Abstract
Single-atom catalysts are often reported to have catalytic properties that surpass those of nanoparticles, while a direct comparison of sites common and different for both is lacking. Here we show that single atoms of Pt-group metals embedded into the surface of Fe3O4 have a greatly enhanced interaction strength with CO2 compared with the Fe3O4 surface. The strong CO2 adsorption on single Rh atoms and corresponding low activation energies lead to 2 orders of magnitude higher conversion rates of CO2 compared to Rh nanoparticles. This high activity of single atoms stems from the partially oxidic state imposed by their coordination to the support. Fe3O4-supported Rh nanoparticles follow the behavior of single atoms for CO2 interaction and reduction, which is attributed to the dominating role of partially oxidic sites at the Fe3O4-Rh interface. Thus, we show a likely common catalytic chemistry for two kinds of materials thought to be different, and we show that single atoms of Pt-group metals on Fe3O4 are especially successful materials for catalyzed reactions that depend primarily upon sites with the metal-O-Fe environment.
Original language | English |
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Pages (from-to) | 5540-5549 |
Number of pages | 10 |
Journal | Journal of the American Chemical Society |
Volume | 143 |
Issue number | 14 |
DOIs | |
State | Published - Apr 14 2021 |
Externally published | Yes |
Funding
This work is supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Transdisciplinary Approaches to Realize Novel Catalytic Pathways to Energy Carriers, FWP 47319). Our research used resources of the Advanced Photon Source, a DOE-Office of Science user facility operated by Argonne National Laboratory, and was supported by DOE under Contract No. DE-AC02-06CH11357 and the Canadian Light Source and its funding partners. Portions of this work were performed at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). Computational resources were provided via user grants at EMSL, at PNNL’s Research Computing facility, and at the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. PNNL is operated by Battelle for DOE under Contract DE-AC05-76RL01830.