Upgrading CO2 to sustainable aromatics via perovskite-mediated tandem catalysis

Guo Tian; Zhengwen Li; Chenxi Zhang; Xinyan Liu; Xiaoyu Fan; Kui Shen; Haibin Meng; Ning Wang; Hao Xiong; Mingyu Zhao; Xiaoyu Liang; Liqiang Luo; Lan Zhang; Binhang Yan; Xiao Chen; Hong-Jie Peng; Fei Wei

doi:10.1038/s41467-024-47270-z

Upgrading CO₂ to sustainable aromatics via perovskite-mediated tandem catalysis

Nat Commun. 2024 Apr 8;15(1):3037. doi: 10.1038/s41467-024-47270-z.

Authors

Guo Tian^#¹, Zhengwen Li^#¹, Chenxi Zhang^{2

3

4}, Xinyan Liu⁵, Xiaoyu Fan¹, Kui Shen⁶, Haibin Meng⁷, Ning Wang⁸, Hao Xiong¹, Mingyu Zhao¹, Xiaoyu Liang¹, Liqiang Luo¹, Lan Zhang⁸, Binhang Yan¹, Xiao Chen^{9

10}, Hong-Jie Peng¹¹, Fei Wei^{12

13}

Affiliations

¹ Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, 100084, Beijing, China.
² Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, 100084, Beijing, China. cxzhang@tsinghua.edu.cn.
³ Ordos Laboratory, Ordos, Inner Mongolia, 017010, China. cxzhang@tsinghua.edu.cn.
⁴ Institute for Carbon Neutrality, Tsinghua University, 100084, Beijing, China. cxzhang@tsinghua.edu.cn.
⁵ Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, 611731, Sichuan, China.
⁶ Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
⁷ College of Chemistry, Taiyuan University of Technology, Taiyuan, 030024, China.
⁸ Faculty of Environment and Life, Beijing University of Technology, 100124, Beijing, China.
⁹ Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, 100084, Beijing, China. chenx123@tsinghua.edu.cn.
¹⁰ Ordos Laboratory, Ordos, Inner Mongolia, 017010, China. chenx123@tsinghua.edu.cn.
¹¹ Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, 611731, Sichuan, China. hjpeng@uestc.edu.cn.
¹² Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, 100084, Beijing, China. wf-dce@tsinghua.edu.cn.
¹³ Ordos Laboratory, Ordos, Inner Mongolia, 017010, China. wf-dce@tsinghua.edu.cn.

^# Contributed equally.

Abstract

The directional transformation of carbon dioxide (CO₂) with renewable hydrogen into specific carbon-heavy products (C₆₊) of high value presents a sustainable route for net-zero chemical manufacture. However, it is still challenging to simultaneously achieve high activity and selectivity due to the unbalanced CO₂ hydrogenation and C-C coupling rates on complementary active sites in a bifunctional catalyst, thus causing unexpected secondary reaction. Here we report LaFeO₃ perovskite-mediated directional tandem conversion of CO₂ towards heavy aromatics with high CO₂ conversion (> 60%), exceptional aromatics selectivity among hydrocarbons (> 85%), and no obvious deactivation for 1000 hours. This is enabled by disentangling the CO₂ hydrogenation domain from the C-C coupling domain in the tandem system for Iron-based catalyst. Unlike other active Fe oxides showing wide hydrocarbon product distribution due to carbide formation, LaFeO₃ by design is endowed with superior resistance to carburization, therefore inhibiting uncontrolled C-C coupling on oxide and isolating aromatics formation in the zeolite. In-situ spectroscopic evidence and theoretical calculations reveal an oxygenate-rich surface chemistry of LaFeO₃, that easily escape from the oxide surface for further precise C-C coupling inside zeolites, thus steering CO₂-HCOOH/H₂CO-Aromatics reaction pathway to enable a high yield of aromatics.