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The isomerization of hydrocarbon in catalytic reforming process can be accomplished by

utilizing Platinum (Pt) catalyst which acts by isomerizing the reactants in presence of small
quantity of “promoter” atoms such as Rhodium (Rh), Iridium (Ir), Rhenium (Re) and Tin (Sn)
supported by acidic support, MCF-17 which provides the C-C and C-H bonds breaking activity.
The addition of promoters to the catalyst will enhance the activity of reaction. In view of turnover
frequency (TOF) and the selectivity, the performance of the catalyst for the isomerization reaction
of n-hexane to produce i-hexane is influenced by the compositions and the size of the catalyst.
Based on the study conducted by Musselwhite et al. (2013) conducted a study which addressing
the potential of Pt-Rh catalyst on the reforming of n-hexane using fixed catalyst bed reactor at
ambient pressure in which this catalyst established high favorable towards isomerization and
cyclization accompanied by two undesired reactions including cracking and aromatization.

Table 1: Characterization of Catalyst

The characterization of the catalyst is performed via Scanning Transmission Electron

Microscope (STEM) equipped with Electron Dispersive Spectrometer (EDS) to analyze the size
and composition of the catalyst. In fact, the surface compositions in regard the reaction conditions
are also analyzed using Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS). By
referring to Table, Monometallic Rh catalyst demonstrated the highest TOF with lowest selectivity
towards the production of desired products such as cyclics and isomers compared to Pt catalyst
which have 78% selectivity. This results depicts that Rh catalyst has high tendency to form a
stronger metal carbon bond as well as high capability to break the C-C bond which can be
translated into its favorability to undergo the undesired reaction such as cracking. Additionally,
the combination of Pt-Rh catalyst established a selectivity of 44% and 55% for Pt80Rh20 and
Pt90Rh10 respectively to undergo isomerization reaction.
Figure: Turnover Frequency of Catalysts

Based on Figure, bimetallic catalyst, Pt90Rh10 was found to have the maximum turnover
frequency (TOF). By referring to the molecular structure of the Pt90Rh10, one Rh atom is encircled
by 5 atoms of Pt which enhanced the favorability of the catalyst to undergo isomerization and
subsequently produce desired isomers product. The variations in terms of TOF of the catalyst can
be explained by the ensemble effect of the surface of the bimetallic catalyst whereby the dilution
of Pt surface with Rh will promotes the C-H bond activation and favors high isomer formation
when the Rh atom is surrounded by Pt atoms. Additionally, high isomers TOF on the bimetallic
catalyst is contributed by the high abundance of Pt surface and least abundance of Rh on the
catalyst surface which reduces the potential of C-C bond breaking activity followed by the
minimization of the potential of undesired reaction such as cracking and aromatization.

Figure: Impact of size of catalyst and the selectivity of Pt80Rh20

Figure, demonstrated the impact of the size of the particles on the selectivity of Pt80Rh20
catalyst. Smaller particles size established high tendency to form aromatics and cracking products
as well as having higher catalytic activity compared to the larger particles. Based on the surface
composition study via AP-XPS, both catalyst (small and larger sized particles) have the
approximately similar composition of 70% Pt and 30% Rh. However, cracking activity is found to
be higher at smaller particles due to the ratio of corner to edge sites which is higher in small
particles compared to the large particles. Rh atom is found to occupy the corner and the edge site
which would have a high catalytic activity compared to Pt rich terraces in the molecular structure
of the catalyst which would have a lower catalytic activity. In short, in high TOF or high abundance
of Rh on the catalyst surface will favor cracking while for Pt, the catalyst has high selectivity to
form desired isomers products. However, the limitation of Pt catalyst is the low activity due its
inability to activate the C-H bond and the Rh. Therefore, by adding the Rh as the promoter to the
Pt surface will enhances its selectivity to form isomers for n-hexane reforming through the
activation of C-H bond by Rh atom.


Musselwhite, N., Alayoglu, S., Melaet, G., Pushkarev, V. V., Lindeman, A. E., An, K., &
Somorjai, G. A. (2013). Isomerization of n-Hexane Catalyzed by Supported Monodisperse
PtRh Bimetallic Nanoparticles. Catalysis Letters, 143(9), 907-911. doi: 10.1007/s10562-