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Small-pore zeolite supported Cu/Fe as selective catalytic reduction catalysts, and Pd/Pt as passive NOx adsorbers and low-temperature methane combustion catalysts

EMSL Project ID


To help meet DOE goals of enabling more fuel-efficient vehicle engine technologies, for the past ~15 years we have been carrying out research programs funded by DOE/Office of Energy Efficiency and Renewable Energy (EERE)/Vehicle Technologies Office (VTO), involving programs that include direct collaboration with industry partners in the form of CRADA programs, and more fundamental programs directly funded by VTO. Currently, the industry-partner CRADA programs with Cummins, Inc. and FCA aim at (1) understanding mechanisms of low-temperature constrains of selective catalytic reduction (SCR) of NOx catalyzed by small-pore zeolite supported Cu/Fe catalysts, and improving long-term stability of industrial SCR catalysts (primarily Cu/SSZ-13); and (2) lowering NOx emissions during vehicle cold start by invoking novel passive NOx adsorber (PNA) materials. The program directly funded by VTO to PNNL aims at developing a practically useful fundamental understanding of low-temperature methane combustion catalysts as part of the natural gas engine exhaust abatement strategy. For these programs to be successful, we rely on the use of a wide array of state-of-the-art catalyst characterization facilities in EMSL. Defect deficient beta zeolite materials will be synthesized as supports for Fe SCR catalysts. Small-pore zeolites SSZ-13, SSZ-16, SSZ-17 and SSZ-39 supported Pd, Pt and alloys containing one of the two metals will be developed as PNA materials and catalysts for low-temperature methane combustion. This project will also leverage previous work at PNNL engaged in developing active and stable noble metal based materials/catalysts for use in biomass upgrading and engine exhaust cleanup. For example, novel small pore zeolite supported Cu catalysts will be developed as alternatives to the current industrial Cu/SSZ-13 SCR catalyst with potentially improved performance and stability. This proposal contains the following essential components: (1) Large-pore beta zeolites, small-pore SSZ-family zeolites and zeolite supported metal materials synthesis; (2) material/catalyst performance evaluation using our home-built plug-flow reaction systems with MKS gas-phase FTIR analyzers; (3) in situ/operando spectroscopic and microscopic characterizations, e.g., solid-state nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), X-ray photoelectron (XPS), Mössbauer and FTIR spectroscopies, scanning transmission electron microscopy (STEM), atom probe tomography (APT) with EMSL support; (4) density functional theory (DFT) calculations in support of the experimental work performed with a mixed Gaussian and plane wave basis sets implemented in the CP2K code. Expected outcomes include 3-5 high impact journal publications, 3-5 national and international conference presentations and annual reports to DOE/EERE/VTO acknowledging the essential support from EMSL.

Project Details

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Principal Investigator

Feng Gao
Pacific Northwest National Laboratory

Team Members

Qiu Jin
Beijing University of Chemical Technology

Yuntao Zhao
Tianjin University

Yanran Cui
University of Washington

Konstantin Khivantsev
Pacific Northwest National Laboratory

Yilin Wang
Pacific Northwest National Laboratory

Miroslaw Derewinski
Pacific Northwest National Laboratory

Donghai Mei
Tiangong University

Ja Hun Kwak
Ulsan National Institute of Science and Technology

Charles Peden
Pacific Northwest National Laboratory

Janos Szanyi
Pacific Northwest National Laboratory

Yong Wang
Washington State University

Related Publications

Khivantsev K., N.R. Jaegers, L. Kovarik, J.c. Hanson, F. Tao, Y. Tang, and X. Zhang, et al. 2018. "Achieving Atomic Dispersion of Highly Loaded Transition Metals in Small-pore Zeolite SSZ-13: High-capacity and High-efficiency Low Temperature CO and Passive NOx Adsorbers." Angewandte Chemie International Edition 57, no. 51:16672-16677. PNNL-SA-136340. doi:10.1002/anie.201809343
Khivantsev K., N.R. Jaegers, L. Kovarik, S. Prodinger, M.A. Derewinski, Y. Wang, and F. Gao, et al. 2018. "Palladium/Beta Zeolite Passive NOx Adsorbers (PNA): Clarification of PNA Chemistry and the Effects of CO and Zeolite Crystallite Size on PNA Performance." Applied Catalysis. A, General 569. PNNL-SA-137831. doi:10.1016/j.apcata.2018.10.021
Khivantsev K., N.R. Jaegers, L. Kovarik, Y. Wang, F. Gao, and J. Szanyi. 2019. "Palladium/ Zeolite Low Temperature Passive NOx Adsorbers (PNA): Structure-adsorption property relationships for hydrothermally aged PNA materials." Emission Control Science and Technology. PNNL-SA-141069. doi:10.1007/s40825-019-00139-w
Peden C.H. 2019. "Cu/Chabazite Catalysts for ‘Lean-Burn’ Vehicle Emission Control." Journal of Catalysis 373. PNNL-SA-140731. doi:10.1016/j.jcat.2019.04.046
Peng B., K.G. Rappe, Y. Cui, F. Gao, J. Szanyi, M.J. Olszta, and E.D. Walter, et al. 2020. "Enhancement of high-temperature selectivity on Cu-SSZ-13 towards NH3-SCR reaction from highly dispersed ZrO2." Applied Catalysis B: Environmental 263. PNNL-SA-146190. doi:10.1016/j.apcatb.2019.118359
Szanyi J., D. Mei, T. Varga, C. Peden, S.H. Oh, and C.H. Kim. 2018. "Where does the sulphur go? Deactivation of a low temperature CO oxidation catalyst by sulphur poisoning." Catalysis Letters 148, no. 5:1445-1450. PNNL-SA-130691. doi:10.1007/s10562-018-2343-2
Zhang Y., Y. Peng, J. Li, K.J. Groden, J. Mcewen, E.D. Walter, and Y. Chen, et al. 2020. "Probing Active-Site Relocation in Cu/SSZ-13 SCR Catalysts during Hydrothermal Aging by in situ EPR Spectroscopy, Kinetic Studies, and DFT Calculations." ACS Catalysis 10, no. 16:9410-9419. PNNL-SA-152624. doi:10.1021/acscatal.0c01590
Zhang Y., Y. Peng, K. Li, S. Liu, J. Chen, J. Li, and F. Gao, et al. 2019. "Using Transient FTIR Spectroscopy to Probe Active Sites and Reaction Intermediates for Selective Catalytic Reduction of NO on Cu/SSZ-13 Catalysts." ACS Catalysis 9, no. 7:6137-6145. PNNL-SA-140065. doi:10.1021/acscatal.9b00759