分级含锰TS-1沸石催化氧气一步氧化环己烷制备己二酸: 钛和锰的协同作用研究

doi:10.1016/S1872-2067(25)64822-4

摘要/Abstract

摘要：

己二酸(AA)是全球产量最大的化学品之一, 主要用于尼龙-66及工程塑料的合成. 由环己烷氧化制备己二酸的传统方法采用两步过程, 且需使用高浓度的HNO₃, 导致该方法不仅过程复杂、污染严重, 而且存在安全隐患. 采用绿色氧化剂一步氧化环己烷制备己二酸是理想的替代方案, 该过程需要同时实现环己烷饱和C-H键的活化和环己酮C-C键的断裂, 因此要求催化剂兼具这两种功能. MnO_x氧化还原性能优异, 能够有效活化氧气, 但其活性高度依赖于Mn所处的微环境. TS-1沸石对有机物具有显著的选择性氧化活性, 且已有多种策略对其孔径与结构进行调控. 因此, 本文将Mn物种锚定到分级TS-1中, 利用Mn与Ti双组分的协同效应, 实现一步高效催化氧化环己烷制备己二酸.
本文采用改进的直接合成法, 成功制备了分级含锰TS-1沸石(HMTS), 在该合成法中, 采用3-(苯基氨基)丙基三甲氧基硅烷为介孔剂, 实现了分子筛分级结构的构建; 介孔剂同时对Mn进入分子筛发挥了重要作用. 通过X射线衍射、X射线光电子能谱、透射电镜、紫外-可见光光谱和扩展X射线吸收精细结构等多种表征, 对HMTS沸石中Ti物种和Mn物种的配位微环境进行了探究, 发现钛物种和锰物种共存于沸石骨架中. 其中钛物种以Ti⁴⁺形式存在, 具有四面体结构, 其X射线吸收特征与传统TS-1完全一致; 高分散锰物种以Mn³⁺及Mn⁴⁺形式存在, 其第一配位壳层O的平均配位数为3.5-3.7, 且第二配位壳层没有观察到Mn. 将Mn引入含Ti分子筛后, 不仅促进了表面氧空位的形成, 还促进了分子筛上中强酸位点的生成, 赋予了HMTS催化剂高效活化氧气和促进底物吸附的能力. 在140 °C, 2 MPa氧气压力的条件下, 以HMTS为催化剂, 一锅氧化环己烷, 可获得81.6%的环己烷转化率和71.5%的AA选择性. 单组分催化剂的对照实验证实, 骨架Ti⁴⁺的Lewis酸性有利于环己烷C-H的活化, 催化环己烷氧化为环己酮和环己醇混合物(KA油), 表现出对环己烷和环己醇更高的氧化活性, 而对环己酮的氧化活性有限. 而骨架Mn则对环己醇和环己酮的进一步氧化表现出很好的活性, 有利于KA油进一步向AA的转化. 分级结构中骨架Ti和Mn的协同催化作用是催化剂表现出良好活性的关键因素. 骨架Ti⁴⁺可活化氧气形成活性Ti-O₂^2-物种, 该物种可高效促进环己烷C-H键的活化; 骨架Mn可活化氧气形成活性Mn⁴⁺-O₂^-物种, 该物种有利于促进环己酮C-C键的断裂. 分级结构不仅暴露了更多的表面活性位点, 促进了底物传质, 还为骨架Mn与Ti的协同作用提供了更好的微环境, 从而促进整个过程的协同进行.
综上, 本工作成功合成了新型HMTS沸石材料, 其中Ti和Mn物种对C-H键和C-C键活化展现出了良好协同催化能力, 有望拓展应用到烃类C-H键选择性活化功能化反应及相关反应, 同时为设计制备多功能TS-1提供了新思路.

关键词: 环己烷氧化, 基质中锰物种, 分级TS-1沸石, 协同作用, 氧气氧化, 己二酸

Abstract:

The direct oxidation of cyclohexane to adipic acid (AA) without the use of HNO₃ is important but still challenging. Herein, hierarchical manganese-containing TS-1 zeolite (HMTS) was prepared using an improved direct synthesis method, in which titanium and manganese coexist within the zeolite matrix, as characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet, extended X-ray absorption fine structure etc. The introduction of matrix Mn species (Mn³⁺, Mn⁴⁺) not only increased the surface oxygen vacancies, but also generated medium-strong acid sites, which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination. On HMTS-3, one-pot oxidation of cyclohexane at 140 °C and 2 MPa O₂ gave 81.6% conversion and 71.5% AA selectivity, the highest value obtained at present. Control experiments with single-component samples confirmed that matrix Ti⁴⁺ catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol (KA oil), and matrix Mn favored the conversion of KA oil to AA. The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity. Specifically, the matrix Ti⁴⁺ might activate oxygen to form Ti-O₂^2- which facilitated the activation of the C-H bond of cyclohexane. The activation of O₂ on matrix Mn³⁺ formed Mn⁴⁺-O₂^- favoring the breaking of the C-C bond of cyclohexanone. The hierarchical structure not only exposed more active sites and promoted mass transfer, but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti, which facilitated the overall reaction. This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.

Key words: Cyclohexane oxidation, Matrix Mn species, Hierarchical TS-1 zeolite, Synergic effect, O₂oxidation, Adipic acid

张铭栋, 巫学双, 李桂英, 胡常伟. 分级含锰TS-1沸石催化氧气一步氧化环己烷制备己二酸: 钛和锰的协同作用研究[J]. 催化学报, 2025, 79: 127-147.

Mingdong Zhang, Xueshuang Wu, Guiying Li, Changwei Hu. Hierarchical manganese-containing TS-1 zeolite for the direct oxidation of cyclohexane to adipic acid with molecular oxygen: Synergy between matrix Ti and Mn species[J]. Chinese Journal of Catalysis, 2025, 79: 127-147.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64822-4

https://www.cjcatal.com/CN/Y2025/V79/I12/127

图/表 19

Scheme 1. Comparison of current industrial process (A) and green approach to produce AA described in this work (B).

Scheme 2. Synthesis process of HMTS by an improved one-step hydrothermal method.

Fig. 1. (a) Survey spectra of TS-1, MTS-1, HTS-1, HMS-3, and HMTS-3. XPS spectra of Ti 2p (b), Mn 2p (c) and O 1s (d) of samples.

Table 1 Surface chemical composition determined by XPS (mol%).

Sample	O	Si	Ti	Mn	Ti^b (wt%)	Mn^b (wt%)
TS-1	56.71	43.28	0.01^a	—	0.02	—
MTS-1	62.70	34.42	0.67	2.21	1.51	5.73
HTS-1	61.61	38.20	0.19	—	0.44	—
HMTS-1	62.18	37.21	0.21	0.40	0.48	1.06
HMTS-2	62.63	36.44	0.16	0.77	0.39	2.04
HMTS-3	64.02	34.54	0.16	1.28	0.38	3.40
HMTS-4	66.85	31.11	0.16	1.88	0.37	5.04
HMS-3	63.86	34.62	—	1.12	—	2.62
HMTS-3^c	62.68	35.61	0.41	1.30	0.94	3.41
HMTS-3^d	62.55	35.82	0.45	1.18	1.01	3.10
HMS-3^c	63.58	35.23	—	1.19	—	3.15
HMS-3^d	63.40	35.34	—	1.26	—	3.33

Table 2 The Ti and Mn contents in different chemical states on the surface.

Sample	Framework Ti species (%)	Extra-framework Ti species (%)	Mn²⁺ (%)	Mn³⁺ (%)	Mn⁴⁺ (%)
TS-1	100.0	—	—	—	—
MTS-1	41.6	58.4	51.3	37.8	10.9
HTS-1	100.0	—	—	—	—
HMTS-1	100.0	—	39.7	34.8	25.5
HMTS-2	100.0	—	35.2	44.6	20.2
HMTS-3	100.0	—	24.5	54.2	21.3
HMTS-4	61.4	38.6	34.4	42.8	22.8
HMS-3	—	—	21.6	56.1	22.3

Fig. 2. (a) N2 adsorption-desorption isotherms of all samples. (b) Pore diameter distribution of all catalyst samples.

Table 3 Physicochemical properties of different catalysts.

Sample	S_BET^a (m² g^-1)	S_mic (m² g^-1)	S_ext (m² g^-1)	Vp^total (cm³ g^-1)	V_mic (cm³ g^-1)
TS-1	415.59	284.16	131.43	0.21	0.12
MTS-1	384.65	258.58	126.08	0.20	0.11
HTS-1	517.82	255.80	262.02	0.34	0.12
HMTS-1	511.15	245.74	265.41	0.35	0.11
HMTS-2	501.15	237.86	263.29	0.35	0.12
HMTS-3	478.65	234.20	244.45	0.33	0.11
HMTS-4	421.97	230.46	191.51	0.29	0.10
HMS-3	483.51	239.73	243.78	0.33	0.12

Fig. 3. (a) XRD patterns of catalyst samples. (b) Enlarged scale between 2θ = 7.4° and 9.7° of (a) for HMS-3, HTS-1, HMTS-1, HMTS-2, HMTS-3, and HMTS-4.

Fig. 4. TEM of catalyst samples prepared using different methods. (a-c) TS-1; (d-f) MTS-1; (g-i) HTS-1; (j-l) HMTS-3. (m) The corresponding EDS mapping of Fig. 4(e). (n) The corresponding EDS mapping of Fig. 4(k).

Fig. 5. (a) UV-vis spectra of TS-1, MTS-1, HTS-1, HMTS-3 and HMS-3 (no significant offset). (b) UV-vis spectra of HMTS-1, HMTS-2, HMTS-3, HMTS-4 and HMS-3 (no significant offset). (c) FT-IR spectra of TS-1, MTS-1, HTS-1 and HMTS-3. (d) FT-IR spectra of HMTS-1, HMTS-2, HMTS-3, HMTS-4 and HMS-3.

Fig. 6. (a) Mn K-edge XANES spectra of HMTS-3, HMS-3 and different reference samples. (b) Ti K-edge XANES spectra of HMTS-3, HTS-1 and different reference samples. (c) Fourier transform k3-weighted Mn EXAFS spectra in the R-spacing of different samples. (d) Fourier transform k3-weighted Ti EXAFS spectra in the R-spacing of different samples.

Fig. 7. WT-EXFAS spectra of Mn species. (a) Mn foil; (b) MnO2; (c) Mn3O4; (d) HMTS-3; (e) HMS-3. WT-EXFAS spectra of Ti species. (f) Ti foil; (g) TiO2; (h) HMTS-3; (i) HTS-1.

Table 4 Catalytic performance of different catalystsa.

Entry	Catalyst	Conv. (%)	Selectivity (%)
Entry	Catalyst	Conv. (%)	A	B	KA oil^b	C	D
1	Blank	trace	—	—	—	—	—
2	TS-1	18.2	40.2	25.7	65.9	20.5	13.6
3	MTS-1	26.4	34.7	20.8	55.5	30.5	14.0
4	HTS-1	43.4	30.2	18.3	48.5	41.1	10.4
5	HMS-3	35.1	27.2	16.5	43.7	46.3	10.0
6	HMTS-1	58.3	22.1	13.4	35.5	54.7	9.8
7	HMTS-2	74.4	19.0	7.3	26.3	62.2	11.5
8	HMTS-3	81.6	11.5	3.6	15.1	71.5	13.4
9	HMTS-4	79.1	11.9	2.6	14.5	68.3	17.2
10^c	HMS-3 & HTS-1	61.2	17.3	10.6	27.9	65.7	10.4
11^d	HMTS-3	—	—	—	—	—	—
12^e	HMTS-3	—	—	—	—	—	—

Fig. 8. Effect of temperature (0.05 g of catalyst, 2.34 g substrate, 27 mL acetonitrile, 2.0 MPa O2, 6 h) (a), reaction pressure (0.05 g of catalyst, 2.34 g substrate, 27 mL acetonitrile, 140 °C, 6 h) (b), catalyst amount (2.34 g substrate, 27 mL acetonitrile, 2.0 MPa O2, 140 °C, 6 h) (c) and reaction time (0.05 g of catalyst, 2.34 g substrate, 27 mL acetonitrile, 2.0 MPa O2, 140 °C) (d) on the conversion of cyclohexane and AA vs. KA oil selectivity over HMTS-3 catalysts (“others” were mainly glutaric acid and succinic acid).

Fig. 9. (a) Reaction results of HTS-1, HMS-3 and HMTS-3 with different substrates. (b) O2-TPD patterns of all catalysts (significant offset can be observed at 100?140 °C). (c) EPR spectra for oxygen vacancy. (d). NH3-TPD patterns of all catalysts. (e) Py-IR patterns of all catalysts. (f) Enlarged scale between wavenumbers = 1510 and 1560 cm?1 of Fig. 9(e).

Table 5 Acidity properties of different samples.

Sample	Total acidity^a (mmol g^-1)	B/L ratio ^b	C_BAS^c (mmol g^-1)	C_BAS^d (mmol g^-1)
TS-1	0.27	0.06	0.015	0.018
MTS-1	0.25	0.04	0.009	0.008
HTS-1	0.25	0.04	0.009	0.011
HMTS-1	0.28	0.05	0.013	0.014
HMTS-2	0.35	0.05	0.017	0.016
HMTS-3	0.42	0.04	0.017	0.019
HMTS-4	0.31	0.04	0.012	0.013
HMS-3	0.35	0.04	0.014	0.016

Fig. 10. In-situ DRIFTS experiments of oxygen adsorption on TS-1 (a), MTS-1 (b), HTS-1 (c), HMS-3 (d), and HMTS-3 (e).

Fig. 11. Mechanistic pathway for oxidative conversion of cyclohexane to AA, (2), (3), (4), (6), (7), (8) represent the possible catalytically active species shown in Scheme 1.

Fig. 12. (a) Recyclability tests of HMTS-3 catalyst for cyclohexane oxidation. XRD patterns (b), and Ti 2p (c) and C 1s (d) XPS spectra of recycled catalysts, of recycled catalysts.

参考文献

[1]	D. Vernekar, M. Dayyan, S. Ratha, C. V. Rode, M. A. Haider, T. S. Khan, D. Jagadeesan, ACS Catal., 2021, 11, 10754-10766.
[2]	Y. Wen, X. Wang, H. Wei, B. Li, P. Jin, L. Li, Green Chem., 2012, 14, 2868.
[3]	M. Wu, J. Di, L. Gong, Y.-C. He, C. Ma, Y. Deng, Chem. Eng. J., 2023, 452, 139320.
[4]	F. Liu, X. Gao, R. Shi, J. Xiong, Z. Guo, E. C. M. Tse, Y. Chen, Adv. Funct. Mater., 2024, 34, 2310274.
[5]	J. C. J. Bart, S. Cavallaro, Ind. Eng. Chem. Res., 2015, 54, 1-46.
[6]	C. Shi, B. Zhu, M. Lin, J. Long, R. Wang, Catal. Today, 2011, 175, 398-403.
[7]	J. Dai, W. Zhong, W. Yi, M. Liu, L. Mao, Q. Xu, D. Yin, Appl. Catal. B, 2016, 192, 325-341.
[8]	F. Liang, W. Zhong, L. Xiang, L. Mao, Q. Xu, S. R. Kirk, D. Yin, J. Catal., 2019, 378, 256-269.
[9]	A. Alshammari, A. Köckritz, V. N. Kalevaru, A. Bagabas, A. Martin, Appl. Petrochem. Res., 2012, 2, 61-67.
[10]	A. A. Alshaheri, M. I. M. Tahir, M. B. A. Rahman, T. B. S. A. Ravoof, T. A. Saleh, Chem. Eng. J., 2017, 327, 423-430.
[11]	C. M. Crombie, R. J. Lewis, D. Kovačič, D. J. Morgan, T. E. Davies, J. K. Edwards, M. S. Skjøth-Rasmussen, G. J. Hutchings, Catal. Lett., 2021, 151, 164-171.
[12]	A. A. Alshehri, A. M. Alhanash, M. Eissa, M. S. Hamdy, Appl. Catal. A, 2018, 554, 71-79.
[13]	A. M. Meireles, D. C. da Silva Martins, Polyhedron, 2020, 187, 114627.
[14]	T. Iwahama, K. Syojyo, S. Sakaguchi, Y. Ishii, Org. Process Res. Dev., 1998, 2, 255-260.
[15]	Y. Liu, D. Yang, G. Zeng, R. Wang, R. Zhang, M. Ji, R. Liu, Chem. Eng. Sci., 2024, 283, 119373.
[16]	M. Wu, W. Zhan, Y. Guo, Y. Wang, Y. Guo, X. Gong, L. Wang, G. Lu, Chin. J. Catal., 2016, 37, 184-192.
[17]	S. Wei, M. Li, K. Li, S. Zhong, Y. Su, R. Zhang, R. Liu, Chem. Eng. Sci., 2024, 295, 120131.
[18]	A. Alshammari, A. Koeckritz, V. N. Kalevaru, A. Bagabas, A. Martin, ChemCatChem, 2012, 4, 1330-1336.
[19]	H. Yu, F. Peng, J. Tan, X. Hu, H. Wang, J. Yang, W. Zheng, Angew. Chem. Int. Ed., 2011, 50, 3978-3982.
[20]	K. Li, S. Wei, Y. Liu, R. Wang, R. Zhang, R. Liu, Chem. Eng. J., 2024, 482, 148762.
[21]	Z. Zhang, M. Hu, Q. Gui, J. Gu, W. Xu, Q. Xiao, W. Huang, Chem. Eng. J., 2023, 467, 143501.
[22]	G. Zou, W. Zhong, Q. Xu, J. Xiao, C. Liu, Y. Li, L. Mao, S. Kirk, D. Yin, Catal. Commun., 2015, 58, 46-52.
[23]	X. Guo, M. Xu, M. She, Y. Zhu, T. Shi, Z. Chen, L. Peng, X. Guo, M. Lin, W. Ding, Angew. Chem. Int. Ed., 2020, 59, 2606-2611.
[24]	S. Sahu, D. P. Goldberg, J. Am. Chem. Soc., 2016, 138, 11410-11428.
[25]	H. M. Neu, J. Jung, R. A. Baglia, M. A. Siegler, K. Ohkubo, S. Fukuzumi, D. P. Goldberg, J. Am. Chem. Soc., 2015, 137, 4614-4617.
[26]	K. Ray, F. F. Pfaff, B. Wang, W. Nam, J. Am. Chem. Soc., 2014, 136, 13942-13958.
[27]	V. L. Pecoraro, M. J. Baldwin, A. Gelasco, Chem. Rev., 1994, 94, 807-826.
[28]	J. M. Thomas, R. Raja, G. Sankar, R. G. Bell, Nature, 1999, 398, 227-230.
[29]	Z. Wang, H. Jia, T. Zheng, Y. Dai, C. Zhang, X. Guo, T. Wang, L. Zhu, Appl. Catal. B, 2020, 272, 119030.
[30]	M. M. Pereira, L. D. Dias, M. J. F. Calvete, ACS Catal., 2018, 8, 10784-10808.
[31]	R. J. Lewis, K. Ueura, X. Liu, Y. Fukuta, T. E. Davies, D. J. Morgan, L. Chen, J. Qi, J. Singleton, J. K. Edwards, S. J. Freakley, C. J. Kiely, Y. Yamamoto, G. J. Hutchings, Science, 2022, 376, 615-620.
[32]	C. Pang, J. Xiong, G. Li, C. Hu, J. Catal., 2018, 366, 37-49.
[33]	T. Zhang, X. Chen, G. Chen, M. Chen, R. Bai, M. Jia, J. Yu, J. Mater. Chem. A, 2018, 6, 9473-9479.
[34]	R. Bai, Q. Sun, Y. Song, N. Wang, T. Zhang, F. Wang, Y. Zou, Z. Feng, S. Miao, J. Yu, J. Mater. Chem. A, 2018, 6, 8757-8762.
[35]	C. J. H. Jacobsen, C. Madsen, J. Houzvicka, I. Schmidt, A. Carlsson, J. Am. Chem. Soc., 2000, 122, 7116-7117.
[36]	Y. Cheneviere, F. Chieux, V. Caps, A. Tuel, J. Catal., 2010, 269, 161-168.
[37]	S. Du, F. Li, Q. Sun, N. Wang, M. Jia, J. Yu, Chem. Commun., 2016, 52, 3368-3371.
[38]	X. Gao, Y. Zhou, J. Gu, L. Li, Y. Li, Microporous Mesoporous Mater., 2019, 275, 263-269.
[39]	W. Zheng, S. Feng, C. Hu, ChemSusChem, 2024, 17, e202400121.
[40]	C.-A. Wang, G. An, J. Lin, X. Zhang, Z. Liu, Y. Luo, S. Liu, Z. Cheng, T. Guo, H. Gao, G. Wang, X. Shu, Aggregate, 2023, 4, e318.
[41]	Y. Yao, Z. Yang, P. Zheng, Z. Diao, Chem. Eng. J., 2023, 475, 146053.
[42]	M. Liu, Z. Xiao, J. Dai, W. Zhong, Q. Xu, L. Mao, D. Yin, Chem. Eng. J., 2017, 313, 1382-1395.
[43]	G. Zou, W. Zhong, L. Mao, Q. Xu, J. Xiao, D. Yin, Z. Xiao, S. R. Kirk, T. Shu, Green Chem., 2015, 17, 1884-1892.
[44]	P. Fabrizioli, T. Bürgi, A. Baiker, J. Catal., 2002, 207, 88-100.
[45]	Y. Fu, Q. Wei, G. Zhang, X. Wang, J. Zhang, Y. Hu, D. Wang, L. Zuin, T. Zhou, Y. Wu, S. Sun, Adv. Energy Mater., 2018, 8, 1801445.
[46]	Y. Meng, H. C. Genuino, C.-H. Kuo, H. Huang, S.-Y. Chen, L. Zhang, A. Rossi, S. L. Suib, J. Am. Chem. Soc., 2013, 135, 8594-8605.
[47]	L.-Y. Lin, H. Bai, Chem. Eng. J., 2016, 291, 94-105.
[48]	M. Jin, J. H. Kim, J. M. Kim, J.-K. Jeon, J. Jurng, G.-N. Bae, Y.-K. Park, Catal. Today, 2013, 204, 108-113.
[49]	W. Zhong, S. R. Kirk, D. Yin, Y. Li, R. Zou, L. Mao, G. Zou, Chem. Eng. J., 2015, 280, 737-747.
[50]	H.-H. She, G.-Q. Ding, X.-Q. Li, H.-X. Wang, D.-B. Cao, Y.-L. Zhu, Y.-W. Li, J. Fuel Chem. Technol., 2021, 49, 1148-1160.
[51]	S. Contarini, P. A. W. van der Heide, A. M. Prakash, L. Kevan, J. Electron Spectrosc. Relat. Phenom., 2002, 125, 25-33.
[52]	J. Wang, L. Xu, K. Zhang, H. Peng, H. Wu, J.-G. Jiang, Y. Liu, P. Wu, J. Catal., 2012, 288, 16-23.
[53]	D. P. Serrano, R. Sanz, P. Pizarro, I. Moreno, Appl. Catal. A, 2012, 435-436, 32-42.
[54]	G. Zou, D. Jing, W. Zhong, F. Zhao, L. Mao, Q. Xu, J. Xiao, D. Yin, RSC Adv., 2016, 6, 3729-3734.
[55]	A. Ramanathan, T. Archipov, R. Maheswari, U. Hanefeld, E. Roduner, R. Gläser, J. Phys. Chem. C, 2008, 112, 7468-7476.
[56]	Y. Song, R. Bai, Y. Zou, Z. Feng, J. Yu, Inorg. Chem. Front., 2020, 7, 1872-1879.
[57]	M. Shamzhy, M. Opanasenko, P. Concepción, A. Martínez, Chem. Soc. Rev., 2019, 48, 1095-1149.
[58]	G. An, C.-A. Wang, H. Gao, G. Wang, Y. Luo, Z. Liu, C. Xia, S. Liu, X. Peng, Z. Cheng, X. Shu, J. Colloid Interface Sci., 2023, 633, 291-302.
[59]	A. Derylo-Marczewska, W. Gac, N. Popivnyak, G. Zukocinski, S. Pasieczna, Catal. Today, 2006, 114, 293-306.
[60]	G. M. Kuz’micheva, R. D. Svetogorov, E. V. Khramov, G. V. Kravchenko, L. G. Bruk, Z. Y. Pastukhova, E. B. Мarkova, A. I. Zhukova, S. G. Chuklina, A. V. Dorokhov, Microporous Mesoporous Mater., 2021, 326, 111377.
[61]	V. Celorrio, A. S. Leach, H. Huang, S. Hayama, A. Freeman, D. W. Inwood, D. J. Fermin, A. E. Russell, ACS Catal., 2021, 11, 6431-6439.
[62]	I. M. Mosa, S. Biswas, A. M. El-Sawy, V. Botu, C. Guild, W. Song, R. Ramprasad, J. F. Rusling, S. L. Suib, J. Mater. Chem. A, 2016, 4, 620-631.
[63]	T. Ressler, S. L. Brock, J. Wong, S. L. Suib, J. Phys. Chem. B, 1999, 103, 6407-6420.
[64]	M. Croft, D. Sills, M. Greenblatt, C. Lee, S.-W. Cheong, K. V. Ramanujachary, D. Tran, Phys. Rev. B, 1997, 55, 8726-8732.
[65]	J. Dong, H. Zhu, Y. Xiang, Y. Wang, P. An, Y. Gong, Y. Liang, L. Qiu, A. Zheng, X. Peng, M. Lin, G. Xu, Z. Guo, D. Chen, J. Phys. Chem. C, 2016, 120, 20114-20124.
[66]	H. K. D. Nguyen, G. Sankar, R. A. Catlow, J. Porous Mater., 2017, 24, 421-428.
[67]	W. Xu, T. Zhang, R. Bai, P. Zhang, J. Yu, J. Mater. Chem. A, 2020, 8, 9677-9683.
[68]	S. Bordiga, S. Coluccia, C. Lamberti, L. Marchese, A. Zecchina, F. Boscherini, F. Buffa, F. Genoni, G. Leofanti, J. Phys. Chem., 1994, 98, 4125-4132.
[69]	F. Jin, C.-C. Chang, C.-W. Yang, J.-F. Lee, L.-Y. Jang, S. Cheng, J. Mater. Chem. A, 2015, 3, 8715-8724.
[70]	R. Bai, Y. Song, Y. Li, J. Yu, Trends Chem., 2019, 1, 601-611.
[71]	R. Bai, Y. Song, R. Bai, J. Yu, Adv. Mater. Interfaces, 2021, 8, 2001095.
[72]	Y. Wei, J. Liu, Z. Zhao, A. Duan, G. Jiang, J. Catal., 2012, 287, 13-29.
[73]	X. Li, X. Wang, J. Ding, M. Ma, S. Yuan, Q. Yang, Z. Wang, Y. Peng, C. Sun, H. Zhou, H. Liu, Y. A. Wu, K. Huang, L. Li, G. Li, S. Feng, ACS Catal., 2023, 13, 6338-6350.
[74]	Y. Liu, S. Zhou, X. Wang, J. Qin, C. Hu, J. Li, ACS Catal., 2024, 14, 7609-7623.
[75]	Q. Shao, Z. Cheng, L. Gao, T. Li, J. Zhang, C. Long, Appl. Catal. B, 2023, 339, 123154.
[76]	Q. Cheng, Y. Tian, S. Lyu, N. Zhao, K. Ma, T. Ding, Z. Jiang, L. Wang, J. Zhang, L. Zheng, F. Gao, L. Dong, N. Tsubaki, X. Li, Nat. Commun., 2018, 9, 3250.
[77]	Y. Xiao, S. Xu, X. Wang, Z. Lu, C. Hu, J. Li, Chem. Eng. J., 2023, 475, 146295.
[78]	Y. Guo, X. Tian, X. Liu, H. Lv, P. Hu, H. Li, F. Lu, C. Hu, L. Zhu, Fuel, 2025, 399, 135636.
[79]	X. Hou, F. Yuan, X. Liu, K. Wang, Y. Zhu, P. Cheng, R. Jia, L. Shi, L. Huang, Chem. Eng. J., 2025, 504, 158868.
[80]	P. Zhao, Z. Li, Y. Zhang, D. Cui, Q. Guo, Z. Dong, G. Qi, J. Xu, F. Deng, Microporous Mesoporous Mater., 2022, 335, 111840.
[81]	R. Feng, Z. Fang, W. Wang, T. Li, X. Hu, X. Yan, Z. Zhang, Ind. Eng. Chem. Res., 2024, 63, 14527-14540.
[82]	P. Y. Dapsens, C. Mondelli, J. Pérez-Ramírez, Chem. Soc. Rev., 2015, 44, 7025-7043.
[83]	Y. Chai, W. Dai, G. Wu, N. Guan, L. Li, Acc. Chem. Res., 2021, 54, 2894-2904.
[84]	C. Li, K. Domen, K.-I. Maruya, T. Onishi, J. Catal., 1990, 123, 436-442.
[85]	Z. Wu, P. Zhang, S. Rong, J. Jia, Appl. Catal. B, 2023, 335, 122900.
[86]	J. Xu, T. Zhang, S. Fang, J. Li, Z. Wu, W. Wang, J. Zhu, E. Gao, S. Yao, Commun. Chem., 2022, 5, 97.
[87]	G. Xiong, Y. Cao, Z. Guo, Q. Jia, F. Tian, L. Liu, Phys. Chem. Chem. Phys., 2016, 18, 190-196.
[88]	P. E. Sinclair, C. R. A. Catlow, J. Phys. Chem. B, 1999, 103, 1084-1095.
[89]	J. S. Reddy, P. A. Jacobs, Catal. Lett., 1996, 37, 213-216.
[90]	S.-O. Lee, R. Raja, K. D. M. Harris, J. M. Thomas, B. F. G. Johnson, G. Sankar, Angew. Chem. Int. Ed., 2003, 42, 1520-1523.
[91]	M. Hartmann, A. G. Machoke, W. Schwieger, Chem. Soc. Rev., 2016, 45, 3313-3330.