A multifunctional Co-based metal-organic framework: heterogeneous catalysis, chemiluminescence sensing and moisture-dependent solvatochromism

Article abstract of DOI:10.1039/C8DT02625D

Crystalline materials with multi-catalytic applications are of great value to both fundamental research and practical applications. The platform of metal-organic frameworks (MOFs) is utilized to fabricate a microporous versatile catalyst with high stability. Self-assembly of a flexible ligand, 4-(4-carboxybenzylamino)benzoic acid (H₂CBBA), with Co(ii) resulted in a 3D framework, CBBA-Co, with Co₃O clusters exposed in the zigzag channels. Upon in situ activation, CBBA-Co exhibited multiple heterogeneous catalytic activities. Theoretical calculations were carried out to give insights into the catalytic process. In addition, CBBA-Co also showed promising potential in optical sensing by virtue of its catalytic activity. The luminol chemiluminescence was greatly enhanced by CBBA-Co, and linear determination of the concentration of H₂O₂ in the range of 0-30% was established. The successful implementation of CBBA-Co indicates the feasibility and promising future of employing MOFs as an efficient platform for the fabrication and study of multifunctional catalysts, both experimentally and theoretically.

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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
rsc.li/dalton

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DOI: 10.1039/C8DT02625D
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A multifunctional Co-based metal-organic framework:
heterogeneous catalysis, chemiluminescence sensing and
moisture dependent solvatochromism
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
b
DOI: 10.1039/x0xx00000x
Ming-Hua Xie, Ya Wang, Ruo-Fei Li, Peng-Yu Dong, Gui-Hua Hou, Rong Shao, Xin-Guo Xi,
*a
*a
Rong-Feng Guan and Xiu-Li Yang
www.rsc.org/
Crystalline materials with multi-catalytic applications are of great value to both fundamental researches and practical
applications. The platform of metal-organic frameworks (MOFs) is utilized to fabricate a microporous versatile catalyst
2
with high stability. Self-assembly of a flexible ligand 4-(4-CarboxyBenzylamino) Benzoic Acid (H CBBA) with Co(II) resulted
in a 3D framework CBBA-Co with Co O clusters exposed in the zigzag channels. Upon in situ activation, CBBA-Co exhibited
3
multiple heterogeneous catalytic activities. Theoretical calculations were carried out to give insights into the catalytic
process. Besides, CBBA-Co also showed promising potential in optical sensing by virtue of its catalytic activity. The luminol
2 2
chemiluminescence was greatly enhanced by CBBA-Co, and linear determination of the concentration of H O in the range
of 0-30% was established. The successful implementation of CBBA-Co indicates the feasibility and promising future of
employing MOFs as an efficient platform for the fabrication and study of multifunctional catalyst both experimentally and
theoretically.
herald the goal-directed designs for targeted applications.
Metal-organic frameworks (MOFs) represent a class of
hybrid materials with varied structures, compositions and
Introduction
Catalysts have played a decisive role in modern industries, and
development of novel catalyst have attracted a great many of
functionalities, and have been widely used as efficient
-16
9
1
-3
heterogeneous catalyst.
Tailorable building blocks, diverse
research interest.
Heterogeneous catalysts take the
inorganic nodes as well as the unambiguously defined
structures offer a promising blueprint in designing the desired
multi-functional materials. During our long-term studies in
catalytic MOFs, cobalt (II) is found a promising candidate in
constructing multi-functional MOFs by virtue of its Lewis acid
activity, catalytic oxidation activity, guest-dependent
adsorption spectra as well as framework construction ability.
Herein, we report a versatile Co-based MOF (CBBA-Co)
featuring multiple functions in Lewis acid catalysis, oxidative
catalysis, chemiluminescence sensing and aqua sensitive
chromism.
advantages of easy separation and high reusability, and the
integrated structures may offer enhanced opportunities for
4
-6
mechanistic studies. Many efforts have been devoted to
synthesize heterogeneous catalyst, and embedding
components into proper supporters is the most frequently
7
,8
employed strategy. It has to be noticed that the introduction
of inert supporters may decrease the density of effective
functional components, and the lack of techniques for direct
structural solution of such composites represent a significant
barrier to realize all their potentials fully due to the limited
mechanistic
understanding.
Unambiguously
solved
microstructures, which is uncommon but highly sought for
such composite materials, could enable remarkable
mechanistic insights into the versatile applications and thus
Experimental Section
Synthesis of 4-(4-CarboxyBenzylamino) Benzoic Acid (H
2
CBBA)
H
2
CBBA was synthesized according to literature methods
1
7
with minor modification.
formylbenzoate with methyl 4-aminobenzoate followed by
direct reduction with NaBH resulted in esterified H CBBA as
pure white powders. H CBBA could be afforded in quantitative
yield after hydrolysis of the dimethyl ligand with NaOH.
Condensation of methyl 4-
4
2
2
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The structure of [(Co
3
O)CBBA
2
] was used without further
optimization, considering the structural integrity of CBBA-Co
during all tests. All the calculations were carried out in the
National Supercomputing Centre in Shenzhen, China.
Catalytic ring opening reactions
0
.1 mmol of amine and CBBA-Co (1 mg, 1% mol) were stirred
o
in 0.5 mL of cyclohexane oxide at 70 C for 12 h. Upon
completion, the catalyst was removed by filtration and the
filtrate was submitted to GC analysis. The product was
determined by comparison of the retention time with
corresponding standard sample. Blank control experiment was
carried out without any catalyst under otherwise identical
conditions. The heterogeneity verification test was carried out
o
by firstly stirring CBBA-Co in cyclohexane oxide at 70 C for 12,
and the filtrate was used to carry out the succeeding ROR in
the absence of catalyst under otherwise identical conditions.
o
GC conditions: Agilent SE-54 column, 190 C; Injector: 220 C;
o
o
FID-Detector: 250 C; using N as the carrier gas, with a flow
2
rate pressure of 0.1 MPa.
Catalytic sulfide oxidation
Fig. 1. Structural illustration of CBBA-Co. a) ORTEP representation of the coordination
3
motif of CBBA ligand, showing the trinuclear Co O cluster. Displacement ellipsoids are
Sulfide (0.1 mmol), CBBA-Co (1 mg, 1% mol) and tert-butyl
hydroperoxide (TBHP, 70%, 0.1 mmol) were stirred in 0.5 mL of
drawn at the 50% probability level. b) 1D channel in CBBA-Co viewed down the a axis.
o
DMF at 50 C for 12 h. The catalyst was filtered, and the
Synthesis of CBBA-Co
filtration was submitted to GC analysis directly. The catalyst
.
Co(NO ) 6H O (5 mg) pre-dissolved in 1.5 mL of deionized was collected and reused in the succeeding runs after being
3
2
2
water was mixed with H CBBA (2 mg) pre-dissolved in 1.5 mL washed with DMF, EtOH, Et O, and dried at room
2
2
of N, N-dimethylformamide (DMF), and the resulted pink temperature. The catalytic oxidation product was determined
solution was transferred to a 5 mL glass vial. Another 4 drops by comparing the retention time with that of corresponding
of NaOH aqueous solution (0.05 M) was added into the vial standard sample. Blank control experiment was carried out in
upon stirring, the final clear solution was left standing in an the absence of any catalyst under otherwise identical
o
oven at 80 C for 3 days. Pink needle-like crystals of CBBA-Co conditions. For heterogeneity verification test, 1 mg of CBBA-
o
were collected after filtration, yield: 2.7 mg, 76% (based on Co was firstly stirred in DMF at 50 C for 12 h, and the filtrate
H2CBBA).
was used as the solvent to carry out the succeeding sulphide
oxidation test in the absence of catalyst under otherwise
identical conditions. GC conditions: Agilent SE-54 column, 210
Quartz crystal microbalance sensing
o
o
o
Freshly prepared CBBA-Co was finely ground and sonicated
C; Injector: 230 C; FID-Detector: 280 C; using N as the
2
for 1 h to afford the nano-sized CBBA-Co (Fig. S6). Nano CBBA- carrier gas, with a flow rate pressure of 0.1 MPa.
Co was dispersed in iso-propanol by sonication (1 mg/mL),
Luminol chemiluminescence and H O sensing
2
2
which was spin-coated on a 5019186.2 Hz AT-cut QCM crystal
with 1 inch diameter Au electrode at 1000 RPM for 60 s (Fig.
177 mg of luminol (1 mmol) was dissolved in 100 mL of
S7). The coated QCM crystal was first treated in high vacuum NaOH aqueous solution (0.5 M) under stirring. The final pH of
o
(
<0.01 Pa) at 50 C for 3 h prior to test, and then placed in a the stock solution was about 8, and the stock solution was
flow cell adapter connected to an SRS QCM-200 quartz crystal stored in dark for 3 days prior to use. To a 1*1 cm quartz
microbalance. N gas flow (1 mL/min) was connected to the cuvette was added 0.5 mg of CBBA-Co and 1 mL of luminol
flow cell by a 2*3 mm PE pipe, and the succeeding absorption stock solution. The quartz cuvette was placed in the dark
2
tests were achieved by bubbling N
analytes (Fig. S8).
2
through the corresponding chamber of a chemiluminescence analyzer, and 1 μL of H
with different concentration was injected into the cuvette
through micro-syringe. The corresponding
2 2
O
a
DFT calculations
chemiluminescence intensity was recorded. The maximum
A
basic binuclear cluster model [(Co
3
O)CBBA
2
]
was emission intensity data was collected to establish linear
constructed according to the crystal data for DFT calculation correlation with the corresponding H
using Gaussian 09 package. B3LYP together with the 6-31G
2 2
O concentration values.
basis set for C, H, O, N, S, and LANL2DZ basis set for Co were
Results and Discussion
chosen for the structure optimization and energy calculation of
the cluster and all the other substance and product molecules.
Structures
2
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Flexible ligand H
2
CBBA (4-(4-CarboxyBenzylamino)Benzoic
Activation of catalyst at elevated temperature under
Acid) could provide abundant possibilities in constructing reduced pressure is a general way of acquiring the desired
2
4,25
frameworks featuring intriguing structures and functionalities coordination vacancy.
Removal of guest and coordinated
in the presence of auxiliary ligands. Direct self-assembly of molecules could be achieved by heating CBBA-Co samples in
CBBA with Co(II) in DMF/H O under solvothermal conditions vacuum, and the colour was turned from pink to blue (Fig. 2a-
yielded CBBA-Co as pink needle-like crystals. Single X-ray 2b), indicating the loss of solvent molecules . The blue sample
diffraction analysis reveals an interesting structural factors of could adsorb H O from ambient air and turn back to pink in
trinuclear Co O clusters, which are bridged by the carboxylate several minutes, indicating the occurrence of deactivation by
1
7
H
2
2
2
3
groups and propagate into 1D metal-oxo chains along the a rehydration (Fig. 2b-2c). The quick colour oscillation of CBBA-
axis (Fig. 1a). The bending shaped CBBA ligands bridge Co could be achieved for several times without losing any
neighbouring Co-O chains to expand into 3D networks, with activity or structural integrity, PXRD analysis of the dehydrated
nano-sized zigzag 1D channels (Figs. 1, S1). The 1D channels samples gave identical diffraction patterns (Fig. S2), making it a
were filled with DMF guest molecules, and the cross section potential humidity indicator for absolute dry environments.
2
0.6 nm . For every trinuclear Co O cluster, The obvious colour variation is caused by the different
size is about 0.7
×
3
two Co atoms show promising coordination vacancies, as the coordination environment of Co(II), which has been well
2
6,27
two occupied aqua molecule could be easily removed under studied.
In this case, the colour changes were caused by
reduced pressure or replaced by guest molecules. CBBA-Co the removal of coordinated H O molecules under high vacuum,
2
gave very poor performance in N adsorption/desorption test. and the blue sample indicated the state of total dehydration.
2
3
The maximum N uptake at 77 K was only 9.6 cm g , and the To verify this, a quartz-crystal microbalance (QCM) , which has
-1
2
2
calculated BET surface area was 4.1 m g .The poor been widely used as a reliable technology to monitor the
-1
performance of CBBA-Co in N adsorption is because of the molecular mass change, was employed to monitor the mass
2
very small pore size and highly polar inside microenvironment change of CBBA-Co thin film during the process of
8,19
1
28-30
(NH group).
However, such structures could provide redehydration.
The mass increase of the thin film is
effective framework-CO2 interactions through N-containing proportional to the decrease of frequency, and the mass
3
1
groups, and the CO uptake test showed that the saturated change was calculated according to Sauerbrey equation.
2
3
-1
CO uptake at 195 K is 73.48 cm g , which corresponds to a
2
2
BET surface area of 179.2 m g (Fig. S3).
-1
18-23
The CO uptake
2
analysis and PXRD test confirmed the permanent micro-
porosity of CBBA-Co, offering us the opportunity to study the
potential catalytic applications of CBBA-Co. However, the
channels could only accommodate small guest molecules (such
as DMF) as revealed by the single crystal analysis, thus surface
exposed Co O should be considered as the major catalysis sites
3
for large substrate molecules. The potential catalytic activity of
CBBA-Co were examined by the Lewis acid activity and typical
oxidative catalytic activity of Co (II), respectively.
Moisture dependent colourchromism
Fig. 3. Frequency spectra of fully dehydrated CBBA-Co coated QCM crystal under humid
flow.
N
2
2
Table 1. QCM sensing data for dehydrated CBBA-Co thin film under humid N flow.
Sensing film mass (ng)
2
Mass of adsorbed H O (ng) Calculated wt% Theoretical wt%
2
2
09 (stage 1)
95 (stage 2)
9.1%
9.6%
2
298
12.8%
12.1%
The dehydrated CBBA-Co coated quartz crystal showed an
obvious two-stage decrease in frequency (Fig. 3). The first
stage should be ascribed to the adsorption of coordinated H
2
O
(ꢀf
1
=11.7 Hz), and the calculated weight increase percentage
Fig. 2. Changes of appearance colour of CBBA-Co under different hydration status. a) of 9.1% is very close to the theoretical value of 9.6% (Table 1).
Freshly prepared sample, showing a pink colour. b) Fully dehydrated CBBA-Co, showing The second frequency decrease stage should be ascribed to
a dark blue colour. c) Rehydration of sample (b): exposing in atmosphere for 10
2
the adsorption of free guest H O, and the calculated 12.8%
minutes.
weight increase is consistent with that of thoretical value
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(12%) (See supporting information for detailed calculations). carboxylate groups (Table 2, entry 2). The catalytic activity of
FT-IR analysis of fuylly dehydrated and rehydrated CBBA-Co the carboxylate group was confirmed by employing benzoic
indicates that in the Co-O stretching vibration region (500-700 acid as the catalyst in ROR, and the poor conversion data may
-1 32
cm ), significant absortion decrease could be observed for be because of the reduced number of carboxylate groups
.
dehyrated sample, and these peaks could be restored upon (Table 2, entry 3). Co(NO
3
)
2
6H
2
O gave much better result than
2+
CBBA, suggesting the catalytic role of Co in RORs
-1
rehydration. Besides, in the region of 3400 cm , which could that of H
2
be ascribed to the stretching vibration of N-H and O-H goup, (Table 2, entry 4). Given the fact that in CBBA-Co all the CBBA
similar peak intensity changes could also be observed upon ligands are deprotonated, hence Co(II) should be the main
dehydration and rehydration (Fig. S5). Taking the results of active site in ROR. FT-IR analysis of CBBA-Co during ROR
QCM, PXRD and FT-IR into consideration, the quick colour catalysis shows a significant change in the region around 3400
-1
oscillation of CBBA-Co upon activation should be only caused cm (N-H and O-H vibration), the intensity decrease should be
by the removal or adsorption of H O coordinated to Co(II), and due to the replacement of coordinated H O by substance, and
2
2
no other structural change was occured during the activation. only N-H vibration could be monitored in this region (Fig. S5).
Given the fact that activated CBBA-Co could be easily The Lewis acidic catalysis of CBBA-Co was studied by catalyzing
deactivated under atmosphere condition, in situ activation was the RORs of cyclohexane oxide with amines. In the absence of
employed to simplify the succeeding experiments.
catalyst, only trace product was detected (Table 2, entry 1),
3
3
suggesting the catalytic effect of CBBA-Co. By carrying out
Ring opening reactions
o
the RORs experiment at 70 C, appreciable conversions for a
Table 2. RORs of cyclohexane oxide with amines catalyzed by CBBA-Co
serious of substrates were achieved. The generation of
coordination vacancy of Co
3
O relies on the endothermic
O, thus a
R
OH
R
cleavage of coordination bond between Co(II) and H
2
CBBA-Co
slight heating is necessary. The hot filtrate of CBBA-Co in
cyclohexane oxide was also used to carry out control
experiment to verify the heterogeneity of the catalytic
reaction, and only neglectable conversion data was detected
o
H2N
O
70 C
N
H
[
a]
Entry
Amine
-H
Yield(%)
(Table 2, entry 5). CBBA-Co showed high catalytic activity for a
[
b]
1
2
3
4
5
6
7
8
9
Trace
variety of substrates except for those with strong electron
withdraw groups (Table 2, entries 6-11). The catalytic activity
th
could be maintained after 6 runs, and the 8 run still gave a
[
c]
d]
e]
-H
40.3
[
-H
17.4
88.2
very good conversion of 90.2% (Table 2, entry 12). ICP-MS test
2
+
[
of the reaction filtrate suggested the existence of Co only at
the ppm level, and PXRD analysis of the recovered samples
also confirmed the structural integrity (Fig S2). The catalytic
superiority of CBBA-Co was further compared with some
literature reports (Table S4). Clearly, CBBA-Co has the best
stability, and the catalytic activity is also very high, considering
the very small catalyst loading in this study and the blocked
catalytic sites.
-H
[
f]
-H
<1
-H
96.1
98.5
89.9
74.3
96.9
N.D.
-CH
-Br
3
-F
Selective sulfide oxidation
1
1
1
0
1
2
-OCH
3
Encouraged by the successful application of CBBA-Co in
RORs, the catalytic oxidation activity was further evaluated.
Selective oxidation of sulfides to the corresponding sulfoxides
play an important role in the modern industries of medical and
-NO
-H
2
[
g]
90.2
[
a] Data collected by GC analysis. [b] Blank control experiment, carried out in the daily chemical productions, and MOFs have exhibited
3
6-38
absence of catalyst. [c] Free H CBBA ligand was used as catalyst. [d] Benzoic acid promising application in catalytic oxidation of sulfides.
2
.
was used as catalyst. [e] Co(NO
3
)
2
6H
2
O was used as catalyst. [f] Heterogeneity
Selective oxidation of thioanisole was employed to screen the
catalytic conditions, including solvent, reaction temperature
and oxidant (Table 3). The catalytic activity of CBBA-Co is
sensitive to reaction temperature, solvent and oxidant, and
th
verification test. [d] The 8 run, Fig. S9.
Ring opening reactions (RORs) of epoxides with nucleophilic
reagents are of important values for medical and chemical
industries, and many MOFs have been explored as efficient
o
high catalytic efficiency at 50 C in DMF using TBHP as the
3
3-35
oxidant was achieved (Table 3, entry 19). Overheating may
cause unnecessary decomposition of oxidant, resulting the
observed decrease in conversion (Table 3, entries 22-23).
Besides, the amount of oxidant or catalyst was also critical to
conversion data (Table 3, entries 24-27). Over addition of
oxidant or catalyst may accelerate the unnecessary
heterogeneous catalyst for RORs.
In this case, the potential
coordination vacancy of the Co(II) should be the catalytic
active site,and free H
2
CBBA ligand and Co(NO
3
)
2
were used as
CBBA showed
catalyst in the ROR to verify this hypotheses. H
2
modest catalytic activity, which should originate from the two
4
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decomposition of oxidant due to the enahnced mutual Table 4. Results of selective oxidation of sulfides catalyzed by CBBA-Co
interactions between the catalyst and oxidant induced by high
concentration
Table 3. Condition screening for the catalytic oxidation of thioanisole
o
[a]
[a]
Entry
Solvent
T ( C) Oxidant
Conversion (%)
Selectivity (%)
Entry
R
1
R
2
Conversion (%)
Selectivity (%)
[
b]
1
2
3
4
5
6
7
8
9
CH CN
25
25
25
25
25
25
25
25
25
40
40
40
40
40
40
40
40
50
50
50
50
60
70
50
50
50
50
TBHP
2.8
1.7
4.3
Trace
2.2
<1
>99.9
98.9
>99.9
/
3
[
b]
1
2
3
4
5
6
7
8
9
16
>99
90
3
CH CN
2
H O
2
[
c]
[c]
DCM
THBP
H O
53.1
DCM
Acetone
Acetone
DMF
2
2
[
[
d]
e]
10
12
>99
>99
>99
91
THBP
H O
/
2
2
/
TBHP
H O
9.7
5.4
Trace
13
99.1
99.7
/
98.8
96.3
90.2
45
DMF
2
2
Octane
3
TBHP
TBHP
H O
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
CH CN
>99.9
97.1
>99.9
96.2
95.1
>99.9
98.9
>99.9
>99.9
>99.9
97.8
>99.9
97.5
97.5
91.1
81.6
98.6
91.8
95.7
96.1
68.4
>99
3
CH CN
2
2
7
DCM
THBP
THBP
H O
25
Acetone
Acetone
DMF
6
75
2
2
5
[f]
TBHP
H O
68
1
0
85.4
DMF
2
2
36
[
a]Data collected by GC analysis. [b] H
2
CBBA ligand was used as catalyst. [c]
.
Octane
TBHP
THBP
TBHP
TBHP
THBP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
13
Co(NO ) 6H O was used as catalyst. [d] Blank control experiment, carried out in
3 2 2
th
the absence of catalyst. [e] Heterogeneity verification test. [f] The 7 run, Fig.
S10.
3
CH CN
21
DMF
98.8
39
Under optimized conditions, a series of control experiments
were carried out to verify the catalytic active site. Comparing
Octane
Acetone
DMF
2
with the blank control test, H CBBA showed barely no catalytic
2+
19
activity, while Co gave modest result (Table 4, entries 1-3).
FT-IR analysis of CBBA-Co during catalysis showed similar
73.7
66.1
-1
absorption change with that of ROR in the region of 3400 cm ,
suggesting the high affinity of CBBA-Co towards these catalysis
substances (Fig. S5). We further carried out QCM tests to study
the selective adsorption of CBBA-Co towards TBHP and
thioanisole (Fig. 4). QCM tests indicate that CBBA-Co has very
high affinity for TBHP and thioanisole, and about 50% of
DMF
[
d]
DMF
87.9
51.2
[
e]
DMF
[
f]
DMF
78.4
2
coordinated H O could be replaced by TBHP (Tables S2, S3).
[
g]
DMF
70.1
The series control experiments, FT-IR and QCM analysis all
confirm the high catalytic sulfide oxidation activity of CBBA-Co
by virtue of its Co(II) sites.
[
a] 0.1 mmol of thioanisole and 1 e.q. of corresponding oxidant were stirred in
.5 mL of solvent under different temperature, and the catalysis data was
collected by GC analysis. [b] tert-butyl hydroperoxide. [c] Dichloromechane. [d]
.5 e.q. TBHP was used. [e] 2 e.q. TBHP was used. [f] 0.5 mg of CBBA-Co (0.5%
mol) was used. [g] 2 mg of CBBA-Co (2% mol) was used.
0
1
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Fig. 5. Illustration of the structural complex of: a) CBBA-Co, TBHP and thioanisole; b)
CBBA-Co, tert-butyl alcohol and methyl phenyl sulfoxide. The yellow zone indicates
strong coordinative interactions between Co and oxygen atom of corresponding
compound.
Fig. 4. Frequency spectra of CBBA-Co coated QCM crystal under mixed gas flow of
N
2 2
/TBHP and N /TBHP/thioannisole.
A variety of sulfides were selected to evaluate the catalytic Chemiluminescence and H O sensing
2
2
oxidation activity of CBBA-Co. Table 4 shows that substrates
with electron donating groups usually give better results than
those with electron withdraw groups (Table 4, entries 5-8), and
larger molecular size may impede the interaction of substrates
The affinity of CBBA-Co for peroxides encouraged us to
further study the potential application in the
chemiluminescent luminol system. CBBA-Co could catalyze and
accelerate the decomposition rate of H
could be observed instantaneously after the introduction of
trace amount of CBBA-Co to a 30% H solution. According to
literature descriptions, Co(II) could efficiently activate H O in
2 2
O , and lots of bubbles
with Co
, entry 9). Heterogeneity verification test confirmed the
heterogeneous catalytic nature of CBBA-Co (Table 4, entries 3-
). CBBA-Co could be used for several times without obvious
3
O sites, resulting the observed low conversions (Table
4
2 2
O
2
2
4
the Luminol system resulting highly reactive luminol radicals,
which could be further oxidized to generate blue
46
losing in activity, ICP-MS test of the reaction filtrate and PXRD
analysis of the recovered samples confirmed the structural
integrity (Table4, entry 10; Figs. S2, S10). Compared with those
reported work, CBBA-Co has the advantages in catalyst
loading, selectivity and stability (Table S5). By only using 1% of
CBBA-Co, almost complete conversion with selectivity higher
than 99% could be achieved, indicating the superiority of
CBBA-Co in selectivity sulfide oxidation. Mechanistic insights
into the catalysis could be acquired by carrying out density
fluorescence. Based on the catalytic activity of Co(II) in CBBA-
Co towards H O decomposition, the chemiluminescence
2
2
activity of CBBA-Co was studied. A strong blue fluorescence
452 nm) was observed when CBBA-Co was introduced (Fig.
a), and the loading of CBBA-Co was also optimized (Fig. 6b).
(
6
By employing 5% mol of CBBA-Co, the intensity of
chemiluminescence was enhanced more than 220 times (Fig.
6c). It is known that hydrogen peroxide plays an important role
3
9
functional theory (DFT) calculations. Although MOFs have
infinite 3D frameworks, the large energy barrier between
ligand-metal bonds usually make them insulator, and most of
the times they act as separated giant “molecules“, and the
properties of MOFs could thus be studied simply by studying
the basic fundamental unit, which have been widely accepted
in life science and clinical diagnostics, and highly sensitive H O
2
2
47
sensors are urgently demanded. The affinity of CBBA-Co for
H O exhibited in the chemiluminescence studies offered us
2
2
the opportunity of exploring the potential sensing capability.
The results showed that a linear line could be achieved
between the concentration of H O (0-30%) and the
4
0-45
2 2
and used.
Based on this, study of the basic binuclear unit
corresponding luminescence intensity, suggesting the
potential H O sensing application of CBBA-Co (Fig. 6d). The Co
of CBBA-Co could be used to give insights into the catalytic
process. The calculations indicate that the Co(II) center could
coordinate and activate the peroxide bond of TBHP, and the
2
2
2p X-ray photoelectron spectroscopy (XPS) test of CBBA-Co
after H O sensing were carried out to monitor the valence
2 2
-1
total energy of the system is lowered about 651 KJmol after
forming stable complex, making it easier for the reactive O
atom to leave with the S atom, forming the corresponding
sulfoxide (Fig. 5).
state of Co (Figs. 7, S11). As can been seen, the Co 2p3/2 peak
at 781.3 eV indicates that the Co component in CBBA is
presented as Co(II), confirmed by the strong stallite peak (4.3
eV higher than the main peak) and the peak at 797.1 eV, which
originates from the spin-orbit coupling (15.8 eV higher than
4
8-50
the main peak).
6
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21775136, 21771158, 21401160,
2
1301149), the Natural Science Foundation of the Higher
Education Institutions of Jiangsu Province (17KJB150039), the
63 program of China (2015AA021003), , research fund of
8
Jiangsu Collaborative Innovation Center for Ecological Building
Materials and Environmental Protection Equipments
(GX2015104 and CP201502), Talent Project of Yancheng
Institute of Technology (KJC2013001 and KJC2014034), and
Research Fund of Key Laboratory for Advanced Technology in
Environmental Protection of Jiangsu Province (AE201310 and
AE201312). We thank National Supercomputing Center in
Shenzhen for providing the computational resources and
Gaussian 09 package (D.01) and Prof. Daqi Wang of Liaocheng
University for single crystal analysis. CCDC 1851859 contains
Fig. 6. Catalytic chemiluminescence application of CBBA-Co. a) Fluorescence spectra
the luminol system before (blue line) and after (yellow line) introduction of CBBA-Co. b)
Catalyst loading optimization results for chemiluminescence study. c) Luminescence the supplementary crystallographic data for this paper.
intensity comparison before and after the introduction of CBBA-Co. d) Linear line for
2 2
the detection of H O in the concentration range of 0-30%.
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There are no conflicts to declare.
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Table of Contents
A highly integrated metal-organic framework with multiple applications in heterogeneous
catalysis, chemiluminescence and sensing was studied both experimentally and
theoretically.