Transactions of Tianjin University (2022) 28:73–79

https://doi.org/10.1007/s12209-021-00305-8

RESEARCH ARTICLE

Electroreduction of Carbon Dioxide by Heterogenized Cofacial

Porphyrins
Pengfei Tian1 · Jianjun Su2 · Yun Song2 · Ruquan Ye2,3 · Minghui Zhu1

Received: 2 July 2021 / Revised: 12 July 2021 / Accepted: 16 July 2021 / Published online: 3 August 2021
© The Author(s) 2021

Abstract
Great attention has been paid to cofacial porphyrins due to their many unique advantages over their monomeric analogs.
However, their synthesis is usually complicated. In this work, a facile impregnation method for preparing heterogenized,
cofacially stacked porphyrins is proposed. An anionic porphyrin is introduced as an underlayer for immobilization of cationic
cobalt porphyrin via electrostatic force. The metal center of the underlying molecule contributes to the electronic structure
of the upper cationic cobalt porphyrin. Screening reveals the anionic iron porphyrin to be the most efficient underlayer
molecule, lowering the activation energy barrier of ­CO2 electroreduction, with an improved turnover frequency by 74% to
8.0 ­s−1 at − 0.6 V versus RHE.

Keywords CO2RR · Porphyrin · Cofacial · Heterogenization

Introduction dehydrogenase, much effort has been devoted to designing

cofacial systems with two porphyrin units [10–14], prob-
Metal porphyrins have received great attention as catalysts ably because the presence of two metal centers can dis-
because of the clear molecular structures, which is benefi- tribute the demands for redox and coordination numbers
cial for understanding the structure–activity relationships. across two sites to favor reactions involving the multielec-
Besides, the electronic structure of the catalytically active tron transfer and a cofacial configuration could optimize
metal center, coordinated with four nitrogen atoms, could be the transition state energy level and therefore result in a
effectively tuned by the surrounding ligands [1–4]. So far, more enhanced activity than their monomeric analogs [15].
there have been a variety of porphyrin-based molecular cata- In the past decade, the synthesis of numerous cofacial por-
lysts reported active for oxygen reduction reaction, oxygen phyrin catalysts has been reported for different reactions
evolution reaction, hydrogen evolution reaction, and ­CO2 [16–21]. Taking the ­CO2RR, an essential reaction to miti-
electroreduction ­(CO2RR) [5–9]. gate greenhouse ­CO2 emissions, as an example [22, 23].
Motivated by natural enzymes with dual metal cent- Mohamed et al. [24] reported a cofacial iron tetraphenyl
ers, such as cytochrome c oxidase and carbon monoxide porphyrin (FeTPP) dimer for electrochemical ­CO2-to-CO
reduction in DMF/H2O solution, achieving high Faradaic
efficiency (FE) of 95% and outstanding turnover frequency
* Ruquan Ye (TOF) number of 4300 ­s−1 at a moderate overpotential of
[email protected]
660 mV. They further assembled the cofacial molecule onto
* Minghui Zhu a fluorine-doped tin oxide electrode with a phosphonic acid
[email protected]
anchor, showing high activity and stability for ­CO2RR in
1
State Key Laboratory of Chemical Engineering, School aqueous electrolytes [10]. Zahran et al. [25] demonstrated
of Chemical Engineering, East China University of Science that the substituents on cofacial porphyrin rings greatly
and Technology, Shanghai 200237, China affected the catalysis process, and electron-donating groups
2
State Key Laboratory of Marine Pollution, Department such as mesityl could lead to increased TOF values. The
of Chemistry, City University of Hong Kong, concept of cofacial porphyrins has also been extended to
Hong Kong 999077, China
fabricating the porous organic cage composed of six iron
3
City University of Hong Kong Shenzhen Research Institute, porphyrin units. The supramolecular catalyst produced CO
Shenzhen 518057, China

13
Vol.:(0123456789)
74 P. Tian et al.

with near-quantitative Faradaic efficiency, with activities Experimental

reaching 55250 turnovers [26].
However, the synthesis of cofacial porphyrins usually Catalyst Synthesis
involves a series of complicated procedures preventing their
large-scale production. Herein, the neutral tetraphenyl por- Reduced graphene oxide (rGO, surface area 500 m ­ 2/g) was
phyrin molecules are functionalized with cationic methylani- purchased from Tokyo Chemical Industry Co., Ltd. and used
linium (–N(CH3)3+) and anionic sulfonate groups (–SO3−) as received. Cobalt tetra-(4-N,N,N-trimethylanilinium) por-
(Scheme 1), with the electrostatic interaction between these phyrin (CoTMAP), cobalt tetrasulfonatophenyl porphyrin
two substituents driving the self-assembly of the cofacial tetrasodium (CoTSPP), iron tetrasulfonatophenyl porphy-
porphyrin system. Characterization measurements, elec- rin tetrasodium (FeTSPP), and nickel tetrasulfonatophenyl
trochemical analysis, and density functional theory (DFT) porphyrin tetrasodium (NiTSPP) were synthesized using a
calculations reveal a strong electronic interaction between reported procedure [27]. Cofacial porphyrins supported on
the metal centers, significantly decreasing the reaction bar- rGO were prepared by two-step incipient wetness impreg-
rier and resulting in a more improved ­CO2RR performance. nation (Fig. 1a). Briefly, CoTSPP (1.5 mg) was dissolved in
deionized water and impregnated on rGO (36.5 mg). The

Scheme 1  Molecular structures

of a CoTMAP and b CoTSPP

Fig. 1  a Two-step impregnation

method to synthesize cofacial
porphyrins supported on rGO.
b TEM image, STEM image,
and the corresponding EDX
maps for C, Co, and N of the
as-prepared Co/Co-Por catalyst.
c XPS spectrum showing the
Co ­2p3/2 signals and d UV–Vis
spectra for CoTMAP, CoTSPP,
and Co/Co-Por

13
Electroreduction of Carbon Dioxide by Heterogenized Cofacial Porphyrins 75

mixture was aged for 12 h followed by vacuum drying at 𝜈⋅x

⋅n⋅F
22400×60
80 ℃ overnight. A second impregnation step was then con- FEi =
I
ducted to further impregnate CoTMAP (2 mg). Again, a 12-h
aging step was performed to allow a sufficient interaction where i represents CO or ­H2; x is the concentration of CO
between the CoTMAP and CoTSPP molecules. The result- or ­H2; ν is the feeding rate of ­CO2; n is the electron transfer
ing catalyst, denoted as Co/Co-Por, was eventually dried in number (2, for both CO and ­H2); F is the Faradaic con-
a vacuum oven at 80 ℃ overnight. The same procedures stant (96,485 C/mol); and I is the average current during
were also done to prepare the Ni/Co-Por and Fe/Co-Por cata- electrolysis.
lysts, but using NiTSPP and FeTSPP, respectively, in the
first impregnation step. Inductively coupled plasma-atomic
Theoretical Calculation
emission spectroscopy (ICP-OES) was carried out to calcu-
late the actual Co contents in Co/Co-Por, Ni/Co-Por, and Fe/
DFT calculations were performed using the Gaussian09 at
Co-Por of 0.51%, 0.24%, and 0.26%, respectively, which are
the PBE0 level using the LanL2DZ basis set [28–31] for
close to their nominal values.
metal atoms (Fe, Co, and Ni) and 6-31G(d) basis set for
non-metal atoms (H, N, C, O, and S).
Catalyst Characterizations

ICP measurements were conducted using an Agilent 725

ICP-OES. Catalyst morphology was analyzed using a JEOL Results and Discussion
JEM-2100F field emission source transmission electron
microscope (TEM) operating at 200 kV. X-ray photoelectron Incipient wetness impregnation can allow anionic porphy-
spectroscopy (XPS) analysis was obtained using a Thermo rins to uniformly immobilize onto the rGO support through
ESCALAB 250Xi spectrometer equipped with a mono- π–π interactions and sufficient interaction between the cati-
chromatic AlK radiation source (1486.6 eV, pass energy onic porphyrins and anionic ones through electrostatic force.
20.0 eV). The diffuse reflectance UV–Vis spectrum was Figure 1b shows the TEM image of the as-prepared Co/Co-
recorded in the 200–800 nm range using a UV–Vis spectro- Por catalyst with a clean two-dimensional morphology. The
photometer (Lambda 750, PerkinElmer, Inc.). energy-dispersive X-ray spectroscopy (EDS) maps also show
the uniform distribution of C, N, and Co and no apparent
Electrochemical Measurements aggregates. To verify, we also prepared the hybrid catalyst
at a high loading by impregnating 15 mg of CoTSPP on
To prepare the working electrode, the catalyst powder (5 mg) 35 mg of rGO. The resulting catalyst shows many porphyrin
and Nafion solution (13 μL, 5 wt%, Sigma-Aldrich) were aggregates with an estimated average size of 5–10 nm (Fig.
dispersed in ethanol (1 mL, Aladdin, ACS, ≥ 99.5%) and S1). From this perspective, a low porphyrin loading, which
sonicated for 1 h to form a uniform catalyst ink. Then, the requires a dilute porphyrin-water solution for impregnation,
ink was drop cast onto carbon paper (Toray, TGP-H-060) is key to the successful preparation of the highly dispersed
to reach a catalyst loading of 0.1 mg/cm2. Its electrochemi- hybrid catalysts.
cal performance in C ­ O2 reduction was tested in a custom- XPS and UV–Vis spectroscopy were performed to study
ized H-cell separated by a Nafion 117 membrane. Platinum the electronic structure of Co/Co-Por. Figure 1c shows the
foil and a leak-free Ag/AgCl electrode (LF-2, Innovative XPS Co 2p spectrum showing Co ­2p3/2 peaks at 781.7 and
Instrument Inc.) were used as the counter and reference elec- 780.6 eV for CoTMAP and CoTSPP, respectively. The dif-
trodes, respectively. Before the experiments, sodium bicar- ferent binding energies of the Co 2­ p3/2 band are due to the
bonate (1.75 mL, 0.5 M, Sigma-Aldrich, ≥ 99.5%) solution distinct electronegativity features of the peripheral function-
was injected into the working and counter compartments. alities. The electron-withdrawing methylanilinium group
­CO2 was purged into the chambers for 10 min before elec- decreases the electron density around the Co center, while
trochemical polarization. Electrochemical responses were the electron-donating sulfonate group increases the elec-
recorded by a CHI650E potentiostat. Electrolyte resistance tron density around cobalt [27]. The two-porphyrin cofa-
between the reference and working electrodes was measured cial Co/Co-Por reveals a neutralized binding energy value
by potential electrochemical impedance spectroscopy and of 781.3 eV for the Co 2­ p3/2 signal, indicating the electrons
manually compensated. During the electrolysis, gas products within the stacked molecule system to be significantly redis-
were analyzed using an online gas chromatograph equipped tributed, as confirmed by the shifted Soret band for Co/Co-
with a Hayesep-D column, TCD detector, and FID detector. Por (419.8 nm) as compared to CoTMAP (426.3 nm) or CoT-
The Faradaic efficiencies of gas products were calculated SPP (413.4 nm) (Fig. 1d). The Q bands for all three samples
using the following equation: could hardly be distinguished from the strong background

13
76 P. Tian et al.

of rGO absorbance. The above results reveal the intimate catalyst. CoTSPP, NiTSPP, and FeTSPP have overall current
contact between the CoTMAP and CoTSPP molecules. densities of 1.4, 0.7, and 1.1 mA/cm2, respectively, at − 0.6 V
Ni/Co-Por and Fe/Co-Por were also prepared by introduc- versus RHE (Fig. S6), in agreement with our previous study
ing NiTSPP and FeTSPP as the sublayer porphyrins, respec- that ­CO2 reduction favors cationic substituents over neutral
tively, for systematically investigating the structure–activity or anionic ones [27]. Excellent selectivities toward CO pro-
relationship of cofacial porphyrins during the electrochemi- duction are shown by all tested catalysts, with F ­ ECO values
cal ­CO2 reduction. For comparison, monomeric CoTMAP, over 90% (Fig. 2b, Fig. S7).
CoTSPP, FeTSPP, and NiTSPP catalysts on rGO were also The resistances of the catalysts were investigated by AC
prepared at a content of 5 wt%. The EDS maps in Fig. S2 impedance analysis at an open-circuit voltage (OCV). The
confirm the highly disperse NiTSPP and CoTMAP in Ni/ Nyquist plots demonstrate that the four samples have similar
Co-Por and uniform distribution of FeTSPP and CoTMAP in interfacial charge transfer resistance (Rct), possibly due to the
Fe/Co-Por. In addition, the binding energies of the Co ­2p3/2 identical and low catalyst loading. TOF values were calcu-
signal are also found to shift in these two catalysts due to the lated for investigating the intrinsic reactivity of each catalyst
electronic interactions (Fig. S3). The steady-state electrore- based on the number of CoTMAP molecules on the top layer.
duction of C ­ O2 was conducted in a customized H-cell in a It could be argued that the underlying MTSPP may not be
­CO2-saturated 0.5 M N ­ aHCO3 electrolyte. Cyclic voltam- completely stacked (i.e., covered) and may still contribute
metry measurements show prominent reduction currents at to the reductive currents. Therefore, a set of H/Co-Por sam-
potentials more negative than approximately − 0.4 V ver- ples were prepared as a control with various ­H2TMAP load-
sus RHE (Fig. S4). CoTMAP exhibits a stable current at a ings for the second impregnation step. As described above,
potential of − 0.6 V versus RHE with an average current den- CoTSPP alone delivers a jCO of 1.3 mA/cm2 (Fig. 2c). The
sity of 4.6 mA/cm2 during 1 h of electrolysis (Fig. 2a, Fig. introduction of H­ 2TMAP, which is inactive for CO produc-
S5). Moreover, the activities for cofacial porphyrins follow tion, suppresses the current densities. This serves as direct
the order Fe/Co-Por (8.0 mA/cm2) > Co/Co-Por (6.5 mA/ proof that the cationic porphyrins preferentially graft on the
cm2) > Ni/Co-Por (5.7 mA/cm2). Current densities are much pre-deposited anionic porphyrins by electrostatic force and
lower in the sulfonate group functionalized metal porphyrin block the underlying metal centers from accessing the reac-
than in the methylanilinium group functionalized CoTMAP tants. The partial current density of CO becomes negligible

Fig. 2  a Overall current densi-

ties and b Faradaic efficiencies
of CO and ­H2 over CoTMAP
and cofacial porphyrins. c The
partial current density of CO
(jCO) over cofacial porphy-
rin containing CoTSPP and
­H2TMAP with different weight
ratios. d Calculated ­TOFCO val-
ues for CoTMAP and cofacial
porphyrin catalysts (reaction
was performed at − 0.6 V versus
RHE in a C ­ O2-saturated 0.5 M
­NaHCO3 electrolyte)

13
Electroreduction of Carbon Dioxide by Heterogenized Cofacial Porphyrins 77

Fig. 3  a Optimized structures

for Co/Co-Por with adsorbed
*COOH and *CO as well as
free-standing ­CO(g). b Free
energy diagrams for CO produc-
tion on CoTMAP, Co/Co-Por,
Ni/Co-Por, and Fe/Co-Por. c
The plot of log(TOF) against
the theoretical overpotential val-
ues showing a linear correlation

(< 10% of the original value) with weight ratios of ­H2TMAP/ for all CoTMAP-based catalysts. While all the cofacial por-
CoTSPP over 1.3, implying the complete assembly of H/Co- phyrins show the same RDS for ­CO2-to-CO conversion as
Por cofacial porphyrin. The control experiment also vali- the monomeric CoTMAP, their reaction energy barriers
dates our calculation protocol of TOF values for the samples appear to be lower (Fig. S11). Then, the calculated theoreti-
discussed here. The CoTMAP catalyst exhibits a T ­ OFCO of cal reaction overpotentials over the tested catalysts follow the
4.4 ­s−1 (Fig. 2d), similar to that of Ref. [27]. Fabricating the order Fe/Co-Por (0.58 V) < Co/Co-Por (0.60 V) < Ni/Co-Por
cofacial porphyrins using MTSPP leads to improved intrinsic (0.65 V) < CoTMAP (0.68 V). The above results show that,
activities with the order of Fe/Co-Por (7.6 ­s−1) > Co/Co-Por in addition to peripheral substituents, metal atoms from the
(6.1 ­s−1) > Ni/Co-Por (5.4 ­s−1). underlying catalytically inactive porphyrin molecules also
DFT calculations were performed for analyzing the ther- play an important role in tuning the electronic structure of
mochemical reaction energetics of ­CO2RR on CoTMAP, Co/ the catalytically active porphyrin molecules on the top layer.
Co-Por, Ni/Co-Por, and Fe/Co-Por. The molecular structures Correspondingly, the log(TOF) values appear to be linearly
were first optimized for the cofacial porphyrins according to correlated with the theoretical overpotential values.
the H-aggregation configuration. The introduced ­H2TMAP
blocked the underlying metal sites (Fig. 2c), which implies
a high overlapping degree (Fig. S8). ­CO 2-to-CO elec- Conclusions
troreduction by molecular catalysts involves *COOH and
*CO intermediates [32–34]. *COOH formation is usually In summary, a two-step impregnation method is proposed to
considered the rate-determining step (RDS), and the *CO prepare cofacially stacked porphyrins by utilizing the elec-
species are believed to desorb promptly to form the CO trostatic force between the cationic and anionic porphyrin
products. CoTMAP, Co/Co-Por, Ni/Co-Por, and Fe/Co-Por molecules, which not only avoids the common tedious chem-
have Tafel slopes of 114.9, 123.8, 118.4, and 133.7 mV/dec ical synthesis route but also effectively tunes the electronic
(Fig. S9). Furthermore, a ­CO2 reaction order of approxi- structure of the molecular catalysts, eventually leading to a
mately 1 is determined for all the catalysts, indicating the lower reaction energy barrier and a significantly improved
­CO2-to-*COOH transformation to be the rate-limiting step reaction rate for ­CO2 electroreduction. Our method should
(Fig. S10)[9]. *COOH formation is the most energy-demand- theoretically be adaptable to other carbonaceous supports
ing, as suggested by the DFT results, associated with the such as carbon black and carbon nanotubes. In addition, the
highest energy barrier of + 0.6 eV compared to other reaction facile approach has the potential to guide the rational design
steps (Fig. 3a). Figure 3b shows the free energy diagrams of other cofacial porphyrin catalysts.

13
78 P. Tian et al.

Supplementary Information The online version contains supplemen- 11. Guilard R, Brandes S, Tardieux C et al (1995) Synthesis and char-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 12209-0​ 21-0​ 0305-8. acterization of cofacial metallodiporphyrins involving cobalt and
Lewis acid metals: new dinuclear multielectron redox catalysts of
Acknowledgements This work was sponsored by the Program for dioxygen reduction. J Am Chem Soc 117(47):11721–11729
Professor of Special Appointment (Eastern Scholar) at Shanghai 12. Peljo P, Murtomäki L, Kallio T et al (2012) Biomimetic oxygen
Institutions of Higher Learning and Shanghai Sailing Program (No. reduction by cofacial porphyrins at a liquid-liquid interface. J Am
19YF1410600). R.Y. acknowledge the Young Scientists Fund of the Chem Soc 134(13):5974–5984
National Natural Science Foundation of China (No. 21905240) and the 13. Takai A, Gros CP, Barbe JM et al (2009) Enhanced electron-trans-
State Key Laboratory of Marine Pollution (SKLMP) Seed Collabora- fer properties of cofacial porphyrin dimers through π–π interac-
tive Research Fund. tions. Chemistry 15(13):3110–3122
14. Collman JP, Kim K, Leidner CR (1987) Synthesis, characteriza-
tion, and electrochemistry of novel diruthenium cofacial porphy-
Declarations rin dimers. Inorg Chem 26(7):1152–1157
15. Oldacre AN, Friedman AE, Cook TR (2017) A self-assembled
Conflict of interest The authors declare that there is no conflict of in- cofacial cobalt porphyrin prism for oxygen reduction catalysis. J
terest. Am Chem Soc 139(4):1424–1427
16. Collman JP, Denisevich P, Konai Y et al (1980) Electrode catalysis
Open Access This article is licensed under a Creative Commons Attri- of the four-electron reduction of oxygen to water by dicobalt face-
bution 4.0 International License, which permits use, sharing, adapta- to-face porphyrins. J Am Chem Soc 102(19):6027–6036
tion, distribution and reproduction in any medium or format, as long 17. Collman JP, Bencosme CS, Durand RR Jr et al (1983)
as you give appropriate credit to the original author(s) and the source, Mixed-metal face-to-face porphyrin dimers. J Am Chem Soc
provide a link to the Creative Commons licence, and indicate if changes 105(9):2699–2703
were made. The images or other third party material in this article are 18. Durand RR, Bencosme CS, Collman JP et al (1983) Mechanistic
included in the article’s Creative Commons licence, unless indicated aspects of the catalytic reduction of dioxygen by cofacial metal-
otherwise in a credit line to the material. If material is not included in loporphyrins. J Am Chem Soc 105(9):2710–2718
the article’s Creative Commons licence and your intended use is not 19. Nakamura T, Ube H, Shionoya M (2013) Silver-mediated formation
permitted by statutory regulation or exceeds the permitted use, you will of a cofacial porphyrin dimer with the ability to intercalate aromatic
need to obtain permission directly from the copyright holder. To view a molecules. Angew Chem Int Ed Engl 52(46):12096–12100
copy of this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/. 20. Oliveri CG, Heo J, Nguyen ST et al (2007) A convergent coor-
dination chemistry-based approach to dissymmetric macrocyclic
cofacial porphyrin complexes. Inorg Chem 46(19):7716–7718
21. Suijkerbuijk BMJM, Tooke DM, Spek AL et al (2007) One-
References dimensional, cofacial porphyrin polymers formed by self-assem-
bly of meso-tetrakis(ERE donor) zinc(II) porphyrins. Chem Asian
1. Manbeck GF, Fujita E (2015) A review of iron and cobalt por- J 2(7):889–903
phyrins, phthalocyanines and related complexes for electrochemi- 22. Hepburn C, Adlen E, Beddington J et al (2019) The technological
cal and photochemical reduction of carbon dioxide. J Porphyrins and economic prospects for ­CO2 utilization and removal. Nature
Phthalocyanines 19(1–3):45–64 575(7781):87–97
2. Sun CF, Gobetto R, Nervi C (2016) Recent advances in catalytic 23. Gruber N, Clement D, Carter BR et al (2019) The oceanic
­CO2 reduction by organometal complexes anchored on modified sink for anthropogenic C ­ O 2 from 1994 to 2007. Science
electrodes. New J Chem 40(7):5656–5661 363(6432):1193–1199
3. Elouarzaki K, Kannan V, Jose V et al (2019) Recent trends, bench- 24. Mohamed EA, Zahran ZN, Naruta Y (2015) Efficient electro-
marking, and challenges of electrochemical reduction of C ­ O2 by catalytic ­CO2 reduction with a molecular cofacial iron porphyrin
molecular catalysts. Adv Energy Mater 9(24):1900090 dimer. Chem Commun Camb Engl 51(95):16900–16903
4. Birdja YY, Pérez-Gallent E, Figueiredo MC et al (2019) Advances 25. Zahran ZN, Mohamed EA, Naruta Y (2016) Bio-inspired cofa-
and challenges in understanding the electrocatalytic conversion of cial Fe porphyrin dimers for efficient electrocatalytic C ­ O2 to CO
carbon dioxide to fuels. Nat Energy 4(9):732–745 conversion: overpotential tuning by substituents at the porphyrin
5. Choi J, Kim J, Wagner P et al (2019) Energy efficient electrochem- rings. Sci Rep 6:24533
ical reduction of ­CO2 to CO using a three-dimensional porphyrin/ 26. Smith PT, Benke BP, Cao Z et al (2018) Iron porphyrins embed-
graphene hydrogel. Energy Environ Sci 2:747–755 ded into a supramolecular porous organic cage for electrochemical
6. Hu XM, Rønne MH, Pedersen SU et al (2017) Enhanced cata- ­CO2 reduction in water. Angew Chem 130(31):9832–9836
lytic activity of cobalt porphyrin in C ­ O2 electroreduction upon 27. Zhu MH, Yang DT, Ye RQ et al (2019) Inductive and electrostatic
immobilization on carbon materials. Angew Chem Int Ed effects on cobalt porphyrins for heterogeneous electrocatalytic
56(23):6468–6472 carbon dioxide reduction. Catal Sci Technol 9(4):974–980
7. Tatin A, Comminges C, Kokoh B et al (2016) Efficient electro- 28. Adamo C, Barone V (1999) Toward reliable density functional
lyzer for C
­ O2 splitting in neutral water using earth-abundant mate- methods without adjustable parameters: the PBE0 model. J Chem
rials. Proc Natl Acad Sci 113(20):5526–5529 Phys 110(13):6158–6170
8. Zion N, Friedman A, Levy N et al (2018) Bioinspired electroca- 29. Hay PJ, Wadt WR (1985) Ab initio effective core potentials for
talysis of oxygen reduction reaction in fuel cells using molecular molecular calculations: potentials for the transition metal atoms
catalysts. Adv Mater 30(41):1800406 Sc to Hg. J Chem Phys 82(1):270–283
9. Zhu M, Chen J, Huang L et al (2019) Covalently grafting cobalt 30. Wadt WR, Hay PJ (1985) Ab initio effective core potentials for
porphyrin onto carbon nanotubes for efficient ­CO2 electroreduc- molecular calculations: potentials for main group elements Na to
tion. Angew Chem Int Ed Engl 58(20):6595–6599 Bi. J Chem Phys 82(1):284–298
10. Mohamed EA, Zahran ZN, Naruta Y (2017) Efficient heteroge- 31. Hay PJ, Wadt WR (1985) Ab initio effective core potentials for
neous ­CO2 to CO conversion with a phosphonic acid fabricated molecular calculations: potentials for K to Au including the out-
cofacial iron porphyrin dimer. Chem Mater 29(17):7140–7150 ermost core orbitals. J Chem Phys 82(1):299–310

13
Electroreduction of Carbon Dioxide by Heterogenized Cofacial Porphyrins 79

32. Lin S, Diercks CS, Zhang YB et al (2015) Covalent organic frame- Technology (2017–2018). His research interests include the develop-
works comprising cobalt porphyrins for catalytic C­ O2 reduction ment of cost-effect methods for materials manufacturing and the inves-
in water. Science 349(6253):1208–1213 tigation of their applications.
33. Costentin C, Drouet S, Robert M et al (2012) A local proton
source enhances C ­ O2 electroreduction to CO by a molecular Fe Minghui Zhu obtained his Ph.D.
catalyst. Science 338(6103):90–94 degree in 2016 from Lehigh Uni-
34. Zhu MH, Ye RQ, Jin K et al (2018) Elucidating the reactivity and versity under the supervision of
mechanism of C ­ O2 electroreduction at highly dispersed cobalt Prof. Israel E. Wachs. After
phthalocyanine. ACS Energy Lett 3(6):1381–1386 spending one year and a half
working as a postdoctoral associ-
ate with Prof. Karthish Manthi-
Ruquan Ye is an assistant profes- ram at the Massachusetts Insti-
sor in Chemistry, City University tute of Technology, he joined the
of Hong Kong. He received his East China University of Science
B.S. (Chemistry) in 2012 from and Technology as a Professor in
Hong Kong University of Sci- 2018. His research interests
ence and Technology under Prof. mainly focus on the development
Ben Zhong Tang’s supervision, of new heterogeneous catalysts
and his Ph.D. (chemistry) in for C1 chemistry.
2017 from Rice University men-
tored by Prof. James M. Tour. He
was a postdoctoral associate in
Chemical Engineering at the
Massachusetts Institute of

13