Abstract
Ni-based catalysts are highly reactive for dry reforming of methane (DRM) but they are prone to rapid deactivation due to sintering and/or coking. In this study, we present a straightforward approach for anchoring dispersed Ni sites with strengthened metal-support interactions, which leads to Ni active sites embedded in dealuminated Beta zeolite with superior stability and rates for DRM. The process involves solid-state grinding of dealuminated Beta zeolites and nickel nitrate, followed by calcination under finely controlled gas flow conditions. By combining in situ X-ray absorption spectroscopy and ab initio simulations, it is elucidated that the efficient removal of byproducts during catalyst synthesis is conducted to strengthen Ni–Si interactions that suppress coking and sintering after 100 h of time-on-stream. Transient isotopic kinetic experiments shed light on the differences in intrinsic turnover frequency of Ni species and explain performance trends. This work constructs a fundamental understanding regarding the implication of facile synthesis protocols on metal-support interaction in zeolite-supported Ni sites, and it lays the needed foundations on how these interactions can be tuned for outstanding DRM performance.
| Original language | English |
|---|---|
| Article number | 8566 |
| Journal | Nature Communications |
| Volume | 15 |
| Issue number | 1 |
| DOIs | |
| State | Published - Dec 2024 |
Funding
This research was sponsored by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. Some of the work including synthesis and XRD was conducted as part of a user project at the Center for Nanophase Materials Science (CNMS), which is a U.S. DOE, Office of Science User Facility located at Oak Ridge National Laboratory. This research used resources of the Center for Functional Nanomaterials and National Synchrotron Light Source II, which are U.S. DOE, Office of Science User Facilities located at BNL under Contract No. DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium (U.S. DOE, Office of Basic Energy Sciences, Grant DE-SC0012335). This research used resources of the Stanford Synchrotron Radiation Lightsource (SSRL) of SLAC National Accelerator Laboratory supported by Basic Energy Sciences under contract No.DE-AC02-76SF00515. This research used resources of the National Energy Research Scientific Computing Center, a U.S. DOE, Office of Science User Facility supported by the Office of Science of the U.S. DOE under contract no. DE-AC02-05CH11231. Notice: this manuscript has been authored by UT-Battelle, LLC under contract no. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).