Direct Synthesis of <i>para</i>-Xylene from CO<sub>2</sub> Hydrogenation with a Record-High Space-Time Yield
The direct synthesis of <i>para</i>-xylene (<i>p</i>-X) from CO<sub>2</sub> hydrogenation with high space-time yield (STY) remains a significant challenge due to two primary limitations: the Anderson-Schulz-Flory distribution, which restricts the C<sub>8</sub> selectivity to ∼6.8 C%, and the thermodynamic equilibrium, which confines the <i>p</i>-X content among xylene isomers to 15-25%. Herein, we report a composite catalyst, K-FeMn/Hollow ZSM-5, that enables the efficient hydrogenation of CO<sub>2</sub> to <i>p</i>-X by integrating two synergistic catalytic functions. The K-FeMn component facilitates the reverse water-gas shift reaction and Fischer-Tropsch synthesis to olefin processes, generating light olefin intermediates. These intermediates are subsequently transformed to <i>p</i>-X within the hollow ZSM-5 zeolite through oligomerization, cyclization, and aromatization. The hollow ZSM-5 features a suitable pore size to facilitate <i>p</i>-X diffusion only, while its passivated external acid sites effectively suppress isomerization and alkylation of <i>p</i>-X outside the zeolite. As a result, the K-FeMn/Hollow ZSM-5 catalyst achieves a <i>p</i>-X STY of 41.7 g kg<sub>cat</sub><sup>-1</sup> h<sup>-1</sup> at a CO<sub>2</sub> conversion of 46.1%, surpassing all previously reported values. This work demonstrates a novel approach to overcome the local thermodynamic equilibria by specific catalyst design and the spatial separation of processes toward CO<sub>2</sub> hydrogenation into <i>p</i>-X.
Authors
- Wenjie Xiang
- Hao Huang (ORCID: https://orcid.org/0000-0001-5067-4490)
- Lijun Zhang (ORCID: https://orcid.org/0000-0002-1958-9404)
- Noritatsu Tsubaki (ORCID: https://orcid.org/0000-0001-6786-5058)
- Zhiliang Jin (ORCID: https://orcid.org/0000-0002-3793-6588)
- Xiuyun Jiang
- Jie Zeng (ORCID: https://orcid.org/0000-0002-8812-0298)
- Guangbo Liu (ORCID: https://orcid.org/0000-0002-9484-1892)
- Teng Li (ORCID: https://orcid.org/0000-0003-3148-643X)
- Hongliang Li (ORCID: https://orcid.org/0000-0003-0348-7910)
- Wei Xia (ORCID: https://orcid.org/0000-0001-8562-8064)
- Zhiwei Ye (ORCID: https://orcid.org/0000-0001-5510-8850)
- Luyao Wu
- Weizhe Gao (ORCID: https://orcid.org/0009-0001-1586-6224)
- Zhihao Liu
Institutions
- University of Science and Technology of China (CN)
- Shanxi University (CN)
- Chinese Academy of Sciences (CN)
- Hefei Institutes of Physical Science (CN)
- North Minzu University (CN)
- Physical Sciences (United States) (US)
- Shanxi University of Traditional Chinese Medicine (CN)
- Qingdao Institute of Bioenergy and Bioprocess Technology (CN)
- University of Toyama (JP)
- Anhui University of Technology (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-06-09
- DOI
- https://doi.org/10.1021/jacs.5c03380
- Citations
- 12
- Primary Topic
- Catalysts for Methane Reforming
- Type
- article
- Field-Weighted Citation Impact
- 4.67
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Fundo para o Desenvolvimento das Ciências e da Tecnologia
- University of Science and Technology of China
- Anhui Provincial Department of Education
- State Key Laboratory of Catalysis
- National Synchrotron Radiation Laboratory
- Yulin University
- Japan Society for the Promotion of Science
- Natural Science Foundation of Anhui Province
- Hefei Science Center, Chinese Academy of Sciences
- National Key Research and Development Program of China
- Fundamental Research Funds for the Central Universities
- Dalian National Laboratory for Clean Energy