(483d) Design of Heterogeneous Catalyst By Stoichiometric Tuning of Intermetallic Gamma-Brass Crystal Structure | AIChE

(483d) Design of Heterogeneous Catalyst By Stoichiometric Tuning of Intermetallic Gamma-Brass Crystal Structure


He, H. - Presenter, Pennsylvania State University
Janik, M. J., Pennsylvania State University
Dasgupta, A., Pennsylvania State University
Rioux, R., Pennsylvania State University
Kumar, G., Pennsylvania State University

DFT Studies of
Intermetallic Gamma-Brass Crystal Structures for Selective Hydrogenation

Haoran He, Anish Dasgupta, Gaurav Kumar, Robert M. Rioux, and Michael J. Janik

Department of
Chemical Engineering, The Pennsylvania State
University, University Park, PA 16802, USA

*mjanik@ psu.edu; (814) 863-9366

compounds can offer tunable site electronics and ensemble structure for
selective hydrogenation catalysis. In this study, we consider the γ-brass
phase (Cu5Zn8 prototype), in
order to expose surfaces with controlled Mx
nuclearity to control the selectivity for
hydrogenation. The γ-brass structure has a 52 atoms unit cell with 4 distinct symmetry sites —outer tetrahedral (OT), inner
tetrahedral (IT) octahedral (OH) cuboctahedral (CO)
as shown in Figure 1. In particular, the Pd-Zn
γ-brass atomic arrangement as well as the substitution pattern of Zn by Pd in the Pd-Zn γ-brass
phase (15.4-24%) has been extensively studied by Edstrom and Westman through x-ray diffraction analysis[1].
Surface energy calculations indicated that the most stable Pd8Zn44
facet is (1 -1 0), which exposes only monomers for Pd8, but includes
Pd trimers for Pd9-11. We vary the number
of Pd atoms per isolated active site and investigate
its effect on H2 dissociation and acetylene hydrogenation
mechanisms. DFT calculations agreed with experimental results that H2
activation is faster on trimer sites, substantiating the formation of Pd3
trimer sites on Pd9Zn43 catalyst surfaces. The activation
barrier for H2 dissociation is nearly identical experimentally on
Pd9, Pd10 and Pd11, further substantiating the isolation of the Pd trimer sites. DFT calculations indicate that acetylene
binds strongly on both monomer bridge and trimer
sites, whereas ethylene binds strongly on monomer atop and trimer side atop
sites. At the same time, H2 dissociation and binding adjacent to
ethylene is only possible on the trimer sites. DFT calculations showed the
apparent barrier of ethylene hydrogenation is higher than the ethylene
desorption barrier, which indicates Pd8Zn44 is superior
catalyst in selectively hydrogenating acetylene to ethylene.  Pd9-11 on the other hand, contains
trimers on the surface, which can lower the ethylene hydrogenation barrier,
compared with Pd8Zn44. The full path of acetylene
hydrogenation on these isolated sites, as well as a microkinetic
model for acetylene hydrogenation on these intermetallics,
will be presented. The gamma-brass intermetallic structures offer isolated
active sites with controlled nuclearity, allowing
both the design of active and selective catalysts as well as the elucidation of
site requirements. 

Figure 1.  Illustration of the sites in the γ-brass
structure: inner tetrahedral (IT, red); outer tetrahedral (OT, blue);
octahedral (OH, green); and cuboctahedral
(CO, orange).


Edstrom, V.A and S. Westman,
X-ray Determination of Structure of Cubic Gamma Pd,
Zn Phase. Acta Chemica Scandinavica, 1969. 23 (1):