Self-aldol condensation of aldehydes over Lewis acidic rare-earth cations stabilized by zeolites

doi:10.1016/S1872-2067(20)63675-0

Abstract

Abstract:

The self-aldol condensation of aldehydes was investigated with rare-earth cations stabilized by [Si]Beta zeolites in parallel with bulk rare-earth metal oxides. Good catalytic performance was achieved with all Lewis acidic rare-earth cations stabilized by zeolites and yttrium appeared to be the best metal choice. According to the results of several complementary techniques, i.e., temperature-programmed surface reactions, in situ diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy, the reaction pathway and mechanism of the aldehyde self-aldol condensation over Y/Beta catalyst were studied in more detail. Density functional theory calculations revealed that aldol dehydration was the rate-limiting step. The hydroxyl group at the open yttrium site played an important role in stabilizing the transition state of the aldol dimer reducing the energy barrier for its hydration. Lewis acidic Y(OSi)(OH)₂ stabilized by zeolites in open configurations were identified as the preferred active sites for the self-aldol condensation of aldehydes.

Key words: Self-aldol condensation, Aldehyde, Rare-earth cations, Zeolite, Lewis acid

Tingting Yan, Sikai Yao, Weili Dai, Guangjun Wu, Naijia Guan, Landong Li. Self-aldol condensation of aldehydes over Lewis acidic rare-earth cations stabilized by zeolites[J]. Chinese Journal of Catalysis, 2021, 42(4): 595-605.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63675-0

https://www.cjcatal.com/EN/Y2021/V42/I4/595

Figures/Tables 16

Fig. 1. Self-aldol condensation of propyl aldehyde over different catalysts. Reaction conditions: 0.16 g catalyst, WHSV = 1.0/h, T = 573 K, TOS = 2 h.

Fig. 2. Propyl aldehyde conversion with time-on-stream of Y/Beta, La/Beta, Sc/Beta and Ce/Beta catalysts. Reaction conditions: 0.16 g catalyst, WHSV = 1.0/h, T = 573 K; Regeneration conditions: calcination in flowing air at 773 K for 4 h.

Table 2 Summary of IR bands observed and their assignments.

IR bands	Assignments
3734 cm^-1	O-H stretching vibrations of Si-OH
3672 cm^-1	O-H stretching vibrations of Y-OH
3000-2700 cm^-1	C-H stretching vibrations of methyl and methylene groups
1741 cm^-1	C=O stretching vibrations of chemisorbed aldehydes
1765 cm^-1	C=O stretching vibrations of gas phase aldehydes
1687 cm^-1	C=O stretching vibrations of α,β-unsaturated carbonyl groups
1643 cm^-1	C=C stretching vibrations of α,β-unsaturated carbonyl groups
1608 &1597 cm^-1	C=C stretching vibrations of carbonaceous or aromatics species
1462 cm^-1	C-H bending vibrations of aromatic ring
1456 & 1404 cm^-1	C-H bending vibrations of aldehyde or aldol dimer
1305 & 1174 cm^-1	Aldehyde molecules coordinated to Lewis acid sites

Table 1 Physicochemical properties of zeolites.

Catalyst	n_si/n_Al^a	Surface area ^b (m²/g)	Pore volume ^c (cm³/g)
H-Beta	14	562	0.194
[Si]Beta	> 1800	581	0.206
Y/Beta	> 1800	527	0.171
La/Beta	> 1800	524	0.170
Ce/Beta	> 1800	532	0.174
Sc/Beta	> 1800	531	0.172

Fig. 3. DRIFTS in the hydroxyl regions of selected zeolite samples.

Fig. 4. 13C CPMAS NMR spectra of zeolite samples after acetone-2-13C adsorption.

Fig. 5. In situ DRIFTS recorded during propyl aldehyde conversion over Y/Beta and Y2O3 for TOS of 60 min. Reaction conditions: WHSV = 1.0/h, T = 573 K.

Fig. 6. In situ UV-vis DRS recorded during propyl aldehyde conversion over Y/Beta and Y2O3 for TOS of 60 min. Reaction conditions: WHSV = 0.3/h, T = 573 K.

Fig. 7. TPSR profiles of propyl aldehyde conversion over Y/Beta and Y2O3 catalysts. Reaction conditions: 0.16 g catalyst, WHSV = 1.0/h.

Fig. 8. Optimized structures of Y/Beta. The active sites in Y/Beta-I and Y/Beta-II are Y(OSi)3 and Y(OSi)2(OH), respectively. (cyan: Y; yellow: Si; red: O; white: H).

Table 3 Energy barriers (Ea) and reaction energies (ΔE) for keto-enol tautomerization of various models.

Entry	Model	E_a (eV)	ΔE (eV)
P1	Y/Beta-I	1.07	0.10
P2	Y/Beta-II^a	1.01	0.49
P3	Y/Beta-II^b	0.82	0.38

Table 4 Energy barriers and reaction energies of alkoxy anion hydrogenation on various models.

Entry	Model	E_a (eV)	ΔE (eV)
P1	Y/Beta-I	0.61	0.01
P2	Y/Beta-II^a	0.33	-0.31
P3	Y/Beta-II^b	—	-0.32

Table 5 Energy barriers and reaction energies for aldol dimer dehydration on various models.

Entry	Model	E_a (eV)	ΔE (eV)
P1	Y/Beta-I	2.24	0.35
P2	Y/Beta-II^a	2.30	0.37
P3	Y/Beta-II^b	1.63	0.15
Gas phase		2.00	0.19

Fig. 9. Configurations of initial and transition states of aldol dimer dehydration on Y/Beta-I and Y/Beta-II. (cyan: Y; yellow: Si; red: O; gray: C; white: H).

Fig. 10. Energy profiles of acetaldehyde self-aldol condensation over Y/Beta. Three distinct reaction pathways (P1, P2 and P3) are considered.

Scheme 1. Reaction pathway and mechanism of the self-aldol condensation of aldehydes over Y/Beta.

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