Ionic Exchange of Metal-Organic Frameworks to Access Single Nickel Sites for Efficient Electroreduction of CO2

Article abstract of DOI:10.1021/jacs.7b02736

Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical reactions because of their unique electronic and geometric structures with respect to their bulk counterparts. Herein we adopt metal-organic frameworks (MOFs) to assist the preparation of a catalyst containing single Ni sites for efficient electroreduction of CO₂. The synthesis is based on ionic exchange between Zn nodes and adsorbed Ni ions within the cavities of the MOF. This single-atom catalyst exhibited an excellent turnover frequency for electroreduction of CO₂ (5273 h^-1), with a Faradaic efficiency for CO production of over 71.9% and a current density of 10.48 mA cm^-2 at an overpotential of 0.89 V. Our findings present some guidelines for the rational design and accurate modulation of nanostructured catalysts at the atomic scale.

Full text of DOI:10.1021/jacs.7b02736

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Communication
Ionic Exchange of Metal-Organic Frameworks to Access
Single Nickel Sites for Efficient Electroreduction of CO2
Changming Zhao, xinyao dai, Tao Yao, Wenxing Chen, Xiaoqian
Wang, Jing Wang, Jian Yang, Shiqiang Wei, Yuen Wu, and Yadong Li
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 08 Jun 2017
Downloaded from http://pubs.acs.org on June 8, 2017
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Ionic Exchange of Metal-Organic Frameworks to Access
Single Nickel Sites for Efficient Electroreduction of CO2
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Changming Zhao,† Xinyao Dai,† Tao Yao,*,§ Wenxing Chen‡, Xiaoqian Wang,† Jing Wang,† Jian
Yang, † Shiqiang Wei,§ Yuen Wu,*,† and Yadong Li*,‡
† Department of Chemistry, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University
of Science and Technology of China, Hefei 230026, China
‡Department of Chemistry and Collaborative Innovation Center for Nanomaterial Science and Engineering,
Tsinghua University, Beijing 100084, China
§Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China,
Hefei, Anhui Province 230026, (China)
Supporting Information Placeholder
transfer at the interface10. Moreover, the modulation of local
structure such as metal-ligands interplay, bonds length,
ABSTRACT: Single atom catalysts often exhibit unexpected
catalytic activity for many important chemical reactions due
to their unique electronic and geometric structures with
respect to bulk counterparts. Herein, we adopt metal-organic
frameworks to assist the preparation of single Ni sites
catalyst for efficient electroreduction of CO2. The synthesis is
based on the ionic exchange between Zn nodes and adsorbed
Ni ions within the cavities of MOFs. This single atoms
catalyst gained an excellent turnover frequency (5273 h-1) for
electroreduction of CO2, with a faradaic efficiency for CO
production over 71.9% and current density of 10.48 mA cm-2
at 0.89
V overpotential. Our findings present some
guidelines for the rational design and accurate modulation
over nanostructured catalysts at atomic scale.
Due to the increase concentration of atmospheric CO2 and
limited reservoir of fossil fuels, there is urgent need for
designing robust and efficient catalysts to convert
greenhouse CO2 into valuable chemicals1-4. Electroreduction
of CO2 into value-added products is an effective approach to
remit the environmental and energy issues, during which the
electricity can be generated from renewable energy sources
such as, solar, wind and tidal power. However, achieving the
electroreduction of CO2 usually needs to overcome some
bottlenecks including large overpotential for electron
transfer from catalyst to CO2 and multiple distribution of
products derived from the competitive side reactions such as
hydrogen evolution reaction (HER)5,6. As a result, searching
for the active and selective catalysts is of paramount crucial
to make practical CO2 electroreduction a reality. Over the
past decades, researchers have evaluated lots of materials as
electrodes for CO2 electroreduction, such as metal, transition
metal oxide, transition metal chalcogenides, carbon-based
material and metal–organic framework.5,7 The intrinsic
reaction mechanism of CO2 electroreduction involves
complicated pathways occurring at solid-liquid-gas three-
phase boundaries8,9. Thus, rational design of the geometric
structure of catalyst to exposed the reactive sites as more as
possibile is important to facilitate the mass and electron
coordination number, and so on over the reactive sites also
play a vital role in the efficient activation of CO2 and
selective desorption of products.
Figure 1. (a) Scheme of the formation of Ni SAs-N/C. (b)
TEM and (c) HAADF-STEM images of Ni SA/N-C. (d)
Corresponding
SAED
pattern
of
an
individual
rhombododecahedron. (e, f) Magnified HADDF-STEM
images of Ni SAs/N-C, and the Ni single atoms were marked
with red circle. (h) The corresponding EDS mapping reveals
the homogeneous distribution of Ni and N on the carbon
support.
Owing to high ratio of low-coordinated metal atoms and
technically uniform structure, the single-atom catalysts have
shown its great potential as ideal catalysts for some chemical
transformation11-13. However, not only the universality of
synthetic methodology for single-atom catalysts but also the
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accurate control over the microstructures still needs
to avoid the aggregation. Hence, the isolated Ni atoms was
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improvement due to the high mobility and diffusivity of sub-
nano species15,16. In this rapidly developed research topic, the
single atoms catalysts have been demonstrated as highly
active catalysts for CO oxidation reactions11,17, hydrogenation
reactions16, oxidation reactions18 and so on19. Nevertheless,
the electroreduction of CO2 catalyzed by the single atoms
materials has been seldomly studied.
Assembled from the Zn2+ nodes and 2-methylimidazole
(MeIm), ZIF-8 [Zn(MeIm)2] is a class of Metal-organic
frameworks (MOFs) with high crystallinity and ultrafine
porosity19-21. In this work, we have developed a ZIFs-assisted
strategy to generate Ni single atoms distributing in nitrogen-
doped porous carbon (Ni SAs/N-C) for active CO2 reduction15.
The turnover frequency (TOF) normalized to single Ni sites
reached a value of 5273 h-1 and the selectivity (based on the
faradaic efficiency) for CO production is over 71.9% at 0.89 V
stabilized by N coordination and further reduced by the
surrounding carbon. Verified by the Brunauer-Emmett-Teller
(BET) measurement (Figure S4), the Ni SAs/N-C inherited
the high surface area and abundant porosity of ZIF-8, which
is conducive to the electrolyte diffusion and mass transfer.
To further demonstrate the Ni SAs/N-C exhibited
remarkably large active surface, endowing excellent CO2
adsorption capacity, we carry out the CO2 adsorption
isotherms (Figure S5) measurement. By increasing the
quantity of adsorbed Ni(NO3)2, a color evolution from white
to green was observed and the Ni NPs would form during the
pyrolysis due to the insufficient anchoring sites (Figure S6,
S7). The formation of large nanoparticles in the sample of Ni
NPs/N-C could be also verified by the external magnet.
(Figure S6 d, h).
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The TEM image (Figure 1b and Figure S8) and high-angle
overpotential.
A
mechanism illustrating the formation
annular dark-field
scanning
transmission
electron
process of Ni SAs/N-C is summarized in Figure 1.
microscope (HAADF-STEM) image (Figure 1c) both reveal
that the as-prepared Ni SAs/N-C structure retains the initial
rhombododecahedral shape and size distribution of the
starting polyhedrons. The ring-like selected area electron
diffraction (SAED) pattern taken from an individual
rhombododecahedron demonstrated its poor crystallinity
(Figure 1d). Aberration corrected HAADF-STEM image of Ni
SAs/N-C showed that the Ni atoms dominantly presented the
atomic dispersion (Figure 1e and 1f). The isolated heavier Ni
SAs could be discerned in the carbon support because of a
different Z-contrast between Ni, N and C. Energy dispersive
X-ray spectroscopy (EDS) analysis in a scanning transmission
electron microscope (STEM) revealed that Ni and
N
homogeneously dispersed on the whole structure (Figure 1g).
The actual loading of Ni is 1.53 %, which was measured by
inductively coupled plasma optical emission spectroscopy
(ICP-OES). One can see there was no characteristic peaks of
Ni crystals emerged in the XRD pattern of Ni SAs/N-C
(Figure 2a), demonstrating the poor crystallinity. With
increasing the content of adsorbed Ni, a set of well-defined
face-centered cubic Ni peaks emerged at 44.3 °and 51.7 °
under similar pyrolysis conditions, indicating the formation
of nanoparticles.
Figure 2. (a) XRD patterns of Ni SAs/N-C, Ni NPs/N-C and
pyrolyzed ZIF-8. (b) Ni K-edge XANES spectra and (c) the k3-
weighted χ(k)-function of the EXAFS spectra. (d) The
corresponding EXAFS fitting curves for Ni SAs/N-C. Inset is
the proposed Ni-N3 architectures.
The initial ZIF-8 was first synthesized in methanol at room
temperature according to the typical method21, which
exhibited uniform rhombododecahedral shape and narrow
size distribution with an average size of 200 nm (Figure S1).
As shown by X-ray powder diffraction (XRD) patterns in
Figure S2, the as-prepared sample showed a typical crystal
patterns as ZIF-8. Subsequently, the ZIF-8 was
homogeneously dispersed in n-hexane, followed with the
injection of Ni(NO3)2 aqueous solution. Through a double
solvents approach, the Ni precursor could be confined within
the pores of ZIF-8 even the small hexagonal window size was
only 3.3 Å21,24. Afterward, this mixture was pyrolyzed at
The X-ray photoelectron spectroscopy (XPS) was further
used to characterize the valence state and composition
evolution during the synthesis (Figure S9, S10). For Ni
SAs/N-C, the binding energy of the Ni 2p3/2 peak was 855.12
eV and thus higher than that reported for Ni0 (852.5-853.0 eV)
and lower than Ni2+ (853.7 eV), which revealed the ionic Niδ+
(0< δ <2) nature in the Ni SAs/N-C. This results coincided
well with the reported results that the valence of Ni species
12,25
usually situated between the Ni (0) and Ni ( Ⅱ )
.
Furthermore, more detailed structural informations can be
obtained from the X-ray absorption fine structure (XAFS).
The Fourier transforms (FT) k3-weighted χ(k)-function of the
extended X-ray absorption fine structure (EXAFS) for Ni
SAs/N-C exhibited dominant Ni-N coordination with a peak
at 1.42 Å (Figure 2b). Together with the deficiency of Ni-Ni
path, the atomic dispersion of single Ni sites could be
corroborated. By contrast, the main peak for Ni NPs/N-C was
closer to 2.18 Å, belonging to the Ni-Ni coordination. As
shown in the X-ray absorption near-edge structure (XANES)
spectra of Ni SAs/N-C (Figure 2c), the intensity of white line
located between the Ni foil and NiO, which clear told the
°
1000 C under the protection of Ar flow, during which the
organic linkers transform into N-doped carbon skeleton. The
pyrolysis of ZIF-8 was clearly tracked by thermogravimetric
analysis (TGA, Figure S3). The typical weight loss at about
°
600 C was attributed to linker decomposition of ZIF-8 such
as CN fragments. When the temperature was elevated over
900 °C, the weight loss may resulted from the release of Zn
species. That is, the Zn nodes with low boiling point of
907 °C would evaporate at such high temperature, leaving
the N-rich defects15. These sites would be easily occupied by
the neighbor ionic Ni atoms and provided a protective fence
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unique electronic structure of Niδ+ (0<
δ
<2). This
catalytic behavior outperformed most of the reported
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observation also agrees well with the aforementioned XPS
results. According to the fitting results, the proposed local
structure of Ni SAs/N-C with three N coordination was
presented as the inset in Figure 3d.
catalysts (Table S2).
The electrocatalytic reduction of CO2 on pyrolyzed ZIF-8
was performed to investigate the crucial role of Ni centers in
the same condition. Both current density and FEs for CO
production decrease obviously, when catalyzed by this Ni-
free material (Figure S14). Moreover, if the commercial Ni
foam was utilized as the cathodic material, a sluggish current
density was found and the main product was detected to be
H2. This result evidenced the downsizing of bulk Ni would
largely vary the surface structure of catalysts and thus affect
a relative different catalytic performance. Interestingly, the
current density of Ni foam was even lower in the CO2-
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Figure 3. (a) LSV curves in the N2-saturated (dotted line) or
CO2-saturated (solid line) 0.5 M KHCO3 electrolyte with a 10
mV s-1 scan rate. (b) FEs of CO and (c) Partial CO current
density (based on geometric surface area) plots and TOFs of
the Ni SAs/N-C and Ni NPs/N-C at different applied
potentials. (d) Stability of the Ni SAs/N-C at the potential of -
1.0 V versus RHE for Ni SAs/N-C during 60 h.
The electroreduction of CO2 was performed in a two-
compartment gas-tight cell, which was separated by a
Nafion-115 proton exchange membrane to prevent the
oxidation of as-generated products. The cathodic
compartment was continuously purged with CO2 with a
constant flow rate of 10 ml min-1 and vented directly into the
gas-sampling loop (20 μL) for the periodic quantification of
the gas-phase products by a gas chromatograph (GC). Liquid
products formed in the CO2 reduction were not detected by
1H nuclear magnetic resonance (NMR) spectroscopy after
reduction processes (Figure S11). The comparison of the CO2
reduction activity based on Ni SAs/N-C and Ni NPs/N-C is
summarized in Figure 3. According to the results of linear
sweep voltammetry (LSV), the Ni SAs/N-C exhibited an onset
saturated electrolyte than in N2-saturated electrolyte (Figure
S15). This confirmed the surface of Ni foam may be poisoned
by the generated CO, which further restricted the HER26. In
contrast, the Ni SAs/N-C exhibited a long-term stability of 60
h operation, during which no obvious decay in Faradaic
efficiency and current density was detected (Figure 3d).
Figure 4. (a) Tafel plots of the partial CO current density for
Ni SAs/N-C at different applied potentials. (b) Partial CO
current density of Ni SAs/N-C vs. potassium bicarbonate
concentration at constant potential. (c) Proposed reaction
paths for CO2 electroreduction of Ni SAs/N-C.
potential of -0.57
V versus RHE (reversible hydrogen
The Ni SAs/N-C shows a clearly improved CO2 reduction
performances may be attributed to the increased surface
active sites, lower adsorption energy of CO over single Ni
sites and improved electronic conductivity27. The result in
Nyquist plots revealed that the Ni SAs/N-C has lower
interfacial charge-transfer resistance (RCT) than Ni NPs/N-C
(Figure S17), hence ensuring faster electron transfer from
electrodes to CO2 and easier formation of CO2•– radical anion
intermediate. As shown in Figure 4a, the Tafel slope of 249
mV dec-1 reached by Ni SAs/N-C was different with the
reported bulk and nanometer-sized materials28,29, which
indicated a different mechanism for the reduction of carbon
electrode; all potentials are with reference to RHE), which
was much more positive relative to Ni NPs/N-C (Figure 3a).
This result was both confirmed in the N2-saturated 0.5 M
NaClO4 solution and CO2-saturated 0.5 M KHCO3 to exclude
-
the affect of HCO3 (Figure S12). In addition, the current
density catalyzed by Ni SAs/N-C reached a high value of
10.48 mA cm-2 at -1.0 V, which was roughly 3 times larger
than that of Ni NPs/N-C (Figure S13). The analysis by 1HNMR
and GC suggested the primary products catalyzed by Ni
SAs/N-C and Ni NPs/N-C were CO and H2. The Faradaic
Efficiencies (FEs) of CO strictly depends on the working
potential. At the potential of -0.9 V, the Ni SAs/N-C attained
a maximum FEs of 71.9%, which was over 3 times than that of
Ni NPs/N-C. As is shown in Figure 3c, the partial CO current
density of the Ni SAs/N-C showed 30 times larger than that
of the Ni NPs/N-C in the applied potentials of -0.95 V to -1.2
V. What’s more, at -1.0 V, the Ni SAs/N-C attained a
maximum of partial CO current density of 7.37 mA cm-2 and
a TOFs of 5273 h-1. To the best of our knowledge, this
-
dioxide2. In addition, a plot of log (jCO) vs. log ([HCO3 ])
-
shows a slope of 0.64 in Figure 4b, indicating the HCO3
concentration could apparently influence the efficiency of
-
CO2 electroreduction. The HCO3 may not only simply act as
a proton donor in the reaction solution, but also increase the
concentration of CO2 via rapid equilibrium with
bicarbonate30. Since the Ni SAs showed abundant low-
coordinated sites on surface, the strong bonding with the
•-
CO2 may account for the excellent performance for CO2
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electroreduction (Figure 4c). Unfortunately, the Ni SAs/N-C
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also exhibited a competitive activity towards HER12,25, which
significantly depress the high Faradaic efficiency for CO
production. The structural modification over the reactive Ni
sites at atomic scale for the purpose of simultaneously
achieving high activity and selectivity for CO2
electroreduction are still demanded in future study.
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In summary, Ni SAs/N-C has been successfully synthesized
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FEs. Our findings shed light to the rational design at
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ASSOCIATED CONTENT
Supporting Information
(13) Jones, J.; Xiong, H.; DeLaRiva, A. T.; Peterson, E. J.; Pham,
H.; Challa, S. R.; Qi, G.; Oh, S.; Wiebenga, M. H.; Hernández,
X. I. P. Science 2016, 353, 150-154.
Detailed experimental procedures; SEM and TEM images;
BET data, TGA data; XPS data. This material is available free
of charge via the Internet at http://pubs.acs.org.
(14) Liu, P.; Zhao, Y.; Qin, R.; Mo, S.; Chen, G.; Gu, L.;
Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D. Science 2016,
352, 797-800.
AUTHOR INFORMATION
(15) Yin, P.; Yao, T.; Wu, Y.; Zheng, L.; Lin, Y.; Liu, W.; Ju, H.;
Zhu, J.; Hong, X.; Deng, Z. Angew. Chem., Int. Ed. 2016, 55,
10800-10805.
Corresponding Author
yaot@ustc.edu.cn;
yuenwu@ustc.edu.cn;
ydli@mail.tsinghua.edu.cn
(16) Zhang, B.; Asakura, H.; Zhang, J.; Zhang, J.; De, S.; Yan, N.
Angew. Chem., Int. Ed. 2016, 55, 8319-8323.
(17) Guan, H.; Lin, J.; Qiao, B.; Yang, X.; Li, L.; Miao, S.; Liu, J.;
Wang, A.; Wang, X.; Zhang, T. Angew. Chem., Int. Ed. 2016,
128, 2870-2874.
Author Contributions
Changming Zhao and Xinyao Dai contributed equally to this
work.
(18) Deng, D.; Chen, X.; Yu, L.; Wu, X.; Liu, Q.; Liu, Y.; Yang,
H.; Tian, H.; Hu, Y.; Du, P. Sci. Adv. 2015, 1, e1500462.
Notes
The authors declare no competing financial interests.
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Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M.
Proc. Natl. Acad. Sci. 2006, 103, 10186.
ACKNOWLEDGMENT
This work was supported by China Ministry of Science and
Technology under Contract of 2016YFA (0202801), and the
National Natural Science Foundation of China (21522107,
21671180, 21521091, 21390393, U1463202). This work made use
of the resources and finance support of National Synchrotron
Radiation Laboratory in Beijing and Shanghai. We thank the
Photoemission Endstations (BL10B) in National Synchrotron
Radiation Laboratory (NSRL) for help in characterizations.
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