Hollow Anatase TiO2 Octahedrons with Exposed High-Index {102} Facets for Improved Dye-Sensitized Photoredox Catalysis Activity

Article abstract of DOI:10.1021/acs.inorgchem.8b00307

The high activity of exposed facets and large surface area have significant effects on the performance of photocatalysts because most of the photoreactivity properties of materials are related to surface processes. The strategy of combining high-index facets and a hollow structure into one material will provide a new way for designing effective photocatalysts, possessing active exposed facets and a large surface area at the same time. However, fabricating one material with both high-index facets and a hollow structure is still a great challenge due to their thermodynamic instability. Here, hollow anatase TiO₂ octahedrons exposed with high-index (102) facets (HTO-102) were successfully fabricated for the first time by a facile hydrothermal method using HF and H₂O₂ as morphology controlling agents. Compared with two other catalysts (a solid sharp octahedron with (101) facets (SSO-101) and a hollow sharp octahedron with (101) facets (HSO-101)), HTO-102 particles exhibit a better photochemical activity for the selective aerobic oxidation of organic sulfides under visible-light irradiation. Experimental results and theoretical calculations indicate that the excellent photocatalytic activity of HTO-102 particles is mainly due to the synergistic effects of its hollow structure and exposed high-index (102) facets.

Full text of DOI:10.1021/acs.inorgchem.8b00307

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
Hollow Anatase TiO Octahedrons with Exposed High-Index {102}
2
Facets for Improved Dye-Sensitized Photoredox Catalysis Activity
†
,§
†,§
‡
†
†
,†
Fan Wang, Liming Sun, Yanan Li, Wenwen Zhan, Xiaojun Wang, and Xiguang Han*
†Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Materials Science, Jiangsu
Normal University, Xuzhou 221116, P. R. China
‡
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, P. R. China
*
S Supporting Information
ABSTRACT: The high activity of exposed facets and large
surface area have significant effects on the performance of
photocatalysts because most of the photoreactivity properties of
materials are related to surface processes. The strategy of
combining high-index facets and a hollow structure into one
material will provide a new way for designing effective
photocatalysts, possessing active exposed facets and a large surface
area at the same time. However, fabricating one material with both
high-index facets and a hollow structure is still a great challenge
due to their thermodynamic instability. Here, hollow anatase TiO2
octahedrons exposed with high-index (102) facets (HTO-102)
were successfully fabricated for the first time by a facile hydrothermal method using HF and H O as morphology controlling
2
2
agents. Compared with two other catalysts (a solid sharp octahedron with (101) facets (SSO-101) and a hollow sharp
octahedron with (101) facets (HSO-101)), HTO-102 particles exhibit a better photochemical activity for the selective aerobic
oxidation of organic sulfides under visible-light irradiation. Experimental results and theoretical calculations indicate that the
excellent photocatalytic activity of HTO-102 particles is mainly due to the synergistic effects of its hollow structure and exposed
high-index (102) facets.
INTRODUCTION
chamber through a porous hull. Meanwhile, the hollow
■
structure can enhance the utilization efficiency of incident
Photoredox catalysis has great potential in converting solar
energy to chemical energy, which can environmentally facilitate
organic transformations to valuable products.
13−15
light by multiple reflections of light in an internal cavity.
1
−4
Therefore, combining the high-index facets and hollow
structure into one material will be a new way to design highly
efficient photocatalysts. However, most of the synthesized
hollow structures are exposed without specific crystal facets,
Although
significant achievements in photocatalytic semiconductor
materials have been realized in recent years, the photocatalytic
efficiency for solar energy is still quite low for practical
16
5
−7
and a few parts are exposed with low-index crystal facets.
applications.
The catalysts with exposed high-index crystal
Thus, fabricating one material that has both high-index facets
and a hollow structure is still a great challenge, owing to the
thermodynamic instability of high-index crystal facets and
hollow structures.
facets usually show chemical activities higher than those of
catalysts with exposed low-index crystal facets, as the high-index
crystal surfaces possess a high density of kinks, edges, steps, and
low-coordinated atoms within the structures which usually
8
−10
Titanium dioxide (TiO ), an n-type metal oxide semi-
2
serve as active sites in chemical reactions.
During the
conductor (bandgap about 3.2 eV), is a promising prospect in
current decade, many noble metals and metal oxides with
exposed high-index crystal facets have been fabricated by
different synthesized strategies. At present, the already reported
metal oxide nanoparticles exposed with high-index crystal facets
usually present microscale solid bulk structures with large sizes
and low surface areas, which greatly limit their practical
application in the field of photocatalysis.
The hollow structures provide a large surface area and low
diffusion resistance for improving accessibility, which can offer
some new opportunities that can make up for the lack of
1
7
18
applications of solar cells, photocatalysis, and photosplitting
of water.
1
9−22
To date, different morphologies of TiO2
nanomaterials with exposed various crystal facets have been
23,24
fabricated via different synthesized methods.
However, the
hollow structure TiO with exposed high-index facets has not
2
been reported. In this article, we first fabricate the hollow
anatase TiO octahedron exposed with high-index {102} crystal
2
facets by a simple hydrothermal route. Due to the synergistic
effects of the hollow strucuture and exposed high-index (102)
11,12
particles with high-index facets.
The hollow cavity can also
serve as a reactor and support efficient diffusion of the
Received: February 4, 2018
reactants, solvent, and products in and out of the inside
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b00307
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Inorganic Chemistry
Article
facets, HTO-102 particles exhibit excellent photochemical
activity for selective aerobic oxidation of organic sulfides
under visible-light irradiation.
EXPERIMENTAL SECTION
Preparation of Anatase Hollow TiO2 Nanoparticles with
102} Facets (HTO-102). Hollow TiO nanoparticles with {102}
■
{
2
facets were fabricated through a one step hydrothermal method by
utilizing a potassium titanate nanowires (KTNWs) precursor (for the
synthetic method see the Supporting Information or ref 25). Typically,
a KTNWs precursor (0.025 g) was dissolved in a solution that
contained deionized water (27 mL), H O (3 mL, 30%), and HF (0.02
2
2
mL, 40 wt %). The solution was loaded into a Teflon-lined autoclave
and was heated at 180 °C for 12 h in the oven. After the autoclave was
cooled to room temperature, the products were obtained after being
washed, centrifuged, and then dried at 60 °C in an oven.
Photocatalytic Test for the Oxidation of Sulfide. Typically,
ARS-TiO2 (10 mg), thioanisole (0.3 mmol), and TEMPO (0.02
mmol) were added to CH OH (3 mL). The solution was illuminated
3
by blue LED light (3W, 450 nm) for 12 h while being constantly
1
stirred in an air atmosphere. The product yield was determined by H
NMR analysis. The recycle experiments were conducted by
centrifuging the catalytic solution and washing it with CH Cl three
2
2
times. Finally, the recycled catalysts were dried at 50 °C in a vacuum
for 24 h.
Figure 1. (a) XRD pattern. (b) SEM image of as-synthesized hollow
TiO octahedral nanocrystals. (c) TEM image of an individual hollow
2
RESULTS AND DISCUSSION
■
TiO octahedron projected from the [111] direction, where the inset
2
̅
̅
The hollow anatase TiO with exposed (102) facets (HTO-
shows the corresponding SAED pattern. (d) Schematic model of an
2
1
02) was synthesized by direct hydrolysis of KTNWs with a
ideal TiO octahedron enclosed within {102} facets viewed along the
2
certain proportion of HF and H O in a hydrothermal system
[1
̅
̅
2
2
image of the TiO octahedron viewed along the [001] direction, inset:
at 180 °C for 12 h (detailed experimental process provided in
ESI). The X-ray powder diffraction (XRD) pattern of HTO-
02 is shown in Figure 1a. All diffraction peaks could be
indexed to be the anatase phase TiO with lattice parameters a
the corresponding SAED pattern. (g) Schematic model of an ideal
TiO octahedron enclosed within {102} facets viewed along the [001]
2
1
direction. (h) The corresponding HRTEM image.
2
=
b = 3.775 Å and c = 9.49 Å (JCPDF no. 00-002-0387),
indicating the high purity of the product. The morphology and
size of the product were first examined by a SEM technique. A
typical low magnification SEM image of the product is shown
angle and the outline of the octahedral particle still coincide
well with the anatase TiO octahedral model with exposed
2
(102) facets viewed from the same direction (Figure 1g).
in Figure 1b, from which large quantities of the TiO particles
Figure 1h shows that the d-spacing is about 0.19 nm, which
2
with a porous polyhedral morphology and an average edge
length of about 90−120 nm can be found (Figure S1). Closer
observations (inset of Figure 1b) indicated that they have a
well-defined hollow octahedral structure.
corresponds well with the (200) facet of anatase TiO . The
2
above TEM result and corresponding structural analysis
indicate HTO-102 particles have a hollow structure with
exposed high-index (102) facets. The nitrogen adsorption−
desorption isotherms show that the specific surface area of
In order to collect details of the morphology and structural
2
−1
information on the hollow octahedral TiO particles, trans-
HTO-102 is about 64.1 m g , and the pore size distribution
indicates a porous structure (Figure S2), which corresponds
well with the SEM and TEM observations. In other words, the
obtained HTO-102 particles possess high-index facets, a hollow
structure, and a large BET surface area, all of which are
favorable for catalysis.
2
mission electron microscopy (TEM) observations were carried
out. The low-magnification TEM image of a single TiO2
octahedron is shown in Figure 1c, where the hollow structure
was further confirmed by the obvious contrast of the dark edges
and the pale center. The relevant selected-area electron
diffraction pattern (SAED) can be indexed to the [1
̅
̅
Their catalytic activities were evaluated by using selective
aerobic oxidation of thioanisole in methanol solvent. In order
to broaden the HTO-102 visible-light adsorption range, the dye
(alizarin red S (ARS)) was anchored onto HTO-102. In
addition, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) was
adopted as a redox mediator for preserving the anchored dye’s
stability. The catalytic reaction was performed in a Schlenk
tube by using blue-light emitting diodes (LEDs, hv 450 nm, 3
W) as the light source (Figure 2a). As shown in Figure 2b, the
conversions of thioanisole for only HTO-102 as a catalyst are
merely 3% under the visible-light irradiation. The inclusion of
the dye could lead to a dramatic increase in yield (53%) owing
to the extended visible-light adsorption range (Figure S3, UV−
vis spectrum). However, after a few minutes of visible-light
irradiation, the color of the solution had changed markedly
zone axis of single-crystal tetragonal TiO (inset Figure 1c).
2
Under electron beam illumation, the octahedron shows a
rhombic shape with a length/width proportion of about 1.15
and a vertex angle between two lateral faces of approximately
8
4°. The profile and angles correspond well with the anatase
TiO2 octahedral model with exposed (102) crystal facets
viewed from the [1 1] direction (Figure 1d). The high-
26
̅ ̅
1
resolution transmission electron microscopy (HRTEM) image
of HTO-102 is shown in Figure 1e. The lattice spacing is 0.351
nm, corresponding to the (101) lattice spacing of the anatase
phase of TiO . To further identify the enclosed facets of the
2
HTO-102, another octahedral particle viewed from the [001]
crystal zone axis was detected by TEM image (Figure 1f) and
SAED pattern analyses (inset of Figure 1f). Both the vertex
B
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Article
catalysts. As shown in Figure 2d, the photocatalytic activity of
HTO-102 particles (hollow structure and enclosed by high-
index (102) facets) is better than that of SSO-101 (solid
structure and enclosed by low-index (101) facets) and HSO-
1
01 (hollow structure and enclosed by low-index (101) facets).
In order to demonstrate the generality for this reaction, various
thioanisole derivatives were used to evaluate HTO-102
catalysts, and the yields and selectivity of the desired oxidized
product were 77−96% and 78−98%, respectively (Table 1). In
Table 1. Scope of Visible-Light-Induced Selective Oxidation
of Sulfides to Sulfoxides in Air on ARS-Sensitized HTO-102
with TEMPO as a Redox Mediator
R1
R2
[H]
R3
[H]
conv. (%)
select. (%)
1
2
3
4
5
6
7
8
[Cl]
90
92
93
90
96
77
82
94
98
98
98
96
97
78
98
98
[F]
[H]
[H]
[Br]
[H]
[H]
Figure 2. (a) Photocatalytic equation and reaction conditions. (b)
Conversion of thioanisole with different experimental conditions,
inset: photograph of before (I) and after (II) with TMMPO and (III)
without TEMPO visible-light reaction. (c) Conversion of thioanisole
irradiated by different light sources. (d) Product yield with respect to
reaction time in the selective oxidation of sulfides into sulfoxides by
various catalysts. (e) Recycling experiments using various catalysts.
[Me]
[MeO]
[NO2]
[H]
[H]
[H]
[H]
[H]
[H]
[H]
[MeO]
[H]
[H]
[H]
[MeO]
order to evaluate the catalytic stability, we carried out the cycle
performance of SSO-101, HSO-101, and HTO-102 catalysts for
the selective aerobic oxidation of thioanisole (Figure 2e). The
results reveal that the HTO-102 catalyst possesses an
outstanding catalytic stability and maintains an above 90%
conversion rate for the selective aerobic oxidation of thioanisole
within 12 h even after four cycles. The above results suggested
that the HTO-102 possessed outstanding catalytic activity and
stability.
(
inset of Figure 2bII and Figure S4), which indicated the
oxidation of ARS itself rather than the oxidation of thioanisole.
With the addition of the TEMPO redox mediator, the
stability and catalytic efficiency of dispersed ARS-TiO could be
2
substantially increased. The above contrast experiments
revealed that dye sensitivity and having a TEMPO redox
mediator were two basic conditions for this catalytic reaction.
When the light source was switched to yellow light (590 nm, 3
W) and green light (530 nm, 3 W), the catalytic conversion was
able to achieve a low conversion of only 13% and 56%,
respectively (Figure 2c). Therefore, suitable experimental
conditions for this catalysis used blue LEDs as the light source
in the presence of ARS and TEMPO. The catalytic reaction
result is shown in Figure 2d. Compared with sharp octahedrons
with (101) facets (SSO-101) (Figure S5), hollow sharp
octahedrons with (101) facets (HSO-101) (Figure S6) show
better reactivity after 12 h irradiation, indicating that the
existence of having hollow structures could enhance the
catalytic activity under the same reaction conditions. The
hollow structures have three advantages for improving the
photocatalytic activity of catalysts: (1) the inner cavity can
enlarge the surface area (the specific surface areas of HSO-101
All catalytic experiments were performed as follows:
photocatalyst (10 mg), sulfide (0.3 mmol), and TEMPO
(0.02 mmol) were added to CH OH (3 mL). The mixture was
3
stirred and then irradiated by blue LEDs (450 nm, 3 W) for 12
1
h under an air atmosphere at room temperature. H NMR
analysis was employed to determine the yield.
Based on the control experiments and others’ previous
findings, a probable reaction mechanism for visible-light
photoredox catalysis by ARS-sensitized TiO with TEMPO as
2
a redox mediator is proposed and illustrated in Scheme 1.
Under blue-light irradiation, dye molecules (ARS) were excited
to an excited state (ARS*) and the generated electrons were
injected into the conduction band of TiO . These electrons
2
travel through the conduction band of TiO to react with
2
2
−1
and SSO-101 are about 59.9 and 26.7 m g , respectively, as
the BET measurement shows in Figure S7), which increases the
active sites of the catalyst; (2) the hollow structure can increase
the multiple light reflections, which can enhance the utilization
efficiency of incident light; and (3) the hollow structure can
shorten the diffusion length of photogenerated electrons and
holes. High-index facets, defined as a series of Miller index
chemisorbed oxygen on the TiO surface, thereby forming
2
•
−
O2 , which prefers to react with an S-centered free-radical
cation for the evolution of sulfide peroxide. Therefore, the
amount of photogenerated electrons played a key role in
determining photocatalytic efficiency. In theory, the two
characteristics of hollow structure and high-index facets will
contribute to more effective contact between HTO-102 and the
dye molecules, resulting in the production of a large number of
photogenerated electrons.
{
hkl} with not less than one index greater than unity, can
generally provide more catalytic active sites (e.g., more atomic
steps and dangling bonds) than low-index facets can. Therefore,
synergistic effects of a hollow structure and high-index plane in
one material will further improve the catalytic activity of
To prove this, the photocurrent density of three ARS-
sensitized TiO samples was measured by using a 0.2 V
2
potential under light (i.e., illuminated) and dark (i.e., non-
C
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Inorganic Chemistry
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Scheme 1. Proposed Mechanism of Selective Aerobic
Oxidation of Thioanisole by ARS-HTO-102 under Blue-
Light Irradiation
ray photoelectron spectroscopy (XPS) analyses were used. The
fully scanned spectra (Figure S9) showed that Ti and O
element signals existed in the SSO-101, HSO-101, and HTO-
1
02 samples. Figure 4a shows the high-resolution XPS spectra
Figure 4. (a) High-resolution XPS spectra of Ti . (b) XPS spectra
2p
and curve fitting of O 1s in SSO-101, HSO-101, and HTO-102.
of Ti , in which the peak located at 464.4 eV corresponds to
2p
Ti2p1/2 and the other peak located at 458.6 eV was assigned to
Ti2p3/2. This indicated that the distribution and position of the
Ti2p XPS peaks of the three samples were basically analogous.
However, the high-resolution O XPS peaks of the three TiO
2
illuminated) conditions with 20 s intervals. Figure 3a shows
that the sequence of average photocurrent densities was HTO-
1s
samples had some slight differences. The O core level peaks
1s
could be resolved into three centered Gaussian components
(
Figure 4b). The OL component (529.6 ± 0.1 eV) was
associated with the lattice oxygen in the anatase TiO phase.
2
The O peak at the medium binding energy (530.2 ± 0.1 eV)
V
2−
was usually assigned to the O ions in the oxygen-deficient
region, and the O component (531.8 ± 0.1 eV) was associated
C
−
−
with the dissociated and chemisorbed oxygen species (O , O ,
and O ). Therefore, the peak area of the O constituents in
2
2
−
C
the O1s XPS spectrum can be used to estimate the oxygen-
27
chemisorbed amount of the three various materials. Table 2
Figure 3. (a) Photocurrent density of three ARS-sensitized TiO2
samples measured at 0.2 V versus Hg/Hg Cl under non-illuminated
2
2
(
i.e., dark) and visible-light illuminated (xenon lamp with an optical
Table 2. Results of Curve Fitting of O 1s Spectra in Three
filter UVCUT-420) conditions. (b) UV−vis adsorption spectra of the
cationic radical of TMPD generated by three ARS-sensitized TiO2
samples in the presence of light and oxygen.
Different TiO Samples
2
TiO2
Ti
2p3/2
Ti
OV
OC
samples
2p1/2 O (Ti−O) (vacancy) (chemisorbed)
L
SSO-101
HSO-101
HTO-102
710.2
710.7
710.2
723.5
724.1
723.8
529.7
530.2
37.6%
530.2
25.6%
530.1
24.1%
531.8
4.8%
531.8
9.1%
1
02 > HSO-101 > SSO-101. Electrochemical impedance
5
7.6%
spectroscopy (EIS) results (Figure S8) further demonstrated
that a high separation efficiency of photogenerated electron−
hole pairs and fast interfacial electron and hole transfers
occurred for HTO-102. The above results show that the
amount of effective photogenerated electrons increases due to
the existence of hollow structures and high-index facets. The
molecular oxygen was reduced by separated electrons to obtain
superoxide radical (O2• ), which was confirmed as generated
by the cationic radical species of N,N,N′,N′-tetramethyl-
phenylenediamine (TMPD) (Figure 3b). Under irradiation
with a blue LED, blue color species with absorption bands at
529.7
6
5.3%
529.6
531.7
6
2.1%
13.8%
shows that the relative proportions of the O component in the
C
−
three various materials are about 4.8% (SSO-101), 9.1% (HSO-
101), and 13.8% (HTO-102). Obviously, HTO-102 samples
could absorb a quantity of oxygen species higher than that of
the HSO-101 and SSO-101 samples. The above comparison of
XPS experimental results confirms that the two factors of
hollow structure and high-index facets play a key role in the
enhancement of capacity for surface oxygen adsorption.
In addition to the large surface area, the structure of the
exposed surface also plays an important role in oxygen
adsorption, because HTO-102 can absorb oxygen species in
an amount greater than that of HSO-101, as the results of XPS
analysis show. In order to further explore the influences of
surface structures on oxygen adsorption, the surface structures
563 and 612 nm were formed by ARS-TiO mediating the
2
abstraction of an electron from TMPD. Compared with those
of ARS-SSO-101 and ARS-HSO-101, the solution after ARS-
HTO-102 reaction had stronger absorption peaks at 563 and
612 nm, which demonstrated ARS-HTO-102 could produce
•
−
more O2 . The above results were consistent with the
photoredox catalysis activity of the three different catalysts.
In the whole photocatalytic process, the amount of
chemisorbed oxygen on the TiO surface, which is determined
2
by the surface structure of the catalyst, also plays a key role in
of anatase TiO (102) and (101) surfaces were calculated, and
the optimized structures are shown in Figure 5a and 5b,
2
the improvement of forming O2• . In order to obtain useful
−
information about chemisorbed oxygen on the TiO surface, X-
respectively. By comparing Figure 5a and 5b, we find that the
2
D
DOI: 10.1021/acs.inorgchem.8b00307
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Inorganic Chemistry
Article
CONCLUSION
■
In conclusion, the hollow anatase TiO octahedrons with
2
exposed high-index (102) facets have been successfully
synthesized by a facile hydrothermal method with HF and
H O as morphology controlling agents. Experimental results
2
2
and theoretical calculations indicate that HTO-102 easily
absorbed sensitized dye molecules and oxygen species, which
resulted in the production of a large amount of photogenerated
•
−
electrons and superoxide radicals (O2 ). Due to the synergistic
influence of exposed high-index crystal facets and its hollow
structure, HTO-102 exhibits a photochemical activity for the
selective aerobic oxidation of organic sulfides under visible-light
irradiation better than that of SSO-101 and HSO-101. This
result can be used as a new strategy for designing highly
efficient photocatalysts for catalyzing many organic reactions.
ASSOCIATED CONTENT
■
*
S
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b00307.
Experiment details; size distribution, BET, and UV−vis
absorption of HTO-102 (Figures S1−S3); and XRD,
SEM, BET, and XPS of SSO-101 and HSO-101 (Figures
S4−S8) (PDF)
AUTHOR INFORMATION
■
Figure 5. Optimized surface structure of anatase TiO (102) (a) and
Corresponding Author
*E-mail: xghan@jsnu.edu.cn.
2
(
101) (b). The optimized stable configurations for O adsorption on
2
TiO2 (102) (c) and (101) (d). The projected density of states
ORCID
(
PDOSs) of O adsorbed TiO (102) (e) and (101) (f).
2 2
Xiaojun Wang: 0000-0002-1461-4922
Xiguang Han: 0000-0003-2469-4572
Author Contributions
Authors contributed equally to this paper.
§
(
102) surface possesses more wrinkles than the (101) surface,
which is beneficial to oxygen adsorption. Ti sites are the main
active sites for oxygen adsorption on TiO surfaces. The anatase
TiO (102) surface is composed of Ti (four-coordination Ti),
Notes
2
The authors declare no competing financial interest.
2
4c
while the (101) surface consists of Ti (five-coordination Ti).
5
c
ACKNOWLEDGMENTS
The Ti on the (102) surface can provide electrons to oxygen
■
4c
more easily than the Ti5c on the (101) surface, resulting in a
This work was supported by the National Natural Science
Foundation of China (21671085, 11674101, and 21333008),
the Jiangsu Province Science Foundation for Youths
(BK20150237), the Natural Science Foundation of Jiangsu
Province (BK20161160), the Qing Lan Project, and the Project
Funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions.
greater oxygen adsorption on the TiO (102) surface. The
2
optimized stable configurations of oxygen adsorbed on anatase
TiO (102) and (101) surfaces are shown in Figure 5c and 5d,
2
respectively. The calculated adsorption energies of these two
configurations are −8.65 and 5.17 eV, respectively. The oxygen
adsorption on the TiO (102) surface is an exothermic process,
2
while the process of oxygen adsorbed on the (101) surface is
endothermic, indicating that the adsorption of oxygen is
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E
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DOI: 10.1021/acs.inorgchem.8b00307
Inorg. Chem. XXXX, XXX, XXX−XXX