有机结构导向剂的异构体影响AEI沸石中铝的分布及其在甲烷氧化中的催化性能

doi:10.1016/S1872-2067(25)64702-4

催化学报 ›› 2025, Vol. 73: 252-260.DOI: 10.1016/S1872-2067(25)64702-4

有机结构导向剂的异构体影响AEI沸石中铝的分布及其在甲烷氧化中的催化性能

肖佩佩^a, 王勇^a, 唐晓敏^b, 郑安民^b^,^c, Trees De Baerdemaeker^d, Andrei-Nicolae Parvulescu^d, Dirk De Vos^e, 孟祥举^f, 肖丰收^g, Hermann Gies^a^,^h, 横井俊之^a^,ⁱ()

^a东京工业大学综合研究所, 横滨, 日本
^b中国科学院精密测量科学与技术创新学院, 武汉国家磁共振重点实验室, 湖北武汉 430071, 中国
^c武汉科技大学化学与化工学院, 湖北省煤转化与新碳材料协同创新中心, 湖北武汉 430081, 中国
^d巴斯夫公司过程研究与化学工程部, 路德维希港, 德国
^e天主教鲁汶大学表面化学与催化中心, 鲁汶, 比利时
^f浙江大学化学系, 浙江杭州 310028, 中国
^g浙江大学化学与生物工程学院, 浙江杭州 310027, 中国
^h波鸿鲁尔大学地质、矿物学与地球物理研究所, 波鸿, 德国
ⁱiPEACE223公司, 东京, 日本

收稿日期:2024-12-30 接受日期:2025-02-23 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: yokoi@cat.res.titech.ac.jp (T. Yokoi).

Isomers of organic structure directing agent influence the Al distribution of AEI zeolite and catalytic performance in methane oxidation

Peipei Xiao^a, Yong Wang^a, Xiaomin Tang^b, Anmin Zheng^b^,^c, Trees De Baerdemaeker^d, Andrei-Nicolae Parvulescu^d, Dirk De Vos^e, Xiangju Meng^f, Feng-Shou Xiao^g, Hermann Gies^a^,^h, Toshiyuki Yokoi^a^,ⁱ()

^aInstitute of Integrated Research, Institute of Science Tokyo, 4259 Nagatsuta, Midori-ku, Yokohama 226-8501, Japan
^b_b State Key Laboratory of Magnetic Resonance Spectroscopy and Imaging, National Center for Magnetic Resonance in Wuhan, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, Hubei, China
^cInterdisciplinary Institute of NMR and Molecular Sciences, Hubei Province for Coal Conversion and New Carbon Materials, School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
^dProcess Research and Chemical Engineering, BASF SE, Ludwigshafen 67056, Germany
^eCenter for Surface Chemistry and Catalysis, K. U. Leuven, Leuven 3001, Belgium
^fDepartment of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
^gCollege of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^hInstitute of Geology, Mineralogy and Geophysics, Ruhr-University Bochum, Bochum 44780, Germany
ⁱiPEACE223 Inc., Konwa Building, 1-12-22 Tsukiji, Chuo-ku, Tokyo, 104-0045, Japan

Received:2024-12-30 Accepted:2025-02-23 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: yokoi@cat.res.titech.ac.jp (T. Yokoi).

摘要/Abstract

摘要：

鉴于甲烷储量丰富但储存和运输存在挑战的特点, 将其直接氧化为高值化学品成为天然气高效利用的重要路径。AEI沸石作为一种小孔沸石在甲烷氧化反应中表现出良好的催化性能而备受关注. AEI沸石的合成高度依赖于有机结构导向剂(OSDA). 研究结果表明, 异构的OSDA会影响AEI沸石晶体颗粒的结晶速率和空间铝分布; 且这种空间铝分布会差异显著影响后续金属阳离子的负载, 从而影响催化活性位点的形成. 然而, 异构OSDA对AEI沸石框架铝分布的影响机制尚不明确。

本文中, 分别采用了反式(80%反式)和顺式(100%顺式)的N,N-二甲基-3,5-二甲基哌啶鎓氢氧化物(DMDMP)作为OSDA来合成AEI沸石, 以探究异构OSDA在合成AEI沸石中对铝分布的影响机制. 采用²⁷Al MQMAS/MAS核磁共振和密度泛函理论(DFT)研究了由反式和顺式富集OSDA导向合成的AEI沸石中铝分布的差异. 顺式OSDA在60-63 ppm处产生更高强度的四配位铝的肩峰. 而反式OSDA导致铝含量和铝对比例比顺式略高. DFT计算表明, 反式和顺式OSDA分别优先导致铝原子位于T3和T1位置. NH₃-TPD分析表明, AEI沸石中铝分布的差异直接影响Cu阳离子与酸性质子之间的交换方式. 鉴于AEI(反式)中的铝含量略高, Cu/AEI(反式)沸石中二铜物种的数量略多于Cu/AEI(顺式). 因此, 在相同Cu/Al比条件下, Cu/AEI(反式)在300°C下表现出更高的甲烷转化率, 并在350 °C下展现出更快的甲醇生成速率.

本文系统报道了Cu/AEI沸石上甲烷活化特性, 并揭示了OSDA异构体对Cu/AEI催化甲烷氧化为甲醇过程中活性的影响机制, 强调了异构体OSDA对铝分布以及结晶动力学的调控作用, 并为沸石合成中OSDA的设计提供了见解.

关键词: AEI沸石, 异构体有机结构导向剂, 铝分布, 甲烷制甲醇

Abstract:

Small pore zeolites have been reported to show salient performance in methane oxidation reactions. Among them, the synthesis of AEI zeolite is highly dependent on organic structure-directing agents (OSDA). The isomer OSDAs have been informed to influence the crystallization rate and spatial Al distribution on the crystalline particle of AEI zeolite. Still, its impact on the framework Al distribution of the AEI zeolite is not well known, which significantly impacts the subsequent loading of metal cations and thus active sites available for catalytic reactions. We herein report the impact of the isomer OSDA for synthesizing AEI-type aluminosilicate zeolite on the Al distribution. The discrepancy of Al distribution in as-synthesized AEI zeolites directed by trans and cis-rich OSDAs was identified by ²⁷Al MQMAS/MAS NMR and density functional theory (DFT). The cis-OSDA gave a higher intensity of bands at 60-63 ppm as the shoulder of tetracoordinated Al. The trans-rich OSDA guided to a slightly higher Al content and a slightly higher proportion of Al pairs than the cis-one. The DFT calculation indicated that trans- and cis-OSDAs preferentially led to the Al atoms at the T3 and T1 sites, respectively. The exchanged Cu/AEI zeolites with varied Cu content were applied in the direct and continuous oxidation of methane reaction and exhibited different activities. Given the results, we report here the methane activation properties of the Cu/AEI zeolites and how the isomer identity of the OSDA impacts the activity of Cu/AEI in methane oxidation to methanol. This work highlighted that isomer OSDA influenced the Al distribution as well as crystallization kinetics and gave an insight into the design of the OSDA for zeolite synthesis.

Key words: AEI zeolite, Isomer organic structure-directing, agents, Al distribution, Methane to methanol

肖佩佩, 王勇, 唐晓敏, 郑安民, Trees De Baerdemaeker, Andrei-Nicolae Parvulescu, Dirk De Vos, 孟祥举, 肖丰收, Hermann Gies, 横井俊之. 有机结构导向剂的异构体影响AEI沸石中铝的分布及其在甲烷氧化中的催化性能[J]. 催化学报, 2025, 73: 252-260.

Peipei Xiao, Yong Wang, Xiaomin Tang, Anmin Zheng, Trees De Baerdemaeker, Andrei-Nicolae Parvulescu, Dirk De Vos, Xiangju Meng, Feng-Shou Xiao, Hermann Gies, Toshiyuki Yokoi. Isomers of organic structure directing agent influence the Al distribution of AEI zeolite and catalytic performance in methane oxidation[J]. Chinese Journal of Catalysis, 2025, 73: 252-260.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64702-4

https://www.cjcatal.com/CN/Y2025/V73/I6/252

图/表 9

Fig. 1. (a) XRD patterns of AEI zeolites synthesized by trans and cis isomers of OSDAs. SEM images of AEI(trans) (b) and AEI(cis) (c). (d) N2 adsorption-desorption isothermals of AEI zeolites synthesized by isomers of OSDAs. Compared TG (e) and DTA (f) curves of AEI zeolites synthesized by isomers of OSDAs.

Fig. 2. 27Al MQMAS NMR spectra for as-synthesized AEI(trans) (a) and AEI(cis) zeolite (b). (c) 27Al MAS NMR spectra of as-synthesized AEI(trans) and AEI(cis) zeolites. (d) The location of three T sites in AEI zeolite. Al location in AEI zeolite directed by trans (e) and cis OSDA (f).

Fig. 3. NH3-TPD curves for xCu/AEI(trans) (a) and yCu/AEI(cis) (b).

Table 1 Chemical composition and acid amount of AEI zeolite measured by NH3-TPD.

Sample	Si/Al ^a	Cu/Al ^a	Cu content (wt%)	Acid amount by NH₃-TPD (mmol/g)
Sample	Si/Al ^a	Cu/Al ^a	Cu content (wt%)	LT ^b	MT ^c	HT ^d	Total
H-AEI(trans)	8.7	—	—	0.50	0.41	0.52	1.43
1Cu/AEI(trans)	9.6	0.07	0.65	0.34	0.48	0.53	1.35
5Cu/AEI(trans)	9.6	0.09	0.88	0.29	0.62	0.47	1.38
50Cu/AEI(trans)	9.7	0.20	1.85	0.28	0.73	0.46	1.46
H-AEI(cis)	9.6	—	—	0.50	0.43	0.50	1.43
1Cu/AEI(cis)	10.1	0.07	0.59	0.33	0.46	0.48	1.27
5Cu/AEI(cis)	10.1	0.09	0.83	0.33	0.61	0.45	1.39
50Cu/AEI(cis)	10.2	0.20	1.80	0.37	0.69	0.39	1.46

Fig. 4. Compare UV-vis spectra (a), NO adsorption (PNO = 80 Pa) FTIR spectra at -120 °C after activation at 500 °C for 1 h (b), and CO adsorption (PNO = 1000 Pa) FTIR spectra at -120 °C after activation at 500 °C for 1 h (c) of 5Cu/AEI (trans) and 5Cu/AEI(cis).

Fig. 5. Reaction performance of 1Cu/AEI(trans) (a), 5Cu/AEI(trans) (b), and 50Cu/AEI(trans) (c) zeolite at 300-450 °C. (d) Compare the CH4 conversion of xCu/AEI(trans) zeolite at 300-450 °C. Reaction conditions: 100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV=15000 mL/(g·h).

Fig. 6. Compare the product distribution of xCu/AEI(trans) (a) and yCu/AEI(cis) (b) zeolite at 300 °C. Compare the methanol formation rate (c) and CH4 conversion (d) of xCu/AEI(trans) and yCu/AEI(cis) zeolite at 300 °C. Reaction conditions:100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV = 15000 mL/(g·h).

Fig. 7. Compare the stability of 1Cu/AEI(trans) (a) and 1Cu/AEI(cis) (b) zeolite at 350 °C. Reaction conditions: 100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV=15000 mL/(g·h). (c) Compare the CO adsorption FTIR spectra of 1Cu/AEI(trans) and 1Cu/AEI (cis) at -120 °C after activation at 500 °C for 1 h.

Fig. 8. Compare the stability of 5Cu/AEI(trans) (a) and 5Cu/AEI(cis) (b) zeolite at 350 °C. Reaction conditions: 100 mg catalyst, CH4/N2O/H2O/Ar = 10/10/2/3 mL/min, WHSV=15000 mL/(g·h).

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有机结构导向剂的异构体影响AEI沸石中铝的分布及其在甲烷氧化中的催化性能

Isomers of organic structure directing agent influence the Al distribution of AEI zeolite and catalytic performance in methane oxidation

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