Iridium-based Catalyst Immobilized on Zeolite Subcrystals and Its Catalytic Transfer Hydrogenation Performance

doi:10.7503/cjcu20230224

Abstract

Abstract:

By immobilizing homogeneous catalysts， the advantages of high reaction activity of homogeneous catalysts and separability of heterogeneous catalysts can be preserved simultaneously. This work used zeolite subcrystals with ultra-small size and ultra-large specific surface area as the carrier to immobilize the homogeneous transfer hydrogenation catalyst［Cp^*Ir（bpyO）］OH^- by physical adsorption， achieving the preparation of an immobilized catalyst ［Cp^*Ir（bpyO）］OH^-/Al-MFI-SC. The immobilization process and stability of the catalyst were preliminarily studied using UV-Vis to determine the amount of catalyst immobilized and demonstrate the stability of the immobilized catalyst. The characterization results of XRD， TEM， ICP-AES， Ar physical adsorption and desorption and XPS demonstrated that［Cp^*Ir（bpyO）］OH^- was uniformly immobilized on the surface of Al-MFI-SC. The strong interaction between the aluminum species in the zeolite subcrystals and the iridium complex was responsible for the stability of the immobilized catalyst. Finally， The catalyst was used for the catalytic transfer hydrogenation of cyclohexanone to cyclohexanol using glucose as the hydrogen donor and able to achieve a cyclohexanol yield of 75.4% under optimal reaction conditions. Compared with the homogeneous catalyst with the same weight percent of iridium， this immobilized catalyst showed better catalytic activity and good recycling performance. Meanwhile， the catalyst had a good reusability property. This work provides an idea for the preparation of immobilized catalysts for catalytic transfer hydrogenation reactions using zeolite subcrystal materials as the carrier.

Key words: Zeolite subcrystal, Catalytic transfer hydrogenation, Immobilization, Interaction

CLC Number:

O643.3

TrendMD:

WANG Shuqi, DU Ke, LI He, ZHANG Yahong. Iridium-based Catalyst Immobilized on Zeolite Subcrystals and Its Catalytic Transfer Hydrogenation Performance[J]. Chem. J. Chinese Universities, 2023, 44(10): 20230224.

Figures/Tables 9

Table 1 Textural properties of Al-MFI-SC and [Cp*Ir(bpyO)]OH-/Al-MFI-SC after hydrothermal treatment

Sample	S $t o t a l a$ /（m²·g^-1）	S $m i c r o b$ /（m²·g^-1）	S $e x t r a b$ /（m²·g^-1）	V $t o t a l c$ /（cm³·g^-1）	V $m i c r o b$ /（cm³·g^-1）
Al⁃MFI⁃SC	720	546	174	0.455	0.268
［Cp^*Ir（bpyO）］OH^-/Al⁃MFI⁃SC	492	302	190	0.340	0.140

Table 1 Textural properties of Al-MFI-SC and [Cp*Ir(bpyO)]OH-/Al-MFI-SC after hydrothermal treatment

Sample	S $t o t a l a$ /（m²·g^-1）	S $m i c r o b$ /（m²·g^-1）	S $e x t r a b$ /（m²·g^-1）	V $t o t a l c$ /（cm³·g^-1）	V $m i c r o b$ /（cm³·g^-1）
Al⁃MFI⁃SC	720	546	174	0.455	0.268
［Cp^*Ir（bpyO）］OH^-/Al⁃MFI⁃SC	492	302	190	0.340	0.140

Table 2 Catalytic transfer hydrogenation reaction results of cyclohexanone towards cyclohexanol with GLU as the hydrogen donor and [Cp*Ir(bpyO)]OH-/Al-MFI-SC as the catalyst a

Entry	Molar ratio of GLU/cyclohexanone	Temperature/℃	Conv.（%）	Yield（%， molar fraction）	Detect. carbon ^b （%， molar fraction）
1	1∶1	120 120 120 120 120	32.8	19.1	86.3
2	3∶1		35.2	32.6	97.4
3	5∶1		98.1	75.4	77.3
4	7∶1		82.4	69.8	87.4
5	9∶1		91.6	68.7	77.1
6	5∶1 5∶1 5∶1 5∶1 5∶1	100	28.0	23.4	95.4
7		110	32.6	29.8	97.2
8		130	79.4	50.5	71.1
9		140	71.9	48.2	76.3
10		150	42.9	35.9	93.0
11 ^c	5∶1	120	53.1	45.5	92.4
12 ^d	5∶1	120	50.1	42.3	92.2
13 ^e	5∶1	120	10.8	2.0	91.2

References 32

1	Linstead R. P.， Braude E. A.， Mitchell P. W. D.， Wooldridge K. R. H.， Jackman L. M.， Nature， 1952， 169（4290）， 100—103
2	Gilkey M. J.， Xu B.， ACS Catal.， 2016， 6（3）， 1420—1436
3	Wang D.， Astruc D.， Chem. Rev.， 2015， 115（13）， 6621—6686
4	Brieger G.， Nestrick T. J.， Chem. Rev.， 1973， 74（5）， 567—580
5	Zassinovich G.， Mestroni G.， Gladlali S.， Chem. Rev.， 1992， 92（5）， 1051—1069
6	Jin X.， Yin B.， Xia Q.， Fang T.， Shen J.， Kuang L.， Yang C.， ChemSusChem， 2019， 12（1）， 71—92
7	Ito J.， Nishiyama H.， Tetrahedron Lett.， 2014， 55（20）， 3133—3146
8	Robertson A.， Matsumoto T.， Ogo S.， Dalton Trans.， 2011， 40（40）， 10304—10310
9	Sheldon R. A.， Curr. Opin. Solid State Mater. Sci.， 1996， 1（1）， 101—106
10	Huber G. W.， Iborra S.， Corma A.， Chem. Rev.， 2006， 106（9）， 4044—4098
11	Alonso D. M.， Wettstein S. G.， Dumesic J. A.， Chem. Soc. Rev.， 2012， 41（24）， 8075—8098
12	Ding K.， Uozumi Y.， Handbook of Asymmetric Heterogeneous Catalysis，Wiley⁃VCH， Weinheim， 2008， 25—72
13	Stefane B.， Pozgan F.， Catal. Rev.： Sci. Eng.， 2014， 56（1）， 82—174
14	Johnstone R. A. W.， Wilby A. H.， Entwistle I. D.， Chem. Rev.， 1985， 85（2）， 129—170
15	Nie R.， Tao Y.， Nie Y.， Lu T.， Wang J.， Zhang Y.， Lu X.， Xu C.， ACS Catal.， 2021， 11（3）， 1071—1095
16	Gates B. C.， Chem. Rev.， 1995， 95（3）， 511—522
17	Baráth E.， Synthesis， 2020， 52（4）， 504—520
18	Zhao X.， Bao X.， Guo W.， Lee F.， Mater. Today， 2006， 9（3）， 32—39
19	Govan J.， Gunko Y. K.， Nanomaterials， 2014， 4（2）， 222—241
20	Fraile J. M.， Garcia J. I.， Mayoral J. A.， Chem. Rev.， 2009， 109（2）， 360—417
21	Chai Y.， Shang W.， Li W.， Wu G.， Dai W.， Guan N.， Li L.， Adv. Sci.， 2019， 6（16）， 1900299
22	Subramanian T.， Pitchumani K.， Catal. Sci. Technol.， 2012， 2（2）， 296—300
23	Rao B. S.， Kumari P. K.， Koley P.， Tardio J.， Lingaiah N.， Mol. Catal.， 2019， 466， 52—59
24	Sheng Z.， Li H.， Du K.， Gao L.， Ju J.， Zhang Y.， Tang Y.， Angew. Chem. Int. Ed. Engl.， 2021， 60（24）， 13444—13451
25	Murata K.， Ikariya T.， Noyori R.， J. Org. Chem.， 1999， 64， 2186—2187
26	Hintermair U.， Campos J.， Brewster T. P.， Pratt L. M.， Schley N. D.， Crabtree R. H.， ACS Catal.， 2013， 4， 99—108
27	Fujita K.， Inoue T.， Tanaka T.， Jeong J.， Furukawa S.， Yamaguchi R.， Catalysts， 2021， 11， 891
28	Yoshida M.， Hirahata R.， Inoue T.， Shimbayashi T.， Fujita K.， Catalysts， 2019， 9， 503
29	Fujita K.， Kawahara R.， Aikawa T.， Yamaguchi R.， Angew. Chem. Int. Ed. Engl.， 2015， 54（31）， 9057—9060
30	Zhang S.， Li M.， Wu Q.， Yang H.， Han J.， Wang H.， Liu X.， Appl. Catal. B， 2018， 236， 466—474
31	Davda R. R.， Shabaker J. W.， Huder G. W.， Cortright R. D.， Dumesic J. A.， Appl. Catal. B， 2005， 56， 171—186
32	Rajagopal S.， Vancheesan S.， Rajaram J.， Kuriacose J. C.， J. Mol. Catal.， 1992， 75（2）， 199—208

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