View Article Online

View Journal

NJC
New Journal of Chemistry A journal for new directions in chemistry

Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: Z. Du, J. Qian, T.
Zhang, C. Ji, J. Wu, H. Li and D. Xiong, New J. Chem., 2019, DOI: 10.1039/C9NJ03936H.
Volume 42
Number 6
21 March 2018
This is an Accepted Manuscript, which has been through the
Pages 3963-4776
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
New Journal of Chemistry A journal for new directions in chemistry Accepted Manuscripts are published online shortly after acceptance,
rsc.li/njc

before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
ISSN 1144-2546 Terms & Conditions and the Ethical guidelines still apply. In no event
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
shall the Royal Society of Chemistry be held responsible for any errors
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.

rsc.li/njc
 Page 1 of 8 New do
Please Journal of Chemistry
not adjust margins

1
2
3 View Article Online

4 DOI: 10.1039/C9NJ03936H

5
6
7 ARTICLE
8
9

New Journal of Chemistry Accepted Manuscript

10
11 Solvothermal Synthesis of CuCoO2 Nanoplates Using Zeolitic
12 Imidazolate Framework-67 (ZIF-67) as Co-derived Precursor
13
14 Received 00th January 20xx, Zijuan Du,§ Jinchen Qian,§ Tianyang Zhang, Chenjie Ji, Jie Wu, Hong Li and Dehua Xiong*
15 Accepted 00th January 20xx

16 In this work, we first report copper based delafossite CuCoO2 nanoplates (ca. 150 nm) successfully prepared by solvothermal
DOI: 10.1039/x0xx00000x
17 method at 140 °C for 24 hours using zeolitic imidazolate framework-67 (ZIF-67) as the precursor of Co source. The crystalline
18 size and morphology can be easily controlled by simply modulating the amount of mineralizer NaOH addition and reactant
19 precursors. The crystal composition, morphology and crystal structure of samples were systematically analyzed by powder
20 X-ray diffraction (PXRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-
21 ray photoelectron spectroscopy (XPS) and inductively coupled plasma-optical emission spectrometry (ICP-OES). Moreover,
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

22 the chemical states, Brunauer-Emmett-Teller (BET) surface area and thermal stability of CuCoO2 sample (ca. 150 nm) were
23 systemically characterized. We believe our synthesis strategy will be open a new route for the preparation and application
24 of CuCoO2, which is combining the advantages of ZIF-67 and various components or structures. Furthermore, the resulting
25 CuCoO2 nanoplates could serve as a potential candidate for cost-effective and active electrode material.
26
been unsatisfactory, far less competitive to that of state-of-the-
27
28
Introduction art OER catalysts (such as IrO2 and RuO2). This issue may be due
to the large crystalline size and small specific surface area of
29 Copper based delafossite oxides of CuMO2 (M = Al, Ga, Cr, Co,
CuMO2, resulting in the limited active sites and low
30 etc.) are an important class of transition metal oxides. As a kind
electrocatalytic activity of these CuMO2. Therefore, improving
31 of p-type semi-conductive materials, a series of CuMO2 oxides
the OER catalytic activity and further making CuMO2 the
32 have been widely reported to be used in the fields of
potential candidates for cost-effective and active electrode
33 transparent conductive oxides [1-3], solar cell devices [4,5],
material motivate us to tune the size and morphology of CuMO2
34 photocatalysts [6,7] and other optoelectronic devices. Lots of
by optimizing the hydrothermal conditions.
35 CuMO2 oxides including CuCrO2, CuGaO2 and CuCoO2 were
As a fact, the synthesis of nano-sized delafossite oxides has
36 demonstrated to be efficient electrocatalysts in water splitting
always been a challenge, and current research reports mainly
37 towards oxygen evolution reaction (OER). For example,
focused on nano-sized CuCrO2 [12,13], CuGaO2 [14,15] and
38 delafossite CuCrO2 powders which were prepared by sol-gel
CuAlO2 [16] materials. And due to the toxicity of Cr and the
39 method demonstrated an exchange current density of 1.8 μA
rarity of Ga, the wide application of these CuMO2 materials in
40 cm-2 with good electrochemical stability in 0.5 M KOH
optoelectronic devices is limited. Therefore, it is an urgent work
41 electrolyte [8]. CuGaO2 nanoflakes were synthesized via SDS-
to explore new methods to prepare high quality, cheap and
42 assisted hydrothermal method and owned a better oxygen
environmentally friendly CuMO2 nanocrystalline materials for
43 evolution reaction activity in comparison with micron-sized
better application. CuCoO2, also belonging to delafossite oxides
44 CuGaO2 plates, and the smallest CuGaO2 nanoflakes exhibited
family, is a new kind of environmentally friendly CuMO2
45 the best (photo) electrocatalytic performance [9]. Recently, our
material. Owing to the hybridization of copper 3D orbital and
46 research group reported that the size of CuCoO2 crystals (1~2
oxygen 2p orbital [17,18] and main conductive hexagonal
47 μm) [10] were reduced to CuCoO2 nanoplates (~400 nm) [11]
copper layer [19], CuCoO2 has a wide band gap of 3.65 eV [20],
48 through one-step polyvinylpyrrolidone-assisted hydrothermal
high conductivity [21] and has a good application prospect in
49 synthesis at 100 °C. The CuCoO2 nanoplates exhibited good
the field of optoelectronic devices. Generally, previous
50 electrocatalytic activity and long-term stability toward the OER,
literatures reported delafossite CuCoO2 crystals which were
51 and it can attain an anodic current density (10 mA cm-2) with a
successfully prepared via the metathesis reaction at 590 °C [22]
52 low over potential of 390 mV in alkaline solution [11]. However,
and the hydrothermal method at 210 °C for 60 hours [23]. We
53 the electrocatalytic performance of these reported CuMO2 has
already reported hydrothermal synthesis of CuCoO2 nanoplates
54
(~400 nm) at 100 °C for 24 hours [11], but the sub-micron size is
55
also large and it is a challenge to reduce the crystalline size.
56 State Key Laboratory of Silicate Materials for Architectures, Wuhan University of
Moreover, there is no study reported on the solvothermal
57 Technology, Wuhan 430070, P. R. China
Email: xiongdehua2010@gmail.com (Dehua Xiong) synthesis of CuCoO2 crystals, so we are going to develop an
58 § Author Contributions, Z. D. and J. Q. contributed equally.
effective solvothermal synthesis method to control the crystal
59 † Footnotes relating to the title and/or authors should appear here.
60

Please do not adjust margins

 New do
Please Journal of Chemistry
not adjust margins Page 2 of 8

1 ARTICLE Journal Name

2
3 morphology and size of CuCoO2 nanocrystals, aiming for crystals with typical rhombic dodecahedron structure View Article were
Online

4 enhancing the electrocatalytic performance. prepared by a simple synthetic route at DOI: 10.1039/C9NJ03936H
room temperature,
5 Metal-organic frameworks (MOFs) are organic-inorganic hybrid which was used as Co-derived precursor during the
6 materials with intramolecular pore formed by self-assembly of solvothermal process to prepare CuCoO2 nanoplates (ca. 150
7 organic ligands and metal ions or clusters through coordination nm) at 140 °C and 24 hours. The influence of the amount of
8 bonds [24,25]. As a subfamily of MOFs, zeolitic imidazolate mineralizer NaOH addition and reactant precursors on crystal
9 frameworks (ZIFs) possess the characteristics of both MOFs and phase and morphology of these CuCoO2 was investigated.

New Journal of Chemistry Accepted Manuscript

10 zeolites, showing highly porous structures, large surface area Moreover, the chemical states of elements, Brunauer-Emmett-
11 and open catalytic active sites [26-28]. In detail, the porous Teller (BET) specific surface area and thermal stability of CuCoO2
12 nanocrystalline materials are assembled by the coordination of nanoplates have been studied.
13 bivalent metal ions (Zn2+, Co2+) and imidazole ligands in a four-
14 coordination manner. ZIFs of excellent performance have
15 potential application value in many aspects such as gas storage Experimental Section
16 and separation, chemical sensors and catalysts, and it attracts Materials preparation
17 much attention of researchers [29-30]. For example, ZIF-67
Each chemical was purchased from Sinopharm and used directly
18 (Co(Hmim)2) was formed by bridging 2-methylimidazolate
without further purification. The illustration of synthesis
19 anions and cobalt cations resulting in a sodalite topology with a
process of ZIF-67 and CuCoO2 crystals is shown in Fig. 1. ZIF-67
20 pore size of about 0.34 nm [31]. It was reported a layered
was prepared according to the procedure reported in previous
21
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

CoP/reduced graphene oxide bifunctional electrocatalyst using

work [35]. Typically, 4 mmol 2-methylimidazole and 1 mmol
22 ZIF-67 as template and precursor which exhibited an excellent
Co(NO3)2·6H2O were dissolved in 25 mL methanol and stirred
23 catalytic activity for both the hydrogen evolution reaction (HER)
about 20 minutes, respectively. Subsequently, the two solutions
24 and OER in basic solution [32]. In addition, by one-step
were quickly mixed and aged at room temperature for 24 hours,
25 carbonization of ZIF-67, nano porous carbon with good
and then purple powders of ZIF-67 were obtained after the
26 dispersed magnetic properties can be prepared while retaining
precipitation has been centrifuged and dried at 70 °C for 6 hours
27 its original shape, which is helpful to achieve high crystallinity
in air. Next, ZIF-67 and Cu(NO3)2·6H2O were used as cobalt and
28 and high configuration of cobalt nanoparticles in nano porous
copper source in these solvothermal synthesis experiments. In
29 carbon matrix (up to 49 wt%) [33]. Furthermore, Co9S8-MoS2
detail, 80 mg ZIF-67 powder was dispersed into 50 mL absolute
30 hierarchical nano boxes were prepared through the reaction of
ethanol under ultrasonication for 20 minutes. Then 0.4 mmol
31 ammonium MoS42- and ZIF-67 nano cubes, and the Co9S8-MoS2
Cu(NO3)2·6H2O and 20 mL deionized water were added to the
32 crystals had a high specific surface area (124.6 m2 g-1) and
above solution and the mixture was further stirred at room
33 excellent electrocatalytic performance [34]. Thus, the ZIF-67
temperature for 2 hours. After that, NaOH with different
34 possesses the characteristics of a tunable pore aperture, highly
concentration was added to the above mixed solution used as a
35 stable structure, catalytic activity and so on. Furthermore, many
mineralizer. Lastly, the dispersion was sealed in a 100 mL
36 works have been focused on ZIF-67 used as a precursor to
Teflon-lined autoclave and kept in an oven at 140 °C for 24
37 synthesize various derivatives, which show a better
hours for reaction. The as-obtained precipitates were collected
38 performance with potential synergistic interaction than original
and washed with suitable solutions (dilute ammonia water,
39 ZIF-67.
deionized water and absolute ethanol) for several times, and
40 In this work, we report that the ZIF-67 materials were used as
then dried at 60 °C for 12 hours for further characterization.
41 Co precursor to synthesize delafossite CuCoO2 through
42 solvothermal method for the first time. The classical ZIF-67
43
44
45
46
47
48
49
50
51
52
53 Fig. 1. Schematic description of the synthesis process for CuCoO2.

54
55 Materials Characterization transmission electron microscopy (TEM, JEM-1400 Plus,
56 The crystal structure of sample was characterized by powder X- operated at 200 keV). In addition, the surface chemical states of
57 ray diffraction (XRD, D8 Advance). The morphology and sample were analyzed by X-ray photoelectron spectroscopy
58 microstructure of sample were analyzed by field emission (XPS, ESCALAB250Xi). The elements content of Cu and Co was
59 scanning electron microscopy (FESEM, QUANTA FEG 450) and quantified analysis by an inductively coupled plasma-optical
60

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 3 of 8 New do
Please Journal of Chemistry
not adjust margins

1 Journal Name ARTICLE

2
3 emission spectrometry (ICP-OES, Agilent ICPOES730). The By using the polyhedron ZIF-67 crystals as Co-derivedViewprecursor,
Article Online

4 Brunauer-Emmett-Teller (BET) specific surface area was carried CuCoO2 was prepared through a solvothermalDOI: 10.1039/C9NJ03936H
method at 140 °C
5 out on a physical nitrogen (N2) adsorption-desorption for 24 hours. Different reaction parameters such as the quantity
6 instrument (Micromeritics ASAP 2460). Meanwhile, the thermal of mineralizer NaOH (1.96, 2.96 and 3.96 g) and the amounts of
7 stability of sample was studied by differential scanning reactant have been examined to find out the optimal conditions,
8 calorimetry-thermogravimetric analysis (DSC-TG) device as summarized in Table 1. It is known that the concentration of
9 (STA449F3) with a heating rate of 10 °C min-1 from 40 °C to NaOH in precursor’s solution is a key factor influencing the

New Journal of Chemistry Accepted Manuscript

10 800 °C in N2 atmosphere. crystal growth of the final product during the solvothermal
11 synthesis [37]. In order to evaluate this effect, different
12 amounts of NaOH (such as No.1-1.96 g, No.2-2.96 g and No.3-
13 Results and discussion 3.96 g) were added to the precursor solution containing 0.08 g
14 In order to optimize the yield of ZIF-67, the reactant of cobalt ZIF-67 and 0.4 mmol Cu (NO3)2. XRD analysis in Fig. 3(a) confirms
15 source was designed with different weight of Co(NO3)2 (ca. 1, 4 the formation of the CuCoO2 crystal phase (JCPDS card No. 21-
16 and 8 mmol). Both the amount of 2-methylimidazole and 0256) with various concentration of NaOH. Furthermore, SEM
17 methanol was scaled up by the same proportion. The three images in Fig. 3(b-d) show that CuCoO2 crystals displayed a
18 products were named as D1 (reference sample), D2 (4 times typical hexagonal morphology. Importantly, the crystalline size
19 proportion of D1 sample) and D3 (8 times proportion of D1 of CuCoO2 grew up gradually while increasing the addition
20 sample). The XRD patterns of the D1, D2 and D3 specimen in Fig. quantity of NaOH from 1.96 g to 3.96 g. And it was found that
21
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

2(a) matched well with the previous literature [34]. The single there are still some small particles after washing which may
22 phase of ZIF-67 can be obtained under the three reaction belongs to the unfinished products (Co3O4) in No.1 sample. The
23 conditions and no impurity phase was detected. The result demonstrated that the alkaline condition of precursor is
24 characteristic diffraction peaks located at around 7.39°, 10.44°, beneficial to the growth of CuCoO2 crystals, which is consistent
25 12.77°, 18.08° and 26.68°, which were correspond to crystal with our previous study on CuMnO2 [37] and CuCoO2 [11]. Thus,
26 planes of (011), (002), (112), (222) and (134), respectively. Fig. the main role of NaOH in solvothermal synthesis is to increase
27 2(b-d) show that ZIF-67 displays a typical morphology of the solubility of metal complexes by increasing the
28 rhombic dodecahedron and the uniform crystalline size of ZIF- concentration of hydroxides, which is conducive to the
29 67 around 800 nm, which is consistent with the previous work formation of CuCoO2 crystal phase.
30 [36]. Considering the actual demand for dosage and the
31 morphological purity, we synthesized pure phase ZIF-67 crystals
32 with 4 mmol Co(NO3)2 used as Co source for further
33 solvothermal synthesis reaction.
34
35
36
37
38
39
40
41
42
43
44
45
46 Fig. 3. XRD pattern (a) and FESEM images of products freshly obtained from solvothermal
47 method with different NaOH dosages (b, No.1; c, No.2; d, No.3).
48
49
50
Fig. 2. XRD pattern (a) and FESEM images of ZIF-67 samples (b: D1 sample; c: D2 sample
51 based on 4 times proportion of D1 sample; d: D3 sample based on 8 times proportion of
52 D1 sample).
53
54
55
56
57
58
59
60

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins

 New do
Please Journal of Chemistry
not adjust margins Page 4 of 8

1 ARTICLE Journal Name

2
3 Table 1. Details of the reaction conditions employed to synthesize CuCoO2 crystals.
View Article Online

4 Samples ZIF-67 (g) Cu(NO3)2 (mmol) Solvent NaOH (g) Time (h)
DOI: 10.1039/C9NJ03936H
Temperature (°C)
5
6
No.1 1.96
7
No.2 0.08 0.4 2.96
8 50 mL absolute ethanol
No.3 3.96 24 140
9 + 20 mL deionized water

New Journal of Chemistry Accepted Manuscript

No.4 0.4 2
10 2.96
No.5 0.8 4
11
12
For scaling up the production of CuCoO2 crystals, the reactants structure can be clearly distinguished as shown in Fig. 5(a).
13
of ZIF-67 and Cu(NO3)2 in precursor were amplified with 5-folds Careful observation showed that the size of CuCoO2 nanoplates
14
and 10-folds based on sample No.2, such as the samples of No.4 is around 80-170 nm, and the thickness is about 40-100 nm. The
15
(0.4 g ZIF-67 and 2 mmol Cu(NO3)2 and No.5 (0.8 g ZIF-67 and 4 nitrogen adsorption/desorption porosimetry was used to study
16
mmol Cu(NO3)2. Subsequently, 2.96 g NaOH was chose to add in the specific surface area (SSA) and porous structure of CuCoO2
17
solution and the solvothermal reaction was carried out at 140 °C nanoplates. Fig. 5(b) shows that the CuCoO2 nanoplates exhibit
18
for 24 hours. As shown in Fig. 4(a), there is no obvious a typical characteristic of a type IV isotherm with a hysteresis
19
difference of the XRD patterns among the three samples. loop, suggesting the presence of mesopores [39,40]. The SSA of
20
Delafossite oxide of CuCoO2 crystal phase was obviously CuCoO2 nanoplates was calculated to be 11.69 m2 g−1, which is
21
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

observed. SEM observation (Fig. 4b) revealed that the average higher than the value of hydrothermal synthesized CuCoO2
22
particle size of No.2 sample is the smallest (ca. 146 nm), which nanoplates (10.12 m2 g−1) [11]. In addition, the corresponding
23
is generally distributed in the range of 50-250 nm. For the pore size distribution in Fig. 5(c) indicates that the CuCoO2
24
scaled-up samples (Fig. 4c-d), the average particle sizes of nanoplates possess an abundant small mesoporous texture (2-
25
CuCoO2 crystal are 230 and 270 nm for the samples of No.4 and 4 nm). It is suggesting that a smaller size (~150 nm) of CuCoO2
26
No.5, respectively, which are larger than that of sample No.2. nanoplates with mesoporous structure have been successfully
27
Furthermore, the hexagonal morphology of these CuCoO2 prepared by using this solvothermal method.
28
crystals almost remained unchanged. But the SEM images in Fig.
29
4(b) and 4(c) reveals that the two specimens contain a mixture
30
of submicron-sized lamellar crystal and nanoparticles. Mass
31
diffusion plays an important role on the crystal nucleation and
32
growth in solvothermal process [38]. Maybe this issue could be
33
attributed to the higher concentration of reactants (such as 5-
34
folds and 10-folds) which caused the nonuniform reaction
35
during the solvothermal process, leading to the formation of
36
these nanoparticle impurities.
37 Fig. 5. TEM images (a) and Nitrogen adsorption/desorption isotherm plots (b) and BJH
38 pore-size distribution (c) of CuCoO2 (No.2 sample). The inset in panel (a) is the high
magnification TEM image.
39
40
The amount of Cu and Co in CuCoO2 nanoplates (the No.2
41
sample) was quantified by ICP-OES measurement. The result
42
showed that the content of Cu and Co was approximately 39.05
43
wt.% and 42.02 wt.% in CuCoO2 sample, respectively. The ratio
44
between Cu and Co element was close to the stoichiometric
45
proportion value (1:1), which indicating that a successful
46
preparation of CuCoO2 through our solvothermal method. The
47
surface composition and elemental chemical states of CuCoO2
48
nanoplates (the No.2 sample) were investigated by XPS
49
measurement, and the result is presented in Fig. 6. All these XPS
50
spectra of CuCoO2 agrees well with our previous reports on
51
CuCoO2 [10,11]. It can be observed from the XPS survey
52
spectrum in Fig. 6(a) confirms the Cu, Co and O elements in
53
Fig. 4. XRD pattern (a) and FESEM images of CuCoO2 crystals under different CuCoO2 nanoplates. Fig. 6(b) shows the peaks near 932.06 and
54
solvothermal conditions (b, No.2; c, No.4; d, No.5). The insets in panels b, c, and d show 951.79 eV correspond to the binding energies of Cu+ 2p3/2 and
55 particle size distribution.
Cu+ 2p1/2, respectively. The results are similar to other copper
56
based delafossite oxides such as CuAlO2 [41] and CuFeO2 [42],
57 To get an insight into CuCoO2 nanoplates, the No.2 sample was indicating the monovalent copper cations (Cu+) in CuCoO2. The
58 further characterized by TEM. The characteristics of hexagonal corresponding Co 2p high resolution spectrum in Fig. 6(c)
59
60

4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 5 of 8 New do
Please Journal of Chemistry
not adjust margins

1 Journal Name ARTICLE

2
3 presents the appearance of two peaks located at binding View Article Online

4 energies of 779.48 and 794.51 eV, which are assigned Co3+ 2p3/2 DOI: 10.1039/C9NJ03936H

5 and Co3+ 2p1/2 [43]. Additionally, there are another two peaks at
6 796.43 and 781.36 eV corresponding to the binding energies of
7 2p1/2 and 2p3/2 for the Co2+ ion [11]. Moreover, there are two
8 shakeup satellite peaks (identified as “Sat.”) centered at 789.56
9 and 804.73 eV. In the O 1s high resolution spectrum as shown

New Journal of Chemistry Accepted Manuscript

10 in Fig. 6(d), the strong peak at the binding energy of 529.73 eV
11 is assigned to metal-oxygen bonding (OL) in metal oxides [44],
12 another weak peak close to the binding energy of 531.4 eV is
13 metal hydroxides (OC) [11]. All these XPS results are consistent
14 with the previous report of CuCoO2 crystals.
15
16
17
Fig. 7. (a) Thermogravimetric (TG) curves of CuCoO2 powder in N2 and in air at the heating
18
rate of 10 °C min-1, also shown are XRD pattern (b) and the corresponding SEM images
19 of CuCoO2 powder in N2 (c) and in air (d) after sintering at 600 °C for 1 hour.
20
21
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

22 Conclusions
23
24 To summary, a novel solvothermal synthesis strategy has been
25 developed to synthesize CuCoO2 crystals by using metal-organic
26 frameworks material ZIF-67 as Co-derived precursor. CuCoO2
27 nanoplates (ca. 150 nm lateral, 40-100 nm thick) have been
28 Fig. 6. XPS survey spectrum (a) and high resolution XPS spectra for Cu 2p (b), Co 2p (c)
successfully prepared under the solvothermal reaction
29 and O 1s (d) of CuCoO2 (No.2 sample). conditions at 140 °C for 24 hours for the first time. By optimizing
30 the ZIF-67 precursor and solvothermal reaction parameters,
31 We previous reported the oxidation reaction of CuCoO2 delafossite oxide CuCoO2 nanoplates with size around 150 nm
32 powders would occur while sintering at 600 °C in air (Fig. 7a), can be obtained. The crystal structure, morphology, surface
33 resulting in the formation of CuO and CuCo2O4 (Fig. 7b) [10]. To chemical states, BET surface area and thermal stability of
34 avoid this oxidation reaction, the thermal stability of the CuCoO2 nanoplates were systemically characterized. Moreover,
35 CuCoO2 under an inert atmosphere (N2) was evaluated in this the TG analysis indicated the studied CuCoO2 nanoplates were
36 work. Fig. 7(a) shows the initial weight loss of CuCoO 2 powders more stable in N2 than in air atmosphere, the CuCoO2
37 below 300 °C in N2, which may be due to the evaporation of nanoplates remained intact when sintering at 600 °C for 1 hour
38 chemically combined water of crystallization and the variation in N2. This quick and facile method opens a new route for the
39 of oxygen [10]. TG analysis of the CuCoO2 powders in N2 preparation of variety delafossite oxides using metal-organic
40 exhibited a little weight changes (~1.28 %) from 300-800 °C, framework precursors, which can be used in optoelectronics
41 suggesting the as-obtained CuCoO2 crystals were stable in N2 devices such as photoelectrochemical cells and photovoltaics
42 atmosphere (Fig. 7a). On the contrary, a sharp and more cells.
43 prominent weight gain occurred above 500 °C in air in Fig. 7(a),
44 which is related to the oxidative reaction of CuCoO2 and
45 generated the new phases of CuO and CuCo2O4. The XRD result
Conflicts of interest
46 is consistent with the SEM images of CuCoO 2 crystals after There are no conflicts to declare
47 sintering at 600 °C. Fig. 7(c) shows the morphology of CuCoO2
48 kept unchanged after sintering in N2, which has an appearance
49 similar to as-synthesized CuCoO2 nanoplates and the crystalline Acknowledgements
50 size is around 200 nm. However, the morphology of CuCoO2 The authors would like to express sincere thanks for the
51 already changed after sintering in air in Fig. 7(d), and the rough financial supports by the Fundamental Research Funds for the
52 surface of CuCoO2 crystals owing to the newly generated CuO Central Universities (WUT: 2018IVA012, 2019 Ⅲ 153CG), and
53 and CuCo2O4 [10]. All these results confirmed the TG results the Undergraduate Innovation and Entrepreneurship Training
54 again. The CuCoO2 nanoplates remained intact under N2 Program at Wuhan University of Technology (WUT:
55 atmosphere in contrast to convert into copper cobalt composite 20181049701044, 20191049701022).
56 oxide of CuCo2O4 and CuO in air when CuCoO2 was kept the
57 same sintering condition at 600 °C for 1 hour. Therefore, the
58 CuCoO2 nanoplates have a better thermally stability in N2 Notes and references
59 atmosphere than in air.
60

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 5

Please do not adjust margins

 New do
Please Journal of Chemistry
not adjust margins Page 6 of 8

1 ARTICLE Journal Name

2
3 1 R. Laskowski, N.E. Christensen, P. Blaha, B. Palanivel, Strong 19 K.K. Kim, A. Hsu, X. Jia, S.M. Kim, Y. Shi, M. Hofmann, D. Nezich,
View Article Online
excitonic effects in CuAlO 2 delafossite transparent conductive J.F. Rodriguez-Nieva, M. Dresselhaus,DOI: T. 10.1039/C9NJ03936H
Palacios, J. Kong,
4 oxides, Phys. Rev. B 79 (2009) 165209. Synthesis of monolayer hexagonal boron nitride on Cu foil
5 2 T. Harada, K. Fujiwara, A. Tsukazaki, Highly conductive PdCoO 2 using chemical vapor deposition, Nano Lett. 12 (2011) 161-
6 ultrathin films for transparent electrodes, APL Mater. 6 (2018) 166.
7 046107. 20 C. Ruttanapun, M. Sa-nguan-cheep, S. Kahatta, P. Buranasiri,
8 3 J. Vidal, F. Trani, F. Bruneval, M.A.L. Marques, S. Botti, Effects P. Jindajitawat, Optical and electronic transport properties of
of electronic and lattice polarization on the band structure of p-type CuCoO2 transparent conductive oxide, ICPS (2013).
9 delafossite transparent conductive oxides, Phys. Rev. Lett. 21 R. Nagarajan, N. Duan, M. Jayaraj, J. Li, K. Vanaja, A. Yokochi,

New Journal of Chemistry Accepted Manuscript

10 104 (2010) 136401. A. Sleight, P-Type conductivity in the delafossite structure, Int.
11 4 Z. Xu, D. Xiong, H. Wang, W. Zhang, X. Zeng, L. Ming, Y.-B. J. Inorg. Mater. 3 (2001) 265-270.
12 Cheng, Remarkable photocurrent of p-type dye-sensitized 22 M. Beekman, J. Salvador, X. Shi, G.S. Nolas, J. Yang,
13 solar cell achieved by size controlled CuGaO 2 nanoplates, J. Characterization of delafossite-type CuCoO2 prepared by ion
Mater. Chem. A 2 (2014) 2968-2976. exchange, J. Alloys Compd. 489 (2010) 336-338.
14 5 M. Yu, T.I. Draskovic, Y. Wu, Cu(I)-based delafossite 23 K. Toyoda, R. Hinogami, N. Miyata, M. Aizawa, Calculated
15 compounds as photocathodes in p-type dye-sensitized solar descriptors of catalytic activity for water electrolysis anode:
16 cells, Phys. Chem. Chem. Phys. 16 (2014) 5026-5033. application to delafossite oxides, J.Phys. Chem. C 119 (2015)
17 6 J. Ahmed, Y. Mao, Synthesis, characterization and 6495-6501.
18 electrocatalytic properties of delafossite CuGaO 2, J. Solid 24 S. Dang, Q.-L. Zhu, Q. Xu, Nanomaterials derived from metal-
State Chem. 242 (2016) 77-85. organic frameworks, Nat. Rev. Mater. 3 (2017) 17075.
19 7 W. Ketir, G. Rekhila, M. Trari, A. Amrane, Preparation, 25 W. Wang, X. Xu, W. Zhou, Z. Shao, Recent progress in metal-
20 characterization and application of CuCrO 2/ZnO organic frameworks for applications in electrocatalytic and
21
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

photocatalysts for the reduction of Cr(VI), J. Environ. Sci. photocatalytic water splitting, Adv. Sci. 4 (2017) 1600371.
22 China 24 (2012) 2173-2179. 26 S. Tan, J. Li, L. Zhou, P. Chen, Z. Xu, A new strategy for the
23 8 N. Benreguia, A. Abdi, O. Mahroua, M. Trari, Semiconducting improvement of direct use of MOFs as supercapacitor
and photoelectrochemical characterizations of CuCrO 2 electrodes, Mater. Lett. 251 (2016) 102-105.
24 powder synthesized by sol-gel method, J. Solid State 27 N. Cheng, L. Ren, X. Xu, Y. Du, S. Dou, Recent development of
25 Electrochem. 22 (2018) 2499-2506. zeolitic imidazolate frameworks (ZIFs) derived porous carbon
26 9 S. Mohan, Y. Mao, Dependence of (photo) electrochemical based materials as electrocatalysts, Adv. Energy Mater. 8
27 properties on geometry factors of hydrothermally (2018) 1801257.
28 synthesized delafossite copper gallium oxide CuGaO 2 toward 28 S. Li, J. Dai, Q. Yan, J. He, J. Lei, J. Li, L. Wang, Effect of zeolitic
oxygen evolution reaction, J. Electrochem. Soc. 165 (2018) imidazole framework (ZIFs) shells of core-shell microspheres
29 H607-H613. on adsorption of roselle red dye from water, Inorg, Chem.
30 10 Z. Du, D. Xiong, S.K. Verma, B. Liu, X. Zhao, L. Liu, H. Li, A low Commun. 97 (2018) 113-118.
31 temperature hydrothermal synthesis of delafossite CuCoO2 as 29 J. Yang, H. Ye, Z. Zhang, F. Zhao, B. Zeng, Metal-organic
32 an efficient electrocatalyst for the oxygen evolution reaction framework derived hollow polyhedron CuCo 2O4
33 in alkaline solutions, Inorg. Chem. Front. 5 (2018) 183-188. functionalized porous graphene for sensitive glucose sensing,
11 D. Xiong, Z. Du, H. Li, J. Xu, J. Li, X. Zhao, L. Liu, Sensor. Actuat. B-Chem. 242 (2017) 728-735.
34 Polyvinylpyrrolidone-assisted hydrothermal synthesis of 30 D. Matatagui, A. Sainz-Vidal, I. Gràcia, E. Figueras, C. Cané, J.M.
35 CuCoO2 nanoplates with enhanced oxygen evolution reaction Saniger, Chemoresistive gas sensor based on ZIF-8/ZIF-67
36 performance, ASC Sustain. Chem. Eng. 7 (2019) 1493-1501. nanocrystals, Sensor. Actuat. B-Chem. 274 (2018) 601-608.
37 12 B. Tong, Z. Deng, B. Xu, G. Meng, J. Shao, H. Liu, T. Dai, X. Shan, 31 J. Qian, F. Sun, L. Qin, Hydrothermal synthesis of zeolitic
38 W. Dong, S. Wang, S. Zhou, R. Tao, X. Fang, Oxygen vacancy imidazolate framework-67 (ZIF-67) nanocrystals, Mater. Lett.
defects boosted high performance p-type delafossite CuCrO 2 82 (2012) 220-223.
39 gas sensors, ACS Appl. Mater. Inter. 10 (2018) 34727-34734. 32 L. Jiao, Y.-X. Zhou, H.-L. Jiang, Metal-organic framework-based
40 13 P. Rattanathrum, C. Taddee, N. Chanlek, P. Thongbai, T. CoP/reduced graphene oxide: high-performance bifunctional
41 Kamwanna, Structural and physical properties of Ge-doped electrocatalyst for overall water splitting, Chem. Sci. 7 (2016)
42 CuCrO2 delafossite oxide, Ceram. Int. 43 (2017) S417-S422. 1690-1695.
43 14 K. Ueda, T. Hase, H. Yanagi, H. Kawazoe, H. Hosono, H. Ohta, 33 N.L. Torad, M. Hu, S. Ishihara, H. Sukegawa, A.A. Belik, M.
M. Orita, M. Hirano, Epitaxial growth of transparent p-type Imura, K. Ariga, Y. Sakka, Y. Yamauchi, Direct synthesis of
44 conducting CuGaO 2 thin films on sapphire (001) substrates by MOF-derived nanoporous carbon with magnetic Co
45 pulsed laser deposition, J. Appl. Phys. 89 (2001) 1790-1793. nanoparticles toward efficient water treatment, Small 10
46 15 M. Yu, G. Natu, Z. Ji, Y. Wu, P-Type dye-sensitized solar cells (2014) 2096-2107.
47 based on delafossite CuGaO 2 nanoplates with saturation 34 V. Ganesan, S. Limand, J. Kim, Hierarchical nanoboxes
48 photovoltages exceeding 460 mV, J. Phys. Chem. Lett. 3 (2012) composed of Co9S8-MoS2 nanosheets as efficient
1074-1078. electrocatalysts for the hydrogen evolution reaction, Chem.
49 16 H. Yanagi, S. Inoue, K. Ueda, H. Kawazoe, H. Hosono, N. Asian J. 13 (2018) 413-420.
50 Hamada, Electronic structure and optoelectronic properties 35 H. Hu, B. Guan, B. Xia, and X. W. (David) Lou, Designed
51 of transparent p-type conducting CuAlO2, J. Appl. Phys. 88 formation of Co3O4/NiCo2O4 double-shelled nanocages
52 (2000) 4159-4163. with enhanced pseudocapacitive and electrocatalytic
53 17 S.-F Wang, L.-Y. Chen, T. Zhang, Y.-L. Song, Half-Metallic properties, J. Am. Chem. Soc. 137 (2015) 5590-5595.
ferromagnetism in Cu-doped ZnO nanostructures from first- 36 Z. Jiang, Z. Li, Z. Qin, H. Sun, X. Jiao and D. Chen, LDH
54 principle prediction, J. Supercond. Nov. Magn. 28 (2015) nanocages synthesized with MOF templates and their high
55 2033-2038. performance as supercapacitors, Nanoscale, 5 (2013), 11770-
56 18 Y. Ohta, T. Tohyama, S. Maekawa, Apex oxygen and critical 11775.
57 temperature in copper oxide superconductors: Universal 37 D. Xiong, Q. Zhang, Z. Du, S.K. Verma, H. Li, X. Zhao, Low
58 correlation with the stability of local singlets, Phys. Rev. B 43 temperature hydrothermal synthesis mechanism and thermal
(1991) 2968-2982.
59
60

6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 7 of 8 New do
Please Journal of Chemistry
not adjust margins

1 Journal Name ARTICLE

2
3 stability of p-type CuMnO2 nanocrystals, New J. Chem. 40 View Article Online
(2016) 6498-6504.
4 38 Y. Cui, G. Chen, J. Ren, M. Shao, Y. Xie, Y. Qian, Solvothermal
DOI: 10.1039/C9NJ03936H

5 syntheses of β-Ag2Se crystals with novel morphologies, J. Solid

6 State Chem. 172 (2003) 17-21.
7 39 M. Liang, M. Zhao, H. Wang, J. Shen, X. Song, Enhanced cycling
8 stability of hierarchical NiCo 2S4@Ni(OH)2@PPy core-shell
nanotube arrays for aqueous asymmetric supercapacitors, J.
9 Mater. Chem. A 6 (2018) 2482-2493.

New Journal of Chemistry Accepted Manuscript

10 40 H.-J. Zhang, F.-N. Meng, L.-Z. Liu, Y.-J. Chen, P.-J. Wang, Highly
11 sensitive H2S sensor based on solvothermally prepared spinel
12 ZnFe2O4 nanoparticles, J. Alloys Compd. 764 (2018) 147-154.
13 41 H.-Y. Chen, J.-H. Ou, P-type transparent conductive CuAlO 2
thin films prepared using atmospheric pressure plasma
14 annealing, Mater. Lett. 228 (2018) 81-84.
15 42 D. Xiong, Q. Zhang, S.K. Verma, X. Bao, H. Li, X. Zhao, Crystal
16 structural, optical properties and mott-schottky plots of p-
17 type Ca doped CuFeO 2 nanoplates, Mater. Res. Bull. 83 (2016)
18 141-147.
43 K.J. Kim, J.H. Lee, T.Y. Koh, M.H. Kim, Improved cyclic stability
19 by octahedral Co3+ substitution in spinel lithium manganese
20 oxide thin-film cathode for rechargeable microbattery,
21
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

Electrochim. Acta 200 (2016) 84-89.

22 44 A.A. Ensafi, S.E. Moosavifard, B. Rezaei, S.K. Kaverlavani,
23 Engineering onion-like nanoporous CuCo2O4 hollow spheres
derived from bimetal-organic frameworks for high-
24 performance asymmetric supercapacitors, J. Mater. Chem. A
25 6 (2018) 10497-10506.
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 7

Please do not adjust margins

 New Journal of Chemistry Page 8 of 8

1
2
3 View Article Online

4 A table of contents entry： DOI: 10.1039/C9NJ03936H

5
6 CuCoO2 nanoplates were prepared through solvothermal method at 140 °C using ZIF-
7
8 67 as Co precursor for the first time.
9

New Journal of Chemistry Accepted Manuscript

10
11
12
13
14
15
16
17
18
19
20
Published on 28 August 2019. Downloaded on 9/4/2019 2:38:09 AM.

21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60