A multifunctional MOF as a recyclable catalyst for the fixation of CO2 with aziridines or epoxides and as a luminescent probe of Cr(VI)

Article abstract of DOI:10.1039/c8dt00254a

A multifunctional metal-organic framework (1) containing 24-nuclear zinc nanocages shows high solvent- and pH-stability. Compound 1 can be employed as a catalyst for the conversion of CO₂ with aziridines or epoxides, which can be reused at leas

Full text of DOI:10.1039/c8dt00254a

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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A Multifunctional MOFs as Recyclable Catalyst for Fixation of
CO2 with Aziridines or Epoxides and Luminescent Probe of
Cr(VI)
Received 00th January 20xx,
Accepted 00th January 20xx
ChunꢀShuai Cao,a Ying Shi,a Hang Xu,a and Bin Zhao*a
DOI: 10.1039/x0xx00000x
A multifunctional metalꢀorganic framework (1) containing 24ꢀnuclear zinc nanocages displays high solventꢀ
and pHꢀstability. Compound 1 can be employed as catalyst for the conversion of CO2 with aziridines or
epoxides, which can be reused at least ten times just by a simple and rapid method. The PXRD of compound 1
after ten recyclings keeps well consistent with the original one. Inductively coupled plasma measurement of
reaction filtrate revealed that only trace amount leakage of Zn2+ was observed, indicating that the framework
did not collapse after recyclings. Compound 1 can effectively catalyze cycloaddition reaction of CO2 and five
aziridines or five epoxides with different substituent groups. To our knowledge, this is the first multifunctional
MOFsꢀbased catalyst serving as the conversion of CO2 with aziridines or eopoxides. Furthermore, luminescent
investigations reveal that compound 1 can also act as a luminescent probe for chromium(VI) anion species,
which is seriously harmful to human and environments. After five cycle tests, the PXRD of compound 1 are
still in accordance with the original one, manifesting compound 1 can be served as a circulatory luminescent
probe for Cr(VI) anions.
www.rsc.org/
people's attention.16 Despite significant progress has been made in
previous works,17 the recycle performance and rigorous reaction
condition of CO2 with aziridines is still restricted for its actually
applications. In addition, cyclic carbonates with wide applications
Introduction
Environment problems and environment protection has becoming
more and more important with the acceleration of industrialization.
Widespread air and water pollution, as major environmental
hazards, have being posing great danger to both human and
animal’s health. For example, Carbon dioxide (CO2), as the major
greenhouse gas from industrial and human activities, has caused
global warming and acid rain in the past few decades.1 Thus, it is a
pressing need to develop novel porous materials to absorb and
degrade pollutants in the atmosphere and water. Metalꢀorganic
frameworks (MOFs) with wellꢀdefined pores, high surface area and
functional groups, have been extensively exploited to meet this
challenge and solve the energy and environmental problems.
Recently, various MOFs have shown not only structural versatility
but also promising applications in gas storage/ separation,2 optical
properties,3 magnetism,4 catalysis,5 fluorescence sensing,6ꢀ7 and
etc.8 Among these applications, the catalytic reaction for CO2
conversion becomes one of the most urgent tasks in CO2 research
field. Carbon dioxide capture and sequestration (CCS) technologies
have been dedicated to meet this challenge,9 which not only reduces
greenhouse gas in the atmosphere but also generates various high
valueꢀadded chemicals, such as cyclic carbonates,10 alkynyl
carboxylic acid products,11 formic acid,12 oxazolidinones,13
dimethyl carbonate14 and so on.15 Of these, oxazolidinones,
searving as one of important intermediates in organic synthesis,
chiral auxiliaries and antibacterial pharmaceuticals, has received
in textile, dyeing, batteries and drug intermediates has attracted
people's great research interest in the scientific community and
industry.18 Though many kinds of homogeneous catalysts (sionic
liquids, alkali metal salts, Schiff bases and metalꢀcentered salen or
porphyrin complexes)19 have been applied in the synthesis of cyclic
carbonate during actual industrial process, while the reaction
requires high temperatures and pressures. Thus, it is important to
develop mild reaction conditions to accelerate the conversion of
CO2 with aziridines or epoxides. At this point, high porosity and
active sites make MOFs be ideal heterogeneous catalysts. Several
existing MOFs with high catalytic activity in CO2 conversion with
aziridines, terminal alkynes, and epoxides have already been
reported.20 However, to the best of our knowledge, multifunctional
MOFsꢀbased catalysts used for the conversion of CO2 with
aziridines or epoxides have been not reported so far.
On the other hand, MOFs employed as chemical sensors have
been of intense interest, such as the detection of cations,21 anions,22
small organic molecules,23 pH,24 etc.25 But comparably, the
luminescent probes of detecting chromium(VI) anions have been
less reported.26 Actually, chromium(VI) anion species (CrO42ꢀ and
Cr2O72ꢀ), widely used in various industrial processes,27 can cause
serious damage to human health and environment, and the two
toxic and carcinogenic anions have been listed as priority pollutants
by Environmental Protection Agency (EPA) in USA.28 Therefore,
extensive efforts should be devoted to develop more novel and
porous materials with high chemical stability and good
regeneration to detect chromate and dichromate species to prevent
chromium(VI) anions from endangering human health and
environment.
a.Department of Chemistry, Key Laboratory of Advanced Energy Material
Chemistry, MOE, and Collaborative Innovation Center of Chemical Science and
Engineering (Tianjin), Nankai University, Tianjin 300071, China.
Electronic Supplementary Information (ESI) available: [Synthesis, Preparation,
PXRD, photoluminescence spectra, UVꢀvis spectra and ICP results]. See
DOI: 10.1039/x0xx00000x
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In this contribution,
a
multifunctional nanocageꢀbased
Catalytic experiment of CO2 with epoxides. Similarly, A (240.0
mg, 2 mmol) and TBAB (32.4 mg, 0.1 mmol, 5 mol% relative to A)
were also put into the reaction tube equipped with CO2 balloon.
After reaction, resulting mixture was dissolved in CH2Cl2, and the
corresponding cyclic carbonates of X1 yield was determined by 1H
NMR analysis using 1,3,5ꢀtrimethoxybenzene (42.1 mg, 0.25 mmol)
as an internal standard.
metalꢀorganic framework (1) with high solventꢀ and pHꢀstability
was prepared (Fig. 1), and it can act as efficient catalyst for the
conversion of CO2 with aziridines or epoxides. Importantly,
compound 1 can be reused at least ten times just by simple and
rapid method without any obvious loss in catalytic activity. And 1
can serve as a recyclable luminescent probe for chromium(VI)
anion species among twenty anions.
Results and discussion
Structure and stability study of 1.29 The zeoliteꢀlike
microporous tetrazoleꢀbased framework of 1 containing 24 nuclear
zinc cages exhibits high CO2 adsorption capacity with 35.6 wt %
(8.09 mmol/g) at 273 K/ 1 bar. The BrunauerꢀEmmettꢀ Teller (BET)
and Langmuir surface areas of activated 1 are estimated to be 1151
and 1222 m2/g, respectively. The pore size is about 5.5 Å in
diameter by nonlocal DFT analysis, and total pore volume is 0.65
cm3/g via calculating from Ar adsorption isotherm. The high CO2
adsorption capacity at 273 K, which is mainly originated from the
multipoint interaction among CO2 and the inner wall motif of cages
based on computational simulations.29 The powder XRD
diffractions of compound 1 and activated sample were measured, as
shown in Fig. S1, and the results show the sample is in pure phase
and activated sample keeps stable. In order to explore the chemical
stability of compound 1, samples of 1 were immersed in several
common solvents for 24 hours, and then the PXRD patterns were
tested. The corresponding PXRD patterns still remain consistent
with the simulated one (Fig. S2), uncovering that compound 1
possesses high solvent stability. Similarly, the acid/base stability of
compound 1 was also investigated. The samples of 1 were
immersed in the solutions with pH values from 1.0 to 14.0 for four
hours, and the PXRD patterns suggest that the frameworks in 1
remain unchanged spanning pH range of 1ꢀ14 (Fig. S3).
Fig. 1 The view of compound 1.
Experimental section
Catalyze cycloaddition of CO2 with aziridines. Considering
significant adsorbing ability of CO2 and abundant lewis acid active
sites of Zn in 1, herein we further explored the reactions of CO2
with aziridines. 1ꢀethylꢀ2ꢀphenylaziridine (a1) was selected as a
model substrate to investigate optimized reaction condition, as
listed in Table 1. The influence of temperature on the reaction was
investigated (Table 1, entries 1ꢀ4), and quantitative yield and
excellent selectivity for a2 were achieved at 70 °C. Thus, 70 °C
was chosen as the optimal temperature. Afterwards, the decrease of
CO2 pressure or coꢀcatalyst reduced the yield of the reaction,
indicative of that 2 MPa CO2 and 5 % TBAB is a suitable pressure
or coꢀcatalyst amount, respectively (Table 1, entries 5ꢀ6). In terms
of catalyst amount (Table 1, entries 7ꢀ8), both 40 mg and 20 mg of
1 can achieve quantitative yields and excellent selectivity for a2. As
a result, the optimized reaction conditions should be 70 °C under 2
MPa CO2 with 20 mg catalyst 1.
Materials and methods
All reagents and reactants were purchased directly by
commercial approach and were used without any purification.
Powder Xꢀray diffraction and thermodiffractogram measurements
were carried out on an Ultima IV Xꢀray diffractometer using
CuꢀKα radiation. The fluorescent spectra were recorded by an
Fꢀ4500 FL Spectrophotometer at room temperature. The metal
content was measured by ICP atomic emission spectrometric
analysis (IRIS Advantage). NMR spectra were recorded on a
Varian Inc Mercury Vxꢀ300 type (1H NMR, 300 MHz)
spectrometer. UVꢀVis spectroscopic studies were collected on
shimadzu UVꢀ3600 spectrophotometer.
Preparation of compound 1. Compound
1 was prepared
according to our previous work.29 The preparation process
was represented in Scheme S1.
In order to further explore and prove catalytic potential of
compound 1, several typical aziridines were prepared and
employed as cycloaddition reaction, and the corresponding
synthesis was shown in Scheme S2. Under optimized reaction
conditions, all of corresponding oxazolidinones were obtained and
summarized in Table 2 (entries 1ꢀ5). For entries 1ꢀ3, three
aziridines bearing different substituent groups at the nitrogen atom
was tested in the reaction. The aziridine with ethyl group achieved
the best yield and selectivity, which is possibly attributed to the
lower stern hindrance of ethyl group than propyl group or butyl
group. Additionally, different substituent groups (ꢀCH3 and ꢀCl) on
phenyl ring were also investigated on the reaction. The yields of
1ꢀethylꢀ2ꢀ(4ꢀchlorophenyl)ꢀaziridine and 1ꢀethylꢀ2ꢀ(4ꢀmethyl)ꢀ
Catalytic experiment of CO2 with aziridines. In typical
experiment, activated catalyst 1 (20 mg, 0.056 mmol) was grinded
and added into 10 mL autoclave equipped with a magnetic stir bar,
then a1 (294.4 mg, 2 mmol) and coꢀcatalyst tetrabutylammonium
bromide (TBAB) (32.4 mg, 0.1 mmol, 5 mol% relative to a1) were
also put into the reaction tube. Then the autoclave was capped
under 2 MPa CO2 and stirred at certain temperature for 12 h. After
reaction, resulting mixture was dissolved in CH2Cl2, and the
corresponding oxazolidinones of 3ꢀethylꢀ5ꢀphenyloxazolidinꢀ2ꢀone
(a2) and 3ꢀethylꢀ4ꢀphenyloxazolidinꢀ2ꢀone (a3) yield was
determined by 1H NMR analysis using 1,3,5ꢀtrimethoxybenzene
(42.1 mg, 0.25 mmol) as an internal standard.
aziridine were high (Table 2, entries
4 and 5). However,
1ꢀethylꢀ2ꢀ(4ꢀchlorophenyl)ꢀaziridine showed low activity, which
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can be explained as the electronꢀwithdrawing effect of chloride
group on the phenyl ring.13 As a result, compound 1 can effectively
catalyze cycloaddition reaction with extensive aziridines.
substrates are activated because of Zn2+ owning Lewis acid site.
Secondly, the nucleophilic Brꢀ attacks the N atoms of aziridines to
lead to ring opening through two different pathways I and II, as
showed in Scheme 1. Then CO2 interacts with the N anion of the
ringꢀopened intermediate to form carbamate salt. At last, Oꢀ attacks
at the CꢀBr carbon to perform intramolecular ringꢀclosure, and the
oxazolidinones can be obtained along with regeneration of 1 and
TBAB. In terms of selectivity, pathway I is the main process and
obtain main product x2. It is attributed to ringꢀopening of the
aziridine at the most substituted carbon, which produced more
stable carbamate salt.
Table 1. Cycloaddition reaction of CO2 with 1ꢀethylꢀ2ꢀphenylaziridine
under various conditions.(a)
Entry
Catalyst 1(mg)
T(°C
)
Yield(b)
%
Regio-sel(c)
Table 2. Synthesis of various oxazolidinones from CO2 and aziridines with
catalyst 1.(a)
1
2
80
80
80
80
80
80
40
20
0
30
50
70
100
100
70
70
70
70
70
70
70
70
20
>99
>99
>99
80
98:2
94:6
99:1
98:2
88:12
95:5
98:2
98:2
98:2
89:11
98:2
91:9
98:2
3
4
5d
6e
7
86
>99
>99
74
Entry
Substrates
Conv.(b)
%
Yield(b)
%
Regio-sel(c)
8
9
1
10f
11g
12h
13i
0
77
98:2
>99
>99
0
62
0
66
0
62
2
>99
91
91:9
(a)Reaction conditions: 1ꢀethylꢀ2ꢀphenylaziridine (a1) (294.4 mg, 2.0 mmol),
solventꢀfree, TBAB (32.4 mg, 0.1 mmol), CO2 (2.0 MPa), 12 h, catalyst 1;
(b)Total yield of a2 and a3 determined by 1H NMR using
1,3,5ꢀtrimethoxybenzene as an internal standard; (c)Molar ratio of a2 to a3;
(d)CO2 (1.0 MPa); (e)TBAB (16.2 mg, 0.05 mmol), 2 MPa; (f)TBAB (32.4 mg,
0.1 mmol) and Zn(OAc)2 (12.3 mg, 0.056 mmol); (g)TBAB (32.4 mg, 0.1
mmol) and Zn(NO3)2 (16.6 mg, 0.056 mmol); (h)TBAB (32.4 mg, 0.1 mmol)
and ZnSO4 (16.1 mg, 0.056 mmol);(i)TBAB (32.4 mg, 0.1 mmol) and ZnCl2
(7.7 mg, 0.056 mmol).
3
4
93
92
93:7
92:8
>99
74
In fact, recyclable performance of catalysts is an necessary
parameter for heterogeneous catalytic reaction. Hence, the recycle
tests of
1
for cycloaddition reaction of CO2 with
5
99
99:1
1ꢀethylꢀ2ꢀphenylaziridine were researched (Fig. 2). 1 can be
recycled at least ten times with no obvious loss in catalytic activity.
The powder Xꢀray diffraction (PXRD) patterns of 1 after ten
recycling processes can be still well consistent with the original one
(Fig. S4). To make clear the nature of the reaction, catalytic
experiment continued to react after removing compound 1 at 3
hours (Fig. S5). Experimental results show that the transformation
rate of aziridines decreases after removal of catalyst, so catalyst 1
has significant impact on the transformation rate of substrates.
Inductively coupled plasma (ICP) measurement of reaction filtrate
revealed that only trace amount leakage of Zn2+ was observed
(Table S1), indicating that the framework did not collapse after
recyclings. Therefore, compound 1 can be employed as the
recyclable catalyst of cycloaddition reaction for CO2 and
1ꢀethylꢀ2ꢀphenylaziridine just by fast and simple method.
>99
(a)Reaction conditions: aziridines (2.0 mmol x1), solventꢀfree, 20 mg catalyst
1 loading (based on metal center, about 2.8 mol%), TBAB (32.4 mg, 0.1
mmol), CO2 (2.0 MPa), 70 °C, 12h; (b)Determined by 1H NMR using
1,3,5ꢀtrimethoxybenzene as an internal standard; (c)Molar ratio of x2 to x3.
Next step, to prove the effect of 1, the influence of different zinc
sources [Zn(OAc)2, Zn(NO3)2, ZnSO4 and ZnCl2] were employed
to replace 1 to conduct the reaction (Table 1, entries 10ꢀ13) and the
yield was less than 77 %, which mainly attributes to interaction
between free Zn2+ and Brꢀ to hinder the nucleophilicity of Brꢀ
ions.30 Finally, the reaction mechanism for cycloaddition reaction
of CO2 with aziridines is proposed based on other reports.13,20a At
first, the substrate aziridines and CO2 are enriched around catalyst
1. Then the N atoms of the aziridines coordinate with zinc sites of 1,
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Fig. 2 Recycle tests of the compound 1 for the cycloaddition reaction of
First, [Zn(OAc)2, Zn(NO3)2, ZnSO4, and ZnCl2] were employed as
catalysts to replace 1 to conduct the reaction (Table S2, entries
15ꢀ18), and the yield was less than 82 %, which mainly attributes to
interaction between free Zn2+ and Brꢀ to hinder the nucleophilicity
of Brꢀ ions.30 Comparably, the yield of reaction employing 1 as
catalysts is over 99 %. The results indicate that 1 has better and
higher catalysis effect on cycloaddition reaction of epoxides and
CO2. The significant catalytic performance maybe result from the
following factors: a) nanoꢀsized [Zn24] cages of 1 can enrich largely
substrates and CO2, and the increased concentration of reactants
can increase the yield; b) the steric hindrance around Zn2+ and the
ligand in the stable Zn24ꢀcage unit effectively prevent the
coordination between Zn2+ and Brꢀ, resulting in more nucleophilic
attack of Brꢀ on epoxides. Namely, cageꢀlike motif in [Zn24]
nanocages plays a vital role in the cycloaddition reaction.
CO2 with 1ꢀethylꢀ2ꢀphenylaziridine.
Table 3. Synthesis of various cyclic carbonates from CO2 and epoxides
with catalyst 1.(a)
Scheme 1. A representation of the tentatively proposed catalytic mechanism
for the cycloaddition of CO2 and aziridines into oxazolidinones catalyzed
by 1 (L+ = tetraꢀnꢀtertbutylammoꢀnium).
Entry
Substrates
Products
Yield(b) [%]
Catalyze cycloaddition of CO2 with epoxides. We continued to
evaluate its performance in the cycloaddition of CO2 with epoxides
to form cyclic carbonates at mild reaction conditions. In order to
optimize the reaction condition, the reactions of CO2 with epoxides
under various conditions were investigated (Table S2). In the
preliminary study, phenylethylene oxide (A) was selected as a
model substrate to investigate the influence of temperature on the
reaction (Table S2, entries 1ꢀ8). The yield increases with the rise
of temperature, so higher temperature can facilitate the reaction
process. Nevertheless, the yield at 90 °C and 100 °C decreased to
some extent, which might be ascribed to the partial decomposition
of TBAB in high temperature.20a As a result, 70 °C is chosen as the
optimal temperature for this reaction. Next, the amount of
cocatalyst TBAB and catalyst 1 were investigated (Table S2,
entries 5, 11ꢀ14). In conclusion, the optimized reaction conditions
should be 70 °C under 0.1 MPa CO2 with 40 mg 1 and 32.4 mg
coꢀcatalyst.
1
>99.00
2
3
96
94
99
4
5
73
To further explore and testify the catalytic generality of
compound 1, several typical epoxides were examined for the
cycloaddition reaction (Table 3) under optimized reaction
conditions. All of corresponding cyclic carbonates were obtained in
comparatively excellent yields (73ꢀ99 %, Table 3). The results
clearly show that 1 can catalyze cycloaddition reaction with
relatively extensive epoxides.
(a)Reaction conditions: epoxides (2.0 mmol), solventꢀfree, 40 mg catalyst 1
loading (based on metal center, about 5.6 mol%), TBAB (32.4 mg, 0.1
mmol), CO2 (0.1 MPa), 12 h; (b)Determined by 1H NMR using
1,3,5ꢀtrimethoxybenzene as an internal standard.
Actually, cyclicity is an essential feature of any catalyst
considered for heterogeneous catalyst in industrial applications. As
shown in Fig. 3, 1 can be reused at least ten times without any
obvious loss in catalytic activity. Similarly, catalytic experiment
continued to react after removal of catalyst 1 at 3 hours, as shown
in Fig. S6. Experimental results uncover that the transformation
rate of epoxides get lower after removal of catalyst, implying that
catalyst 1 serves as an important role in the catalytic reactions. ICP
measurement of reaction filtrate after the first and the tenth
recycling process revealed that only trace amount leakage of Zn2+
was observed (Table S3). The PXRD patterns of 1 after ten
recycling processes can be still well consistent with original one
(Fig. S7), indicating that 1 may be reused just by a simple and
rapid method.
Fig. 3 Recycle tests with the compound 1 for the cycloaddition reaction of
Next step, to explain reaction mechanism, the influence of zinc
sources on catalytic reaction were measured as control experiments.
CO2 with phenylethylene oxide.
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In combination with previous reports,20 a plausible mechanism
was proposed for cycloaddition reaction of epoxides with CO2 to
form cyclic carbonates with the synergistic catalytic effect of Zn2+
and Brꢀ. As shown in Scheme S3: initially, the oxygen atom of
epoxide coordinates with Lewis acidic zinc sites of 1, which
activates the epoxy ring. Concomitantly, the Brꢀ generated from
nꢀBu4NBr attacks the lessꢀhindered carbon atom in the activated
epoxide, thereby resulting in opening epoxide ring. Following this,
CO2 interacts with oxygen anion of the ringꢀopened intermediate to
form alkylcarbonate anion. In the subsequent step, Oꢀ attacks at the
CꢀBr carbon to perform intramolecular ringꢀclosure, cyclic
carbonate together with regeneration of TBAB and the original
structure could be formed. In this process, nucleophilic species is
anions (0.1 moL/L) except for CrO42ꢀ/Cr2O72ꢀ were added into
the 1.96 mL suspension of 1, the luminescent measurement of
solutions was tested (Fig. S10) Other anions did not show
obvious quenching effect, uncovering 1 can selectively detect
Cr(VI) anions among the above anions.
Moreover, the detection limit of 1 as an efficient fluorescent
probe was explored. The different concentrations of 20 ꢁL
2ꢀ
CrO42ꢀ/Cr2O7 (1×10ꢀ4 to 1×10ꢀ1 mol Lꢀ1) solutions were dropped
2ꢀ
into 1.98 mL suspension of 1, forming a series of 1ꢀCrO42ꢀ/Cr2O7
(1×10ꢀ6 to 1×10ꢀ3 mol Lꢀ1) suspensions. The luminescence intensity
of 1ꢀCrO42ꢀ/Cr2O7 gradually decreases with the addition of
2ꢀ
CrO42ꢀ/Cr2O72ꢀ (Fig. S11 ). The detection limit of 1 for detecting
CrO42ꢀ and Cr2O7 can reach 3×10ꢀ6 mol Lꢀ1. In order to evaluate
2ꢀ
essential for the ring opening of the epoxide to form
a
whether dilution of adding water affect luminescent intensity,
some amount of pure water was dropped into suspension of
compound 1. As shown in Fig. S12, the luminescent intensity
did not decrease significantly with the addition of water, which
implies the dilution did not cause luminescence quenching.
bromoꢀalkoxide. Thus, we conclude that high density of zinc Lewis
acid sites in 1 could promote the synergistic catalytic effect of
nꢀBu4NBr, thus facilitate the cycloaddition reaction of epoxides
with CO2 under ambient conditions.
Luminescent Behavior and Sensing Property. The solid
In order to further explore the relationship between the
concentration of the quenching effect and CrO42ꢀ, the luminescence
intensity vs. CrO42ꢀ concentration plot was made (Fig. S13). And it
can be linearly fitted into I0/I = 1.067 + Ksv[CrO42ꢀ] (I0 and I
photoluminescence spectra of
1 and 1,5ꢀbis(5ꢀtetrazolo)ꢀ3ꢀ
oxapentane ligand (H2btz) were recorded at room (Fig. S8). Under
excitation at 260 nm, 1 exhibits characteristic emission peaks at
360 and 420 nm, which can be attributed to π*→π and π*→n
transitions of H2btz, respectively.
represent the luminescence intensity of
1 before and after adding
CrO42ꢀ, [CrO42ꢀ] represents the concentration of CrO42ꢀ, and Ksv
represents the quenching rate constant), which is close to the
SternꢀVolmer equation: I0/I = 1 + Ksv[CrO42ꢀ].31 Anaylysis results
reveal that luminescent intensity follows the equation of I0/I =
1.067 + 1998.22 [CrO42ꢀ] in the range of 3.0×10ꢀ6 ~ 9×10ꢀ4 mol Lꢀ1
of CrO42ꢀ; luminescent intensity follows the equation of I0/I = 1.068
+ 1789.07 [Cr2O72ꢀ] in the range of 3.0×10ꢀ6 ~ 9×10ꢀ4 mol Lꢀ1 of
2ꢀ
Cr2O7
.
In fact, recycling performance is necessary for luminescent
probe to be applied in practice. is immersed in an aqueous
solution of 0.1 M CrO42ꢀ/Cr2O72ꢀ for 20 s to form ꢀCrO42ꢀ/Cr2O7
,
1
2ꢀ
1
then
times. The samples of
mg of samples of
1
ꢀCrO42ꢀ/Cr2O72ꢀ were washed with water and ethanol for five
2ꢀ
1
ꢀCrO42ꢀ/Cr2O7 were ground and then 12
2ꢀ
1
ꢀCrO42ꢀ/Cr2O7 were dispersed in 2 mL of
aqueous solution to form a suspension by an ultrasound method.
2ꢀ
Then the emission of
luminescence intensity was nearly identical to the original one (Fig.
S14). The PXRD patterns of after recycling are still well
consistent with the original ones (Fig. S15), revealing that can be
served as circulatory luminescent probe for Cr(VI).
Inductively coupled plasma (ICP) measurement (Table S4
1
ꢀCrO42ꢀ/Cr2O7 were tested, and
1
Fig. 4 The luminescence intensity of 1
ꢀX at 420 nm in 10ꢀ3 mol Lꢀ1 different
1
anions.
a
)
2ꢀ
1
does not contain Cr(VI). CrO42ꢀ/Cr2O7
In order to explore the influence behaviors of various anions on
luminescence of 1, 10 mg of 1 was ground and dispersed in 1.96
mL of aqueous solution to form a suspension by ultrasound, and 40
reveals that recycled
have almost been removed by a simple and rapid method.
ꢀ
ꢀ
ꢁL of NaX solution (1 × 10ꢀ1 mol Lꢀ1) (X = BF4 , Fꢀ, OAcꢀ, ClO4 ,
Then, possible mechanism that the introduction of
2ꢀ
CrO42ꢀ/Cr2O7 decreased luminescence intensity is discussed.
Brꢀ, CO32ꢀ, SCNꢀ, Iꢀ, SO32ꢀ, C2O42ꢀ, NO3 , Clꢀ, PO43ꢀ, N3 , IO3 , SO4
,
ꢀ
ꢀ
ꢀ
2ꢀ
Based on previous literatures,6e,32 the luminescence quenching
of MOFs caused by anions may result from the several aspects:
(a) the collapse of the MOFs; (b) energy losing caused by the
collision between frameworks and anions during energy
HCO3 , MnO4 , CrO4 or Cr2O72ꢀ) was slowly dropped into the
ꢀ
ꢀ
2ꢀ
above solutions to form a 1ꢀX suspension (2 × 10ꢀ3 mol Lꢀ1). The
2ꢀ
2ꢀ
addition of CrO4 or Cr2O7 solution lead to luminescence
quenching, and MnO4 makes the luminescent intensity slightly
ꢀ
transfering process. The PXRD patterns of
1
after being immersed
in H2O, CrO4 or Cr2O72ꢀ are still well consistent with the original
one Fig. S16 , supporting high stability of compound in
detecting Cr(VI) in aqueous system. Thus, luminescence
quenching did not result from the collapse of the frameworks in
decrease, while other anions have no obvious effect on the
luminescent intensity (Fig. 4). Considering mixed anions in waste
water, luminescence quenching of mixed solutions containing
2ꢀ
(
)
1
2ꢀ
2ꢀ
Cr2O7 and another anions was investigated. 40 ꢁL of Cr2O7
solution (0.1 mol Lꢀ1) and 40 ꢁL of another anion solution (0.1 mol
Lꢀ1) were slowly dropped into a 1.92 mL suspension (2 × 10ꢀ3 mol
Lꢀ1) of 1. Similarly, luminescent intensity of the solutions
containing CrO42ꢀ and another anion was also measured at once. As
show in Fig. S9, quenching effect of Cr(VI) on 1 was hardly
influenced by other anions. To verify whether other anions in the
absence of Cr(VI) anions affects the detection, 40 ꢁL other mixed
1
.
2ꢀ
2ꢀ
The UVꢀvis spectra of CrO4 and Cr2O7 solutions show
absorption at about 270 and 370 nm for CrO42ꢀ, 260 and 350 nm
2ꢀ
for Cr2O7
of
(Fig. S17). While the strong excitation wavelength
2ꢀ 2ꢀ
1
is 260 nm, thus CrO4 and Cr2O7 in the solution can
significantly absorb the energy of the excited light, resulting in
luminescence decrease. In conclusion, the collision between the
2ꢀ
CrO42ꢀ/ Cr2O7 anions and the frameworks, as well as the
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2ꢀ
adsorption of CrO42ꢀ/ Cr2O7 in the UVꢀvis region, reduce
energy of transmission process, and finally lead to
luminescence quenching.
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Conclusions
In summary, a multifunctional metalꢀorganic framework 1 with
high solventꢀstability and pHꢀstability was prepared. Compound 1
can serve as an efficient, recyclable and environmentally friendly
catalyst for the conversion of CO2 with five aziridines or epoxides
containing different substituent groups. Importantly, catalyst 1 can
be reused at least ten times without any obvious loss in catalytic
activity, and PXRD of compound 1 after recyclings keep well
consistent with the original one. To the best of our knowledge, this
is the first multifunctional MOFsꢀbased catalyst serving as the
conversion of CO2 with aziridines or eopoxides. Furthermore, the
material can also act as a recyclable luminescent probe for
chromium(VI) anion species among twenty anions.
Conflicts of interest
There are no conflicts to declare.
10 (a) H. ꢀF. Zhou, B. Liu, L. Hou, W. ꢀY. Zhang and Y. ꢀY. Wang, Chem.
Commun., 2018, 54, 456; (b) X. ꢀY. Li, Y. ꢀZ. Li, Y. Yang, L. Hou, Y. ꢀY.
Wang and Z. Zhu, Chem. Commun., 2017, 53, 12970; (c) J. Liang, Y. ꢀB.
Huang and R. Cao, Coord. Chem. Rev., doi.org/10.1016/j.ccr.2017.
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Chem. Soc., 2015, 137, 15988; (e) Z. Zhou, C. He, J. ꢀH. Xiu, L. Yang
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Wang, J. Liu, J. S. Lim, R. ꢀQ. Zou and Y. ꢀL. Zhao, J. Am. Chem. Soc.,
2016, 138, 2142; (g) M. H. Beyzavi, R. C. Klet, S. Tussupbayev, J.
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Acknowledgements
This work was supported by NSFC (21625103, 21571107, and
21421001), SFC of Tianjin (15JCZDJC37700) and 111
Project (B12015).
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Dalton Transactions
Page 8 of 8
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DOI: 10.1039/C8DT00254A
Table of Contents
A multifunctional metal-organic framework (1) with high solvent-stability and pH-stability was prepared.
Compound 1 can serve as an efficient, recyclable and environmentally friendly catalysts for the conversion of CO2
with five aziridines or epoxides containing different substituent groups. To the best of our knowledge, this is the
first multifunctional MOFs-based catalyst serving as the conversion of CO2 with aziridines or eopoxides.
Furthermore, the material can also act as a recyclable luminescent probe for chromium(VI) anion species among
twenty anions.