Research Article J. Electrochem. Sci. Technol.

, 2017, 8(1), 61-68

Journal of Electrochemical Science and Technology

Facile Synthesis of M-MOF-74 (M=Co, Ni, Zn) and its Applica-

tion as an ElectroCatalyst for Electrochemical CO2 Conversion
and H2 Production
Insoo Choi1,2, Yoo Eil Jung3, Sung Jong Yoo1, Jin Young Kim1, Hyoung-Juhn Kim1, Chang Yeon Lee3**,
and Jong Hyun Jang1*
1
Fuel Cell Research Center, Korea Institute of Science and Technology, Hawolgok-dong, Sungbuk-gu, Seoul 02792, Republic of Korea
2
Division of Energy Engineering, Kangwon National University, Kyo-dong, Samcheok 25913, Republic of Korea
3
Department of Energy and Chemical Engineering, Incheon National University, 119 Academy-ro, Yeonsu-gu, Incheon
22012, Republic of Korea

ABSTRACT
Electrochemical conversion of CO2 and production of H2 were attempted on a three-dimensionally ordered, porous metal
organic framework (MOF-74) in which transition metals (Co, Ni, and Zn) were impregnated. A lab-scale proton exchange
membrane-based electrolyzer was fabricated and used for the reduction of CO2. Real-time gas chromatography enabled the
instantaneous measurement of the amount of carbon monoxide and hydrogen produced. Comprehensive calculations, based
on electrochemical measurements and gaseous product analysis, presented a time-dependent selectivity of the produced
gases. M-MOF-74 samples with different central metals were successfully obtained because of the simple synthetic process.
It was revealed that Co- and Ni-MOF-74 selectively produce hydrogen gas, while Zn-MOF-74 successfully generates a
mixture of carbon monoxide and hydrogen. The results indicated that M-MOF-74 can be used as an electrocatalyst to selec-
tively convert CO2 into useful chemicals.
Keywords : Electrochemical conversion, CO2, H2, Metal organic framework, Catalyst
Received : 9 November 2016, Accepted : 20 January 2017

1. Introduction posed, such as chemical [5], biological [6], photo-

chemical [7,8], and electrochemical methods [9-12].
In recent years, the threat of global warming and Among these technologies, the electrochemical
the emerging awareness of the increasing atmo- method is the most promising and benign, owing to
spheric CO2 concentrations have placed a spotlight its convenient operation and ability to control the
on carbon capture, storage, and utilization (CCSU) yield and selectivity of the produced chemicals.
[1,2]. CCSU technologies are garnering considerable Metallic catalysts have mainly been investigated
attention as they allow for the conversion of CO2 to for electrochemical CO2 conversion. Various low-
useful chemicals, thereby decreasing the atmo- carbon species are generated during this process, e.g.,
spheric concentration of CO2 substantially [3-5]. CO2 HCOOH [11,13-15], CH4 [9,16], CO [17-19], and
is an attractive building block for C1-chemistry; how- C2H4 [20]. When a simultaneous hydrogen evolution
ever, the conversion of CO2 is quite challenging due reaction (HER) occurs, CO/H2 mixture (syngas) can
to its inert and stable nature. Several methods for the be produced in a single electrochemical cell [11,14].
activation and conversion of CO 2 have been pro- This strategy has drawn great attention because the
syngas can be utilized and transformed into other
*E-mail address: *[email protected], **[email protected] valuable chemicals such as methanol and ethanol via
DOI: https://doi.org/10.5229/JECST.2017.8.1.61 the Fischer-Tropsch process. In all previous studies,

− 61 −
62 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68

each metal was found to show exclusive selectivity known to exhibit an exceptionally large surface area
for a converted product. For example, the d-block and higher CO 2 adsorption capacity under atmo-
transition metals such as Au, Ag, and Co were effec- spheric conditions compared to the other MOFs
tive in converting CO2 to CO, while the p-block transi- [31,32]. In particular, M-MOF-74 (M = transition
tion metals such as Sn and In could actively produce metal) is designated for isostructural compounds with
HCOOH [21]. In addition, Zn, Ni, and Cu, which are the composition M2(dhtp)(H2O)2·8H2O (dhtp = 2,5-
attractive candidates due to their abundance and low dihydroxyterephthalate), in which the metal species
cost, were found to selectively generate CO, H2, and act as vertices of the hexagons connected by organic
CH4, respectively [21]. Unfortunately, the conven- linkers [33]. Because the M-MOF-74 structure exhib-
tional metal catalysts normally require high energies its Lewis acidic sites (open metal sites) upon heating
for the activation of CO2, and therefore, exhibit low in vacuum, the CO2 molecules, which act as Lewis
energy efficiency. Moreover, the metal catalysts, bases, strongly bind with the open metal sites [33]. In
whether planar or covalently bound to supports, pos- addition, M-MOF-74 can be easily obtained because
sess limited electrochemically active surface areas. In its synthesis is relatively simple and requires mild
terms of kinetics, the rate of the electrochemical reac- condition, which in turn makes it possible to change
tion is governed by the rate of the catalytic reaction the central metal impregnated in MOF-74. In fact, the
and the areal concentration of the active catalyst. present synthetic process for M-MOF-74 involves
Therefore, in addition to the modification of such only heating, mixing, and cooling. This is more facile
metal catalysts, it is necessary to explore other types than other methods such as electrophoretic deposition
of catalysts for the electrochemical conversion of [25], atomic layer deposition [26], and electrochemi-
CO2. Notably, there have also been reports on the use cal deposition [27], which require complex appara-
of enzymes as catalysts toward the electrolytic con- tus such as a sealed chamber or a three-electrode
version of CO2. However, the reaction conditions for electrochemical cell. More importantly, the represen-
the enzymatic conversion of CO2 should be restricted tative MOF-74 can retain its original structure during
to neutral pH and mild temperatures, as otherwise, the catalysis or even after any further treatment. To
the enzymes would easily become unstable and inac- the best of our knowledge, M-MOF-74 has not yet
tive [22-24]. been explored as a catalyst for electrochemical CO2
Recently, there have been attempts to apply metal conversion. Therefore, M-MOF-74 can be a reliable
organic frameworks (MOFs) as catalysts for the elec- catalyst for CO2 conversion among the other MOFs
trochemical conversion of CO2 [25-28] and H2 pro- and help us investigate the effect of the central metal
duction [29,30]. MOFs are made of metal ions on the catalysis.
coordinated to organic ligands, giving rise to charac- In this work, we attempted aqueous electrochem-
teristic three-dimensionally ordered crystalline struc- ical reduction of CO2 on the M-MOF-74 (M = Co,
tures. MOFs are highly porous, thermally stable, and Ni, Zn) catalyst, using a proton exchange mem-
chemically functional. In addition, MOFs can uni- brane (PEM)-based electrolyzer. The synthesis of
formly retain active metal nanoparticles at high den- the MOF-74 catalyst is relatively facile as com-
sities within their structure, and therefore, increase pared to the synthesis of other types of catalysts
the amount of surface-bound catalyst, resulting in a because it just requires simple mixing, heating, and
large active surface area. These extraordinary proper- cooling for structuring. Hence, M-MOF-74 with
ties of MOFs are attractive for use in the electro- various central metals can be obtained via an inex-
chemical conversion of CO2 and production of H2. pensive and high-yield process. Thus far, only Fe
Previous studies focused on different types of MOF [25], Co [26], and Cu [27,28] have been investi-
structures such as porphyrin-based [25,26], benzenet- gated as the central metal in the MOF structure for
ricarboxylate (BTC)-based [27], and rubeanate-based the electrochemical conversion of CO 2, regardless
MOFs [28] for CO2 reduction. Even though some of the type of MOF. From this experiment, we
samples showed promising activity, the previously expect to demonstrate the effect of the type of cen-
suggested MOF structures required long and multiple tral metal in MOF-74 on the electrochemical con-
steps for synthesis. version of CO2, in terms of the reduced product and
Among the current MOF materials, MOF-74 is conversion efficiency.
 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68 63

2. Experimental Section N 2 adsorption/desorption isotherms were mea-

sured volumetrically at 77 K over the range 7.0 × 10-6
2.1. Synthesis of M-MOF-74 ≤ P/P0 ≤ 1.00 by an Autosorb-iQ gas sorption ana-
All the chemicals were purchased from Sigma- lyzer outfitted with a micropore option from Quanta-
Aldrich (Seoul, Korea) and used as received. Ni- and chrome Instruments (Boynton Beach, Florida, USA)
Co-MOF-74 were synthesized by a modification of using the Autosorb-iQ Win software package. After
the literature procedure [34]. For Ni-MOF-74, a mix- solvent exchange of the as-synthesized materials with
ture of 2,5-dihydroxyterephthalic acid (H4DOBDC, MeOH (2 × 10 mL, 12 h each time), the samples
0.478 g, 2.41 mmol) and Ni(NO3)2·6H2O (2.378 g, were activated (i.e., degassed) at 250oC for 5 h using
8.18 mmol) was added to a mixed solvent of N,N- the outgas port of the Autosorb-iQ instrument. The
dimethyformamide (DMF)-ethanol-deionized water specific surface areas available for N2 adsorption
(1:1:1, v/v/v%, 200 mL). The suspension was uni- were calculated using the Brunauer-Emmett-Teller
formly mixed by ultrasonic stirring. A vial containing (BET) model in the linear range, as determined using
the suspension was placed in an oven at 100oC for the consistency criteria.
24 h, followed by cooling to room temperature. The
supernatant was separated from the precipitate and 2.3. Electrochemical Characterization with Gas
replaced with methanol. The precipitate was rinsed Analysis
with methanol four times in two days. The remaining We have developed a laboratory-made PEM-
solvent was removed under vacuum at 250oC for over embedded electrolyzer, where the cathodic and
5 h, leaving a brownish-yellow crystalline powder, Ni- anodic compartments are separated by a polymer
MOF-74. The final product was stored under vacuum membrane (NRE-211, 25.4 μm, Dupont™). The
to avoid contamination. The synthetic procedure for specification of the three-electrode system is as
Co-MOF-74 is almost the same as that described described here. A catalyst-coated rotating disk electrode
above, except for the composition of the mixture: (RDE, 0.126 cm2) with a glassy carbon tip was used as
H 4 DOBDC (0.482 g, 2.43 mmol) and Co(NH 3 ) 2 the cathode. A saturated calomel electrode (-0.241 V vs.
·6H2O (2.377 g, 8.67 mmol). A dark red-purple pow- standard hydrogen electrode) and a Pt mesh (Pt
der, Co-MOF-74, was obtained and vacuum stored. thickness = 100 μm, 4 cm 2) were used as the refer-
Zn-MOF-74 was synthesized and activated accord- ence and counter electrodes, respectively.
ing to a method described in literature [35]. H4DOBC A potentiostat (PGSTAT302N, Autolab) was used
(2.5 g, 13 mmol) and Zn(NO 3 ) 2 ·4H 2 O (10.0 g, in all the electrochemical measurements. The electro-
38 mmol) were dissolved in 500 mL of DMF with lyte, 0.5 M KHCO3, was de-aerated with N2 gas for
stirring, followed by the addition of 25 mL of deion- 30 min and saturated with CO2 via purging at a flow
ized water. The mixture was heated in an oven at rate of 30 mL min-1 for at least 30 min. The electro-
100oC for 20 h. After decanting the supernatant, the chemical reduction potential of CO 2 was investi-
product was rinsed with DMF and immersed in meth- gated by performing linear sweep voltammetry (LSV)
anol for 6 days, during which time the activation sol- from 0.0 to -1.2 VSCE at a sweep rate of 10 mV s-1. The
vent was decanted and replenished three times. The time-dependent current decay upon the application of
solvent was finally removed under vacuum at 270oC, a step potential was measured by chronoamperome-
yielding the porous material, Zn-MOF-74. try at -1.6 VSCE (overpotential η = -0.8 V) for 60 min.
All the potentials in this study are expressed with ref-
2.2. Material Characterization erence to the reversible hydrogen electrode. The cata-
The powder X-ray diffraction (PXRD) patterns of lytic activity was measured based on the reduction
M-MOF-74 were recorded by a diffractometer (XDS current during the experiment and the concentration
2000, Rigaku, Texas USA) using Ni-filtered Cu Kα of the produced CO and H2 determined from the gas
radiation (λ = 1.5412 Å) over the range 3o < 2θ < 50o analysis.
in 0.1o steps, with a counting time of 1 s per step. The The concentration of the product gas was measured
morphologies and shapes of the M-MOF-74 samples by real-time gas chromatography (GC, 7890B, Agi-
were obtained by using a transmission electron lent, Santa Clara, USA). The gas was directly deliv-
microscope (TEM, F20, Tecnai). ered to the sampling loop of the GC system in a
64 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68

Fig. 1. Apparatus for the electrochemical reduction of CO2 and analysis of the product gases.

Fig. 2. (a) X-ray diffraction results and (b) BET isotherms of M-MOF-74.

stream of CO2. CO2 was continuously supplied into literature data and simulated patterns, indicating suc-
the catholyte at 10 ccm, controlled by the mass flow cessful synthesis of the desired MOFs. The micro-
controller. The dual-detector (a thermal conductivity porosities of the samples were measured via N 2
detector, TCD and a methanizer-combined flame ion- adsorption-desorption isotherms. As depicted in Fig-
ization detector, methanizer-FID)-embedded GC sys- ure 2(b), all the isotherms exhibited type-I behavior
tem can analyze both permanent and organic gases. without hysteresis, which implied a microporous
The apparatus used for the electrochemical reduction structure. Moreover, the isotherms were found to
of CO2 and successive analysis of the product gases quickly rise at the low-pressure region (P/P0 < 0.1)
is depicted in Fig. 1. indicating that the open metal sites are easily accessi-
ble to the gas molecules. The BET surface areas of
3. Results and Discussion the degassed Co-, Ni-, and Zn-MOF-74 were 1356,
1239, and 1134 m 2 g-1, respectively, which were in
The MOFs, i.e., Co-, Ni-, and Zn-MOF-74, were excellent agreement with the reported M-MOF-74
prepared and purified according to a reported proce- values [34]. Because the surface area is reported as
dure [34,35]. Fig. 2(a) shows that the PXRD patterns area per unit mass, the material with a lighter central
of the as-synthesized samples matched well with the metal had a larger surface area.
 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68 65

Fig. 3. TEM results of M-MOF-74 with magnified images (inset).

Fig. 3 shows the electron microscopic images of

M-MOF-74. It appeared that the frameworks pos-
sessed polygonal shapes. From the TEM-EDX anal-
ysis, it was found that Co-MOF-74, with a size of
~0.3 μm, contained 15.2 wt% Co uniformly distrib-
uted throughout the framework. The size of the indi-
vidual Co nanoparticles was ~1.93 (± 0.21) nm. Ni-
MOF-74 contained 16.7 wt% Ni, whose individual
particle size was ~1.48 (± 0.14) nm. Zn-MOF-74
had the highest metal content among the M-MOFs
(19.4 wt%), although the individual Zn nanoparti-
cles were not clearly observed. Generally, the metal
loading in the MOF structure was limited to a few
wt% because of restricted space [36]. The observed Fig. 4. Linear sweep voltammogram of M-MOF-74 for
CO2 reduction at 10 mV/s and 0 to -1.2 VRHE.
high metal loading in M-MOF-74 makes it increas-
ingly suitable for the role of an electro-catalyst, in
which the loading is normally 20-30 wt%. It is to be of CO2 (Eo = -0.11 VRHE), it is more probable that the
noted that TEM-EDX can provide similar quantita- initial current response was due to the hydrogen evo-
tive results as ICP-MS, as reported previously lution. It is known that Co and Ni are efficient hydro-
[37,38]. gen evolution catalysts, and they have been
Fig. 4 demonstrates the electrochemical response intensively investigated [39–41]. Hence, the smaller
of M-MOF-74, as measured by LSV in the potential overpotentials for Co- and Ni-MOF-74 compared to
range of 0 to -1.2 VRHE in 0.5 M KHCO3 (aq). The Zn-MOF-74 were ascribed to their superior catalytic
current response with voltage was reproducible, indi- activities toward hydrogen evolution. Meanwhile, the
cating that the structure of the framework is stable. A shift of the on-set potential could also be rationalized
clear increase in the reduction current was observed in terms of the activity toward CO 2 reduction,
for all the M-MOF-74 samples as the potential was because Zn required a higher potential than Co and
swept in the negative direction. Because the electro- Ni to electrochemically reduce CO2, as reported by Y.
lyte was fully saturated with CO2, the reduction cur- Hori [42] and K. Hara [43].
rent was responsible for both the electrochemical Fig. 5 presents the time-dependent electrochemi-
reduction of CO2 and H2 production. The reduction cal activity and stability of M-MOF-74 catalysts,
current of Co-MOF-74 and Ni-MOF-74 started evaluated through chronoamperometric measure-
increasing at -0.25 and -0.56 V RHE , respectively. ments for 60 min at a controlled potential of -0.91
However, the on-set potential of Zn-MOF-74 was VRHE. The abrupt current decrease observed in the
shifted to ~-0.65 VRHE. Given that the hydrogen evo- chronoamperometry experiments was attributed to
lution reaction (Eo = 0.0 VRHE) precedes the reduction the double-layer charging current [44,45]. The geo-
66 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68

Fig. 5. Chronoamperometry results for M-MOF-74 at -0.91

VRHE for 60 min.

metric current density of Co- and Zn-MOF-74

reached a stable state a few minutes after applying the
potential. The current density of Ni, however, gradu-
ally increased with time, probably due to slow activa-
tion of the Ni particles bound to the framework, and
became stable with time. All the steady-state current
densities matched well with the values obtained from
LSV, as shown in Figure 4. The applied potential was
determined based on the fact that the current density,
greater than 5 mA cm-2, seemed to be academically
meaningful as evidenced by the previous study [42].
Figs. 6(a-c) provide the partial current densities of
CO2 and H2 reduction on M-MOF-74 at -0.91 VRHE
as a function of electrolysis time. The partial current
densities (j) were calculated from the comprehensive
product gas analysis and the electrochemical activity
[46]. Co-MOF-74 exhibited superior selectivity
toward H2 reduction (jH2) over CO2 reduction (jCO2).
Likewise, Ni-MOF-74 generated a large quantity of
H2 at the given potential, and showed a low jCO2. This
suggested that between the competitive reactions of
H2 evolution and CO2 conversion, the former pre-
vailed on both Co- and Ni-MOF-74. It can be
assumed that Co-/Ni-MOF-74 would be an effective
H2-evolving catalyst in the electrolysis of water. In
Fig. 6. Partial current density for H2 production (triangles),
the case of CO2 reduction on both the catalysts, the
CO2 reduction (solid squares), and CO production in CO2
current initially increased but gradually decreased reduction (open squares) on (a) Co-MOF-74, (b) Ni-MOF-
with electrolysis time, indicating that Co-/Ni-MOF- 74, and (c) Zn-MOF-74 at -0.91 VRHE for 60 min.
74 possessed low durability for CO2 reduction. On
the other hand, Zn-MOF-74 presented a much greater electrolysis time.
jCO2 compared to the others, indicating that Zn-MOF- The fact that no CO was detected from the GC
74 could substantially reduce CO2. It is also notable analysis of Co-/Ni-MOF-74 and j CO2/CO remained
that jCO2 was maintained almost constant during the zero suggested that the jCO2 was related to the conver-
 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68 67

4. Conclusions

In this study, we have demonstrated the applicability

of the M-MOF-74 (M = Co, Ni, Zn) catalyst for the elec-
trochemical reduction of CO2. The as-synthesized M-
MOF-74 possessed a microporous structure and con-
tained uniformly distributed metal nanoparticles in its
interior. According to the BET measurements, all the M-
MOF-74 catalysts had a surface area greater than
1134 m2 g-1. The metal content of M-MOF-74 varied
from 15 to 20 wt%. The results of the study demon-
strated that M-MOF-74 showed different electrochemi-
Fig. 7. Relative composition of the products of CO2 cal activities toward the reduction of CO2 and production
reduction on M-MOF-74 at -0.91 VRHE for 60 min. of H2. Smaller overpotentials were observed for the reac-
tions with Co- and Ni-MOF-74 than for those with Zn-
sion of CO 2 to compounds other than CO. These MOF-74, owing to the superior catalytic activities of the
compounds were not detectable by GC; therefore, it former catalysts toward H2 evolution. It was revealed
was assumed that they were in liquid state. It was ear- that the reduced products and their selectivity strongly
lier reported that Co and Ni could convert CO2 into depended on the type of central metal. Co- and Ni-MOF-
formate with relatively low efficiency [42]. There- 74 presented superior selectivity toward H2 reduction
fore, we could tentatively conclude that the liquid over CO2 reduction. On the other hand, Zn-MOF-74
component would be formic acid. Unlike Co- and Ni- could produce both CO and H2 with selectivities of
MOF-74, Zn-MOF-74 produced a notable amount of 15.4% and 78.28%, respectively, suggesting that it could
CO. This suggested that Zn-MOF-74 shows higher be a potential heterogeneous catalyst for syngas produc-
CO selectivity than the other types of M-MOFs, in tion via the electrochemical conversion of CO2. In this
the conversion of CO2. preliminary attempt to apply M-MOF-74 as a catalyst for
Fig. 7 shows the relative proportion of the the electrochemical reduction of CO2, the improvement
reduced products when the electrolysis proceeded in the conversion efficiency and the kinetics fell short of
for 60 min. It was concluded that Co-/Ni-MOF-74 our expectation. Based on the results, however, it would
could electrochemically convert a small quantity of be of great interest to fabricate binary metal catalysts
CO 2 , and produce a large quantity of H 2 . Mean- impregnated in MOF-74, i.e., CoZn-MOF-74 or NiZn-
while, Zn-MOF-74 led to 21.72% CO2 conversion MOF-74, and use them for the production of high yield
and 78.28% H 2 production. The CO selectivity syngas in future research.
obtained from Zn-MOF-74 (15.40%) was greater
than that reported for a Cu rubeanate-based MOF Acknowledgments
(2%) [28] but smaller than that reported for an Fe
porphyrin-based MOF (50%) [25]. However, the This work was supported by the Korean Govern-
CO productivity (-0.69 mA cm-2) of CO partial cur- ment through the New & Renewable Energy Core
rent was higher than that of Cu rubeanate-based (- Technology Program of the Korea Institute of Energy
0.36 mA cm -2 ) and Fe-porphyrin-based MOFs (- Technology Evaluation and Planning (KETEP) funded
0.65 mA cm -2 ) at the same reduction potential. by MOTIE (No.20133030011320) and the National
From this result, we could conclude that the electro- R e s e a r c h F o u n da t i o n of K o r e a ( N R F -
catalytic activity of Zn-MOF-74 is more promising 2015M1A2A2056554) funded by the MSIP. This
than the other MOFs. Moreover, the simultaneous study was also financially supported by the KIST
production of CO + H 2 (syngas) on Zn-MOF-74 through the Institutional Project and K-GRL program.
would definitely lead to the production of a value-
added fuel via a gas-to-liquid reaction, thus con- References
firming the potential use of this material as an elec-
trocatalyst in the selective conversion of CO2. [1] P. Markewitz, W. Kuckshinrichs, W. Leitner, J. Linssen,
68 Insoo Choi et al. / J. Electrochem. Sci. Technol., 2017, 8(1), 61-68

P. Zapp, R. Bongartz, A. Schreiber and T.E. Müller, [23] K. Sugimura, S. Kuwabata. H. Yoneyama, J. Am. Chem.
Energy Environ. Sci, 2002, 5(6), 7281-7305. Soc, 1989, 111 (6), 2361-2362.
[2] K.M.K. Yu, I. Curcic, J. Gabriel, S.C.E. Tsang, [24] H.A. Hansen, J.B. Varley, A.A. Peterson, J.K. Norskov,
ChemSusChem, 2010, 3(6), 644-644. J. Phys. Chem. Lett, 2013, 4(3) 388-392.
[3] I. Ganesh, Renew. Sustainable Energy Rev, 2014, 31, [25] I. Hod, M.D. Sampson, P. Deria, C.P. Kubiak, O.K.
221-257. Farha, J.T. Hupp, ACS Catal, 2015, 5 (11), 6302-6309.
[4] C.M. Pradier, in: J. Paul, C.M. Pradier (Eds.), Carbon [26] N. Kornienko, Y. Zhao, C.S. Kley, C. Zhu, D. Kim, S.
Dioxide Chemistry: Environmental Issues, The Royal Lin, C.J. Chang, O.M. Yaghi, Peidong Yang, J. Am.
Soc. Chem., Cambridge,, UK, 1994, pp. 3-4. Chem. Soc, 2015, 137(44), 14129-14135.
[5] M. Peters, B. Köhler, W. Kuckshinrichs, W. Leitner, P. [27] R.S. Kumar, S.S. Kumar, M.A. Kulandainathan,
Markewitz, T.E. Müller, ChemSusChem, 2011, 4(9), Electrochem. Commun, 2012, 25, 70-73.
1216-1240. [28] R. Hinogami, S. Yotsuhashi, M. Deguchi, Y. Zenitani,
[6] A.S. Hawkins, P.M. McTernan, H. Lian, R.M. Kelly, H. Hashiba, Y. Yamada, ECS Electrochem. Lett, 2012,
M.WW. Adams, Curr. Opin. Biotechnol, 2013, 24(3), 1(4), H17-H19.
376-384. [29] X. Dai, M. Liu, Z. Li, A. Jin, Y. Ma, X. Huang, H. Sun,
[7] Zhai, Q., Xie, S., Fan, W., Zhang, Q., Wang, Y., Deng, H. Wang, X. Zhang, J. Phys. Chem.C, 2016, 120 (23),
W., & Wang, Y, Angew. Chem, 2013, 125(22), 5888- 12539-12548.
5891. [30] W. Guo, H. Lv, Z. Chen, K.P. Sullivan, S.M. Lauinger,
[8] S.C. Roy, O.K. Varghese, M. Paulose, C.A. Grimes, Y. Chi, J.M. Sumliner, T. Lian, C.L. Hill, J. Mater.
ACS Nano, 2010, 4(3), 1259-1278. Chem. A, 2016, 4 (16), 5952-5957.
[9] K.P. Kuhl, T. Hatsukade, E.R. Cave, D.N. Abram, J. [31] J.A. Mason, K. Sumida, Z.R. Herm, R. Krishna, J.R.
Kibsgaard, T.F. Jaramillo, J. Am. Chem. Soc, 2014, Long, Energy Environ. Sci, 2011, 4 (8) 3030-3040.
136(40), 14107-14113. [32] D-A. Yang, H-Y. Cho, J. Kim, S-T. Yang, W-S. Ahn,
[10] C. Costentin, M. Roberta, J-M. Savéant, Chem. Soc. Energy Environ. Sci, 2012, 5(4), 6465-6473.
Rev, 2013, 42(6), 2423-2436. [33] H. Wu, W. Zhou, T. Yildirim, J. Am. Chem. Soc, 2009,
[11] H-Y. Kim, I. Choi, S.H. Ahn, S.J. Hwang, S.J. Yoo, J. 131(13) 4995-5000.
Han, J. Kim, H. Park, J.H. Jang, S-K. Kim, Int. J. [34] S.R. Caskey, A.G. Wong-Foy, A.J. Matzger, J. Am.
Hydrogen Energ, 2014, 39(29), 16506-16512. Chem. Soc, 2008, 130(33, ) 10870-10871.
[12] J.L. DiMeglio, J. Rosenthal, J. Am. Chem. Soc, 2013, [35] J.L.C. Rowsell, O.M. Yaghi, J. Am. Chem. Soc, 2006,
135(24), 8798-8801. 128(4), 1304-1315.
[13] S. Zhang, P. Kang, T.J. Meyer, J. Am. Chem. Soc, 2014, [36] B. Gole, U. Sanyal, R. Banerjee, P.S. Mukherjee, Inorg.
136(5), 1734-1737. Chem, 2016, 55(5), 2345-2354.
[14] S.R. Narayanan, B. Haines, J. Soler, T.I. Valdez, J. [37] J. Zhu, M. Xiao, Y. Zhang, Z. Jin, Z. Peng, C. Liu, S.
Electrochem. Soc, 2011, 158(2), A167-A173. Chen, J. Ge, W. Xing, ACS Catalm 2016, 6(10), 6335-
[15] M. Alvarez-Guerra, S. Quintanilla, A. Irabien, Chem. 6342.
Eng. J, 2012, 207, 278-284. [38] R. Liang, F. Jing, L. Shen, N. Qin, L. Wu, Nano Res,
[16] A.A. Peterson, J.K. Nørskov, Phys. Chem. Lett, 2012, 2015, 8(10), 3237-3249.
3(2), 251-258. [39] E.J. Popczun, C.G. Read, C.W. Roske, N.S. Lewis, R.E.
[17] B.A. Rosen, A. Salehi-Khojin, M.R. Thorson, W. Zhu, Schaak, Angew. Chem, 2014, 126 (21) 5531-5534.
D.T. Whipple, P.J. A. Kenis, R.I. Masel, Science, 2011, [40] S.H. Ahn, S.J. Hwang, S.J. Yoo, I. Choi, H-J. Kim, J.H.
334 (6056) 643-644. Jang, S.W. Nam, T-H. Lim, T. Lim, S-K. Kim, J.J. Kim,
[18] Y. Chen, C.W. Li, M.W. Kanan, J. Am. Chem. Soc, J. Mater. Chem, 2012, 22(30), 15153-15159.
2012, 134(49), 19969-19972. [41] M. Gong, D-Y. Wang, C-C. Chen, B-J. Hwang, H. Dai,
[19] W. Zhu, R. Michalsky, Ö. Metin, H. Lv, S. Guo, C.J. Nano Res, 2016, 9(1), 28-46.
Wright, X. Sun, A.A. Peterson, S. Sun, J. Am. Chem. [42] Y. Hori, H. Wakebe, T. Tsukamoto, O. Koga,
Soc, 2013, 135(45), 16833-16836. Electrochim. Acta, 1994, 39(11-12), 1833-1839.
[20] D. Ren, Y. Deng, A.D. Handoko, C.S. Chen, S. [43] K. Hara, A. Kudo, T. Sakata, J. Electroanal. Chem,
Malkhandi, B.S. Yeo, ACS Catal, 2015, 5 (5), 2814- 1995, 391(1-2), 141-147.
2821. [44] C. Zhang, S.Y. Hwang, Z. Peng, J. Mater. Chem, 2013,
[21] Y. Hori, in: C.G. Vayenas, R.E. White, M.E. Gamboa- A 1(45), 14402-14408.
Aldeco, (Eds.) Modern Aspects of Electrochemistry no. [45] E. M. Sherif, Molecules, 2014, 19(7), 9962-9974.
42, Springer, New York, 2008, pp. 89-189. [46] Y. Chen, C.W. Li, M.W. Kanan, J. Am. Chem. Soc,
[22] S. Kuwabata, R. Tsuda, H. Yoneyama, J. Am. Chem. 2012, 134(49), 19969-19972.
Soc, 1994, 116 (12), 5437-5443.