Effect of Promoter Nature on Synthesis Gas Conversion to Alcohols over (K)MeMoS2/Al2O3 Catalysts

Article abstract of DOI:10.1002/cctc.201901698

The influence of the promoter nature and of a modifier in (K)(Me)MoS₂/Al₂O₃ (Me=Fe, Co, Ni) catalysts on the conversion and selectivity of products of synthesis gas conversion to alcohols and jnl oxygenates was investigated. Relationships between promoter nature, hydrocarbon chain length and selectivity in the formed alcohols were established. Electronic structure of a promoter atom in an active site (AS) was found to strongly affect selectivity of alcohol formation. Promotion of the S-edge by Fe, Co or Ni suppressed hydrogen activation, which resulted in a lower synthesis gas conversion. Promotion of the M-edge by Fe, Co, or Ni entailed the formation of double vacancies which are active sites of synthesis gas conversion. Potassium affected the oxophilicity of Mo atoms and reduced Co/Ni-promoted MoS AS. It decreased the probability of C?O bond breaking in the adsorbed intermediate and shifted selectivity from the formation of alkyl towards alkoxide fragments over these catalysts.

Full text of DOI:10.1002/cctc.201901698

Accepted Article
Title: Effect of promoter nature on synthesis gas conversion to alcohols
over (K)MeMoS2/Al2O3 catalysts
Authors: Vladimir V. Maximov, Eugenii A. Permyakov, Viktor S.
Dorokhov, Anjie Wang, Patricia J. Kooyman, and Victor M.
Kogan
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To be cited as: ChemCatChem 10.1002/cctc.201901698
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10.1002/cctc.201901698
ChemCatChem
ChemCatChem
Effect of promoter nature on synthesis gas conversion to alcohols over
(K)MeMoS2/Al2O3 catalysts
--Manuscript Draft--
Manuscript Number:
cctc.201901698R2
Article Type:
Full Paper
Corresponding Author:
Victor M. Kogan, Ph.D., D. Sc., Prof.
Moscow, RUSSIAN FEDERATION
vmk@ioc.ac.ru
Corresponding Author E-Mail:
Order of Authors (with Contributor Roles): Vladimir V. Maximov, Ph.D. student
Eugenii A. Permyakov
Viktor S. Dorokhov
Anjie Wang
Patricia J. Kooyman
Victor M. Kogan, Ph.D., D. Sc., Prof. (Conceptualization: Lead; Project administration:
Lead; Supervision: Lead; Writing – review & editing: Lead)
Keywords:
Abstract:
Higher alcohol synthesis * Synthesis gas conversion * K-modified MeMoS2 catalysts *
FeMoS2 * CoMoS2 * NiMoS2
The influence of the promoter nature and of a modifier in (K)(Me)MoS2/Al2O3 (Me =
Fe, Co, Ni) catalysts on the conversion and selectivity of products of synthesis gas
conversion to alcohols and other oxygenates was investigated. Relationships between
promoter nature, hydrocarbon chain length and selectivity in the formed alcohols were
established. Electronic structure of a promoter atom in an active site (AS) was found to
strongly affect selectivity of alcohol formation. Promotion of the S-edge by Fe, Co or Ni
suppressed hydrogen activation, which resulted in a lower synthesis gas conversion.
Promotion of the M-edge by Fe, Co, or Ni entailed the formation of double vacancies
which are active sites of synthesis gas conversion. Potassium affected the oxophilicity
of Mo atoms and reduced Co/Ni-promoted MoS AS. It decreased the probability of C-O
bond breaking in the adsorbed intermediate and shifted selectivity from the formation
of alkyl towards alkoxide fragments over these catalysts.
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ChemCatChem
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10.1002/cctc.201901698
ChemCatChem Effect of promoter nature on synthesis gas conversion to alcohols over
(K)MeMoS2/Al2O3 catalysts
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List of authors
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Name
V.V. Maximov
Title
Affiliation
E-mail
maximovzioc@gmail.com
Ph.D
student
N.D. Zelinsky Institute of
Organic Chemistry, Russian
Academy of Sciences, 47
Leninsky prospect, Moscow
119991, Russia
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E.A.
Permyakov
Researcher N.D. Zelinsky Institute of
Organic Chemistry, Russian
Academy of Sciences, 47
Leninsky prospect, Moscow
119991, Russia
permeakra@gmail.com
viktor.s.dorokhov@yandex.ru
ajwang@dlut.edu.cn
V.S. Dorokhov Dr.
N.D. Zelinsky Institute of
Organic Chemistry, Russian
Academy of Sciences, 47
Leninsky prospect, Moscow
119991, Russia
A. Wang
Prof.
State Key Laboratory of Fine
Chemicals, School of Chemical
Engineering, Dalian University
of Technology, Dalian 116024,
China
P.J. Kooyman
V.M. Kogan
Prof.
Prof.
ChemEng, University of
Cape Town, Private Bag X3,
Rondebosch 7701, South Africa
N.D. Zelinsky Institute of
Organic Chemistry, Russian
Academy of Sciences, 47
Leninsky prospect, Moscow
119991, Russia
patricia.kooyman@uct.ac.za
vmk@ioc.ac.ru
This article is protected by copyright. All rights reserved.

10.1002/cctc.201901698
ChemCatChem
Appropriate text and color graphic:
Effects of promoter and of a modifier of (K)(Me)MoS2/Al2O3 (Me = Fe, Co,
Ni) catalysts on syngas conversion into alcohols and their selectivity have been
investigated. Relationships between promoter nature, hydrocarbon chain length
and selectivity in the formed alcohols were established. Electronic structure of a
promoter atom in an active site was found to strongly affect selectivity of alcohol
formation. Potassium affected oxophilicity of Mo atoms and reduced Co/Ni-
promoted MoS active sites.
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Alcohol selectivity on (K)(Me)MoS2
Chain growth factor αi
CO + H2
Alcohols
(% , K-free / K-modified)
0.8
0.4
0.0
0.8
0.4
0.0
100
75
50
25
0
K(Co/Ni)MoS
2
S
S
S
S
S
S
S
Low
conversion
KFeMoS2
Mo
Me
Mo
S
S
S
S
S
S
S
S
1
2
3
4
S
S
K(Co/Ni)MoS2
KMoS2
Mo
Me
Mo
KMoS
2
S
S
S
S
Alkanes
Alcohols
S
S
S
S
S
Mo
S
Mo
Mo
S
Mo
FeMo
CoMo
NiMo
S
1
2
3
4
S
S
This article is protected by copyright. All rights reserved.

10.1002/cctc.201901698
ChemCatTChaemble of contents
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Abstract .........................................................................................................................................................4
1. Introduction...............................................................................................................................................4
2. Experimental .............................................................................................................................................6
2.1. Preparation of materials and catalysts................................................................................................6
2.2. Physical characteristics of supports and catalysts ..............................................................................6
2.2.1. Textural characteristics of the samples .......................................................................................6
2.2.2. Elemental composition characterization .....................................................................................7
2.3. Catalytic experiments and analysis of products .................................................................................7
3. Results.......................................................................................................................................................8
4. Discussion ...............................................................................................................................................10
5. Conclusions.............................................................................................................................................14
Acknowledgement.......................................................................................................................................14
Conflict of Interest ......................................................................................................................................14
References...................................................................................................................................................16
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This article is protected by copyright. All rights reserved.

10.1002/cctc.201901698
ChemCatChem Effect of promoter nature on synthesis gas conversion to alcohols over
(K)MeMoS2/Al2O3 catalysts
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V.V. Maximov1, E.A. Permyakov1, V.S. Dorokhov1, A. Wang2, P.J. Kooyman3, and V.M.
Kogan1*
*vmk@ioc.ac.ru
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1N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky
prospect, Moscow 119991, Russia
2State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of
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Technology, Dalian 116024, China
3ChemEng, University of Cape Town, Private Bag X3, Rondebosch 7701, South Africa
Abstract
The influence of the promoter nature and of a modifier in (K)(Me)MoS2/Al2O3
(Me = Fe, Co, Ni) catalysts on the conversion and selectivity of products of
synthesis gas conversion to alcohols and other oxygenates was investigated.
Relationships between promoter nature, hydrocarbon chain length and selectivity
in the formed alcohols were established. Electronic structure of a promoter atom in
an active site (AS) was found to strongly affect selectivity of alcohol formation.
Promotion of the S-edge by Fe, Co or Ni suppressed hydrogen activation, which
resulted in a lower synthesis gas conversion. Promotion of the M-edge by Fe, Co,
or Ni entailed the formation of double vacancies which are active sites of synthesis
gas conversion. Potassium affected the oxophilicity of Mo atoms and reduced
Co/Ni-promoted MoS AS. It decreased the probability of C-O bond breaking in the
adsorbed intermediate and shifted selectivity from the formation of alkyl towards
alkoxide fragments over these catalysts.
1. Introduction
Growth in global demand for major energy sources, including liquid fuels,
requires a revision of the world energy consumption structure. Today, 96% of
liquid fuels is produced from petroleum. Liquid fuel production processes from
coal (coal-to-liquids, CTL) and light hydrocarbons (gas-to-liquids, GTL) have been
the focus of R&D since the beginning of the 20th century.[1] Nonetheless, these
processes have not found extensive applications so far and cannot compete with
liquid fuels produced from crude oil.
CTL and GTL processes usually proceed via intermediate production of
synthesis gas. Synthesis gas can be sourced from natural and associated gas, coal,
other combustible minerals, and biomass.[2,3] Synthesis gas is a very convenient
intermediate for the synthesis of petrochemicals and can yield long-chain linear
This article is protected by copyright. All rights reserved.

10.1002/cctc.201901698
ChemCataChlkemanes and terminal alkenes, fatty alcohols, aldehydes, carboxylic acids, and other
oxygenates.[1] Alcohols like ethanol and methanol can be used to increase octane
rating of gasoline in particular. Higher alcohols are more favorable as fuel
additives than methanol because of their lower volatility and better solubility in
hydrocarbons (HC). In the environmental context, higher alcohols are preferable
because they reduce the amount of soot particles, carbon, and nitrogen oxides in
exhaust gases. Furthermore, higher alcohols are widely used as precursors in
petrochemistry and medical chemistry.[4,5]
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Review[4] describes various methods for the preparation of higher alcohols
such as fermentation of sugars, synthesis and subsequent carbonylation of
methanol, methanol cross-coupling with CO, etc. In terms of future applications, of
most interest is a direct synthesis of higher alcohols from synthesis gas over Rh,
Cu, Co, and Fe catalysts. However, a majority of metal and oxide catalysts has a
significant drawback – they are susceptible to poisoning with sulfur-containing
compounds, even if the latter are present in raw materials in trace quantities (ppm).
Sulfides of transition metals do not have this disadvantage and, moreover, their
catalytic activity is comparable to or higher than that of metal and oxide
catalysts.[6]
Various (Me)MoS2-based catalysts can be used for catalytic synthesis gas
conversion.[7–10] A high content of sulfidic impurities in the feedstock (50-100 ppm
H2S) helps inhibits sulfur removal from these catalysts, preventing deactivation
and extending catalyst life.[11,12] Sulfide catalysts are more resistant to carbon
deposition, than conventionally applied oxide ZnCu and ZnCr catalysts.[12]
Catalysts based on transition metal sulfides are tolerant to the presence of sulfur in
the feedstock and can improve performance of industrial processes for catalytic
synthesis gas conversion to alcohols.
Catalysts based on potassium-modified molybdenum disulfide for the
production of alcohols from synthesis gas were introduced by Dow Chemical
Company and Union Carbide Corporation in the mid-1980s.[13,14] A special feature
of these catalysts is that a mixture of methanol, C2+ alcohols and hydrocarbons is
formed in the course of synthesis gas conversion. The products are mainly primary
linear alcohols.
Catalysis occurs mainly on coordinative unsaturated sites (CUS) formed on the
edges of (Co/Ni)MoS2 catalysts.[10,15–22] Co and Ni promoter atoms located on the
MoS2 crystallite edges participate in the CUS formation.[11,12,22-25] Addition of
potassium to the (Co/Ni)MoS2 system reduces metal atoms and increases the MoS2
slab length and stacking degree.[22,26-28] In hydrodesulfurization reactions, this
induces a decrease in catalytic activity and a shift in selectivity from hydrogenation
to hydrodesulfurization.
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Computer simulation of MoS CUS in (K)(Me)MoS (Me = Fe, Co, Ni,
collectively referred to as promoters in this study) showed that Lewis acidity of the
promoter atom and affinity for sulfur decreased in the order Fe>Co>Ni. Addition
of potassium (referred to as a modifier) increased the Me-S bond strength and
decreased the number of vacancies for MoS and FeMoS, but not for CoMoS and
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10.1002/cctc.201901698
ChemCatNChieMm oS. On the other hand, addition of potassium increased the Me-H bond
strength facilitating H2 activation.[22,29]
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In this study, we report experimental results regarding the influence of the
promoter metal nature both in the presence and in the absence of potassium
(modifier) on the catalytic activity of (K)(Me)MoS2 (Me = Fe, Co, Ni) samples in
synthesis gas conversion to higher alcohols and/or hydrocarbons and on the carbon
chain size of the products. The results are discussed using previously obtained DFT
computational data on the electronic structure and on the affinity of model active
sites for sulfur, CO, and hydrogen.[22]
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2. Experimental
2.1. Preparation of materials and catalysts
Textural characteristics of the γ-Al2O3 support material are listed in Table 1.
To study the effect of d-metals (Fe, Co and Ni) and potassium on the catalytic
performance of MoS2, catalysts of different composition were prepared and
evaluated. As a r=Me/(Me+Mo) molar ratio (promotion degree, Table 2) of 0.3
previously provided maximum promotion of molybdenum disulfide edges as well
as the highest alcohol yield.[24-28] Promotion degree r ≈ 0.3 was used in this study.
The composition of the catalysts was determined using XRF (see Section 2.2.2 and
Table 2).
The catalysts were prepared via wet impregnation. A typical preparation
procedure for solution impregnation is:
0.48 g (5 mmol) of ammonium heptamolybdate (Alfa Aesar, tetrahydrate,
chemically pure 99%) was dissolved in a mixture of 1.5 ml of distilled water and 1
ml of 20% NH4OH solution before 0.40 g (10 mmol) of KOH (analytical grade,
98%) was added. This solution 1 was added to solution 2 of Me acetate (Me=Fe3+,
Co2+, Ni2+) (Alfa Aesar, tetrahydrate, chemically pure 98%) (2.5 mmol) and 1.05 g
(5 mmol) of citric acid in 1 ml of distilled water. Al2O3 (3 g) was impregnated with
resulting solution 3 following by drying on air for 2 hours at 60°C and then for 5
hours at 100-110°C.
2.2. Physical characteristics of supports and catalysts
2.2.1. Textural characteristics of the samples
Textural characteristics were determined from N2 adsorption and desorption
isotherms measured using an ASAP 2020 Plus instrument (Micromeritics, USA) at
77 K. Before degassing, oxide samples were kept under argon flow for 3 hours and
sulfide samples were kept under hydrogen flow for 3 hours. The oxide samples
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10.1002/cctc.201901698
ChemCatwCheemre degassed at 110°C for 4 h at 10–4 mm Hg and the sulfide samples at 250°C
for 4 h at 10–4 mm Hg.
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2
The specific surface was determined using the BET equation. The total pore
volume was determined at a relative pressure P/Po = 0.99. The mesopores size
distribution was calculated from the desorption branch of the isotherm using the
method of Barrett, Joyner and Halenda (BJH).[30] The cumulative pore volume
during desorption, according to the BJH method, was taken as the mesopore
volume (considering the adsorption film thickness on the mesopore surface). The
micropore volume in the samples was determined using the t-plot method[31] and
by comparing the total pore and mesopore volumes.
Gas sorption analysis was performed according to standard procedures. All
sample cells were calibrated before use. Approximately 0.1 g of any given sample
was taken for analysis. Analysis was programmed to obtain at least 25 points on
the adsorption curve (with 10 points in the 0.01-0.30 p/po region for BET and 6
points between 0.3-0.6 p/po for t-plot/α-S) and 45 points on the desorption curve
for BJH. Some samples were checked for reproducibility and the error was found
to be less than 5%. The obtained specific surface, volume and pore size values are
summarized in Table 1.
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2.2.2. Elemental composition characterization
The elemental composition of the catalysts was determined using an EDX-
7000 X-ray fluorescence spectrometer (Shimadzu); tube anode – Rh, tube current
8–200 mA, voltage 15–50 kV. All samples were crushed before measurements.
The error of the XRF method was found to be ± 1 wt.%. The spectra were
processed using the method of fundamental parameters.[32] The elemental
composition data are given in Table 2.
2.3. Catalytic experiments and analysis of products
Before catalytic experiments, the samples were sulfided in an autoclave using
elemental sulfur under the following conditions: temperature 360 °С and hydrogen
pressure 60 atm (catalyst:sulfur weight ratio = 5:1) during 1 hour. After sulfiding,
the samples were placed in the catalytic reactor under inert atmosphere.
Synthesis gas conversion was carried out in a fixed-bed flow reactor using 3 g
of the catalyst, P = 5 MPa, T = 300-360 °C, mass feed rate 760 l h–1 (g cat)–1, feed gas
composition CO:H2:Ar=45%:45%:10%. Argon was used as an internal standard
for gas chromatography (GC).
The gas products were analyzed using an LHM-80 GC with a thermal
conductivity detector and two one-meter packed columns (molecular sieves CaA
(Ar, CH4, CO) and Porapak Q (CO2, C2+)). The liquid products (alcohols,
aldehydes, esters, etc.) were analyzed using a Crystal-2000M GC with a flame
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10.1002/cctc.201901698
ChemCatiCohenmization detector and a 50-meter HP-FFAP capillary column. Carrier gas was
high purity helium for both GCs.
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The synthesis gas conversion results are given for the carbon atom. Data on
the elemental composition of the catalysts were used to calculate specific
conversion (activity per mmole of Mo) of synthesis gas 푋퐶푀표 (Table 2) according to
Eq 1 and 2:
퐴푓푡푒푟 푟푒푎푐푡푖표푛
푛
퐶푂
푋퐶 = 1 −
퐼푛 푓푒푒푑
푛
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퐶푂
(1)
푋퐶
푋퐶푀표
=
휗푀표
(2)
where 푋퐶 – synthesis gas conversion; 푋퐶푀표- specific synthesis gas conversion;
– CO content, in mmol, in initial synthesis gas and in the
products, respectively; 휗푀표 - molybdenum content, in mmol, in the corresponding
sample.
푓푒푒푑
퐶푂
퐴푓푡푒푟푟푒푎푐푡푖표푛
퐶푂
푛
and 푛
It is commonly accepted[13,33-35] that selectivity in this reaction is calculated in
CO2 free basis approximation. The reason for that is the following: the CO2 is
mainly formed in the course of water gas shift or Boudouard reactions and is
considered as by-product does not affecting the selectivity of the target products.
That is why we excluded CO2 from selectivity balance calculations. CO2-free
selectivity was calculated using Eq. 3:
푆푖
푆푖퐶푂 −푓푟푒푒
=
2
1 − 푆퐶푂
,
(3)
2
Where 푆푖퐶푂 −푓푟푒푒 — CO2 free selectivity to i component; 푆푖 – selectivity to i
2
component; 푆퐶푂 – CO2 selectivity.
2
The carbon chain growth factor αi was calculated using Eq. 4.
푌
푘
푘>푖
푘
훼푖 =
푌
푘
푘
푘≥푖
,
(4)
where 훼푖— chain growth factor for the intermediate with i carbon atoms; Yk –
yield of the component with the k number of carbon atoms.
The factor α1 corresponds to the probability of the CO insertion to an
intermediate containing one carbon atom with the formation of an intermediate
with two carbon atoms; α2 corresponds to the next step of CO addition to the
intermediate with two carbon atoms to the intermediate with three carbon atoms,
and so on.
3. Results
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10.1002/cctc.201901698
ChemCatChem Specific surface, pore volume and particle size data for the molybdenum
sulfide catalysts as well as for the bare alumina support are summarized in Table 1.
The alumina support has a bimodal pore size distribution with maxima at 4.5 and
14.9 nm. Loading of the support material with the active phase reduces both the
specific surface area and the pore volume. This effect was more pronounced for the
potassium promoted catalysts. It should be noted that only minor part of potassium
is intercalated, as for KxMoS2 intercalates only x~0.4 is achievable by more
efficient process of direct intercalation of K(0) from dry liquid ammonia solution.
The rest of potassium can either replace protons in Brønsted acidic sites on support
or grab anion from environment during preparation, for example, forming (hydro)
carbonates, obstructing small pores.
Elemental analysis data are presented in Table 2. The molybdenum content in
the samples varies from 11 to 14% wt. The promotion degree r=Me/(Mo+Me)
[molar ratio] ranges from 0.22 to 0.30. The presence of potassium does not affect r.
The modification degree t= K/(Me+Mo) [molar ratio] ranges from 0.62 to 0.83.
The results of the catalytic experiments are summarized in Table 3 and
considered in corresponding Figures 1-6. Figure 1 shows the specific conversion
(per mmole Mo) of synthesis gas over the (Me)MoS2 catalysts at temperatures
between 300 and 360 °C at 50 atm. Addition of the promoter significantly reduces
conversion as compared to that of non-promoted MoS2. Of note is that nature of
the promoter atom exerts a noticeable effect on the specific conversion value.
Conversion decreased in the order of MoS2>FeMoS2>CoMoS2>NiMoS2. An
increase in reaction temperature predictably increased synthesis gas conversion.
Figure 2 shows specific conversion of synthesis gas over the same samples,
but modified with potassium. Potassium addition to MoS2 and FeMoS2 led to a
decrease in conversion, whereas for CoMoS2 and NiMoS2 conversion increased
upon potassium addition.
Addition of K did not affect the temperature dependence of the specific
conversion for the (K)MoS2, (K)NiMoS2 and (K)FeMoS2 samples. In the case of
the KCoMoS2 catalysts, the introduction of potassium essentially influenced the
temperature dependence and an increase in synthesis gas conversion was observed
(from 12.3% at 300 °С to 27.0% at 360°С).
Figures 3 and 4 show methane and C2+ hydrocarbon selectivity at T = 340 °C
and p = 50 atm. Methane was the dominant product in the gas phase when the
MoS2 catalyst was utilized. In the case of MeMoS2 (Me = Fe, Co, Ni), selectivity
to C2+ hydrocarbons was higher than that to methane (Fig.3). Addition of
promoters to molybdenum disulfide increased C2+ hydrocarbon selectivity (Fig. 4).
K-modification of the (Me)MoS2 catalysts (Me = Fe, Co, Ni) suppressed
hydrocarbon formation in favor of alcohols formation. The most pronounced
reduction is observed for MoS2 (from 50.5% to 11.5% for methane and from
45.5% to 13.0% for C2+-hydrocarbons) and FeMoS2 (from 63.1% to 16.7% for C2+-
hydrocarbons). The generation of C2+-hydrocarbons (including alkenes) over
KCoMoS2 and KNiMoS2 was almost completely suppressed. With temperature
increasing methane and C2+ hydrocarbon yields increased for all samples.
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10.1002/cctc.201901698
ChemCatChem The products of synthesis gas conversion over the molybdenum sulfide
catalysts contained ethylene in small amounts (ethylene was found in larger
amount on MeMoS2, where Me = Fe, Co, Ni).
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Selectivity to liquid products, including alcohols as major products and
aldehides, ethers, esters, etc. as minor products (4% in sum), obtained on the
(K)(Me)MoS2 catalysts (Me = Fe, Co, Ni) at 340 °C and 50 atm. are depicted in
Figures 5 and 6. Promotion by Fe, Co or Ni of K-free molybdenum disulfide did
not affect the selectivity of the liquid products.
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Modification of the FeMoS2 catalyst with potassium did not bring about an
increase in the liquid products yield. In the case of MoS2, CoMoS2 and NiMoS2,
potassium increased the liquid product yield approximately tenfold (Table 4). The
yield of the liquid product over the KFeMoS2 catalyst close to K-free sample
(1.8% and 1.7% respectively).
Figure 6 shows selectivities for the individual products. It is seen that
methanol was the main product for the KMoS2/Al2O3 catalyst. No amyl alcohols
were detected over non-promoted molybdenum disulfide. Co and Ni addition
contribute to the increase in selectivity to C2+ alcohols. Maximum ethanol and
propanol-1 selectivity is observed for the KNiMoS2/Al2O3 catalyst.
Figure 7 shows dependences of the liquid product yield and efficiency of the
potassium additive effect on the liquid products yield from the degree of
molybdenum promotion by iron, nickel or cobalt. As seen from Figure 7, the
values for the promoted catalysts are in a narrow region r – from 0.22 to 0.27,
while the difference in these values is notable. This is indicative of a slight effect
of the promotion degree in this range and, at the same time, of a significant effect
of the promoter nature on the liquid products yield and of the difference in
efficiency of the potassium effect on iron, cobalt and nickel, as promoting metals,
in the composition of the MeMo-sulfide active site. The observed dependences
testify to a stronger effect of potassium addition to the CoMoS site, a significant,
though less strong, effect of its addition to NiMoS, and the lowest effect where it is
added to the FeMoS site.
Figure 8 shows the dependence of the hydrocarbon chain growth factor αi from
the number of carbon atoms in the intermediate product on the (Me)MoS2
catalysts. MoS2 promotion by iron increased hydrocarbon chain growth factors α1,
α2 and α3. In the case of Co and Ni promoters, only α1 increased, whereas α2 was
lower than that of the non-promoted sample and α3 was zero. For all potassium-
free samples, α4 was zero.
Figure 9 shows the chain growth factors for the K(Me)MoS2 catalysts.
Modification with potassium dramatically increases the chain growth factor α1 for
the KCoMoS2 and KNiMoS2 catalysts. The influence of potassium on the MoS2
catalyst is not significant. As for the Fe-containing catalyst, its modification with
potassium substantially reduced the hydrocarbon chain growth factor α1, whereas
α2, α3 and α4 were zero.
4. Discussion
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10.1002/cctc.201901698
ChemCatChem
According to,[19,22,36-39] activity of MoS2-based catalysts is associated with the
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presence of CUS on the S- and M-edges. There is a significant number of
vacancies on the S-edge of MoS2 (Scheme 1a) in the thermodynamically stable
state, whereas very few, if any, are present on the M-edge,[22] suggesting that the
M-edge of the unpromoted catalyst does not exhibit activity in synthesis gas
conversion. The DFT calculations show that adsorption of CO and dissociative
adsorption of hydrogen can occur on the S-edge at (K)MoS sites with the
formation of hydride hydrogen.[20,40,41] Reactions of hydride hydrogen with CO and
other ligands are well known in metal complex chemistry. We believe that CO and
other intermediate species are reduced by hydride hydrogen.
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When MoS2 is promoted with late d-metals (Fe,Co,Ni and similar metals), a
mixed MeMoS phase is formed. In this phase, promoter atoms substitute a part of
molybdenum atoms on the crystallite edges.[4] Promotion of the S-edge by single
Fe, Co or Ni atoms leads to the formation of (K)MeMoS sites that are not capable
of activating hydrogen and thus are inactive in the CO hydrogenation reaction.
Double sulfide vacancies (Scheme 1 b,c) form on the M-edge at MeMoS (Me = Fe,
Co, Ni) and KMeMoS (Me = Co, Ni) sites, which can participate in synthesis gas
conversion. We found that sulfur affinity of double vacancies on the M-edge of
KFeMoS sites was much higher than for Co and Ni analogs.[22] All the (Me)MoS2
catalysts show comparable activities. Addition of potassium completely inhibits
activity only for the FeMoS2 catalyst, slighly increases activity for the MeMoS2,
(Me=Co,Ni) catalysts and moderately decreases activity of MoS2 catalyst. We
suppose that activity of Fe,Co,Ni-promoted catalysts is defined by double
vacancies and similar structures.
When the oxide form of the MoS2 based catalyst is sulfided, potassium ions
build a complex with the sulfide phase.[42] The nature of the complex was not
established. Assumingly, potassium intercalates between MoS2 crystallite layers.[43]
Such intercalation is well known for bulk MoS2 and results in the interlayer gap
expansion according to XRD.[44] This increase was detected for a spent catalyst.[45]
using XRD. However, TEM data do not show this increase in another study.[46]
The formation of vacancies on MeMoS sites on the M-edge and their
properties can be understood using calculated formal oxidation states of edge
atoms and determining corresponding electron states. By a formal electron count,
metal atoms on the half-sulfided M-edge and at a single vacancy on the M-edge
have oxidation numbers +4.66 and +3.66, respectively. These numbers are not
typical for Fe-Ni. In double vacancies on MeMoS sites on the M-edge, the
calculated oxidation state of the central atom is only +2.66, which is within the
characteristic values for Fe and Co and occurs for Ni. Thus, double vacancies form
fairly easily on these sites. However, since the +3 oxidation state is fairly common
for Fe, the introduction of a small amount of electron density on the FeMoS slab is
enough to stabilize single vacancies of KFeMoS sites on the M-edge.
In contrast, Ni in a double vacancy on the M-edge has the oxidation state
+2.66, and the electron density donation can, at best, reduce it to the +2 oxidation
state, which is characteristic for this metal. Furthermore, it is especially stable in
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10.1002/cctc.201901698
ChemCattChheemsquare planar coordination which is highly common for metal atoms with the d8
electron configuration. Further reduction is impeded because electrons then would
have to go into the high-energy orbital dx2-y2. In this state, the Ni atom only weakly
binds the fifth ligand, if at all, and Mo atoms of the double vacancy of KNiMoS
sites should bind CO stronger than Ni atoms of those sites. The high activity
observed for the KNiMoS catalyst and its unusual temperature dependence of
conversion suggest that its apparent conversion rate is limited by a process
different from that in the other catalysts, probably due to greatly enhanced
desorption.
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In terms of properties, CoMoS sites on the M-edge rank between FeMoS and
NiMoS. No sulfides of Co(III) are known. The closest compound is Co3S4 which at
best can be described as mixed Co(II,III) sulfide. In contrast, Fe2S3 is known
though it is not the most stable Fe sulfide. For this reason, KCoMoS sites on the
M-edge exist in the form of active double vacancies under synthesis gas
conversion conditions although their Lewis acidity is greatly reduced in
comparison with CoMoS sites.
According to Ref.,[22] potassium modification of double vacancies of the M-
edge of FeMoS sites results in the sulfur affinity increase (by the [vac][vac] + H2S
= H2 + [vac][S] process) from ~0.7 eV to ~1.3 eV. Since the reaction energy
Ssurf + H2 = CUSsurf + H2S
is below 1.2 eV, the process is thermodynamically feasible,[47-50] so double
vacancies can form on FeMoS active sites on the M-edge though not on KFeMoS
active sites. In contrast, we found that affinity to sulfur for (K)NiMoS sites on the
M-edge was negative both for K-modified and K-free cases. CoMoS sites are
somewhere between in terms of properties, exhibiting negative sulfur affinity for
the CoMoS site and 0.8 eV for the KCoMoS site, still allowing the formation of
double vacancies.
From this we can suppose that synthesis gas conversion over the (K)MeMoS2
catalysts occurs on double vacancies on the M edge while the S-edge is not active.
In contrast, synthesis gas conversion with the (K)MoS2 catalyst is likely to occur
on the S-edge. For the MoS2 S-edge, each molybdenum atom has two coordination
vacancies whereas vacancies of neighboring atoms group in pairs (Scheme 1a).
Two coordination vacancies of one Mo atom on the 50% sulfided S-edge are
separated by sulfur atoms. Thus, molecules or intermediates adsorbed on them are
unlikely to interact with each other. On the other hand, each vacancy is close to a
similar vacancy on one neighboring Mo atom and adsorbates on the two
neighboring Mo-atoms can interact (Scheme 1bc). The qualitative distinction
between the active sites related to (K)MoS2 and (K)MeMoS2 results in a difference
in the chain growth factor between the (K)MoS2 and (K)MeMoS2 (Me=Co, Ni)
catalysts.
Modification by potassium leads to an increase in synthesis gas conversion on
both KNiMoS2 and KCoMoS2 catalysts. The increase in activity of KNiMoS2
correlates with the increase in stability of the Mo-H bond on NiMoS sites on the
M-edge shown in our earlier calculations.[22] The increased Mo-H bond energy is
likely to imply an increased Mo-CH3 bond energy. On the other hand, increased
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10.1002/cctc.201901698
ChemCataChcetmivity of the CoMoS2 catalyst correlates with the decrease in Mo-H and Co-CO
bond energies. KNiMoS2 has lower adsorption energies for CO and H as compared
to KCoMoS2, so we may conclude that the reaction rate in this case is determined
by desorption or another reaction involving a Ni-X bond scission. Meanwhile the
reaction rate on the K-free catalysts clearly correlates with bond energies and
Lewis acidity of double vacancies on the M-edge. It should be noted that
potassium addition almost completely suppresses the hydrocarbon formation on
KCoMoS and the KNiMoS sites in favor of alcohol formation.
Selectivity to products of syngas conversion is determined by the rate of
alkane elimination form alkyl intermediates and reactivity of aldehyde-type
intermediate (Scheme 2). Reactivity of an aldehyde-type intermediate depends on
polarization of C-O bond. Potassium addition to Mo-sulfide systems reduces metal
atoms. It, in its turn, decreases probability of C-O bond cleavage in adsorbed
intermediate on an active site and hinders reducing elimination of alkanes shifting
selectivity from alkyl to alkoxide fragments.
Analysis of the synthesis gas conversion products on the KCoMoS2/KNiMoS2
catalysts shows measurable amounts of C5 products with linear and branched
chains. The chain growth factor (α) on KCoMoS2 and KNiMoS2 is much higher
than on the other catalysts. Their high apparent activity is mostly due to greatly
enhanced chain growth. A possible explanation is that, since potassium addition
reduces metal atoms, it also leads to much higher nucleophilicity of alkyl and
hydride intermediates which should greatly enhance the CO insertion rate even if
CO is adsorbs only weakly. Hydrogenation/hydrodeoxygenation activity, on the
other hand, is significantly lowered, leading to lower production of hydrocarbons.
The consistent and gradual decrease of αi with increase of chain length was
observed for all the studied catalysts. M-Alk bond reactivity toward the CO
insertion is guarded by sterical factors. Thus, we can expect methyl and ethyl
intermidiates have very different reactivity, but fairly similar for ethyl and n-propyl
intermidiates, and even more so for n-propyl/n-butyl pair. On the other hand, CO
insertion rate into primary (like ethyl) and secondary (like i-propyl) alkyl
intermediates should be significantly different and, indeed, we found large
amounts of branched products. Thus, the gradual decrease of αi with increase of
chain length can be attributed to sterical hindered CO-insertion of branched alkyl
intermidiates
The branched products can form via isomerization of alkyl intermediates
through alkene intermediates. Alkene formation by beta-elimination in alkyl
intermediates has been well studied in organometallic chemistry and is known to
be reversible. Addition of ethylene into synthesis gas leads to a marked increase in
CO conversion, with formation of mostly C3-products.[29] Scheme 3 shows
equilibrium between n-propyl and iso-propyl fragments. Alcohols containing iso-
propyl fragments were detected among other products (Fig. 6). The fraction of iso-
products was higher over the KCoMoS2 catalyst than over KNiMoS2, i.e.
isomerization of the alkyl fragment proceeded faster over the KCoMoS2 catalyst.
Secondary alcohol formation cannot be explained by given mechanism
because alcohol formation via the CO insertion can only produce primary alcohols.
This article is protected by copyright. All rights reserved.
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10.1002/cctc.201901698
ChemCatTChhemis assumes co-elimination of alkyl- and aldehyde-type intermediates (Scheme
4). Coupling of C2-fragments was earlier observed in ethanol conversion
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experiments with 13C labels.[51]
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At least two factors could cause low selectivity toward HC on the
KCoMoS2/KNiMoS2/KMoS2: potassium addition could stabilize alkyl
intermediates, preventing desorption of alkanes, or the enhanced CO insertion rate
could promote transformation of alkyl intermediates before they desorb.
Suppression of the hydrodeoxygenation capability per se clearly does not play a
role, because the CO bond scission is necessary for chain growth.
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5. Conclusions
The influence of the promoter nature and the presence of potassium in the
(K)MeMoS2/Al2O3 catalysts on conversion and selectivity of the products of
synthesis gas conversion to alcohols and other oxygenates was studied.
In synthesis gas conversion over the MeMoS2 catalysts, the potassium additive
is a promotor for CoMoS2 and NiMoS2, but an inhibitor for MoS2 and especially
for FeMoS2.
Addition of potassium to molybdenum sulfide systems reduces metal atoms of
the catalyst. Modification by potassium increases the CO molecule introduction
into the metal-carbon bond of the surface alkyl intermediate. Potassium decreases
oxophilicity of Mo atoms by reducing them.
The presence of secondary alcohols in the products indicates co-elimination of
the carbon-containing intermediates. The presence of branched-chain products
indicates isomerization of alkyl C4+ intermediates.
It has been supposed that synthesis gas conversion can occur either on the non-
promoted S-edge of the (K)MoS2 catalysts or on multiple vacancies on the M-edge
of the (K)MeMoS2 catalyst. Promotion of the S-edge by Fe, Co or Ni suppresses
hydrogen activation, which results in lower synthesis gas conversion. Promotion of
the M-edge by Fe, Co or Ni leads to the formation of double vacancies which are
active sites of synthesis gas conversion.
Acknowledgement
The study was supported by the RFBR grant № 19-53-60002.
Authors thank Dr. D. Krivoruchenko and R. Boldushevskii for XRF analysis of the
catalyst samples.
Conflict of Interest
The authors declare no conflict of interest.
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10.1002/cctc.201901698
ChemCatKCheemywords: Higher alcohol synthesis • Synthesis gas conversion • K-modified
MeMoS2 catalysts • FeMoS2 • CoMoS2 • NiMoS2
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10.1002/cctc.201901698
ChemCatTChaemble 1
Surface area and pore size analysis results
Specific
1
2
3
4
5
6
7
Pore
Catalyst
surface area, volume,
Pore diameter*, nm
m2/g
cm3/g
8
9
Al2O3
171.2
114.5
131.0
122.6
126.9
79.3
0.64
0.44
0.38
0.34
0.37
0.35
0.28
0.28
0.31
4.5 and 14.9
3.7 and 16.1
3.7 and 16.0
3.9 and 14.9
3.8 and 17.4
3.9 and 15.0
3.8 and 16.0
3.7 and 15.0
3.7 and 14.5
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
MoS2/Al2O3
FeMoS2/Al2O3
CoMoS2/ Al2O3
NiMoS2/ Al2O3
KMoS2/ Al2O3
KFeMoS2/ Al2O3
KCoMoS2/ Al2O3
KNiMoS2/ Al2O3
69.6
77.4
85.7
* – bimodal pore diameter distribution.
Table 2
Results of elemental analysis of catalysts by XRF
Content, wt %
Catalyst
Ratio
Mo
Me
K
t**
r*
MoS2/Al2O3
12.2
10.9
11.1
12.8
12.5
12.8
12.6
14.3
—
—
—
—
FeMoS2/Al2O3
CoMoS2/Al2O3
NiMoS2/Al2O3
KMoS2/Al2O3
KFeMoS2/Al2O3
KCoMoS2/Al2O3
KNiMoS2/Al2O3
2.1
2.9
3.1
—
—
—
0.25
0.30
0.28
—
—
—
—
—
10.4
9.3
8.1
10.2
0.83
0.62
0.64
0.71
2.1
2.8
3.1
0.22
0.27
0.26
*) r = Me/(Me+Mo), molar ratio
**) t=K/(Me+Mo), molar ratio
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10.1002/cctc.201901698
ChemCatChem
Table 3
1
2
Synthesis gas conversion on (K)(Me)MoS2 catalysts and product selectivity (at 340
3
4
°С, P=5.0 MPa)
5
6
7
8
Catalyst
MoS2 FeMoS2 CoMoS2 NiMoS2
Conversion %
KMoS2
20.2
KFeMoS2 KCoMoS2 KNiMoS2
9
63.0
24.1
14.6
11.5
5.6
20.4
15.1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
Selectivity, %
CO2
46.9
26.8
14.4
7.3
46.0
12.9
17.5
10.2
6.4
49.6
16.6
18.5
6.9
52.7
12.1
18.5
8.9
29.5
8.1
9.1
0.0
0.0
21.7
10.8
9.9
3.2
0.0
3.5
2.5
1.6
0.0
48.0
11.2
8.7
28.3
7.8
2.1
0.7
0.0
6.5
16.5
16.2
6.2
2.8
0.6
7.6
1.1
3.6
25.8
4.6
0.0
0.0
0.0
3.8
17.5
21.2
8.7
3.9
0.9
8.0
1.7
3.7
CH4
C2H6
C3H8
0.0
C4H10
2.4
0.0
0.0
0.0
MeOH
EtOH
PrOH-1
BuOH-1
AmOH-1
PrOH-2
i-BuOH
BuOH-2
i-AmOH
2.2
8.5
7.8
32.2
7.0
Table 4.
Influence of the promotor nature on the liquid products yield (at 340 °С, P=5.0 MPa)
Liquid products (LP)
Effect of promoter
yield, %
Catalyst
addition on LP yield*
K-free
1.4
K
(K)MoS2/Al2O3
10.8
1.8
7.9
1.1
(K)FeMoS2/Al2O3
(K)CoMoS2/Al2O3
(K)NiMoS2/Al2O3
1.7
1.2
12.5
10.5
10.1
11.8
0.9
*) Ratio of LP yields on the K-modified catalysts to LP yields on the K-free
catalysts. LP – liquid products.
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10.1002/cctc.201901698
ChemCatChem
1
2
3
4
5
6
7
8
20
18
16
14
12
10
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
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40
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
MoS
MoS2
FeMoS
FeMoS2
6
4
CoMoS
CoMoS2
2
Ni
NiMoS2
0
300
320
340
360
Temperature, ͦ C
Fig. 1. Specific conversion of synthesis gas over the potassium-unmodified
(Me)MoS2 catalysts where Me = Fe, Co, Ni for different temperatures. Reaction
conditions: T = 300-360 °С, P = 5.0 MPa, synthesis gas flow rate 760 l•h-1•(kgcat)-1,
catalyst loading 3 grams, synthesis gas composition: CO:H2:Ar = 45:45:10.
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10.1002/cctc.201901698
ChemCatChem
1
2
3
4
5
6
7
8
20
18
16
14
12
10
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
KMoS2
KFeMoS2
6
4
KCoMoS2
2
KNiMoS2
0
300
320
340
360
Temperature,
ͦ C
Fig. 2. Specific conversion of synthesis gas over the potassium-modified
(Me)MoS2 catalysts where Me = Fe, Co, Ni for different temperatures. For reaction
conditions see Fig. 1.
60
K-free
50
K-modified
40
30
20
10
0
(K)MoS2
(K)FeMoS2
(K)CoMoS2
(K)NiMoS2
Fig. 3. Selectivity to methane at 340 °С. For detail reaction conditions see Fig. 1.
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10.1002/cctc.201901698
ChemCatChem
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
7
8
9
K-free
K-modified
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
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46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
(K)MoS2
(K)FeMoS2
(K)CoMoS2
(K)NiMoS2
Fig. 4. Selectivity to С2+ hydrocarbons at 340 °С. For detail reaction conditions see
Fig. 1.
100
K-free
90
80
70
60
50
40
30
20
10
0
K-modified
(K)MoS2
(K)FeMoS2
(K)CoMoS2
(K)NiMoS2
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10.1002/cctc.201901698
ChemCatChem
Fig. 5. Selectivity to liquid products (LP) at 340 °С. For detail reaction conditions
see Fig. 1.
1
2
3
4
5
35
6
7
8
9
KMoS /Al O
2O3
/
2
30
25
20
15
10
5
2
3
KCoMoS /Al O
KCoMoS2/Al2O3
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
KNiMoS /Al O
2O3
o
2
2
3
0
MeOH
EtOH
PrOH-1
PrOH-2
BuOH-1
i-BuOH
BuOH-2
AmOH-1
i-AmOH
Fig. 6. Comparison of selectivity to various alcohols formed on KMoS2/Al2O3,
KCoMoS/Al2O3 and KNiMoS/Al2O3 at 340 °С. For detail reaction conditions see
Fig. 1.
14
12
B
C
12
Co
Ni
10
8
10
8
6
6
4
4
2
2
Fe
0
0
0.35
0.00
0.05
0.10
0.15
0.20
0.25
0.30
r = Me/(Me+Mo), at. ratio
Fig. 7. Dependences of the liquid products yield and of efficiency of the
potassium additive effect on the liquid products yield from the
molybdenum promotion degree by iron, nickel or cobalt (r).
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10.1002/cctc.201901698
ChemCatChem
Chain growth factor α
1
2
3
4
5
6
7
8
9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
i=1
i=2
i=3
i=4
NiMoS2
CoMoS2
FeMoS2
MoS2
Fig. 8. Chain growth factors αi for the steps i=1, 2, 3, 4 over the (Me)MoS2
catalysts (Me = Fe, Co and Ni). For reaction conditions see Fig. 1.
Chain growth factor α
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
i=1
i=2
i=3
i=4
KNiMoS2
KCoMoS2
KFeMoS2
KMoS2
Fig. 9. Chain growth factors αi for the steps i=1, 2, 3, 4 over the
K(Me)MoS2 catalysts (Me = Fe, Co and Ni). For reaction conditions see
Fig. 1.
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10.1002/cctc.201901698
ChemCatChem
S
S
S
S
S
Mo
Mo
Mo
1
2
3
S
S
S
S
S
(a)
4
5
6
7
8
9
S
S
S
S
S
S
S
S
S
S
S
S
S
S
Mo
Me
Mo
=
Mo
Me
(c)
Mo
S
S
S
S
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
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48
49
50
51
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59
60
61
62
63
64
65
S
S
(b)
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
Mo
S
S
Me
(d)
Mo
=
Mo
Me
(e)
Mo
S
S
S
S
S
Scheme 1: Structure of the active site of the molybdenum sulfide catalyst with
vacancies on molybdenum atoms. Coordination vacancies are denoted with empty
squares. (а) Active site (non-promoted) on the S-edge, front view. (b) Active site
(Me=Mo, Fe, Co, Ni) on the M-edge, side view. (c) Me-promoted active site (M-
edge) with a double vacancy, top view. (d) Active site (Me=Mo, Fe, Co, Ni) on the
M-edge, side view. (e) Me-promoted active site (M-edge) with a single vacancy,
top view.
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10.1002/cctc.201901698
ChemCatChem
H
O
CO+H2
CH4
H CO
(1)
CH3OH
1
2
3
(2)
[H]
4
5
6
7
8
H3C
[H]
[H], -H2O
H
O
H2C O
[H]
H3C
H3C H
(6)
9
(4)
(5)
CO
(3)
H3C
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
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48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
H3C
CH2
OH
H3C CO
CO
CH3
CH3
(7)
(8)
[H]
CH3
H3C
[H], -H2O
H3C
H2C
H3C
[H]
H
CH O
CH2
O
CH2
H
(9)
(11)
(12)
(10)
CH3
H2C
CO
CH3
CH2
H2C CH2
H
CO
CO
C3+
(13)
(14)
Scheme 2: Reaction pathways of synthesis gas conversion over the molybdenum
sulfide catalysts.
H3C
H3C
H2C
HO
H3C
CH CH
H2C
CH CH2
H
CH3
H2C
CH2
CH2
H3C CH3
CH
CH2
OH
(a)
(b)
i-butanol
n-butanol
Scheme 3: Equilibrium of adsorbed alkenes and alkyl intermediates. Formation of
products with the normal and branched carbon chain.
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10.1002/cctc.201901698
ChemCatChem
1
2
3
H3C
H3C
CH O
CH2
H3C
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
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30
31
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34
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39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
H3C
CH3
H3C
CH2
CH
CH
OH
CH3
OH
iso-PrOH
sec-BuOH
Scheme 4. Secondary alcohol formation pathway by co-elimination of aldehyde
and alkyl type intermediates.
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