Construction of modularized catalytic system for transfer hydrogenation: Promotion effect of hydrogen bonds

doi:10.1016/S1872-2067(23)64499-7

Abstract

Abstract:

The construction of enzyme-mimicking catalysts is a crucial route for achieving green chemical transformations; however, integrating multiple sites into one catalyst is challenging. Herein, a facile method is reported to combine different active sites by constructing a modularized catalytic system. A modularized catalytic system composed of covalent organic frameworks (COFs) and Cu₂Cr₂O₅ exhibits remarkable efficiency in the transfer hydrogenation of cinnamaldehyde, with a selectivity of over 99% towards cinnamyl alcohol, surpassing the reaction rate of Cu₂Cr₂O₅ by more than fourfold. The results of the mechanistic study and density functional theory calculations suggest that the enhanced activity of the modularized catalytic system is derived from the hydrogen bonds between the COFs and isopropyl alcohol, which promote isopropyl alcohol dehydrogenation and hydride transfer. In addition, the modularized catalytic system is efficient for various saturated and unsaturated aldehydes and could be replaced by different submodules. This study demonstrates the efficiency of a modularized catalytic system for mimicking the functions of enzymes in catalysis.

Key words: Modularized catalytic system, Transfer hydrogenation, Hydrogen bond, Enzyme-mimic catalyst, Covalent organic framework

Xin Liu, Maodi Wang, Yiqi Ren, Jiali Liu, Huicong Dai, Qihua Yang. Construction of modularized catalytic system for transfer hydrogenation: Promotion effect of hydrogen bonds[J]. Chinese Journal of Catalysis, 2023, 52: 207-216.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64499-7

https://www.cjcatal.com/EN/Y2023/V52/I9/207

Figures/Tables 6

Scheme 1. Chemical structures of COFs used in this work.

Fig. 1. (a) Conversion and selectivity to COL as a function of reaction time, and (b) reaction rate in CTH of CAL with isopropyl alcohol, (I) Cu2Cr2O5 and Cu2Cr2O5 with (II) 10% TPTTA, (III) 50% TPTTA, (IV) 100% TPTTA. (c) Arrhenius plots showing apparent activation barriers of Cu2Cr2O5 and Cu2Cr2O5 with 100% TPTTA in CTH of CAL. (d) Recycling stability of Cu2Cr2O5 with 100% TPTTA in the CTH of CAL (The second run was without calcination of Cu2Cr2O5. For the other runs, Cu2Cr2O5 was separated from the reaction system and calcined at 400 °C in air. Reaction condition: 0.1 mmol CAL, 26.5 mg Cu2Cr2O5, 150 °C, 0.5 MPa N2, 2 mL isopropyl alcohol.

Table 1 Substrate scope of modularized catalytic systems (Cu2Cr2O5 with 100% TPTTA) and Cu2Cr2O5 in the CTH of unsaturated aldehydes with isopropyl alcohol.

Entry ^a	t (h)	Conv. (%)	Sel. (%)
1	0.7	96 (34)	> 99 (> 99)
2	0.7	90 (15)	> 99 (> 99)
3	1	97 (44)	> 99 (> 99)
4	12	81 (< 1)	> 99 (-)
5 ^b	0.5	99 (22)	> 99 (> 99)
6	0.5	92 (21)	> 99 (> 99)
7 ^c	0.5	90 (22)	> 99 (> 99)
8 ^d	0.5	91 (30)	> 99 (> 99)
9 ^b	0.5	93 (26)	> 99 (> 99)

Fig. 2. (a) Acetone yields in isopropyl alcohol dehydrogenation catalyzed by Cu2Cr2O5 and Cu2Cr2O5 with 100% TPTTA. (b) Kinetic isotope effect (KIE) experiments on transfer hydrogenation of CAL over Cu2Cr2O5 and Cu2Cr2O5 with 100% TPTTA using (CH3)2CHOH and isotopic deuterium (CH3)2CHOD as hydrogen sources at 150 °C.

Fig. 3. (a) Chemical structures of model compounds. (b,c) Conversion and selectivity of CAL to COL over Cu2Cr2O5 in the presence of different types of COFs and model compounds. Reaction conditions: 0.1 mmol CAL, 26.5 mg Cu2Cr2O5, 150 °C, 0.5 MPa N2, t = 1 h, 2 mL isopropyl alcohol, a mass ratio of 0.1 between COFs, and Cu2Cr2O5.

Table 2 Adsorption energies (Ead) and bond length of the hydroxyl group of isopropyl alcohol on different sites of model compounds.

Model compound	Site	E_ad (eV)	Bond length (Å)
Model compound 1	Site 1	‒0.23	0.97449
Model compound 1	Site 2	‒0.43	0.98582
Model compound 2	Site 3	‒0.26	0.97505
Model compound 2	Site 4	‒0.19	0.97512

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