A new cobalt metal-organic framework as a substrate for Pd nanoparticles applied in high-efficiency nitro phenol degradation and cinnamaldehyde hydrogenation

Article abstract of DOI:10.1039/c9dt04051j

In recent years, attributed to the excellent catalytic performance of precious metal materials, metal nanoparticles?MOF catalyst has been a popular research direction. Herein, we have synthesized a new 3D cobalt metal-organic framework [Co(TATAB)(344-pytpy)·DMF]_n(H₃TATAB = 4,4′,4″-s-triazine-1,3,5-triyltri-p-aminobenzoic acid; 344-pytpy = 4′-(3-pyridyl)-4,2′:6′,4″-terpyridine)(1)(P1) by solvothermal method. Its crystal structure was determined with single-crystal X-ray diffraction (SC-XRD) techniques. The final composite Pd-NPs?1 catalyst was synthesized by a reduction method. The catalyst showed high catalytic performance and high recycling stability for nitrophenol degradation and cinnamaldehyde hydrogenation reaction.

Full text of DOI:10.1039/c9dt04051j

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A new Cobalt Metal-Organic Frameworks as a substrate for Pd
nanoparticles applied in high efficiency nitro phenol degradation and
cinnamaldhyde hydrogenation
a
a
b
b
a
a
Zhida Liu, Liangmin Ning, Kaiyuan Wang, Lixi Feng, Wen Gu* and Xin Liu*
a. College of Chemistry, Key Laboratory of Advanced Energy Materials
Chemistry(MOE), Tianjin Key Laboratory of Matal and Molecule Based Material
Chemistry, Collaborative Innovation Centre of Chemical Science and Engineering,
Nankai University, Tianjin, 300071, China.
E-mail: liuxin64@nankai.edu.cn; guwen68@nankai.edu.cn
b. College of Chemistry, School of Applied Chemistry, Nankai University, Tianjin,
3
00071, China.
c. Tianjin Key Laboratoty of Organic Solar Cells and Photochemical Conversion,
School of Chemistry and Chemical Engineering, Tianjin University of Technology,
Tianjin, 300384, China.
INTRODUCTION
Palladium nanoparticles (Pd-NPs) have been a usual metal nanoparticles material in many
regions recent years. Owing to their unique physical and chemical properties such as high
specific surface area and bare metal site, Pd-NPs have been quite applied for different regions
like catalysis,[1-4]sensing,[5-6]biomedical,[7] and so on. Based on these reasons, synthesis of
Pd-NPs based catalyst become a hot topic in recent years. However, Pd-NPs catalysts also
suffer from some stubborn problem such as self-agglomeration and oxidation which cause
catalytic performance loss. [8-9] Thus, it is quite important to select a suitable carriers for Pd
nanoparticles to improve the catalytic performance and stability. In previous literature, there
were many carrier such as titanate nanotubes[10], activated carbon[11], polymeric material[12]
and Metal-Organic Frameworks[18]
.
Metal-organic framworks (MOFs) belong to a kind of hybrid porous materials.[13-15]
Thanks to their unique structure feature such as high porosity, large surface areas, relatively
stable structure and tuneable pore size, which have been quite widely applied. [16] Due to their
special pore structure, MOFs can be a high performance substrate for the growth of metal
nanopaticles. [17-18] Through the improvement in the morphology of metal nanoparticles and
the synergy of host-guest, the catalytic performance of the composite material can be greatly
improved which far better than single individual.[19-25] Thus, porous metal-organic
frameworks material can be an excellent substance for Pd-NPs. Thanks to the fixation and
synergy of MOFs, the distribution and stability of Pd-NPs based catalyst can be great improve.
In 2017, Chen CJ synthesized a Heterogeneous Catalyst Pd-Au@Mn(II)-MOF for the
synthesis of Imines.[26] In 2018, Mokhtari, J has synthesized a Pd/Cu-MOF catalyst applied in
the produce of benzoazoles.[27] In 2019, Jiong Xu has synthesized Pd@MOF-808 applied for
photocatalytic.[28]
1

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In recent years, nitroaromatics have been widely used in various fields such as
pharmaceuticals, dyes, solvents, explosives and fungicidal agents.[29] However, this kind of toxic
substances have serious harm in ecological environment and human beings.[29] It is important to
select a suitable catalyst for nitro phenol degradation.[30] On the other hand, the hydrogenation of
α,β-unsaturated aldehydes especially cinnamaldehyde is an important part in chemical industry
and the pharmaceutical industry.[31-32] In previous reports, Pd-based catalysts show excellent
performance in that two reactions against.[30,33] In 2018, Lennon Gregor has synthesized a Pd
catalyst Pd-PEI for the degradation of 4-Nitrophenol.[34] In 2019, Semakaleng Bewana has
[33]
synthesized a Pd catalyst Pd/LaFeO for cinnamaldhyde hydrogenation reaction.
3
Herein, we synthesized a new 3D Cobalt Metal-Organic Framework using ligand
H TATAB and 344-pytpy(showed in Scheme S1) as a matrix to load Pd nanoparticles. The
3
composite material had high catalytic performance which can reduce nitro phenol to amino
phenol. Moreover, it also enhanced catalytic activity for hydrogenation of CAL to
HCAL(showed in Scheme S2). Compared to many others catalysts, the unique advantage
such as mild reaction condition, short reaction time and high reusability is worth to pay
attention.
EXPERIMENTAL SECTION
1
. Chemicals and Characterization methods
All the reagents in this work were from commercial source and without further purification.
[35-36]
The ligand H TATAB and 344-pytpy was synthesized based on literature reported.
X-ray
3
single crystal diffraction (Mo) is from Rigaku 007 Saturn 70. X-ray diffraction is determined
by Rigaku SmartLab. X-ray photoelectron spectroscopy(XPS) is determined by Axis Ultra
DLD from Kratos Analytical Ltd. TG is determined by TG209 from NETZSCH.
ICP(Inductive Coupled Plasma Emission Spectrometer) is determined by IRIS Advantage
from Thermo. N adsorption was determined by ASAP2460 from American micromeritics
2
company.
2
. Synthesis
.1 Synthesis of 1.
Generally as-synthesized H TATAB (19.46mg, 0.04mmol), 344-pytpy (27.92mg,
2
3
0
.09mmol), Cobaltous Nitrate Hexahydrate(29.10mg, 0.1mmol) was added into 8ml
N,N-Dimethylformamide( DMF) and 4ml deionized water mixed solvent with 20ul
concentrated nitric acid . After dispersed by ultrasound for several minutes, the suspension
was transferred to a 25ml Teflon-lined stainless steel Parr autoclave and heated to 120℃
for 3 days. After cool about to room temperature in 2 days, a purple red colored crystals
were obtained. To further purification, several DMF and deionized water was used to wash
to the product. Then repeat this step for twice times. After drying at 60℃ for 6 hours, the
new structured MOFs 1 was obtained. The final yield were 52.3% based on Co. Element
analysis: C: 60.79% H:3.97% N:16.63%.(Theoretical content: C: 60.85% N: 16.62% H:
3
2
.99%)
.2 Synthesis of Pd-NPs@1.
2

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1
00mg as-synthesized 1 and 65mg palladium acetate was added into 100ml
DOI: 10.1039/C9DT04051J
round-bottomed flasks with 30ml toluene. The suspension was stirred at room temperature
2
+
for 6 hours. After washing with 8ml toluene for three times, Pd @1 was obtained.
2
+
Then as-synthesized Pd @1 was added into 100ml round-bottomed flask with 10ml
deionized water. And then 10ml NaBH aqueous solution(0.52mmol) was dropped into it.
4
After reacting for 1 hour under room temperature, the black product was filtered and
washed by deionized water for three times. The product was then dried by air for 1 day.
The Pd element loading content was 14.5% based on ICP characterization.
. Catalytic reaction
3
3
.1 Nitrophenol degradation reaction.
To verify the catalytic action of nitro phenol degradation reaction, p-nitrophenol and
o-nitrophenol was selected as substrate. Firstly, 5mg Pd-NPs@1 was added into 10ml
deionized water. After stirring for a few minutes, 3ml mixture solution contains nitrop
henol (0.3mg/ml) and NaBH (1.8mg/ml) was added into the reaction system. Each 20
4
seconds, several reaction solutions was filtered and finally measured by UV-visible
spectrophotometer to determined the reaction process. Moreover, o-nitrophenol was used
as reaction substrate verifies the universal applicability of the catalyst at same condition.
3
.2 Cinnamaldhyde hydrogenation reaction.
To certificate bifunctional of the catalyst, catalyst(from 0 to 10mg) and 10ml solvent
contain 1mmol cinnamaldhyde were added into 100ml high pressure
reactor(HT-50FC-F002). The vintage condition was selected by varying reaction time and
temperature. The conversion and yield was determined by gas chromatograph analyzer
(GC).
3
.3 Substrates and products adsorption test
To confirm the adsorption performance of MOF based, generally 1mmol CAL(cinnamic
aldehyde) or HCAL( phenylpropionaldehyde), 10mg Co-MOF or Pd@Co-MOF and 10ml
ethyl acetate was putted into 20ml round-bottomed flask. After stirring for 15min at
atmospheric temperature, the solids were removed by centrifugation. The adsorption ratio
compared with blank condition was determined by GC.(CAL adsorption ratio of Co-MOF:
6
.9%, HCAL adsorption ratio of Co-MOF: 1.1%, CAL adsorption ratio of
Pd@Co-MOF:8.0%, HCAL adsorption ratio of Pd@Co-MOF:1.3%)
.4 Recycling performance.
3
The catalyst was respectively washed by deionized water and ethanol for three times after
nitro phenol degradation and cinnamaldhyde hydrogenation reaction. Then all dried by air
for one day. And then repeated the reaction until the conversion dropped below 90%.
RESULTS AND DISCUSSION
The specific crystal data and structure refinement of the MOFs were showed in Table S1. The
X-ray single crystal diffraction indicated that 1 attribution to P-1 spaces group. Each
3
-
asymmetric unit contained 1 Co(Ⅱ) coordination center, 1 TATAB and 1 344-pytpy ligand.
Figure S1a and S1b respectively shows that six-coordinated Cobalt (Ⅱ) was coordinated to
four O from four TATAB ligand and two N from two 344-pytpy ligand which formed a
regular octahedral configuration. Each carboxyl group was mono dentate coordination modes.
Each 344-pytpy ligand provided two N to coordinated with central Co(Ⅱ). The carbonic acid
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ligands and pyridine ligands formed two planes which intersected with each other. As figure
S1c shows, one of the carbonic acid group from TATAB bridge two Co(Ⅱ) and formed a
dual-core SBU. Finally, the two intersected plane formed a 3D-structured framework by
further bridging in figure S1d.
The comparison of thermal analysis data was showed in Figure S2. About 10mg sample
was putted into Thermal Analysis System which N flowed rate was 15ml/min. The test
2
temperature risen from room temperature to 900℃ at a scan rate of 10℃/min. As Figure S1a
shows, the two step weight loss of 1 was about 25% from 180℃ to 300℃ which due to
crystalline molecules H O and DMF lost. From 300℃ to 400℃, the weight loss was about
2
7
5% due to collapse of 1 frame. While for Pd-NPs@1, the first two step loss was not
particularly obvious, a smooth thermal decomposition happened from 200℃ to 400℃ which
only caused about 39% weight loss. That is to say, the introduction of Pd-NPs can increase
the thermal stability of 1. As Figure S3 showed, the color for ground powder of 1 became
shallower after the soaking of Pd(Ⅱ). While black powder was obtained after NaBH4
reduction due to the absorbance of nanoparticles.
Figure S4 shows the XRD patterns comparison of simulated 1, 1 and Pd@1. The
o
characteristic peak of 1 appear before 35 dose not occurred significant changes. That is to say,
the skeleton structure of CoMOF has not changed from Pd-NPs loading and catalytic reaction.
o
The stability of 1 has been further proved. While a new characteristic appeared at 40 after
Pd-NPs loading. That due to the generation of Pd(1,1,1) crystal flat.[37]
The TEM image (Fig. 1a) shows the lamellar structure of Pd-NPs@1, which is formed by
amorphous stacked structure. The loaded Pd NPs located inside the Co-MOFs which are
relatively uniform distribution. The TEM image taken in 20nm (Fig. 1b) shows the
microscopic appearance of loaded Pd-NPs. Furthermore, the particle size distribution can be
obtained. The diameter of most nanoparticles is in the range of 2-4nm, which means larger
relative specific surface area. That lay a great foundation for providing excellent catalytic
performance. HRTEM image (Fig. 1c, 1d) clearly shows the characteristic lattice fringe
Pd(1,1,1) with crystal plane distance between 0.22nm, which further to prove the existence of
Pd-NPs.[38-40]
(a)
(b)
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(c)
(d)
Figure 1. TEM image of Pd-NPs@1 taken in 100nm scale (a), HRTEM image (b), TEM image taken in 20nm
scale with particle size distribution of Pd-NPs (c,d), TEM image taken in 10nm scale and lattice fringe of Pd(1,1,1)
display.
The TEM mapping (Fig. S5) clearly shows the uniform distribution of Pd, C, Co, N, O
element in Pd-NPs@1. Furthermore, the loading of Pd-NPs in the MOF was found to be
1
4.5wt% by inductively coupled plasma-optical emission spectrometry (ICP-OES)
investigation. The X-ray photoelectron full spectrum of Pd-NPs@1 (Fig. 2a) shows the
elements exist on Pd-NPs@1. Besides, in X-ray photoelectron fine spectrum of Pd element
(Fig. 2b) the characteristic peak at 335eV and 341eV was found. That separately represented
3
d3/2 and 3d transitions, which suggest the zero-valent oxidation state of Pd-NPs.[41]
5/2
(a)
(b)
Figure 2. (a), XPS full spectral of Pd-NPs@1 (b), XPS transitions for 3d3/2 and 3d5/2 of Pd(0).
The N adsorption measurement for 1 and Pd@1 at 77 K both show type-II adsorption
2
profile(Figure S6). It is noteworthy that the N adsorption performance improved to some
2
extent after Pd loading. While the BET Surface Area enlarged about six times(from
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2
2
[42]
1
.5607m g to 10.1375m /g) after Pd loading. Based on previous literature , the introduction
DOI: 10.1039/C9DT04051J
of Pd nanoparticles can increase the specific surface area of the matrix to a certain extent. At
the same time, Pd nanoparticles itself also has a certain adsorption effect on N2.[43] The
substrate adsorption test also shows similar results. A small increase of CAL and HCAL
adsorption performance occurred respectively from 6.9% to 8.0% and 1.1% to 1.3%, which
further confirmed the adsorption performance improvement after Pd loading. Moreover, the
adsorption performance of CAL is much better than that of HCAL. Because of the small BET
surface area, the physical adsorption capacity of the catalyst is not very strong. While the
main adsorption power is from π-π interaction and hydrogen bonding between substrate and
organic liagand of the MOF. After C=C reduction, that two interaction will be greatly
weakened, which may facilitates the adsorption of reactants and separation of products.
Furthermore, the central metal atom Co(II) is full coordination structure which cannot
coordinate with substrate. So the metal clusters have little contribution to adsorption capacity.
Thanks to high loading and uniform distribution of Pd NPs, Pd-NPs@1 shows excellent
catalytic performance of nitro phenol degradation and cinnamaldhyde hydrogenation. The
degradation of 4-NP and 2-NP was selected as the model reaction due to their extensive and
easy to detect. The reaction process was determined by UV-vis spectroscopy. Fig. 3a shows
the reaction process of 4-NP. As is known, the absorption peak of 4-NP in alkaline solution is
at about 400nm.[44-45] As the reaction proceeds, the absorption peak of 4-NP decreases rapidly
while a new absorption peak appears at about 290nm, which representing the product 4-AP.[46]
Thanks to the excellent catalytic performance of Pd-NPs@1, the degradation ratio of 4-NP
can achieve about 90% after 20s even complete degradation after 80s. It is also noted that the
color of 4-NP solution changes from light yellow to nearly colorless in Fig. 3a. The
degradation process of 2-NP is showed in Fig. 3b. Similar as 4-NP, the absorption peak of
2
-NP appears at about 410nm while the 2-AP peak is not particularly obvious. It is also
appeared a color change of yellow to colorless after 20s which means the degradation reaction
is almost completely.
Moreover, to certificate the stability of Pd-NPs@1, a recycling experiment of 4-NP
degradation was performed in Fig. 3c. After 8 times recycling, the degradation of 4-NP can
still reach about 90%( Fig. 3d) thanks to the high stability and reusability of Pd-NPs@1.
(a)
(b)
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(c)
(d)
Figure 3. (a), Time dependent UV-vis spectra for the reduction of 4-nitrophenol and the color change of solution.
(b), Time dependent UV-vis spectra for the reduction of 2-nitrophenol and the color change of solution. (c),
Recycling time dependent UV-vis spectra for the reduction of 4-nitrophenol. (d), Recycling performance bar chart
for the reduction of 4-nitrophenol.
To confirm the catalytic performance of Pd-NPs@1 in cinnamaldhyde hydrogenation, a
comparison experiment of different catalyst was first established in Table 1. It is noted that
both block condition and 1 without Pd NPs shows a low conversion (9.2% and 16.3%), which
further confirmed the active sites of Pd NPs. While both catalyst condition show high
selectivity to HCAL because of the higher activity of C=C bond.[47] On the other hand, we
also choose Pd-C catalyst from commercial sources as comparing objects. Pd-NPs@1 shows
quite higher activity than Pd-C catalyst at short time based on the same Pd element content,
which further to prove the superiority of Pd-NPs@1. The reason is mainly because the
particles size of Pd nanoparticles in Pd@1(2-4nm) are far away smaller than that in
Pd-C(200-250μm). With higher specific surface area of Pd nanoparticles, the catalytic
performance will be further improved.[48-50]
It is known that the catalytic performance may also affect by some reaction conditions such as
catalyst content, reaction temperature, reaction solvent.[51-52] To obtain the optimal condition,
a series of comparison experiments was established. The solvent effect are showed in Fig. 4a.
The solvent has a great effect on the catalytic performance in the present, especially on the
selectivity of hydrogenation of ɑ,β-unsaturated aldehyde attributed to their different polarity
and solubility.[47] It is noted that all the chooses solvent can cause the highest conversion but
ethyl acetate shows best selectivity attributed to its higher stability and solubility than others.
Thus, ethyl acetate was chosen as the optimal solvent for the reaction. Fig. 4b shows the
reaction temperature effect. Lower temperature will cause lower conversion while much
higher temperature will cause energy waste or lower selectivity. When the temperature
gradually rises to 50℃, the catalytic performance reaches the highest point. Thus, 50℃ was
chosen as the optimal reaction temperature. Finally, the optimal catalyst content 10mg (about
1
.3mol% based on Pd) was chosen in Fig. 4c.
The stability and recyclability of Pd-NPs@1 in cinnamaldhyde hydrogenation reaction
was investigated through a recycling test. As Fig. 4d shows, the conversion was reduced
slowly to about 95% after 11 recycling while slight fluctuations appeared on the selectivity.
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Overall, within over 10 recycling, not too much activity loss appeared on Pd-NPs@1. Based
on the XRD results (Fig. S7), the crystal structure of Pd-NPs@1 did not change after 10
recycling. That further proved the stability of the catalyst. Moreover, the XRD patterns
comparison of catalyst Pd@1 before and after that two reactions are showed in Figure S5. The
characteristic peaks have no significant changes, which directly indicates the stability of
catalyst Pd@1.
To compare the catalytic performance with previous literature reports, table of different
catalyst of p-nitrophenol degradation (Table 2) and cinnamaldhyde hydrogenation reaction
(Table 3) is summarized. Thanks to the high loading and uniform distribution of Pd NPs,
catalyst from this work shows relatively greater performance such as shorter time or lower
temperature than the previous.
Table 1. Comparison of cinnamaldhyde hydrogenation reaction catalytic performance with different catalyst.
O
O
OH
+
CAL
HCAL(main product)
HCOL(by-product)
Catalyst screening for cinnamaldhyde hydrogenation reactiona
Entry
Catalyst
T
Time
min
15
Sel
%
Covb
%
℃
50
50
50
50
1
2
3
/
100
100
100
98.5
9.2
1
15
16.3
43.1
100
Pd-Cc
15
4
Pd-NPs@1
15
a
Reaction condition: Cinnamaldhyde 1mmol, catalyst 10mg( about 1.3mol%Pd content, ethyl acetate 5ml, H
pressure 2 MPa, 600rpm.
2
b
Selectivity and conversion are determined by GC.
c
Based on Pd content( 1.3mol%).
8

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(a)
(b)
(c)
(d)
Figure 4. (a), The effect of solvent on the hydrogenation of CAL. (b), The effect of reaction temperature on the
hydrogenation of CAL. (c), The effect of catalyst content on the hydrogenation of CAL. (d), Catalytic recycling
performance of Pd-NPs@1 for cinnamaldhyde hydrogenation reaction.
Table 2. Comparison of different catalytic performance of p-nitrophenol degradation.
(a)
cat(b)[mg
Entry
Catalyst
c(p-NP) [mM]
0.498
M
5
t(s)
80
Ref.
1
2
3
1
This work
[53]
@CeO
Fe @PDA-Pd@[Cu(btc)
(n=3)
2
/Pd@Pd/TiO
2
0.074
2
300
480
2
O
4
2
3.306
0.025
[54]
]
4
5
6
7
CuO/ZnO
2.5
0.5
0.12
0.1
0.1
5
180
1200
40
[55]
[56]
[44]
[57]
[45]
Resin-Au NPs
Ag NPs/SiNSs
Ag NPs@MOF-199s
Pd NPs@ZIF-8
100
10
0.6
5
600
300
8
a
The concentration of p-nitrophenol in reacting solution.
The mass of catalyst
b
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Table 3. Comparison of different catalytic performance of cinnamaldehyde hydrogenation.
a
b
Entry
Catalyst
t(h)
0.25
2
P
2
1
1
H2(MPa)
T(℃)
50
Conv. % Sel. %
Ref.
1
2
3
4
1
>99.9
>99.9
>99.9
88.3
>99.9
98.6
86
This work
[47]
Pd-0.3Ag/MCM-41
110
90
Pd/La
2
O
2
CO
3
-NRs
3
[58]
0.2%Pd-1.2%Ni/S
BA-15
2
1.2
80
87.8
[59]
5
HDT2-5TD
0.5
0.5
120
81.28
96.92
[60]
a
The conversion of CAL.
The yield of HCAL.
b
CONCLUSION
In summary, we sucessfully synthesis a new 3D Cobalt MOF [Co(TATAB)(344-pytpy)] and
n
then Pd nanoparticles were uniformly distribute in the MOF by in-situ synthesis method.
Thanks to the high loading and uniform distribution of Pd NPs, this material showed great
catalytic performance and excellent recycling stability on nitrophenol degradation and
cinnamaldehyde hydrogenation which quite benefit to environmental protection and industrial
production.
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Catalyst
for
Selective
Hydrogenation
of
Cinnamaldehyde
to
[
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Zhao, Selective hydrogenation of the CC bond in cinnamaldehyde over an ultra-small Pd-Ag alloy
catalyst, Chem.Eng.J., 2018,351. 995-1005.
ABSTRACT
In recent years, attributed to the excellent catalytic performance of precious metal materials,
Metal nanoparticles@MOF catalyst has been a popular research direction. Herein, we have
synthesized
a
new
3D
Cobalt
Metal-Organic
Frameworks
[
Co(TATAB)(344-pytpy)·DMF] (H TATAB =4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoic
n
3
acid ； 344-pytpy = 4'-(3-pyridyl)-4,2':6',4''-terpyridine)(1)(P1) by solvothermal method. Its
crystal structure was determined with single-crystal X-ray diffraction (SC-XRD) techniques.
The final composite Pd-NPs@1 catalyst was synthesized by reduction method. The catalyst
showed high catalytic performance and high recycling stability for nitro phenol degradation
and cinnamaldhyde hydrogenation reaction.
1
4