[Ga(OH)]2+负载介孔中空结构H-ZSM-5: 一种高效低碳烷烃芳构化催化剂

doi:10.1016/S1872-2067(25)64678-X

催化学报 ›› 2025, Vol. 72: 359-375.DOI: 10.1016/S1872-2067(25)64678-X

[Ga(OH)]²⁺负载介孔中空结构H-ZSM-5: 一种高效低碳烷烃芳构化催化剂

石德志^a^,^b, 陈艳艳^a, 陈晓^c, 王森^a^,^*(), 王强^d, 王鹏飞^a, 朱华青^a, 董梅^a, 徐君^d, 邓风^d, 王建国^a, 樊卫斌^a^,^*()

^a中国科学院山西煤炭化学研究所, 煤炭高效低碳利用全国重点实验室, 山西太原 030001
^b山西工程技术学院, 矿区生态修复与固废资源化厅市共建山西省重点实验室培育基地, 山西阳泉 045000
^c清华大学化学工程系, 绿色反应工程与工艺北京市重点实验室, 北京 100084
^d中国科学院精密测量科学与技术创新研究院, 波谱与原子分子物理国家重点实验室, 湖北武汉 430071

收稿日期:2024-11-06 接受日期:2025-03-11 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: wangsen@sxicc.ac.cn (王森),fanwb@sxicc.ac.cn (樊卫斌).
基金资助:
国家重点研发项目(2023YFB4103700);国家重点研发项目(2020YFA0210900);国家重点研发项目(2020YFA0210902);国家重点研发项目(2020YFB0606402);国家自然科学基金(U1910203);国家自然科学基金(21991090);国家自然科学基金(21991092);国家自然科学基金(22322208);国家自然科学基金(22272195);国家自然科学基金(U22A20431);山西省自然科学基金(202203021224009);山西省自然科学基金(202303021222277);山西省高等学校科技创新项目(2021L586);中国博士后面上基金(2022TQ0351);中国科学院山西煤炭化学研究所创新基金(SCJC-DT-2023-06);中国科学院山西煤炭化学研究所青年创新促进会项目(2021172)

Single [Ga(OH)]²⁺ species supported on mesoporous hollow-structured H-ZSM-5: A highly efficient light alkanes aromatization catalyst

Dezhi Shi^a^,^b, Yanyan Chen^a, Xiao Chen^c, Sen Wang^a^,^*(), Qiang Wang^d, Pengfei Wang^a, Huaqing Zhu^a, Mei Dong^a, Jun Xu^d, Feng Deng^d, Jianguo Wang^a, Weibin Fan^a^,^*()

^aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
^bThe Cultivation Base of Shanxi Key Laboratory of Mining Area Ecological Restoration and Solid Wastes Utilization, Shanxi Institute of Technology, Yangquan 045000, Shanxi, China
^cBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
^dNational Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, Hubei, China

Received:2024-11-06 Accepted:2025-03-11 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: wangsen@sxicc.ac.cn (S. Wang), fanwb@sxicc.ac.cn (W. Fan).
Supported by:
National Key R&D Program of China(2023YFB4103700);National Key R&D Program of China(2020YFA0210900);National Key R&D Program of China(2020YFA0210902);National Key R&D Program of China(2020YFB0606402);National Natural Science Foundation of China(U1910203);National Natural Science Foundation of China(21991090);National Natural Science Foundation of China(21991092);National Natural Science Foundation of China(22322208);National Natural Science Foundation of China(22272195);National Natural Science Foundation of China(U22A20431);Natural Science Foundation of Shanxi Province of China(202203021224009);Natural Science Foundation of Shanxi Province of China(202303021222277);Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L586);China Postdoctoral Science Foundation(2022TQ0351);Innovation foundation of Institute of Coal Chemistry, Chinese Academy of Sciences(SCJC-DT-2023-06);Youth Innovation Promotion Association CAS(2021172)

摘要/Abstract

摘要：

芳烃, 尤其是苯, 甲苯和二甲苯(BTX)等轻质芳烃, 是现代化学工业中重要的基础原料, 可以用于生产合成橡胶、合成纤维、合成树脂等多种化工产品和精细化学品. 低碳烷烃芳构化是将石油化工和煤化工领域产生的低价值烷烃进行高值化利用的重要途径. 该反应过程的关键在于开发兼具有高活性、高选择性和高稳定性的催化剂. 然而, 烷烃芳构化过程中存在的裂解、氢转移等副反应会导致大量副产物生成; 此外, 催化剂积碳的生成容易造成其快速失活. 这些都是该反应过程面临的主要挑战.

本文设计了一种具有介孔中空结构的ZSM-5分子筛(MH-ZSM-5), 并采用离子交换法, 成功制备了单[Ga(OH)]²⁺物种负载介孔中空ZSM-5催化剂(Ga-MH-ZSM-5). 该催化剂在低碳烷烃芳构化反应中展现出优异的催化活性、芳烃产物选择性和稳定性. 在600 °C, 质量空速(WHSV)为0.8 h^-1条件下, 乙烷芳构化反应28 h内的芳烃平均收率达到~18.4%, 且BTX等轻质芳烃占总芳烃比例高达~96%. 在580 °C, WHSV为1.1 h^-1条件下, 丙烷芳构化反应20 h内的芳烃平均收率达到70.8%, 其中BTX占总芳烃比例为~88%. Ga负载量为0.41 wt%时(即Ga-MH-ZSM-5-0.41样品), 丙烷芳构化反应的芳烃生成转化数(TON)高达57479, 在乙烷芳构化过程中, 其芳烃TON值也达到了3845. 本文利用智能重量分析仪(IGA)和二甲苯探针分子红外扩散实验证明了具有介孔中空结构的ZSM-5分子筛其芳烃产物的扩散速率是传统ZSM-5的2.4-3.1倍. 同时, 热重、拉曼光谱以及紫外可见漫反射光谱等实验结果也表明介孔中空结构的ZSM-5分子筛在烷烃芳构化过程中可以显著抑制积碳物质的生成, 从而大幅提高了催化剂寿命. 同步辐射、密度泛函理论计算(DFT)和固体核磁等手段进一步指出了Ga-MH-ZSM-5的催化活性主要依赖于Ga物种的结构. 当Ga负载量≤ 0.3 wt%时, 主要以[Ga(OH)]²⁺物种为主; 随着Ga负载的增加, 开始形成较多的[Ga(OH)₂]⁺物种和GaO_x团簇. 经过H₂处理后, [Ga(OH)]²⁺和[Ga(OH)₂]⁺分别转变为[GaH]²⁺和[GaH₂]⁺. 这两个镓物种的丙烷脱氢速率分别是H⁺位点的300倍和15倍. 此外, 本文通过气质联用, 质子转移反应飞行时间质谱及DFT计算揭示了低碳烷烃芳构化的完整反应网络, 低碳烷烃首先在[GaH]²⁺位点脱氢形成低碳烯烃, 随后在临近的H⁺位点上发生齐聚, 环化反应形成环戊烷类中间体, 并进一步在H⁺位点上扩环形成环己烷类中间体, 这些环状中间体最后在[GaH]²⁺位点上脱氢生成芳烃.

综上, 本文不仅开发出一种具有优异反应性能的低碳烷烃芳构化催化剂, 同时也阐明了分子筛B酸位点与负载的金属Ga物种的协同催化机制. 通过利用多种原位表征技术和理论计算手段对不同Ga物种的本征催化活性进行了定量解析. 本工作将为低碳烷烃、烯烃芳构化乃至石脑油芳构化过程的高性能Ga基催化剂的设计和研制提供关键理论依据与参考.

关键词: 低碳烷烃芳构化, 介孔中空结构H-ZSM-5, 孤立Ga物种, 活性位点, 反应机理

Abstract:

Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries. Here, single [Ga(OH)]²⁺ ion-exchanged mesoporous hollow-structured ZSM-5 (Ga-MH-ZSM-5) material was prepared, and it shows unprecedented catalytic performance in light alkane aromatization, considering activity, product selectivity and catalytic stability. The average aromatics yields in ethane aromatization at 600 °C and WHSV of 0.8 h^-1 within 28 h and in propane aromatization at 580 °C and WHSV of 1.1 h^-1 within 20 h reach ’18.4% and ’70.8% with benzene, toluene and xylenes (BTX) accounting for ’96% and ’88% of aromatics, respectively. Ga-MH-ZSM-5-0.41 gave a TON for formation of aromatics (TON_aromatics) from propane as high as 57479, whereas the reported catalysts maximally show a TON_aromatics of 5514. This also holds true for ethane aromatization; the TON_aromatics obtained on Ga-MH-ZSM-5-0.41 was ≥ 3845 in contrast to £ 392 on reported non-noble metal catalysts. The catalytic activity of Ga-MH-ZSM-5 highly depends on Ga species structures. [Ga(OH)]²⁺ ions are predominant species at Ga loading ≤ 0.3 wt%, while more [Ga(OH)₂]⁺ and GaO_x oligomers are formed with increasing Ga content. Upon reduction with H₂, [Ga(OH)]²⁺ and [Ga(OH)₂]⁺ are transformed into [GaH]²⁺ and [GaH₂]⁺ species, which show a propane dehydrogenation rate of 300 and 15 times of that of Brønsted acid sites respectively. The light alkanes are mainly dehydrogenated into light olefins on [GaH]²⁺ species, and then, oligomerized and cyclized into (alkyl)cycloalkanes on H⁺ sites, which is followed by possible ring expansion on H⁺ and sequential dehydrogenations into aromatics primarily on [GaH]²⁺.

Key words: Light alkane aromatization, Mesoporous hollow-structured, H-ZSM-5, Isolated Ga species, Active site, Reaction mechanism

石德志, 陈艳艳, 陈晓, 王森, 王强, 王鹏飞, 朱华青, 董梅, 徐君, 邓风, 王建国, 樊卫斌. [Ga(OH)]²⁺负载介孔中空结构H-ZSM-5: 一种高效低碳烷烃芳构化催化剂[J]. 催化学报, 2025, 72: 359-375.

Dezhi Shi, Yanyan Chen, Xiao Chen, Sen Wang, Qiang Wang, Pengfei Wang, Huaqing Zhu, Mei Dong, Jun Xu, Feng Deng, Jianguo Wang, Weibin Fan. Single [Ga(OH)]²⁺ species supported on mesoporous hollow-structured H-ZSM-5: A highly efficient light alkanes aromatization catalyst[J]. Chinese Journal of Catalysis, 2025, 72: 359-375.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64678-X

https://www.cjcatal.com/CN/Y2025/V72/I5/359

图/表 9

Fig. 1. (a) Schematic illustration for the preparation of MH-ZSM-5. TEM images of parent ZSM-5 (b), HH-ZSM-5 (c) and MH-ZSM-5 (d) samples. (e,f) Aberration-corrected HAADF-STEM images (the generated mesopores are highlighted by yellow circles). iDPC-STEM image (the Ga species are highlighted by red circles) (g) and corresponding EDX elemental mappings (h-j) of Ga-MH-ZSM-5-0.41. STEM-HAADF images with EDS line scanning profiles of Ga/H-ZSM-5 (k), Ga/HH-ZSM-5 (l) and Ga/MH-ZSM-5 (m) samples.

Fig. 2. Propane conversion, product selectivity and aromatic product distribution with the time-on-stream (TOS) over Ga/H-ZSM-5 (a,b), Ga/HH-ZSM-5 (c,d) and Ga/MH-ZSM-5 (e,f) sample. Reaction conditions: 540 °C, 1 atm, WHSVpropane = 1.4 h-1 (N2/C3H8 = 2.5 (vol/vol)).

Fig. 3. Propane conversions, aromatics selectivities and yields (a), and aromatic product distributions (b) obtained on MH-ZSM-5 and Ga-MH-ZSM-5-x samples (reaction conditions: T = 540 °C, 1 atm, WHSVpropane = 0.96 h-1 and N2/C3H8 = 2.5 (vol/vol)). Propane conversion, product selectivity (c), and aromatic products distribution (d) with TOS obtained on the Ga-MH-ZSM-5-0.41 (reaction conditions: T = 580 °C, 1 atm, WHSVpropane = 1.1 h-1 and N2/C3H8 = 2.5 (vol/vol)). (e) Aromatics and BTX yields obtained on our synthesized and reported catalysts. (f) TONs (green and pink columns represent the catalytic results of various reported Ga and Zn catalysts respectively). Data in this work were obtained from Fig. S14(c) (540 °C and TOS of 100 h) and Fig. S10 (580 °C and TOS of 50 h). TON is the accumulated amount (moles) of generated aromatics per mole of Ga or Zn species, as obtained from the equation of TON = $\left[F_{\mathrm{C}_{3} \mathrm{H}_{8}} \times \int_{0}^{t} Y_{\text {aro }, t} d t\right] / \mathrm{n}_{\mathrm{M}}$, where FC3H8 is propane carbon molar flow rate; Yaro,t is instantaneous aromatics carbon molar yield at the time on stream of t; t is reaction time, and nM is the moles of Ga or Zn species of catalysts.

Fig. 4. (a) Normalized Ga K-edge XANES spectra collected at ambient temperature of Ga-MH-ZSM-5-0.082 (1), Ga-MH-ZSM-5-0.13 (2), Ga-MH-ZSM-5-0.30 (3), Ga-MH-ZSM-5-0.47 (4), Ga-MH-ZSM-5-0.70 (5), Ga-MH-ZSM-5-1.10 (6), Ga-MH-ZSM-5-1.62 (7) and β-Ga2O3 in the first-coordination shell. (b) The magnitudes of the k3-weighted Fourier-transformed Ga K-edge EXAFS spectra of Ga-MH-ZSM-5-x, Ga foil and β-Ga2O3 samples. (c) The wavelet transform of the k3-weighted EXAFS spectra of Ga-MH-ZSM-5-0.13, Ga-MH-ZSM-5-0.30, Ga-MH-ZSM-5-0.47, Ga-MH-ZSM-5-1.62, Ga foil and β-Ga2O3 samples. (d) 71Ga MAS NMR spectra of Ga-MH-ZSM-5-0.13, Ga-MH-ZSM-5-0.3, Ga-MH-ZSM-5-0.47 and Ga-MH-ZSM-5-1.6. (e) Optimized structures for ion-exchanging [Ga(OH)2]+ and [Ga(OH)]2+ cations in Ga-MH-ZSM-5. (f) Schematic illustrations of two or one Br?nsted protons exchanged with one Ga3+ cation to form [Ga(OH)]2+ and [Ga(OH)2]+, respectively. (g) Relationship between the content of Br?nsted protons exchanged with Ga3+ cations, as determined by comparing the bridged OH vibration band areas at 3610 cm-1 (IR) of Ga-MH-ZSM-x samples with that of MH-ZSM-5, and the Ga/Al ratio of Ga-MH-ZSM-5-x samples (black dotted lines refers to the faction of two Br?nsted H+ exchanged with one Ga3+ cations in total Br?nsted H+).

Fig. 5. Propane conversion (a) and products carbon molar selectivity (b,c) obtained on the Ga-MH-ZSM-5-0.3 at atmospheric pressure, propane partial pressure of 0.54 kPa, 500 °C and WHSVpropane of 1.18 h?1 (hollow circles represent the catalytic results obtained on the sample pretreated in N2 at 500 °C for 1 h after calcining in static air; hollow blocks and solid balls are the catalytic results on the samples pretreated at 500 °C for 5 min and 1 h in 10%H2/Ar respectively). (d) The ratios of the difference in carbon molar selectivity of propene to those of (aromatics + ethene) and aromatics every 40 min from TOS of 10 to 170 min on the Ga-MH-ZSM-5-0.3 pretreated at 500 °C for 1 h in N2. (e) In situ FTIR spectra obtained at 150 °C on the Ga-MH-ZSM-5-0.15, Ga-MH-ZSM-5-0.25, Ga-MH-ZSM-5-0.38 and Ga-MH-ZSM-5-0.41 samples treated at 500 °C for 1 h in 10% H2/Ar (background spectrum was collected at 150 °C after the self-supported sample wafer was dehydrated at 500 °C and 7 × 10?3 Pa for 1 h).

Fig. 6. (a) Proposed alkyl mechanism for propane dehydrogenation over [GaH]2+ cations. (b) Dependence of the apparent propane dehydrogenation rate coefficients on Ga-MH-ZSM-5-x samples, and for comparison and on parent MH-ZSM-5, on the Ga contents in the samples; calculated free energy profiles for propane dehydrogenation via alkyl mechanism on [GaH]2+ (c) and [GaH2]+ (d) at 500 °C.

Fig. 7. Reaction network for propane aromatization. The blue data are calculated free energy barriers (kJ/mol) of various elemental steps on MH-ZSM-5 (a) and Ga-MH-ZSM-5-0.3 (b) DH, CR, O, C, HT and RE represent dehydrogenation, cracking, oligomerization, cyclization, hydrogen transfer and ring expansion reactions, respectively.

Fig. 8. GC-MS chromatograms of effluents on MH-ZSM-5 (a) and Ga-MH-ZSM-5-0.3 (b) in temperature-dependent propene conversion probe experiments. Reaction conditions: the temperature was ramped from room temperature to 440 °C at a rate of 5 °C/min in a (propene (1 mL/min) and N2 (160 mL/min)) gaseous mixture flow. The reaction was conducted in a U-type quartz tube micro-reactor loaded 20 mg catalyst. The gaseous products were collected for 30 s with a gas sample bag each time and analyzed by GC-MS.

Fig. 9. PTR-TOF-MS results for the formation of various cyclic hydrocarbon intermediates and aromatic products in temperature-programmed surface reaction of propane on MH-ZSM-5 (a-c) and Ga-MH-ZSM-5-0.3 (d-f).

参考文献

[1]	R. Ahuja, B. Punji, M. Findlater, C. Supplee, W. Schinski, M. Brookhart, A. S. Goldman, Nat. Chem., 2011, 3, 167-171.
[2]	B. Zhao, P. Zhai, P. Wang, J. Li, T. Li, M. Peng, M. Zhao, G. Hu, Y. Yang, Li, W. Y. Q. Zhang, W. Fan, D. Ma, Chem, 2017, 3, 323-333.
[3]	C. Wei, W. Zhang, K. Yang, X. Bai, S. Xu, J. Li, Z. Liu, Chin. J. Catal., 2023, 47, 138-149.
[4]	Z. Li, Y. Qu, J. Wang, H. Liu, M. Li, S. Miao, C. Li, Joule, 2019, 3, 570-583.
[5]	D. Zhao, X. Tian, D. E. Doronkin, S. Han, V. A. Kondratenko, J. D. Grunwaldt, A. Perechodjuk, T. H. Vuong, J. Rabeah, R. Eckelt, U. Rodemerck, D. Linke, G. Jiang, H. Jiao, E. V. Kondratenko, Nature, 2021, 599, 234-238.
[6]	H. Zhou, X. Yi, Y. Hui, L. Wang, W. Chen, Y. Qin, M. Wang, J. Ma, X. Chu, Y. Wang, X. Hong, Z. Chen, X. Meng, Q. Zhu, L. Song, A. Zheng, F. S. Xiao, Science, 2021, 372, 76-80.
[7]	A. Bhan, W. N. Delgass, Catal. Rev. Sci. Eng., 2008, 50, 19-151.
[8]	M. Guisnet, N. S. Gnep, F. Alario, Appl. Catal. A, 1992, 89, 1-30.
[9]	M. Guisnet, S. Gnep, Catal. Today, 1996, 31, 275-292.
[10]	H. Xiao, J. Zhang, X. Wang, Zhang, Q. H. Xie, Y. Han, Y. Tan, Catal. Sci. Technol., 2015, 5, 4081-4090.
[11]	N. A. Yassir, M. N. Akhtar, S. A. Khattaf, J. Porous Mater., 2012, 19, 943-960.
[12]	N. A. Yassir, M. N. Akhtar, K. Ogunronbi, S. A. Khattaf, J. Mol. Catal. A, 2012, 360, 1-15.
[13]	M. S. Scurrell, Appl. Catal., 1988, 41, 89-98.
[14]	J. A. Biscardi, G. D. Meitzner, E. Iglesia, J. Catal., 1998, 179, 192-202.
[15]	G. Krishnamurthy, A. Bhan, W. N. Delgass, J. Catal., 2010, 271, 370-385.
[16]	V. O. Rodrigues, A. C. Faro Júnior, Appl. Catal. A, 2012, 435-436, 68-77.
[17]	R. Gen, Y. Liu, J. Gao, Y. Guo, M. Dong, S. Wang, W. Fan, J. Wang, Z. Qin, Catal. Sci. Technol., 2022, 12, 4201-4210.
[18]	N. Rane, A. R. Overweg, V. B. Kazansky, R. A. van Santen, E. J. M. Hensen, J. Catal., 2006, 239, 478-485.
[19]	M. W. Schreiber, C. P. Plaisance, M. Baumgartl, K. Reuter, A. Jentys, R. Bermejo-Deval, J. A. Lercher, J. Am. Chem. Soc., 2018, 140, 4849-4859.
[20]	A. C. Faro Jr, V. O. Rodrigues, J. G. Eon, J. Phys. Chem. C, 2011, 115, 4749-4756.
[21]	E. A. Pidko, V. B. Kazansky, E. J. M. Hensen, R. A. van Santen, J. Catal., 2006, 240, 73-84.
[22]	E. J. M. Hensen, E. A. Pidko, N. Rane, R. A. van Santen, Angew. Chem. Int. Ed., 2007, 46, 7273-7276.
[23]	Y. Zhou, H. Thirumalai, S. K. Smith, K. H. Whitmire, J. Liu, A. I. Frenkel, L. C. Grabow, J. D. Rimer, Angew. Chem. Int. Ed., 2020, 59, 19592-19601.
[24]	E. A. Pidko, R. A. van Santen, E. J. M. Hensen, Phys. Chem. Chem. Phys., 2009, 11, 2893-2902.
[25]	E. Mansoor, M. Head-Gordon, A. T. Bell, ACS Catal., 2018, 8, 6146-6162.
[26]	N. M. Phadke, E. Mansoor, M. Bondil, M. Head-Gordon, A. T. Bell, J. Am. Chem. Soc., 2019, 141, 1614-1627.
[27]	N. M. Phadke, J. V. Mynsbrugge, E. Mansoor, A. B. Getsoian, M. Head-Gordon, A. T. Bell, ACS Catal., 2018, 8, 6106-6126.
[28]	E. A. Pidko, E. J. M. Hensen, R. A. van Santen, J. Phys. Chem. C, 2007, 111, 13068-13075.
[29]	V. R. Choudhary, A. K. Kinage, C. Sivadinarayana, P. Devadas, S. D. Sansare, M. Guisnet, J. Catal., 1996, 158, 34-50.
[30]	B. Xu, M. Tan, X. Wu, H. Geng, S. Zhao, J. Yao, Q. Ma, G. Yang, N. Tsubaki, Y. Tan, ChemCatChem, 2021, 13, 3601-3610.
[31]	X. Gao, L. Zhang, Z. Tao, H. Chen, Y. Zhang, H. Gong, X. Wen, Y. Yang, Y. Li, Catal. Today, 2021, 368, 232-242.
[32]	W. Zhou, J. Liu, L. Lin, X. Zhang, N. He, C. Liu, H. Guo, Ind. Eng. Chem. Res., 2018, 57, 16246-16256.
[33]	K. E. Ogunronbi, N. Al-Yassir, S. Al-Khattaf, J. Mol. Catal. A, 2015, 406, 1-18.
[34]	T. V. Choudhary, A. Kinage, S. Banerjee, V. R. Choudhary, Microporous Mesoporous Mater., 2005, 87, 23-32.
[35]	W. A. Maksoud, L. E. Gevers, J. Vittenet, S. Ould-Chikh, S. Telalovic, K. Bhatte, E. Abou-Hamad, D. H. Anjum, M. N. Hedhili, V. Vishwanath, A. Alhazmi, A. Almusaiteer, J. M. Basset, Dalton Trans., 2019, 48, 6611-6620.
[36]	W. Zhou, J. Liu, J. Wang, L. Lin, X. Zhang, N. He, C. Liu, H. Guo, Catal. Lett., 2019, 149, 2064-2077.
[37]	Y. H. Lim, H. Kim, H. Lee, K. Nam, H. W. Ryu, D. H. Kim, J. Catal., 2023, 422, 24-35.
[38]	B. Xu, M. Tan, X. Wu, H. Geng, F. Song, Q. Ma, C. Luan, G. Yang, Y. Tan, Fuel, 2021, 283, 118889.
[39]	L. Lin, J. Liu, X. Zhang, J. Wang, C. Liu, G. Xiong, H. Guo, Ind. Eng. Chem. Res., 2020, 59, 16146-16160.
[40]	I. B. Dauda, M. Yusuf, S. Gbadamasi, M. Bello, A. Y. Atta, B. O. Aderemi, B. Y. Jibril, ACS Omega, 2020, 5, 2725-2733.
[41]	S. Baradaran, M. Sohrabi, P. M. Bijani, S. J. Royaee, S. Sahebdelfar, Can. J. Chem. Eng., 2015, 93, 727-735.
[42]	J. C. Groen, L. A. A. Peffer, J. A. Moulijn, J. Perez-Ramirez, Chem. Eur. J., 2005, 11, 4983-4994.
[43]	X. Xu, Y. Zhang, X. Li, X. Xia, H. Jiang, A. Toghan, Microporous Mesoporous Mater., 2021, 315, 110926.
[44]	E. A. Uslamin, H. Saito, Y. Sekine, E. J. M. Hensen, N. Kosinov, Catal. Today., 2021, 369, 184-192.
[45]	A. Samanta, X. Bai, B. Robinson, H. Chen, L. Hu, Ind. Eng. Chem. Res., 2017, 56, 11006-11012.
[46]	C. Tu, H. Fan, D. Wang, N. Rui, Y. Du, S. D. Senanayake, Z. Xie, X. Nie, J. G. Chen, Appl. Catal. B, 2022, 304, 120956.
[47]	A. M. Lauritzen, A. M. Madgavkar, US 8946107 B2, 2014.
[48]	V. O. Rodrigues, J. G. Eon, A. C. Faro Jr, J. Phys. Chem. C, 2010, 114, 4557-4567.
[49]	F. H. Larsen, H. J. Jakobsen, P. D. Ellis, N. C. Nielsen, J. Phys. Chem. A, 1997, 101, 8597-8606.
[50]	P. Gao, J. Xu, G. Qi, C. Wang, Q. Wang, Y. Zhao, Y. Zhang, N. Feng, X. Zhao, J. Li, F. Deng, ACS Catal., 2018, 8, 9809-9820.
[51]	P. Gao, Q. Wang, J. Xu, G. Qi, C. Wang, X. Zhou, X. Zhao, N. Feng, X. Liu, F. Deng, ACS Catal., 2018, 8, 69-74.
[52]	M. García-Sánchez, P. C. M. M. Magusin, E. J. M. Hensen, P. C. Thüne, X. Rozanska, R. A. van Santen, J. Catal., 2003, 219, 352-361.
[53]	M. L. Occelli, G. Schwering, C, Fild, H. Eckert, A. Auroux, P. S. Iyer, Microporous Mesoporous Mater., 2000, 34, 15-22.
[54]	A. Arnold, S. Steuernagel, M. Hunger, J. Weitkamp, Microporous Mesoporous Mater., 2003, 62, 97-106.
[55]	D. Massiot, I. Farnan, N. Gautier, D. Trumeau, A. Trokiner, J. P. Coutures, Solid State Nucl. Mag., 1995, 4, 241-248.
[56]	B. Zheng, W. Hua, Y. Yue, Z. Gao, J. Catal., 2005, 232, 143-151.
[57]	Y. Yuan, C. Brady, L. Annamalai, R. F. Lobo, B. Xu, J. Catal., 2021, 393, 60-69.
[58]	Y. Yuan, R. F. Lobo, B. Xu, ACS Catal., 2022, 12, 1775-1783.
[59]	V. B. Kazansky, I. R. Subbotina, R. A. van Santen, E. J. M. Hensen, J. Catal., 2004, 227, 263-269.
[60]	V. B. Kazansky, I. R. Subbotina, R. A. van Santen, E. J. M. Hensen, J. Catal., 2005, 233, 351-358.
[61]	J. A. Biscardi, E. Iglesia, Catal. Today, 1996, 31, 207-231.
[62]	W. Wu, W. Guo, W. Xiao, M. Luo, Chem. Eng. Sci., 2011, 66, 4722-4732.
[63]	X. Huang, D. Aihemaitijiang, W. D. Xiao, Chem. Eng. J., 2015, 280, 222-232.
[64]	Y. Chen, H. Wu, S. Wang, D. Shi, M. Dong, Z. Qin, J. Wang, W. Fan, J. Catal., 2023, 425, 260-268.
[65]	C. Wang, X. Zhao, M. Hu, G. Qi, Q. Wang, S. Li, J. Xu, F. Deng, Angew. Chem. Int. Ed., 2021, 60, 23630-23634.
[66]	W. Dai, C. Wang, M. Dyballa, G. Wu, N. Guan, L. Li, Z. Xie, M. Hunger, ACS Catal., 2015, 5, 317-326.
[67]	D. McCann, D. Lesthaeghe, P. W. Kletnieks, D. R. Guenther, M. J. Hayman, V. V. Speybroeck, M. Waroquier, J. F. Haw, Angew. Chem. Int. Ed., 2008, 47, 5179-5182.
[68]	W. Zhang, M. Zhang, S. Xu, S. Gao, Y. Wei, Z. Liu, ACS Catal., 2020, 10,4510-4516.

[Ga(OH)]²⁺负载介孔中空结构H-ZSM-5: 一种高效低碳烷烃芳构化催化剂

Single [Ga(OH)]²⁺ species supported on mesoporous hollow-structured H-ZSM-5: A highly efficient light alkanes aromatization catalyst

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 9

参考文献

相关文章 15

编辑推荐

Metrics

[1]	李显泉, 庞纪峰, 赵于嘉, 李林, 于文广, 徐斐斐, 苏扬, 杨小峰, 罗文豪, 郑明远. 乙醇乙醛催化转化制丁二烯的双分子协同吸附机制研究[J]. 催化学报, 2025, 71(4): 297-307.
[2]	班涛, 王建伟, 余希阳, 田海阔, 高新, 黄正清, 常春然. 机器学习辅助筛选SA-FLP双活性位催化剂用于甲烷与水共转化制甲醇反应[J]. 催化学报, 2025, 70(3): 311-321.
[3]	Yunha Hwang, Dong-Heon Lee, Seung Jae Lee. 可溶甲烷单氧酶中不同组分对甲烷羟基化的协调作用[J]. 催化学报, 2025, 68(1): 204-212.
[4]	高绍磊, 卢鹏, 亓良, 王莹利, 李华, 叶茂, Valentin Valtchev, Alexis T. Bell, 刘中民. 超大孔分子筛ZEO-1催化甲缩醛羰基化及歧化反应: 反应网络与机理研究[J]. 催化学报, 2025, 68(1): 230-245.
[5]	秦嘉恒, 赵婉彤, 宋劼, 罗楠, 马正兰, 王宝俊, 马建泰, 章日光, 龙雨. 单原子掺杂诱导电荷特异分布的Cu₁-TiO₂通过新机理催化苯胺选择性氧化[J]. 催化学报, 2024, 64(9): 98-111.
[6]	罗旭宇, 王颖, 杨光, 刘璐, 郭诗颖, 崔义, 许小勇. 在硫化钼基面上调控原子级协同活性中心用于碱氢演化反应[J]. 催化学报, 2024, 61(6): 281-290.
[7]	杜晨宇, 盛剑平, 钟丰忆, 何烨, 孙艳娟, 董帆. 光催化二氧化碳还原制多碳产物的先进光催化剂设计与机制: 现状与挑战[J]. 催化学报, 2024, 60(5): 25-41.
[8]	王超琛, 葛旺鑫, 唐雷, 齐宴宾, 董磊, 江宏亮, 沈建华, 朱以华, 李春忠. 单原子修饰原子簇的多配位Cu基催化剂上CO₂高选择性电还原CO的研究[J]. 催化学报, 2024, 59(4): 324-333.
[9]	陈思雨, 管景奇. 氮还原电催化剂的结构调控策略[J]. 催化学报, 2024, 66(11): 20-52.
[10]	耿仕鹏, 陈利明, 陈海鑫, 王毅, 丁朝斌, 蔡丹丹, 宋树芹. 揭示层状晶态CoMoO₄的水裂解电催化机制: 从晶面选择到活性位点设计的理论研究[J]. 催化学报, 2023, 50(7): 334-342.
[11]	刘诗瑶, 巩玉同, 杨晓, 张楠楠, 刘会斌, 梁长海, 陈霄. 具有富电子镍位点的耐酸金属间化合物CaNi₂Si₂催化剂用于不饱和有机酸酐/酸的水相加氢[J]. 催化学报, 2023, 50(7): 260-272.
[12]	李显泉, 庞纪峰, 赵于嘉, 吴鹏飞, 于文广, 颜佩芳, 苏扬, 郑明远. Cu-MFI催化剂上Cu^δ⁺催化乙醇脱氢制乙醛[J]. 催化学报, 2023, 49(6): 91-101.
[13]	杜乘风, 胡尔海, 余泓, 颜清宇. 二维电催化剂的局域电子调控策略[J]. 催化学报, 2023, 48(5): 1-14.
[14]	张文静, 李静, 魏子栋. 碳基氧还原电催化剂: 机理研究和多孔结构[J]. 催化学报, 2023, 48(5): 15-31.
[15]	刘丹卿, 张丙兴, 赵国强, 陈建, 潘洪革, 孙文平. 原位电化学扫描探针显微镜技术在电催化领域的应用进展[J]. 催化学报, 2023, 47(4): 93-120.