Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density
Abstract
The support–metal interaction is an important element of heterogeneous catalyst design and is particularly critical for the rapidly growing field of single-atom catalysts (SACs). In this work, we investigate the impact of varying the defect density of the titania support on metal–organic Pt SACs for hydrosilylation reactions. Pt SACs are decorated on the powder titania support, employing a metal–ligand interaction with a dipyridyl-tetrazine ligand (DPTZ). The single-atom nature of Pt is verified by X-ray absorption spectroscopy (XAS) on both pristine and defective titania surfaces. These Pt species have a +2 oxidation state and are stabilized by bonding with DPTZ, surface oxygen, and residual chloride from the metal precursor. The catalytic activity is evaluated for the alkene hydrosilylation reaction and it is discovered that the activity of Pt-ligand is positively correlated with the defect density of the titania support. The turn-over number (TON) is calculated to be 12 530 for Pt SACs on a defective surface, which is significantly higher than Pt SACs on a pristine titania surface (830) for the same reaction period (10 min) under the same conditions (70 °C). We ascribe the high activity of Pt SACs on defective titania surfaces to two aspects: the coordination of Ptmore »
- Authors:
-
[1];
[1];
[3];
[3];
[1]
- Indiana Univ., Bloomington, IN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1616793
- Alternate Identifier(s):
- OSTI ID: 1616631
- Grant/Contract Number:
- AC05-00OR22725; SC0016367; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Science and Technology
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 10; Journal ID: ISSN 2044-4753
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhou, Xuemei, Chen, Linxiao, Sterbinsky, George E., Mukherjee, Debangshu, Unocic, Raymond R., and Tait, Steven L. Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density. United States: N. p., 2020.
Web. doi:10.1039/C9CY02594D.
Zhou, Xuemei, Chen, Linxiao, Sterbinsky, George E., Mukherjee, Debangshu, Unocic, Raymond R., & Tait, Steven L. Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density. United States. https://doi.org/10.1039/C9CY02594D
Zhou, Xuemei, Chen, Linxiao, Sterbinsky, George E., Mukherjee, Debangshu, Unocic, Raymond R., and Tait, Steven L. Mon .
"Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density". United States. https://doi.org/10.1039/C9CY02594D. https://www.osti.gov/servlets/purl/1616793.
@article{osti_1616793,
title = {Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density},
author = {Zhou, Xuemei and Chen, Linxiao and Sterbinsky, George E. and Mukherjee, Debangshu and Unocic, Raymond R. and Tait, Steven L.},
abstractNote = {The support–metal interaction is an important element of heterogeneous catalyst design and is particularly critical for the rapidly growing field of single-atom catalysts (SACs). In this work, we investigate the impact of varying the defect density of the titania support on metal–organic Pt SACs for hydrosilylation reactions. Pt SACs are decorated on the powder titania support, employing a metal–ligand interaction with a dipyridyl-tetrazine ligand (DPTZ). The single-atom nature of Pt is verified by X-ray absorption spectroscopy (XAS) on both pristine and defective titania surfaces. These Pt species have a +2 oxidation state and are stabilized by bonding with DPTZ, surface oxygen, and residual chloride from the metal precursor. The catalytic activity is evaluated for the alkene hydrosilylation reaction and it is discovered that the activity of Pt-ligand is positively correlated with the defect density of the titania support. The turn-over number (TON) is calculated to be 12 530 for Pt SACs on a defective surface, which is significantly higher than Pt SACs on a pristine titania surface (830) for the same reaction period (10 min) under the same conditions (70 °C). We ascribe the high activity of Pt SACs on defective titania surfaces to two aspects: the coordination of Pt with more chloride than on pristine titania surfaces, which shortens the induction period of the reaction, and the preferential dispersion of Pt–DPTZ units on defective regions of titania surfaces, allowing facile contact between Pt sites and reactants. The supported Pt–DPTZ SACs show high stability through multiple cycles of batch reactions. This work demonstrates an efficient approach to improve the activity and stability of SACs by optimizing the metal–support interaction, which can also be applied to other oxide surfaces to further develop next-generation heterogeneous single-atom catalysts.},
doi = {10.1039/C9CY02594D},
journal = {Catalysis Science and Technology},
number = 10,
volume = 10,
place = {United States},
year = {Mon Apr 27 00:00:00 EDT 2020},
month = {Mon Apr 27 00:00:00 EDT 2020}
}
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