The role of C1 species in the methanol-to-hydrocarbons reaction: Beyond merely being reactants

doi:10.1016/S1872-2067(24)60228-7

Abstract

Abstract:

In the methanol-to-hydrocarbons (MTH) process, C1 species, including methanol, dimethyl ether, and surface methoxy species (SMS), play crucial roles in the evolution of organic species and the construction of reaction networks. Understanding the roles of C1 species throughout the entire MTH process is both essential and challenging. Herein, the dynamic evolution of organic species and unique variation of C1 species during the real-time MTH process were observed by operando diffused reflectance Fourier transform infrared spectroscopy and ex-situ ¹³C cross polarization/magic-angle spinning nuclear magnetic resonance experiments. Importantly, density functional theory calculations thoroughly illustrated that methanol and SMS serve as key C1 species, in the form of not only methylation agents but also hydride acceptors, and their contributions vary across different reaction periods. Initially, SMS acts as the preferential C1 surface intermediate, methylating with hydrocarbons to propagate C-C bond, while also accepting hydrides to generate precursors for active hydrocarbon pool species. As reaction progresses, the role of SMS gradually diminishes, and thereby methanol becomes the predominant C1 species, in methylation for efficient product formation, meanwhile in hydride-transfer causing catalyst deactivation. Additionally, it was demonstrated that the confined zeolite microenvironment modified by large organics affects methanol adsorption and SMS formation, also accounting for the absence of SMS during the later period of reaction. This work provides a comprehensive and systematic understanding of the dynamic roles of C1 species throughout the MTH process, beyond the role as reactants.

Key words: Methanol-to-hydrocarbons, C1 species, Methylation, Hydride-transfer, Confined zeolite microenvironments, SAPO-34

Yanan Zhang, Wenna Zhang, Chengwei Zhang, Linhai He, Shanfan Lin, Shutao Xu, Yingxu Wei, Zhongmin Liu. The role of C1 species in the methanol-to-hydrocarbons reaction: Beyond merely being reactants[J]. Chinese Journal of Catalysis, 2025, 71: 169-178.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60228-7

https://www.cjcatal.com/EN/Y2025/V71/I4/169

Figures/Tables 4

Scheme 1. Dynamic catalytic process of MTH reaction with C1 species participation.

Fig. 1. (a) Operando DRIFT spectra for continuous flow conversion of methanol over SAPO-34 at 623 K. (b) Methanol conversion and methane selectivity versus time on stream for methanol conversion over SAPO-34 at 623 K. (c) 13C CP/MAS NMR spectra of SAPO-34 with retained organics recorded after 12C/13C-methanol switch experiments (12C-methanol feeding for 2, 25, 50, 70, and 100 min followed by 13C-methanol feeding for 30 sec) over SAPO-34 at 623 K. The signals of adsorbed methanol, SMS, and adsorbed DME are labelled in orange, pink, and purple colors, respectively.

Fig. 2. (a) The schematic diagram of methylation and hydride-transfer reaction routes of SMS/MeOH with representative organic species. (b) The Gibbs free energy profile of methylation and hydride-transfer reactions with SMS (solid line) and MeOH (dash line) participation at 673 K.

Fig. 3. (a) The schematic diagram of methanol adsorption and SMS formation in an empty cavity or with large confined organic species. (b) Gibbs free energy profile for SMS formation from methanol dehydration without/with large confined organic species at 673 K. (c) Optimized structures for methanol adsorption and transition states of SMS formation with confined PMCP or pyrene species in zeolite microenvironment.

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