Tailoring the Selectivity of Bio-Ethanol Transformation by Tuning the Size of Gold Supported on ZnZr10Ox Catalysts

Article abstract of DOI:10.1002/cctc.201800844

The selective bio-ethanol cascade transformation to hydrocarbons over multifunctional catalysts is a highly promising sustainable pathway to high-value chemicals and fuels. However, principles to control the selectivity of the bio-ethanol transformation using the effects of the size of nanoparticle catalysts have remainedlargely unexplored. Here, using bio-ethanol transformation reactions catalyzed by Au/ZnZr₁₀O_x as examples, we demonstrate that changing the fashion of gold loading enables control over product distribution. Our results reveal that larger gold particles tendto show much higher selectivity for 1,3-butadiene, whereas smaller gold nanoparticles favor the formation of acetaldehyde.This study uncovers general principles for tailoring the selectivity of bio-ethanol transformation by carefully engineering the size of gold. It opens a new avenue for the rational design of multifunctional catalysts to enhance the production of desired reaction products in complex cascade reaction sequences.

Full text of DOI:10.1002/cctc.201800844

Accepted Article
Title: Tailoring the Selectivity of Bio-ethanol Transformation by Tuning
the Size of Gold Supported on ZnZr10Ox Catalysts
Authors: Rong He, Yong Men, Jixing Liu, Jinguo Wang, Wei An,
XiaoXiong Huang, Weiyu Song, Jian Liu, and Sheng Dai
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
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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
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201800844
Link to VoR: http://dx.doi.org/10.1002/cctc.201800844
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10.1002/cctc.201800844
ChemCatChem
COMMUNICATION
Tailoring the Selectivity of Bio-ethanol Transformation by Tuning
the Size of Gold Supported on ZnZr10Ox Catalysts
Rong He,[a] Yong Men,*[a] Jixing Liu,[b,c] Jinguo Wang,[a] Wei An,[a] Xiaoxiong Huang,[a] Weiyu Song,[b]
Jian Liu,[b] Sheng Dai[c]
Abstract: The selective bio-ethanol cascade transformation to
hydrocarbons over multifunctional catalysts is a highly promising
sustainable pathway to high-value chemicals and fuels. However,
principles to control the selectivity of the bio-ethanol transformation
using the effects of the size of nanoparticle catalysts have remained
largely unexplored. Here, using bio-ethanol transformation reactions
catalyzed by Au/ZnZr10Ox as examples, we demonstrate that
changing the fashion of gold loading enables control over product
distribution. Our results reveal that larger gold particles tend to show
much higher selectivity for 1,3-butadiene, whereas smaller gold
nanoparticles favor the formation of acetaldehyde. This study
uncovers general principles for tailoring the selectivity of bio-ethanol
transformation by carefully engineering the size of gold. It opens a
new avenue for the rational design of multifunctional catalysts to
enhance the production of desired reaction products in complex
cascade reaction sequences.
selectivity at 250 oC.[13] Flytzani-Stephanopoulos et al. showed
that atomically dispersed nanosize gold on a ZnZrOx support
was very active in achieving low-temperature ethanol
dehydrogenation exclusively to acetaldehyde and hydrogen.[2]
Recently, Bell et al. showed that gold supported on MgO : SiO2
is an active catalyst for converting ethanol to 1,3-BD; and gold
improved the dehydrogenation activity, resulting in increased
ethanol conversion and 1,3-BD yield.[14]
In spite of tremendous advances in gold-catalyzed bio-ethanol
transformation, principles for controlling the selectivity of bio-
ethanol transformation by controlling the sizes of nanosize gold
catalysts have remained largely unexplored. In this research,
gold catalysts with well-controlled cluster sizes (3–22 nm) were
prepared and investigated for their size-dependent selectivity in
bio-ethanol transformation. We show for the first time how the
selectivity of this reaction can be tailored toward specific
cascade formation of either acetaldehyde or 1,3-BD as major
products by tuning the size of gold nanoparticles.
Bio-ethanol has emerged as a chemical feedstock available from
biomass and could provide alternative routes to producing value-
added chemicals,[1] such as acetaldehyde,[2] ethyl acetate,[3]
acetic acid,[4] and lower olefins[5] over various catalysts.
Upgrading bio-ethanol to C4-olefins has been recognized as one
of the most important strategic reactions to produce highly
valuable chemicals.[6] Direct conversion of bio-ethanol into 1,3-
butadiene (1,3-BD) (Lebedev process; Scheme 1) is quite
complex because of the nature of the cascade reaction.[7] Mixed
metal oxides with multiple catalytic functionality, in particular
MgO-SiO2 binary composite oxides, have been found to be very
effective for the Lebedev process.[8] It is generally accepted that
the crucial factor affecting BD formation is a subtle optimal ratio
of acid-to-base sites to enhance the reactivity.[9]
Since the pioneering work showing exceptional catalytic
activity of gold in low-temperature oxidation of CO by Haruta,
and in hydrochlorination of ethylene by Hutchings,[10] he catalytic
activity of supported nanosize gold catalysts has become a
fascinating fundamental issue and attracted a great deal of
attention in heterogeneous catalysis.[11] Recent progress in
nanocatalysis based on sizing and shaping gold nanoparticles
provides new approaches for tuning catalytic reactivity and
stability.[12] Hensen et al. reported a ternary spinel (MgCuCr2O4)-
supported gold catalyst for aerobic oxidation of ethanol to
acetaldehyde that is capable of achieving unprecedented
reactivity of ~100% ethanol conversion with ~95% acetaldehyde
A ZnZr10Ox support was prepared by a hard-template method.
Au/ZnZr10Ox catalysts with identical gold loading of 3wt% were
prepared by the anion-adsorption (AA) method[2] (3Au/ZnZr-AA)
and the deposition−precipitation (DP) method[15] (3Au/ZnZr-DPNa
for comparison purposes. A well-defined tetragonal phase was
confirmed by x-ray diffraction (XRD) (Figure S1). The
introduction of gold did not change the structure of the support.
Initially, we investigated the influence of the preparation
method on the catalytic performance and the product distribution
for catalysis carried out at the same reaction conditions. The
product distribution observed in the continuous-flow experiments
is shown as an inset in Figure 1. Ethylene was a main product of
the ethanol conversion reaction on the bare ZnZr10Ox support
(Figure S2a). Figure 1 compares the product distribution for
ethanol conversion over catalysts at various reaction
temperatures. For both gold-loaded catalysts, ethylene
production via ethanol dehydration was suppressed by the
)
o
beneficial effect of gold addition. At low temperature (200 C),
the conversion was low (28%), and the main product was
o
acetaldehyde on 3Au/ZnZr-AA. Starting from 250 C, 1,3-BD
became the predominant product, with decreased selectivity for
acetaldehyde. This finding is not consistent with Flytzani-
Stephanopoulos’s work, in which Au/ZnZrOx catalysts prepared
by AA exhibited an extraordinary selectivity toward acetaldehyde
and hydrogen from ethanol at low temperature.[2] Notably,
3Au/ZnZr-DPNa exhibits a lower catalytic activity for 1,3-BD (<5%)
and yields acetaldehyde as the main reaction product in the
temperature range investigated. Evidently, changing the fashion
of gold loading enables control over product distribution. The
influence of sodium on selectivity control was effectively ruled
out by performing the reaction over 3Au/ZnZr-DP samples
[a]
R. He, Prof. Y. Men, Dr. J.G.Wang, Prof. W. An, X.X. Huang
College of Chemistry and Chemical Engineering, Shanghai
University of Engineering Science, Shanghai 201620, China
E-mail: men@sues.edu.cn
[b]
[c]
Dr. W.Y. Song, Prof. J. Liu, State Key lab of Heavy Oil, China
University of Petroleum, Changping, Beijing 102249, China
J.X. Liu, Prof. S. Dai, Chemical Sciences Division, Oak Ridge
National Laboratory, Oak Ridge, USA
prepared by
a modified DP method using an ammonia
solution.[16] The results illustrate that the 3Au/ZnZr-DP and
3Au/ZnZr-DPNa catalysts show a very similar product distribution
(Figure S2b).
The effects of the conversion on the product distribution were
explored for a wide range of weight hour space velocity values
at 300 oC over both 3Au/ZnZr-AA and 3Au/ZnZr-DPNa catalysts.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cctc.201800844
ChemCatChem
COMMUNICATION
As shown in Figure 2, high acetaldehyde selectivity was found
on 3Au/ZnZr-AA at a low ethanol conversion rate, and 1,3-BD
selectivity increased with increasing conversion at the expense
of acetaldehyde. This finding suggests that acetaldehyde is a
primary product that undergoes secondary reactions through
aldol condensation over acidic/basic sites. It is clear that the
dehydrogenation step readily takes place at low conversion,
evidencing that the dehydrogenation step is the primary and also
crucial step for cascade ethanol conversion. 3Au/ZnZr-AA is
very selective for 1,3-BD formation within a wide conversion
range of 10–75%. Interestingly, a remarkable change in product
selectivity is observed over the 3Au/ZnZr-DPNa catalyst
compared with the 3Au/ZnZr-AA catalyst. Acetaldehyde was
found to be the primary product at a low ethanol conversion rate
(8%) over the 3Au/ZnZr-DPNa catalyst; the yield was much
higher (85%) than over 3Au/ZnZr-AA (only 35%). Note that
acetaldehyde remained the predominant product on 3Au/ZnZr-
literature values.[18] The coexistence of Au3+, Au1+, and Au0 can
also be readily seen on all Au/ZnZr10Ox catalysts. Obviously, as
shown in Table S2, significantly different fractions of gold
species can be identified. The predominant presence of metallic
gold, plus a minor fraction of oxidized Au+ and Au3+ species were
found on the samples prepared by AA. On the contrary, larger
amounts of oxidized gold species were found on the surfaces of
the DP-prepared samples. These samples exhibited high
catalytic activity for the formation of acetaldehyde. Correlating
the activity data, our results suggest that Au0 species played an
important role in cascade formation of 1,3-BD, while partially
oxidized gold was responsible for acetaldehyde formation. This
is in agreement with the results reported by Flytani-
Stephanopoulos[11b] and Xu[19], that the numbers of highly
dispersed ionic Au in smaller gold nanoparticles were much
higher than that in larger gold particles. Accordingly, this
difference in particle size and oxidation state of gold species
DPNa when the reaction proceeded at 75% conversion of ethanol. may dictate the catalytic activity of ethanol transformation.
An appreciable amount of ethyl acetate may be formed by
dehydrogenative dimerization of ethanol. Our results offer firm
evidence that the observed selectivity control toward either 1,3-
BD or acetaldehyde over two catalysts was not governed by the
conversion process.
Correlating the activity data, our results suggest that Au0 species
played an important role in cascade formation of 1,3-BD, while
partially oxidized gold was responsible for acetaldehyde
formation. A down-shift of the binding energy in the Zn 2p and Zr
3d spectra is also observed after gold deposition (Figure S5),
which might be attributed to a strong electronic interaction
between gold and ZnZr10Ox. It is inferred that gold affects the
surface properties of the composite oxides via charge transfer, in
good agreement with literature reports.[11b]
Combining the results of catalytic study with those of
microscopy and spectroscopy measurements, we think that the
selectivity change observed over gold nanoparticles with
average sizes of 3 nm and of 22 nm for gas-phase ethanol
conversion is likely due to the effects of the size of the gold
nanoparticles.
To ascertain the effects of the gold particle size on selectivity
control over ethanol conversion, gold nanoparticles with
intermediate sizes of 8 and 12 nm were synthesized by a
modified DP method on ZnZr10Ox supports. (Figure S6) As
shown in Figure 4, a clear trend of correlation of gold particle
size with selectivity toward acetaldehyde or 1,3-BD can be
observed; that is, the smaller the gold nanoparticle is, the more
acetaldehyde will form at the expense of lower 1,3-BD
generation. These results clearly confirm our hypothesis that
small gold particles deposited on ZnZr10Ox are mainly active for
acetaldehyde formation, whereas catalysts with large gold
particles favor the cascade formation of 1,3-BD. A high yield of
acetaldehyde or 1,3-BD can be implemented by simple tuning of
the gold nanoparticles.
To further unravel the origin of the effect of gold particle size
on selectivity control, kinetic studies were performed to obtain
the respective activation energies of the desired intermediate
and final products of acetaldehyde and 1,3-BD. (Figure 5) Our
kinetic study determined that the activation energy difference
between ethanol dehydrogenation and 1,3-BD formation can
serve as a key selectivity descriptor. The initial dehydrogenated
intermediates of acetaldehyde are the precursors for 1,3-BD
formation in the course of cascade ethanol transformation. On
the catalysts with large gold particles, the activation energies of
acetaldehyde and 1,3-BD formation were 33.5 and 127.4 kJ/mol,
respectively. On the catalysts with small gold particles, the
activation energy of acetaldehyde formation was slightly lower
than that on large gold particles. However, the activation energy
of 1,3-BD formation on 3 nm gold nanoparticles was significantly
higher than that on 22 nm gold nanoparticles, leading to a strong
Temperature-programmed desorption (TPD) profiles were
obtained to investigate the surface acid/base properties (Figure
S3). The surface acid/base properties of different materials are
considered essential to catalyst performance in cascade ethanol
conversion.[8b,17] In our previous work,[6a, 8a] we also concluded
that the proper balance between acidic and basic components
on the catalyst surface determined their catalytic activity in the
conversion of ethanol into 1,3-BD and isobutene. Table S1
summarizes the basicity and acidity of each sample. The relative
strengths of Zn1Zr10Ox, 3Au/ZnZr-AA and 3Au/ZnZr-DPNa in
basicity/acidity were 0.55, 0.50 and 0.77, respectively. The
enhanced surface basicity may facilitate the reaction step of
ethanol initial dehydrogenation and sequential aldol
condensation, which occurred favorably over basic sites of the
multifunctional catalysts.
Transmission electron microscope (TEM) measurements were
used to obtain further insights into the gold-support interaction.
In TEM images (Figure S4), ZnZr10Ox supports in all catalysts
exhibit similar polyhedral shapes. As can be clearly seen from
the TEM image, the sizes of the gold nanoparticles on the
ZnZr10Ox supports varied remarkably with the preparation
method. Note that gold nanoparticles of only ~3 nm diameter
were formed using DP, as opposed to large gold nanoparticles of
22 nm diameter prepared by AA. As is well documented in the
literature, nanosized gold catalysts with 3~5 nm gold
nanoparticles imposed distinctly different catalytic properties
compared with corresponding catalysts with large gold
particles.[11] This size-dependent selectivity control can also
account for the different reactivities between the gold catalysts
prepared in this research and Flytani-Stephanopoulos’s gold
catalysts prepared by AA, as chemical leaching with NaCN in
the latter case would eventually lead to a nanosize gold catalyst
with exceptional ethanol dehydrogenation capability. [2]
X-ray photoelectron spectroscopy (XPS) measurements were
performed to investigate the chemical state of Au, Zn, and Zr in
the Au/ZnZr10Ox catalysts (Figure 3). There are three sets of
spin-orbital doublets for the Au4f7/2 and Au4f5/2 signals. The two
Au4f7/2 and Au4f5/2 peaks can be split into doublets at binding
energies of 87.3 for Au3+, 85.6 for Au1+, and 84.0 eV for metallic
gold in its zero-valent state, which is consistent with the
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10.1002/cctc.201800844
ChemCatChem
COMMUNICATION
preference for the formation of acetaldehyde as a stabilized
intermediate product. As
a result, the selectivity toward
acetaldehyde and 1,3-BD can be tailored by tuning the sizes of
the gold nanoparticles. When the size of the gold nanoparticles
was reduced to 3 nm, the gold atoms became more oxidized
rather than being in a metallic state.[11b,19] Such changes could
lead to significant alterations in the adsorption/desorption of the
ethanol intermediates on the oxidized gold surface and gold-
Scheme 1. Generally accepted cascade reaction pathway of ethanol to 1,3-
BD conversion.
support interface,[10b,20] and
a subsequent higher ethanol
conversion rate, as well as lower selectivity toward cascade
transformation of ethanol to 1,3-BD. It has been reported that
the facilitated desorption of intermediates may improve the
performance of catalysts in various complex cascade
reactions,[21] particularly in achieving a high selectivity for the
intermediates. These studies show that the adsorption strength
of products plays a critical role in determining the selectivity of
reaction intermediates. Likewise, the size effect of gold
nanoparticles in our current work may impart the significantly
weakened adsorption strength of the key intermediate
acetaldehyde on various gold-containing multifunctional
catalysts resulting in acetaldehyde as a stabilized product.
However, the detailed reaction mechanism remains to be
elucidated by future study.
(a)
100
80
60
40
20
0
Conv.
CH
4
CH CHO
3
CH COCH
3
3
CH COOH
3
CH COOC
H
5
3
2
C
C
H
2
3
4
8
H
t-C
H
4
8
n-C
H
4
8
i-C
H
4
8
c-C
H
4
8
C
H
4
6
200
250
300
350
Temperature (ºC)
(b)100
80
Conv.
CH
4
CH CHO
3
CH COCH
3
3
In conclusion, bio-ethanol can be transformed efficiently into
either acetaldehyde by initial ethanol dehydrogenation or
cascade formation of 1,3-BD, depending on the fashion of the
gold loading on a ZnZr10Ox support. Ethanol conversion studies
demonstrated that catalysts with smaller gold particles tend to
be selective for the acetaldehyde formation, whereas catalysts
with larger gold particles favor the specific cascade formation of
1,3-BD. At this point, the implication of the different surface
properties of Au/ZnZr10Ox catalysts as a function of the particle
size may present a tentative explanation for this trend. The
intrinsic impact of the gold particle sizes on ethanol
transformation need to be further explored. Overall, the size of
the gold nanoparticles was shown to be the key structure-
selectivity indicator in cascade bio-ethanol transformation. This
study highlights previously unaddressed aspects of exceptional
control over catalytic product selectivity by tuning of the sizes of
gold nanoparticles. It may open a new avenue for catalytic
design principles of fundamental importance to enhancing the
production of desired reaction products in complex cascade
reaction sequences.
CH COOH
3
CH COOC
H
5
3
2
60
C
C
H
2
4
H
3
8
40
t-C
H
4
8
n-C
H
8
4
i-C
H
4
8
20
c-C
H
4
8
C
H
4
6
0
200
250
300
350
Temperature (ºC)
Figure 1. Temperature-dependent reactivity of the selective conversion of
ethanol on (a) 3Au/ZnZr-AA and (b) 3Au/ZnZr-DPNa. Reaction conditions:
T=200-350 oC, Pethanol=5.87 kPa, Mcat=100 mg.
(a)100
CH CHO
3
C H
2
4
6
80
60
40
20
0
C H
4
Experimental Section
0
10 20 30 40 50 60 70 80
Conversion (%)
The ZnZr10Ox supports were synthesized by employing conductive
carbon black T100 as the hard template, and the ternary Au/ZnZr10Ox
catalysts were prepared by AA and DP methods. The actual gold
contents were obtained by quantifying the residual gold ions in the
precursor solution using inductively coupled plasma analysis.
100
80
60
40
20
0
(b)
CH CHO
3
C
H
4
2
CH COOC
H
5
3
2
C
H
6
4
The specific surface areas (SBET), pore volume (VP), and pore diameter
(DP) of the catalysts were measured by a Micromeritics ASAP 2460 using
nitrogen adsorption at 77 K. The acidic and basic properties of catalysts
were obtained by NH3-TPD and CO2-TPD using
Autochem II 2920.
a Micromeritics
TEM images of various samples were obtained on a field emission high-
resonance TEM (HRTEM, JEOL JEM-2100).
0
10 20 30 40 50 60 70 80
Conversion (%)
XPS was performed on a PerkinElmer PHI 5000 to analyze the surface
electronic states. All the binding energy values were calibrated using
C1s=284.6eV as the reference.
Figure 2. Conversion-dependent product selectivity of ethanol transformation
over (a) 3Au/ZnZr-AA and (b) 3Au/ZnZr-DPNa Catalysts. Reaction conditions:
T=300 oC, Pethanol=5.87 kPa.
Catalytic reactions were evaluated in a fixed-bed continuous-flow reactor
using an online Shimadzu 2014 gas chromatograph.
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10.1002/cctc.201800844
ChemCatChem
COMMUNICATION
Keywords: Bio-ethanol · 1,3-butadiene · acetaldehyde · gold
catalyst · particle size effect
Au 4f
5/2
Au 4f
7/2
3Au/ZnZr-DP
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1000/T (K-1)
Figure 5. Arrhenius-type plot of reaction rates of 3Au/ZnZr-AA and
3Au/ZnZr-DPNa catalysts.
Acknowledgements
We thank The Program for Professor of Special Appointment
(Eastern Scholar) at Shanghai Institutions of Higher Learning,
The Talent Program of Shanghai University of Engineering
Science, National Natural Science Foundation of China
(21503133, 21673137, U1662103), Science and Technology
Commission of Shanghai Municipality (18030501100), Shanghai
Talent Development Foundation (2017076), and Shanghai
Automotive Industry Science and Technology Development
Foundation (1721).
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10.1002/cctc.201800844
ChemCatChem
COMMUNICATION
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Rong He, Yong Men,Jixing Liu,
Jinguo Wang, Wei An, Xiaoxiong
Huang, Weiyu Song, Jian Liu, Sheng
Dai
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Tailoring the Selectivity of Bio-ethanol
Transformation by Tuning the Size of
Gold Supported on ZnZr10Ox
Catalysts
The selective bio-ethanol cascade transformation to hydrocarbons over multifunctional catalysts is a highly promising sustainable
pathway to high-value chemicals and fuels. Bio-ethanol can be transformed efficiently into either acetaldehyde by initial ethanol
dehydrogenation or 1,3-BD, depending on the fashion of gold loading on a ZnZr10Ox support. Larger gold particles tend to show much
higher selectivity for 1,3-butadiene, whereas smaller gold nanoparticles favor the formation of acetaldehyde.
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Author,Author*
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This article is protected by copyright. All rights reserved.