidation, Toluene, Benzaldehyde, Hexadecylphosphate acid, Enzyme-like, Mechanism

邓长顺, 崔韵, 陈俊超, 陈腾, 郭学锋, 季伟捷, 彭路明, 丁维平. 烷基膦酸键合的纳米氧化物上甲苯选择氧化制苯甲醛的类酶机理[J]. 催化学报, 2021, 42(9): 1509-1518.

Changshun Deng, Yun Cui, Junchao Chen, Teng Chen, Xuefeng Guo, Weijie Ji, Luming Peng, Weiping Ding. Enzyme-like mechanism of selective toluene oxidation to benzaldehyde over organophosphoric acid-bonded nano-oxides[J]. Chinese Journal of Catalysis, 2021, 42(9): 1509-1518.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63758-5

https://www.cjcatal.com/CN/Y2021/V42/I9/1509

图/表 8

Fig. 1. Schematic of methane monooxygenase and HDPA-Fe2O3. (a) Structure of sMMO hydroxylase and the reaction cycle for the transformation of methane to methanol over methane monooxygenase summarized from previous investigations. (b) HDPA-Fe2O3 and the possible catalytic cycle of the reaction for the oxidation of toluene presented in this work.

Table 1 Catalytic performances of reported catalysts in the O2 oxidation of toluene to benzaldehyde.

Entry ^a	Cat.	Oxidant	Pressure (MPa)	Temp. (°C)	pH	Time (h)	Conv. (%)	Sel. (%)	STY ^c	Ref.
1	Fe₃O₄	O₂	3	180	2.5	4	< 1	—	—	[2]
2	HDPA-Fe₃O₄	O₂	3	180	2.5	4	64	> 99	1.6	[2]
3	25Fe₂O₃/Al₂O₃	O₂	2	180	2.5	4	< 8	40	—	[7]
4	HDPA-25Fe₂O₃/Al₂O₃	O₂	2	180	2.5	4	71	> 99	2.0
5	(20Fe₂O₃-5NiO)/Al₂O₃	O₂	2	180	2.5	4	< 8	30	—
6	HDPA-(20Fe₂O₃-5NiO)/Al₂O₃	O₂	2	180	2.5	4	83	> 99	2.4
7 ^b	HDPA-FeVO_x/γ-Al₂O₃	O₂	0.1	160	—	4000 ^d	~0.8	> 99	—	This work

Fig. 2. General synthetic procedure and morphology of the catalysts and the arrangement of HDPA on the catalysts. (a) Nano γ-Al2O3 used as catalytic support and its TEM image, with the {111} crystal plane as its main external surface [27]. (b) 25 wt% Fe2O3/γ-Al2O3 prepared by the impregnation and calcination method and its TEM image. (c) HDPA-Fe2O3/γ-Al2O3 prepared by bonding HDPA to 25 wt% Fe2O3/γ-Al2O3 in a density of 0.4/nm2 and its typical TEM image. The TEM observations indicate similar morphologies for the samples. (d) P 2p binding energy measured by XPS for HDPA, HDPA-Fe2O3/γ-Al2O3, and HDPA-FeVOx/γ-Al2O3. (e) FTIR result of pyridine adsorbed on Fe2O3/γ-Al2O3 (i), fresh HDPA-Fe2O3/γ-Al2O3 (ii), and HDPA-Fe2O3/γ-Al2O3 after use in toluene/O2 (iii) or toluene/Ar (iv). The inset shows the proposed Br?nsted acid site that originated from monodentate-bonded HDPA on Fe2O3/γ-Al2O3.

Fig. 3. Operando FTIR measurements with the catalysts on stream. The FTIR spectra of FeVOx/γ-Al2O3 ((a) and (d)) and HDPA-FeVOx/γ-Al2O3 ((b) and (e)) in flowing toluene and oxygen at different temperatures. (c) and (f) depict the FTIR spectra of HDPA-FeVOx/γ-Al2O3 in flowing toluene and argon at different temperatures. (Toluene: 1 μL/min, vaporized in the line; O2 or Ar: 20 mL/min; catalyst of ~0.01 g pressed into a disk; temp.: 30-130 °C).

Table 2 Changes in the IR bands with the catalysts on stream during heating (30-130 °C).

FeVO_x/γ-Al₂O₃(Toluene + O₂)		HDPA-FeVO_x/γ-Al₂O₃(Toluene + O₂)		HDPA-FeVO_x/γ-Al₂O₃(Toluene + Ar)		Assignment ^a	Ref.
Position	Intensity	Position	Intensity	Position	Intensity	Assignment ^a	Ref.
2934	n.c. ^b	2934	weak	2933	weak	ν_as(CH)	[34-36]
2879		2879	weak	2877	weak	ν_s(CH)	[34-36]
—		2833	↑ from 70 °C	2836	↑ from 100 °C	ν(CH), aldehyde	[39-42]
1948-1799		1946-1797	weak	1945-1800	weak	ring, freq. doubling
—		1742	↑ from 70 °C	1741	↑ from 120 °C	ν(C=O)	[39-42]
1605		1603	weak	1602	weak	ν_s(C=C), ring	[37]
1540		1538		1536		ν(CC), ring
1495		1494		1496		ν(CC), ring
1460		1455		1457		β_as(CH)	[34,38]
1383		1384		1381		β_s(CH)	[34,38]
—		1340	↑ from 70 °C	1337	↑ from 110 °C	δ(CH), aldehyde	[39-42]
1081		1080	Interesting (cf. Fig. 4)	1080	Interesting (cf. Fig. 4)	β(CH), ring	[37,38]
1043		1031	Interesting (cf. Fig. 4)	1031	Interesting (cf. Fig. 4)	β(CH), ring	[37,38]

Fig. 4. Specificity of the catalyst toward toluene oxidation. (a) Turnover frequency (TOF) for benzyl alcohol oxidation over HDPA-FeVOx/γ-Al2O3 and FeVOx/γ-Al2O3 based on surface area. (Benzyl alcohol: 1 μL/min, vaporized in the line; O2: 20 mL/min; cat.: 0.3 g; temp.: 130-190 °C). (b) The adsorption of toluene and benzyl alcohol by the two catalysts in a mixed ethanol solution of toluene and benzyl alcohol (cat.: 0.3 g; 30 mg toluene and 30 mg benzyl alcohol in 50 mL ethanol; temp.: 50 °C). (c) The intensity ratio of the two IR peaks related to the in-plane C-H bending vibrations of the toluene aromatic ring for toluene adsorption over the catalysts during heating between 40 and 130 °C.

Fig. 5. Redox behavior of the catalysts. (a) H2-TPR results of Fe2O3/γ-Al2O3 before and after HDPA bonding; (b) Gas-phase concentrations of benzaldehyde and O2 over HDPA-Fe2O3/γ-Al2O3 during the switch from toluene + O2 to toluene + Ar (toluene: 1 μL/min, vaporized in the line; O2 or Ar: 20 mL/min; cat.: 1 g; temp.: 160 °C).

Fig. 6. Kinetic measurements of the toluene oxidation reaction. (a) Arrhenius plots for the gas-phase toluene conversion over HDPA-Fe2O3/γ-Al2O3 and HDPA-FeVOx/γ-Al2O3 (130-170 °C); (b) Dependences of the reaction rate on the partial pressure of toluene or oxygen over HDPA-FeVOx/γ-Al2O3 (oxygen: 6-18 mL/min; toluene: 0.4-2.0 μL/min (liquid); cat.: 0.3 g; temp.: 170 °C. The total flow of the reactant was kept constant at 20 mL/min with argon used as balance); (c) Effect of the H2O pressure on the TOF of the toluene conversion over HDPA-FeVOx/γ-Al2O3 (toluene: 1 μL/min, vaporized in the line; O2: 20 mL/min; cat.: 0.3 g; temp.: 170 °C).

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烷基膦酸键合的纳米氧化物上甲苯选择氧化制苯甲醛的类酶机理

Enzyme-like mechanism of selective toluene oxidation to benzaldehyde over organophosphoric acid-bonded nano-oxides

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