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Bridging adsorption analytics and catalytic kinetics for metal-exchanged zeolites


Metal-exchanged zeolites have been widely used in industrial catalysis and separation, but fundamental understanding of their structure–property relationships has remained challenging, largely due to the lack of quantitative information concerning the atomic structures and reaction-relevant adsorption properties of the embedded metal active sites. Here, we report on using low-temperature reactive adsorption of NO to titrate copper-exchanged ZSM5 (Cu-ZSM5). Quantitative descriptors of the atomic structures and adsorption properties of Cu-ZSM5 are established by combining atomistic simulation, density functional theory c, operando molecular spectroscopy, chemisorption and titration measurements. These descriptors are then applied to interpret the catalytic performance of Cu-ZSM5 for NO decomposition. Linear correlations are established to bridge low-temperature adsorption analytics and high-temperature reaction kinetics, which are demonstrated to be generally applicable for understanding the structure–property relationships of metal-exchanged zeolites and foregrounded the development of advanced catalytic materials.

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Fig. 1: Graphical illustration and characterization of Cu sites in Cu-ZSM5 zeolites.
Fig. 2: DFT-calculated Cu dimer fractions in Cu-ZSM5.
Fig. 3: DFT-calculated pathways for the reactive adsorption of NO on Cu-ZSM5.
Fig. 4: Characterization and quantification of Cu dimers in Cu-ZSM5 zeolites.
Fig. 5: NO isothermal adsorption profiles.
Fig. 6: Catalytic performance and kinetics of NO decomposition.
Fig. 7: Catalytic study of MTM using Cu-ZSM5 from the literature and this work.

Data availability

The data that support the findings of this study are available on the Figshare platform at (ref. 55). Source data are provided with this paper.


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This work was supported by the Department of Energy, Advanced Research Projects Agency-Energy (ARPA-E). P.X. and C.W. also acknowledge support from the Petroleum Research Fund, American Chemical Society. A.K. acknowledges the use of computing resources provided by the National Energy Research Scientific Computing Center (NERSC; a US Department of Energy Office of Science User Facility operated under contract number DE-AC02-05CH11231) and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI-1548562.

Author information




C.W. and P.X. conceived of the idea and experimental design. P.X. and T.P. carried out the experiments. P.X. and C.W. wrote the paper. M.D. and G.A. contributed to analysis of the NOad isotherms using Ono–Kondo coordinates. A.K. and J.G. performed DFT calculations for this work. All of the authors discussed the results and contributed to manuscript preparation.

Corresponding authors

Correspondence to Ambarish Kulkarni or Chao Wang.

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The authors declare no competing interests.

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Peer review information Nature Catalysis thanks Dennis Palagin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Discussion, Tables 1–15, Figs. 1–38 and References.

Supplementary Data 1

Electronic structure calculations.

Source data

Source Data Fig. 1

Characterization of Cu sites in ZSM5.

Source Data Fig. 2

DFT-calculated fraction of Cu dimer in different ZSM5 frameworks.

Source Data Fig. 3

DFT-calculated pathways of reaction and adsorption of NO on Cu-ZSM5.

Source Data Fig. 4

Characterization and quantification of Cu dimers in Cu-ZSM5 zeolites.

Source Data Fig. 5

NO isothermal adsorption and corresponding analytics.

Source Data Fig. 6

Catalytic performance and kinetics of NO decomposition.

Source Data Fig. 7

Catalytic study of MTM using Cu-ZSM5 from the literature and this work.

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Xie, P., Pu, T., Aranovich, G. et al. Bridging adsorption analytics and catalytic kinetics for metal-exchanged zeolites. Nat Catal 4, 144–156 (2021).

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