Abstract
We develop higher loadings of isolated noble metal atoms and clusters on a mildly reducible metal oxide. We demonstrate the approach for Pt supported on TiO2 and confirmed it by XRD, AC-HAADF-STEM, CO-FTIR, XAS, and XPS. Density functional theory calculations rationalize the experimental stability and the IR shifts using mixtures of CH3I and CO. The redispersed catalysts are thermally stable in inert gas or H2 and afford enhanced selectivity and activity in hydrodeoxygenation reactions compared to metal nanoparticles by creating surface oxygen vacancies that promote C-O cleavage without side reactions. Higher metal loadings, e.g., 1%Pt/TiO2, on the oxide surface profoundly increase the activity of the bare oxide catalyst tenfold compared to ultra-low loadings typically used for single atom catalysis.
| Original language | English |
|---|---|
| Journal | Catalysis Science and Technology |
| DOIs | |
| State | Accepted/In press - 2022 |
| Externally published | Yes |
Funding
This work was supported and intellectually defined by the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the US Dept. of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-SC0001004. The TEM work was performed in part at the Singh Center for Nanotechnology at the University of Pennsylvania, a member of the National Nanotechnology Coordinated Infrastructure (NNCI) network, which is supported by the National Science Foundation (Grant NNCI-1542153). A. F. and E. S. gratefully acknowledge use of facilities and instrumentation supported by NSF through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) (DMR-1720530) and the support from the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012573. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DESC0012704. QAS beamline operations were supported in part by the Synchrotron Catalysis Consortium (U.S. DOE, Office of Basic Energy Sciences, Grant No. DE-SC0012335). This work was supported and intellectually defined by the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the US Dept. of Energy, Office of Science, Office of Basic Energy Sciences under award number DE-SC0001004. The TEM work was performed in part at the Singh Center for Nanotechnology at the University of Pennsylvania, a member of the National Nanotechnology Coordinated Infrastructure (NNCI) network, which is supported by the National Science Foundation (Grant NNCI-1542153). A. F. and E. S. gratefully acknowledge use of facilities and instrumentation supported by NSF through the University of Pennsylvania Materials Research Science and Engineering Center (MRSEC) (DMR-1720530) and the support from the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award #DE-SC0012573. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. QAS beamline operations were supported in part by the Synchrotron Catalysis Consortium (U.S. DOE, Office of Basic Energy Sciences, Grant No. DE-SC0012335).
| Funders | Funder number |
|---|---|
| Catalysis Center for Energy Innovation | |
| Integrated Mesoscale Architectures for Sustainable Catalysis | |
| Synchrotron Catalysis Consortium | |
| University of Pennsylvania Materials Research Science and Engineering Center | |
| National Science Foundation | NNCI-1542153 |
| National Science Foundation | |
| U.S. Department of Energy | DE-SC0012335 |
| U.S. Department of Energy | |
| Office of Science | |
| Basic Energy Sciences | -SC0012573, DE-SC0001004 |
| Basic Energy Sciences | |
| Brookhaven National Laboratory | DE-SC0012704 |
| Brookhaven National Laboratory | |
| Materials Research Science and Engineering Center, Harvard University | DMR-1720530 |
| Materials Research Science and Engineering Center, Harvard University |