Cathodized copper porphyrin metal-organic framework nanosheets for selective formate and acetate production from CO2 electroreduction

Article abstract of DOI:10.1039/c8sc04344b

An efficient and selective Cu catalyst for CO₂ electroreduction is highly desirable since current catalysts suffer from poor selectivity towards a series of products, such as alkenes, alcohols, and carboxylic acids. Here, we used copper(ii) paddle wheel cluster-based porphyrinic metal-organic framework (MOF) nanosheets for electrocatalytic CO₂ reduction and compared them with CuO, Cu₂O, Cu, a porphyrin-Cu(ii) complex and a CuO/complex composite. Among them, the cathodized Cu-MOF nanosheets exhibit significant activity for formate production with a faradaic efficiency (FE) of 68.4% at a potential of ?1.55 V versus Ag/Ag⁺. Moreover, the C-C coupling product acetate is generated from the same catalyst together with formate at a wide voltage range of ?1.40 V to ?1.65 V with the total liquid product FE from 38.8% to 85.2%. High selectivity and activity are closely related to the cathodized restructuring of Cu-MOF nanosheets. With the combination of X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy and Fourier transform infrared spectroscopy, we find that Cu(ii) carboxylate nodes possibly change to CuO, Cu₂O and Cu₄O₃, which significantly catalyze CO₂ to formate and acetate with synergistic enhancement from the porphyrin-Cu(ii) complex. This intriguing phenomenon provides a new opportunity for the rational design of high-performance Cu catalysts from pre-designed MOFs.

Full text of DOI:10.1039/c8sc04344b

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Cathodized copper porphyrin metal–organic
framework nanosheets for selective formate and
Cite this: DOI: 10.1039/c8sc04344b
acetate production from CO2 electroreduction†
All publication charges for this article
have been paid for by the Royal Society
of Chemistry
Jian-Xiang Wu, Shu-Zhen Hou, Xiang-Da Zhang, Ming Xu, Hua-Fei Yang,
*
Pei-Sheng Cao and Zhi-Yuan Gu
An efficient and selective Cu catalyst for CO2 electroreduction is highly desirable since current catalysts suffer
from poor selectivity towards a series of products, such as alkenes, alcohols, and carboxylic acids. Here, we
used copper(II) paddle wheel cluster-based porphyrinic metal–organic framework (MOF) nanosheets for
electrocatalytic CO2 reduction and compared them with CuO, Cu2O, Cu, a porphyrin–Cu(II) complex and
a CuO/complex composite. Among them, the cathodized Cu-MOF nanosheets exhibit significant activity
for formate production with a faradaic efficiency (FE) of 68.4% at a potential of ꢀ1.55 V versus Ag/Ag+.
Moreover, the C–C coupling product acetate is generated from the same catalyst together with formate at
a wide voltage range of ꢀ1.40 V to ꢀ1.65 V with the total liquid product FE from 38.8% to 85.2%. High
selectivity and activity are closely related to the cathodized restructuring of Cu-MOF nanosheets. With the
combination of X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission electron
microscopy and Fourier transform infrared spectroscopy, we find that Cu(II) carboxylate nodes possibly
change to CuO, Cu2O and Cu4O3, which significantly catalyze CO2 to formate and acetate with synergistic
enhancement from the porphyrin–Cu(II) complex. This intriguing phenomenon provides a new opportunity
for the rational design of high-performance Cu catalysts from pre-designed MOFs.
Received 30th September 2018
Accepted 14th December 2018
DOI: 10.1039/c8sc04344b
rsc.li/chemical-science
high potential for formate generation.26,27 In addition, very few
electrocatalysts perform CO2 reduction to acetate due to the low
activity of C–C coupling.28 Therefore, it is urgent to develop new
catalysts for the transformation of CO2 to formate and acetate.
Copper-based CO2RR catalysts are well-known for their capability
of producing C2+ products, but they suffer from low selectivity and
product diversity.29,30 Recent Cu-based catalysts have demon-
strated great potential for the production of formate and
acetate,28,29 however, with lower faradaic efficiency (FE).
Metal–organic frameworks (MOFs) with high porosity and
designable metal clusters and organic linkers arouse signicant
research interest in biomedical, energy and environmental
applications, such as drug delivery, enzyme inhibition, separa-
tion and catalysis.31–34 The atomic-level periodicity of metal
complexes or metal clusters in MOFs allows the precise control
over the rational design of the active metals as potential elec-
trocatalysts for the CO2RR.15,19,35–38 The successful application of
most bulk MOFs as electrocatalysts is largely hindered by their
poor electrical conductivity and inevitable gas diffusion
barrier,39 which could be signicantly improved by adjusting
the synthetic method to form nano-MOFs, especially two-
dimensional (2-D) MOF nanosheets.40,41 Nevertheless, to the
best of our knowledge, 2-D MOF nanosheets have not yet been
explored in the CO2 electroreduction.
Introduction
The reduction of CO2 to useful chemicals holds great promise for
reducing humanity's enormous carbon footprint.1–5 Electro-
chemical conversion of CO2 using electricity generated from
renewable energy sources could provide a viable solution to the
production of carbon-neutral fuels and chemicals.6–8 Current
products from the CO2 reduction reaction (CO2RR) include carbon
monoxide, alkenes, acids, and alcohols.9 Although many research
studies focus on the production of potential fuels, such as C2H4,
CH3OH, and C2H5OH,10–12 a recent gross-margin model counter-
intuitively revealed that HCOOH and CO are the most economi-
cally viable products.13 Compared with gaseous CO,14–20 the liquid
products HCOOH and CH3COOH are easy to collect and store.21
However, the formate and acetate production from the CO2RR still
remains a scientic challenge.22 Major Sn-based catalysts usually
suffer from limited reaction selectivity and a narrow range of
active voltage,23–25 although a recent Bi-based catalyst has shown
Jiangsu Key Laboratory of Biofunctional Materials, Jiangsu Collaborative Innovation
Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power
Batteries, School of Chemistry and Materials Science, Nanjing Normal University,
Nanjing, 210023, P. R. China. E-mail: guzhiyuan@njnu.edu.cn; Fax: +86-25-
85891952; Tel: +86-25-85891952
It is now well accepted that an electrocatalyst undergoes in
situ structural transformation under reaction conditions, which
† Electronic supplementary information (ESI) available: Synthetic experimental
details and additional gures (XRD and SEM data). See DOI: 10.1039/c8sc04344b
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has been largely underestimated.42,43 2-D MOF nanosheets adjacent layers stack in parallel, generating vertical 1D channels
under cathodization conditions have not been studied before. along the c axis. The XRD pattern of the as-prepared product
Thus, we choose copper(II)-5,10,15,20-tetrakis(4-carboxyphenyl) was consistent with that of Cu2(CuTCPP) (Fig. 1a).46,47 The broad
porphyrin–Cu(II) (Cu2(CuTCPP)) nanosheets with two different peaks in the XRD pattern were due to the nanosheet feature.
copper chemical environments as a potential CO2 electro- Aer dispersion in ethanol by ultrasonication, these nanosheets
catalyst. One is the porphyrinic Cu, which has been shown as an showed layered structures with thin thickness in the SEM image
electrocatalyst for the formation of CH4.44 The other is the Cu (Fig. 1c). The TEM image revealed that the Cu2(CuTCPP)
paddle wheel, the cluster in the famous HKUST-1, which is nanosheets had a smooth surface, and uniform and ultrathin
efficient in CH4 and C2H4 production.44,45
thickness with high aspect ratio, which resulted in the partial
Here, we report the efficient and selective electroreduction of curling of nanosheet edges (Fig. 1d). Atomic force microscopy
CO2 to formate and acetate by a 2-D Cu-MOF nanosheet catalyst. (AFM) measurements showed that the nanosheets had
The FE for the formation of two liquid products reached up to a homogeneous thickness of ꢁ3.7 nm, indicating only 8 layers
85.2% with a total current density of 4.5 mA cmꢀ2. The turnover (Fig. 1b and S1†). Notably, the direct synthesis of few-molecular-
frequency (TOF) of the catalyst for formate and acetate formation layer MOF nanosheets on a large scale is rarely reported,46,47
could reach as high as 2037 hꢀ1 and 148 hꢀ1, respectively. This although this type of at and high-aspect-ratio nanosheet is very
high efficiency is signicantly different from that of common Cu desirable for electrocatalysis because of its advantages over bulk
catalysts, such as Cu2O, CuO, Cu and a porphyrin–Cu(II) complex materials in regard to reducing the diffusion kinetics barrier
(CuTCPP). Ex situ powder X-ray diffraction (XRD), scanning elec- and enhancing the electron transfer.
tron microscopy (SEM), X-ray photoelectron spectroscopy (XPS),
transmission electron microscopy (TEM) and Fourier transform
Electrochemical CO2 reduction by Cu2(CuTCPP) nanosheets
infrared spectroscopy (FT-IR) conrmed the cathodized recon-
struction of 2-D MOF nanosheets to the heterostructures of CuO,
Cu2O and Cu4O3 through the Cu(HCOO)2 and Cu(OH)2 inter-
mediates. Meanwhile, the CuTCPP complex was still anchored on
the catalyst and could enhance the activity of the catalyst. This
result reveals the fundamental signicance of cathodized
restructuring for highly selective production of formate and
acetate on pre-designed MOF electrocatalysts.
The electrocatalytic CO2RR activity of Cu2(CuTCPP) nanosheets
on a FTO electrode was evaluated in CH3CN solution with 1 M
H2O and 0.5 M ionic liquid 1-ethyl-3-methylimidazolium tetra-
uoroborate (EMIMBF4) in a two-compartment electrochemical
H-type cell (Scheme 1b).3 The organic electrolyte with water and
ionic liquid components was chosen to control proton
concentration and enhance CO2 solubility, respectively.48–50 The
linear sweep voltammetry (LSV) curves of Cu2(CuTCPP) in N2-
saturated and CO2-saturated electrolytes showed different
cathodic waves from 0.5 V to ꢀ2.0 V versus Ag/Ag+ (Fig. S2†). In
the CO2-saturated electrolyte, a steep increase of current density
Results and discussion
Preparation and characterization of Cu2(CuTCPP) nanosheets
Cu2(CuTCPP) has a porous 2D layered reticular framework in the negative sweep started from ꢀ1.2 V versus Ag/Ag+ indi-
structure with Cu porphyrin ligands connected through cating signicant CO2 reduction (Fig. S2†). Meanwhile, a blank
Cu2(COO)4 paddle wheels (Scheme 1a and Fig. S1†). The experiment with a FTO electrode was also performed since FTO
Scheme 1 (a) Crystal structure of Cu2(CuTCPP) nanosheets along the c axis. Red is O, blue is N, grey is C and cyan is Cu; (b) CO2 electrochemical
reduction system with Cu2(CuTCPP) nanosheets as the catalyst.
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Fig. 2 CO2RR performance in CO2-saturated CH3CN solution with 1
M H2O and 0.5 M EMIMBF4. (a) Faradaic efficiencies of Cu2(CuTCPP)
nanosheets; (b) faradaic efficiencies of Cu2(CuTCPP) nanosheets at
different times; (c) faradaic efficiencies of pre-electrolyzed Cu2(-
CuTCPP) nanosheets; and (d) total and partial current densities for
CO2RR products on pre-electrolyzed Cu2(CuTCPP).
Fig. 1 (a) XRD pattern of Cu2(CuTCPP) nanosheets; (b) AFM image of
the nanosheets, inset: the thickness curve; (c) SEM image of Cu2(-
CuTCPP) nanosheets; (d) TEM image of Cu2(CuTCPP) nanosheets.
is F-doped SnO2, which is also the active material for the CO2RR
(Fig. S3†). We found that only a small amount of CO (FE < 10%)
was produced as the reduction product, ruling out the possible
formate generation from the FTO substrate.
investigated at ꢀ1.55 V (Fig. 2b). In the rst 1 h, the HER
became the dominant cathodic process with a small amount of
CO and CH4. Then, aer 90 min, formate appeared, while H2
from the HER decreased. Aer 3 h, acetate appeared. Aer that,
stable production of formate and acetate occurred.
In order to identify and quantify the reduction products,
electrolysis was performed at different potentials between
ꢀ1.40 V and ꢀ1.65 V versus Ag/Ag+ for 5 h. Resultant gaseous
products were periodically sampled and examined using gas
chromatography (GC), while the liquid products were analyzed
aer electrolysis by nuclear magnetic resonance (NMR) spec-
troscopy. We found that formate and acetate were the two
dominant reduction products, accompanied by a small amount
of CO and CH4 from the CO2RR as well as H2 from the HER. The
FEs for the formation of different products at various potentials
were calculated and are shown in Fig. 2a. Formate and acetate
were reliably and reproducibly detected at as positive as ꢀ1.40 V
versus Ag/Ag+. Initially, the faradaic efficiencies were 28.1% and
11.6%, respectively, which then quickly rose to 61.5% and
12.3% at ꢀ1.55 V versus Ag/Ag+. The faradaic efficiency for the
formation of the two gaseous products, CO and CH4, remained
small (<5%) in this range of potentials. Moreover, H2 produc-
tion from the competing HER was well controlled from ꢀ1.50 V
to ꢀ1.65 V.
To eliminate the side reactions during the initial process and
further conrm the activity of the nal cathodized catalyst,
Cu2(CuTCPP) nanosheets were pre-electrolyzed at ꢀ1.55 V.
Then, the CO2RR was performed with fresh electrolyte at
various potentials (Fig. 2c). The highest faradaic efficiencies for
formate and acetate formation were increased to 68.4% and
16.8% at ꢀ1.55 V versus Ag/Ag+, respectively, with a total fara-
daic efficiency of 85.2%. Furthermore, the partial current
densities for CO2RR products on the Cu2(CuTCPP) catalyst were
calculated and plotted against the working potentials (Fig. 2d).
The maximum values of jformate and jacetate are 3.5 mA cmꢀ2 and
1.0 mA cmꢀ2, respectively, at ꢀ1.60 V versus Ag/Ag+. What's
more, at ꢀ1.55 V versus Ag/Ag+, with a maximum total faradaic
efficiency of 85.2% and a surface active site density of 3.16 ꢂ
10ꢀ8 mol cmꢀ2 (Fig. S4†), the TOF of the catalyst for formate and
acetate production could reach as high as 2037 hꢀ1 and 148 hꢀ1
,
respectively (Fig. S5†), which outperformed that of most of the
reported catalysts.51,52
However, the catalyst delivered a signicant decrease of
cathodic current density during the rst 1 h and then a stable
cathodic current density of 4.5 mA cmꢀ2 (Fig. 2b). The rst 1 h
changes of current density indicated possible chemical
restructuring of the catalyst under the cathodization condi-
tions. It is also worth noting that the decrease from a total FE of
100% at ꢀ1.60 V and ꢀ1.65 V might indicate the hidden
consumption of electrons by the side reactions as well (Fig. 2a).
The initial increase in i–t curves and the insufficient total FE
values both indicated the possible redox-based chemical
restructuring of the Cu2(CuTCPP) catalyst. Thus, the production
of formate and acetate as a function of electrolysis time was
To conrm the carbon source of the CO2RR process,
a control experiment under a N2 atmosphere was performed
(Fig. S6†). H2 was the only product, which demonstrated that
formate and acetate were produced from the reduction of CO2,
but not from the organic part or the impurities in the electrolyte
or MOF material. The continual production of formate and
acetate as shown by the kinetic data also supports that the
carbon source was CO2. Water concentration was also an
important factor and was optimized since the competitive HER
also uses H2O as the proton source (Fig. S7†). Without H2O, no
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products could be detected, for both the HER and CO2RR. The obtained with Cu2O with an FE up to 21.5% (Table S1†). The
CO2RR is signicant because of the unusually low FE for the above results indicated that the production of formate and
HER at a water concentration of 1.0 M, indicating that H2O is acetate on Cu2(CuTCPP) was superior to that on the four indi-
not only the proton source but also important in the cathod- vidual Cu counterparts. Thus, no single component was possibly
ization procedure to generate an effective catalyst (Fig. S8†). responsible for the high activity and selectivity of formate and
Since CO is a possible intermediate,53 we explored the direct CO acetate production, while the functionalities of the porphyrin
reduction. However, only the HER occurred with Cu2(CuTCPP) ligand and copper paddle wheel clusters should be reconsidered.
as the catalyst for the electrocatalytic CO reduction (Fig. S9†).
Cathodized reconstruction of Cu2(CuTCPP) nanosheets
Comparison with other Cu catalysts
The high selectivity and activity towards formate and acetate
production with the reductive formation from Cu2(CuTCPP)
encouraged us to pursue the “real catalyst”. These structural
changes were explored with ex situ XRD, SEM, TEM, XPS and FT-
IR characterization.
The restructuring of a Cu catalyst to other active Cu-containing
species is not rare in electrocatalyst research.42 Before the
elucidation of structural changes of the Cu2(CuTCPP) catalyst,
we rst surveyed the CO2RR activity of Cu, CuTCPP, Cu2O, and
CuO, which are common Cu catalysts (Fig. 3 and S10†). The
catalysts were conrmed by XRD (Fig. S11–S14†) and were
evaluated as CO2 electrocatalysts under identical conditions
compared to those of Cu2(CuTCPP) nanosheets.
Control experiments with Cu, CuTCPP, CuO, and Cu2O sug-
gested that although in the presence of CO2, the HER became the
dominant cathodic process for all four catalysts, accompanied by
the co-generation of a small amount of CO, CH4, HCOOH and
CH3COOH. The FE and yield of products at different potentials
were calculated and are shown in Fig. 3 and Table S1,† respec-
tively. Negligible CO2RR was observed on the Cu catalyst with
mainly CO and CH4 as products (FE < 5%) while no formate and
acetate were observed. The CuTCPP complex was chosen as the
counterpart since it is one of two Cu components in Cu2(-
CuTCPP). However, although CO was produced with a FE of 20%
at potentials from ꢀ1.50 V to ꢀ1.65 V, H2 from the HER was still
the major product. CuO and Cu2O were two common forms of
copper oxides for the CO2RR.54 In our results, CuO was signicant
to generate both HCOOH (an FE of 14.7% at ꢀ1.5 V) and CH3-
COOH (an FE of 5.8% at ꢀ1.45 V), while only HCOOH was
The potential Cu species from the Cu(II) paddle-wheel nodes
during cathodized reconstruction were rst revealed at ꢀ1.55 V
with different reaction times (Fig. 4a and S15†). Aer the
optimal electrocatalysis at ꢀ1.55 V for 15 min, the XRD peak of
the Cu2(CuTCPP) catalyst on FTO electrodes shied from 20.39ꢃ
to a lower value of 20.04ꢃ with the appearance of three new
peaks (Cu(HCOO)2 at 13.40ꢃ, an unassigned peak at 21.37ꢃ, and
Cu(OH)2 at 23.42ꢃ). At 15 min, the morphology changed from
well-shaped nanosheets to partially amorphous layered struc-
tures (Fig. S16a and S16b†). Then, aer 30 min, two XRD peaks
disappeared (21.37ꢃ and 23.42ꢃ), and the peak intensity of
Cu(HCOO)2 at 13.40ꢃ increased, while three new peaks
(Cu(HCOO)2 at 26.55ꢃ, 40.68ꢃ and 53.74ꢃ) appeared. At 30 min,
the morphology changed from partially amorphous layered
structures to amorphous solid (Fig. S16c†). Next, aer 60 min,
other XRD peaks of Cu(HCOO)2 disappeared with only one peak
at 13.40ꢃ remaining, while two peaks at 21.37ꢃ and 23.42ꢃ were
observed again. At the same time, new dendritic structures
appeared (Fig. S16d†). Finally, aer 90 min, the XRD showed
multiple peaks of CuO, Cu2O and Cu4O3, while the amorphous
morphology was observed again (Fig. S16e†). These resultant
products could be the real active catalysts in regard to the
CO2RR results at the same time interval (Fig. 2b).
Meanwhile, we also performed ex situ XRD and SEM char-
acterization at different voltages (Fig. S17 and S18†). Similar
intermediate species, Cu(HCOO)2, and morphology changes
were observed with the same conrmed nal catalysts CuO,
Cu2O and Cu4O3. These continual changes in XRD patterns and
SEM pictures at different reaction times and working potentials
showed that the Cu2(CuTCPP) catalyst had changed to CuO,
Cu2O and Cu4O3 with conrmed intermediates Cu(HCOO)2 and
Cu(OH)2. It is worth noting that the above ex situ XRD and SEM
monitored cathodization process was fully consistent with the
rst 1 h current density uctuation in electrolysis and the
CO2RR time course experiment, further conrming the reli-
ability of ex situ characterization techniques in our system.
To further elucidate the nal catalyst and active sites of
cathodized Cu2(CuTCPP) nanosheets, TEM and XPS were
utilized. HRTEM images with d ¼ 0.230 nm for Cu2O (111) and
d ¼ 0.257 nm for CuO (111), Cu2O (ꢀ111) and/or Cu4O3 (211)
were obtained from ex situ cathodized catalysts with a longer
electrolysis time of 5 h. Furthermore, the Cu2(CuTCPP)
Fig. 3 Faradaic efficiencies for formation of different products in the
CO2RR with different catalysts: (a) Cu, (b) CuTCPP, (c) CuO, and (d)
Cu2O.
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Fig. 4 (a) XRD of Cu2(CuTCPP) nanosheets on a FTO electrode with different reaction times (C Cu(HCOO)2; A Cu4O3; : Cu(OH)2; ; CuO; +
Cu2O); (b) HRTEM after 5 h reaction; (c) Cu 2p XPS spectra and (d) O 1s XPS spectra of Cu2(CuTCPP) on FTO before and after 5 h reaction. All
potentials were set at ꢀ1.55 V vs. Ag/Ag+.
nanosheets and cathodized Cu2(CuTCPP) on FTO electrodes status and possible functionality of the TCPP ligand. First, from
before and aer the CO2RR were characterized by XPS (Fig. 4c the pictures of the electrolyte before and aer electrocatalysis,
and d). The spectra of Cu 2p clearly showed that the as-prepared we could exclude the possibility that the porphyrin ligand dis-
Cu2(CuTCPP) surface has Cu2+ states which are distinct from solved in the electrolyte aer reaction (Fig. S20†). The NMR
their lower binding energy states, the Cu+ or Cu0, aer 5 h spectra further showed no TCPP peaks for the electrolyte
electrocatalysis. Although the binding energies of the Cu+ and samples (Fig. S21†). Second, the peak at 1650 cmꢀ1 in the FT-IR
Cu0 states were very close in the XPS spectra, Auger spectra spectrum conrmed that the ligand was still anchored to the
could possibly distinguish these two states with overlapped surface of the catalyst during the reaction (Fig. S22†).46,47,58
peaks at 569.5 eV and 572.5 eV, which were ascribed to the Third, a control experiment in which a physical mixture of CuO
kinetic energy of Cu+ and Cu2+, respectively.55 Only Cu+ was and CuTCPP with a molar ratio of 2 : 1 was tested as a catalyst
observed, ruling out the possible existence of metallic copper for the CO2RR (Fig. S23†) showed that CuO/CuTCPP was
(Fig. S19†). Meanwhile, XPS O1s spectra also showed that the as- signicant to generate both HCOOH (FE of 31.1% at ꢀ1.55 V)
prepared Cu2(CuTCPP) surface has C related oxygen, which was and CH3COOH (FE of 17.3% at ꢀ1.55 V), the FEs being higher
distinctively reduced to the lower binding energy O states than that of individual CuO and CuTCPP (Fig. 3). It is worth
associated with Cu2O and CuO aer 5 h reaction (Fig. 4d).42 noting that our cathodized catalyst was possibly anchored by
Additional peaks in O 1s spectra were related to chemisorbed TCPP through chemical bonds, in which the activity was even
oxygen in carboxylic groups or water.56,57
better than that of the physical mixture of CuO/CuTCPP. Thus,
The strong intensity of O 1s XPS peaks indicated the exis- the inorganic species of the cathodized Cu2(CuTCPP) nano-
tence of O-containing species. Thus, it is crucial to elucidate the sheets were conrmed as CuO, Cu2O and Cu4O3, while the
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anchored CuTCPP could synergistically enhance the activity of 11 W. Zhang, Q. Qin, L. Dai, R. Qin, X. Zhao, X. Chen, D. Ou,
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Conflicts of interest
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There are no conicts to declare.
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Acknowledgements
This work is nancially supported by the NSFC (No. 21505076),
the Young Elite Scholar Support (YESS) Program from CAST, the 20 C. Zhao, X. Dai, T. Yao, W. Chen, X. Wang, J. Wang, J. Yang,
Program of Jiangsu Specially-Appointed Professor, the NSF of
Jiangsu Province of China (No. BK20150967), the Innovation
S. Wei, Y. Wu and Y. Li, J. Am. Chem. Soc., 2017, 139, 8078–
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Team Program of Jiangsu Province of China, and the Priority 21 Y. Liu, S. Chen, X. Quan and H. Yu, J. Am. Chem. Soc., 2015,
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