Selective Hydrogenation of CO2 Dictated by Isomers in Au28(SR)20 Nanoclusters: Which One is Better?

Article abstract of DOI:10.1002/chem.201901698

It is a challenge to make clear how isomerism in a heterogeneous catalyst induces distinct differences in catalytic properties, as attainment of the structural isomerism in a conventional catalyst is difficult. By successfully identifying the isomerism in the atomically precise Au nanoclusters, an exciting opportunity for unravelling catalysis of isomeric catalysts is opened up. Herein, we report that the isomerism in the Au₂₈(SR)₂₀ nanoclusters with different surface atom arrangements can indeed render different catalytic behaviors in the selective hydrogenation of CO₂. We anticipate that our studies will serve as a starting point for fundamental investigations about how to control the catalytic activity and selectivity by the isomerism-induced catalysis.

Full text of DOI:10.1002/chem.201901698

A Journal of
Accepted Article
Title: Selective Hydrogenation of CO2 Dictated by Isomers in
Au28(SR)20 Nanoclusters: Which One is Better
Authors: Jiayu Xu, Mingyang Chen, and Yan Zhu
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To be cited as: Chem. Eur. J. 10.1002/chem.201901698
Link to VoR: http://dx.doi.org/10.1002/chem.201901698
Supported by

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COMMUNICATION
Selective Hydrogenation of CO
2
Dictated by Isomers in Au28(SR)20
Nanoclusters: Which One is Better
[a]
[b]
[a]
Jiayu Xu, Mingyang Chen,* and Yan Zhu*
Abstract: It is a challenge to make clear how isomerism in a
arrangements of surface atoms: the remaining eight gold atoms
and twelve ligands form two trimetric staples in Au28(SPh-Bu)20
(Figure 1A), while the eight gold and twelve ligands are arranged
into two trimeric staples and two monomeric staples in
heterogeneous catalyst induces distinct differences in catalytic
properties, as attainment of the structural isomerism in
a
conventional catalyst is difficult. By successfully identifying the
isomerism in the atomically precise Au nanoclusters, an exciting
opportunity for unravelling catalysis of isomeric catalysts is opened
up. Herein, we report that the isomerism in the Au28(SR)20
nanoclusters with different surface atom arrangment can indeed
render different catalytic behaviours in the selective hydrogenation of
6 11
Au28(SC H )
20 (Figure 1B).[3a,3b] Despite the two isomeric
Au28(SR)20 differ only by an eight-gold-atom arrangment, drastic
differences in their catalytic proformances for the selective
hydrogenation of CO are observed. The investigation offers
2
new insights into the isomerism-induced catalysis at the
unprecedented level of atomic precision.
2
CO . We anticipate that our studies will serve as a starting point for
fundamental investigations about how to control the catalytic activity
and selectivity by the isomerism-induced catalysis.
A
B
Isomers with the same molecular formula but different atomistic
arrangements are of special concerns in the organic and
biological chemistry, due to the possibly distinct differences in
their physical and chemical properties.[1] Owing to the inherent
heterogeneity of the practical catalysts, however, it is not clear
yet whether the structural isomerism also exists in
heterogeneous catalysts. If so, a fundamental question is to be
addressed: do isomers of catalysts exhibit similar or different
catalytic behaviors? At nanoscale, a subtle change in the
geometry of a catalyst can have large impacts on the catalytic
Structural
Isomerism
Figure 1. Isomers in Au28(SR)18: (A) Au28(SPh-Bu)20 and (B) Au28(SC
The Au20 kernels (upper panel) and the Au28 20 frameworks (lower panel).
Color labels: Au, green; S, magenta. C and H are omitted for clarity.
6 11 20
H ) .
performance, and the catalytic activity and selectivity can
strongly rely on the atomistic arrangement of a catalyst.[2]
S
Therefore, it is very interesting to unveil isomerism-induced
catalysis for the heterogeneous catalysts, which will enhance the
diversity of heterogeneous catalysis. Yet such tasks are
extremely challenging, mainly because the discovery and
identification of structural isomerism in the catalysts are difficult
by conventional characterization techniques.
The compositions of the two nanoclusters were determined
by matrix-assisted laser desorption ionization mass
spectrometry (Figure S1), confirming that the nanoclusters are
both composed by 28 gold atoms that are protected by twenty
thiolate ligands. The blue shifts of the UV-vis absorption bands
Fortunately, with recent advances on atomically precise
metal nanoclusters, identification of the structural isomerism
were found for Au28(SC
Au28(SPh-Bu)20; similar HOMO-LUMO gaps were observed for
6 11
H )20, with respect to the spectrum for
becomes possible. Recently, isomerism in the Au
nanoclusters was successfully discovered.[3] Au
n
(SR)
(SR)
m
6 11
Au28(SC H )20 and Au28(SPh-Bu)20, which is attributed to the
two clusters sharing the same Au20 kernels (Figure S2).[3a,3b]
Considering the importance of an effective conversion of
n
m
nanoclusters are ideally composed of an exact number of atoms
and behave like molecules.[4] The isomerism of Au
(SR)
n
m
CO
into liquid fuels for mitigating global warming and energy
2
nanoclusters allows us to discover unknown catalysis for new
isomers of the heterogeneous catalysts, which is typically not
possible for the traditional catalysts.
[5]
2
supply problems, the selective hydrogenation of CO was used
as a pivotal reaction to gain insights into catalysis of isomers in
Au28(SR)20. As shown in Figure 2A and 2B, Au28(SPh-Bu)20 was
In this work, two isomers of Au28(SR)20 nanoclusters are
used as model catalysts to catalyze the selective hydrogenation
more effective than Au28(SC
hydrogenation of CO The conversion rate of CO
Au28(SPh-Bu)20 was faster than that over Au28(SC 20. More
interestingly, the isomeric Au28 nanoclusters can exhibit different
selectivity for products. The conversion of CO to methanol was
achieved over Au28(SPh-Bu)20 (Figure 2A), whereas over
Au28(SC 20 both methanol and methyl formate were obtained
as major products with a mole ratio of ~2:1 between methanol
and methyl formate (Figure 2B). Notably, other than the
methane by-product, CO, a common by-product in the reaction
over practical Cu-ZnO catalysts, that is responsible for poor
methanol selectivity, was not found in the two Au28 systems.
Base on the turnover frequency (TOF) of the two clusters for
6
H
11
)
20
for the catalytic
2
.
2
over
of CO
butylphenyl) and Au28(SC
same face-centered-cubic
2
. The two isomers, Au28(SPh-Bu)20 (Ph-Bu = 4-tert-
11 = cyclohexyl), have the
kernel but different
6
11
H )
6
H
11
)
20 (C
6
H
Au20
2
6
11
H )
[
[
a]
b]
J. Xu, Prof. Y. Zhu
Key Lab of Mesoscopic Chemistry, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing 210093, China
E-mail: zhuyan@nju.edu.cn
Prof. M. Chen
Beijing Computational Science Research Center, Beijing 100193,
China
E-mail: mychen@csrc.ac.cn
CO
2
hydrogenation at different reaction temperatures, it is found
Supporting information for this article is given via a link at the end of
the document.
that the apparent activation energy of the Au28(SPh-Bu)20
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catalyst was lower than that of the Au28(SC
6
H
11
)
20 catalyst
synthesized for further comparison (note that the corresponding
UV-vis spectra and the atomic structures were shown in Figure
(
Figure 2C).
S7). Although the Au18(SC
same ligand (SC 11) with Au28(SC
product selectivity from Au28(SC
6
H
11
)
14 catalyst was protected by the
20, it exhibited different
20 for CO hydrogenation
A
B
6
H
6 11
H )
6
H
11
)
2
under identical reaction conditions, as shown in Figure 2F. As
much, the Au44(SPh-Bu)28 catalyst with same thiolate ligand
(
SPh-Bu) with Au28(SPh-Bu)20 showed different catalytic
performance for CO hydrogenation: the products such as
2
ethanol, methanol, formic acid and methane can be obtained
over the former, while methanol and methane were produced on
the latter (Figure 2F). These results clearly ruled out the ligand
effects of the two Au28(SR)20 catalysts on the performance of
C
D
CO
2
hydrogenation. The catalytic properties are mainly
determined by the atomic structure of gold atoms rather than
thiolate ligands.
Attenuated total reflection infrared (ATR-IR) spectroscopy
was conducted to detect the potential intermediates adsorbed
over the two isomers in the hydrogenation reaction of CO
Figure S8 shows ATR-IR spectra obtained from exposure of the
isomers to a mixture gas of CO and H . The bands at 2962 and
960 cm-1 can be assigned to asymmetric CH stretches of
methoxy groups produced by the reaction of methanol with
2
.
2
2
2
E
F
-1
catalysts, whereas the apparent bands at 2887 and 2886 cm
[
6]
were associated with formate. A set of peaks at 1383, 1239,
-
1
[7]
and 1056 cm , corresponding to methoxy species, were
observed for Au28(SPh-Bu)20, and the corresponding peaks were
-1
observed at 1383, 1241, and 1053 cm for Au28(SC
results imply that the methoxy is the major intermediate in the
hydrogenation of CO catalyzed by the two isomers.
6 11
H )20. The
2
The difference in the catalytic selectivity toward methanol
for the two isomers is understood by the chemical desorption
capacity of methanol onto the two isomeric catalysts. The
methanol-temperature-programmed desorption was carried out
and the temperature was ramped to 300 oC (note that higher
Figure 2. Catalytic performance of CO
Au28(SR)18 catalysts: (A) Au28(SPh-Bu)20 and (B) Au28(SC
Corresponding Arrhenius plots. (D) Comparison experiments with differnet
reaction gas. (E) Comparison of catalytic properties of Au28(SR)20 catalysts
with different pretreatments. (F) Catalytic results of Au18(SC
2
hydrogenation over isomeric
20. (C)
6 11
H )
6
H
11
)14 and
temperatures were not allowed because it might lead to
decomposition and aggregation of nanoclusters following the
ligands desorption which can be deduced from Figure S6). As
shown in Figure S9, the peaks of methanol desorption were
Au44(SPh-Bu)28 for CO
2
hydrogenation. Reaction conditions: 2 MPa CO /H
2 2
o
(1:3), 130 C, 24 h. Au28T: Au28(SPh-Bu)20 and Au28C: Au28(SC
6
H
11 20
) .
The two isomers showed an excellent durability and the
conversion and product selectivity in the cycles of the
o
o
CO
2
located at 197
Au28(SC 20, suggesting that Au28(SPh-Bu)20 favors the leave
of methanol from the active sites. In particular, the asymmetric
C
for Au28(SPh-Bu)20 and 210
C for
reused catalysts were comparable with the first run results
Figure S3). We compared the UV-vis spectroscopic fingerprints
6 11
H )
(
of the fresh and used catalysts and no obvious spectral change
was observed (Figure S4). The retention of characteristic optical
spectra after reactions ruled out the possibility for Au28(SR)20
decomposition under the reaction conditions. Transmission
electron microscopy studies showed that the two nanoclusters
had no obvious aggregation throughout the reactions (Figure
S5). Considering isomers themselves containing carbon sources
shape of the desorption peak of methanol over Au28(SPh-Bu)20
,
which implies a first order desorption kinetics,[ indicates that
the adsorption of methanol over the Au28(SPh-Bu)20 is non-
dissociative. In contrast, the symmetric methanol desorption
8]
peak over Au28(SC
order desorption kinetics, implies that the adsorption of
11
methanol over Au28(SC H )20 is dissociative. It is proposed that
6 11
H )20, which is associated with the second
[
9]
6
(
ligands), the comparison experiments were carried out; when
no reaction gas was introduced, no product was obtained; with
either CO or H being introduced, no product was detected
Figure 2D), indicating that the products derive from the reaction
the differences in the desorption capacity of methanol onto the
isomeric Au28(SR)20 may partially account for the different
selectivity of methanol on the two catalysts.
2
2
(
D/H and H/D exchange studies are shown in Figure S10.
During the first run of D/H exchange (black and red curves; note
2 2
of CO and H rather than organic ligands. To study the effect of
the thiolate ligands on the catalytic performance, the catalysts
were pretreated at 400 C (above ligand desorption temperature,
o
that the two isomers were pretreated in the Ar at 150 C for 1h
o
2
and then D was introduced to exchange with H species), H
Figure S6) to remove all the thiolate ligands, leaving exposed
Au(0) atoms on the surface of particles. From Figure 2E, the
reactivity of the bare gold catalysts decreased and the major
species associated with the two Au28 catalysts are identical and
assigned to the H of organic ligands. Immediately after the
exchange of D
catalysts under a D
second run of H/D exchange. The new peaks (blue and pink
curves) were observed (284 oC for Au28(SC 20 and 371 o
for Au28(SPh-Bu)20), which are tentatively ascribed to the
2
with H species of ligands and the cooling of
product was CH
may have been changed. Moreover, the Au18(SC
nanoclusters (where C 11 = cyclohexyl) and the Au44(SPh-Bu)28
nanoclusters (where Ph-Bu 4-tert-butylphenyl) were
4
, suggesting that underlying reaction pathway
2
stream, H was introduced to perform the
2
6
11 14
H )
6
H
6
H
11
)
C
=
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chemically adsorbed deuterium on the gold sites.[10] Deduced
Au28C form Au-(H)-Au with H
with endothermicities of 12.4 and
2
from the second run of H/D exchange results, Au28(SC
6
H
11
)
20
9.7 kcal/mol, respectively. Natural atomic charge analysis of
Au28C and Au28T (Figure S11) reveals that RS-H-AuH or Au-(H)-
Au might be related to the metallicity of the two Au atoms in Au-
SR-Au in the raw catalyst. The formation of Au-(H)-Au seems to
occur when the one of the two Au atoms is highly positively
charged, and the other is slightly negatively charged, as seen in
the Au(2)-SR-Au(9) and Au(3)-SR-Au(9). Such charge
separation might acount for the formation of Au-Au bond in Au-
(H)-Au and the desorption of HSR.
was easier to adsorb and activate H compared to Au28(SPh-
2
Bu)20. However, the results deviated from the above catalytic
results. One possible answer is that the true active species are
no longer the original clusters at the high temperatures of H/D
experiments. Interestingly, the H/D exchange results can
account for the catalytic performance of the catalysts pretreated
at 400 oC. The structures of the pretreated nanoclusters
decomposed and the Au surface atoms were exposed, in which
6 11
the ligand-off Au28(SC H )20 was easier to adsorb and activate
H
2
(Figure S10) and thus exhibited higher activity for CO
2
A
hydrogenation than the ligand-off Au28(SPh-Bu)20 (Figure 2E).
10.6
+
H
2
+
-
H2
H O
2
A
0.4
0
+
CO
2
-
2.5
+
H
2
-
3
CH OH
-
25.4
B
46.3
+
H
2
B
C
26.7
+
H
2
+
2 H
2
21.4
1
8.2 - 2 H O
2
0
+
2CO
2
-0.9
+
H
2
-
HCOOCH
3
-
13.0
Figure 3. DFT calculation: (A) hydrogenation energy for Au-thiol bond of
Au28C and Au28T. The hydrogenated catalysts (B) with a RS-H-Au moiety and
Figure 4. Potential energy surfaces (A) for formation of CH
3
OH at a RS-H-Au
(
C) with an Au-(H)-Au moiety. Color code: orange: surface Au; purple interior
site of hydrogenated Au28T and (B) for formation of HCOOCH
of hydrogenated Au28C.
3
at a Au site
3 2
H
Au; yellow: S.
To further understand catalysis of the two isomeric Au28
catalysts, density functional theory (DFT) calculations were
performed. simplified computational model, where the
thiolates were replaced with SCH , was used for each Au28
catalyst; therefore, the two clusters share the same formula,
Au28(SCH 20. To distinguish the two Au28(SCH 20 clusters, the
simplified Au28(SC 20 is denoted as Au28C and the simplified
Au28C has a D
H)-Au can be formed at both sides on Au(3) and Au(9) of Au28C,
leading to two doubly hydrogenated Au triangle sites. The two
hydrides of Au can reduce 2 CO molecules, which might
lead to the reaction product containing 2 C atoms (2C product).
Note that unlike Au(3) of Au28C, Au(9) is not a surface Au where
the two hydrides at Au(9) is separated by the 3 Au atoms of the
2
point group symmetry, and therefore Au-
(
A
3
3
3
H
2
2
3
)
3
)
6
11
H )
Au28(SPh-Bu)20 is denoted as Au28T. Due to the point group
symmetries of the structures, there are 9 distinct types of Au
sites in Au28C and 8 types of Au sites in Au28T (Figure 3A).
outmost Au
be formed at Au(9). Potential energy surfaces for CO
hydrogenation reaction at a RS-H-Au site of hydrogenated Au28
and an Au moiety of hydrogenated Au28C were calculated at
the DFT level and compared. At the RS-H-Au site, methanol can
be formed with a total reaction: CO + 3H → CH OH + H O, via
COOH, -CHO, and -OCH mono-adsorption complexes (Figure
3 4
(SR) staple, implying that 2C product is not likely to
2
T
x
Au28C contains three types of Au (SR)x+1 staples with 10 distinct
3
H
2
Au-thiolate (Au-SR) bonds, and Au28T contains two types of
staples with 10 distinct Au-SR bonds. First, we analyzed the site
activities for all the Au-SR moieties in Au28C and Au28T (Figure
2
2
3
2
-
3
3
A), as H
reduction of CO
with the Au-SR bonds with low endothermicities (endothermic by
0-20 kcal/mol, Figure 4A), resulting in a hydrothiolate (HSR)
2
adsorption and activation are prerequistes for
4A). The two hydrides of the Au
3
H
2
site of hydrogenated Au28
C
2
on metal catalysts. H can dissociate and react
2
can react with 2 CO
2
to form Au
3
(COOH) (Figure 4B). The two
2
COOH adsorb at the same asymmetric sites as the two hydrides,
forming a terminal ligand and a bridge ligand. No coupling
reaction products were found for the two adsorbed COOH. The
COOH ligands can be further reduced to form two CHO. The
bridge CHO, like the bridge COOH, have an orientation
potentially favoring ligand-ligand coupling, as the O and H atoms
1
moiety and a hydrogold (AuH) moiety. Note that the surface
HSR only exists transiently. It continues to either form a RS-H-
AuH moiety with AuH (Figure 3B), which repairs the cleavage of
the staple, or to desorb from the catalyst, acompanied by
formation of Au-(H)-Au moiety (Figure 3C). All of the Au-SR
moieties of Au28T and most of the Au-SR moieties of Au28C tend
2
of CHO are confined in the C(HOAu ) tetrahedron so that the
connecting path between the two CHO ligands are not blocked
by O or H. The O of the terminal CHO can possibly couple with
the C of the bridge CHO to form HC-O-CHO; this reaction step,
2
to form RS-H-AuH with H . Only two Au-SR moieties, Au(3)-SR
and Au(9)-SR (the labels of Au atoms are in Figure 3A), of
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Chemistry - A European Journal
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[
8] R. S. Smith, R. A. May, B. D. Kay. J. Phys. Chem. B 2016, 120, 1979-
however, is found to be endothermic by ~20 kcal/mol. More
1987.
likely, CHO will be further reduced by H
2 3
. Formation of OCH
[
[
9] A. S. Bolina, A. J. Wolff. J. Chem. Phys. 2005, 122, 044713.
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from CHO is mostly likely via a transition state with an AuOC
[
11]
triangle geometry. Such a triangle geometry is less likely to be
formed from the bridge CHO as compared to the terminal CHO
case, as C of bridge CHO is more confined. Therefore, the
bridge CHO is more difficult to be reduced than the terminal
[11] S. Kattel, P. J. Ramirez, J. A. Rodriguez, J. G. Chen, P. Liu. Science 2017,
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12] Q. Li, J. C. Russell, T. Luo, X. Roy, N. L. Rosi, Y. Zhu, R. Jin. Nat.
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CHO, and a reaction intermediate with a terminal OCH
bridge CHO will be first formed at the Au active site. The
coupling of OCH and CHO to form methyl formate is found to
be exothermic by 22.3 kcal/mol, while the ligand orientations are
also favorable. The terminal OCH might also form methanol in
3
and a
3
3
3
an alternative reaction path, similar to the final reaction step at
the RS-H-Au site (Figure 4A) with an exothermcity of ~23
kcal/mol, but this path is expected to be less kinetically favorable
as additional hydrogen activation is required.
In summary, we have explicitly revealed that the structural
isomerism in the Au28(SR)20 nanoclusters impacts the catalytic
properties, as demonstrated in the selective hydrogenation of
2
CO . The results of the present study shed light on the intriguing
role of the surface-atom arrangement in tuning the catalytic
activity and selectivity, which will not only open up future exciting
opportunities for understanding the origin of isomerism-induced
catalysis but also expand the horizons of structural isomer
catalysts.
Acknowledgements
We acknowledge financial support from the Fundamental
Research Funds for the Central Universities and National
Natural Science Foundation of China (21773109, U1530401,
91845104).
Keywords: isomer • Au28 • nanoclusters • atomicity • catalysis
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Entry for the Table of Contents (Please choose one layout)
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It is unclear whether and how
Jiayu Xu, Mingyang Chen*, and Yan
isomerism in a catalyst affect the
catalytic performance. Here we
demonstrate that the structural
isomerism in Au28(SR)20 really renders
distinct catalytic behaviour to the
Zhu*
Page No.1 – Page No.4
Selective Hydrogenation of CO
Dictated by Isomers in Au28(SR)20
Nanoclusters: Which One is Better
2
2
selective hydrogenation of CO .
The isomerism-induced catalysis
provides guidances for how to control
the catalytic activity and selectivity by
the position arrangement of atoms in
catalysts.
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Author(s), Corresponding Author(s)*
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Title
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