Highly Selective CO2Electroreduction to C2H4Using a Metal-Organic Framework with Dual Active Sites

Organic Framework with Dual Active Sites

Communication

Highly Selective CO Electroreduction to C H Using a Metal−

2 4

‡

Xiao-Feng Qiu, Hao-Lin Zhu, Jia-Run Huang, Pei-Qin Liao,* and Xiao-Ming Chen

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sı Supporting Information

ABSTRACT: Conversion from CO to C H is important for the development of energy and the environment, but the high energy

barrier of hydrogenation of the *CO intermediate and C−C coupling step tend to result in C compounds as the main product and

thus restrict the generation of C H . Here, we report a metal−organic framework (denoted as PcCu-Cu-O), composed of

,3,9,10,16,17,23,24-octahydroxyphthalo-cyaninato)copper(II) (PcCu-(OH) ) ligands and the square-planar CuO nodes, as the

electrocatalyst for CO to C H . Compared with the discrete molecular copper-phthalocyanine (Faradaic eﬃciency (FE) of C H =

5%), PcCu-Cu-O exhibits much higher performance for electrocatalytic reduction of CO to C H with a FE of 50(1)% and a

2 2 4

−

current density of 7.3 mA cm at the potential of −1.2 V vs RHE in 0.1 M KHCO solution, representing the best performance

reported to date. In-situ infrared spectroscopy and control experiments suggested that the enhanced electrochemical performance

may be ascribed to the synergistic eﬀect between the CuPc unit and the CuO unit, namely the CO on the CO-producing site

(

CuO site) can eﬃciently migrate and dimerize with the *CO intermediate adsorbed on the C H -producing site (CuPc), giving a

lower C−C dimerization energy barrier.

17−19

n recent years, electrocatalytic carbon dioxide reduction

CO RR tend to yield CO as the main product.

Among all

reaction (CO RR) has attracted extensive attention from

metal-phthalocyanine compounds, only discrete molecular

copper-phthalocyanine (CuPc) exhibit electrochemical activity

for yielding C H , but the selectivity (FE(C H ) = 25%,

researchers due to its potential application on the mitigation of

−4

the greenhouse gas eﬀect and energy crisis.

Currently,

HCOOH and CO account for the majority of reduction

products in electrochemical CO RR; on the other hand,

hydrocarbons are rare, especially for C H . As the

FE(CH ) = ∼5%, FE(CO) = ∼4.5%) needs to be improved.

It is widely accepted that the C−C dimerization is an

important step during the reduction of CO to C H , and

petrochemical capturing the largest volume among other

petrochemicals, C H is mainly obtained industrially by the

optimizing the energy barrier of the dimerization should be

beneﬁcial for yielding C H . As a catalyst with one type of

cracking reaction of naphtha and the distillation of cracking

catalytically active site (Scheme 1a), when the distance

between a pair of active sites is suitable, it is easy for the

*CO intermediate to dimerize with the *CHO intermediate

adsorbed on the adjacent active site to generate the *OCCOH

gas. In this regard, employing electrochemistry for the

eﬃcient reduction of CO to C H could be meaningful for the

C H industry. However, the high overpotential (almost 0.6−

.0 V for yielding C H

CO ) and the multielectron transfer processes (12 electrons

for yielding C H compared to 2 for yielding CO or HCOOH

while a low value of 0.016 V yields

intermediate. And, further hydrogenation of *OCCOH

intermediate can yield C H as the ﬁnal product. When the

distance is unsuitable, it is needed for one of the two *CO

and 8 for yielding CH ) in CO RR encumber the electro-

intermediates to be desorbed and migrate to the *CHO

conversion of CO to C H . Therefore, the development of

intermediate for C−C dimerization (Scheme 1b). However,

^e^ﬃ^cⁱ^eⁿ^t^e^l^e^c^t^r^o^c^a^t^a^l^y^s^t^s^t^o^a^c^hⁱ^e^v^e^t^h^e^e^l^e^c^t^r^o^r^e^d^u^c^tⁱ^oⁿ^o^f^C^O2

the formation of the *CHO intermediate from the *CO

intermediate needs high adsorption enthalpy, which goes

against desorption of CO, resulting in a high C−C

to C H is a very signiﬁcant and challenging task.

Metal-phthalocyanine compounds have been proved to be

1−15

eﬃcient for electrochemical CO RR.

For instance,

dimerization energy barrier. Combining a CO-producing

discrete molecular cobalt-phthalocyanine (CoPc) exhibits

site with a C H -producing site might be feasible to balance

high activity for the electroreduction of CO to CO with a

the desorption and hydrogenation of CO. As shown in Scheme

c, such a catalyst with dual active sites may be beneﬁcial for

current density of 54.1 mA cm⁻at a potential of −1.71 V vs

RHE. Recently, researchers achieved improved electrochemical

performances for CO RR by constructing metal−organic

Received: February 6, 2021

Published: May 6, 2021

frameworks (MOFs) or covalent organic frameworks

(

COFs) with metal-phthalocyanine as secondary building

12,13

units.

This improvement could be attributed to the highly

ordered framework structure, strong designability of active

sites, and high crystallinity of MOFs and COFs. However,

most metal-phthalocyanine compounds for electrochemical

2021 American Chemical Society

J. Am. Chem. Soc. 2021, 143, 7242−7246

242

Journal of the American Chemical Society

Communication

Scheme 1. Illustration of the C−C Dimerization Pathways

its proposed structure was conﬁrmed by its mass spectrum

(Figure S1a). Solvothermal reaction of PcCu-(OH)₈and

copper(II) acetylacetonate at 85 °C could give a microcrystal-

line powder of PcCu-Cu-O. In view of the potential eﬀect of

the particle size on reaction activity, exfoliation was performed

by ultrasonic treatment to obtain a PcCu-Cu-O sample with

and Corresponding Energy Barriers

25−28

smaller particle size.

.2°, 7.2°, 10.1°, and 27.5° are ascribed to the (100), (110),

200), and (001) facets of PcCu-Cu-O, respectively (Figure

S2). Electrochemical impedance spectroscopy measurement of

Powder X-ray diﬀraction peaks at

at the potentials of −1.0 to −1.3 V vs RHE (Figure 2 a), which

−

PcCu-Cu-O revealed an impressive conductivity (5 S m )

Figure S3). Such a high conductivity is beneﬁcial for eﬃcient

(

electron transfer in electrocatalysis and yielding hydrocarbons

with a high current density.

In order to verify our conjecture, we carried out electro-

catalytic performance measurement of PcCu-Cu-O. The

microcrystalline powder of PcCu-Cu-O was coated on a glassy

carbon electrode (GCE) with Naﬁon binder to prepare the

working electrode for measurement of the electrochemical

M represents one type of catalytically active site; M₁and M₂

represent two diﬀerent active sites, respectively.

the *CO on the CO-producing site (M ) to desorb, migrate,

and then dimerize with the *CO intermediate on the C H -

producing site (M ), thus resulting in a lower C−C

dimerization energy barrier. Nevertheless, to be our best

knowledge, such a catalyst possessing dual active sites has not

been investigated for electrochemical CO reduction to C H .

CO RR activity in an H-type cell with two compartments.

Cyclic voltammetry (CV) measurements were carried out in

0.1 M KHCO aqueous solution saturated with CO /Ar. In the

The metallo-ligand (2,3,9,10,16,17,23,24-octahydroxy-

Ar atmosphere, the reduction of the compound were observed

phthalo-cyaninato)copper(II) (PcCu-(OH) ) is very similar

to CuPc and should be able to serve as a single active site for

C H production. Compared to CuPc, it should be noted that

the electron donating eﬀect of eight hydroxyl groups on the

ligand PcCu-(OH)₈should be able to enhance the

coordination ability of the nitrogen atoms, as a result of

4,22

enhancing the Cu−N interaction.

Therefore, we anticipate

that the combination of PcCu-(OH) with a CO-producing

site will be promising to achieve high selectivity and durability

for CO RR to C H . PcCu-Cu-O is a two-dimensional MOF

constructed by PcCu-(OH) ligands and the square-planar

CuO nodes (Figure 1 ). Since the CuO nodes of MOFs have

Figure 2. (a) CV curves of PcCu-Cu-O. (b) FEs of C H , CH , CO,

and H for PcCu-Cu-O. (c) Comparisons of FE(C H ) obtained

under neutral condition between PcCu-Cu-O and some previously

reported electrocatalysts. (d) Durability of PcCu-Cu-O in the

electrocatalysis at the potential of −1.2 V vs RHE.

Figure 1. Illustration of the structure of PcCu-Cu-O.

can be ascribed the reduction of Cu(II) to Cu(I) ion. The

current density was enhanced in the CO saturated electrolyte,

been proven to be active for the electroreduction of CO to

indicative of the process of CO RR. The FEs of diﬀerent

0,23,24

CO,

such a two-dimensional structure is beneﬁcial for an

reduced products at diﬀerent potentials were tested (Figure

2b). Gas chromatography (GC) revealed the generation of

C H , CH , CO, and H (Figure S4). The PcCu-Cu-O

electrocatalyst with high activity and high selectivity for

CO RR to C H . In this work, PcCu-Cu-O was employed to

investigate the structure and performance for selective

exhibited high selectivity toward C H (FE(C H ) = 50%) and

2 4 2 4

−2

conversion of CO . Interestingly, with the help of the active

current density of 7.3 mA cm at −1.2 V vs RHE (Figure 2b),

site CuO , the FE(C H ) given by PcCu-Cu-O was

and no liquid phase product was observed in the H nuclear

signiﬁcantly enhanced compared to that of discrete molecular

magnetic resonance ( H NMR) spectra (Figure S5). The

CuPc.

measurements of FE(C H ) were repeated three times, and

The PcCu-(OH) ligand was obtained by the solvothermal

FE(C H ) of 50(1)% was obtained, indicative of good

2 4

reaction of 1,2-dicyano-4,5-dimethoxybenzene and CuCl , and

repeatability. Compared to the exfoliated sample, the as-

243

J. Am. Chem. Soc. 2021, 143, 7242−7246

Journal of the American Chemical Society

Communication

synthesized bulk sample exhibited poor performance (FE-

activity, PcCo-Cu-O and CuHHTP (HHTP = 2,3,6,7,10,11-

hexahydroxytriphenylene) (Figure S12) were selected as

comparative materials. PcCo-Cu-O and CuHHTP were

−

(

C H ) = 43%, current density = 4.2 mA cm ) under the

2 4

same conditions (Figure S6c and d ), indicative of the potential

eﬀect of particle size on electrochemical activity. In order to

further increase the conductivity of the catalyst, we deposited

PcCu-Cu-O on carbon nanotubes (CNTs) with weight ratios

12,37

prepared according to the previous reports,

and their

purities were conﬁrmed by PXRD patterns (Figure S13).

PcCo-Cu-O is isostructural to PcCu-Cu-O, being constructed

by the PcCo-(OH) ligands and the square-planar CuO

of 2:1. However, PcCu-Cu-O/CNT just gave H as the main

reduction production at all applied potential ranges (−1.0 to

nodes. CuHHTP is constructed by tripodal bridging HHTP

−

1.6 V vs RHE) and yielded no C H (Figure S7a), which

ligands and CuO nodes. The electrocatalytic activities for

might be ascribed to the high catalytic activity for hydrogen

evolution reaction of CNT (Figure S7b ). Importantly, the

performance of PcCu-Cu-O is not only much higher than

CO RR of PcCo-Cu-O and CuHHTP were examined under

12,37

the same conditions. Similar to the reported performances,

both of PcCo-Cu-O and CuHHTP just gave CO as the main

reduction production at all applied potential ranges (−1.0 to

−1.6 V vs RHE) and yielded no C H (Figure S6c and d),

those of discrete molecular PcCu with a FE(C H ) of 25%

and all reported MOFs and MOF derivatives (Table S1)

9−31

but also higher than those of most copper salts, copper

nanoparticles, and copper alloys (Figure 2c), such as

suggesting that the CuPc unit should serve as the C H -

2 4

producing active site and both the CoPc and CuO units

CuOHFCl (FE(C H ) of 36.3%), CuPd (FE(C H ) of

should serve as the CO-producing active sites. On the other

8%), and Cu nanocube-O (FE(C H ) of 45%) under

hand, the performance of PcCu-Cu-O (FE(C H ) of 50%) is

similar conditions. Actually, to our best knowledge, only a

reconstructed nanocopper electrocatalyst exhibited a higher

much higher than that of PcCu (FE(C H ) of 25%), thus the

2 4

enhanced electrochemical performance of PcCu-Cu-O may be

ascribed to the synergistic eﬀect between CuPc and CuO₄

units.

FE(C H ) than that of PcCu-Cu-O in neutral electrolyte,

but the high selectivity was obtained at a higher potential of

about −2.0 V vs RHE, indicative of a higher energy

consumption (Figure 2c and Table S1).

To understand the synergistic eﬀect between CuPc and

CuO units in PcCu-Cu-O during electrocatalytic CO RR, the

To evaluate the durability, PcCu-Cu-O was treated with

adsorption energies of *CO intermediates adsorbed on them

were calculated by the periodic density functional theory

(PDFT). The two *CO intermediates adsorbed on the CuPc

continuous electroreduction of CO at −1.2 V. The i−t curve

indicates that the performance of PcCu-Cu-O is durable for at

least 4 h (Figure 2d). According to PXRD patterns, scanning

electron microscope (SEM), and transmission electron micro-

and CuO units are separated by 8.95 Å, obviously not suitable

for direct C−C dimerization into the *OCCOH intermediate.

Thus, one of the *CO intermediates needs to be desorbed

before the C−C dimerization. For the CuPc unit, the *CO

scope (TEM) images, no Cu or Cu O clusters were generated

during electrocatalysis (Figures S2, S8, and S9 ). The X-ray

photoelectron spectroscopy (XPS) pattern revealed negligible

changes during the electrocatalysis (Figure S10). Most

importantly, in-situ operando X-ray absorption spectroscopy

−

adsorption energy is about 48 kJ mol , being much higher

−

than that of the CuO unit (16 kJ mol ), which can be

ascribed to the diﬀerent coordination ﬁelds around the metal

(

XAS) experiments of PcCu-Cu-O indicated that no

signiﬁcant change in Cu K-edges, or no visible metallic Cu

0) signals, could be observed in the X-ray absorption near-

ions. Since the CuO unit has a high activity for reduction of

CO to CO, the lower *CO adsorption energy of the CuO₄

(

unit implies that it could serve as the ideal CO source for C−C

edge structure (XANES) pro ﬁ les of PcCu-Cu-O during the

catalytic process (Figure S11a ), and no Cu−Cu bond was

observed in the extended X-ray absorption ﬁne structure

dimerization on CuPc during electrocatalytic CO RR. On the

other hand, the higher *CO adsorption energy of the CuPc site

is beneﬁcial for the hydrogenation of CO into *CHO before

the C−C dimerization. Therefore, the combination of CuPc

(

EXAFS) spectrum. Therefore, PcCu-Cu-O has suﬃcient

durability for electroconversion of CO to C H . In the

and CuO units in PcCu-Cu-O signiﬁcantly reduces the energy

,14

literature,

during the electrocatalytic CO RR process, the

barrier of C−C dimerization, compared with those of the

Cu−N interaction in the discrete molecular CuPc catalyst is

not strong enough to stabilize the copper ion centers, and the

aggregation of these atomically dispersed Cu atoms leads to

the generation of Cu clusters and nanoparticles. By

comparison, as for PcCu-Cu-O, on the one hand, the electron

donating eﬀect of the oxygen atoms in PcCu-Cu-O can

enhance the coordination ability of nitrogen atoms, thus

enhancing the Cu−N interactions; on the other hand, we think

that the high crystallinity and the strong π−π interaction

between MOF layers can limit the distortion of Cu ions from

tetragonal to tetrahedral. Therefore, CuPc based MOFs with

high crystallinity exhibit high stability during electrocatalysis

without distortion of Cu ions.

Aspired by XANES and EXAFS results, we think that no

aggregated Cu(0) atoms exist during the catalytic process, and

thus the excellent electrochemical performance should not be

ascribed to the aggregated sites which has been illustrated in

many literature works.

possesses two types of potential Cu-based active sites, namely

discrete molecular PcCu and PcCu-(OH) in the catalysis,

leading to a much better performance. In other words, the CO

molecule desorbed on the CuO unit can easily migrate to

dimerize with the *CHO intermediate adsorbed on CuPc unit,

forming the *OCCHO intermediate, as shown in the proposed

mechanism of CO RR to C H depicted in Figure 3a. A similar

mechanism of C−C dimerization on a catalyst with a single

active site has been documented previously.

In order to verify this mechanism, in-situ ATR-FTIR

measurements were performed (Figure S14 ). In the spectra

(Figure 3b and c), the absorption peaks at 1253 and 1396

−

cm could be attributed to the C−O stretch and symmetric

vibration (vibration of O−CO) of the *COOH inter-

−1

mediate, respectively, and the peak at 1575 and 1713 cm

could be attributed to the asymmetric vibration of *COCHO

and CO stretching of carbonyl intermediates, respectively.

−

Additionally, the peak at 1031 cm could be ascribed to the

14,36

As shown in Figure 1, PcCu-Cu-O

nonplanar vibration (OC−H) of the *CHO intermedi-

7,38

ate.

Most importantly, the absorption peaks of the

−

CuPc and CuO units. In order to clarify the electrocatalytic

*CH  intermediate (894 cm for C−H bending vibration

244

Journal of the American Chemical Society

J. Am. Chem. Soc. 2021, 143, 7242−7246

University, Guangzhou 510275, China; orcid.org/0000-

Communication

AUTHOR INFORMATION

■

Corresponding Author

Pei-Qin Liao − MOE Key Laboratory of Bioinorganic and

Synthetic Chemistry, School of Chemistry, Sun Yat-Sen

0001-5888-1283 ; Email: liaopq3@mail.sysu.edu.cn

Authors

Xiao-Feng Qiu − MOE Key Laboratory of Bioinorganic and

Synthetic Chemistry, School of Chemistry, Sun Yat-Sen

University, Guangzhou 510275, China

Hao-Lin Zhu − MOE Key Laboratory of Bioinorganic and

Synthetic Chemistry, School of Chemistry, Sun Yat-Sen

University, Guangzhou 510275, China

Jia-Run Huang − MOE Key Laboratory of Bioinorganic and

Synthetic Chemistry, School of Chemistry, Sun Yat-Sen

University, Guangzhou 510275, China

Xiao-Ming Chen − MOE Key Laboratory of Bioinorganic and

Synthetic Chemistry, School of Chemistry, Sun Yat-Sen

University, Guangzhou 510275, China

Complete contact information is available at:

https://pubs.acs.org/10.1021/jacs.1c01466

Author Contributions

‡

X.F.Q. and H.L.Z. contributed equally.

Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

■

This work was supported by the NSFC (21890380 and

1821003), Local Innovative and Research Teams Project of

Guangdong Pearl River Talents Program (2017BT01C161),

and Guangdong Natural Science Funds for Distinguished

Young Scholar (2018B030306009).

Figure 3. (a) Proposed CO RR mechanism of PcCu-Cu-O. Color

codes: carbon (gray), nitrogen (blue), oxygen (red), hydrogen

(

white), copper (orange). (b, c) In-situ ATR-FTIR spectra of PcCu-

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■

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