Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation

Article abstract of DOI:10.1021/jacs.8b03121

The hydrosilylation reaction is one of the largest-scale application of homogeneous catalysis and is widely used to enable the commercial manufacture of silicon products. However, considerable issues including disposable platinum consumption, undesired side reactions and unacceptable catalyst residues still remain. Here, we synthesize a heterogeneous partially charged single-atom platinum supported on anatase TiO₂ (Pt₁^δ+/TiO₂) catalyst via an electrostatic-induction ion exchange and two-dimensional confinement strategy, which can catalyze hydrosilylation reaction with almost complete conversion and produce exclusive adduct. Density functional theory calculations reveal that unexpected property of Pt₁^δ+/TiO₂ originates from atomic dispersion of active species and unique partially positive charge Pt^δ+ electronic structure that conventional nanocatalysts do not possess. The fabrication of single-atom Pt₁^δ+/TiO₂ catalyst accomplishes a reasonable use of Pt through recycling and maximum atom-utilized efficiency, indicating the potential to achieve a green hydrosilylation industry.

Full text of DOI:10.1021/jacs.8b03121

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Communication
Discovering Partially Charged Single-Atom Pt for
Enhanced Anti-Markovnikov Alkene Hydrosilylation
Yuanjun Chen, Shufang Ji, Wenming Sun, Wenxing Chen, Juncai Dong, Junfeng Wen, Jian
Zhang, Zhi Li, Lirong Zheng, Chen Chen, Qing Peng, Dingsheng Wang, and Yadong Li
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b03121 • Publication Date (Web): 04 Jun 2018
Downloaded from http://pubs.acs.org on June 4, 2018
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Discovering Partially Charged Single-Atom Pt for Enhanced Anti-
Markovnikov Alkene Hydrosilylation
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Yuanjun Chen, † Shufang Ji, † Wenming Sun, † Wenxing Chen, Juncai Dong, Junfeng
1
1
1
3
1
1
1
Wen, Jian Zhang, Zhi Li, Lirong Zheng, Chen Chen, Qing Peng, Dingsheng Wang, * and
1
Yadong Li
1
Department of Chemistry, Tsinghua University, Beijing 100084, China
2
State Key Laboratory of Green Building Materials, China Building Materials Academy, Beijing 100041, China
3
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing
100049, China
Supporting Information
a combination of the advantages of homogeneous and hetꢀ
erogeneous catalysts.
ABSTRACT: The hydrosilylation reaction is one of the
largestꢀscale application of homogeneous catalysis and is
widely used to enable the commercial manufacture of siliꢀ
con products. However, considerable issues including disꢀ
posable platinum consumption, undesired side reactions
and unacceptable catalyst residues still remain. Here, we
Singleꢀatom catalysts (SACs) have attracted significant
7
research attention. Homogenized active sites and coordiꢀ
nation environment, similar to their homogeneous anaꢀ
logues, make SACs idea bridges to connect homogeneous
8
synthesize a heterogeneous partially charged singleꢀatom
and heterogeneous catalysis. Furthermore, with full metal
δ+
platinum supported on anatase TiO
2
(Pt
1
/TiO
2
) catalyst via
dispersity and maximum atom efficiency, SACs exhibit enꢀ
9
an electrostaticꢀinduction ion exchange and twoꢀ
dimensional confinement strategy, which can catalyze hyꢀ
drosilylation reaction with almost complete conversion and
hanced catalytic performance with low metal consumption.
However, it is not easy to maintain atomic dispersion of
active species under preparation and reaction against agꢀ
7
a,10
produce exclusive adduct. Density functional theory calculaꢀ
gregation owing to high surface energy.
The spatial conꢀ
δ+
tions reveal that unexpected property of Pt
1
/TiO
2
origiꢀ
finement of these species to prevent their mobile trend with
the aid of suitable supports, such as cavities of MOFs and
tunnels of zeolites, has been developed to address this isꢀ
nates from atomic dispersion of active species and unique
δ+
partially positive charge Pt electronic structure that conꢀ
11
ventional nanocatalysts do not possess. The fabrication of
sue. Lamellar metal oxides are a class of towꢀdimensional
(2D) functional materials, consist of layers and abundant
δ+
singleꢀatom Pt
1 2
/TiO catalyst accomplishes a reasonable
1
2
use of Pt through recycling and maximum atomꢀutilized effiꢀ
ciency, indicating the potential to achieve a green hydrosiꢀ
lylation industry.
interlayer metal ions. The subnanometer interlayer can
efficiently trap active species in 2D spaces and interlayered
ions can serve as a fence to further expand the adjacent
distances of active species, assisting in restricting their agꢀ
glomeration and maintaining atomic dispersion.
Scheme 1. Illustration of preparation process of
The hydrosilylation reaction, the mild and atomꢀeconomic
route for the formation of SiꢀC bond, is one of the most inꢀ
dustrial process in silicon chemistry because of its wideꢀ
spread application in the commercial manufacture of orgaꢀ
δ+
Pt
1 2
/TiO .
1
nosilicon compounds. Despite widespread application,
homogeneous Ptꢀbased catalysts still suffer from many
considerable issues. Owing to unwanted isomerization,
highꢀcost and energyꢀintensive purifications have to be carꢀ
1
b,2
ried out.
And the decomposition of catalysts usually
gives rise to undesired side reactions and the coloration of
products, which has significant deleterious effects on the
quality of products and limit their applications, especially in
Inspired by great features of lamellar metal oxides, we
develop a novel approach to accomplish synthesis of singleꢀ
atom materials via an electrostaticꢀinduction ion exchange
and twoꢀdimensional confinement strategy. As illustrated in
Scheme 1, this strategy includes three steps: (1) inducing
3
medical supplies. Moreover, the disposable consumption of
platinum not only contributes to high catalyst cost, but also
4
results in appalling waste of scarce platinum resources.
These drawbacks push the development of heterogeneous
adsorption of the cationic metal complex onto the negatively
5
catalysts, featured with facile separation and recycling.
2ꢀ
charged 2D Ti
3
O
7
sheets of titanate via electrostatic attracꢀ
However, owing to low efficiency of atom utilization or
leaching of active species, current heterogeneous catalysts
tion and intercalation into the interlayers through ion exꢀ
+
change with interlayered ions Na ; (2) calcination for phase
6
exhibit unsatisfying performance and limited stability. It is
transformation and enhanced metalꢀsupport interaction; and
urgent but challenging to develop remarkable materials with
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δ+
(
3) further reduction treatment to give the final Pt /TiO
1 2
δ+
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1 2
catalyst. The Pt /TiO containing Pt up to 0.58 % exhibit
remarkable activity (100%) and optimal selectivity (100%)
towards antiꢀMarkovnikov alkene hydrosilylation. Density
functional theory calculations reveal that excellent perforꢀ
mance is attributed to atomic dispersion of active species
and unique electronic structure of intermediate valence.
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δ+
Figure 2. (a) EXAFS FT spectra of Pt
1
/TiO
2
, Pt foils and
2 1 2
. (b,c) EXAFS WT spectra of Pt /TiO , Pt foils. (d)
δ+
δ+
PtO
XPS spectra for Pt 4f of Pt
1
/TiO
2
. (e) XANES spectra of
δ+
Pt
1
2 2
/TiO , Pt foils and PtO .
δ+
To reveal the local structure of Pt
1
2
/TiO , extended Xꢀray
absorption fine structure (EXAFS) measurement and waveꢀ
let transform (WT) analysis were performed. Figure 2a
shows the Pt EXAFS Fourier transform (FT) curves of
δ+
δ+
Pt
1 2 1 2
/TiO and references. Pt /TiO exhibits only one
prominent peak at about 1.6 Å, associated with the first
shell of PtꢀO scattering. And no reflection from PtꢀPt contriꢀ
bution is observed, compared with FT curve of Pt foils. It
well demonstrates the sole existence of atomically disꢀ
persed Pt in Pt1 /TiO . To further reinforce this finding, WT
analysis of Pt EXAFS oscillations was performed (Figure
2b), which can provide powerful resolution in both k and R
spaces. As illustrated by the WT contour plots of Pt foils
and PtO (Figures 2c and S4), the intensity maxima at 5.5
and 8.5 Å are ascribed to the PtꢀO and PtꢀPt contribuꢀ
tions, respectively. In the WT contour plots of Pt
there is only one intensity maximum at about 5.3 Å from
the PtꢀO contributions, while no intensity maximum near 8.5
indexed to PtꢀPt path is detected. Taken together with
AC HAADFꢀSTEM, EXAFS and WT analysis, it can be eviꢀ
denced that Pt atoms are atomically dispersed in Pt
and stabilized by O atoms. The quantitative EXAFS fitting
was performed (Figure S5), and structural parameters of Pt
Figure 1. (a) TEM image, (b) HRTEM image, (c) HAADFꢀ
STEM image and corresponding element maps, Pt (blue), Ti
δ+
2
(
green), O (red), respectively, and (d) AC HAADFꢀSTEM
δ+
image of Pt
1 2
/TiO .
1
4
The titanate Na
prepared based on our previously reported methods. As
revealed by transmission electron microscopy (TEM) image
x 3 7
H2ꢀxTi O (x=0.75) nanotubes were firstly
13
2
ꢀ
1
ꢀ1
Å
δ+
1 2
/TiO ,
ꢀ1
in Figure S1, the obtain materials show multilayered tubular
δ+
structure. In a typical synthesis of Pt
1 2
/TiO , the cationic Pt
2
+
complex [Pt(NH
3
)
4
]
was injected into acid aqueous soluꢀ
ꢀ1
Å
tion containing titanate nanotubes, followed by stirring to
2+
induce adsorption of [Pt(NH
3
)
4
]
onto the negatively
δ+
2ꢀ
1 2
/TiO
charged 2D Ti
ion exchange with interlayered Na ions, [Pt(NH
located between interlayers and confined by 2D Ti
sheets and abundant interlayered ions. Then, the Ptꢀ
intercalated titanate transformed into anatase TiO via calꢀ
cination in air at 400 C, as confirmed by XRD peaks inꢀ
dexed to anatase TiO (Figure S2). Followed by treatment
atmosphere, partially charged isoꢀ
3 7
O
sheets via electrostatic attraction. After
+
2+
3
)
4
]
was
2ꢀ
3
O
7
δ+
in Pt
1 2
/TiO are listed in Table S1. For comparisons, the
fitting results of Pt foils and PtO
S6 and S7.
2
are displayed in Figures
2
o
δ+
2
The oxidation state of Pt in Pt1 /TiO was analyzed by Xꢀ
2
o
at 160 C in a 5% H
2
/N
2
ray photoelectron spectroscopy (XPS) and shown in Figure
2d. The Pt 4f spectrum can be deconvoluted into two peaks
at binding energies of 75.8 eV and 72.4 eV, corresponding
to 4f5/2 and 4f7/2 level, respectively. The peak positions are
between those of Pt (II) and Pt (0), indicating Pt atoms carry
partially positive charge through electron tranfer between
metal and supports owing to enhanced metalꢀsupport
interaction. Further electronic structure can be verified by Xꢀ
ray absorption nearꢀedge structure (XANES) spectra. The
white line intensities feature associated with the oxidation
lated Pt atoms were formed. To achieve electrostaticꢀ
induction ion exchange, selecting cationic complex as preꢀ
cursors is important, as supported by the presence of Pt
2ꢀ
nanoparticles in control sample by employing anionic PtCl
6
(
Figure S3). As shown in TEM and highꢀresolution TEM
δ+
(HRTEM) images of Pt
1 2
/TiO (Figure 1a and 1b), the tubuꢀ
lar layered structure partially shrinks. The highꢀangle annuꢀ
lar darkꢀfield scanning TEM (HAADFꢀSTEM) image indiꢀ
cates no obvious nanoparticles are observed (Figure 1c).
As revealed by energyꢀdispersive Xꢀray spectroscopy
state of Pt. As shown in Figure 2e, the white line intensity of
Pt1 /TiO is higher than that of Pt foils and lower than that
of PtO , demonstrating the partial oxidation state of Pt.
δ+
2
(EDS), Pt, Ti and O elements are uniformly dispersed. Aberꢀ
rationꢀcorrected HAADFꢀSTEM (ACꢀHAADFꢀSTEM) image
demonstrates several isolated bright dots marked by yellow
circles, corresponding to individual Pt atoms (Figure 1d).
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from d state of Pt to TiO support, leaving the electron denꢀ
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sity at Pt sites depleted compared with metallic Pt. The calꢀ
δ+
culated Hirshfeld charge on Pt in Pt
1
/TiO
2
is +0.51 (Figure
δ+
S15), revealing that Pt
1 2
/TiO possesses unique partially
positive valence electronic structure, consistent with the
XPS and XAENS results. Kinetically, the excellent hydrosiꢀ
δ+
lylation performance of Pt
1 2
/TiO catalyst may be attributed
to the intrinsic nature of partially charged Pt (δ+) atoms.
Since the partially charged Pt (δ+) electronic structure of
δ+
Pt
1 2
/TiO has been generated prior to reaction proceeding,
it does not need to undergo an extra reduction process to
form a lower oxidation state to initiate hydrosilylation reacꢀ
tion compared with other higher oxidation state platinum (IV
1
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Figure 3. (a) The scheme of hydrosilylation reactions with
ꢀoctene and (EtO) SiH. (b) Conversion (%) of 1ꢀoctene vs
, Pt NPs, and commercial Pt/C. (c) Correꢀ
6a,15
or II) catalysts.
1
3
δ+
time for Pt
1 2
/TiO
sponding TOFs obtained at 20% conversion of 1ꢀoctene.
δ+
When we applied Pt
1 2
/TiO to catalyze hydrosilylation of
1
ꢀoctene as a representative substrate with triethoxysilane
(
(EtO) SiH) (Figure 3a), we find it achieves almost complete
3
conversion and exquisite selectivity, which only antiꢀ
Markovnikov addition product triethoxy(octyl)silane is deꢀ
tected by gas chromatographyꢀmass spectrometer (GCꢀMS)
analysis (Figure 3b), and no obvious alkene isomerization is
observed. The calculated turnover frequency (TOF) of
δ+
ꢀ1
Pt
1 2
/TiO is achieved as high as 780 h (Figure 3c). And it
also exhibits excellent reusability (Figure S8). Moreover, the
δ+
spent Pt
1 2
/TiO catalyst was fully characterized, indicating
atomic dispersion of Pt atoms is well maintained (Figures
S9ꢀS12).
For comparison, Pt nanoparticles supported TiO
NP/TiO ) was prepared and examined (Figure S13), which
exhibits only 47% conversion of 1ꢀoctene with a low TOF of
2
(Pt
2
ꢀ
1
1
(
36 h (Figure 3c). In addition, much lower conversion
ꢀ1
38%) of 1ꢀoctene and TOF (67 h ) is observed over the
commercial Pt/C.
In addition, we examined the alkene and silane scope of
δ+
Figure 4. (a) Optimized structure of Pt
plots of Pt
1 2
/TiO . (b) EDD
δ+
hydrosilylation reaction with Pt
1
/TiO
2
, and the results are
δ+
1 2
/TiO . The positive (in red) or negative (in blue)
presented in Table S2. 1ꢀhexene can be well catalyzed with
(EtO) SiH (entry 1) in nearly complete conversion, only disꢀ
region indicates where the electron density is enriched or
3
depleted. (c) Reaction paths for hydrosilylation reactions on
playing the corresponding linear antiꢀMarkovnikov product.
The functionalized terminal alkenes bearing ether (allyl glycꢀ
idyl ether, entry 2) and ester (entry 3) are demonstrated to
react successfully to obtain excellent selective target moꢀ
lecular. When the substituted alkene substrate is aryl ring,
the desired product is achieved in 98% conversion and ~
90% selectivity (entry 4). The aminoꢀ, hydroxylꢀ and chloricꢀ
functionalized alkenes also are catalyzed smoothly in ~97%
conversion and ~99% selectivity (entrys 5 to 7). Moreover,
δ+
Pt NP and Pt
1 2
/TiO . The gray, blue, light blue, red, and
white balls represent Pt, N, Ti, O, and H atoms, respectiveꢀ
ly. To highlight the reaction sites, pink and green balls repꢀ
2 3
resent the C1 and C2 in CH =CHꢀCH , respectively.
1
5a
As proposed by Chalk and Harrod, the reaction mechꢀ
anism of Ptꢀcatalyzed alkene hydrosilylation consists of SiꢀH
oxidative addition to Pt and alkene insertion into the PtꢀH
bond followed by SiꢀC reductive elimination. As shown in
Figures S16 to S18, our results confirm that on both Pt NP
different tertiary silane types of hydrosilylation like HSiEt
and HSiCl Me (entry 8 and 9), can also work well with 1ꢀ
3
δ+
and Pt
1 2
/TiO , the ChalkꢀHarrod mechanism is more favorꢀ
2
able than the modified ChalkꢀHarrod mechanism, where
alkene inserts into the PtꢀSi bond. The energy profiles of
detailed reaction pathway along the ChalkꢀHarrod mechaꢀ
nism of two catalyst models are shown in Figure 4c. The
energy barriers in the SiꢀC reductive elimination step are the
highest, suggesting that the third step is the rateꢀ
determining step of this reaction. For the rateꢀdetermining
step, the atomic dispersion of isolated Pt atoms plays a key
role in facilitating the SiꢀC reductive elimination (Figure
octene and provide 99% selectivity to relevant products in
conversion of 97% and 96%, respectively.
Furthermore, density functional theory (DFT) calculation
was performed to investigate structural and electronic propꢀ
δ+
erties of Pt
1 2
/TiO and understand reaction mechanism.
Two catalyst models (Figure S14) were constructed to repꢀ
resent different aggregation of Pt species. Pt nanoparticle
(
Pt NP) represents the smallest 3D nanoparticle without
δ+
TiO
single atom on TiO
Figure 4b shows the electron density difference (EDD)
2
support. Pt
1
2
/TiO represents the interfacial model of
S20). Overall, in the three elementary steps, energy barriers
2
support (Figure 4a).
δ+
for Pt
1 2
/TiO are lower than those for Pt NP thermaldynamꢀ
ically. The calculated results are consistent with high activity
δ+
δ+
2
plot of Pt
1
/TiO2. The electron density between Pt atom and
and selectivity for Pt1 /TiO observed in experiment.
their adjacent O atoms increases, indicating the formation of
chemical bonds. Moreover, the EDD around Pt shows a
typical d characteristic. A significant electron transfer occurs
In summary, we have developed a new and robust cataꢀ
lyst with partially charged Pt as single atomic sites on anaꢀ
tase TiO , which exhibits remarkable activity, optimal selecꢀ
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tivity and excellent reusability towards antiꢀMarkovnikov
Tondreau, A. M.; Atienza, C. C.; Weller, K. J.; Nye, S. A.; Lewis, K.
M.; Delis, J. G.; Chirik, P. J. Science 2012, 335, 567.
(2) Marko, I. E.; Sterin, S.; Buisine, O.; Mignani, G.; Branlard, P.;
Tinant, B.; Declercq, J. P. Science 2002, 298, 204.
(3) (a) Lewis, L. N., Stein, J., Gao, Y., Colborn, R. E., Hutchins,
G. Platinum Met. Rev. 1997, 41, 66; (b) Lykissa, E. D.; Maharaj, S.
V. Anal. Chem. 2006, 78, 2925; (c) Arepalli, S. R.; Bezabeh, S.;
Brown, S. L. J. Long-Term Eff. Med. Implants. 2002, 12, 8.
(4) (a) Holwell, A. J. Platinum Met. Rev. 2008, 52, 243; (b) Yang,
C.ꢀJ. Energy Policy 2009, 37, 1805.
1
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alkene hydrosilylation. The unexpected property of
δ+
Pt
1 2
/TiO can be attributed to unique partially positive vaꢀ
lence electronic structure and atomic dispersion of Pt speꢀ
δ+
cies. The fabrication of Pt
1 2
/TiO achieves reasonable use
of catalysts by reducing consumption of precious platinum
through recycling and maximum atomꢀutilized efficiency in
the form of singleꢀatom Pt, demonstrating the potential to
achieve a green hydrosilylation industry. This work provides
a concrete example to demonstrate singleꢀatom catalysts
can be a bridge to realize the heterogenization of homogeꢀ
neous catalysis.
(5) (a) Li, F.; Li, Y. J. Mol. Catal. A: Chem. 2016, 420, 254; (b)
Alonso, F.; Buitrago, R.; Moglie, Y.; RuizꢀMartínez, J.; Sepúlvedaꢀ
Escribano, A.; Yus, M. J. Org. Chem. 2011, 696, 368; (c) Silbestri,
G. F.; Flores, J. C.; de Jesús, E. Organometallics 2012, 31, 3355.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
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0
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0
1
2
3
4
5
6
7
8
9
0
(
6) (a) Bandari, R.; Buchmeiser, M. R. Catal. Sci. Technol. 2012,
ASSOCIATED CONTENT
Supporting Information
2
, 220; (b) Pagliaro, M.; Ciriminna, R.; Pandarus, V.; Béland, F. Eur.
J. Org. Chem. 2013, 2013, 6227.
(7) (a) Yang, X. F.; Wang, A.; Qiao, B.; Li, J.; Liu, J.; Zhang, T.
Acc. Chem. Res. 2013, 46, 1740; (b) Fei, H.; Dong, J.; Feng, Y.;
Allen, C. S.; Wan, C.; Volosskiy, B.; Huang, Y. Nat. Catal. 2018, 1,
3; (c) Guo, X.; Fang, G.; Li, G.; Ma, H.; Fan, H.; Yu, L.; Bao, X.
Science 2014, 344, 616.
(8) (a) Wang, L.; Zhang, W.; Wang, S.; Gao, Z.; Luo, Z.; Wang,
X.; Zeng, J. Nat. Commun. 2016, 7, 14036; (b) Liu, P.; Zhao, Y.; Qin,
R.; Mo, S.; Chen, G.; Gu, L.; Zheng, N. Science 2016, 352, 797.
Detailed experimental sections; figures; tables. This materiꢀ
al is available free of charge via the Internet at
http://pubs.acs.org.
6
AUTHOR INFORMATION
Corresponding Author
(9) (a) Qiao, B.; Liang, J.ꢀX.; Wang, A.; Xu, C.ꢀQ.; Li, J.; Zhang,
T.; Liu, J. J. Nano Res. 2015, 8, 2913; (b) Lin, L.; Zhou, W.; Gao, R.;
Yao, S.; Zhang, X.; Xu, W.; Ma, D. Nature 2017, 544, 80.
*
wangdingsheng@mail.tsinghua.edu.cn
(10)Corma, A.; Concepcion, P.; Boronat, M.; Sabater, M. J.;
Author Contributions
Navas, J.; Yacaman, M. J.; Mayoral, A. Nat. Chem. 2013, 5, 775.
(11) (a) Chen, Y.; Ji, S.; Wang, Y.; Dong, J.; Chen, W.; Li, Z.; Li, Y.
Angew. Chem. Int. Ed. 2017, 56, 6937; (b) Liu, L.; Diaz, U.; Arenal,
R.; Agostini, G.; Concepcion, P.; Corma, A. Nat. Mater. 2017, 16,
Y. Chen, S. Ji, and W. Sun contributed equally to this work.
Notes
The authors declare no competing financial interests.
1
32; (c) Wang, N.; Sun, Q.; Bai, R.; Li, X.; Guo, G.; Yu, J. J. Am.
Chem. Soc. 2016, 138, 7484.
12) (a) Khan, A. I.; O’Hare, D. J. Mater. Chem. 2002, 12, 3191;
b) Lu, K.; Hu, Z.; Xiang, Z.; Ma, J.; Song, B.; Zhang, J.; Ma, H.
Angew. Chem. Int. Ed. 2016, 55, 10448.
13) Sun, X.; Li, Y. Chemistry 2003, 9, 2229.
ACKNOWLEDGMENT
(
(
This work was supported by China Ministry of Science and
Technology under Contract of 2016YFA (0202801), the
National Natural Science Foundation of China (21521091,
(
(14) Funke, H.; Scheinost, A. C.; Chukalina, M. Phys. Rev. B
005, 71, 094110.
2
1390393, U1463202, 21471089, 21671117, 21703219).
2
(15) (a) Chalk, A. J.; Harrod, J. F. J. Am. Chem. Soc. 1965, 87,
REFERENCES
16; (b) Stein, J.; Lewis, L. N.; Gao, Y.; Scott, R. A. J. Am. Chem.
Soc. 1999, 121, 3693.
(1) (a) Nakajima, Y.; Shimada, S. RSC Adv. 2015, 5, 20603; (b)
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