(617cn) Multiple H2O and NH3 Adsorbed on Cu-SSZ-13: XANES and XES Study from First Principles

Nitrogen oxides (NOx) are one of the main air pollutants present in the
exhaust from diesel engines, which are popular for vehicle transportation due
to their efficiency and durability [1]. However, NOx emission control is a
challenge in these "lean-burn" engines [2]. As is well known, the
selective catalytic reduction (SCR) of NOx with NH3 is a reaction between the
NO, NO2, and O2 oxidants and the NH3 reductant to form N2 and H2O.
Copper-exchanged small-pore micro-crystalline materials with the chabazite structure
(Cu/CHA), such as Cu-SSZ-13, display excellent catalytic activity and
hydrothermal stability in SCR of NOx, as has been shown in a number of recent
studies [3, 4]. Although Cu-SSZ-13 have been commercialized as diesel
after-treatment catalysts, the fundamental chemical and physical properties
need to be characterized in order to aid in the design of new and better
catalysts [5].

X-ray absorption spectroscopy (XAS) is a versatile tool to determine the
oxidation state and the local structure of Cu in Cu/CHA. Cu K-edge X-ray
absorption near edge spectra (XANES) has been widely used to study the
properties of Cu-SSZ-13 because of its high activity and selectivity in the NH3
SCR of NOx. It is demonstrated that XANES is extremely sensitive to the local
structure of Cu ions [6, 7]. However, the exact relationship between XANES
features and local structure is still unclear. In this work, we examine how the
geometry of a Cu+ ion with a linear configuration and Cu2+ ion with a square
planar configuration in Cu-SSZ-13 correlate with the XANES features. When water
and ammonia binds to a Cu+ ion with a linear configuration, a strong intensity peak
around 8983 eV in Cu K-edge XANES appears. When two ammonia molecules bind at a
Cu+ ion, it is also found that the intensity of the peak around 8983 eV
decreases as one decreases the N-Cu-N bond angle from 180 to 100 degree (see
Figure 1). By analyzing the corresponding PDOS, it is found that the splitting
of 4p state correlates with the N-Cu-N bond angle and the corresponding
decrease in the K-edge intensity. Concerning the case of Cu2+ ions with a
square planar configuration bounded to four ammonia molecules, it is found that
there are two feature peaks around 8986 and 8993 eV in their Cu K-edge XANES.
By studying this simple model, we find that changing the N-Cu-N angle between
one of the bonded NH3 and the Cu-centered ion from 180 to 100 degree results in
a decrease in the intensity of both peaks around 8986 and 8993 eV. It is also
found that the broken of square planar configuration results in the
delocalization of 4p state.

An important limitation of XANES is that it is difficult to distinguish the nitrogen
and oxygen atoms in the proximity of the metal center. X-ray emission
spectroscopy (XES) could overcome this limitation. It is reported that the
Kbeta'' peak in XES of a Cu-SSZ-13 sample presents a blue shift with the
formation of Cu-N bond [8]. This can be understood by the fact that the Kbeta''
peak originates from the ligand 2s to a metal 1s crossover transition and the
nitrogen 2s level lies higher in energy than the one for oxygen. By comparing
the XES results between H2O and NH3 adsorbed on Cu-SSZ-13, it is found that the
Kbeta'' peak of Cu-O bond appears at lower energy than that of Cu-N bond. In
addition, the coordination number of Cu ions significantly affects on the
energy difference between the position of the Kbeta'' peak. By performing a
density of states (DOS) analysis, these results can be understood at the
electronic level. Overall, our careful elucidation of the spectroscopic
properties of Cu ions in Cu-SSZ-13 via theoretical techniques can assist us in
interpreting the XANES experimental results so as to gain a deeper
understanding of the SCR of NOx with NH3 throughout its catalytic cycle.

Figure 1. Variation
of Cu K-edge XANES for 2 NH3 adsorbed on Cu+-SSZ-13 with changing the angle of
N-Cu-N (as shown insert in the right bottom) from 180 degree (black line) to
100 degree (blue line) with decrement of 10 degree.

References

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