The Catalyst Review August 2019 - 17

EXPERIMENTAL
in POC decreased in the
Figure 1. (a) X-ray diffraction patterns and (b) Raman spectra of the metal
order CuPO>> VPO>
phosphate catalysts in fresh form and after propane oxychlorination,
POC, which are labeled using the color code given in the bottom of panel
CoPO>> CrPO> FePO>
a. Reference diffraction patterns are shown as vertical lines below the
MnPO ≈NiPO ≈TiPO, which measured diffractograms or filled symbols above them and are identified
with their ICDD-PDF numbers. Equilibration conditions: C3H8:HCl:O2:Ar:He =
is comparable to the
FT:Wcat = 6000 cm3 h−1 gcat −1, P = 1 bar, and tos = 5 or
activity rankings observed 6:6:3:4.5:80.5,
62 h.
for phosphate- and/or
oxide-based material
of these elements.
Finally, selected systems
representing each of
the identified catalyst
categories were assessed
in the oxidation of
propane and HCl as well
as in propyl chloride
dehydrochlorination. This
analysis revealed that the
phosphate's reactivity
is a function of the
materials' ability to evolve
chlorine from its surface,
while a high selectivity
toward propylene is a
consequence of fast
dehydrochlorination
kinetics in combination
with a hindered ability
to generate molecular
chlorine in the gas phase and a low propensity toward propane cracking and combustion.
Source: Zichittella G, Stähelin S, Goedicke FM, et al. (2019). ACS Catal., 9: 5772−5782.

Figure 2. (a) Rate of propane consumption and
(b) product selectivity in propane oxychlorination
over the metal phosphate catalysts. In panel
a, the rates are determined at 723 K, while in
panel b, the product selectivities are determined
at ca. 20% propane conversion. In panel b,
C3−Cl and cracking products refer to the sum
of chloropropanes (C3H7Cl, C3H5Cl) and of
any observed cracking products (C2H4, CH4,
C2H5Cl, C2H3Cl, and CH3Cl). Reaction conditions:
C3H8:HCl:O2:Ar:He = 6:6:3:4.5:80.5, FT:Wcat = 6000
cm3 h−1 gcat−1, T = 723−813 K, P = 1 bar.

Neutrons Shed Light on Industrial Catalyst for Hydrogen Production...
Collaborators at the Department of Energy's Oak Ridge National Laboratory (ORNL) and U.S. universities used neutron scattering
and other advanced characterization techniques to study how a prominent catalyst enables the "water-gas shift" (WGS) reaction to
purify and generate hydrogen at industrial scale. Results published in the Journal of the American Chemical Society settled a longstanding debate about the catalyst's reaction mechanism, opening routes to improve the cost and efficiency of large-scale hydrogen
production. Collaborators investigated a copper-chromium-iron oxide catalyst (CuCrFeOx) provided by Lehigh University. "We already
know the existing CuCrFeOx catalyst works, but how it works has been the subject of debate," said ORNL's Felipe Polo-Garzon. The
goal was to study how the catalyst behaves in real-world conditions to find evidence of either an oxidation-reduction ("redox") or an
associative mechanism-two predominant theories about how CuCrFeOx works to produce hydrogen. All results pointed to the same
conclusion-a redox reaction. The team's fundamental discovery could eliminate guesswork and tell researchers precisely where
to look for opportunities to synthesize a better catalyst for generating hydrogen. Source: Oak Ridge National Laboratory (ORNL),
7/30/2019.

The Catalyst Review 										

	

August 2019

17


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The Catalyst Review August 2019

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