Temperature-responsive dissolution/recrystallization of Zn MOF enables the maximum efficiency and recyclability of catalysts

Article abstract of DOI:10.1039/c9cc09342g

A novel strategy through a temperature-responsive dissolution and recrystallization process has successfully achieved 100% atomic utilization and easy recyclability of heterogeneous metal organic framework dimethylammonium zinc formate (DMZnF) catalysts for highly efficient dehydrogenation of DMF-H₂O for hydrogen generation. DMZnF dissolves as a homogeneous catalyst at high reaction temperatures and then is recrystallized and recycled as a heterogeneous catalyst at low temperatures.

Full text of DOI:10.1039/c9cc09342g

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S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
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Temperature-responsive dissolution/recrystallization of Zn MOF
enables the maximum efficiency and recyclability of catalysts
a#
a,b#
a
a
a
a
Xiao Chen, Huan Zhang, Mingkai Zhang, Yong Zou, Sai Zhang * and Yongquan Qu *
1
0:Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A novel strategy through temperature-responsive dissolution and limited chemical diffusion of reactants/products and thereby
recrystallization process has successfully achieved the 100% atomic poor chemical kinetics during reactions, making them
1
4
utilization and easy recyclability of heterogeneous metal organic impossible to reach 100% atom utilization of all active centers.
framework dimethylammonium zinc formate (DMZnF) catalysts for Therefore, it is still significant to explore new strategies to
high-efficiently dehydrogenation of DMF-H for hydrogen maximize atomic utilization.
generation. DMZnF dissolves as a homogeneous catalyst at high As for the homogeneous catalysts, their main feature is that
reaction temperature, and then is recrystallized and recycled as a each active site can catalyze the reaction with the same catalytic
2
O
heterogeneous catalyst at low temperature.
performance, leading to the 100% atomic utilization efficiency
1
5
during the reaction. Nevertheless, they are hard to be
separated and reused from reaction system compared with
Heterogeneous catalysts with the features of the recovery, re-
utilization and easy separation of product from catalytic system
exhibit higher capability in practical applications than
homogeneous ones.1 However, these particle-like active
components only allow the availability of surface atoms for
catalysis, leading to their much lower atomic utilization
16-18
heterogeneous ones.
Therefore, the strategy to combine
the advantages of homogeneous and heterogeneous catalysis
may realize the maximum efficiency and recyclability of
catalysts.
Herein, a metal organic framework dimethylammonium zinc
2
efficiency compared to the homogeneous counterparts. Thus,
formate ([(CH
3 2 2 3
) NH ]Zn(HCOO) , DMZnF) with perovskite
maximizing the atomic utilization efficiency of heterogeneous
catalysts is an ideal but challenging topic. Many efforts have
been attempted to achieve this goal via designing the catalysts
structure has been successfully demonstrated as
a
temperature-responsive dissolution/recrystallization catalyst
with 100% atomic utilization efficiency for hydrogen production
through the dehydrogenation of N,N-dimethylformamide
3
-5
with the multilevel structures. Recently, the single atom
catalysts with specific coordination environments have been
developed to expose each metal atom for catalysis through
(
2 2
DMF) and H O. The use of DMF and H O is a promising
19
hydrogen generation system, because of their involatile,
inflammable, inexplosive and incorrosive properties compared
with other carbon hydrides such as formic acid,
6
, 7
complex synthetic method.
However, the natural catalytic
activity of each single active site is greatly determined by their
20, 21
8
, 9
chemical coordination environments. Also, it is difficult to
modulate the chemical states of single active centers, limiting
their potentials for a variety of catalytic reactions. Metal organic
frameworks (MOFs) with the same active sites as another
typical heterogeneous catalyst exhibit the theoretical maximum
atom utilization efficiency, which is considered to bridge the
22, 23
24, 25
formaldehyde
and methanol.
However, there is lack of
efficient and reusable non-noble metal catalysts for this desired
and prospective hydrogen generation system. Thus, the DMF-
H O hydrogen generation system is selected as a model reaction
2
to explore the unique catalytic performance of DMZnF catalysts.
The “smart” properties are that DMZnF catalysts can catalyze
2
the hydrogen generation reaction from DMF-H O system as
homogeneous catalysts at 120 °C and could be spontaneously
separated from the reaction system at room temperature and
reused for the next cycle without any treatment.
1
0-13
gap between homogeneous and heterogeneous catalysis.
However, the narrow pore of MOFs generally leads to the
a. Center for Applied Chemical Research, Frontier Institute of Science and Technology
Initially, the DMZnF catalysts were easily synthesized via
and School of Chemical Engineering and Technology, Xi'an Jiaotong University,
Xi'an, 710049, China.
Western Metal Materials Co., Ltd, Xi’an, 710201, China.
2
adding zinc nitrate to DMF-H O mixed solution at 120 °C under
Ar atmosphere. During the preparation process, white solids of
b.
Email: yongquan@mail.xjtu.edu.cn and zhangsai058@mail.xjtu.edu.cn
These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: [details of any supplementary
ZnO (Figure S1) were generated in the solution, possibly owing
#
-
to the precipitation between zinc salts and OH in DMF and H
2
O
information available should be included here]. See DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C9CC09342G
Figure 1. (a) The crystal structure of DMZnF metal organic framework. The inset is the
optical image of a DMZnF micro-crystal. (b) The XRD patterns of the simulated DMZnF
and as-synthesized DMZnF. (c) The hydrogen production from DMF-H O vs. time.
2
Reaction conditions: DMZnF/ZnO (40.0 mg) or none catalysts, DMF (4.0 mL), H O (0.2
2
mL), 120 °C and Ar atmosphere.
Figure 2. Catalytic performance of DMZnF for hydrogen production from DMF and water.
(a) Optical images of the reaction solution before and after catalytic reactions for 4
cycles. (b) The recycling stability of DMZnF for the hydrogen production from DMF and
solution.26, 27 On account of easy removal of undesired ZnO
solids through hot filtration, the DMZnF catalysts with hundreds
of microns were slowly appeared and separated out from the
remained supernatant solution (Figure 1a). Single-crystal X-ray
diffraction analysis reveals that the solids of DMZnF possess a
H
2
O system. Reaction condition: DMZnF catalysts (40.0 mg), DMF (4.0 mL), H
2
O (0.2 mL),
1
20 °C and Ar atmosphere.
dispersed in the reaction system at room temperature (25 °C),
forming a turbid solution (Figure 2a). Then, the heterogeneous
catalytic reaction was transferred to a homogeneous one during
the hydrogen generation process at 120 °C, along with the
dissolution of DMZnF, giving a clear solution (Figure 2a). After 6
h reaction, when the reaction system was cooled to room
temperature again to terminate the hydrogen generation, the
DMZnF catalysts could be spontaneously recrystallized and
2
8
perovskite-type architecture (Figure 1a, Table S1-S2), in which
2
+
Zn ions are octahedrally coordinated by six oxygen atoms from
-
formate groups (HCOO ). Meanwhile, the trigonal disordered
+
+
dimethylammonium ((CH
the channel of [Zn(HCOO)
3
)
2
-
NH
2
, DMA ) cations are located in
3
]. Besides, XRD pattern of synthetic
DMZnF was highly consistent with simulative one (Figure 1b).
As-synthesized DMZnF with R3c space group is accordant with
the previously reported structure of DMZnF (CCDC number is
separated from the DMF-H
2
O system, becoming a turbid
2
66350).29 Furthermore, the Fourier-transform infrared
2+
solution again. After this process, the Zn concentration with
spectroscopy (FT-IR) and Raman spectra (Figure S2, and Table
-4
-1
6
.82×10 mmol mL could be detected by the ICP-MS analysis,
S3-S4) could further identify the successful formation of DMZnF
indicating almost complete separation (98.3%) of the catalyst
from the liquid solution. Meanwhile, the XRD analysis, FT-IR
spectra and Raman spectra revealed that the structure of the
recrystalized solids were maintained as DMZnF MOFs through
this dissolution and recrystallization process (Figure S5-S6).
More importantly, the catalytic performance of DMZnF MOFs
could be repeated at least for 4 times with the preserved
crystals.3
0, 31
In addition, TGA (Thermogravimetric Analysis) and
DSC (Differential Scanning Calorimeter) graphs could also reveal
the structure of DMZnF catalysts (Figure S3, the detailed
3
2
description could be found in the supporting information).
The specific surface area of DMZnF was 22.8 cm
-3
-1
g measured
by the nitrogen adsorption-desorption isotherms at 77 K (Figure
S4a). The relatively small surface area might be attributed to the
hydrogen generation rates (Figure 2b), which could be
+
presence of DMA in the pores of MOF (Figure S4b).
-1 -1
maintained at the range from 0.151 molH2 molZn
molH2 molZn h .
h to 0.159
Then, as-synthesized DMZnF crystals were used to catalyze
the base-free hydrogen generation from DMF-H O system
2
without treatments. Under the optimized reaction condition,
hydrogen was linearly increased with a rate of 0.158 molH2
-1 -1
To further highlight the critical function of this transformation
process from heterogeneous catalysis to homogeneous one,
the hydrogen generation from DMF and H O system was
2
molZn-1
h
-1
(turnover frequency, TOF, was 0.158 h ) at 120 °C
under Ar atmosphere, as shown in Figure 1c. In contrast, no
hydrogen could be released from the DMF-H O system in the
-1
performed in the typical nonpolar solvent n-heptane, in which
the DMZnF catalysts could not be dissolved under the reaction
condition. In other words, the hydrogen generation in n-
heptane represents a typically heterogeneous one. As shown in
Figure S6, the hydrogen production rate was only 0.002 molH2
2
absence of DMZnF under the same reaction condition. As a
referred catalyst, the ZnO powder, which was generated during
the synthesis of DMZnF as shown in Figure S1, exhibited bare
catalytic activity for the hydrogen generation (Figure 1c).
Therefore, the natural catalytic capability of DMZnF could be
-1 -1
molZn h in n-heptane solutions via a heterogeneous catalysis,
which was 79 times lower than the rate via a homogeneous
-1
-1
catalysis (0.158 molH2 molZn h ). The phase of used solid
DMZnF catalysts were maintained according to the XRD
patterns (Figure S7), revealing the undestroyed catalytic
structure. Therefore, this dissolution/recrystallization process
benefits not only for the separation of catalysts, but also for the
2
confirmed by the hydrogen generation from DMF-H O system.
Generally, the metal organic frameworks catalysts are
considered as heterogeneous catalysis without any phase
transformation. Herein, the different phenomenon was
observed from DMZnF catalysed hydrogen generation reaction.
At initial state, the heterogeneous DMZnF catalysts were
1
00% atomic utilization of metal catalysts.
2
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Then, the operating temperature range was also explored for
this unique hydrogen generation system. As shown in Figure S8,
the DMZnF catalysts could not be dissolved in the reaction
system and show no hydrogen generation at 60 °C, indicating
the unsuitable reaction temperature. When the reaction
temperature was raised to 80 °C, this dissolution and
recrystallization process could be successfully initiated, giving a
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DOI: 10.1039/C9CC09342G
-1
-1
hydrogen generation rate of 0.003 molH2 molZn h . Also, the
-
rate could be further increased to 0.041 and 0.158 molH2 molZn
h
1
-1
at the reaction temperature of 100 °C and 120 °C,
respectively. Meanwhile, the phase of DMZnF catalysts were
well preserved during the dissolution and recrystallization
process (Figure S9). Therefore, the successful operating
temperature should be higher than 80 °C to ensure the
transformation from heterogeneous catalyst to homogeneous
one.
From the above analysis, the DMZnF catalysts exhibited
unique catalytic characteristic for the base-free DMF-H
2
O
hydrogen generation system. Specially, the catalysts could
promote the hydrogen generation through a homogeneous Figure 3. Catalytic mechanism (a) The hydrogen production profile with addition of
various amount of H
2
O at intervals. Reaction condition: DMZnF (10.0 mg), DMF (2.0 mL),
O (5.0 μL), 120 °Cand Ar atmosphere. MS analysis of the gaseous products of (b) DMF-
O and (c) DMF-D O systems. Reaction conditions: DMZnF (40.0 mg), DMF (4.0 mL),
O/H O (0.2 mL), 120 °Cand Ar atmosphere. (d) The hydrogen generation from HCOOH.
catalytic process, meanwhile, it could be recycled as a
heterogeneous catalyst owing to the recrystallization of
homogeneous catalysts. Therefore, the DMZnF catalysts
H
2
H
2
D
2
2
2
realized an efficient and recyclable catalytic performance for Reaction conditions: Zn(NO ) ·6H O/Zn(HCOO) ·2H O (0.3/0 mmol), HCOOH (3.0 mmol),
3
2
2
2
2
3
Et N (1.0/0 mmol), toluene (4.0 mL), 120 °C and Ar atmosphere (details in supporting
information).
2
the hydrogen generation from DMF-H O system through
combining the advantages of both homogeneous and
heterogeneous catalysts.
which consequently lead to the reduced hydrogen generation
rate. This phenomenon confirmed that one of the hydrogen
atoms should be contributed from the water.
To further explore the catalytic process of DMZnF for the
hydrogen production from DMF and H
were employed. Previous reports have proved that DMF could
react with H O to produce formic acid and dimethylamine with
3-35 experiments were also performed, in which H O and D O was
2
O, various techniques
2
To further confirm the origin of H molecule, isotope
2
3
the assistance of metal complexes, as shown in Equation 1.
2
2
used for hydrogen production. The gaseous products were
monitored by gas chromatography (GC) and mass spectrometry
Afterwards, the existence of formic acid in the reaction solution
was confirmed by the chromogenic reaction between formic
acid and bromocresol green, as shown in Figure S10. Then,
hydrogen could be released from the decomposition of formic
(
MS). When H
2
O was used as reactant, the MS signals of the
+
produced gas at 2 m/z and 1 m/z were assigned to H
2
and H ,
respectively (Figure 3b). In contrast, the strong MS signal at 3
m/z was observed and assigned to HD, when H O was replaced
by D O under the identical reaction condition (Figure 3c).
Therefore, the presence of HD strongly revealed H generation
with one H atom from water and another H atom from DMF.
Both of the formic acid generation and H origination can prove
the possible reaction processes as shown in Equation 1 and 2.
In addition, CO was also detected in the gaseous products
Figure 3b-3c and Figure S11a). As shown in Figure S12, the
amount of CO increased with the hydrogen generation process.
Theoretically, the molar ratio of H :CO could be maintained
2
acid along with the generation of CO (Equation 2).
2
2
2
2
2
Obviously, water should play a critical role in this hydrogen
generation system. One hydrogen atom in the generated
hydrogen gas molecule should be originated from water. When
(
2
2
2
5
.0 μL of water was added in the DMZnF catalyzed reaction
with 1:1 due to the decomposition of formic acid. However, the
final molar ratio reached 1.8:1, which could be attributed to the
-1
-
system, the hydrogen generation rate was 0.09 molH2 molZn
h
1
at the initial reaction stage and trended to be halted at 100 –
26 h (0.002 molH2 molZn h ). At this stage, the yield of
consumption of the generated CO
an acid-base reaction, as shown in Equation 3.
From the above analysis, hydrogen could be successfully
generated from the DMF-H O system with DMZnF as catalysts.
The structure unit of DMZnF contains one Zn ion, one
2
by the dimethylamine with
-1
-1
1
3
4, 36, 37
hydrogen was 0.27 mmol, which was consistent with the
theoretical value based on the amount of the added water (0.28
mmol, Figure 3a). Then, the hydrogen generation rate could
2
2+
-1
-1
immediately increase to 0.05 molH2 molZn
another 5.0 μL of H O in the system. Due to the lack of water in (HCOO
the reaction system, the formate group in the DMZnF catalysts formic acid and dimethylamine. However, the formic acid could
h
after adding
+
+
dimethylammonium (DMA , (CH
3 2 2
) NH ) and three formate
-
). Zn2+ species can catalyze the DMF and H O to produce
2
2
2
+
at the stage of platform during the 100-126h was consumed,
not be decomposed to release hydrogen only with Zn as
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catalysts, as shown in Figure 3d. It should be noted that the
weak basic of DMA might promote the hydrogen generation
from formic acid decomposition. Hence, we employed a similar
3
trimethylamine (Et N) as a substitution to replace gaseous
dimethylamine to verify the role of weak basic property in the
HCOOH system. As expected, no hydrogen could be generated
7
8
H. B. Zhang, G. G. Liu, L. Shi and J. H. Ye, Adv. EnVieewrgAyrtiMcleaOtnelirn.e,
2018, 8, 1701343.
+
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from formic acid in Et
generate from the formic acid in the presence of Zn and Et
3
N. While hydrogen could successfully
1
2
+
3
N
(
Figure 3d). To further identify the role of formate in the
2
reaction system, the zinc formate (Zn(HCOO)
2
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2
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1
1
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2
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Conflicts of interest
There are no conflicts to declare.
2
Acknowledgments
We acknowledge the financial support from the National Nature
Science Foundation of China (21872109) and the China Postdoctoral 27 M. E. Aguirre, H. B. Rodríguez, E. S. Román, A. Feldhoff and M.
Science Foundation (2018M640994; 2018T111034). Y. Qu is
supported by the Cyrus Tang Foundation through the Tang Scholar
program. S. Zhang is supported by the Fundamental Research Funds
for the Central Universities (xjj2018033) and the National Nature
Science Foundation of Shannxi (2019JQ-039). We also thank Mr.
Zhou at the Instrument Analysis Center of Xi'an Jiaotong University
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