Conversion of Ethanol via C-C Splitting on Noble Metal Surfaces in Roomerature Liquid-Phase

Article abstract of DOI:10.1021/jacs.8b13115

Rh-catalyzed decomposition of ethanol into CO₂ and CH₄ via C-C bond splitting is reported in roomerature liquid phase under atmospheric pressure. Mechanistic investigations show that C-C bond splitting of ethanol on the noble metal s

Full text of DOI:10.1021/jacs.8b13115

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Communication
Conversion of Ethanol via C-C Splitting on Noble
Metal Surfaces in Room-temperature Liquid-phase
Guangxing Yang, Lida Farsi, Yuhan Mei, Xing Xu, Anyin Li, N. Aaron Deskins, and Xiaowei Teng
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b13115 • Publication Date (Web): 31 May 2019
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Conversion of Ethanol via C-C Splitting on Noble Metal Surfaces in
Room-temperature Liquid-phase
Guangxing Yang,‡,€ Lida Farsi £, Yuhan Mei£, Xing Xu¥, Anyin Li¥, N. Aaron Deskins£, and Xiaowei Teng*,‡
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‡Department of Chemical Engineering, University of New Hampshire, Durham, New Hampshire 03824, United States
€School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong 510640, China
£Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester, Massachusetts 01609, United States
¥Department of Chemistry, University of New Hampshire, Durham, New Hampshire 03824, United States
Supporting Information Placeholder
what are the reaction pathways for the complete dissociation of
ethanol are still under debate. This may be attributed to the
complexity of the reaction environment that involves ethanol, water
and/or oxygen gas. We envisioned that considering ethanol
conversion on the surface of noble metal nanoparticles without the
presence of water and oxygen, a much less complicated system,
would possibly unravel the reaction pathways and clarify the rate
determining step of liquid phase ethanol conversion.
ABSTRACT: Rh-catalyzed decomposition of ethanol into CO2
and CH4 via C-C bond splitting is reported in room-temperature
liquid phase under atmospheric pressure. Mechanistic
investigations show that C-C bond splitting of ethanol on the noble
metal surface is rapid, and CO2 forms through the oxidation of α-
CHxO and β-CHx fragments after C-C bond splitting, while CH4
forms through the hydrogenation of β-CHx utilizing H atoms from
-OH, β-CHx and α-CHxOH fragments.
It is known that during PtRh-based catalysts are active for
electrochemical conversion of ethanol via C-C bond splitting,
where the Rh plays a critical role in promoting β-hydrogenation of
ethanol, and thus decreasing the energy barrier of C-C splitting with
a decreased onset potential for CO2 generation.23-24 Based on the
success of Rh for the electrochemical conversion of ethanol, we
hypothesize that Rh nanoparticles could be used as catalysts for
complete decomposition of ethanol to C1 species via C-C splitting
without water and/or oxygen gas. Notably, there are no reports of
complete splitting the C-C bond of ethanol using Rh or any other
noble metal catalysts in room-temperature liquid-phase without an
electrical field.
Activation and splitting C-C bond is an important step in the
conversion of primary alcohols especially ethanol for producing
hydrogen via catalytic process or electricity via 12-electron-
transfer electrochemical process. However, these processes are
mostly conducted in high vacuum (~10-7 Pa) or high temperature
(> 550 oC) gas phase, high pressure/temperature liquid phase, or in
electrochemical systems.1-10 There are considerable efforts on
liquid-phase conversion of alcohols at mild conditions since the
explorative work by Cole-Hamilton.11-12 Beller’s group developed
molecular complexes to decompose methanol into CO2 and H2 at
low temperatures (65-95 oC) under ambient pressure.13-15 Intensive
efforts have been devoted to developing heterogeneous catalysts
for ethanol dissociation in the liquid-phase in the presence of water
and/or oxygen gas. Christensen et al reported the oxidation of
ethanol into acetic acid using Au catalysts at 100-200 °C with
oxygen gas.16-17 Sapi et al reported that with oxygen at 60 °C Pt
nanoparticles (2 to 6 nm) were able to catalyze the C-C bond
splitting of ethanol to form CO2, while acetaldehyde (CH3CHO)
was still the main product.18
To investigate the feasibility of our hypothesis, we studied the
decomposition of liquid ethanol at room temperature using carbon
supported Rh nanoparticles with an average size of 2.1 + 0.5 nm
(Figure S1). Carbon was chosen as the support since it was inert
towards ethanol decomposition (Figure S2). The reaction was
carried in a batch reactor under an argon atmosphere at 25 °C
atmospheric pressure. Gas phase products were drawn from the
reactor headspace and analyzed by GC-MS, where rapid production
of CH4 and CO2 was observed in the first 30 minutes of the reaction
with initial turnover frequencies of 68.6 and 8.7 h-1, respectively
(Figure 1a and Figure S3). After that, only minor gas product was
observed, indicating the quick deactivation of the catalyst. The
deactivated catalyst can be easily regenerated (see Supporting
Information). The CH4 and CO2 generation remained constant and
the Rh catalysts remained unchanged after five cycles of
regeneration (Figure S1d and S4). An online membrane inlet mass
spectrometer (MIMS) was used to detect liquid-phase products on
the surfaces of the catalysts (Figure 1c), showing various chemicals
with different mass to charge (m/z) ratios such as acetic acid,
acetaldehyde, carbon dioxide, methane, and hydrogen. It is notable
that an ethanol and water mixture was used for the MIMS
measurement due to poor stability of the membrane in pure ethanol.
Extensive theoretical work has also been carried out studying
ethanol dissociation in the presence of water on various noble metal
surfaces with mixed understanding of the reaction pathways. Some
work suggested that ethanol decomposition was limited by the C-C
bond splitting on Pt (111) surface10, 19, while the dehydrogenation
of β-C-H bond of ethanol became the rate determining step on the
Rh (111) surface20. Hu’s group studied ethanol decomposition on
various platinum-group-metal surfaces and concluded that ethanol
decomposition was not limited by C-C splitting or
dehydrogenation, but instead by the removal of *CO species that
were the reaction intermediates after C-C splitting. Among all the
catalysts studied, the Pt (111) surface was found to be the best
catalyst for the formation of CO2.21-22
Despite the significant progress in understanding ethanol
conversion in aqueous phase, what is the rate determining step and
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Figure 1. Liquid phase conversion of ethanol using Rh/C catalyst. (a) CO2 and CH4 generation. (b, c) liquid-phase product analysis using
online MIMS.
CH313CH2OH was used to determine the origin of the C atoms in the
formation of the final products. Table 1 shows one form of CH4
A mass spectrometer coupled with electrospray ionization was
(12CH4) and two forms of CO2 (54% 12CO2 and 46% 13CO2)
used to analyze acetaldehyde and acetic acid (Figure S5-S9).
detected (Figure S14), suggesting that α- and β-carbons equally
contributed to the CO2 formation. Since two oxygen atoms must
Acetaldehyde was derivatized and detected with intensities not
significantly higher (2.25 ppm) than the blank ethanol solutions
come from separate ethanol molecules, this result indicated an
(Table S1). Acetic acid was detected in the negative mode with
inter-molecular reaction during ethanol decomposition. Moreover,
intensities not significantly higher than the blank ethanol solutions.
Similarly, only trace amount of hydrogen gas was detected by
MIMS, while GC-MS analysis showed that the most predominant
products during reaction were CH4 and CO2 (Figure S10). Our
results suggest nearly complete dissociation of ethanol via C-C
splitting.
the absence of 13CH4 indicated that hydrogenation of α-CHX to CH4
is unlikely (although α-C-O bond cleavage must occur in order to
provide oxygen atoms for CO2 formation) and only β-CHX
participates in the formation of CH4. However, it is possible that
some α-13C fragments might exist on catalyst surface and/or in the
solution in the forms of C2 (acetic acid and/or acetaldehyde) and
C1 product (*CHO) due to the incomplete ethanol conversion.
Table 1. C-C splitting of 13C and D-labeled ethanol a
CH313CH2OH  CH4 + 13CO2 + CO2
CH3CH2ODCH3D +CO2
CD3CH2OHCD3H +CD4 + CD2H2 +CO2
CD3CD2OD + CH3CH2OH  CH4 + CD4+CH3D + CHD3 + CH2D2
Eq. 1
Eq. 2
Eq. 3
Eq. 4
Products
Isotope-labeled Reactants
(%)
CH313CH2OH
CH3CH2OD
CD3CH2OH
CD3CD2OD
CH3CH2OH
Figure 2. (a) In situ ATR-FTIR spectra during the ethanol decomposition.
The peak assignment can be found in Figure S5 and Table S2. (b) Integrated
absorbance of ethanol, *COH residue, acetic acid or acetaldehyde, and
*OCO stretching as functions of reaction time.
12CO2
13CO2
13CH4
CH4
54.0
~ 100
100
100
/
46.0
/
/
/
/
/
/
In situ attenuated total reflection-Fourier transform infrared
spectroscopy (ATR-FTIR) was used to examine the species formed
on Rh surface during the reaction (Figure 2a and Figure S11). The
*COH residue (1262 cm-1) confirmed the complete C-C bond
splitting, and the negative-going peaks at 1050 cm-1 and 1090 cm-1
can be assigned to ethanol consumption. The formation of
acetaldehyde and acetic acid was confirmed by the C=O stretching
(1714 cm-1 and 1639 cm-1),25 and the *OCO stretching (1404 cm-1)
from the adsorbed acetate via two oxygen atoms touching the Rh
surface.26 Figure 2b shows the time-resolved integrated
absorbance, showing a fast consumption of ethanol and rapid
accumulations of products from complete (*COH residue) and
incomplete (acetate, acetaldehyde or acetic acid) processes. The
accumulation of *COH in Figure 2b showed a similar line shape
with the generation of CH4 and CO2 in Figure 1a, suggesting that
*COH could block the surface and lead to catalysts deactivation.
This indicates that C-C bond splitting on the Rh surface is rapid,
while the removal of C1 species from the catalyst surface seems
sluggish. Notably, *CHx residues (2950 cm-1) were also observed
(Figure S12), possibly resulting from C-O and C-C cleavages.
~100
94.4
/
69.9
8.2
3.9
8.2
9.9
CH3D
CH2D2
CHD3
CD4
/
/
/
/
5.6
/
/
/
/
18.0
71.8
10.1
a 10 mg Rh/C catalysts (10wt % Rh), 0.3 mL isotope-labeled ethanol, 25 °C
and normal atmospheric pressure, 1 h reaction under magnetic stirring.
To understand CH4 formation, three types ethanol reagents
(CH3CH2OD, CD3CH2OH and CD3CD2OD) were used to
determine the partition of H atoms from hydroxyl (-OH),
methanediyl (-CH2-) and methyl (-CH3) groups. Table 1 shows that
the decomposition of CH3CH2OD yielded CH4 (94.4%) and CH3D
(5.6%). Fewer CH3D suggested that formation of CH4 via
combining a methyl group (-CH3) with a D atom from an -OD
group is less favorable. We postulate that though O-H cleavage is
facile (as DFT calculations show in Figure 3), H from -CH2-
dehydrogenation is also facile and more available for *CH3 to
produce CH4. This argument is also supported by isotope
We also studied the decomposition of isotope-labeled ethanol to
understand the reaction pathways proposed in Figure S13. First,
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experiments, which indicated a very dynamic H movement even
where Au and Ag have much higher reaction energy for C-C
splitting and are inactive for ethanol decomposition.
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between inter-molecular C-H fragments. Therefore, after the C-C
bond is cleaved, the resulting -CH3 group quickly combines with
an H atom from CHx fragments to form CH4.27 The decomposition
of CD3CH2OH yielded CD4, CD3H and CH2D2 (Figure S15). The
major form of methane was CD3H, suggesting that combining a -
CH3 group with an H atom from -CH2- group is favorable, since an
H atom from the -OH group made a minor contribution to CH4
formation. A relatively large amount of CH2D2 (18%) was
observed, implying that a -CH3 moiety easily dehydrogenated and
recombined with an H atom from the -CH2- group to form CH4
since β-carbon from the -CD3 group is the only source of CH4.
Formation of CD4 suggested that a -CD3 moiety can combine with
a D atom from the -CD3 of a neighboring ethanol, direct evidence
of an inter-molecular reaction. When equal amounts of CD3CD2OD
and CH3CH2OH were used, all forms of methane were detected
(Table 1), again suggesting an inter-molecular reaction. The high
concentration of CH4 compared to CD4 indicates that the
deuteration of the methane produces a primary kinetic isotope
effect (kH/kD = 69.9%/9.9% = 7),28 where CH4 formation is limited
by the combination between –CH3 and the H atom from –CH2-
moiety.
In summary, we report room-temperature liquid-phase
conversion of ethanol into CH4 and CO2 via C-C bond splitting.
Reported results are different from reforming process,1, 6, 8 where
ethanol and water can be easily activated at high
temperature/pressure for H2 and CO2 productions. The reaction
pathways were studied using isotope-labeled ethanol. DFT
calculations in vacuum and liquid conditions suggested that C-C
bond splitting remains mechanistically difficult, but that the
reaction energy for C-C breaking is lowered in liquid compared to
vacuum. This study provides the understanding of breaking C-C
bonds in alcohols or other hydrocarbons via room-temperature
liquid-phase reaction using noble metal nanocatalysts.
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ASSOCIATED CONTENT
Supporting Information
Material synthesis/characterization and DFT calculations are
presented in the Supporting Information. The Supporting
Information is available free of charge on the ACS Publications
website.
AUTHOR INFORMATION
Corresponding Author
xw.teng@unh.edu.
ACKNOWLEDGMENT
This work was supported by the National Science Foundation
(CBET–1159662). Research conducted at the Advanced Photon
Source at the Argonne National laboratory and Center for
Functional Nanomaterials at Brookhaven National Laboratory was
sponsored by the U.S. Department of Energy.
Figure 3. DFT calculations conducted in (a) vacuum and (b) liquid ethanol
for the ethanol decomposition. Blue numbers are reaction energies and red
number are activation energies (all in eV).
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Figure 3 shows the DFT calculations of catalytic cycles for
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51
52
53
54
55
56
57
58
59
60
5
ACS Paragon Plus Environment