Atomically intimate assembly of dual metal-oxide interfaces for tandem conversion of syngas to ethanol

Shang Li; Li Feng; Hengwei Wang; Yue Lin; Zhihu Sun; Lulu Xu; Yuxing Xu; Xinyu Liu; Wei-Xue Li; Shiqiang Wei; Jin-Xun Liu; Junling Lu

doi:10.1038/s41565-024-01824-w

Atomically intimate assembly of dual metal-oxide interfaces for tandem conversion of syngas to ethanol

Nat Nanotechnol. 2024 Nov 25. doi: 10.1038/s41565-024-01824-w. Online ahead of print.

Authors

Shang Li^#¹, Li Feng^#¹, Hengwei Wang², Yue Lin³, Zhihu Sun⁴, Lulu Xu¹, Yuxing Xu¹, Xinyu Liu⁵, Wei-Xue Li^{1

6}, Shiqiang Wei⁴, Jin-Xun Liu^{7

8}, Junling Lu^{9

10}

Affiliations

¹ Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China.
² Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China. whw@ustc.edu.cn.
³ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China.
⁴ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, China.
⁵ Suzhou Laboratory, Suzhou, China.
⁶ Hefei National Laboratory, University of Science and Technology of China, Hefei, China.
⁷ Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China. jxliu86@ustc.edu.cn.
⁸ Hefei National Laboratory, University of Science and Technology of China, Hefei, China. jxliu86@ustc.edu.cn.
⁹ Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, China. junling@ustc.edu.cn.
¹⁰ Suzhou Laboratory, Suzhou, China. junling@ustc.edu.cn.

^# Contributed equally.

PMID: 39587351
DOI: 10.1038/s41565-024-01824-w

Abstract

Selective conversion of syngas to value-added higher alcohols (containing two or more carbon atoms), particularly to a specific alcohol, is of great interest but remains challenging. Here we show that atomically intimate assembly of FeO_x-Rh-ZrO₂ dual interfaces by selectively architecting highly dispersed FeO_x on ultrafine raft-like Rh clusters supported on tetragonal zirconia enables highly efficient tandem conversion of syngas to ethanol. The ethanol selectivity in oxygenates reached ~90% at CO conversion up to 51%, along with a markedly high space-time yield of ethanol of 668.2 mg g_cat^-1 h^-1. In situ spectroscopic characterization and theoretical calculations reveal that Rh-ZrO₂ interface promotes dissociative CO activation into CH_x through a formate pathway, while the adjacent Rh-FeO_x interface accelerates subsequent C-C coupling via nondissociative CO insertion. Consequently, these dual interfaces in atomic-scale proximity with complementary functionalities synergistically boost the exclusive formation of ethanol with exceptional productivity in a tandem manner.

Abstract

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