Potassium Ions Induced Framework Interpenetration for Enhancing the Stability of Uranium-Based Porphyrin MOF with Visible-Light-Driven Photocatalytic Activity

Article abstract of DOI:10.1021/acs.inorgchem.0c02473

The stability of many MOFs is not satisfactory, which severely limits the exploration of their potential applications. Given this, we have proposed a strategy to improve the stability of MOFs by introducing alkali metal K+ capable of coordinating with met

Full text of DOI:10.1021/acs.inorgchem.0c02473

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Article
Potassium Ions Induced Framework Interpenetration for Enhancing
the Stability of Uranium-Based Porphyrin MOF with Visible-Light-
Driven Photocatalytic Activity
Zhi-Wei Huang,⊥ Kong-Qiu Hu,⊥ Lei Mei,* Cong-Zhi Wang, Yan-Mei Chen, Wang-Suo Wu,
Zhi-Fang Chai, and Wei-Qun Shi*
Cite This: Inorg. Chem. 2021, 60, 651−659
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ABSTRACT: The stability of many MOFs is not satisfactory, which
severely limits the exploration of their potential applications. Given this,
we have proposed a strategy to improve the stability of MOFs by
introducing alkali metal K+ capable of coordinating with metal nodes,
which finally induces the interpenetrating uranyl-porphyrin framework to
connect as a whole (IHEP-9). The stability experiments reveal that the
IHEP-9 has good thermal stability up to 400 °C and can maintain its
crystalline state in the aqueous solution with pH ranging from 2 to 11.
The catalytic activity of IHEP-9 as a heterogeneous photocatalyst for
CO2 cycloaddition under the driving of visible light at room temperature
is also demonstrated. This induced interpenetration and fixation method
may be promising for the fabrication of more functional MOFs with improved structural stability.
occurrence of an interpenetrating structure usually reduces the
pore volume and size, but this may improve the stability of a
MOF to a certain extent.13,30 However, it is difficult to
accurately improve the stability of a MOF through inter-
penetration, because the intermolecular forces between the
networks are not strong enough, and the structure may
undergo deformation or slip in response to the removal of
guest molecules. It should be noted that the distance between
adjacent metal ions in the interpenetration structure will be
greatly shortened. If the metal ions can be connected and fixed
in a certain way, the interpenetrating structure can be
connected as a whole, which may further improve the stability
of the MOF.31 In the recent work, we have reported a
uranium-based porphyrin MOF IHEP-4 ([(CH3)2NH2]4-
[(UO2)4(Co-TCPP)3]·6DMF·33H2O), which has certain
chemical stability and can be applied in organic systems, but
it cannot be stable in aqueous solutions.32 At the same time, by
changing the synthesis conditions, MOF TCPP-U1 ([(CH3)4-
N]4[(UO2)4(TCPP)3]) with a similar coordination mode but
interpenetrated structure can also be obtained, while its
stability has not been significantly improved.33 The distance
INTRODUCTION
■
Metal−organic frameworks (MOFs) are a class of crystalline
materials formed by self-assembly of metal ions and organic
ligands through coordination.1−3 By adjusting metal nodes and
organic ligands, a MOF can serve as an ideal carrier, enabling it
to have a huge application potential in many fields.4−11
However, due to the relatively weak coordination bonds, the
poor stability (including chemical, thermal, and mechanical
stability) of some MOF materials greatly hinders their practical
application.12 Therefore, because of its sufficient urgency and
significance, the synthesis and application of stable MOFs have
captured ample attention.13−16
It is generally believed that the stability of MOF materials is
mainly determined by structural features of both the building
units of the metal node and the organic linking group, and the
strength of the coordination bonds between them.9,17,18 For
the metal node, the stability of MOF materials synthesized by
metal ions with high coordination numbers and high valence
electron numbers is usually better. The actinides generally have
a larger ionic radius and higher coordination numbers, and
their chemical valence states also present multivalent states.
The strength of the coordination bond between the metal ion
and the organic ligand can be predicted by Pearson’s hard soft
acid base theory, which is beneficial for guiding the synthesis of
highly stable MOFs.19−21 Therefore, MOF materials con-
structed by actinides and oxygen-containing carboxylic acid
ligands can be expected to have promising stability.22−29
The frameworks interpenetration is often found in MOF
construction, especially when semi-rigid ligands are used. The
Received: August 19, 2020
Published: December 31, 2020
https://dx.doi.org/10.1021/acs.inorgchem.0c02473
© 2020 American Chemical Society
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between the coordination sphere of the adjacent uranyl ions is
greatly shortened, nearly 6.88 Å, and the distance between the
carboxyl oxygen coordinate with uranyl is even shorter. The
coordination connection can be achieved by introducing a
simple metal atom or organic linker. Alkali metals have
abundant coordination modes, which can effectively connect a
variety of components, including ligands, clusters, and
macromolecular compounds, and may be used to connect
adjacent uranyl ions.34−37 The alkali metal is connected to the
oxygen of the carboxyl groups and can form a multi-metal
oxygen cluster with uranyl. In the MOF structure, there is no
longer a single metal atom as a metal node connecting
framework, but the metal oxygen cluster bridges the organic
ligands to form the framework. Therefore, the stability of the
structure may be further improved.
In this work, we have proposed a feasible strategy to improve
the stability of a MOF via inducing an interpenetrated
structure to be fixed together. As a proof-of-concept case, a
new uranium-based porphyrin MOF IHEP-9 [(UO2)4K2-
(MnTCPP)3(H2O)10]·5DMF·5H2O with enhanced stability
has been successfully prepared by adding alkali metal
potassium ions (K+) into the reaction system. It is revealed
that the presence of K+ ions induces the formation of a doubly
interpenetrated framework in IHEP-9 that is coordinatively
linked by K+ ions through two adjacent uranyl ions. The
special structural architecture is helpful to improving the
framework stability of IHEP-9 as evidenced by its good
thermal stability up to 400 °C, and high hydrolytic stability,
maintaining the intact crystalline state in the pH range of 2−
11. Moreover, IHEP-9 has been applied to the photocatalytic
conversion of CO2 and is of potential as a promising visible-
light-driven photocatalyst.
Figure 1. (a) Optical images of IHEP-9. (b) The asymmetric unit of
IHEP-9. Color scheme: U (yellow), K (purple), Mn (pink), C (gray),
O (red), N (blue). H atoms were omitted for clarity. (c) Two
adjacent uranyl groups are connected via the K atom. (d) The metal
node U-K-U cluster is connected by a metalloporphyrin ligand.
Center (CCDC). Thermogravimetric analysis (TGA) was recorded
from a TA Q500 analyzer over the temperature range of 25−800 °C
in an air atmosphere with a heating rate of 5 °C/min. The Fourier
transform infrared (FT-IR) spectra were performed on KBr pellets in
the range of 4000−400 cm−1 on a Bruker Tensor 27 spectrometer.
The XPS spectra were recorded on a Thermo ESCALAB 250 electron
spectrometer with a multi-detection analyzer using an Al Kα X-ray
source (1486.6 eV). Surface charging effect was corrected with the C
1s peak at 284.6 eV as a reference. High resolution Mn 2p and U 4f
peaks were fitted by using the CasaXPS program after subtraction of
the background (Shirley baseline correction). The N2 adsorption
experiments were measured on a micromeritics ASAP 2020 HD88
instrument at liquid nitrogen temperature (−196 °C). The samples
were degassed under vacuum at 60 °C before measurements. The
specific surface area was calculated by the Brunauer−Emmett−Teller
(BET) method. The pore size distributions were derived using the
nonlocal density functional theory model. 1H NMR spectra were
performed on a Bruker Avance III analyzer in chloroform-d (CDCl3)
using TMS as an internal standard.
Single crystal X-ray data were collected on a Bruker APEXII X-ray
diffractometer equipped with a CMOS PHOTON 100 detector with a
Cu Kα X-ray source (Kα = 1.54178 Å). Data were indexed,
integrated, and scaled using DENZO and SCALEPACK from the
HKL program suite (Otwinowski and Minor, 1997).40 The structures
were solved by the direct method (SHELXS-97) and refined by full-
matrix least-squares (SHELXL-2014) on F2. Anisotropic thermal
parameters were used for the non-hydrogen atoms and isotropic
parameters for the hydrogen atoms. The SQUEEZE routine of
PLATON was used to remove the diffraction contribution from
disordered solvents of compound IHEP-9.41
MATERIALS AND METHODS
■
Caution! The uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) is a
radioactive and chemically toxic compound; strict preventive and
protective measures should be taken, albeit a natural low radionuclide.
The dust or solution of uranyl nitrate entering the body can cause heavy
metal poisoning and internal exposure.
UO2(NO3)2·6H2O was dissolved in deionized water (50 mL) to
obtain a uranyl nitrate stock solution (0.50 M). The tetrakis(4-
carboxyphenyl) porphyrin (H4TCPP) and metalloporphyrins
MnTCPP were prepared by a modified method.38,39 All chemicals
and solvents are commercially available and can be used directly
without further purification.
Synthesis. The synthesis of IHEP-9 is detailed, introduced as a
representative: UO2(NO3)2 (0.03 mmol), MnTCPP (0.02 mmol),
KCl (0.1 mmol), DMF (4.0 mL), and acetic acid (0.08 mL) were
loaded into a 10 mL autoclave. The autoclave was sealed and heated
to 150 °C in an oven for 2 days, then cooled to room temperature
naturally. A brown positive tetragonal double cone crystal of IHEP-9
was produced and washed three times with DMF (Figure 1a). Yield:
79.4% based on MnTCPP. The actinides metalloporphyrin MOFs
with other transition metals were synthesized by similar methods.
Actinide porphyrin MOFs with different metal loadings were
synthesized via a post-synthesis strategy. The uranyl and H4TCPP
were constructed into the actinide porphyrin MOF in advance, which
is washed with DMF to obtain pure samples of IHEP-9 (H2). The
resulting crystal sample was immersed in a DMF solution containing
MnCl2 (0.05 mmol) and 2,6-lutidine, and heated at 120 °C for 1 day.
The obtained crystal sample was washed three times with DMF.
Characterization. Powder X-ray diffraction measurements
(PXRD) were obtained with a Bruker D8 Advance diffractometer
with Cu Kα radiation (λ = 1.5406 Å) in the range of 3.5−50° (step
size: 0.02°). Simulated PXRD patterns were obtained from SCXA
data using Mercury 3.3 software from the Cambridge Crystal Data
Theoretical Methods. The structures of the model fragments of
IHEP-4 and IHEP-9 were optimized by the PBE0 method with the
Gaussian 09 program.42 The quasi-relativistic effective core potentials
(RECPs) and ECP60MWB-SEG were applied to the U atom,43−45
while the 6-31G(d) basis sets were used for H, C, O, and K atoms.
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Figure 2. (a) Single-layer planar structure of the interpenetrated MOF. (b) Single-layer channel structure of the interpenetrated MOF. (c) Single-
layer channel structure of IHEP-9 viewed along the b axis. (d) The 3D structure of IHEP-9. (e) Double-layered interpenetrated MOF connected
by K atom. Color scheme: U (yellow), K (purple), Mn (pink), O (red).
Solvation effect was considered in DMF (ε = 36.7) using the
conductor-like polarizable continuum model (CPCM) with Klamt
atomic radii.46,47 At the PBE0/RECP/6-31G(d) level of theory, the
fragments have no imaginary frequencies in DMF. To gain more
accurate energies, single-point calculations were performed at the
PBE0/RECP/6-311+G(d) level of theory.
nodal net (Figure S2) with a topology point symbol of
{63.83}4{64.82}3. The distance between the Mn(II) in the
center of the porphyrin and the N atom on the porphyrin ring
is approximately 2.02 Å, and the distances between Mn and the
O atoms of the coordination water molecule are 2.19−2.28 Å.
The original double-penetrating structure is woven into a
MOF containing dense channels by the connection of K atoms
(Figure 2d,e), which greatly reinforces its stability. Due to the
coordination of the potassium atoms, the plane oxygen of the
uranyl group is twisted, not in a plane, which results in the
MOF material to be irregularly cubic in space. Two porphyrin
rings with different torsional degrees make the structure more
complicated. In terms of a single layer of the interpenetrated
structure, the uranyl ion as a metal node coordinated with the
carboxyl group of the porphyrin derivative, the MOF forms a
three-level pore structure in the space (Figure 2b,c). The
potassium atom is like a steel nail that connects two separate
interpenetrating structures together, turning the original single
metal node into a U-K-U metal oxygen cluster (Figure 1c,d),
which will inevitably lead to increased stability of the MOF at
the metal node.
Enhanced Stability of the Interpenetrated Frame-
work. Compared to our previously reported actinide
porphyrin MOF IHEP-4,32 IHEP-9 has a much richer pore
structure. The pore shape of IHEP-9 is a slender row of
channels, and its pore sizes range from 7 to 15 Å (Figure 3).
IHEP-4 has a more uniform aperture distribution, with channel
diameters as high as 23 Å. Despite that the pore size of IHEP-9
is slightly reduced, a reasonable explanation is that the
connected double-layer interpenetrating structure sacrifices a
part of the hole space, but its stability is consolidated greatly
compared with IHEP-4. In order to verify the stability of
IHEP-4 and IHEP-9, we optimized the structures of the model
fragments of IHEP-4 and IHEP-9 in DMF (Figure S3). The
parameters of bond lengths calculated at the PBE0/RECP/6-
31G(d) level of theory are very close to the corresponding
experimental values (Tables S2 and S3), which suggests that
the theoretical method is suitable for calculating these systems.
RESULTS AND DISCUSSION
■
Structure Description and Characterization of IHEP-
9. The single crystal X-ray diffraction (SCXRD) analysis
indicates that IHEP-9 crystallizes in the tetragonal I41/amd
space group. Pertinent crystal parameters and structure
refinement are summarized in Table S1 (Supporting
Information). There are two fully deprotonated metal-
loporphyrin ring ligands, one UO2 ion, one K+ ion, and
2+
five water ligands in the asymmetric unit of IHEP-9 (Figure
1b). The dimethylamine molecules present in the MOF cavity
for charge balancing are generated in situ by the decomposition
of DMF.48 The Mn1 porphyrin ring in the two metal-
loporphyrin rings is slightly bent, while the Mn2 porphyrin ring
is an almost perfect plane (Figure S1). The uranyl ion achieves
eight-coordination, including two oxygen atoms in the axial
direction and six oxygen atoms derived from the carboxyl
group of the porphyrin derivative. The distance of U−O bonds
in the equatorial plane is in the range of 2.42−2.47 Å, and the
axial U−O bond length is between 1.77 and 1.75 Å, which is
similar to those reported in the literatures.49 Two adjacent U···
U distances are 6.69 Å. O4 and O5 of the uranyl equatorial
plane is bridged through a K atom, which gave rise to the
oxygen in the equatorial plane to be slightly twisted and not on
a plane. The K atom is also coordinated with the water
molecule, and the lengths of the K−O bonds range from 2.64
to 2.71 Å. It is precisely because potassium ions participate in
the coordination, which makes the two isolated uranyl groups
connected to each other, further increasing the compact
degrees of the MOF and making the pores’ size more
diversified. Structure simplification and calculations by the
TOPOS40 program showed that IHEP-9 exhibits a 4,4,4-c 3-
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Thermodynamic analysis was estimated by the reaction of
2[UO2TCPP3]− + K+ + 2H2O → [(UO2TCPP3)2K(H2O)2]−.
At a higher level of theory (PBE0/RECP/6-311+G(d)), the
calculated reaction energy ΔE is −23.4 kcal/mol, indicating
that this reaction is an exothermic reaction; i.e., IHEP-9 is
more stable compared to IHEP-4. Therefore, the uranyl ions in
IHEP-9 are bridged by potassium ions to from U-K-U metal
clusters, which greatly improves the stability of IHEP-9. As
expected, the consequences of the stability test demonstrated
that IHEP-9 remained exceedingly stable after soaking and
shaking for 24 h in an aqueous solution of pH 2−11 (Figure
4d). The FT-IR spectra of IHEP-9 (Figure 4a) show the U
O absorption band in the region of 920 cm−1.50,51 The typical
vibrations corresponding to carboxylate groups and B3u
vibration of porphyrin correspond to 1660 and 1388 cm−1,
respectively.52 The BET surface area is 121 m3/g for IHEP-9,
and the pore size distribution also reveals that the crystal
presents multi-level mesoporous channels, which is consistent
with the crystal structure (Figure 4c). The pore volume ratio
calculated by PLATON reaches 71.9%. The results of TGA
(Figure 4b) prove that the thermal stability of IHEP-9 reached
400 °C, and there was about 14.1% weight loss before thermal
decomposition, which can be attributed to disordered water
molecules and DMF solvents. The weight loss did not further
increase until 500 °C, which indicates the complete
decomposition of IHEP-9, and the remaining 34.8% mass
Figure 3. (a, b) The planar structure of IHEP-4 and IHEP-9. (c, d)
The channel structure of IHEP-4 and IHEP-9. (e, f) The channel
structure of IHEP-4 and IHEP-9 viewed along the c axis. Color
scheme: U (yellow), K (purple), Mn (pink), C (gray), O (red), N
(blue).
residue can be regarded as a mixture of U3O8, Mn2O3, and
53,54
K2O2.
On the basis of the mass loss of IHEP-9 during
heating, we estimate that the molar mass of the compound
should be 4467 g/mol. Therefore, the number of H2O and
DMF molecules can be reckoned by the equations, (4467 ×
0.062)/18 ≈ 15; (4467 × 0.079)/73 ≈ 5, and the molecular
Figure 4. (a) The FT-IR spectrum of IHEP-9. (b) TGA of IHEP-9 measured under an air atmosphere. (c) N2 sorption/desorption isotherm and
pore-size distribution of IHEP-9. (d) The PXRD patterns of IHEP-9 after soaking in an aqueous solution of pH 2−11 for 24 h.
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formula of IHEP-9 is [(UO2)4K2(MnTCPP)3(H2O)10]·
5DMF·5H2O.
increase of the atomic number, it shows a trend of decreasing
first and then increasing, which is consistent with experimental
and theoretical calculation results reported in the litera-
ture.58,59 Among them, IHEP-9 (Mn) has the highest catalytic
efficiency (Table 2). On the basis of previous reports, the CO2
Visible-Light-Driven Photocatalytic Cycloaddition
Reaction of CO2. The presence of easily substituted sites in
metalloporphyrins indicates the availability of Lewis acidity,
and both uranyl and porphyrin rings can act as photo-
sensitizers.31,55 More importantly, by utilizing the character-
istics of a highly ordered structure and uniform pore sizes and
environments of MOF, a metal-porphyrin ligand with catalytic
activity can be used as secondary building units (SBUs) to
synthesize a single-atom catalyst, which can be predicted to
have good catalytic activity.56,57 Therefore, we explored the
utilization of IHEP-9 as a heterogeneous catalyst for
photocatalytic CO2 cycloaddition. Under typical reaction
conditions, 1 mmol of epoxides catalyzed by 0.01 mmol of
catalysts under 0.1 MPa CO2 and room temperature for 12 h.
A 45 W, 6500 K compact fluorescent lamp was applied as the
visible light source. 16.2 mg (5 mol %) of tetrabutylammonium
bromide (TBAB) was used as a cocatalyst, and 1 mL of
acetonitrile was added as a diluent to the system. The
photocatalytic reaction was performed in a high-pressure glass
reactor, and the catalyst was separated by centrifugation. The
product was eventually separated by column chromatography
and weighed to determine the catalytic yield. The recovered
solid catalyst was washed three times with fresh methanol and
dried under vacuum before use in a catalytic cycle experiment.
Styrene oxide was first selected as a quintessential substrate
for studying CO2 cycloaddition reactions. As display in Table
1, in the presence of the cocatalyst TBAB, IHEP-9 has high
Table 2. Photocatalytic Efficiency of IHEP-9 with Different
Transition Metals
entry
IHEP-9 (M)
TBAB (mg)
T (°C)
yield (%)
1
2
3
4
5
Mn2+
Fe3+
Co2+
Cu2+
Zn2+
16.2
16.2
16.2
16.2
16.2
RT
RT
RT
RT
RT
>99
95
47
67
85
cycloaddition reaction usually requires coordination of
transition metals with epoxy compounds, and MOFs
constructed based on different metalloporphyrin ligands will
exhibit greatly different catalytic activities.60−62 Furthermore,
we adjusted the content of manganese in the center of the
porphyrin plane by a postsynthetic method. As visible in Table
S4, the catalytic efficiency of IHEP-9 (Mn) gradually increased
from the lowest 48% to 99% with the increase of the ratio of
metal ion Mn. Therefore, in this system, transition metals as a
single-atom catalyst in the framework will greatly affect the
photocatalytic efficiency of CO2 cycloaddition.
Under the same reaction conditions, we applied the catalyst
system to a broad variety of epoxides, providing the respective
cyclic carbonates. As appears in Table 3, a series of epoxides
successfully undergo cycloaddition with CO2, and correspond-
ing carbonate compounds have been prepared, with
satisfactory yields (78−99%). After the catalysis was
completed, the catalyst was collected by centrifugation, and
then rinsed with methanol three times and then dried under
vacuum. Two more times, catalysis experiments were
performed; despite that the catalytic effect is slightly reduced,
the high catalytic efficiency is still maintained (Figure S8). The
PXRD of IHEP-9 after three cycles of catalysis points out that
the MOF shows excellent stability (Figure S9). According to
the results of XPS, as illustrated in Figure S10, the valence state
of manganese at the center of the porphyrin plane did not
change significantly after catalysis, and remained stable Mn2+,
which again verified the stability of IHEP-9.63,64 The valence
state of uranium has also not converted.51
Table 1. Synthesis of Styrene Carbonate from CO2 and
Epoxy Styrene with Photocatalyst IHEP-9
entry
catalyst (0.01 mM)
IHEP-9
IHEP-9
TBAB (mg) T (°C) yield (%)
1
2
3
4
5
6
7
8
16.2
RT
RT
RT
RT
RT
RT
RT
RT
>99
<1
6
UO2(NO3)2
16.2
16.2
16.2
16.2
16.2
16.2
<1
12
<1
7
MnCl2
ligand (H4TCPP)
ligand (MnTCPP)
MIX (Mn + H4TCPP + U)
Taking into consideration our data and previous reports, a
feasible mechanism for this photocatalytic reaction is proposed
(Figure 5). First, under the excitation of visible light, the
photogenerated electrons of the porphyrin derivative can
22
photocatalytic activity for CO2 fixation. For the single
component in the catalyst, whether it is UO2(NO3)2, MnCl2,
or porphyrin ligand, the catalytic effect on CO2 cycloaddition
is very poor or even ineffective. We mixed the inorganic salts
and organic ligands by physical doping, and the catalytic
efficiency was still unsatisfactory, roughly equal to the sum of
the catalytic efficiency of each catalyst component. Apparently,
the catalytic efficiency has been greatly improved by
constructing ligands and metals into a metal−organic frame-
work.
−
activate CO2 into free radical CO2 , and the corresponding
photogenerated hole can convert the epoxide into a betatopic
epoxide radical cation (Figure S11).65−68 Second, after the
epoxide radical cation coordinated with the metal ion at the
center of the porphyrin, a ring-opening reaction occurred
under the attack of nucleophilic Br−.69,70 Third, the CO2− can
quickly react with ring-opened epoxy compounds, and further
convert it into the cyclic carbonate through the intramolecular
ring closure.71,72
In order to investigate the role of transition metals in the
catalytic process, we prepared a series of actinide porphyrin
MOFs by a solvothermal method based on different metal-
loporphyrin ligands and used these materials in CO2
photocatalytic cycloaddition experiments. With the gradual
CONCLUSIONS
■
In summary, we present a method to enhance the stability of a
MOF through introducing K+ to improve the stability of metal
nodes via coordinatively linked framework interpenetration.
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Table 3. Substrate Scope for the Conversion of Epoxides
a
b
1
Reaction conditions: epoxide (1 mmol), CO2 (0.1 MPa), 12 h, RT, catalyst/TBAB (0.5/5 mol %). Total yield determined by H NMR using
c
d
1,3,5-trimethoxybenzene as an internal standard. TON: moles of cyclic carbonate per mole of catalyst used. TOF: moles of cyclic carbonate per
mole of catalyst used per hour.
Accession Codes
CCDC 1993868 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Authors
Lei Mei − Laboratory of Nuclear Energy Chemistry, Institute
of High Energy Physics, Chinese Academy of Sciences, Beijing
100049, China; orcid.org/0000-0002-2926-7265;
Email: meil@ihep.ac.cn
Wei-Qun Shi − Laboratory of Nuclear Energy Chemistry,
Institute of High Energy Physics, Chinese Academy of
Sciences, Beijing 100049, China; orcid.org/0000-0001-
9929-9732; Email: shiwq@ihep.ac.cn
Figure 5. Schematic mechanism of the photocatalytic reactions by
IHEP-9.
Authors
Zhi-Wei Huang − Engineering Laboratory of Advanced Energy
Materials, Ningbo Institute of Industrial Technology, Chinese
Academy of Sciences, Ningbo 315201, China; Radiochemistry
Laboratory, School of Nuclear Science and Technology,
Lanzhou University, Lanzhou 730000, China; orcid.org/
0000-0003-2660-3136
Kong-Qiu Hu − Laboratory of Nuclear Energy Chemistry,
Institute of High Energy Physics, Chinese Academy of
Sciences, Beijing 100049, China
Cong-Zhi Wang − Laboratory of Nuclear Energy Chemistry,
Institute of High Energy Physics, Chinese Academy of
Sciences, Beijing 100049, China
Yan-Mei Chen − Engineering Laboratory of Advanced Energy
Materials, Ningbo Institute of Industrial Technology, Chinese
Academy of Sciences, Ningbo 315201, China
Wang-Suo Wu − Radiochemistry Laboratory, School of
Nuclear Science and Technology, Lanzhou University,
Lanzhou 730000, China
Zhi-Fang Chai − Engineering Laboratory of Advanced Energy
Materials, Ningbo Institute of Industrial Technology, Chinese
Academy of Sciences, Ningbo 315201, China; Laboratory of
Nuclear Energy Chemistry, Institute of High Energy Physics,
Chinese Academy of Sciences, Beijing 100049, China
Specifically, the K+ induces the formation of doubly inter-
penetrating frameworks, participates in metal coordination,
and connects two uranyl ions together to realize a novel U-K-U
metal oxygen cluster. The actinide porphyrin MOF IHEP-9
can be thermally stable up to 400 °C and still maintain a
crystalline state in an aqueous solution of pH 2−11. This
method is valuable for improving the stability of MOF
materials. Owing to the large conjugate system of the
porphyrin and exposed Mn2+ Lewis acid sites, IHEP-9 can
be very efficient in visible-light-driven photocatalytic CO2
conversion.
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02473.
The synthesis and characterization methods of materials,
crystal data and structure refinement, typical figures
including PXRD, cycle experiments, stability test, XPS,
photoelectric test, and NMR spectra (PDF)
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Article
phobicity by doping metal ions. Chem. Commun. 2016, 52, 6513−
6516.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c02473
(15) He, H. M.; Sun, Q.; Gao, W. Y.; Perman, J. A.; Sun, F. X.; Zhu,
G. S.; Aguila, B.; Forrest, K.; Space, B.; Ma, S. Q. A Stable Metal-
Organic Framework Featuring a Local Buffer Environment for
Carbon Dioxide Fixation. Angew. Chem., Int. Ed. 2018, 57, 4657−
4662.
Author Contributions
⊥These authors contributed equally to this work.
Notes
(16) McHugh, L. N.; McPherson, M. J.; McCormick, L. J.; Morris, S.
A.; Wheatley, P. S.; Teat, S. J.; McKay, D.; Dawson, D. M.; Sansome,
C. E. F.; Ashbrook, S. E.; Stone, C. A.; Smith, M. W.; Morris, R. E.
Hydrolytic stability in hemilabile metal-organic frameworks. Nat.
Chem. 2018, 10, 1096−1102.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Science Fund for Distinguished Young
Scholars (21925603) and the National Natural Science
Foundation of China (Nos. 21701178, 21671191, 11875057,
22076187). We also acknowledge the support of the Science
Challenge Project (TZ2016004). We appreciate the help from
beamline 3W1A of Beijing Synchrotron Radiation Facility
(BSRF) for X-ray single crystal measurements.
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