Interfacial Frustrated Lewis Pairs of CeO2 Activate CO2 for Selective Tandem Transformation of Olefins and CO2 into Cyclic Carbonates

Article abstract of DOI:10.1021/jacs.9b03217

Effective activation of CO₂ is a prerequisite for efficient utilization of CO₂ in organic synthesis. Precisely controlling the interfacial events of solids shows potential for activation. Herein, defect-enriched CeO₂ with constructed interfacial frustrated Lewis pairs (FLPs, two adjacent Ce³⁺···O^2-) effectively activates CO₂ via the interactions between C/Lewis basic lattice O^2- and the two O atoms in CO₂/two adjacent Lewis acidic Ce³⁺ ions. Selective cyclic carbonate production from a catalytically tandem protocol of olefins and CO₂ is used to demonstrate FLP-inspired CO₂ activation.

Full text of DOI:10.1021/jacs.9b03217

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Communication
Interfacial frustrated Lewis pairs of CeO2 activate CO2 for selective
tandem transformation of olefins and CO2 into cyclic carbonates
Sai Zhang, Zhaoming Xia, Yong Zou, Fangxian Cao, Yuxuan Liu, Yuanyuan Ma, and Yongquan Qu
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b03217 • Publication Date (Web): 10 Jul 2019
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Interfacial frustrated Lewis pairs of CeO activate CO for selective
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†
#
†#
†
†
†
†
Sai Zhang, Zhaoming Xia, Yong Zou, Fangxian Cao, Yuxuan Liu, Yuanyuan Ma and Yongquan
Qu *
†
†
School of Chemical Engineering and Technology and Center for Applied Chemical Research, Frontier Institute of Science and
Technology, Xi'an Jiaotong University, Xi'an, 710049, China.
#
These authors contributed equally to this work.
Supporting Information Placeholder
both O atoms of CO
enriched CeO to achieve CO
demonstrated by the selective tandem transformation of
olefins and CO into cyclic carbonates.
CeO (110) instead of CeO (100) and (111) exhibits the
2
. Such interfacial FLPs acting on defect-
ABSTRACT: Effective activation of CO
efficient utilization of CO in organic synthesis. Precisely
controlling the interfacial events of solids shows potential for
activation. Herein, defect-enriched CeO with constructed
interfacial frustrated Lewis pairs (FLPs, two adjacent Ce …O ,
Figure 1) effectively activates CO via the interactions
between C/Lewis basic lattice O and the two O atoms in
CO
/two adjacent Lewis acidic Ce3+ ions. Selective cyclic
carbonate production from a catalytically tandem protocol of
2
is a prerequisite for
2
2
activation is further
2
2
2
3
+
2-
2
2
2
highest possibility for FLPs construction due to the unique
FLPs configuration and formation energy of oxygen vacancies
2
-
19
2
on various surfaces. When two adjacent oxygen atoms were
removed from CeO (110), adjacent reduced surface Ce atoms
2
olefins and CO
activation.
2
is used to demonstrate FLP-inspired CO
2
and lattice O atoms are independent Lewis acidic and basic
sites at a proper distance, constructing the interfacial FLPs.
However, FLPs cannot be created on CeO
2
(111) due to its
unique crystal structure and large oxygen vacancy formation
1
9, 22-24
energy.
2
Although CeO (100) exhibits the possibility of
The catalytic transformation of CO
into value-added chemicals has attracted increasing attention
2
as a C1 building block
constructing FLPs, it is difficult to fix these surface Lewis
acidic and basic sites due to the easily diffused oxygen
atoms/vacancies on the less stable CeO (100) surface.
2
1-5
19, 22-24
due to the potential for CO
reactions of CO are highly energy-intensive because of its
chemical inertness and extremely high C=O bond energy of
06 kJ/mol. Thus, the effective activation of CO under mild
2
reutilization. However, the
2
8
2
conditions is pivotal for practical applications. Among various
strategies, homogeneous frustrated-Lewis-pairs (FLPs), the
combinations of a sterically hindered Lewis acid and Lewis
base, offer promising opportunities for CO
2
activation and
6-13
conversion into CO, CH , CH OH and formamides.
4
3
Inspired
by the benefits of heterogeneous catalytic systems, including
facile separation, elongated lifetime and scalable productivity,
2
constructing heterogeneous FLP sites for CO activation is
fundamentally and practically attractive.
Recently, heterogeneous FLPs composed of Lewis acidic
and basic block copolymers activated CO for the N-
2
1
4
formylation of amines. FLP sites within metal organic
frameworks with B-based ligands as Lewis acids catalyzed the
conversion of diamines into benzimidazoles by using CO
2
as a
15
C1 feedstock.
To date, most homogeneous and
Figure 1. Adsorption and activation of CO
2 2
on CeO (110).
heterogeneous FLPs have activated CO
2
through the
Density functional theory (DFT) calculations were initially
1
4, 16-18
performed to explore the adsorption and activation of CO on
CeO (110) (Figure 1, S1-S2). The most stable adsorption
configurations on both ideal and defective CeO were
carbonate-like, consistent with previous reports. On an ideal
CeO (110) surface, CO is bent with an adsorption energy of -
.5 eV, where the O–C–O angle is 128.5° and the C=O bond
2
2
2
25
2
2
1
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elongates from 1.177 to 1.284 Å. Upon introducing one oxygen
vacancy (CeO (110)-1O ), the carbonate-like CO
configuration is such that one O of CO falls into the oxygen-
selectivity of 47% to phenylethylene carbonates. Serious
hydrolysis with 38% selectivity of diols was observed due to
the presence of water in the catalytic solution. Next, 40 mg of
1
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2
V
2
2
3
+
vacancy-site and binds with Ce and the C atom of CO
2
binds
CeO
conversion was only slightly increased to 32% and 30% for
NC-CeO and NO-CeO , respectively. NR-CeO delivered the
highest styrene conversion of 69%. Importantly, the
selectivity towards cyclic carbonates was >70% for all CeO
much higher than that without catalysts. Among the catalysts,
NR-CeO achieved the highest selectivity of >80% for cyclic
2
catalyst was used under the same conditions. Styrene
2
-
with lattice O . Compared to CO
surface, the two C=O bonds of CO
Å with similar adsorption energies (-1.5 eV), and the O–C–O
angle is decreased to 119.1°. Thus, CO can be activated on
defective CeO . FLPs can further enhance CO adsorption (-2.2
eV), in which a C atom binds to a Lewis basic lattice O and
2
on an ideal CeO (110)
2
2
elongate to 1.339 and 1.266
2
2
2
2
2
,
2
2
2
-
2
3
+
the two O atoms of CO
2
bind to two Lewis acidic Ce ions
on CeO (110)-1O , in addition to
carbonates.
(
Figure 1). Compared to CO
2
2
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Even after normalizing to their surface area, 8 mg of NR-
the further decreased O-C-O angle (118.8°) and slightly
elongated C=O bonds (1.339 and 1.267 Å), the more
CeO
than 40 mg of NC-CeO
calculations, the formation of interfacial FLP sites is critical for
effective CO activation and tandem reaction. The literature
2
still delivered a much higher styrene conversion of 43%
2
and NO-CeO . As determined by DFT
2
2
negatively charged O (-2.13 e) of CO suggests its further
3, 26
activation on FLPs.
2
Then, cyclic carbonate production from a catalytically
tandem transformation of olefins and CO was used to
examine the capability of CeO to promote CO activation.
Industrial production of cyclic carbonates is a two-step
process of olefin epoxidation and subsequent CO
suggests that Lewis acids enable the epoxidation of olefins
and Lewis bases to catalyze the cycloaddition of epoxides and
2
3, 32
2
2
2
CO .
2
Herein, the abundant defects on CeO not only form
the defect clusters for constructing the interfacial FLPs but
3
+
33-34
2
also produce “isolated” Ce sites.
peroxidase-like activity of CeO
Ce ,
Based on that and the
cycloaddition, which suffers from serious safety and
environmental issues due to the sensitivity, combustibility
and explosibility of epoxides during handling and transport.
By using olefins as an inexpensive feedstock, the tandem
2
for peroxide activation by
ions can catalyze styrene
3
+ 35
3+
those “isolated” Ce
epoxidation. Hence,
a catalytically tandem pathway is
3
+
proposed: (1) olefin epoxidation on Lewis acidic Ce ; (2) CO
activation on FLPs; (3) electrophilic attack of in situ-generated
and released epoxides on the activated CO (Figure 3a).
2
conversion of olefins and CO
safe, environmentally friendly and economical strategy.
2
to cyclic carbonates provides a
27
2
Figure 2. Catalytic performance of various CeO
Reaction conditions: styrene (4 mmol), TBHP (0.65 mL, 70
wt% aqueous solution), TBABr (40 mg), CeO (40/8 mg), 80
C, 2 MPa CO , 14 h.
2
catalysts.
2
°
2
To highlight the advantages of FLPs for tandem
transformation, CeO nanorods (NR-CeO ) with FLPs and CeO
cubes (NC-CeO ) and octahedra (NO-CeO ) without FLPs were
prepared with specific surface areas of 91, 15 and 18 m /g,
2
2
2
2
2
2
28-29
respectively (Figure S3-S4).
Based on their X-ray
photoelectron spectra (XPS, Figure S5-S6 and Table S1), NR-
Figure 3. (a) Proposed catalytic process for the tandem
transformation of olefins (propylene) and CO into cyclic
carbonates on FLPs. (b) H -TPR of NR-CeO -T. (c) Catalytic
activity and (d) selectivity of NR-CeO -T vs. their surface Ce
3
+
CeO
CeO
2
2
exhibited a similar surface Ce fraction (20.8%) to NC-
2
3
0-31
(20.6%) and NO-CeO
2
(20.9%).
Additionally, from
2
2
the O 1s profiles (Figure S6), the similar surface oxygen
vacancy percentages of NR-CeO (26.7%), NC-CeO (24.4%)
and NO-CeO (23.1%) were consistent with their surface Ce
3+
2
2
2
fractions. Reaction conditions: styrene (2 mmol), TBHP (0.35
mL, 70 wt% aqueous solution), TBABr (50 mg), catalysts (40
3
+
2
fractions (Table S2). The tandem reactions were optimized
and assessed by using styrene as an olefin, t-
mg), 80 °C, 2 MPa CO
propylene oxide on defective CeO
2
and 14 h. (e) Adsorption energy of
(110).
2
butylhydroperoxide
tetrabutylammonium bromide (TBABr) as an initiator and
CeO as a catalyst for 14 h (Figure 2). Without catalysts, the
reaction yielded a 23% conversion of styrene and a poor
(TBHP)
as
an
oxidant,
Generally, the abundance of CeO
2
defects benefits the
formation of oxygen vacancy clusters, which can promote the
creation of interfacial FLPs. The formation of oxygen vacancy
2
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clusters can be revealed from the oxygen migration or
carbonates within 14 h (Figure 4b).19 The tandem reaction
continuously proceeded to reach 94% conversion of styrene
after 24 h with a selectivity of 94% for cyclic carbonates. After
3
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reducibility of CeO
2
.
Then, H
temperature-programmed
2
reduction (H -TPR) of various catalysts was recorded (Figure
2
S7). The peak over 300 °C can be attributed to the reduction of
2
recovery by centrifugation, PN-CeO maintained its catalytic
surface lattice oxygen.37-39 The lowest reduction temperature
activity and selectivity for at least 3 cycles (Figure 4c). The
3
+
of NR-CeO
abundance of oxygen vacancy clusters on NR-CeO
thereby effective CO activation, enabling the best catalytic
performance of NR-CeO for the tandem transformation.
Then, to eliminate the influence of morphology on the
formation of FLPs, the surface defects of NR-CeO were
modulated by calcination at 300 and 500 °C (NR-CeO -T) in air
with the preserved morphology and surface areas (Figure S8).
2
over NO-CeO
2
and NC-CeO
2
indicated the most
unaltered morphology and surface Ce fraction of the spent
catalysts indicated their structural and catalytic stability
(Figure S14).
2
and
2
2
2
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+
Derived from their XPS profiles (Figure S9), the surface Ce
fractions of NR-CeO -300 and NR-CeO -500 decreased to
5.5% and 11.3%, respectively. Derived from their O 1s
spectra (Figure S10), the surface percentages of oxygen
vacancies were also reduced from 26.7% of NR-CeO to 19.9%
of NR-CeO -300 and 12.5% of NR-CeO -500, consistent with
2
2
1
2
2
2
3+
the changes in the surface Ce fractions. These changes in
their surface properties can be further revealed by the Raman
spectra (Figure S11). The intense band at 459 cm can be
ascribed to the Raman-active F2g vibrational mode of the CeO
fluorite-type structure. The weak band at 600 cm is
associated with oxygen vacancy. At elevated temperatures,
the decreased values of the ratio of integrated peak areas at
00 and 459 cm (A600/A459) suggest a decrease in the surface
defect density of the thermal-treated catalysts. Similarly, NR-
CeO exhibits the lowest beginning temperature (250 °C) and
the smallest reductive peak temperature (484 °C) compared
-1
Figure 4. (a) TEM image of PN-CeO
and selectivity of cyclic carbonates vs. time; (c) recyclability at
0 h. Reaction conditions: styrene (4 mmol), TBHP (0.65 mL,
2
; (b) styrene conversion
2
-1
2
4
0
70 wt% aqueous solution), TBABr (40 mg), CeO
°C and 2 MPa CO
2
(40 mg), 80
2
.
-1
6
2
Table 1. Tandem conversions of olefins with CO .
2
Entry
Olefin
Product
Conv. (%)
Sel. (%)
92
O
O
with NR-CeO
2
-300 and NR-CeO
2
-500, as determined from H
2
-
1
97
TPR analysis (Figure 3b). Thus, the defect-enriched NR-CeO
2
O
exhibits the highest possibility for the formation of the
O
O
3
6
structural defect clusters , leading to the construction of
more surface FLP sites for CO activation. As expected, in
terms of activity, the styrene conversions increased from 25%
to 32% and 69% for NR-CeO -500, NR-CeO -300 and NR-CeO
respectively, indicating the benefits of the rich surface defect
for FLP construction and thereby CO activation (Figure 3c).
The defect-enriched NR-CeO also exhibited the highest
2
80
93
O
2
O
O
O
O
3
4
5
99
64
99
85
86
92
2
2
2
,
O
O
O
2
2
O
O
selectivity for cyclic carbonates (Figure 3d). Generally, the
Reaction conditions: substrates (4 mmol), TBHP (0.65 mL,
strong interaction between in-situ generated epoxides and
3
+
70 wt% aqueous solution), TBABr (50 mg), PN-CeO (40 mg),
Ce
can impede epoxide release and lead to further
2
3
+
80 °C, 2 MPa CO2.
hydrolysis of epoxides into diols on acidic Ce . Thus,
weakening this interaction can suppress the hydrolysis side-
reaction. DFT calculations were used to assess the defect-
PN-CeO
various olefins for 20 h (Table 1). For 4-methylphenylene and
-t-butyl styrene, 97% and 80% conversions were achieved
2
was then used for this tandem conversion with
2
dependent adsorption of epoxides on CeO . To save
4
computing resources, propylene oxide instead of styrene
oxide was used (Figure 3e, S12-S13). Epoxide has an
adsorption energy of -0.58 eV by forming a bond between O of
with 92% and 93% selectivity for cyclic carbonates,
respectively (Entries 1-2). The conversion of α-methylstyrene
reached 99% with 85% for cyclic carbonates (Entry 3). Also,
64% of vinylcyclohexane was converted into cyclic
carbonates, with 86% selectivity (Entry 4). cis-Cyclooctene
was converted to cyclic carbonates, with 99% conversion with
epoxides and surface Ce on ideal CeO
energy of epoxide on CeO (110)-1O is enhanced to -0.47 eV
and further increased to -0.28 eV on FLPs, indicating its
significantly weakened interaction on the defective CeO
Figure 3e). Thus, the defect-rich CeO leads to the easy
2
(110). The adsorption
2
V
2
9
2% selectivity (Entry 5).
(
2
In summary, the constructed interfacial FLPs on CeO
2
release of in situ-generated epoxide from the catalyst,
suppressed its hydrolysis and improved the yield of cyclic
carbonates.
effectively activate CO
selective tandem conversion of olefins and CO
carbonates. Defect-enriched CeO benefits this tandem
protocol by providing more FLP sites for efficient CO
2
, which is demonstrated by the
2
to cyclic
2
Based on the above understanding, further increases in
surface defects might create more FLPs for CO activation and
2
weaker interactions between epoxide and catalyst for the
improved selectivity of cyclic carbonates. Then, porous
2
activation for cycloaddition and weakening the adsorption of
in situ-produced epoxides to suppress their hydrolysis. We
anticipate that such CO
contribute to other catalytic CO
2
activation by solid FLPs can
utilizations.
2 2
nanorods of CeO (PN-CeO , Figure 4a) with a high surface
2
3+
Ce fraction (28.2%, Figure S14a) delivered a styrene
conversion of 63% and the highest selectivity of 95% to cyclic
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5. Shyshkanov, S.; Nguyen, T.; Ebrahim, F. M.; Stylianou, K.; Dyson, P.,
ASSOCIATED CONTENT
Supporting Information
In situ formation of frustrated Lewis pairs in a water-tolerant metal-
organic framework for the transformation of CO . Angew. Chem. Int.
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Ed. 2019, 58, 5371-5375.
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The Supporting Information is available free of charge on the
ACS Publications website.
6. Voicu, D.; Abolhasani, M.; Choueiri, R.; Lestari, G.; Seiler, C.;
Menard, G.; Greener, J.; Guenther, A.; Stephan, D. W.; Kumacheva, E.,
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F )
AUTHOR INFORMATION
7
1
760.
Corresponding Author
8. Liu, L.; Lukose, B.; Ensing, B., A free energy landscape of CO
2
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* yongquan@mail.xjtu.edu.cn.
capture by frustrated Lewis pairs. ACS Catal. 2018, 8, 3376-3381.
19. Zhang, S.; Huang, Z. Q.; Ma, Y.; Gao, W.; Li, J.; Cao, F.; Li, L.; Chang, C.
R.; Qu, Y., Solid frustrated-Lewis-pair catalysts constructed by
regulations on surface defects of porous nanorods of CeO . Nat.
2
Commun. 2017, 8, 15266.
Author Contributions
#
S. Z. and Z. X. contributed equally to this work.
2
0. Ma, Y.; Zhang, S.; Chang, C.; Huang, Z.; Ho, J. C.; Qu, Y., Semi-solid
Notes
and solid frustrated Lewis pair catalysts. Chem. Soc. Rev. 2018, 47,
The authors declare no competing financial interests.
5
2
541-5553.
1. Huang, Z. Q.; Liu, L.-P.; Qi, S.; Zhang, S.; Qu, Y.; Chang, C. R.,
ACKNOWLEDGMENTS
2
Understanding all-solid frustrated-Lewis-pair sites on CeO from
theoretical perspectives. ACS Catal. 2018, 8, 546-554.
We acknowledge the financial support from the National
Nature Science Foundation of China (21872109) and the
China Postdoctoral Science Foundation (2018M640994;
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2. Huang, W.; Gao, Y., Morphology-dependent surface chemistry and
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catalysis of CeO nanocrystals. Catal. Sci. Technol. 2014, 4, 3772-3784.
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3. Huang, W., Oxide nanocrystal model catalysts. Acc. Chem. Res.
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018T111034). Y. Qu is supported by the Cyrus Tang
2016, 49, 520-527.
Foundation through the Tang Scholar program. S. Zhang is
supported by the Fundamental Research Funds for the Central
Universities (xjj2018033). The calculations were performed
by using the HPC Platform at Xi’an Jiaotong University.
24. Nolan, M.; Grigoleit, S.; Sayle, D. C.; Parker, S. C.; Watson, G. W.,
Density functional theory studies of the structure and electronic
structure of pure and defective low index surfaces of ceria. Surf. Sci.
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005, 576, 217-229.
25. Chen, S.; Cao, T.; Gao, Y.; Li, D.; Xiong, F.; Huang, W., Probing
surface structures of CeO , TiO , and Cu O nanocrystals with CO and
CO chemisorption. J. Phys. Chem. C 2016, 120, 21472-21485.
6. Zhou, H.; Lu, X., Lewis base-CO adducts as organocatalysts for CO
transformation. Sci. China Chem. 2017, 60, 904-911.
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