Tuning metal-support interactions in nickel-zeolite catalysts leads to enhanced stability during dry reforming of methane

Junyan Zhang; Yuanyuan Li; Haohong Song; Lihua Zhang; Yiqing Wu; Yang He; Lu Ma; Jiyun Hong; Akhil Tayal; Nebojsa Marinkovic; De-En Jiang; Zhenglong Li; Zili Wu; Felipe Polo-Garzon

doi:10.1038/s41467-024-50729-8

Tuning metal-support interactions in nickel-zeolite catalysts leads to enhanced stability during dry reforming of methane

Nat Commun. 2024 Oct 3;15(1):8566. doi: 10.1038/s41467-024-50729-8.

Authors

Junyan Zhang¹, Yuanyuan Li¹, Haohong Song², Lihua Zhang³, Yiqing Wu¹, Yang He¹, Lu Ma⁴, Jiyun Hong⁵, Akhil Tayal⁴, Nebojsa Marinkovic⁶, De-En Jiang^{2

7}, Zhenglong Li^{8

9}, Zili Wu^{1

10}, Felipe Polo-Garzon¹¹

Affiliations

¹ Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA.
² Interdisciplinary Materials Science, Vanderbilt University, Nashville, TN, USA.
³ Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York, USA.
⁴ National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York, USA.
⁵ Stanford Synchrotron Radiati on Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
⁶ Synchrotron Catalysis Consortium and Department of Chemical Engineering, Columbia University, New York, NY, USA.
⁷ Chemical and Biomolecular Engineering Department, Vanderbilt University, Nashville, TN, USA.
⁸ National Key Laboratory of Biobased Transportation Fuel Technology, College of Biosystems Engineering and Food Science, Zhejiang University, Hangzhou, China.
⁹ Institute of Zhejiang University, Quzhou, China.
¹⁰ Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, USA.
¹¹ Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA. [email protected].

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.