In situ bottom-up synthesis of porphyrin-based covalent organic frameworks

Article abstract of DOI:10.1021/jacs.9b10787

Synthesis and processing of two-or three-dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electrochemical deposition of poly(5,10,15,20-tetrakis(4-aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.

Full text of DOI:10.1021/jacs.9b10787

Subscriber access provided by WESTERN SYDNEY U
Communication
In Situ Bottom-up Synthesis of Porphyrin-
based Covalent Organic Frameworks
Elham Tavakoli, Arvin Kakekhani, Shayan Kaviani, Peng Tan, Mahdi Mohammadi
Ghaleni, Mohsen Asle Zaeem, Andrew M. Rappe, and Siamak Nejati
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b10787 • Publication Date (Web): 04 Dec 2019
Downloaded from pubs.acs.org on December 5, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 12
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
In Situ Bottom-up Synthesis of Porphyrin-based Covalent Organic Frameworks
a*
b*
c*
b,d
Elham Tavakoli , Arvin Kakekhani , Shayan Kaviani , Peng Tan , Mahdi Mohammadi
c
e
b
a,c
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Ghaleni , Mohsen Asle Zaeem , Andrew M. Rappe , Siamak Nejati
a
Department of Mechanical and Materials Engineering,
University of Nebraska-Lincoln, Lincoln, NE 68588-8286, USA
b
Department of Chemistry, University of Pennsylvania,
Philadelphia, Pennsylvania 19104-6323, USA
c
Department of Chemical and Biomolecular Engineering,
University of Nebraska-Lincoln, Lincoln, NE 68588-8286, USA
d
Department of Physics, Harbin Institute of Technology,
Harbin 150001, China
e
Department of Mechanical Engineering, Colorado School of Mines,
Golden, CO 80401-1887, USA
*
Contributed equally
KEYWORDS: covalent organic frameworks, porphyrin, Pyridine, Co-crystallization, crystalline
dendrite,  stacking, oxygen reduction reaction, density functional theory
ABSTRACT: Synthesis and processing of two- or three-dimensional covalent organic frameworks
(
COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on
the electrochemical deposition of poly(5,10,15,20-tetrakis (4-aminophenyl) porphyrin)-covalent organic
frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we
demonstrate the bottom-up synthesis of COF dendrites. Both experiment and density functional theory
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 12
(
DFT) underline the prominent role of pyridine, not only as a polymerization promoter, but as a stabilizing
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
sublattice, co-crystallizing with the framework. The crucial role of pyridine in dictating the structural
properties of such a co-crystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for
this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction (ORR)
in alkaline media, is reported.
Covalent organic frameworks (COFs) represent organized and intrinsically porous networks constructed
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
using a variety of rigid organic units. Among various building blocks of COFs, macrocyclic structures
such as phthalocyanine and porphyrin are of special interest due to their metal coordination chemistry.2-5
Having delocalized -electrons and high surface area, the porphyrin-based COFs (POR-COFs) have found
applications in optoelectronics, molecular electronics, separation, and catalysis.6-10 Despite the promise
of POR-COFs in electrocatalysis, especially in carbon dioxide and oxygen electroreduction, their
processing is hindered by their low solubilities.11-12 The electroreduction of oxygen on porphyrinic
structures is of special interest, as the respiratory enzymes with similar active centers catalyze this reaction
1
3
in-vivo, with an unsurpassed selectivity. Development of porphyrin-based ORR catalysts has thus been
an active research field,12, 14-16 achieving electrocatalytic activities comparable to those of Pt-based
catalysts.17-18 Here, we demonstrate a novel approach for assembling POR-COFs via in-situ
electrocrystallization of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin known as TAPP. We discuss the
1
9
importance of stacking the 2D-COF sheets and intercalated guest molecules in determining the structure
and subsequently the electrocatalytic activity of such frameworks.
We use a three-electrode electrochemical cell connected to a potentiostat for the electrodeposition of
TAPP. The electropolymerization is performed through galvanostatic, potentiostatic, and
potentiodynamic methods in a solution of TAPP monomer in dichloromethane, containing supporting
electrolyte salt and pyridine; a Ag/AgNO electrode and a platinum gauze are used as the reference and
3
counter electrodes, respectively. The polymerization proceeds via formation of radical cations of TAPP,
followed by a series of coupling reactions of the oxidized para-aminophenyl substituents. Initially,
diphenylamines form, and subsequently they convert to dihydrophenazines and phenazine linkages (see
Section 2.3 of the Supporting Information).16, 20
Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and X-ray
diffraction (XRD), shown in Figures S2-4, were performed to characterize the electrodeposited materials.
As shown in Figure 1a, atomic force microscope infrared spectroscopy (AFM-IR) reveals that the
deposited films on the glassy carbon (GC) electrode possess dendritic structures and are organic. The
deposited films remain stable upon lifting and transfer to a polar aprotic solvent such as acetonitrile (see
Figures S5 and S6). The IR spectra of the dendrites (see Figure 1b) agree with the FTIR spectra of the
2
ACS Paragon Plus Environment

Page 3 of 12
Journal of the American Chemical Society
2
0
free-standing polymeric film of TAPP (pTAPP), synthesized after Walter et al. As shown in Figures 1b
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
-1
-1
and S2, the characteristic peaks of pTAPP appeared between 1000-1100 cm and 1660-1630 cm . We
assigned the former to the C-H deformations of the phenyl rings, beta-pyrrolic, and phenazine ring, and
the latter to the C=C and C=N of phenazine ring vibrations.21-22 XPS reveals that the films are organic,
-
and a small content of fluorine in the samples was assigned to the residual hexafluorophosphate (PF )
6
anion (section 3.2 of Supporting Information). The X-ray diffractograms for the pTAPP dendrites,
deposited on gold and GC electrodes, are shown in Figures 2a and 4S, respectively. The diffraction
patterns demonstrate a distinct peak at 15.8 degrees. This peak is the fingerprint of crystalline pTAPP,
corresponding to an interlayer distance of 5.60 Å for the stacked 2D-COF sheets. However, such spacing
is unexpectedly large for COFs.23-25 Our DFT calculations reveal that the pyridine molecules can
intercalate within the pTAPP network and increase the interlayer spacing between the 2D sheets (see
Figure 2a). Our calculations suggest that the experimental samples possess a (6:1) ratio of pyridine to
TAPP (Figure 2b). Such a structure is polymorphous; for example, for each TAPP molecule, zero, one or
two out of the six pyridine molecules (denoted by 6Py-0, 6Py-1 and 6Py-2, respectively), can be located
between the stacked porphyrin rings. These configurations are close in energy (within 2 meV per atom)
and can be thermally explored. The simulated XRD patterns for a few such structures are shown in Figure
2a. A common feature among these patterns is the peak appearing around 15.8 degrees.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 1. (a) AFM height image of pTAPP, electrodeposited on GC electrode. (b) FT-IR spectra of a spot
(the blue circle in (a)) on the dendrite. The electropolymerization was carried out in a 5% v/v pyridine in
dichloromethane solution containing 0.25 mM TAPP and 0.05 M TEA(PF ) as the supporting electrolyte
6
salt.
3
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 12
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 2. (a) Experimental XRD pattern of Py-POR-COF electropolymerized on a gold substrate, along
with the DFT-predicted XRD patterns for a few heterostructures with 6 pyridines per pTAPP unit. The
electropolymerization of TAPP was carried out in a solution containing 0.25 mM TAPP and 0.05 M
TEA(PF ) as the supporting electrolyte salt, and 5% v/v pyridine in dichloromethane. (b) The DFT-
6
derived structure for the lowest internal-energy structure with 6 pyridines (6Py-2). The color code for
COF is: C (black), N (blue) and H (white). For pyridine: C (gray), N (cyan), and H (magenta). The a, b
and c axes are the cell lattice vectors.
Here, the non-planar geometry of TAPP (see Figure S16) forces the resulting POR-COF structure into an
inclined (J-aggregate) stacking, allowing accommodation of the maximal - stacking between the
layers.23, 26 Additionally, the pyridine additive not only neutralizes protonated amine groups and increases
the polymerization efficiency,20 but also stabilizes the overall heterostructure and improves the
crystallinity through co-electrocrystallization with the pTAPP. This phenomenon is presented in Figure
3d, where the intercalated pyridine is shown to stabilize the internal energy of the whole system. The
structure with four pyridines (per TAPP) is a thermodynamic sink, when the internal energy contribution
alone is considered. Comparing Young’s moduli of structures with four and six pyridines (4- and 6-Py),
shown in Figure 3e, we find that the latter is considerably softer. This softness and the excess free volume
of the 6-Py structures lead to increased entropy and lower Gibbs free energy for the system. Therefore,
we expect entropy stabilization to play a role in experimental realization of the 6-Py phase (for more
details see Section 4 of the Supporting Information). By examining Figures 3a-c and Figure 2b, we note
that increasing the pyridine content enhances the tilting of the J-aggregate stacking. This phenomenon is
concomitant with an increase in the estimated interlayer distance. Nonetheless, the average values for the
peak position in the simulated XRD, shown in Figure 2a, are slightly higher when compared with the
position of the peak in the experimental result. We attribute this discrepancy to the out-of-plane thermal
4
ACS Paragon Plus Environment

Page 5 of 12
Journal of the American Chemical Society
expansion of the structure, not accounted for in DFT models. For details on the elastic moduli and other
DFT calculations, see Section 4 of the Supporting Information.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 3. The DFT-derived structures for Py-POR-COF with 0 (a), 1 (b) and 4 (c) intercalated pyridines.
The color code for the atoms is the same as in the previous figure. (d) Binding energy (BE) of pyridine
(Py) in Py-POR-COF computed relative to the bare stacked COF and bulk pyridine phase. (e) Young’s
modulus for some relevant material phases.
In order to understand the parameters influencing the morphology of pTAPP, we performed a set of
electropolymerization experiments. Figure 4a demonstrates the morphological changes of pTAPP as a
function of temperature and potential scanning rate. The statistical analyses of the SEM images (Figure
S8) suggest that the dendrite size increases at lower temperatures or higher scan rates. It has been
previously proposed that dendrite growth during electropolymerization is governed by the linear and
spherical diffusion of the active species to the electrode surface.27-29 Here, we assume that the dendrite
1
7
growth starts with the initial coverage of the substrate by pTAPP nanowire networks. Soon after the
dendrite nucleation takes place, due to the spherical diffusion on the nuclei and protrusions (Figure 4d),
3
0
pTAPP crystals grow from the edges of {110} planes. The impact of the diffusion boundary layer on
the electropolymerization of TAPP and the formation of dendrites are discussed in Section 3.6 of the
Supporting Information. To elucidate the effect of substrate on the electropolymerization of TAPP, we
performed experiments on substrates with various surface energies and roughness factors. As shown in
Figures S11-15, a smoother surface favors formation of larger dendrites by providing fewer possible
nucleation sites; therefore, greater distances may exist between nuclei, permitting growth of larger
dendrites.
5
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 12
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 4. (a) SEM images of pTAPP films, electrodeposited with scan rates of 2 mV/s, 10 mV/s, and
o
o
o
5
0 mV/s at temperatures of 5 C, 25 C, and 35 C on GC (scale bar is 50 m). (b) Dendrite angle of the
o
pTAPP electrodeposited with a scan rate of 2 mV/s at 5 C. (c) SEM image of the pTAPP dendrite
o
supported on an amorphous pTAPP, deposited on GC electrode at 2 mV/s and 5 C. The scale bar in the
inset is 300 nm. (d) The schematic mechanism of dendrite formation during the electropolymerization of
pTAPP. Electropolymerization is carried out in a 5% v/v pyridine in dichloromethane solution containing
0.25 mM TAPP and 0.05 M TEA(PF6).
We evaluate the ORR electrocatalytic performance of the Py-POR-COF films, deposited on GC
electrodes, using a three-electrode electrochemical cell, in an aqueous phosphate buffer solution (PBS).
The experimental procedure is reported in Section 5 of the Supporting Information. Figure 5a presents the
cyclic voltammograms of the prepared films in the electrolyte solutions. For the electrolyte saturated with
oxygen, a salient cathodic peak is observed at ≈ 0.54 V versus reversible hydrogen electrode (RHE). We
attribute this peak to the oxygen electroreduction on the deposited frameworks.
We performed rotating disk experiments on the coated electrodes and used the Koutecky-Levich (K-L)
equation to obtain the electron transfer number (n). The estimated values for n were found to be 3.21±0.51
and 3.97±0.44, for the wire- and dendrite-like samples, respectively. These values suggest that the ORR
3
1
is taking place via mixed two- and four-electron pathways (Figure S21). The larger n for the Py-POR-
COF, compared to the wire-like pTAPP, points to the superior electrocatalytic activity of Py-POR-COF.
Changing the potential scanning rate used for electrodeposition, we observed a change in the onset
potential of the cathodic waves and the normalized ORR current density (Figure S22). As mentioned
earlier, morphology of the electropolymerized Py-POR-COF is also correlated with the scan rate.
Comparing these morphologies (Figure 4a) to the voltammograms in Figure 5b and S22 reveals that the
6
ACS Paragon Plus Environment

Page 7 of 12
Journal of the American Chemical Society
films with larger crystalline dendrites display higher ORR activity. We expect that such enhanced
electrocatalytic activity is correlated with a better crystal quality, i.e., lower density of structural defects
and a more ordered arrangement of the Py-POR-COFs, leading to better charge mobility (relative to the
amorphous structures).17, 32-35 In addition to temperature, scan rate and electrode material, the stabilizing
effect of pyridine is yet another factor contributing to the ordered networks of (pyridine-mediated) -
stacked COFs (Figure S23). For more details on the enhancement of charge mobility and ORR, see Section
S5 of the Supporting Information.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
The pyridine co-crystallization leads to an increased interlayer distance. Hence, in addition to the surface
binding sites, the enlarged spacing allows the oxygen species to explore the 3D binding motifs, created
by the stacked COF layers. Such motifs (and the resulting confinement) can potentially change the
energetics of the ORR intermediates, break some scaling relations and improve the current density.36-39
Additionally, the stacking pattern, by changing the interlayer vdW and - interactions, can change the
energetics of different reaction intermediates, and, consequently, the overall catalytic activity. The
important role of vdW interactions in tuning the catalytic activity of 2D materials has been previously
reported.40-41
Figure 5. The electrocatalytic activity of Py-POR-COF in ORR. (a) The cyclic voltammogram of a Py-
POR-COF in a phosphate buffer solution (PBS) (pH=13) deaerated with argon (Ar) and saturated with
oxygen (O ). The film was deposited at 25 C and a scan rate of 50 mV/s. (b) The normalized cyclic
2
voltammogram of Py-POR-COF films in an O -saturated PBS with (pH=13), presenting a correlation
2
between Py-POR-COF crystallinity and the ORR catalytic performance. The potential scanning rate for
ORR was set at 20 mV/s. The scale bars on the SEM image are 60 m. Here, (i), (ii) and (iii) represent
the respective structure of the samples prepared at a deposition temperature of 25 C.
In summary, we reported the in situ electropolymerization of porphyrin derivatives (TAPP) and the
formation of crystalline domains (Py-POR-COF). We investigated the parameters influencing the
7
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 12
electropolymerization of TAPP and developed a methodology to control the growth and deposition of
COFs. We demonstrated that the highly-ordered 3D stacking of the Py-POR-COFs enhances the ORR
activity of the sample. High crystalline order is achieved by controlling the temperature, potential
scanning rate, electrode materials, and through co-crystallization with pyridine. The pyridine sublattice
not only stabilizes the Py-POR-COF superlattice, but it also controls the interlayer spacing and stacking
in this class of materials.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI:
General procedures, experimental details of synthesis, electrochemistry studies, and DFT calculations.
1
Characterizations, containing FT-IR, H-NMR spectra, XRD data and crystal structures, SEM images,
AFM images, and stability test. Additionally, the DFT-derived .cif files which contain the structural
information of the systems discussed in this paper are available online for readers interested in the
crystallographic aspects of our systems.
AUTHOR INFORMATION
Corresponding Author
*
snejati2@unl.edu
ORCID
Elham Tavakoli: http://orcid.org/0000-0002-2077-0577
Arvin Kakekhani: https://orcid.org/0000-0002-8553-7776
Shayan Kaviani: http://orcid.org/0000-0002-9868-7757
Mahdi Mohammadi Ghaleni: http://orcid.org/0000-0002-9824-450X
Mohsen Asle Zaeem: https://orcid.org/0000-0002-5164-6122
Andrew M. Rappe: https://orcid.org/0000-0003-4620-6496
Siamak Nejati: http://orcid.org/0000-0002-1807-2796
Notes
The authors declare no competing financial interest.
8
ACS Paragon Plus Environment

Page 9 of 12
Journal of the American Chemical Society
ACKNOWLEDGMENT
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
The research was performed in part in the Nebraska Nanoscale Facility: National Nanotechnology
Coordinated Infrastructure and the Nebraska Center for Materials and Nanoscience, which are supported
by the National Science Foundation under Award ECCS: 1542182, and the Nebraska Research Initiative.
A.K. and A.M.R. acknowledge the support of the US Department of Energy, Office of Basic Energy
Sciences, under grant DE-SC0019281. PT acknowledges the scholarship from Chinese Scholarship
Council (CSC). We also acknowledge computational support from NERSC of the DOE.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
REFERENCES
1
.
Kandambeth, S.; Dey, K.; Banerjee, R., Covalent Organic Frameworks: Chemistry beyond the
Structure. J. Am. Chem. Soc. 2019, 141 (5), 1807-1822.
Lin, G.; Ding, H.; Yuan, D.; Wang, B.; Wang, C., A pyrene-based, fluorescent three-dimensional
covalent organic framework. J. Am. Chem. Soc. 2016, 138 (10), 3302-3305.
Day, N. U.; Wamser, C. C.; Walter, M. G., Porphyrin polymers and organic frameworks. Polym.
Int. 2015, 64 (7), 833-857.
Chen, X.; Gao, J.; Jiang, D., Designed synthesis of porphyrin-based two-dimensional covalent
organic frameworks with highly ordered structures. Chem. Lett. 2015, 44 (9), 1257-1259.
Liu, Q.-Y.; Li, J.-F.; Wang, J.-W., Research of covalent organic frame materials based on porphyrin
units. J. Inclusion Phenom. Macrocyclic Chem. 2019, 1-15.
Pachfule, P.; Acharjya, A.; Roeser, J. r. m.; Langenhahn, T.; Schwarze, M.; Schomäcker, R.;
2
.
3
.
4
.
5
.
6
.
Thomas, A.; Schmidt, J., Diacetylene functionalized covalent organic framework (COF) for photocatalytic
hydrogen generation. J. Am. Chem. Soc. 2018, 140 (4), 1423-1427.
7
.
Huang, N.; Krishna, R.; Jiang, D., Tailor-made pore surface engineering in covalent organic
frameworks: systematic functionalization for performance screening. J. Am. Chem. Soc. 2015, 137 (22),
7
8
079-7082.
Lin, S.; Diercks, C. S.; Zhang, Y.-B.; Kornienko, N.; Nichols, E. M.; Zhao, Y.; Paris, A. R.; Kim, D.;
.
Yang, P.; Yaghi, O. M., Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2
reduction in water. Science 2015, 349 (6253), 1208-1213.
9
.
Diercks, C. S.; Lin, S.; Kornienko, N.; Kapustin, E. A.; Nichols, E. M.; Zhu, C.; Zhao, Y.; Chang, C. J.;
Yaghi, O. M., Reticular electronic tuning of porphyrin active sites in covalent organic frameworks for
electrocatalytic carbon dioxide reduction. J. Am. Chem. Soc. 2018, 140 (3), 1116-1122.
10.
frameworks. J. Am. Chem. Soc. 2017, 139 (25), 8705-8709.
1. Yang, S.; Hu, W.; Zhang, X.; He, P.; Pattengale, B.; Liu, C.; Cendejas, M.; Hermans, I.; Zhang, X.;
Lin, G.; Ding, H.; Chen, R.; Peng, Z.; Wang, B.; Wang, C., 3D porphyrin-based covalent organic
1
Zhang, J., 2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO2
Reduction. J. Am. Chem. Soc. 2018, 140 (44), 14614-14618.
1
2.
oxygen reduction catalysis. J. Am. Chem. Soc. 2017, 139 (4), 1424-1427.
13. Peljo, P.; Murtomäki, L.; Kallio, T.; Xu, H.-J.; Meyer, M.; Gros, C. P.; Barbe, J.-M.; Girault, H. H.;
Oldacre, A. N.; Friedman, A. E.; Cook, T. R., A self-assembled cofacial cobalt porphyrin prism for
Laasonen, K.; Kontturi, K. s., Biomimetic oxygen reduction by cofacial porphyrins at a liquid–liquid
interface. J. Am. Chem. Soc. 2012, 134 (13), 5974-5984.
9
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 10 of 12
1
4.
oxygen reduction reaction. J. Am. Chem. Soc. 2012, 134 (15), 6707-6713.
15. Friedman, A.; Landau, L.; Gonen, S.; Gross, Z.; Elbaz, L., Efficient Bio-Inspired Oxygen Reduction
Electrocatalysis with Electropolymerized Cobalt Corroles. ACS Catal. 2018, 8 (6), 5024-5031.
6. Day, N. U.; Wamser, C. C., Poly-tetrakis-5, 10, 15, 20-(4-aminophenyl) porphyrin Films as Two-
Jahan, M.; Bao, Q.; Loh, K. P., Electrocatalytically active graphene–porphyrin MOF composite for
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
Electron Oxygen Reduction Photoelectrocatalysts for the Production of H2O2. J. Phys. Chem. C 2017,
121 (21), 11076-11082.
1
7.
derived from a Co-porphyrin-based covalent organic framework. Electrochem. Commun. 2015, 52, 53-
7.
18.
porphyrin for electrocatalytic oxygen reduction. Chin. Chem. Lett. 2019, 30 (4), 911-914.
9. Hisaki, I.; Affendy, N. E.; Tohnai, N., Precise elucidations of stacking manners of hydrogen-bonded
two-dimensional organic frameworks composed of X-shaped π-conjugated systems. CrystEngComm
Ma, W.; Yu, P.; Ohsaka, T.; Mao, L., An efficient electrocatalyst for oxygen reduction reaction
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
Zhao, C.-X.; Li, B.-Q.; Liu, J.-N.; Huang, J.-Q.; Zhang, Q., Transition metal coordinated framework
1
2
2
017, 19 (33), 4892-4898.
0. Walter, M. G.; Wamser, C. C., Synthesis and characterization of electropolymerized
nanostructured aminophenylporphyrin films. J. Phys. Chem. C 2010, 114 (17), 7563-7574.
21.
2
2
1
Hu, Y. Two-dimensional (2D) functional molecular networks. UCL (University College London),
Bidman, T., Oxidation of 2-alkyl-5, 10-dihydrophenazines. Russ. J. Gen. Chem. 2004, 74 (9), 1433-
Hayashi, T.; Hijikata, Y.; Page, A.; Jiang, D.; Irle, S., Theoretical analysis of structural diversity of
016.
2.
434.
23.
covalent organic framework: Stacking isomer structures thermodynamics and kinetics. Chem. Phys. Lett.
016, 664, 101-107.
24. Chen, R.; Shi, J. L.; Ma, Y.; Lin, G.; Lang, X.; Wang, C., Designed Synthesis of a 2D Porphyrin-Based
2
sp2 Carbon-Conjugated Covalent Organic Framework for Heterogeneous Photocatalysis. Angew. Chem.,
Int. Ed. 2019, 58 (19), 6430-6434.
2
N.; Becker, D.; Addicoat, M.; Senkovska, I., Nonlinear Optical Switching in Regioregular Porphyrin
Covalent Organic Frameworks. Angew. Chem. 2019, 131 (21), 6970-6974.
5.
Biswal, B. P.; Valligatla, S.; Wang, M.; Banerjee, T.; Saad, N. A.; Mariserla, B. M. K.; Chandrasekhar,
2
6.
Keller, N.; Calik, M.; Sharapa, D.; Soni, H. R.; Zehetmaier, P. M.; Rager, S.; Auras, F.; Jakowetz, A.
C.; Görling, A.; Clark, T., Enforcing extended porphyrin J-aggregate stacking in covalent organic
frameworks. J. Am. Chem. Soc. 2018, 140 (48), 16544-16552.
2
7.
Appl. Mater. Interfaces 2018, 10 (31), 26320-26327.
8. Bae, S.; Kim, H.; Lee, H. S., Formation mechanism of PbTe dendritic nanostructures grown by
electrodeposition. Mater. Chem. Phys. 2017, 187, 82-87.
9. Ding, F.; Xu, W.; Graff, G. L.; Zhang, J.; Sushko, M. L.; Chen, X.; Shao, Y.; Engelhard, M. H.; Nie, Z.;
Hao, F.; Verma, A.; Mukherjee, P. P., Mesoscale Complexations in Lithium Electrodeposition. ACS
2
2
Xiao, J., Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem.
Soc. 2013, 135 (11), 4450-4456.
3
0.
Electrochemical production of metal powders, Springer: 2012; pp 1-62.
1. Kaviani, S.; Mohammadi Ghaleni, M.; Tavakoli, E.; Nejati, S., Electroactive and Conformal
Popov, K. I.; Nikolić, N. D., General theory of disperse metal electrodeposits formation. In
3
Coatings of Oxidative Chemical Vapor Deposition Polymers for Oxygen Electroreduction. ACS Appl.
Polym. Mater. 2019, 1 (3), 552-560.
10
ACS Paragon Plus Environment

Page 11 of 12
Journal of the American Chemical Society
3
2.
Lin, C. Y.; Zhang, D.; Zhao, Z.; Xia, Z., Covalent organic framework electrocatalysts for clean energy
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
conversion. Adv. Mater. 2018, 30 (5), 1703646.
33. Kim, T. W.; Jun, S.; Ha, Y.; Yadav, R. K.; Kumar, A.; Yoo, C.-Y.; Oh, I.; Lim, H.-K.; Shin, J. W.; Ryoo,
R., Ultrafast charge transfer coupled with lattice phonons in two-dimensional covalent organic
frameworks. Nat. Commun. 2019, 10 (1), 1873.
3
4.
electrocatalytic activity on crystalline carbon-conjugated g-C3N4. ACS Catal. 2018, 8 (3), 1926-1931.
5. Scholes, D. T.; Yee, P. Y.; Lindemuth, J. R.; Kang, H.; Onorato, J.; Ghosh, R.; Luscombe, C. K.; Spano,
Niu, W.; Marcus, K.; Zhou, L.; Li, Z.; Shi, L.; Liang, K.; Yang, Y., Enhancing electron transfer and
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
F. C.; Tolbert, S. H.; Schwartz, B. J., The Effects of Crystallinity on Charge Transport and the Structure of
Sequentially Processed F4TCNQ-Doped Conjugated Polymer Films. Adv. Funct. Mater. 2017, 27 (44),
1702654.
3
2
37.
6.
015, 2 (2), 140-143.
Christensen, R.; Hansen, H. A.; Dickens, C. F.; Nørskov, J. K.; Vegge, T., Functional independent
scaling relation for ORR/OER catalysts. J. Phys. Chem. C 2016, 120 (43), 24910-24916.
8. Wan, H.; Østergaard, T. M.; Arnarson, L.; Rossmeisl, J., Climbing the 3D Volcano for the Oxygen
Reduction Reaction Using Porphyrin Motifs. ACS Sustainable Chem. Eng. 2018, 7 (1), 611-617.
39. Szécsényi, Á.; Khramenkova, E.; Chernyshov, I. Y.; Li, G.; Gascon, J.; Pidko, E. A., Breaking Linear
Vojvodic, A.; Nørskov, J. K., New design paradigm for heterogeneous catalysts. Natl. Sci. Rev.
3
Scaling Relationships with Secondary Interactions in Confined Space: A Case Study of Methane Oxidation
by Fe/ZSM-5 Zeolite. ACS Catal. 2019, 9 (10), 9276-9284.
4
0.
2016, 18 (42), 29092-29100.
1. Tsai, C.; Abild-Pedersen, F.; Nørskov, J. K., Tuning the MoS2 edge-site activity for hydrogen
Gutzler, R., Band-structure engineering in conjugated 2D polymers. Phys. Chem. Chem. Phys.
4
evolution via support interactions. Nano Lett. 2014, 14 (3), 1381-1387.
11
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 12 of 12
"
For Table of Contents Only"
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
12
ACS Paragon Plus Environment