DOI: 10.1002/cctc.
201600245 Full Papers
A New Approach to the Mechanism of FischerTropsch
Syntheses Arising from Gas Phase NMR and Mass
Spectrometry
Alexis Bordet, Lise-Marie Lacroix, Katerina Soulantica,* and Bruno Chaudret*[a]
We used 13CO labeling to show that gas-phase NMR spectros-
copy and mass spectrometry are simple tools for mechanistic
investigations of the FischerTropsch (FT) reaction. Thus, mon-
odisperse Fe nanoparticles (NPs) react with syngas to form
monodisperse iron carbide (FeCx) NPs. As expected, the heat-
ing of 13C-labeled monodisperse FeCx NPs under H2 results in
the desorption of the carbide carbons as 13CH4 and, interest-
ingly, restores the initial Fe NPs in terms of size and dispersity.
The Fe13Cx NPs catalyze the hydrogenation of 12CO at 210 8C to
Introduction
The mechanism of Fe-catalyzed FischerTropsch Syntheses
(FTS) has been studied extensively for several decades but still
remains controversial. One of the difficulties of the study of
this mechanism lies in the ability of metals to transform into
carbides under catalysis conditions.[1] The exact role of the iron
carbide phase is not totally clear and represents an important
source of discussion. It is quite well accepted that iron carbide
is the most active iron phase in FTS catalysis,[2] but the main
question is its exact role in the reaction mechanism. Among
the different FTS mechanisms proposed, three are accepted
widely today that involve, respectively, surface carbides, enol
formation, and CO insertion.
In the surface carbide mechanism,[3] CO undergoes a dissocia-
tive adsorption at the surface of Fe to give carbides that are
then hydrogenated to form hydrocarbons. This mechanism
became accepted widely thanks to the development of surface
science techniques, which evidenced the absence of oxygen
atoms at the catalyst surface.[4] The surface carbide mechanism
has received support from many groups,[5] and more recently
from Niemantsverdriet and co-workers[6] who used DFT calcula-
tions to model CO hydrogenation over Fe5C2. Very recently,
Khodakov et al.[7] investigated the role of the carbon atoms of
supported 13C-labeled iron carbide in FTS at 300 8C. They evi-
denced the incorporation of the carbide carbon atoms into the
[a] A. Bordet, Dr. L.-M. Lacroix, Dr. K. Soulantica, Dr. B. Chaudret
INSA; Laboratoire de Physique et Chimie des Nano-Objets (LPCNO)
CNRS; UMR 5215
Universit de Toulouse
135 Avenue de Rangueil, 31077 Toulouse (France)
E-mail: bruno.chaudret@insa-toulouse.fr
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under http://dx.doi.org/10.1002/
cctc.201600245.
ChemCatChem 2016, 8, 1727 1731
yield only 12C-labeled FT products, which evidences the ab-
sence of the incorporation of FeCx carbon atoms in the prod-
ucts. In addition, this approach shows for the first time that
the formation of 13CH4 at 250 8C does not result from direct
carbide hydrogenation but from an intermediate step that in-
volves a reaction between Fe13Cx and H2O to give 13CO2, which
is subsequently hydrogenated. These results rule out the in-
volvement of FeCx carbon atoms in the chain growth process
under our conditions.
reaction products (initial fraction of 13C in C2C4 : 1016 %), but
the isotope distribution in the C2C4 fraction led them to con-
clude that the carbide may play the role of a chain growth ini-
tiator. The enol mechanism[8] deals with the nondissociative
chemisorption of CO that reacts with adsorbed hydrogen to
form enolic units. A combination of surface polymerization,
condensation, and water elimination steps by adjacent groups
leads to the formation of hydrocarbons. In an early study,
Emmett and co-workers showed that the incorporation of the
carbide in the hydrocarbon products (carbide mechanism) is
only marginal (maximum 30 %).[9] Further investigations, espe-
cially with 14C-labeled alcohols, led several groups to support
the enol mechanism as the predominant one.[2d, 10, 11] The CO in-
sertion mechanism, also known as the PichlerSchulz mecha-
nism, was introduced later and consists of the insertion of CO
into a metalalkyl bond that is then hydrogenated to produce
alcohols, alkenes, and alkanes.[12] Variants of this mechanism in-
clude the insertion of CO into the OH bond of an adsorbed
OH group[13] and even the hydrogenation of CO to lead to
oxygen atoms bonded directly to the metal surface.[14]
We have shown recently that it is possible to transform
monodisperse Fe0 nanoparticles (NPs) into monodisperse iron
carbide (FeCx) NPs by a two-step procedure. The first step in-
volves the synthesis of Fe0 NPs by the reduction of an organo-
metallic complex [Fe{N(SiMe3)2}2]2 under H2 in the presence of
a mixture of hexadecylamine (HDA) and HDAHCl as li-
gands.[1516] In the second step, the resulting NPs were reacted
with Fe(CO)5 and H2 to produce iron carbide nanocrystals.[17]
Here we show that monodisperse iron carbide NPs can be
formed directly and more easily through the reaction of a mix-
ture of CO and H2 with Fe0 NPs obtained by the reduction of
[Fe{N(SiMe3)2}2]2 under H2 in the presence of palmitic acid (PA)
and HDA[15] in a FTS-like process. The carburation is reversible
1727 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

under H2 and leads back to monodisperse Fe0 NPs. In addition,
following previous work on the use of gas-phase NMR spec-
troscopy for reactivity studies,[18] we show here that simple
NMR experiments can shed light on the role of the carbide
carbon atoms in the FTS and rule out the involvement of car-
bide carbon atoms in the chain growth process under these
conditions.
Results and Discussion
The reduction of the precursor [Fe{N(SiMe3)2}2]2 under H2 in the
presence of HDA and PA gives homogeneous Fe0 nanocrystals
with a tunable average size between 2 and 30 nm. As reported
previously, the size and the shape of the NPs can be tuned by
varying the experimental conditions (ligand concentration,
temperature, reaction time, etc).[12] In this study 9.0 nm Fe0 NPs
were prepared as described in the Experimental Section. The
formation of carbides, inspired by the FTS process, was per-
formed by heating the Fe0 NPs at 150 8C in solution in mesity-
lene in the presence of CO and H2 (syngas, 2 bar/2 bar). Both
Fe0 and iron carbide NPs were characterized by using TEM and
Figure 1. Analysis of Fe NPs before and after the incorporation of carbon
and the after desorption of carbon: a) TEM image and b) XRD pattern of Fe0
NPs; c) TEM image, d) XRD pattern, and e) Mssbauer spectrum of the iron
carbide NPs; f) TEM image and g) XRD pattern of the NPs after carbon de-
sorption at 210 8C. TEM scale bar: 100 nm.
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XRD (Figure 1 ad). Thus, after 24 h under syngas, TEM eviden-
ces the presence of spherical NPs with a mean size of 9.7 nm.
The XRD pattern of these NPs displays the characteristic peaks
of Fe2.2C and no sign of the presence of body-centered cubic
(bcc) Fe0 peaks. The carbide was further characterized by using
Mssbauer spectroscopy at 4 K (Figure 1 e). The analysis shows
that the NPs contain a mixture of two different iron carbide
phases Fe2.2C (67 %) and Fe5C2 (21 %) together with a small
amount of Fe0 (12 %). Interestingly, the Fe5C2 phase is not visi-
ble in the XRD pattern, probably because of its lack of crystal-
linity, associated with a low crystallographic symmetry.
As the NPs are carburated easily with CO in the presence of
H2, it was of interest to synthesize 13C-labeled NPs using 13CO
instead of 12CO to study the low-temperature, low-pressure
FischerTropsch (FT) mechanism and to avoid the presence of
artifacts that result from ligand decomposition, for example.
The aim of the first experiment was to determine if the in-
corporation of carbon into the Fe NPs is reversible and if CC
bonds could be formed during the desorption step. Thus, the
isolated 13C-labeled iron carbide NPs were heated (at 210 and
250 8C) in a batch reactor under 3 bar H2 for 48 h. At the end
of the reaction, the NPs were analyzed by using XRD and TEM
(Figure 1 f and g) and the gas-phase was analyzed by using 1H
and 13C NMR spectroscopy (Figure 2). TEM observations evi-
dence the conservation of the morphological characteristics of
the NPs throughout the process. After heating at both temper-
atures, XRD analysis evidences the presence of pure Fe0 NPs,
which indicates that the carbide desorption is complete. The
Figure 2. Gas-phase NMR spectra after carbide desorption under H2 at
210 8C. a) Gas-phase 1H NMR spectrum and b) gas-phase 13C{1H} NMR spec-
trum.
1728 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

NMR spectra show the formation of 13CH4 and H2O as well as
that of very small amounts of 12CH4, which presumably results
from ligand decomposition (see Figure S1 for desorption at
250 8C). Carbide formation is thus an easily reversible process
that does not modify the NP morphology and that, under H2,
produces methane. Interestingly, but not surprisingly according
to previous studies,[6, 19] we could not find any evidence for the
formation of hydrocarbons other than methane, which means
that no chain growth occurs during the carbide desorption in
the presence of H2 alone under these conditions.
In a further experiment, 13C-labeled iron carbide NPs were
reacted with a 1:1 H2/12CO mixture at 210 8C for 48 h. NMR
spectroscopy of the gas phase showed the formation of sever-
al hydrocarbons and olefins, as expected for a FTS reaction,
but none of these products showed any evidence of 13C en-
richment (Figure 3 a and b). This demonstrates the absence of
the incorporation of the carbide carbon atom into the reaction
products under these conditions. Furthermore, XRD analysis of
the NPs after the reaction confirmed that they still consisted
entirely of iron carbide (Figure SI2). Therefore, the iron carbide
NPs remain unchanged during the FTS reaction, and the
carbon contained in the hydrocarbons formed comes exclu-
sively from the gas phase.
A similar experiment was performed at 250 8C. In this case,
the 1H NMR spectrum evidences again the formation of nonla-
beled hydrocarbons together with a very small amount of
13
CH4 (Figure 3 c). XRD analysis of the NPs after reaction con-
firmed that they still consisted entirely of iron carbide (Fig-
ure S3). In addition, gas-phase 13C NMR spectroscopy evidences
Figure 3. NMR spectra after FT reaction (500 MHz). a) 1H NMR spectrum after reaction at 210 8C. b) 13C NMR spectrum after reaction at 210 8C. c) 1H NMR spec-
trum after reaction at 250 8C. d) 13C NMR spectrum after reaction at 250 8C.
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the presence of significant amounts of 13CO2 clearly (Fig-
ure 3 d). The first possibility to form CO2 under these condi-
tions is the water gas shift reaction (WGSR) with water pro-
duced from CO hydrogenation. As we used nonlabeled CO,
a direct WGSR cannot be the origin of 13CO2. An alternative
possibility to account for the presence of 13CO2 could be direct
exchange between 12CO and Fe13C to give 13CO and Fe12C after
CO dissociation. To test this hypothesis, labeled iron carbide
NPs were heated at 250 8C under 12CO. MS of the gas phase
after 48 h did not show any enrichment of 13CO (Figure S4).
This result is in agreement with previous observations of Ben-
nett and co-workers for a Fe/Al2O3 catalyst at 285 8C.[20] Other
pathways for CO2 formation under FT conditions include the
reaction between adsorbed oxygen atoms, which likely arises
either from CO dissociation or from water, namely, one of the
two hypotheses tested here, and adsorbed CO,[21] or decarbox-
ylation of organic acids formed through the oxidation of FTS
alcohols.[22] Although the decarboxylation of organic acids
would not explain the formation of CO2 that contains carbide
carbon atoms, a reaction between carbide carbon atoms and
adsorbed oxygen atoms is possible. However, such a reaction
would also lead to the formation of 13CO, which does not
occur here.
To explain the formation of 13C-labeled CO2 here, we consid-
ered a direct reaction that occurs between the carbide and
water. Indeed, a reaction between carbon and water to pro-
duce either CO and H2 or CO2 and H2 is possible but at a very
high temperature (> 550 8C).[23] In this case, to investigate this
hypothesis, 13C-labeled iron carbide NPs were reacted with H2O
1729 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

under Ar at 250 8C. By using both 13C{1H} NMR spectroscopy
and MS, we evidenced the presence of excess 13CO2 in the gas
phase at the end of the reaction (Figure S5). Therefore, we can
assume that at 250 8C, the labeled carbide reacts with water
produced during the FTS process to give 13CO2. The reaction of
the as-obtained 13CO2 with H2 can then lead to the formation
of methane and other hydrocarbons at higher temperature
and hence account for the presence of 13CO2 and 13CH4 in the
gas phase. At 250 8C, the WGSR (forward and reverse) is slow
and the reaction of iron carbide with water is not very efficient,
which explains the amount of 13CO2 and 13CH4 observed by
using NMR spectroscopy. In addition, the carbidization degree
of the NPs at the end of the reaction remains constant accord-
ing to the XRD pattern. This means that some CO present in
the syngas is incorporated into Fe NPs to restore the carbide
phase after the exclusion of some 13C converted into 13CO2.
This hypothesis was confirmed experimentally. Fe12C NPs were
reacted with 13CO and H2 at 250 8C. The resulting NPs were
washed and treated again with H2 at 250 8C. NMR spectroscopy
of the gas phase shows the presence of 13CH4 clearly among
the desorption products and thus confirms the incorporation
of carbon that arises from CO(g) into the NPs under FT condi-
tions at 250 8C (Figure S6). This reaction pathway is likely to ex-
plain the incorporation of 13C into the FT products if both
Fe13Cx and 12CO-containing syngas are used. This can also ac-
count for previous observations as at 300 8C the WGSR is fast
and could lead to a higher amount of labeled hydrocarbons,
as reported by Emmett et al.[9] and Khodakov et al.[7]
Conclusions
We report the easy and reversible low-temperature incorpora-
tion of carbon into Fe0 nanoparticles (NPs) to lead to the syn-
thesis of monodisperse iron carbide NPs. We show that this
process preserves the size and shape of the NPs. Furthermore,
the iron carbide NPs could be labeled easily with 13C to investi-
gate the role of iron carbide in Fe-catalyzed CO hydrogenation
using simple analytical techniques, namely, gas-phase NMR
spectroscopy and MS (Figure 4). The heating of iron carbide
NPs at 210 or 250 8C under H2 leads to the complete desorp-
tion of the carbon and, in agreement with previous studies, to
Figure 4. Summary of the different reactions investigated using iron carbide
NPs.
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the exclusive formation of methane without inducing any coa-
lescence, restructuration, or morphology changes in the NPs. A
similar reaction performed under FischerTropsch synthesis
(FTS) conditions, that is, in the presence of H2 and CO at
210 8C, leads to a mixture of unlabeled hydrocarbons and
hence evidences the absence of direct exchange between the
carbide carbon atoms and the carbon oxides present in the
gas phase. However, at 250 8C, the presence of some 13CH4 in
the products was demonstrated to result from a reaction be-
tween iron carbides (Fe13Cx) and water that arises from CO
hydrogenation. Therefore, under our reaction conditions, this
experiment rules out the direct participation of carbide carbon
atoms in the FTS process through the surface carbide mecha-
nism. It could, however, explain some 13C enrichment in hydro-
carbons observed previously in FischerTropsch reactions
through a complex series of reactions that involve water pro-
duced during the FTS process.
We show in this study how the use of gas-phase NMR spec-
troscopy can help in the study of complex mechanisms such
as that that involves iron carbide in FTS.
Experimental Section
All manipulations were performed in anhydrous solvents under an
Ar atmosphere.
Preparation of iron carbide NPs
Iron carbide NPs were obtained through the carbidization of pre-
formed Fe0 NPs. Typically, 9.0 nm Fe0 NPs (50 mg, 0.45 mmol of Fe)
were dispersed in mesitylene (9 mL), and the mixture was pressur-
ized with CO/H2 (2 bar/2 bar; 6.5 mmol for each gas) at 150 8C for
24 h. At the end of the reaction, the 9.7 nm NPs were recovered by
decantation assisted by a magnet and were washed three times
with toluene (3 5 mL). The NPs were then dried under vacuum.
According to elemental analysis, the black powder obtained con-
tained ~ 65 % of Fe. TEM grids were prepared by drop casting a col-
loidal solution that contained NPs on a copper grid covered with
amorphous carbon. The grids were observed by using a MET JEOL
JEM 1011. XRD samples were prepared in the glovebox and were
analyzed by using a PANalytical Empyrean diffractometer using
CoKa radiation at 45 kV and 40 mA.13C-labeled iron carbide NPs
were prepared by using 13CO in the syngas mixture.
Carbide carbon desorption
Dried 13C-labeled iron carbide NPs (10 mg) were reacted in a batch
reactor under H2 (3 bar) at 210/250 8C for 48 h in the absence of
solvent. At the end of the reaction, the gas phase was analyzed by
1
H and 13C NMR spectroscopy. The 8.8 nm NPs were collected in
a glovebox and characterized by using XRD and TEM (Figure 1 and
Figure S1).
FT reaction
Dried 13C-labeled iron carbide NPs (10 mg) were reacted in a batch
reactor under H2/CO (2 bar/2 bar; 6.5 mmol for each gas) at 210/
250 8C overnight in the absence of solvent. At the end of the reac-
tion, the gas phase was analyzed by gas-phase 1H and 13C NMR
1730 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

spectroscopy (Figure 3). The NPs were collected in a glovebox and
characterized by using XRD and TEM (Figures S2 and S3).
Acknowledgements
The authors thank ERC Advanced Grant (NANOSONWINGS 2009-
246763) for financial support, C. Bijani and Y. Coppel for NMR
measurements, and F. Dumestre for discussions concerning the
synthesis of Fe0 nanoparticles.
Keywords: iron isotope labeling nanoparticles NMR
spectroscopy reaction mechanisms
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Received: March 1, 2016
Published online on April 26, 2016
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