Identifying a bi-molecular synergetic adsorption mechanism for catalytic transformation of ethanol/acetaldehyde into 1,3-butadiene

doi:10.1016/S1872-2067(24)60262-7

Abstract

Abstract:

The catalytic synthesis of 1,3-butadiene (1,3-BD) from bio-based ethanol offers an alternative and sustainable process beyond petroleum. However, the intrinsic active sites and corresponding mechanism of 1,3-BD formation have not been fully elucidated yet. By correlating systematic characterization results with catalytic performance, the open Zr species, i.e., Zr(OH)(OSi)₃ moieties, were identified as the active site over the Zr/MFI-BM catalysts for the catalytic transformation of ethanol-acetaldehyde into 1,3-BD. In conjunction with controlled experiments and theory calculations, ethanol and acetaldehyde are proposed to synergistically co-adsorb on the Zr(OH)(OSi)₃ species in a bi-molecular mode, which assists the acetaldehyde condensation and accelerates the critical Meerwein-Ponndorf-Verley-Oppenauer reduction, and accordingly promotes 1,3-BD formation. These findings will stimulate the search towards new metal-zeolite combinations for efficient production of value-added 1,3-BD via biomass-derived ethanol and beyond.

Key words: 1,3-Butadiene, Bi-molecular, Co-adsorption-mechanism, Reaction mechanism, Ethanol conversion

Xianquan Li, Jifeng Pang, Yujia Zhao, Lin Li, Wenguang Yu, Feifei Xu, Yang Su, Xiaofeng Yang, Wenhao Luo, Mingyuan Zheng. Identifying a bi-molecular synergetic adsorption mechanism for catalytic transformation of ethanol/acetaldehyde into 1,3-butadiene[J]. Chinese Journal of Catalysis, 2025, 71: 297-307.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60262-7

https://www.cjcatal.com/EN/Y2025/V71/I4/297

Figures/Tables 5

Fig. 1. Synthesis and catalytic performance of Zr-based catalysts for the EATB reaction. (a) The main reaction steps for the EATB process. (b) Schematic diagram for the synthesis of Zr/MFI-BM catalysts. (c) Catalytic performance of ZrO2, Zr/MFI, and Zr/MFI-BM catalysts in the EATB reaction. (d) Ethanol-acetaldehyde conversion and 1,3-BD selectivity in the 125 h TOS over Zr/MFI-BM (350 °C, WHSV = 0.64 h?1, ethanol/acetaldehyde = 2).

Fig. 2. Microstructural characterization of Zr-based catalysts. (a) XPS. (b) 29Si MAS NMR. (c) EXAFS spectra. (d) Fitting of k2-weighted EXAFS data. (e) CO-FTIR spectra for typical Zr-based catalysts. (f) Schematic diagram for the Zr(OH)(OSi)3 sites on the Zr/MFI-BM catalyst.

Fig. 3. Identification of the inherent catalytic center of the EATB reaction. FTIR spectra for the adsorption of ethanol (orange line), acetaldehyde (pink line), and reactants mixture (blue line) at 30 °C over ZrO2 (a), Zr/MFI (b) and Zr/MFI-BM (c) catalysts. (d) IGA results of ethanol or/and acetaldehyde chemisorption over ZrO2, Zr/MFI and Zr/MFI-BM catalysts. Productivity of 1,3-BD over ZrO2, Zr/MFI and Zr/MFI-BM catalysts (e) and different Zr active sites (f). ETOH, ACH and ETOH-ACH are abbreviations for ethanol, acetaldehyde, and ethanol-acetaldehyde mixture, respectively.

Fig. 4. Revealing the co-adsorption model for EATB reaction. (a) DFT calculations for Gibbs free energy of ethanol and/or acetaldehyde adsorbed on Zr(OH)(OSi)3 species and (b) the possible reaction pathways.

Fig. 5. The elucidation of the EATB reaction mechanism. DFT calculation for Gibbs free energy of aldol condensation (a) and MPVO step (b) over the ZrOx and Zr(OH)(OSi)3 species. (c) Proposed catalytic cycle for the EATB process over the Zr(OH)(OSi)3 site.

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