Selective oxidation of alcohols by porphyrin-based porous polymer-supported manganese heterogeneous catalysts

Article abstract of DOI:10.1002/aoc.5259

A series of porphyrin-based porous polymers to support Mn heterogeneous catalysts (Mn/TFP-DPM, Mn/TFP-DPM-2, Mn/TFP-DPM-3, and Mn/TFP-DPM-4) in the selective oxidation of alcohols were designed. TFP-DPM and TFP-DPM-2 demonstrated micro/nanoscale spherical morphology, whereas TFP-DPM-3 and TFP-DPM-4 exhibited nanosheets structure. According to surface area and porosity analysis results, the specific surface areas of these catalysts were less than 300 m² g^–1. Thermogravimetric analysis indicated that the synthesized catalysts maintain their stability even at 300 °C. Catalysts Mn/TFP-DPM and Mn/TFP-DPM-3, which had the smallest and largest specific surface area among the four catalysts, respectively, were used to perform selective oxidation reaction of alcohols, with experimental results indicating that both have excellent catalytic performance. As these catalysts possess good catalytic performance despite their low specific surface area, we suggest that porphyrin-based porous polymer-supported Mn heterogeneous catalysts are promising materials for selective oxidation of alcohols.

Full text of DOI:10.1002/aoc.5259

Received: 6 January 2019
DOI: 10.1002/aoc.5259
Revised: 9 July 2019
Accepted: 3 September 2019
F U L L P A P E R
Selective oxidation of alcohols by porphyrin‐based porous
polymer‐supported manganese heterogeneous catalysts
1
,2
1
2
2
Jian Chen
| Yan Zhang | Dajian Zhu
| Tao Li
1
Hubei Key Laboratory of Processing and
Application of Catalytic Materials, School
of Chemistry and Chemical Engineering,
Huanggang Normal University, Number
A series of porphyrin‐based porous polymers to support Mn heterogeneous cat-
alysts (Mn/TFP‐DPM, Mn/TFP‐DPM‐2, Mn/TFP‐DPM‐3, and Mn/TFP‐DPM‐4)
in the selective oxidation of alcohols were designed. TFP‐DPM and TFP‐DPM‐2
demonstrated micro/nanoscale spherical morphology, whereas TFP‐DPM‐3
and TFP‐DPM‐4 exhibited nanosheets structure. According to surface area
and porosity analysis results, the specific surface areas of these catalysts were
1
4
2
46, Xingang 2 Road, Huanggang City
38000Hubei Province, China
Hubei Key Laboratory of Material
Chemistry and Service Failure; Key
Laboratory of Material Chemistry for
Energy Conversion and Storage, Ministry
of Education; School of Chemistry and
Chemical Engineering, Huazhong
University of Science and Technology,
Number 1073, Luoyu Road, Wuhan
2
–1
less than 300 m g . Thermogravimetric analysis indicated that the synthe-
sized catalysts maintain their stability even at 300 °C. Catalysts Mn/TFP‐
DPM and Mn/TFP‐DPM‐3, which had the smallest and largest specific surface
area among the four catalysts, respectively, were used to perform selective oxi-
dation reaction of alcohols, with experimental results indicating that both have
excellent catalytic performance. As these catalysts possess good catalytic per-
formance despite their low specific surface area, we suggest that porphyrin‐
based porous polymer‐supported Mn heterogeneous catalysts are promising
materials for selective oxidation of alcohols.
430074Hubei Province, China
Correspondence
Dajian Zhu and Tao Li, Hubei Key
Laboratory of Material Chemistry and
Service Failure; Key Laboratory of
Material Chemistry for Energy Conversion
and Storage, Ministry of Education;
School of Chemistry and Chemical
Engineering, Huazhong University of
Science and Technology, Number 1073,
Luoyu Road, Wuhan 430074, Hubei
Province, China.
KEYWORDS
good catalytic performance, Mn heterogeneous catalysts, porphyrin‐based porous polymers, selective
oxidation of alcohols
Email: zhudj@hust.edu.cn; taoli@hust.
edu.cn
Funding information
National Natural Science Foundation of
China (21473064), Grant/Award Number:
2
1473064; PhD Start‐Up Fund
04201802203), Grant/Award Number:
4201802203
(
0
1
| INTRODUCTION
homogeneous catalysts can be realized by a simple and
[
4]
direct method (bottom–up approach).
Using this
As the active center of heterogeneous and homogeneous
catalysts, noble/transition metals have been widely used
approach, polymers containing heteroatoms, such as
[
5–8]
[9–11]
[12]
[13–15]
N,
P,
S,
and O,
have been exploited as
[1,2]
in organic synthesis.
Compared with homogeneous
catalysts. These heteroatoms in the skeleton of the porous
polymers can also be used as binding sites to disperse
active components and prolong the life and reusability
catalysts, heterogeneous catalysts are more suitable for
practical applications because they are easy to
[3]
[16–18]
recover, recycle, and separate.
Heterogenization of
of the heterogeneous catalysts.
Appl Organometal Chem. 2019;e5259.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
1 of 12
https://doi.org/10.1002/aoc.5259

2
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CHEN ET AL.
As significant intermediates produced during the syn-
not always useful in organic synthesis. To minimize the
impact of steric hindrance of active sites, the substituents
of metalloporphyrin‐contained monomer should as fewer
as possible.
thesis of pharmaceuticals and agrochemicals, aldehydes
and ketones are often prepared through selective oxida-
[19]
tion of alcohols.
This reaction is generally catalyzed
by Pd‐, Ru‐, or Au‐based catalysts because of their excel-
The diffusion of reactants and products in porous cata-
lysts is extremely important to ensure efficiency of catalysis,
because the rate of the overall reaction is ultimately deter-
[19–22]
lent activity, selectivity, and reusability.
However,
limited availability and high cost restrict their extensive
usage. Developing novel types of catalysts using low‐cost
and environmentally friendly transition‐metals, such as
[
37]
mined by molecular mobility. Active sites within porous
catalysts are located in porous channels and experience
severe mass‐transfer constraints because of the compatibil-
ity between the size of substance molecules and pore size
[23,24]
[25,26]
[27]
[28]
Cu,
Ni,
V,
and Mn,
have attracted
increasing attention for application in selective oxidation
of alcohols. Manganese oxide species have long been used
as oxidizing reagents because of their high oxidation abil-
[
45]
(especially micropore size). Diffusion restriction, because
of limited access and slow desorption from active sites,
results in limited utilization of active sites over the heteroge-
neous catalysts, thereby not allowing these catalysts to exert
their function completely. Thus, there is an urgent need to
explore the catalytic process of porphyrin‐based polymers;
however, constructing macropores or mesopores in micro-
porous polymers remains a challenge.
[28]
ity, excellent selectivity, and reusability.
Besides, Schiff
base Mn(III) complexes exhibit excellent catalytic activity
[
29–31]
and selectivity in homogeneous oxidation reactions.
Furthermore, N‐containing polymer‐supported Mn cata-
lysts exhibit excellent catalytic activity, selectivity, and
[28]
reusability in alcohol selective oxidation.
Therefore, it
[
46]
is necessary to synthesize functionalized organic porous
material‐supported manganese catalysts with excellent
catalytic performance and to investigate the underlying
mechanism of reactions involving these catalysts.
Bhaumik et al.
have synthesized two high surface
area catalysts based on porphyrins using a simple
solvothermal method that involves aromatic substitution
of pyrrole and aldehyde derivatives in the presence of fer-
ric salts. The porphyrin‐based catalysts are significant
because they contain dense built‐in catalytic sites in their
skeleton, having a well‐developed porous structure with a
lipophilic organic framework that is conducive to organic
reactions, accessible to substrates, and dispersible to the
reaction products. 1,3,5‐Triformylphloroglucinol (TFP),
with three formyl groups in the small conjugate mole-
cule, can be used as a link in the synthesis of porous
porphyrin‐based polymers (POPs) using pyrrole through
the solvothermal method. However, steric hindrance of
the coordination center maybe very large as the four huge
substituents will crowd the coordination center of por-
phyrin rings in the polymer. To reduce steric hindrance
in the closely connected porphyrin units of the polymer,
2,2′‐dipyrrolylmethane (DPM) was chosen instead of
pyrrole to synthesize the porphyrin‐based polymer. More-
over, the resulting porphyrin‐based polymer possesses
smaller space resistance and conjugate structure, which
may increase the performance of the catalyst. In this
work, porous porphyrin‐based polymer–supported man-
ganese catalysts were synthesized and their catalytic per-
formance evaluated in the selective oxidation of alcohols.
Porphyrin is a highly conjugated heterocyclic macro-
molecular compound consisting of four pyrrolidine sub-
[
32]
units interconnected by submethyl (=CH–) bridges.
The four N heteroatoms in the macrocycles of porphyrin
[33]
can coordinate with various active metals
to form
metalloporphyrins which have been widely used in catal-
[34–36]
ysis.
Metalloporphyrins should be carefully designed
and integrated into the framework of porphyrin‐based
porous material catalysts, which will allow further
[37]
enhancement of catalytic activity.
The N atoms in the
porphyrin ligands have strong coordination ability toward
Mn species, thus favoring development of heterogeneous
[28,38]
Mn‐based catalysts.
Moreover, the conjugated brid-
ges in the skeleton of the polymer facilitate the flow of
electrons to and from lively valence ions, making reduc-
tion of metals easier, thereby enhancing the activity and
[28]
selectivity of these catalysts in alcohol oxidation.
Thus,
the synthesis of conjugated porphyrin‐based porous
organic polymers (POPs) and their use in heterogeneous
Mn catalysts offer a novel method to synthesize catalysts
to be used in the oxidation of alcohols.
Various porous solid materials, such as metal–organic
[39]
[40]
frameworks, covalent organic frameworks and POPs
have been evaluated as catalyst support in reactions involv-
[
41]
ing metalloporphyrins.
The catalytic performance of
2 | EXPERIMENTAL
2.1 | Materials
metalloporphyrin‐based catalysts is strongly influenced
by the degree of space crowding on the surface of porphy-
[42,43]
rins.
As a result, metalloporphyrins with different
range of steric hindrances have been used in region‐ or
Hexamethylenetetramine and EO1 ‐PO ‐EO
= 12,600 g mol ) were obtained from Sigma‐Aldrich.
(Mav
106
06
70
[44]
–1
shape‐selective reactions.
However, steric hindrance is

CHEN ET AL.
3 of 12
Phloroglucinol, pyrrole, trifluoroacetic acid, boric acid,
chloroform‐d (99.8 atom % D), tert‐butyl hydroperoxide,
2.4 | Synthesis of porous porphyrin‐based
polymer
benzhydrol,
1‐phenylethanol,
benzyl
alcohol,
cyclohexanol, octanol, 2‐octanol, n‐hexanol, 2‐hexanol,
Porous porphyrin‐based polymers were synthesized
tetrabutylammonium bromide, tetrabutylammonium
according to the procedure described previously, but with
[
46]
iodide, CaCl , LiCl, and iodobenzene diacetate (PIDA)
some modifications.
DPM (2.50 mmol) and TFP (0.7
2
were
obtained
from
Adamas
Reagent
Ltd.
mmol) were added into 60 ml glacial acetic acid and dis-
solved completely by constant stirring under an inert
argon atmosphere. The product mixture was stirred again
for 4 hr and allowed to stay at 180 °C for 3 days in an
autoclave (hydrothermal condition). After cooling the
mixture down to 25 °C, the black product was separated
using a Buchner funnel. The crude product was thor-
oughly washed and subjected to Soxhlet extraction with
anhydrous ethanol, tetrahydrofuran (THF), and dichloro-
methane for 1 day, respectively, and then dried in a vac-
uum oven at 70 °C for 12 hr, to produce TFP‐DPM
4‐(Trifluoromethoxy)benzyl alcohol, 4‐tert‐butylbenzyl
alcohol, 2‐methylbenzyl alcohol, and 3‐(hydroxymethyl)
pyridine were obtained from Alfa Aesar. Common organic
solvents were purchased from National Medicines Corpo-
ration Ltd (Shanghai, China). Unless otherwise specified,
all reagents purchased from commercial suppliers were
used directly.
2
.2 | General experimental procedure for
(
yield: 0.45 g). The TFP–pyrrole material was also synthe-
synthesis of 2,2′‐dipyrrolylmethane
sized according to this procedure using pyrrole as the raw
material instead of DPM (0.25 g, yield: 93%).
DPM was synthesized according to the procedure
reported previously.
About 1.60 g F127 and 0.46 g trifluoroacetic acid were
dissolved in 30 ml ethanol to form a clarified solution. To
this solution, 0.0426 g of TFP was added and stirred vigor-
ously for 1 hr. Then, 0.1754 g of DPM was added into the
solution and stirred vigorously for 4 hr under an argon
atmosphere. The mixture was transferred into a 100‐ml
Teflon autoclave and treated at 180 °C to initiate hydro-
thermal synthesis (reaction time: 72 hr). The resulting
material was filtered, washed, and dried in the same
manner as for TFP‐DPM synthesis, to give 0.18 g yield
of TFP‐DPM‐2 (yield: 84%).
[47]
Freshly distilled pyrrole (0.52
mol) was dispersed in a clarified aqueous solution of
boric acid (0.2 mol in 500 ml of water) at 25 °C, to which
a solution of formaldehyde (37%, 0.25 mol) was added,
following extract water layer with 150 mL dichlorometh-
ane for three times. The extraction of dichloromethane
was analyzed by column chromatography. Finally, white
powder of DPM was obtained. Melting point: 72–73 °C;
1
H‐nuclear magnetic resonance (NMR; 500 MHz) δ =
3
.97 (s, 2H, CH ), 6.03 (s, 2H, pyrrole ring‐C‐3‐H), 6.14
2
(m, 2H, pyrrole ring ‐C‐4‐H), 6.64 (m, 2H, pyrrole ring –
For the synthesis TFP‐DPM‐3 (yield: 67%), acetic acid
was used as the solvent. During the synthesis of mesopo-
rous TFP‐DPM‐3, F127, TFP, and DPM were dissolved in
C–5‐H), 7.80 (br s, 2H, NH; Figure S1).
30 ml acetic acid. The remaining steps were the same as
2
1
.3 | Synthesis of
,3,5‐triformylphloroglucinol
those for TFP‐DPM‐2.
For the synthesis of mesoporous TFP‐DPM‐4 (yield:
80%), ethanol–water–mesitylene were used as cosolvents.
TFP was synthesized according to the procedure reported
About 3.00 g F127 was added to 40 ml of 95% ethanol–
water and 5.0 ml mesitylene solution to obtain a clear
solution. Then, 0.0426 g of TFP, 0.1754 g of DPM,
and 0.46 g trifluoroacetic acid were added into this
solution and stirred vigorously for 4 hr under an Ar atmo-
sphere. The remaining steps were the same as those for
TFP‐DPM‐2.
[45]
previously.
In a typical process, dried phloroglucinol
(47.66 mmol) was added to 90 ml trifluoroacetic acid
and stirred for 5 min under an argon atmosphere. Hexa-
methylenetetramine (107.07 mmol) was added to the
stirred mixture which was then heated at 100 °C for 3
hr. Subsequently, the reaction mixture was treated with
1
50 ml of 3 M hydrochloric acid and allowed to react
for another 1 hr at 100 °C. After cooling to about 30 °C,
the mixture was filtered using Celite and extracted with
2.5 | Synthesis of polymer‐supported Mn
catalysts
4
50 ml of dichloromethane. The organic phase was dried
by adding anhydrous magnesium sulfate and filtered. Off‐
white powder was obtained from the organic phase by
rotary evaporation. The dried product was characterized
About 2.50 g of porphyrin porous materials, 8.12 mmol
Mn(OAc) ·4H O, 120 ml ethanol, and 60 ml
methylbenzene were added into a 250‐ml three‐port
2
2
1
by H‐NMR (Yield: 19%; Figure S2).

4
of 12
CHEN ET AL.
round‐ bottomed flask with a reflux condenser. The reac-
tion mixture was heated to reflux at 85 °C for 2 hr under
the protection of argon gas. Then, 0.45 g of solid LiCl was
added, and the air was bubbled for an additional 3 hr.
After refluxing the resulting mixture, products were
filtered and rinsed sequentially with ethanol, THF,
dichloromethane, and finally dried in vacuum to yield a
dark power. The resulting corresponding catalysts were
named as Mn/TFP‐DPM, Mn/TFP‐pyrrole, Mn/TFP‐
DPM‐2, Mn/TFP‐DPM‐3, and Mn/TFP‐DPM‐4. The con-
tents of manganese in the catalysts, as determined by
atomic absorption spectroscopy (AAS), were 1.38%,
using TFP and DPM monomers. FT‐IR spectroscopy
experiments were used to further confirm the formation
of porphyrin‐based polymers (Figure 1a). The absorption
peaks of TFP samples at 1828 cm– and 1732 cm were
1
–1
attributed to the C=O group of cyclic lactones or anhy-
–
1
drides. The absorption peak at 1465 cm was attributed
to C–H deformation and the broad peak at 3377 cm– to
the OH group in the plane of TFP monomer. The absorp-
tion peaks at 2930 and 2850 cm– were attributed to the –
1
1
–
1
CH – groups and the aiguille at 3300 cm to the N–H
2
–1
stretch of DPM. The absorption peaks at 1828 cm and
–1
1732 cm , indicating the presence of C=O group in the
TFP monomer, disappeared after the aromatic substitu-
tion reaction, confirming that the porphyrin‐based poly-
mer (TFP‐DPM) was successfully synthesized.
3
.87%, 1.45%, 1.58%, and 2.26%, respectively.
2.6 | Selective oxidation of alcohols
The crystalline feature of TFP‐DPM polymer was stud-
ied by X‐ray diffraction (XRD) characterization. As
shown in Figure 1b, TFP‐DPM shows a unique broad
peak at 2θ value of 20°, which implies its amorphous fea-
ture. Thermal stability is an important property of poly-
mer materials. Therefore, TGA data were recorded
under a nitrogen atmosphere with a temperature ramp
The catalytic performance of alcohol oxidation was evalu-
ated as follows: a solution containing catalyst (Mn cata-
lyst = 0.000125 mmol), substrates (0.1 mmol), oxidants
(0.3 mmol), and additives (0.06% mol) in 3 ml solvents
was heated to a desired temperature. The reaction process
was monitored by gas chromatography and the products
were characterized by NMR.
–1
rate of 15 °C min . Data revealed that the samples did
not decompose until 340 °C in the nitrogen atmosphere
(
Figure 1c). Furthermore, TFP‐DPM remains stable in
water, common organic solvents, strong acids (2 M HCl,
0 °C), and even strong bases (2 M NaOH, 30 °C) for
2.7 | Characterization methods
3
many days, indicating that the polymer has strong chem-
ical stability. The molecular mobility in pores of porous
catalysts is extremely important for catalytic perfor-
mance. To further investigate the porous structure of
Catalyst surface area, nitrogen adsorption isotherm (77.3
K), and porosity distribution were determined using an
Micromeritics ASAP 2020 M surface area analyzer.
Fourier transform infrared (FT‐IR) spectra were recorded
on a Bruker VERTEX 70 FT‐IR spectrometer. Tecnai G20
microscope (FEI Corp., USA) with 200‐kV accelerating
voltage was used to produce the transmission electron
microscopy (TEM) images. The manganese content was
determined using Perkin Elmer AA‐800 (USA). Scanning
electron microscopy (SEM) images were observed on an
FEI Sirion 200 scanning electron microscope at 10.0 kV.
X‐ray photoelectron spectroscopy (XPS) was tested on a
VG MULTILAB 2000 spectrometer with an Mg–Al Kα X‐
ray source with passing energy flow of 100 eV. The C1s
transition was adjusted to 284.6 eV. Thermogravimetric
analysis (TGA) was performed using a PerkinElmer Dia-
mond TG/DTA instrument. GC analyses were performed
in a Fuli GC9790 equipped with an FFAP (30 m × 0.25
mm × 0.25 μm) capillary column and a flame ionization
detector.
porphyrin‐based polymers, N adsorption/desorption iso-
2
therms (Figure 1d) were analyzed, and identified as type
IV hysteresis loop with the relative pressure ranging from
0.70 to 0.98, indicating that both TFP‐DPM‐3 and TFP‐
DPM‐4 possessed a large number of mesopores or
macropores in the pore structure, which can result in
the condensation of nitrogen in the macropores and
[
48]
interparticle voids.
The Brunauer–Emmett–Teller
(
BET) specific surface area of TFP‐DPM‐3 and TFP‐
2
–1
DPM‐4 is 284.4 and 178.6 m g , respectively, and the
corresponding pore volumes are 0.5782 and 0.8170 cm
g . TFP‐pyrrole, TFP‐DPM, and TFP‐DPM‐2 samples,
3
–1
stacked by compact spheres of porphyrin polymer, show
no
obvious
hysteresis
loop
in
the
N2
adsorption/desorption isotherms, suggesting that no obvi-
ous pore structure exists in these samples. The specific
surface areas of TFP‐pyrrole, TFP‐DPM, and TFP‐DPM‐
2
–1
2
samples are 7.6, 17.2, and 30.8 m g , respectively.
3
| RESULTS AND DISCUSSION
Moreover, their corresponding pore volumes are rela-
3
–
tively low, measuring 0.0046, 0.0142, and 0.0913 cm g
1
Porphyrin‐based porous polymer materials were synthe-
sized by an easy one‐pot aromatic substitution method
, respectively. The significant interaction of large num-
bers of hydrogen bonds within the framework may be

CHEN ET AL.
5 of 12
FIGURE 1 (a) Fourier‐transform infrared spectra of the samples, (b) X‐ray diffraction pattern of TFP‐DPM, (c) thermogravimetric analysis
plot of TFP‐DPM, (d) nitrogen adsorption–desorption isotherms of the samples. DPM, 2,2′‐dipyrrolylmethane; TFP, 1,3,5‐
triformylphloroglucinol
[
49]
the main reason for the unexpected low surface area.
acid as a catalyst, F127 as a template, and synthesizing
the materials in an ethanol solvent, the resulting TFP‐
DPM‐2 polymer exhibits a micron‐scale spherical distri-
bution accompanied by a small amount of fragments
(Figure 2c). However, TFP‐DPM‐3 piles up as a mass of
nanosheets ranging from tens to hundreds of nanometers
(Figure 1d). Noticeably, TFP‐DPM‐3 materials possess
rough surface with plenty of stacking holes, through
which substrates and products may diffuse, facilitating
the reaction. As shown in Figure 2e, TFP‐DPM‐4 presents
an accumulation of nanosheets when using ethanol–
water–mesitylene as cosolvent and F127 as the soft
template. Remarkably, the polymer TFP‐DPM‐4
exhibits a scabrous surface with a large number of
cavities in the materials. The detailed nanostructure was
further examined by TEM as shown in illustrations of
Figure 2a–e. TEM images in Figure 2a–c confirmed that
Pore‐size distribution of porous catalysts has a great influ-
ence on molecular mobility. The average pore size, listed
in Table 1, suggests that pores in the porphyrin‐based
polymer are mesoporous. Noticeably, the average pore
size of TFP‐pyrrole and TFP‐DPM are 4.8 and 6.6 nm,
respectively. However, the usage of soft template in the
solvothermal synthesis enlarges the pore size of the
porphyrin‐based polymer to 23.7, 16.3, and 39.4 nm,
respectively. This indicates that soft templates act as a
pore‐enlarging agent during the synthesis, which agree
well with the TEM characterization results.
The morphology of the porphyrin‐based polymers is
greatly affected by the synthesis conditions. FE‐TEM
images show that TFP‐pyrrole and TFP‐DPM are assem-
bled as spherical particles with diameters ranging from
1
.0 to 3.5 μm (Figure 2a,b). When using trifluoroacetic
TABLE 1 Comparison of porosity of the polymers
2
−1
3
−1
Sample
S
BET (m g
)
Pore value (cm g
)
The average pore size (nm)
TFP‐pyrrole
TFP‐DPM
7.6
0.0046
0.0142
0.0913
0.5782
0.8170
4.8
6.6
17.2
30.8
TFP‐DPM‐2
TFP‐DPM‐3
TFP‐DPM‐4
23.7
16.3
39.4
284.4
178.6
BET, Brunauer–Emmett–Teller; DPM, 2,2′‐dipyrrolylmethane; TFP, 1,3,5‐triformylphloroglucinol

6
of 12
CHEN ET AL.
FIGURE 2 Transmission electron microscopy images: (a) TFP‐pyrrole, (b) TFP‐DPM, (c) TFP‐DPM‐2, (d) TFP‐DPM‐3, (e)TFP‐DPM‐4, and
f) X‐ray photoelectron spectroscopy Mn2p spectra of Mn/TFP‐DPM. DPM, 2,2′‐dipyrrolylmethane; TFP, 1,3,5‐triformylphloroglucinol
(
TFP‐pyrrole, TFP‐DPM, and TFP‐DPM‐2 possessed a
compact surface. More importantly, the HR‐TEM image
shown in Figure 2d,e depicts a large number of randomly
oriented pores that were spread through the whole sam-
ples of TFP‐DPM‐3 and TFP‐DPM‐4.
The valence state of the active metal in the catalyst has
a great influence on the catalytic performance of the
catalyst. Therefore, to illustrate the chemical states of
manganese species in the Mn/TFP‐DPM‐3 catalyst, XPS
analysis was performed. Three prominent peaks at
pyrrole (Figure 3a–d) and TFP‐DPM (Figure 3e–h)
confirmed their micron‐scale spherical morphology.
Furthermore, the SEM images show that TFP‐DPM‐2
(Figure 3i–l) has a morphology of micron‐scale spheres
and nanosheets. As shown in Figure 3m–p and Figure
3q–t, TFP‐DPM‐3 and TFP‐DPM‐4 present nanosheet
accumulation. Moreover, the C, N, and O elements are
uniformly distributed in the porphyrin polymer structure
(Figure 3).
Selective oxidation of alcohol is one of the powerful
and useful tools to produce aldehydes and ketones, which
are significant intermediates in the synthesis of pharma-
ceuticals and agrochemicals. To evaluate and compare
the catalytic performance of manganese catalysts, 1‐
phenylethanol was selected as a model substrate in the
selective oxidation of alcohol. The effect of solvent and
reaction temperature on the yield of 1‐phenylethanol oxi-
dation was first studied and optimized. Heating a mixture
of 1‐phenylethanol and different oxidants in water
medium at 100 °C for 1 hr in the presence of Mn/TFP‐
DPM catalyst led to the formation of acetophenone (yield:
2
84.6, 401.0, and 531.2 eV corresponding to C1s, N1s,
and O1s are observed in Figure S3, confirming the pres-
[
50]
ence of C, N, and O in the Mn/TFP‐DPM catalyst.
Noticeably, no other significant peaks were found in the
XPS spectra. The nitrogen, oxygen, and manganese
content in the catalyst was 10.01%, 11.76%, and 1.38%,
respectively, according to the XPS data. Many burrs in
the high‐resolution manganese XPS spectral images can
be observed (Figure 2f). This maybe because the content
of manganese is extremely low in the catalyst, which is
well consistent with the AAS test result. In the fitted
3/2
1/2
curve, the XPS spectra of Mn 2p and Mn2p show
the characteristic peaks at 641.72 and 653.33 eV, indicat-
46.9%–68.3%; Table 2, entries 1–5). PhI(OAc) (PIDA) was
2
chosen as the oxidant, as it presented the highest oxida-
tive activity (68.3%) among all the oxidants (data not
shown). Noticeably, the additive also has a strong effect
3
+
ing that manganese exists in the Mn
Mn/TFP‐DPM catalyst.
state in the
[51,52]
The SEM images of TFP‐

CHEN ET AL.
7 of 12
FIGURE 3 Scanning electron microscopy images: (a–d) TFP‐pyrrole; (e–h) TFP‐DPM; (i–l) TFP‐DPM‐2; (m–p) TFP‐DPM‐3; (q–t) TFP‐
DPM‐4 and their corresponding element distribution. DPM, 2,2′‐dipyrrolylmethane; TFP, 1,3,5‐triformylphloroglucinol
on the catalytic performance in the selective oxidation of
alcohols. The usage of additive and organic/inorganic
mixed solvent can promote the smooth oxidation of alco-
hol at room temperature. Low to moderate yields were
obtained when using N(C H ) I, N(C H ) Br, CaCl , LiCl,
or KCl as additive (65.8%–80.9%, Table 2, Entries 6–10,
respectively). In sharp contrast, the KBr‐promoted reac-
tion achieved 92.6% yield at room temperature in an
ethanol/dichloromethane mixed solvent within 30 min.
Furthermore, in the next step, solvents were optimized,
which increased the yield overall. The highest yield
performed in the absence of Mn/TFP‐DPM or manganese
active species in TFP‐DPM. In both cases, the target prod-
uct cannot be detected (Table 2, Entries 18 and 19).
Mn/TFP‐pyrrole and Mn(OAc) ·4H O catalysts only
exhibited 64.7% and 72.7% yield, respectively, with the
same manganese content and reactive conditions as the
Mn/TFP‐DPM catalyst, indicating that the optimization
of pore parameters and active sites can indeed improve
the overall catalytic performance of the oxidation reac-
tion (Table 2, Entries 20 and 21). When air was used
instead of PIDA as the oxidant, the activity of the catalyst
was less than the original, indicating that the choice of
oxidant also has a significant impact on the oxidation of
2
2
4
9 4
4
9 4
2
(
(
95.7%) was obtained with 1,4‐dioxane as co‐solvent
Table 2, Entries 11–17). Control experiments were also

8
of 12
CHEN ET AL.
a
TABLE 2 Optimization of reaction conditions
b
Entry
T (°C)
Additive
Solvent
Oxidant
Conversion (%)
c
1
100
100
100
100
100
30
—
—
—
—
—
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
O
H
2
O
2
50.1
64.4
46.9
54.6
68.3
65.8
78.3
72.9
73.7
80.9
92.6
87.2
89.8
93.4
93.1
48.1
95.7
—
c
2
O
NaClO
TBHP
Air
c
3
O
c
4
O
c
5
O
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
—
6
7
8
9
N(C
N(C
4
4
H
9
9
)
)
4
4
I
O/DCM
30
H
Br
O/DCM
30
CaCl
LiCl
KCl
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
KBr
2
O/DCM
30
O/DCM
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
30
O/DCM
30
O/DCM
30
O/Methanol
O/Cyclohexane
O/Ethyl acetate
O/Petroleum ether
O/DMF
30
30
30
30
30
O/1,4‐Dioxane
O/DCM
d
e
30
30
O/DCM
—
30
O/DCM
64.7
62.7
88.4
98.3
94.5
88.2
f
30
O/DCM
g
i
30
O/1,4‐Dioxane
O/1,4‐Dioxane
O/1,4‐Dioxane
O/1,4‐Dioxane
30
PIDA
PIDA
PIDA
h
i
30
30
a
2
Reaction conditions: Mn mol% =0.125 mol % (Mn/TFP‐DPM); 1‐phenylethanol, 0.5 mmol; Oxidant, 3 eq; additive, 0.0006 eq; solvent: VH O/Vorganic sol-
vent = 2/1. Reaction performed at room temperature for 30 min.
b
Determined by gas chromatography analysis.
c
At 100 °C for 1 hr.
d
No catalyst was used.
e
Catalyst: TFP‐DPM.
f
Mn/TFP‐pyrrole.
f
Catalyst: Mn(OAc)
2
·4H
2
O.
g
i
Catalyst: Mn/TFP‐DPM‐2. Catalyst: Mn/TFP‐DPM‐3, 15 min.
h
Catalyst: Mn/TFP‐DPM‐4, 15 min.
i
No PIDA was used and in air atmosphere.DCM, dichloromethane; DMF, dimethylformamide; DPM, 2,2′‐dipyrrolylmethane; PIDA, iodobenzene diacetate;
TFP, 1,3,5‐triformylphloroglucinol,TBHP,tert‐Butyl hydroperoxide.
alcohol (Table 2, Entry 22). By contrast, the Mn/TFP‐
DPM‐2 catalyst with larger pore size and BET surface
area in the support material exhibited better activity
under the same reaction conditions (98.3%). Moreover,
Mn/TFP‐DPM‐3 and Mn/TFP‐DPM‐4 catalysts with
larger pore diameter and BET surface area exhibited bet-
ter activity than the Mn/TFP‐DPM‐2 catalyst, indicating
that the larger pore diameter and specific surface area
can contribute to improved catalytic performance
(Table 2, Entries 23–25).

CHEN ET AL.
9 of 12
Between 273 and 325 K, the apparent activation energy
E ) of C–H bond fracture was determined by Arrhenius
substances, additives, and solvent molecules is extremely
important for catalysis. Larger BET surface resulted in
utilization of more active sites over the heterogeneous
catalysts, enabling them to fully exert their catalytic per-
formance. According to Table 1, the pore size, pore value,
and surface area of Mn/TFP‐DPM‐3 are 2.5, 57.5, and 16.5
times that of Mn/TFP‐DPM, respectively. The activity of
Mn/TFP‐DPM‐3 is about three to five times higher than
that of Mn/TFP‐DPM, indicating that, among these fac-
tors, the pore diameter may be the main reason for the
difference in activity of Mn/TFP‐DPM‐3 and Mn/TFP‐
DPM. Activity and recycling performance are important
parameters for heterogeneous catalysts. Figure 4b shows
that Mn/TFP‐DPM‐3 and Mn/TFP‐DPM catalysts can be
easily centrifuged and reused at least six times without
any obvious loss of the catalytic activity, which is attrib-
uted to the built‐in nature of active sites in the polymer
skeleton. Noticeably, the effect of pore parameters on
the catalytic performance of the heterogeneous catalyst
is mainly reflected in the catalyst activity. However, no
obvious effect of pore parameters on the reusability of
the catalyst is noted. In addition, the hot filtration exper-
iment clearly suggested that the catalyst has a heteroge-
neous catalytic nature in the selective oxidation reaction.
Substrates expansion reaction are performed in an
(
a
[53]
plot (Figure 4 a).
The E values obtained by fitting
a
analysis were 10.68, 5.60, 2.80, and 0.72 kJ mol– for
1
Mn(OAc) ·4H O, Mn/TFP‐pyrrole, Mn/TFP‐DPM, and
2
2
Mn/TFP‐DPM‐3, respectively. Noticeably, porphyrin‐
based polymer‐supported catalysts possess lower Ea
values than homogeneous Mn(OAc) ·4H O catalyst in
2
2
the 1‐phenylethanol oxidation reaction, indicating that
porous porphyrin‐based polymer supports have positive
effect on the catalytic performance of the catalyst. More-
over, Mn/TFP‐DPM and Mn/TFP‐DPM‐3 exhibited lower
Ea values than the Mn/TFP‐pyrrole catalyst with fewer
substituents adjacent to the active sites (meaning lesser
steric hindrance adjacent to the active sites), suggesting
that the reduction of steric hindrance in the active center
can promote the oxidation of alcohols. In addition,
Mn/TFP‐DPM‐3 with larger surface area, pore size, and
pore volume in the catalyst also present lower E values
a
than Mn/TFP‐DPM, indicating that the increase of pore
size and specific surface area can further improve the cat-
alytic performance.
The model substrate of 1‐phenylethanol was almost
completely converted within 90 min on Mn/TFP‐DPM
catalyst (Figure 4b). By contrast, the TFP‐DPM‐3‐
supported
catalyst
Mn/TFP‐DPM‐3
significantly
optimized reactions: Mn catalyst (Mn catalyst =
increased the reaction rate, with about three to five time
superior activity than the Mn/TFP‐DPM catalyst. TFP‐
DPM‐3 polymer possessed larger surface area and pore
0.000125 mmol), substrates (0.1 mmol), PIDA (0.3 mmol),
and KBr(0.06% mol) in 3 ml H2O/1,4‐dioxane mixed sol-
vents at room temperature. The results summarized in
Table 3 show that Mn/TFP‐DPM and Mn/TFP‐DPM‐3
had high activity and selectivity for the oxidation of all
substrates, indicating the high universality of the Mn cat-
alyst. Substituted benzyl alcohols containing electron‐
donating groups such as OCF , C(CH ) , OCH , or CH
(Table 3, Entries 2–4) can be easily oxidized into their
corresponding carbonyl compounds over the Mn/TFP‐
DPM catalyst in 0.5 hr. Noticeably, the Mn/TFP‐DPM‐3
catalyst, with larger surface area, pore size, and pore vol-
ume can yield products in less than half the time required
2
–1
value, but average pore size (284.4 m g , 16.3 nm,
3
−1
0
.5782 cm g , respectively). Mass diffusion in the
porous catalyst is the main mechanism of heterogeneous
[
37]
catalysis, which is important for catalytic efficiency.
Smaller pore size in the porous heterogeneous catalysts
lead to larger diffusion limitation, especially for the
3
3 3
3
3
[37]
micropore, as its pore size is smaller than 2 nm.
Larger
pore volumes can accommodate more molecules, such as
substrates, products, additives, solvents. The approach-
ability of active sites in heterogeneous catalysts by
FIGURE 4 (a) Apparent activation energy (E
a
) of C–H bond fracture; (b) conversion versus time plots, reusability, and Arrhenius plots for
the oxidation 1‐phenylethanol over the catalysts

10 of 12
CHEN ET AL.
a
TABLE 3 Oxidation of alcohols in the exist of the catalysts
Mn/TFP‐DPM
Mn/TFP‐DPM‐3
b
b
Entry
1
Substrate
Time (hr)
Concentration (%)
Time (hr)
Concentration (%)
0.5
99.6
0.25
98.7
2
0.5
97.8
0.25
97.5
3
4
0.5
0.5
95.0
98.8
0.25
0.25
98.8
97.8
5
6
0.5
0.5
91.6
97.9
0.25
0.25
95.7
97.1
7
8
2.5
2.5
92.1
71.4
1.5
1.5
98.3
83.2
9
2.5
2.5
97.9
80.2
1.5
1.5
98.6
89.1
1
0
1
1
1
2
2.5
2.5
96.9
79.6
1.5
1.5
97.8
86.2
1
3
2.5
94.1
1.5
96.3
a
Reaction conditions: Mn catalyst (Mn catalyst = 0.000125 mmol), substrates (0.1 mmol), PIDA (0.3 mmol), and KBr(0.06% mol) in 3 ml H2O/1,4‐dioxane(2/1)
mixed solvents at room temperature.
b
Entries 1–6, the products were gathered and purified by column chromatography; Entries 7–13, the activity and selectivity were analyzed by gas
chromatography.
for oxidation of the alcohols into their corresponding
products. Heterocyclic aromatic carbonyl compounds
are very important intermediates in the synthesis of phar-
maceuticals and agrochemicals. 3‐Pyridinemethanol, a
heterocyclic alcohol, was also oxidized smoothly to its
corresponding aldehyde with excellent yield over
Mn/TFP‐DPM and Mn/TFP‐DPM‐3 in 30 and 15 min,
respectively (Table 3, Entry 6). In general, oxidation of
aliphatic alcohols into their corresponding aldehydes or
ketones is difficult. However, the Mn/TFP‐DPM and
Mn/TFP‐DPM‐3 catalysts can also be used for the oxida-
tion of various fatty alcohols, including primary and sec-
ondary linear fatty alcohols, as well as cyclic fatty
alcohols, to obtain their corresponding aldehydes or
ketones with excellent yields within 2.5 and 1.5 hr under
mild reaction conditions, respectively (Table 3, Entries 7–
13). The Mn/TFP‐DPM catalyst exhibited a moderate
turnover frequency(TOF) value of 1593.6 h , which is
higher than the activity of many precious metal catalysts
(Table S1), indicating that the catalyst exhibits excellent
catalytic performance in the selective oxidation of
alcohols.
–1
The possible mechanism (Scheme 1) of selective oxida-
tion alcohols was proposed based on Corey‐s mechanism:
(1) Br species is formed in aqueous solution by the reac-
2
tion of PhI(OAc) (oxidant) with KBr (additive) (R1). (2)
2

CHEN ET AL.
11 of 12
(
04201802203) for Young Teachers in Huanggang Normal
University. We are also grateful to the Analytical and
Testing Center of Huazhong University of Science and
Technology, ATC School of Chemistry and Chemical
Engineering, Wuhan, China.
ORCID
Jian Chen https://orcid.org/0000-0002-2602-9878
Dajian Zhu https://orcid.org/0000-0001-6500-0763
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