H2-Free Selective Dehydroxymethylation of Primary Alcohols over Palladium Nanoparticle Catalysts

Article abstract of DOI:10.1002/cctc.202001866

The dehydroxymethylation of primary alcohols is a promising strategy to transform biomass-derived oxygenates into hydrocarbon fuels. In this study, a novel, highly efficient, and reusable heterogeneous catalyst system was established for the H₂-free dehydroxymethylation of primary alcohol using cerium oxide-supported palladium nanoparticles (Pd/CeO₂). A wide range of aliphatic and aromatic alcohols including biomass-derived alcohols were converted into the corresponding one-carbon shorter hydrocarbons in high yields in the absence of any additives, accompanied by the production of H₂ and CO. Pd/CeO₂ was easily recovered from the reaction mixture and reused, retaining its high activity, thus, providing a simple and sustainable methodology to produce hydrocarbon fuels from biomass-derived oxygenates.

Full text of DOI:10.1002/cctc.202001866

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: H2-Free Selective Dehydroxymethylation of Primary Alcohols
over Palladium Nanoparticle Catalysts
Authors: Sho Yamaguchi, Hiroki Kondo, Kohei Uesugi, Katsumasa
Sakoda, Koichiro Jitsukawa, Takato Mitsudome, and Tomoo
Mizugaki
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.202001866
Link to VoR: https://doi.org/10.1002/cctc.202001866
01/2020

10.1002/cctc.202001866
ChemCatChem
COMMUNICATION
H2-Free Selective Dehydroxymethylation of Primary Alcohols over
Palladium Nanoparticle Catalysts
Sho Yamaguchi,[a] Hiroki Kondo,[a] Kohei Uesugi,[a] Katsumasa Sakoda,[a] Koichiro Jitsukawa,[a] Takato
Mitsudome,[a] and Tomoo Mizugaki*[a]
[a]
S. Yamaguchi, H. Kondo, K. Uesugi, K. Sakoda, K. Jitsukawa, T. Mitsudome, T. Mizugaki
Department of Materials Engineering Science, Graduate School of Engineering Science
Osaka University
1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
E-mail: mizugaki@cheng.es.osaka-u.ac.jp
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: The dehydroxymethylation of primary alcohols is
a
require additives or poisonous phosphine ligands, which severely
restrict their industrial application. Alternatively, heterogeneous
Ni-kieselguhr or supported Ru catalysts were reported that show
activity for the DHM of primary alcohols.[8] However, these catalyst
systems inevitably require H2 to remove in-situ-generated CO that
strongly adsorbs on the active metal surface. Consequently, the
development of highly active and reusable heterogeneous
catalysts for the H2-free DHM reaction has not yet been realized.
This is an important goal for practical reasons and in view of a
sustainable green chemistry. Therefore, this paper reports a novel,
highly efficient, and reusable heterogeneous catalyst system for
the H2-free DHM of primary alcohols (Scheme 1). A cerium oxide-
supported palladium nanoparticle catalyst (Pd/CeO2) exhibited
high activity for the H2-free selective DHM reaction of various
alcohols to the corresponding hydrocarbons in the absence of any
additives, even in air, co-producing CO and H2. Moreover,
Pd/CeO2 was reusable, retaining its original activity and selectivity.
Pd/CeO2 and other supported catalysts were prepared by
impregnation method (see Supporting Information for details).
The obtained heterogeneous catalysts were evaluated using
DHM to synthesize hydrocarbons, applying 1-decanol as a model
compound of biomass-derived primary alcohols.[9] The results are
summarized in Table 1. When 1-decanol was added to n-hexane
in the presence of Pd/CeO2 and heated to 180 °C in an air
atmosphere, DHM generated n-nonane (1) in 84% yield with small
amounts of ester 3 as a by-product (entry 1). The resulting gas
was analyzed by GC, and CO and H2 were observed as major
promising strategy to transform biomass-derived oxygenates into
hydrocarbon fuels. In this study, a novel, highly efficient, and reusable
heterogeneous catalyst system was established for the H2-free
dehydroxymethylation of primary alcohol using cerium oxide-
supported palladium nanoparticles (Pd/CeO2). A wide range of
aliphatic and aromatic alcohols including biomass-derived alcohols
were converted into the corresponding one-carbon shorter
hydrocarbons in high yields in the absence of any additives,
accompanied by the production of H2 and CO. Pd/CeO2 was easily
recovered from the reaction mixture and reused, retaining its high
activity, thus, providing a simple and sustainable methodology to
produce hydrocarbon fuels from biomass-derived oxygenates.
The significant quantities of fossil fuels currently being used
worldwide and their associated CO2 emissions have led to a
significant interest in a key technology to realize the “biorefinery”
concept for the production of chemicals and fuels from biomass.[1]
Due to the high oxygen content in biomass-derived carbon
resources, the development of efficient deoxygenation methods
to synthesize value-added chemicals is required. In this regard,
deoxygenation using H2, i.e. hydrodeoxygenation, is recognized
as a powerful method to remove high oxygen contents;
considerable efforts have been devoted to develop highly efficient
catalysts for hydrodeoxygenation.[2,3] For instance, the
hydrodeoxygenation of lignocellulosic biomass is the most
popular method to synthesize downstream products, such as
polyols, furan derivatives, and hydrocarbons. However, the
current H2-using biorefinery faces
a roadblock because
renewable chemicals are obtained, which consume the H2
produced from fossil resources.[4] Therefore, to establish a next-
generation biorefinery technology, it is necessary to develop
highly efficient deoxygenation methods that do not need H2.
Among
the
H2-free
deoxygenation
reactions,
dehydroxymethylation (DHM) is the most promising that converts
primary alcohols into one-carbon shorter hydrocarbons
concomitantly producing CO and H2, which can be utilized as
energy sources. H2-free DHM was achieved using several
homogeneous metal (Pd, Ru, and Ir) complexes. Maiti et al.
reported a Pd-catalyzed DHM reaction with Na2CO3 and 4 Å
molecular sieves as additives.[5] Madsen et al. described that Ru[6]
and Ir[7] catalyst complexes possessing phosphine ligands
showed DHM activity for aliphatic and aromatic primary alcohols.
Although these catalysts are active, they present serious
drawbacks with respect to recovery and reuse of the catalyst, and
Scheme 1. Dehydroxymethylation of primary alcohols into hydrocarbons.
1
This article is protected by copyright. All rights reserved.

10.1002/cctc.202001866
ChemCatChem
COMMUNICATION
Table 1. Dehydroxymethylation of 1-decanol using various catalysts.[a]
Table 2. Dehydroxymethylation of various primary alcohols using Pd/CeO2.[a]
Entry
1
Substrate
Product
Time [h]
Yield [%][b]
Entry
Catalyst
Conv.[%][b]
Yield [%][b]
5
5
84
78
1
2
3
2
1
Pd/CeO2
Pd/Al2O3
Pd/MgO
Pd/ZrO2
Pd/SiO2
Pd/C
>99
90
83
20
17
10
50
38
33
19
0
84
75
74
2
0
0
3
2
<1
0
3
18
12
18
24
5
87
69
85
86
88
97
95
85
74
92
3
0
4
4
0
0
5
0
0
0
5
6
<1
2
0
<1
28
8
6
7
Ir/CeO2
Pt/CeO2
Ru/CeO2
Rh/CeO2
0
8
<1
2
2
7
9
7
12
5
8
5
10
11
12[d]
<1
-
0
[c]
CeO2
-
-
9
5
Pd/CeO2
91
72
<1
4
10
11
12
13
5
[a] Reaction conditions: 1-decanol (1 mmol), cat (M: 3 mol%), n-hexane (3 mL).
[b] Conversion and yield were determined by GC-MS using an internal standard.
[c] 110 mg. [d] The reaction under Ar atmosphere.
12
5
constituents (Figure S3). The basic Al2O3 and MgO supports
provided moderate yields of 1 (entries 2 and 3), while the use of
ZrO2, SiO2, and active carbon-supported Pd catalysts did not
produce 1 (entries 4–6). Various metals such as Ir, Pt, Ru, and
Rh on CeO2 were tested next, resulting in a lower activity and
selectivity compared to Pd/CeO2 (entries 7–10). It was also
confirmed that the CeO2 support has no DHM activity (entry 11).
These results indicate that the combination of Pd and CeO2 is
crucial for the DHM of 1-decanol. Furthermore, Pd/CeO2
dehydroxymethylated 1-decanol to 1 in 72% yield under an Ar
atmosphere (entry 12). This is the first time that a heterogeneous
catalyst promoted the H2-free DHM of primary alcohols.
9
86
14
15
12
18
78
85
[a] Reaction conditions: Substrate (1 mmol), n-hexane (3 mL). [b] Determined
by GC-MS using an internal standard.
This Pd/CeO2 catalyst system was also applied to various
primary alcohols including biomass-derived ones (Table 2). The
biogenic aliphatic alcohols, 1-decanol and 1-octanol were
successfully deoxygenated, generating the corresponding one-
carbon shorter hydrocarbons in high yields (entries 1 and 2). 2-
Tetrahydrofurfuryl alcohol and furfuryl alcohol that were obtained
from furfural[10] provided tetrahydrofuran and furan in 87% and
69% yields, respectively (entries 3 and 4) without C−O bond
cleavage. 2-Phenoxyethanol, which is regarded as the simplest
lignin model (-O-4) structure, afforded anisole in 85% yield (entry
5). High tolerance of etheric C−O bond against the present DHM
system was further exemplified in the reaction of diethylene glycol
monomethyl ether, giving diethylene glycol dimethyl ether
selectively in 86% yield (entry 6). Several aromatic derivatives
were also converted into dehydroxymethylated products in
excellent yields, which was in sharp contrast with previously
reported heterogeneous catalysts requiring H2, where aromatic
rings were inevitably hydrogenated (entries 7–15).[8] These
results clearly proved the versatility of Pd/CeO2 and its suitability
for the H2-free DHM.
Scheme 2. New green route to ethylene glycol from biomass-derived glycerol.
The further application of this Pd/CeO2 catalyzed DHM
system was demonstrated, transforming biomass-derived
glycerol to ethylene glycol (EG)[11], which is a highly important
chemical currently produced by the consecutive oxidation and
2
This article is protected by copyright. All rights reserved.

10.1002/cctc.202001866
ChemCatChem
COMMUNICATION
hydration of ethylene as the petrochemical feedstock (Scheme
2).[12] First, glycerol was converted into solketal using acetone
catalyzed by titanium-exchanged montmorillonite (Ti4+-mont).[13]
Then, solketal was dehydroxymethylated over Pd/CeO2 to provide
the desired C−C cleavage product dimethyldioxolane (DMDO).
The obtained DMDO was treated in water with Ti4+-mont[14] to
afford EG with regeneration of acetone. This is a new synthetic
strategy to produce EG from biomass using heterogeneous
catalysts, providing a novel and sustainable green EG production
route that can replace conventional EG derived from fossil
resources.
The reusability of heterogeneous catalyst is one of the most
important advantages over homogeneous catalysts. The
reusability of Pd/CeO2 using 2-phenylethanol as a substrate was
also investigated. After the DHM reaction, the used Pd/CeO2 was
easily recovered from the reaction mixture by centrifugation and
then reused without any loss of catalytic activity after eight
recycling experiments (Figure 1). Inductively coupled plasma
atomic emission spectroscopy (ICP-AES) analysis of the fresh
and recovered catalyst showed the same amounts of Pd loading,
confirming that Pd leaching did not occur (Table S1). Furthermore,
the hot-filtration test of Pd/CeO2 as depicted in Figure S4 clearly
revealed that products were not formed under the reaction
conditions after removal of the Pd/CeO2 catalyst. These results
proved that the Pd/CeO2 catalyst has high durability and the DHM
reaction occurs heterogeneously.
To elucidate the reasons for the high Pd/CeO2 activity, the
local structure of Pd species on the CeO2 support was
characterized using X-ray absorption fine structure (XAFS)
analysis. Pd K-edge X-ray absorption near edge structure
(XANES) spectra of Pd/CeO2 before and after the reaction are
depicted in Figure 2a. The absorption edge energy in the Pd K-
edge XANES spectrum of the fresh Pd/CeO2 was similar to that
of PdO, suggesting that Pd species in Pd/CeO2 are present in the
2+ valence state. After the reaction, the absorption edge energy
of the Pd XANES spectrum was lower, similar to that of Pd foil,
thus indicating that the oxidation state of Pd changed to a zero
valence state. The Fourier transformation (FT) of the k3-weighted
Pd K-edge extended X-ray absorption fine structure (EXAFS)
spectrum of the Pd/CeO2 treated under reaction conditions
exhibits a peak at approximately 2.5 Å that is attributed to the
Pd−Pd shell (Figure 2b).[15] These XANES and EXAFS results
Figure 1. Pd/CeO2 reuse experiments in the DHM reaction of 2-phenylethanol
to toluene. Reaction conditions: 2-phenylethanol (1 mmol), n-hexane (3 mL)
suggest that Pd2+ on Pd/CeO2 is reduced during the reaction to
form Pd nanoparticles with 1-decanol as
a
reductant.[16]
Furthermore, Ce L3-edge XANES spectra of Pd/CeO2 before and
after the reaction are shown in Figure 2c. The absorption edge of
the Ce L3-edge XANES spectrum shifted toward lower energy,
similar to that of Ce2(CO3)3, indicating that the Ce4+ species
(CeO2) were partly reduced to Ce3+ (CeOx). This was
accompanied by the formation of oxygen vacancies.[17] These
XAFS results suggested that the Pd nanoparticle and partly
reduced CeOx are generated in-situ, which may play key roles
during DHM.
Based on the aforementioned unique catalytic performance
of Pd/CeO2 derived from the combination of Pd with CeO2, a
possible DHM reaction path converting primary alcohols through
the cooperative catalysis between Pd nanoparticles and CeO2 is
presented in Figure 3. First, Pd nanoparticles are formed by a
reduction with the alcohol substrate (I), and then surface oxygen
vacant (Ov) sites on CeOx are formed adjacent to Pd
nanoparticles. The primary alcohol adsorbs to the Ov sites,
facilitating the formation of a metal alcoholate species (II).[18]
Subsequently, the alcoholate undergoes a -elimination by the
adjacent Pd site to provide the corresponding aldehyde together
Figure 2. a) Pd K-edge XANES spectra of Pd/CeO2 catalysts and b) FT spectra of Pd K-edge EXAFS of Pd foil, PdO, fresh Pd/CeO2 and used Pd/CeO2. c) Ce L3-
edge XANES of Ce2(CO)3, CeO2, fresh Pd/CeO2 and used Pd/CeO2.
3
This article is protected by copyright. All rights reserved.

10.1002/cctc.202001866
ChemCatChem
COMMUNICATION
Keywords: dehydroxymethylation • hydrocarbon • primary
alcohol • palladium nanoparticle • cerium oxide
[1]
a) G. W. Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106, 4044; b) A.
J. Ragauskas, C. K. Williams, B. H. Davison, G. Britovsek, J. Cairney, C.
A. Eckert, W. J. Frederick Jr., J. P. Hallett, D. J. Leak, C. L. Liotta, J. R.
Mielenz, R. Murphy, R. Templer, T. Tschaplinski, Science 2006, 311,
484; c) J. N. Chheda, G. W. Huber, J. A. Dumesic, Angew. Chem. Int.
Ed. 2007, 46, 7164; d) P. A. Willems, Science 2009, 325, 707; e) R.
Rinaldi, F. Schìth, Energy Environ. Sci. 2009, 2, 610; f) D. M. Alonso, J.
Q. Bond, J. A. Dumesic, Green Chem. 2010, 12, 1493; g) S. De, B. Saha,
R. Luque, Bioresour. Technol. 2015, 178, 108. h) J.-P. Lange,
ChemSusChem 2018, 11, 997; i) G. M. Lari, G. Pastore, M. Haus, Y.
Ding, S. Papadokonstantakis, C. Mondelli, J. Perez-Ramirez, Energy
Environ. Sci. 2018, 11, 1012.
[2]
Recent reviews on hydrodeoxygenation of biomass-derived compounds:
a) Y. Nakagawa, S. Liu, M. Tamura, K. Tomishige, ChemSusChem 2015,
8, 1114; b) M. J. Gilkey, B. Xu, ACS Catal. 2016, 6, 1420; c) A. M.
Robinson, J. E. Hensley, J. W. Medlin, ACS Catal. 2016, 6, 5026; d) H.
Li, A. Riisager, S. Saravanamurugan, A. Pandey, R. S. Sangwan, S.
Yang, R. Luque, ACS Catal. 2018, 8, 148; e) S. Kim, E. E. Kwon, Y. T.
Kim, S. Jung, H. J. Kim, G. W. Hubere, J. Lee, Green Chem. 2019, 21,
3715; f) X. Jin, B. Yin, Q. Xia, T. Fang, J. Shen, L. Kuang, C. Yang,
ChemSusChem 2019, 12, 71; g) T. Mizugaki, K. Kaneda, Chem. Rec.
2019, 19, 1179. h) S. Dutta, ChemSusChem 2020, 13, 2894.
a) R. Arundhathi, T. Mizugaki, T. Mitsudome, K. Jitsukawa, K. Kaneda,
ChemSusChem 2013, 6, 1345; b) T. Urayama, T. Mitsudome, Z. Maeno,
T. Mizugaki, K. Jitsukawa, K. Kaneda, Chem. Lett. 2015, 44, 1062.
J. M. Ogden, Annual Review of Energy and the Environment 1999, 24,
227. (doi:10.1146/annurev.energy.24.1.227)
Figure 3. A schematic illustration of a possible reaction path for the DHM
reaction.
[3]
[4]
with H2 (III). Next, the consecutive oxidative addition occurs (IV),
and the decarbonylation of the aldehyde generates the desired
R−H and CO (V)[19], which completes the catalytic cycle. Overall,
Pd nanoparticles mitigate the dehydrogenation of the primary
alcohol and decarbonylation of the aldehyde. A partly reduced
CeOx promotes both the dehydrogenation and decarbonylation
through coordination at its Ov sites. Hence, such cooperative
catalysis between Pd nanoparticles and CeOx successfully
promotes the DHM of primary alcohols.
In conclusion, a highly efficient and reusable heterogeneous
Pd/CeO2 catalyst system for the H2-free DHM of primary alcohols
was established for the first time. A wide range of aliphatic and
aromatic alcohols including biomass-derived alcohols was
converted in the absence of any additives into the corresponding
one-carbon shorter hydrocarbons in moderate to excellent yields
(69–97%) with the co-production of CO and H2. The H2-free DHM
strategy made it possible to realize the green EG production from
glycerol and acetone. Characterization of the Pd/CeO2 catalyst
showed a cooperative catalysis between Pd and CeO2 for the
promotion of consecutive dehydrogenation and decarbonylation.
The high activity and reusability of Pd/CeO2 is of significant
importance to achieve a simple and clean synthetic method to
produce hydrocarbon fuels from biomass-derived oxygenates.
[5]
[6]
[7]
A. Modak, T. Naveen, D. Maiti, Chem. Commun. 2013, 49, 252.
A. Mazziotta, R. Madsen, Eur. J. Org. Chem. 2017, 5417.
a) E. P. K. Olsen, R. Madsen, Chem. Eur. J. 2012, 18, 16023; b) E. P. K.
Olsen, T. Singh, P. Harris, P. G. Andersson, R. Madsen, J. Am. Chem.
Soc. 2015, 137, 834.
[8]
a) V. N. Ipatieff; G. J. Czajkow, H. Pines, J. Am. Chem. Soc. 1951, 73,
4098; b) H. Pines, H. G. Rodbnberg, V. N. Ipatieff, J. Am. Chem. Soc.
1953, 77, 6065; c) H. Pines, H. G. Rodenberg, V. N. Ipatieff, J. Am. Chem.
Soc. 1954, 771; d) H. Pines, M. Shamaiengar, W. S. Postl, J. Am. Chem.
Soc. 1955, 77, 5099; e) M. Ishige, K. Sakai, M. Kawai, K. Hata, Bull.
Chem. Soc. Jpn. 1970, 43, 2186; f) L. Di, S. Yao, M. Li, G. Wu, W. Dai,
G. Wang, L. Li, N. Guan, ACS Catal. 2015, 5, 7199; g) T. Mizugaki, K.
Togo, Z. Maeno, T. Mitsudome, K. Jitsukawa, K. Kaneda, Sci. Rep. 2017,
7, 14007.
[9]
J. Falbe, H. Bahrmann, W. Lipps, D. Mayer, G. D. Frey, in ULLMANN'S
Encyclopedia
of
Industrial
Chemistry,
Wiley
2013,
DOI:
doi:10.1002/14356007.a01_279.pub2.
[10] a) R. V. Sharma, U. Das, R. Sammynaiken, A. K. Dalai, Applied Catalysis
A: General 2013, 454, 127; b) A. Mandalika, L. Qin, T. K. Sato, T. Runge,
Green Chem. 2014, 16, 2480; c) H. Guo, H. Zhang, L. Zhang, C. Wang,
F. Peng, Q. Huang, L. Xiong, C. Huang, X. Ouyang, X. Chen, X. Qiu, Ind.
Eng. Chem. Res. 2018, 57, 498; d) X. Meng, Y. Yang, L. Chen, M. Xu,
X. Zhang, M. Wei, ACS Catal. 2019, 9, 4226.
[11] a) P. N. R. Vennestrøm, C. M. Osmundsen, C. H. Christensen, E.
Taarning, Angew. Chem. Int. Ed. 2011, 50, 10502; b) K. Wagemann,
ChemBioEng Rev. 2015, 2, 315; c) K. Dong, S. Elangovan, R. Sang, A.
Spannenberg, R. Jackstell, K. Junge, Y. Li, M. Beller, Nat. Commun.
2016, 7, 12075; d) A. Satapathy, S. T. Gadge, B. M. Bhanage,
ChemSusChem 2017, 10, 1356.
Acknowledgements
This study was supported by JSPS KAKENHI (16K14479,
17H03456, 17H03457, 18H01790). T.M. thanks the Iwatani Naoji
Foundation’s Research Grant. The authors would like to thank Dr.
Tetsuo Honma and Dr. Toshiaki Ina (JASRI) for the XAFS
experiments (2017A1239, 2017A1820, 2017B1620, 2017B1155,
2017B1830 and 2018A1537). The TEM experiments were carried
out at a facility in the Research Center for Ultrahigh Voltage
Electron Microscopy, Osaka University.
[12] S. Rebsdat, D. Mayer, in ULLMANN'S Encyclopedia of Industrial
Chemistry, Wiley 2000, DOI: doi:10.1002/14356007.a01_101.
[13] T. Mitsudome, T. Matsuno, S. Sueoka, T. Mizugaki, K. Jitsukawa, K.
Kaneda, Heterocycles 2012, 84, 371.
[14] T. Kawabata, M. Kato, T. Mizugaki, K. Ebitani, K. Kaneda, Chem. Lett.
2003, 32, 648.
[15] The curve-fitting analysis of the Pd−Pd shell revealed that the
coordination number of the Pd−Pd shell was 6.3, indicating the formation
of Pd clusters having ca 1−2 nm diameter (Table S2).
4
This article is protected by copyright. All rights reserved.

10.1002/cctc.202001866
ChemCatChem
COMMUNICATION
[16] As shown in Table 1 entry 12, the desired DHM product was also
obtained in good yield under Ar atmosphere, indicating that 1-decanol
acts as a reductant of Pd2+ species.
[17] a) Y. Wang, F. Wang, Q. Song, Q. Xin, S. Xu, J. Xu, J. Am. Chem. Soc.
2013, 135, 1506; b) J. Li, Z. Zhang, W. Gao, S. Zhang, Y. Ma, Y. Qu,
ACS Appl. Mater. Interfaces 2016, 8, 22988.
[18] a) Z. Yan, A. Tomer, G. Perrussel, M. Ousmane, B. Katryniok, F.
Dumeignil, A. Ponchel, A. Liebens, M. Pera-Titus, ChemCatChem 2016,
8, 3347; b) M. Zhang, S. Wu, L. Bian, Q. Cao, W. Fang, Catal. Sci.
Technol. 2019, 9, 286.
[19] a) T. Ishida, K. Kume, K. Kinjo, T. Honma, K. Nakada, H. Ohashi, T.
Yokoyama, A Hamasaki, H. Murayama, Y. Izawa, M. Utsunomiya, M.
Tokunaga, ChemSusChem 2016, 9, 3441; b) T. Ishida, T. Honma, K.
Nakada, H. Murayama, T. Mamba, K. Kume, Y. Izawa, M. Utsunomiya,
M. Tokunaga, J. Catal. 2019, 374, 320; c) N. A. Diana, A. C. Reid, K.
Samudrala, K. Wilson, A. F. Lee, A. Voutchkova ‐ Kostal
ChemSusChem 2020, 13, 312.
5
This article is protected by copyright. All rights reserved.

10.1002/cctc.202001866
ChemCatChem
COMMUNICATION
Entry for the Table of Contents
A novel, highly efficient and reusable heterogeneous catalyst for the H2-free dehydroxymethylation of primary alcohols was established
using CeO2-supported palladium nanoparticles (Pd/CeO2). Pd/CeO2 converted aliphatic and aromatic alcohols in high yields into the
corresponding one-carbon shorter products, providing a simple and sustainable methodology to prepare hydrocarbon fuels from
biomass-derived oxygenates.
6
This article is protected by copyright. All rights reserved.