Selective hydrogenation of CO2 into dimethyl ether over hydrophobic and gallium-modified copper catalysts

doi:10.1016/S1872-2067(23)64535-8

Abstract

Abstract:

Supported Cu catalysts are widely studied for the hydrogenation of CO₂ to dimethyl ether (DME). However, they suffer from insufficient durability and DME selectivity. Herein, we overcome these issues by modulating the gallium species and hydrophobic methyl groups to obtain a silica-supported copper catalyst, achieving a Cu/Ga-SiO₂-Me catalyst with significantly improved DME selectivity and catalyst durability. Characterizations of the catalysts showed that the gallium species electronically modulated the Cu nanoparticles, resulting in abundant Cu^δ⁺ species in the catalyst, which minimized the reverse water-gas shift reaction and thus reduced CO selectivity. In addition, the methyl groups contributed to the rapid removal of water from the catalyst surface, which hindered Cu sintering and accelerated catalysis. Consequently, the Cu/Ga-SiO₂-20Me exhibited a CO₂ conversion of 9.7%, selectivities of DME and methanol of 59.3% and 28.4%, and CO selectivity of only 11.3%. The strategy used in this study may provide rational guidance for improving current industrial catalysts.

Key words: Hydrogenation of CO₂, Copper catalyst, Hydrophobic modulation, Gallium promoter, Catalyst stability

Hangjie Li, Yuehua Xiao, Jiale Xiao, Kai Fan, Bingkuan Li, Xiaolong Li, Liang Wang, Feng-Shou Xiao. Selective hydrogenation of CO₂ into dimethyl ether over hydrophobic and gallium-modified copper catalysts[J]. Chinese Journal of Catalysis, 2023, 54: 178-187.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64535-8

https://www.cjcatal.com/EN/Y2023/V54/I11/178

Figures/Tables 7

Fig. 1. XRD patterns (A), Nitrogen sorption isotherms (B), and H2-TPR profiles (C). Note: In this manuscript, the Cu/Ga-SiO2 and Cu/Ga-SiO2-20Me catalysts imply the samples with a Ga/Cu molar ratio of 1.0 unless something else is mentioned.

Fig. 2. SEM images of Cu/SiO2 (a) and Cu/Ga-SiO2-20Me (b). TEM images of Cu/SiO2 (c) and Cu/Ga-SiO2-20Me (d).

Fig. 3. In situ XPS-AES spectra of Cu/SiO2 (A), Cu/Ga-SiO2 (B), and Cu/Ga-SiO2-20Me (C). In situ CO adsorption DRIFTS of Cu/SiO2 (D), Cu/Ga-SiO2 (E), and Cu/Ga-SiO2-20Me (F).

Fig. 4. (A) Data showing the performances of different catalysts in the hydrogenation of CO2 to DME. (B) Data summarizing the DME selectivity as a function of CO2 conversion in the previous tests. (C) Data showing the catalytic performances of Cu/Ga-SiO2-20Me in the hydrogenation of CO2 to DME under different reaction temperatures. Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72. (D) Durability evaluation of the Cu/Ga-SiO2-20Me catalyst in the hydrogenation of CO2. Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72, and TOS at 100 h.

Fig. 5. In situ DRIFTS of Cu/SiO2 (A), Cu/Ga-SiO2 (B), and Cu/Ga-SiO2-20Me (C) in a flow of Ar/CO2/H2 (4/24/72, vol%) at 240 °C. Water adsorption isotherms (D) and water-TPD profiles (E) of different catalysts. (F) Water droplet contact angles of different catalysts.

Fig. 6. (A) MS profiles showing the CH4 signal by evaluating the Cu/SiO2-20Me and Cu/Ga-SiO2-20Me catalysts in contact with 10 vol% H2/Ar at 300 °C. (B) Water-desorption profiles of the spent Cu/SiO2 and Cu/Ga-SiO2-20Me catalysts. (C) Water droplet contact angle of spent Cu/Ga-SiO2-20Me catalyst. (D) TG-DSC profiles of the spent Cu/Ga-SiO2-20Me catalyst.

Fig. 7. Data showing the catalytic performances of Cu/Gax-SiO2-yMe catalysts with various contents of gallium (A) and methyl groups (B). Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72. (C) Catalytic performance of the physically mixed Cu/SiO2-20Me and Ga/SiO2-20Me catalysts with various mixing manners and Cu/Ga-SiO2-20Me catalyst in the hydrogenation of CO2 to DME. Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72. (D) Scheme showing the diffusion of intermediates over the physically mixed Cu/SiO2-20Me with Ga/SiO2-20Me catalyst and bifunctional Cu/Ga-SiO2-20Me catalyst in the hydrogenation of CO2 to DME.

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Selective hydrogenation of CO₂ into dimethyl ether over hydrophobic and gallium-modified copper catalysts

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