Selective conversion of CO2 to isobutane-enriched C4 alkanes over InZrOx-Beta composite catalyst

Han Wang; Sheng Fan; Shujia Guo; Sen Wang; Zhangfeng Qin; Mei Dong; Huaqing Zhu; Weibin Fan; Jianguo Wang

doi:10.1038/s41467-023-38336-5

Selective conversion of CO₂ to isobutane-enriched C₄ alkanes over InZrO_x-Beta composite catalyst

Nat Commun. 2023 May 6;14(1):2627. doi: 10.1038/s41467-023-38336-5.

Authors

Han Wang^#^{1

2}, Sheng Fan^#^{1

2}, Shujia Guo^{1

2}, Sen Wang³, Zhangfeng Qin⁴, Mei Dong¹, Huaqing Zhu¹, Weibin Fan¹, Jianguo Wang^{5

6}

Affiliations

¹ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi, 030001, P. R. China.
² University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
³ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi, 030001, P. R. China. wangsen@sxicc.ac.cn.
⁴ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi, 030001, P. R. China. qzhf@sxicc.ac.cn.
⁵ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi, 030001, P. R. China. iccjgw@sxicc.ac.cn.
⁶ University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. iccjgw@sxicc.ac.cn.

^# Contributed equally.

Abstract

Direct conversion of CO₂ to a single specific hydrocarbon with high selectivity is extremely attractive but very challenging. Herein, by employing an InZrO_x-Beta composite catalyst in the CO₂ hydrogenation, a high selectivity of 53.4% to butane is achieved in hydrocarbons (CO free) under 315 °C and 3.0 MPa, at a CO₂ conversion of 20.4%. Various characterizations and DFT calculation reveal that the generation of methanol-related intermediates by CO₂ hydrogenation is closely related to the surface oxygen vacancies of InZrO_x, which can be tuned through modulating the preparation methods. In contrast, the three-dimensional 12-ring channels of H-Beta conduces to forming higher methylbenzenes and methylnaphthalenes containing isopropyl side-chain, which favors the transformation of methanol-related intermediates to butane through alkyl side-chain elimination and subsequent methylation and hydrogenation. Moreover, the catalytic stability of InZrO_x-Beta in the CO₂ hydrogenation is considerably improved by a surface silica protection strategy which can effectively inhibit the indium migration.

Abstract

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