Cross-Linked Surface Engineering to Improve Iron Porphyrin Catalytic Activity

Article abstract of DOI:10.1002/smll.201905889

Quasi-two-dimensional (QTD) structural heterogeneous catalysts have attracted a broad interest in multidisciplinary research due to their unique structure, preeminent surface properties and outstanding catalytic performance. Herein, a HZIF@TCPP-Fe/Fe hete

Full text of DOI:10.1002/smll.201905889

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Cross-Linked Surface Engineering to Improve Iron
Porphyrin Catalytic Activity
Dongxu Zhang, Jia Liu, Peiyao Du, Zhen Zhang, Xingming Ning, Yang Deng, Dan Yin,
Jing Chen, Zhengang Han, and Xiaoquan Lu*
straightforward and universal method for
Quasi-two-dimensional (QTD) structural heterogeneous catalysts have attracted
a broad interest in multidisciplinary research due to their unique structure,
preeminent surface properties and outstanding catalytic performance. Herein,
a HZIF@TCPP-Fe/Fe heterogeneous catalyst based on cross-linked surface
engineering is constructed by supporting QTD TCPP-Fe/Fe ultra-thin metallized
film (≈2 nm) on hollow skeleton of zeolite imidazolate frameworks. The designed
QTD structure exhibits high efficiency for the catalytic oxidative dehydrogenation
of aromatic hydrazides reactions which is the key technology in various industrial
processes. Taking advantage of QTD structure with excellent accessibility,
the metallized film with irregular defects not only enhances electron transfer
during the reaction but also exposes more surface-active sites. Furthermore, the
prepared HZIF@TCPP-Fe/Fe heterogeneous catalyst can be recycled and reused,
which is of great significance in the field of green chemistry.
obtaining hollow nanostructures and, the
hollow nanostructures can be acted as a
skeleton for heterogeneous catalysts to
catalyze specific reactions.[11] Distinctively,
construction of quasi-two-dimensional
(QTD) porous solid based MOFs film is
one of most efficiency strategy to endow
materials with desired surface properties
(e.g., permeability, adhesion, erosion, elas-
ticity, and photoelectric properties) and
large-scale contactable active sites, but still
a challenge until now. Suboptimal control-
lability and complexity of synthesis, finite-
ness of available MOFs resources as well
as poor stability are the main obstacles
hinder QTD film based material’s appli-
cation. We proposed an alternate of QTD
Nanoreactors, with controllable elaborate microstructure, ideal
local voids, and hollow nanostructures, show excellent perfor-
mance on catalysis, supercapacitors, chemical sensors, and
biomedicine.[1–5] Particularly, for catalysis, the well-designed
hollow nanomaterials do not only provide platform for the
specific catalytic reaction but also can be used as model to
reveal the mechanism of nano-catalytic reaction. Generally,
metal organic frameworks (MOFs) have shown a lot of advan-
tages as an important type of catalyst and have emerged as
promising platforms for diverse applications.[6–10] However,
the microporous structure property of MOFs hinders the
large-scale molecules entering their internal pores, and in
some cases significantly limits their application in the cata-
lytic field. As such, using of MOFs as a hard-template is a
ultra-thin metallized film by depositing organic ligands and
metal nodes on a hollow skeleton combined with the external
cross-linked surface engineering, typically by post-synthetic
modification (PSM) methodologies, for tuning the chemical
and physical properties which determines their performance
in catalysis.[12–14] As a consequence, the heterogeneous catalyst
having a QTD film structure combines the merits of homoge-
neous and heterogeneous catalyst, which can be sufficiently
contacted with a reactant and easily separated and recovered.
Heterogenization of homogeneous metal complex catalysts
occurs in some simple steps due to the coordination mecha-
nism involved, and it provides a method for anchoring specific
functional molecules into the catalyst structure without com-
promising the integrity of the framework structure.[15] With the
development of controllable synthesis methods, a large number
of functionalization methods have been used to implement
the catalysts design, such as: “single site” immobilized,[16,17]
variants and sequences introduced,[18–20] and catalytic environ-
ment coordinated.[21,22] Herein, the QTD film is deposited on
the surface of the hollow skeleton, so that the ultra-thin metal-
lized film has inherent stability compared with the traditional
2D analog, and its catalytic activity can be fully demonstrated.
Therefore, this method has broad prospects in the preparation
of heterogeneous catalysts.
D. Zhang, Dr. J. Liu, Dr. P. Du, Dr. Z. Zhang, X. Ning, Y. Deng,
D. Yin, Prof. X. Lu
Tianjin Key Laboratory of Molecular Optoelectronic Science
Department of Chemistry School of Science
Tianjin University
Tianjin 300072, P. R. China
E-mail: luxq@tju.edu.cn, luxq@nwnu.edu.cn
Dr. J. Chen, Dr. Z. Han, Prof. X. Lu
Key Laboratory of Bioelectrochemistry & Environmental Analysis
of Gansu Province
College of Chemistry and Chemical Engineering
Northwest Normal University
Lanzhou 730070, P. R. China
Recently, metal-complex with specific catalytic activity
have been immobilized on various carrier surfaces to con-
struct organic/inorganic interfaces by surface molecular engi-
neering to form a solid catalytic center with a clear chemical
structure and function, thereby converting a homogeneous
catalytic reaction into a heterogeneous catalytic reaction,
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.201905889.
DOI: 10.1002/smll.201905889
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Scheme 1. Design strategy to synthesize HZIF@TCPP-Fe/Fe heterogeneous catalyst.
improving catalytic efficiency, and solving the problem of
catalysts recovery.[23–27] Taking account of advantages and
unique properties of metal-porphyrins such as excellent
electron donors with delocalized π systems, rigid and planar
geometry, high thermal stability, high electron stability, small
band, adjustable band gap, excellent optical, and ideal redox
behavior,[28–31] a type of tetrakis(4-carboxyphenyl)-porphyrin-
Fe (TCPP-Fe) based QTD ultra-thin metallized film materials
was constructed by in-situ deposition of TCPP-Fe molecule
chelated with iron ions (Fe(III)) on the surface of hollow
nanocages by cross-linked surface engineering. Our aim is
to improve the catalytic performance of HZIF@TCPP-Fe/Fe
catalyst on oxidative dehydrogenation of aromatic hydrazides
and investigate the basic mechanism. The larger voids pro-
vided by irregular defects in metalized films as the “holes”
can effectively enhance the accessibility of active sites, which
is conducive to improving their catalytic activity.[32–34] Hence,
the unique QTD ultra-thin metallized film structural cross-
linked on the surface of hollow skeleton generally exhibits
higher catalytic performance than their monomer presence
counterparts, mainly due to stabilization of the films through
immobilization, the electron deficient iron-oxo complexes
are much better electron acceptors, they will be more pow-
erful oxidants than the corresponding species derived from
non-metal porphyrin molecule, and it can effectively enhance
the catalytic activity of porphyrin-Fe by cross-linked surface
engineering.
The main synthesis steps are briefly described as shown in
Scheme 1. By cation exchange with Au3+ ions, the homometallic
zeolite imidazolate frameworks-8 (ZIF-8) nanoparticles trans-
forms into hollow ZIF (HZIF) nanocages skeleton due to Kirk-
endall effect.[35] The Au and Zn focus mostly on the shell of the
as-prepared HZIF nanocage, and the β-mercaptoethylamine
were anchored on the Au atom to form an amino-functional

( NH2) hollow ZIF-8 (HZIF/NH2) skeleton. The exposed

NH2 group on the surface bind with TCPP-Fe to construct an
organic/inorganic interface to form a HZIF@TCPP-Fe catalyst
precursor. After adding Fe(III) ions, the TCPP-Fe cross-linked
via the coordination interaction between Fe(III) and carboxyl
group (-COOH) of TCPP to form QTD ultra-thin metallized
film on the surface of HZIF/NH2 skeleton. As an ideal hetero-
geneous carrier, HZIF/NH2 skeleton effectively supports the
TCPP-Fe/Fe ultra-thin metallized film, which exposed large
amount of isolated catalytic active sites for reactants easily
approaching. The synthesis routes and structure details of TCPP-
Fe are described in the Supporting Information (Figures S1–S5,
Supporting Information).
Transmission electron microscopy (TEM) image (Figure 1a)
shows obviously hollow structure of HZIF@TCPP-Fe/Fe. The
shell thickness is about 20 nm determined by the high-resolu-
tion transmission electron microscope (HR-TEM), as shown
in Figure 1b. It also can be observed that the QTD TCPP-Fe/Fe
ultra-thin metallized film is about 2 nm with clearly edge as
shown in Figure 1c. Some defects can also be identified in
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Figure 1. a) TEM images of HZIF@TCPP-Fe/Fe. b–d) HR-TEM images of HZIF@TCPP-Fe/Fe. e–i) EDS elemental (Au, Zn, O, N, and Fe) mapping
of HZIF@TCPP-Fe/Fe. j) Diameter distribution histogram of HZIF@TCPP-Fe/Fe. High-resolution XPS spectra of k) Fe 2p, l) N 1s, m) O 1s, n) C 1s,
o) Au 4f, and p) Zn 2p of HZIF@TCPP-Fe/Fe.
Figure 1d indicate that the cross-linked TCPP-Fe/Fe film does
not full cover the surface of hollow ZIF-8 skeleton. Energy
dispersive spectrometer (EDS) mappings (Figure 1e–i) indi-
cate the elements distributing uniformly. The as-synthesized
HZIF@TCPP-Fe/Fe presents a relatively uniform diameter
of 150 30 nm (Figure 1j). During the preparation process,
collapse or large-scale aggregations did not occur, at the same
time, no metallized film existed on the surface of the HZIF@
TCPP-Fe catalyst precursor, which can be confirmed by scan-
ning electron microscope (SEM) and TEM images (Figure S6a–j,
Supporting Information). The large-field SEM images, EDS
mappings (Figure S7, Supporting Information) and Fourier
transform infrared spectroscopy (FT-IR) spectra (Figure S8,
Supporting Information) show no obvious change indicating
the structural integrity of the material, which ensure their orig-
inal excellent properties were retained.[36] In addition, regarding
the relationship between TCPP-Fe and Fe(III), the above two
were directly mixed, unexpectedly, a large number of precipi-
tates (TCPP-Fe/Fe bulk complex) with irregular shapes were
generated, and uniform QTD TCPP-Fe/Fe ultra-thin metallized
film cannot be achieved (Figure S9, Supporting Information).
To investigate the chemical composition and oxidation states
of the as-synthesized nanocomposites, X-ray photoelectron spec-
troscopy (XPS) analysis were performed. The survey spectra of
the HZIF@TCPP-Fe/Fe was shown in Figure S10, Supporting
Information. High-resolution Fe 2p spectrum of HZIF@TCPP-
Fe/Fe could be deconvoluted into five peaks at 710.4, 714.8, 718.6,
724.7, and 727.9 eV, which were attributed to the Fe(II) 2p3/2
,
Fe(III) 2p3/2, satellite, Fe(II) 2p1/2, and Fe(III) 2p1/2 peak, respec-
tively, suggesting that Fe existed as Fe(II) and Fe(III) in the
possible form of HZIF@TCPP-Fe/Fe (Figure 1k).[37–39] High-
resolution XPS spectra of N 1s, C 1s, and O 1s deconvoluted into
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
the peaks at 399.3 and 530.2 eV, corresponding to Fe N and
metallized film (Figure 2c). To obtain the porous structure infor-
mation of the desolated ZIF-8, HZIF@TCPP-Fe, and HZIF@
TCPP-Fe/Fe, the N2 adsorption-desorption isotherms were
measured at 77 K, as displayed in Figure 2d. These materials
exhibit Brunauer–Emmett–Teller (BET) surface of 1739, 788,
and 140 m2g−1, respectively. The large hysteresis loop appeared
on the latter two materials at high pressure can be attributed to
the hollow structure. Moreover, significant decrease in surface
area was observed for the HZIF@TCPP-Fe/Fe, which prove
that the formation of the metallized film blocks micropores of
the hollow skeleton and indicate that QTD TCPP-Fe/Fe ultra-
thin metallized film was successfully constructed and possessed
high density and rich catalytically active sites. Furthermore, the
time-resolved photoluminescence (TRPL) spectroscopy is a very
important means to understand the quenching mechanism of
TCPP-Fe in cooperation with Fe(III). The results illustrated that
excited-state molecules of TCPP-Fe interacted with Fe(III) in the
outer surface of HZIF/NH2, because the average emission life-
time was reduced from 28.439 to 16.792 ns (Figure 2e see also
Table S2, Supporting Information).
Aromatic azo compounds are widely used in the chem-
ical industry, it is of great significance for people to explore
highly-efficient catalysts and apply it widely in the field of azo
compounds production.[44] As a number of prior reports have
already described the preparation of aromatic azo compounds
using iron (II) phthalocyanine (Fe(Pc)) as the catalyst.[45–49] To
our knowledge, Fe(Pc) as catalyst has great potential as oxida-
tion catalysts, however, the Fe(Pc) molecule cannot be recycled,
resulting in a significant waste and environmental pollution.
Against this backdrop, we particularly focus on the cross-
linked surface engineering with respect to the hollow skeleton
for the rational design of heterogeneous catalysts in terms of
[40,41]

Fe O (Figure 1i–n).
The XPS spectra of Au 4f and Zn 2p
as shown in Figure 1o,p.[42,43] Comparing with the XPS spectra
of HZIF@TCPP-Fe (Figure S11, Supporting Information), the
appearance of peak at 714.8 eV indicates the successful embed-
ding of Fe(III). The mole ratio of Fe in HZIF@TCPP-Fe and
HZIF@TCPP-Fe/Fe is about 1/1.5 calculated by the result
of inductively coupled plasma mass spectrometry (ICP-MS)
(Table S1, Supporting Information). The type of porphyrin-Fe
based QTD materials by in-situ deposition of TCPP-Fe molecule
chelated with Fe(III) on the surface of hollow nanocages by
cross-linked surface engineering was successfully constructed.
X-ray powder diffraction (XRD) was measured to verify the
composition and structural information. It can be derived that
the as-prepared HZIF@TCPP-Fe/Fe maintains well-resolved
diffraction peaks corresponding to ZIF-8 (Figure 2a). In addition,
we optimized the amount of Fe(III) added. After a cross-linked
surface engineering treatment, the XRD peaks are identical to
pure ZIF-8 (Figure S12, Supporting Information). The thermal
stabilities of as-prepared materials were studied by using ther-
mogravimetric analysis (TGA). As shown in Figure 2b, the TGA
profile taken in the nitrogen of HZIF@TCPP-Fe/Fe suggests
the nanocages structures are stable up to 230 °C. The obviously
weight loss occurred in the temperature range of 230 and 450 °C
is ascribed to the decomposition of TCPP-Fe and 2-methylim-
idzole from the HZIF@TCPP-Fe/Fe. The UV-vis absorption
spectra of HZIF@TCPP-Fe and HZIF@TCPP-Fe/Fe displayed
new bands attributed to the Soret band (424 nm) and the Q
bands (577, 630, and 691 nm) of the TCPP-Fe units respectively,
which proved that the TCPP-Fe was successfully supported on
the surface of the hollow skeleton and the relative intensity
increased with the formation of QTD TCPP-Fe/Fe ultra-thin
Figure 2. a) Powder XRD patterns for ZIF-8, HZIF, HZIF/NH2, HZIF@TCPP-Fe, and HZIF@TCPP-Fe/Fe. b) TGA profiles of ZIF-8, HZIF, HZIF/NH2,
HZIF@TCPP-Fe, and HZIF@TCPP-Fe/Fe in N2 atmosphere. c) UV–vis spectra of ZIF-8, HZIF, HZIF/NH2, HZIF@TCPP-Fe, and HZIF@TCPP-Fe/Fe
(powder sample). d) N2 sorption isotherms at 77 K of ZIF-8, HZIF@TCPP-Fe and HZIF@TCPP-Fe/Fe. e) Time-resolved photoluminescence emission
decay spectra of HZIF@TCPP-Fe and HZIF@TCPP-Fe/Fe.
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functionalization methods and structure correlated catalysis.
Compared with structure-related Fe(Pc), the catalytic perfor-
mance of porphyrin-Fe complexes for catalyzing the oxidative
dehydrogenation of aromatic hydrazides to azo products has
not been fully studied. It is noticeable that TCPP-Fe molecules
can be used as oxidation catalysts, and the combination of
TCPP-Fe and atmospheric oxygen would be conceptually ideal
to realize practical oxidation methods.[50,51] Since TCPP-Fe was
capable to catalyze the oxidative dehydrogenation of aromatic
hydrazide, therefore, a novel method for the preparation of
QTD TCPP-Fe/Fe ultra-thin metallized film was further devel-
oped. In this work, we deeply explored the oxidative dehydroge-
nation of aromatic hydrazide in detail, including optimization
of catalytic conditions and investigation of reaction mechanism.
When a mixture of ethyl 2-phenylhydrazine-1-carboxylate (1a)
and a catalytic amount of as prepared HZIF@TCPP-Fe/Fe
heterogeneous catalyst (5 mol %) was exposed to atmospheric
oxygen, ethyl 2-phenyldiazene-1-carboxylate (2a) was obtained
in good yield (92%) in a shorter reaction time (4 h) after
purification by chromatography compared to the porphyrin cat-
alysts (Fe(Tpp)Cl) reported in the literature.[52] The reaction was
neither induced in absence of the catalyst nor presence of only
hollow skeleton without TCPP-Fe units (Table 1, Entries 1–4).
Next, replacement of TCPP-Fe with other different coordination
FeCl3 6H2O) were tested (Table 1, Entries 5–8). All above cata-
lysts have no significant catalytic effect, which prove that the
iron salt supported on the surface or pore of the hollow skeleton
does not play a major role in the HZIF@TCPP-Fe/Fe catalyst.
HZIF@TCPP-Fe catalyst precursor with TCPP-Fe units have
the potential ability to act as catalysts for activation of molecular
oxygen (Table 1, Entry 9). The THF solvents gave good results
under HZIF@TCPP-Fe/Fe catalyst (Table 1, Entries 10–13).
Thus, HZIF@TCPP-Fe/Fe catalyst was clearly the best catalyst
for oxidative dehydrogenation of ethyl 2-phenylhydrazine-1-car-
boxylate. With the optimal reaction conditions (0.25 mmol 1a,
5 mol % TCPP-Fe/Fe bulk, 4 mL THF under ambient condi-
tions), we evaluated the oxidative dehydrogenation strategy to
obtain 2a, the corresponding desired products in good yields
(85%) (Table 1, Entry 14). The catalyst performance of HZIF@
TCPP-Fe/Fe in various atmosphere was also evaluated (Table 1,
Entries 15, 16), compared with air and N2, HZIF@TCPP-Fe/
Fe exhibited the best catalytic effect under O2 atmosphere. For
the above experimental results, we can preliminarily confirm
that in the structure of the heterogeneous catalyst, the complex
structure of TCPP-Fe/Fe composed with TCPP-Fe and Fe(III)
plays the major catalytic role for oxidative dehydrogenation of
aromatic hydrazides reaction.
A plausible mechanism for the oxidative dehydrogenation
of aromatic hydrazide reaction under HZIF@TCPP-Fe/Fe het-
erogeneous catalyst is shown in Figure 3a. First, the Fe(III) was
reduced to the Fe(II) by the aromatic hydrazides 1(i), and cation
radical (ii) was generated. Subsequently, the radical interme-
diate (iii) was formed by the deprotonation process. Finally, the
intermediate (iii) was oxidized by Fe(III) to obtain the product
2 (iv).[53–55] For effectively improving the catalytic performance,
the catalytic active site can be provided in the form of QTD
TCPP-Fe/Fe ultra-thin metallized film. As shown in Figure 3b,
QTD TCPP-Fe/Fe ultra-thin metallized film formed by depo-
sition of TCPP-Fe chelated with Fe(III) was loaded on the
surface of hollow nanocage skeleton. Thus, we have used
surface-mounted ultra-thin metallized film grown on suitably
functionalized substrates, providing inter digitated bottom con-
tacts. This approach allows the demonstrate of catalytic prop-
erties of as-prepared materials in a straightforward fashion. In
addition, as shown in Figure 3c, the designed HZIF@TCPP-
Fe/Fe catalyst can be easily recovered by centrifugation, the
catalyst morphology is generally maintained intact (Figure S13,
Supporting Information), and repeatedly used for at least five
consecutive reaction cycles with only slight activity loss. To
prove that the preparation of QTD TCPP-Fe/Fe film is one
of the necessary strategies for preparing the catalyst, Ni(II),
Mn(II), Co(II), and Ce(III) were chosen as the coordina-
tion metal to prepare other four different catalysts: HZIF@
TCPP-Fe/Ni, HZIF@TCPP-Fe/Mn, HZIF@TCPP-Fe/Co, and
HZIF@TCPP-Fe/Ce (Figure S14, Supporting Information). The
SEM images, EDS mappings and XRD measurements of them
are shown in Figures S15 and S16, Supporting Information.
From the catalytic results, the introduction of other four tran-
sition metals did not achieve the desired catalytic effect in 4 h
(Figure S17, Supporting Information). Hence, the development
of heterogeneous catalyst with QTD TCPP-Fe/Fe ultra-thin
metallized film by cross-linked surface engineering for the oxi-
dative dehydrogenation of aromatic hydrazide is indispensable,
.
modes of iron (HZIF@Fe(II), HZIF@Fe(III), FeCl2 4H2O, and
Table 1. Optimization of the reaction conditions.
a)
Cat.
–
Solvent
THF
Atmosphere Time [h] Yield [%]
Entry
1
O2
O2
O2
O2
O2
O2
O2
O2
O2
O2
O2
O2
O2
O2
N2
Air
24
24
24
24
24
24
24
24
24
4
<1
<1
<1
<1
25
27
10
14
2
ZIF-8
THF
3
HZIF
THF
4
HZIF/NH2
HZIF@Fe(II)
HZIF@Fe(III)
THF
5b)
6c)
7d)
8e)
9f)
THF
THF
.
FeCl2 4H2O
THF
.
FeCl3 6H2O
THF
HZIF@TCPP-Fe
HZIF@TCPP-Fe/Fe
HZIF@TCPP-Fe/Fe
HZIF@TCPP-Fe/Fe
THF
72
92
90
52
60
85
<1
54
10g)
11g)
12g)
13g)
14h)
15g)
16g)
THF
CH2Cl2
Toluene
4
4
HZIF@TCPP-Fe/Fe Ethyl acetate
4
TCPP-Fe/Fe bulk
HZIF@TCPP-Fe/Fe
HZIF@TCPP-Fe/Fe
THF
THF
THF
4
4
4
a)Reaction conditions: 1 (0.25 mmol), catalysts (5 mol %), solvent (4 mL) at room
temperature; b)5 mol % of HZIF@Fe(II) catalyst; c)5 mol % of HZIF@Fe(III) cata-
lyst; d)5 mol % of FeCl2.4H2O catalyst; e)5 mol % of FeCl3.6H2O catalyst; f)5 mol %
of HZIF@TCPP-Fe catalyst; g)5 mol % of HZIF@TCPP-Fe/Fe catalyst; h)5 mol % of
TCPP-Fe/Fe bulk catalyst.
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Figure 3. a) Plausible mechanism. b) Scheme of the TCPP-Fe/Fe ultra-thin metallized film catalyzed oxidative dehydrogenation of aromatic hydrazides
reactions. c) Catalytic efficiency in the reaction over the five cycles.
because 1) the QTD TCPP-Fe/Fe ultra-thin metallized film
constructed by cross-linked surface engineering has abundant
unsaturated Fe active sites with excellent accessibility for reac-
tion substrate; 2) the carboxyl group electron-withdrawing sub-
stituent electrically shifts Fe(III)/Fe(II) potential to more posi-
tive values, increases the rate of reaction with oxygen-active spe-
cies; 3) the in-situ deposition of ultra-thin metallized films will
produce some irregular defects, such as “holes”, increase the
roughness and accessibility of the catalyst surface and the prob-
ability of contact with the reaction substrate; 4) the hollow skel-
eton may be employed as nanoscale containers to load small
organic molecules. Inspired by these facts, we have synthe-
sized the HZIF@TCPP-Fe/Fe heterogeneous catalyst, for the
catalytic oxidative dehydrogenation of aromatic hydrazide reac-
tions. Combine the structural advantages of the catalyst with
the hypothetical mechanisms, the outstanding activity of the
halogenated HZIF@TCPP-Fe/Fe can be ascribed to the above
factors, for the catalytic oxidative dehydrogenation of aromatic
hydrazide reactions. With the established optimal reaction con-
ditions in hand (Table 1, Entry 10), substrate scopes were inves-
tigated (Table S3, Supporting Information). The as-prepared
HZIF@TCPP-Fe/Fe mainly committed the efficient with QTD
TCPP-Fe/Fe catalytically active sites and distinguished oxidative
dehydrogenation of aromatic hydrazides obviously discloses a
reactivity order of primary > secondary > tertiary carbon.
film has been widely explored, typically by post-synthetic modi-
fication methodologies, to endow multifunctionality into hollow
skeleton that cannot be directly introduced by de novo syntheses.
Thus, this work demonstrates that HZIF@TCPP-Fe/Fe as het-
erogeneous catalyst can provide a specific environment to deter-
mine the main direction of a chemical reaction.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors thank the Natural Science Foundation of China (21575115,
21705117); the Program for Chang Jiang Scholars and Innovative
Research Team, Ministry of Education, China (IRT-16R61); and the
Program of Gansu Provincial Higher Education Research Project
(2017-D-01); the Program of Tianjin Science and Technology Major
Project and Engineering (19ZXYXSY00090).
Conflict of Interest
The authors declare no conflict of interest.
In summary, we have proposed new strategy to prepare a novel
kind of highly efficient, robust, and reusable HZIF@TCPP-Fe/
Fe heterogeneous catalyst, for the catalytic oxidative dehydroge-
nation of aromatic hydrazide reactions. The resulting HZIF@
TCPP-Fe/Fe has highly dispersed multiple active sites, control-
lable morphology and ultra-thin metallized film thickness, which
have prominent contribution to improving the catalytic perfor-
mance of the heterogeneous catalyst. The external cross-linked
surface engineering of QTD TCPP-Fe/Fe ultra-thin metallized
Keywords
aromatic hydrazides, green chemistry, heterogeneous catalysts, iron
porphyrin, quasi-two-dimensional films, ultra-thin metallized films
Received: October 15, 2019
Revised: January 18, 2020
Published online:
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[1] S. Horike, S. Shimomura, S. Kitagawa, Nat. Chem. 2009, 1, 695.
[2] Z. Cai, Z. Wang, J. Kim, Y. Yamauchi, Adv. Mater. 2019, 31, 1804903.
[3] L. Yu, X. Yu, X. Lou, Adv. Mater. 2018, 30, 1800939.
[4] W. Zhao, G. Li, Z. Tang, Nano Today 2019, 27, 178.
[5] X. Wang, J. Feng, Y. Bai, Q. Zhang, Y. Yin, Chem. Rev. 2016, 116,
10983.
[6] L. Chen, R. Luque, Y. Li, Chem. Soc. Rev. 2017, 46, 4614.
[7] H. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673.
[8] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science 2013,
341, 1230444.
[9] H. Wang, P. Rassu, X. Wang, H. Li, X. Wang, X. Wang, X. Feng,
A. Yin, P. Li, X. Jin, S. Chen, X. Ma, B. Wang, Angew. Chem., Int. Ed.
2018, 57, 16416.
[10] Q. Xia, H. Wang, B. Huang, X. Yuan, J. Zhang, J. Zhang, L. Jiang,
T. Xiong, G. Zeng, Small 2019, 15, 1902459.
[11] W. Zhu, Z. Chen, Y. Pan, R. Dai, Y. Wu, Z. Zhuang, D. Wang,
Q. Peng, C. Chen, Y. Li, Adv. Mater. 2019, 31, 1800426.
[12] X. Qiao, B. Su, C. Liu, Q. Song, D. Luo, G. Mo, T. Wang, Adv. Mater.
2018, 30, 1702275.
[13] M. G. Marqués, E. Bellido, T. Berthelot, T. S. Yarza, T. Hidalgo,
R. S. Vázquez, Á. G. Fernández, J. Avila, M. C. Asensio, R. Gref,
P. Couvreur, C. Serre, P. Horcajada, Small 2018, 14, 1801900.
[14] M. Pinault, V. Picholt, H. Khoda, P. Launois, C. Reynaud,
M. M. L’Hermite, Nano Lett. 2005, 5, 2394.
[15] Z. Xue, P. Wang, A. Peng, T. Wang, Adv. Mater. 2019, 31, 1801441.
[16] P. Elumalai, H. Mamlouk, W. Yiming, L. Feng, S. Yuan, H. Zhou,
S. T. Madrahimov, ACS Appl. Mater. Interfaces 2018, 10, 41431.
[17] S. T. Madrahimov, J. R. Gallagher, G. Zhang, Z. Meinhart,
S. J. Garibay, M. Delferro, J. T. Miller, O. K. Farha, J. T. Hupp,
S. T. Nguyen, ACS Catal. 2015, 5, 6713.
[29] X. Ning, Y. Wu, X. Ma, Z. Zhang, R. Gao, J. Chen, D. Shan, X. Lu,
Adv. Funct. Mater. 2019, 29, 1902992.
[30] X. Ning, W. Li, Y. Meng, D. Qin, J. Chen, X. Mao, Z. Xue, D. Shan,
S. Devaramani, X. Lu, Small 2018, 14, 1703989.
[31] Y. Li, Z. Gao, F. Chen, C. You, H. Wu, K. Sun, P. An, K. Cheng,
C. Sun, X. Zhu, B. Sun, ACS Appl. Mater. Interfaces 2018, 10,
30930.
[32] L. Feng, S. Yuan, L. Zhang, K. Tan, J. Li, A. Kirchon, L. Liu, P. Zhang,
Y. Han, Y. J. Chabal, H. Zhou, J. Am. Chem. Soc. 2018, 140, 2363.
[33] L. Liu, Z. Chen, J. Wang, D. Zhang, Y. Zhu, S. Ling, K. Huang,
Y. Belmabkhout, K. Adil, Y. Zhang, B. Slater, M. Eddaoudi, Y. Han,
Nat. Chem. 2019, 11, 622.
[34] M. Guo, J. Balamurugan, X. Li, N. H. Kim, J. H. Lee, Small 2017, 13,
1701275.
[35] L. Tang, S. Zhang, Q. Wu, X. Wang, H. Wu, Z. Jiang, J. Mater. Chem.
A 2018, 6, 2964.
[36] F. Zhang, Y. Wei, X. Wu, H. Jiang, W. Wang, H. Li, J. Am. Chem. Soc.
2014, 136, 13963.
[37] L. An, J. Feng, Y. Zhang, Y. Zhao, R. Si, G. Wang, F. Cheng, P. Xi,
S. Sun, Nano Energy 2019, 57, 644.
[38] Y. Wang, M. Zhao, J. Ping, B. Chen, X. Cao, Y. Huang, C. Tan,
Q. Ma, S. Wu, Y. Yu, Q. Lu, J. Chen, W. Zhao, Y. Ying, H. Zhang,
Adv. Mater. 2016, 28, 4149.
[39] Z. Wang, H. Jin, T. Meng, K. Liao, W. Meng, J. Yang, D. He, Y. Xiong,
S. Mu, Adv. Funct. Mater. 2018, 28, 1802596.
[40] Y. Wang, D. Adekoya, J. Sun, T. Tang, H. Qiu, L. Xu, S. Zhang,
Y. Hou, Adv. Funct. Mater. 2019, 29, 1807485.
[41] L. Jiao, G. Wan, R. Zhang, H. Zhou, S. Yu, H. Jiang, Angew. Chem.,
Int. Ed. 2018, 57, 8525.
[42] Y. Huang, M. Zhao, S. Han, Z. Lai, J. Yang, C. Tan, Q. Ma, Q. Lu,
J. Chen, X. Zhang, Z. Zhang, B. Li, B. Chen, Y. Zong, H. Zhang,
Adv. Mater. 2017, 29, 1700102.
[18] L. Feng, S. Yuan, J. L. Li, K. Y. Wang, G. S. Day, P. Zhang, Y. Wang,
H. C. Zhou, ACS Cent. Sci. 2018, 4, 1719.
[19] S. Zhang, B. Zhang, H. Liang, Y. Liu, Y. Qiao, Y. Qin, Angew. Chem.,
Int. Ed. 2018, 57, 1091.
[43] M. Zhang, Q. Shang, Y. Wan, Q. Cheng, G. Liao, Z. Pan, Appl. Catal.,
B 2019, 241, 149.
[20] M. Hu, S. Zhao, S. Liu, C. Chen, W. Chen, W. Zhu, C. Liang,
W. Cheong, Y. Wang, Y. Yu, Q. Peng, K. Zhou, J. Li, Y. Li, Adv. Mater.
2018, 30, 1801878.
[44] P. T. Wong, S. K. Choi, Chem. Rev. 2015, 115, 3388.
[45] D. Hirose, T. Taniguchi, H. Ishibashi, Angew. Chem., Int. Ed. 2013,
52, 4613.
[21] N. Huang, S. Yuan, H. Drake, X. Yang, J. Pang, J. Qin, J. Li, Y. Zhang,
Q. Wang, D. Jiang, H. Zhou, J. Am. Chem. Soc. 2017, 139, 18590.
[22] L. Feng, Y. Wang, S. Yuan, K. Wang, J. Li, G. S. Day, D. Qiu, L. Cheng,
W. Chen, S. T. Madrahimov, H. Zhou, ACS Catal. 2019, 9, 5111.
[23] G. Li, S. Zhao, Y. Zhang, Z. Tang, Adv. Mater. 2018, 30, 1800702.
[24] Y. Wang, H. Cui, Z. Wei, H. Wang, L. Zhang, C. Su, Chem. Sci. 2017,
8, 775.
[46] A. B. Sorokin, Chem. Rev. 2013, 113, 8152.
[47] E. Wang, Y. Ping, Z. Li, H. Qin, Z. Xu, C. Che, Org. Lett. 2018, 20,
4641.
[48] D. Hirose, M. Gazvoda, J. Košmrlj, T. Taniguchi, Org. Lett. 2016, 18,
4036.
[49] D. Hirose, M. Gazvoda, J. K. Smrlj, T. Taniguchi, Chem. Sci. 2016, 7,
5148.
[25] R. Yang, R. Li, Y. Cao, Y. Wei, Y. Miao, W. Tan, X. Jiao, H. Chen,
L. Zhang, Q. Chen, H. Zhang, W. Zou, Y. Wang, M. Yang, C. Yi,
N. Wang, F. Gao, C. R. McNeill, T. Qin, J. Wang, W. Huang,
Adv. Mater. 2018, 30, 1804771.
[50] R. Jiang, L. Li, T. Sheng, G. Hu, Y. Chen, L. Wang, J. Am. Chem. Soc.
2018, 140, 11594.
[51] J. Yi, R. Xu, Q. Wu, T. Zhang, K. Zang, J. Luo, Y. Liang, Y. Huang,
R. Cao, ACS Energy Lett. 2018, 3, 883.
[26] S. G. Kwon, G. Krylova, A. Sumer, M. M. Schwartz,
E. E. Bunel, C. L. Marshall, S. Chattopadhyay, B. Lee, J. Jellinek,
E. V. Shevchenko, Nano Lett. 2012, 12, 5382.
[27] Z. Niu, Y. Li, Chem. Mater. 2014, 26, 72.
[28] X. Ning, B. Lu, Z. Zhang, P. Du, H. Ren, D. Shan, J. Chen, Y. Gao,
X. Lu, Angew. Chem., Int. Ed. 2019, 58, 16800.
[52] T. Hashimoto, D. Hirose, T. Taniguchi, Adv. Synth. Catal. 2015, 357,
3346.
[53] T. Taniguchi, D. Hirose, H. Ishibashi, ACS Catal. 2011, 1, 1469.
[54] X. Wang, X. Wang, C. Xia, L. Wu, Green Chem. 2019, 21, 4189.
[55] T. Taniguchi, Y. Sugiura, H. Zaimoku, H. Ishibashi, Angew. Chem.,
Int. Ed. 2010, 49, 10154.
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