1/2/25, 6:34 PM Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O - ScienceDirect

Applied Catalysis B: Environmental

Volume 58, Issues 3–4, 28 June 2005, Pages 255-264

Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2

and H2O
Todd J. Toops a , D. Barton Smith a, William S. Epling b, Jim E. Parks b, William P. Partridge a

Show more

Share Cite

https://doi.org/10.1016/j.apcatb.2004.10.022
Get rights and content

Refers to Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts
Applied Catalysis B: Environmental, Volume 58, Issues 3–4, 28 June 2005, Pages 245-254
Todd J. Toops, D. Barton Smith, William P. Partridge

Referred to by Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts
Applied Catalysis B: Environmental, Volume 58, Issues 3–4, 28 June 2005, Pages 245-254
Todd J. Toops, D. Barton Smith, William P. Partridge

Abstract

A multi-component NOx-trap catalyst consisting of Pt and K supported on γ-Al2O3 was studied at 250 °C to determine the roles of the individual
catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H2O and CO2 on NOx storage. The
Al2O3 support was shown to have NOx trapping capability with and without Pt present (at 250 °C Pt/Al2O3 adsorbs 2.3 μmols NOx/m2). NOx is
primarily trapped on Al2O3 in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared
Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NOx/m2, and the
primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al2O3 catalyst are coordinated
on the Al2O3 support at saturation.

When 5% CO2 was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by 45% after 1 h on
stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H2O was included in a feed stream with
300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al2O3-based nitrates decreased by 92%.
Interestingly, with both 5% CO2 and 5% H2O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al2O3
destabilized the K–CO2 bond; specifically, H2O mitigates the NOx storage capacity losses associated with carboxylate competition.

Introduction

Multi-component NOx adsorber catalysts are a leading solution for the impending stricter diesel emissions regulations [1]. They are based on the
ability of alkali, alkaline, and alkaline earth elements to trap NOx under lean conditions in the form nitrates [2], [3], [4]. The stored nitrates are
then released and reduced by H2, CO, or hydrocarbons in a brief rich interval to obtain benign N2. These catalysts require an oxidation component,
typically a noble metal like Pt, a storage component, commonly Ba, and a high surface area support such as γ-Al2O3. Potassium is another element
that has shown potential as a storage component [5], [6], especially in conjunction with Ba [7], [8]. Numerous studies have shown that K has a
strong interaction with Al2O3 supports [9], [10], [11], [12], but there is scarce information on the specific contributions of K to NOx storage,
especially in the presence of CO2 and H2O.

This study was primarily focused on understanding the NOx adsorption step of a catalyst consisting of Pt and K phases on an Al2O3 support.
Additionally, the contributions of each catalyst component were explored by studying the following model catalysts: Pt on Al2O3, K on Al2O3, and
Al2O3 only. Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) was the primary analytical tool used to determine the form
of stored NOx. A method for quantifying DRIFT absorbance spectra, described in an earlier publication [13], was used to analyze some portions of
the NOx adsorption.

https://www.sciencedirect.com/science/article/abs/pii/S0926337304006290 1/4
1/2/25, 6:34 PM Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O - ScienceDirect
In addition to the component contribution study, the individual and combined effects of CO2 and H2O were also studied. Often during evaluations
of preliminary catalysts the effects of common exhaust components are ignored, however, it has been shown that these ubiquitous components
can have considerable, and at times detrimental effects, on the functionality of lean-NOx reducing catalysts [14], [15], [16], [17], [18], [19], [20].

Access through your organization

Check access to the full text by signing in through your organization.

Access through University of Gujrat

Section snippets

Experimental

The model catalysts were γ-Al2O3, 1 wt% Pt on γ-Al2O3 (Pt/Al2O3), 8.0% K2CO3 on γ-Al2O3 (K/Al2O3), and the complete NOx adsorber catalyst, 8%
K2CO3 on 1% Pt/Al2O3 (Pt/K/Al2O3).1 An 8% loading of K2CO3 corresponds to 64% of a monolayer. The catalyst formulations are summarized in Table
1 along with results from H2 chemisorption and N2 physisorption measurements. Before experimentation, all catalysts underwent a pretreatment
with 50 cm3 (STP)/min …

Results

Experiments were performed with two specific goals. The first goal was to determine the contributions of the various catalyst phases and identify
the functional groups associated with specific DRIFTS features. The second goal was to quantify the effects of H2O and CO2 on the NOx adsorption
capacity of the Pt/K/Al2O3 catalyst.

Al2O3 without Pt was the first material evaluated, at 250 °C with 10 sccm of 500 ppm NO in N2. Fig. 1a shows the DRIFT spectra after 1, 10, 20, and
60 min of NO exposure. The …

Discussion

Pt/K/Al2O3 is the catalyst of interest in this paper, but before discussing its NOx chemistry it is necessary to discuss the state of the catalyst surface
with respect to its three components. Gamma alumina is commonly used as a catalyst support primarily for its high specific surface area and low
cost, however, it does not always behave as a classical support because it interacts with both the catalyst and the reactants primarily via surface
hydroxyl groups. As was shown in our earlier paper …

Summary

Numerous findings were revealed in this study of the Pt/K/Al2O3 lean NOx trap catalyst that elucidate some of the chemistry and key conflicts of
this system. The Al2O3 support was shown to have NOx trapping capability, with or without Pt present, by primarily forming nitrates with
unidentate, chelating and bridged forms, as determined by DRIFTS analysis. Compared to alumina, the K-based catalysts show an increase in
adsorption capacity with the primary storage form being free nitrate ions. We …

Acknowledgments
The authors thank Dr. Louis Powell of the Oak Ridge Y-12 National Security Complex for use of the DRIFT spectrometer. This research was
sponsored by the US Department of Energy under contract number DE-AC05-00OR22725 with the Oak Ridge National Laboratory, managed by UT-
Battelle, LLC. The contribution of T.J. Toops was supported in part by an appointment to the Oak Ridge National Laboratory Postdoctoral Research
Associates Program administered jointly by the Oak Ridge Institute for Science and …

Recommended articles

References (43)

H. Shinjoh et al.
Appl. Catal. B (1998)

M. Konsolakis et al.

https://www.sciencedirect.com/science/article/abs/pii/S0926337304006290 2/4
1/2/25, 6:34 PM Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O - ScienceDirect
Appl. Catal. B (2001)

L.G. Neal, J.L. Haslbeck, H. Tseng, U.S. Patent Number 475599...

B.W. Krupay et al.

J. Catal. (1982)

T.J. Toops et al.

Appl. Catal. B. (2005)

H. Ohtsuka et al.
Appl. Catal. B (1999)

Z. Chajar et al.
Catal. Lett. (1998)

P. Budi et al.
Stud. Surf. Sci. Catal. (1997)

E. Kikuchi et al.
Catal. Today (1996)

G.L. Powell et al.

Appl. Spec. (1992)

View more references

Cited by (142)

Pt dispersion effects during NOx storage and reduction on Pt/BaO/Al<inf>2</inf>O<inf>3</inf> catalysts

2009, Applied Catalysis B: Environmental

Show abstract

NO<inf>x</inf> storage and reduction over Pt based catalysts with hydrogen as the reducing agent. Influence of H<inf>2</inf>O
and CO<inf>2</inf>
2007, Applied Catalysis B: Environmental
Show abstract

Perovskites as substitutes of noble metals for heterogeneous catalysis: Dream or reality

2014, Chemical Reviews

Characterization of ceria's interaction with NO<inf>x</inf> and NH <inf>3</inf>

2013, Journal of Physical Chemistry C

A review of NO<inf>x</inf> storage/reduction catalysts: Mechanism, materials and degradation studies

2011, Catalysis Science and Technology

NO<inf>x</inf> Storage-reduction catalysis: From mechanism and materials properties to storage-reduction performance
2009, Chemical Reviews

View all citing articles on Scopus

View full text

Copyright © 2004 Elsevier B.V. All rights reserved.

https://www.sciencedirect.com/science/article/abs/pii/S0926337304006290 3/4
1/2/25, 6:34 PM Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O - ScienceDirect

All content on this site: Copyright © 2025 Elsevier B.V., its licensors, and contributors. All rights are reserved, including those for text and data mining, AI training, and similar technologies. For all open access content, the Creative Commons
licensing terms apply.

https://www.sciencedirect.com/science/article/abs/pii/S0926337304006290 4/4