Abstract
Propane dehydrogenation (PDH) is a commercial propylene production technology, but high reaction temperatures result in cracking and coking. Isolating active metal components into single atoms can maximize atomic efficiency, and the resulting single-atom catalysts (SACs) could inhibit structure-sensitive side reactions with unprecedented selectivity. Herein, we report a single-site [PtZn4] catalyst by assembling atomically ordered PtZn intermetallic alloys, which enables more than 95% selectivity of propylene over a broad temperature range of 520°C to 620°C. No obvious deactivation is observed within the 160-h industrial PDH test. We reveal that the surface [PtZn4] ensembles in PtZn IMAs serve as the stable active site structures, wherein the geometry-isolated and electron-rich Pt in [PtZn4] ensembles readily promotes desorption of surface-bounded propylene and improves the stability by prohibiting coke side reactions.
| Original language | English |
|---|---|
| Pages (from-to) | 387-405 |
| Number of pages | 19 |
| Journal | Chem |
| Volume | 7 |
| Issue number | 2 |
| DOIs | |
| State | Published - Feb 11 2021 |
| Externally published | Yes |
Funding
This work is supported by the National Science Foundation of China (21525626 and U1862207) and the Program of Introducing Talents of Discipline to Universities (BP0618007). S.C.P. and J.T.M. were supported by the US National Science Foundation under cooperative agreement no. EEC-1647722. This research used resources from the Advanced Photon Source, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. MRCAT (APS/10-BM) operations are supported by the Department of Energy and the MRCAT member institutions. A.J.K. gratefully acknowledges support from the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, Catalysis Science Program under contract DE-AC-02-06CH11357. J.G. conceived and coordinated the research. S.C. contributed to catalyst synthesis and catalytic experiments. S.C. and G.S. performed DRIFTS experiments, TPSR, and long-term stability experiments. J.L. collected and analyzed the AC-HAADF-STEM data. S.C.P. A.J.K. and J.T.M. performed the EXAFS measurements and analyzed the data. X.C. and Z.-J.Z. screened PtZn IMA catalyst by DFT. S.C. Z.-J.Z. X.C. R.M. and J.G. wrote the manuscript. All authors participated in discussion of the research. The authors declare no competing interests. This work is supported by the National Science Foundation of China ( 21525626 and U1862207 ) and the Program of Introducing Talents of Discipline to Universities ( BP0618007 ). S.C.P. and J.T.M. were supported by the US National Science Foundation under cooperative agreement no. EEC-1647722 . This research used resources from the Advanced Photon Source, a US Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357 . MRCAT (APS/10-BM) operations are supported by the Department of Energy and the MRCAT member institutions. A.J.K. gratefully acknowledges support from the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, Catalysis Science Program under contract DE-AC-02-06CH11357.
Keywords
- Pt catalyst
- SDG12: Responsible consumption and production
- intermetallic alloy
- propane dehydrogenation
- single-site catalysts