Front.

Energy 2024, 18(3): 378–389

https://doi.org/10.1007/s11708-024-0924-x

RESEARCH ARTICLE

Zhao-ting SHANG, Tang-ming LI, Bing-qian HU, Min LIU, Wang-ting LU, Fan YU, Yun ZHENG

Two-dimensional bimetallic selenium-containing metal-

organic frameworks and their calcinated derivatives as
electrocatalysts for overall water splitting

© Higher Education Press 2024

Abstract The use of two-dimensional (2D) layered Keywords 2D MOF, selenium (Se)-containing
metal-organic frameworks (MOFs) as self-sacrificial tem- materials, hydrogen evolution reaction (HER), oxygen
plates has been proven to be a successful method to create evolution reaction (OER)
high-efficiency Selenium (Se)-containing electrocatalysts
for overall water splitting. Herein, two strategies are then
utilized to introduce Se element into the Co–Fe MOF, one 1 Introduction
being the etching of as-prepared MOF by SeO2 solution,
and the other, the replacing of SCN− with SeCN− as the
construction unit. The electrochemical activity of the Hydrogen is thought to be a suitable energy vehicle for
pristine 2D MOF and their calcinated derivatives for energy conservation and delivery for its extreme energy
catalyzing the hydrogen evolution reaction (HER) and density and zero-carbon nature. In the industrial field,
oxygen evolution reaction (OER) is evaluated and further hydrogen is also a critical chemical raw ingredient. The
discussed. It is found that the effect of introducing Se on conventional hydrogen production process (e.g., natural
improving electrochemical catalytic activity is significant gas reforming) will not only increase fossil fuel use, but
for the HER process. Specifically, the calcinated derivative also significantly increase global carbon dioxide
in the replacing method exhibits an overpotential of emissions [1–4]. Electrolysis of water is a highly
235 mV for HER and 270 mV for OER at a current economical and sustainable method of synthesizing
density of 10 mA/cm2. For comparing the two methods of hydrogen [5–8]. Two crucial reactions in the entire
introducing Se element into MOF, similar electrocatalytic process of water splitting are the hydrogen evolution
activity can be achieved on the their calcinated derivatives. reaction (HER) and the oxygen evolution reaction (OER)
The high electrochemical performance of 2D CoFe-MOF [9–16]. It is significant to investigate catalytically active
derivatives may be resulted from the unique 2D materials for the application of electrochemical hydrogen
hierarchical porous structure and strong synergistic effect production. Different materials, such as metal
between different components in the material.
chalcogenides, metal carbides, and metal oxides, have
been reported to have good catalytic effects on producing
Received Sept. 19, 2023; accepted Nov. 29, 2023; online Mar. 10, 2024 oxygen and hydrogen [17–20]. Metal sulfides have been
Zhao-ting SHANG, Tang-ming LI, Bing-qian HU, Min LIU, Wang- reported to exhibit outstanding catalytic performance for
✉
ting LU ( ), Fan YU ( )✉ water splitting [21]. Compared to sulfur atoms, selenium
Key Laboratory of Optoelectronic Chemical Materials and Devices of atoms have lower ionization energies, more metallicity
Ministry of Education, College of Optoelectronic Materials and
Technology, Jianghan University, Wuhan 430056, China
(greater conductivity), and a larger atomic radius.
E-mails: [email protected] (W. LU); Correspondingly, transition metal selenides have a higher
[email protected] (F. YU) metallicity, a narrower band gap, a great stability, and a
Yun ZHENG ( ) ✉ low cost, making them a good choice for electrocatalytic
Institute of New Energy Materials and Engineering, School of water splitting [22–24].
Materials Science and Engineering, Fuzhou University, Fuzhou Metal-organic frameworks (MOFs) are a sort of high
350108, China; Department of Chemical Engineering, University of
Waterloo, Waterloo, Ontario N2L 3G1, Canada porosity crystal material created by combining metal ions
E-mail: [email protected] and organic ligands [25–30]. Because MOFs have a
Special Issue: Electrochemical Energy Storage and Conversion of unique coordination connection mechanism, they can be
Hydrogen Energy paired with a variety of metal centers and organic ligands.
 Zhao-ting SHANG et al. 2D MOFs and their derivatives as electrocatalysts for overall water splitting 379

The structural advantages of MOFs, such as porous 2 Experimental

structure, structural tailor-ability, and easy component
control, dictate their practical implementation in a broad 2.1 Materials
diversity of fields, and they also show tremendous
promise as a potential precursor for total water splitting Potassium hydroxide (KOH, 99.9%), ferrous sulfate hep-
[31–36]. In addition, the modification of bimetallic tahydrate (FeSO4·7H2O,99.9%), potassium selenocyanate
MOFs and their derived materials has been used to make (KSeCN, 98.5%), selenium dioxide (SeO2, 99.9%), N,N-
catalysts with good electrocatalytic capabilities [37–41]. dimethylformamide (DMF, 99.8%), and 1-methyl-2-
Traditionally, the MOF-derived selenides are produced pyrrolidinone (NMP, 99.9%) were obtained from the
via the self-sacrificing MOF template method, i.e., the Aladdin Co. (Shanghai, China), while cobalt sulfate
pyrolysis of MOF followed by selenidation with selenium heptahydrate (CoSO4·7H2O, 99.5%), methanol solution
powder at high temperature. However, this strategy is (CH3OH, 99.5%), potassium thiocyanate (KSCN,
high-energy consuming. In addition, it is difficult to 98.5%), and poly (vinylidene fluoride) (PVDF) were
precisely control the structure and component supplied by Sinopharm Chemical Reagent Co., Ltd.
homogeneity of the product during pyrolysis. Moreover, (Shanghai, China) and used as received without any
the advantages of the component homogeneity and tailor- purification.
ability of MOFs can be fully employed to resolve the
above problems and govern the number of specific
2.1.1 Synthesis of Co0.6Fe0.4-MOF
components. For example, selenium (Se)-containing
MOFs can be prepared in a single step using a Se-
The synthetic procedure for CoFe-MOF was slightly
containing ligand (SeCN−) as initial component, which
modified from Ref.[56]. CoSO4·7H2O (0.06 mmol),
can be used as the catalysts directly or as the templates to
KSCN (0.2 mmol), and FeSO4·7H2O (0.04 mmol) were
prepare selenides by pyrolysis, avoiding the difficulties
combined in 5 mL of methanol solution and vigorously
of component in-homogeneity and excessive defects
caused by post-doping of selenium powders. stirred for several minutes. The mixture appeared to
2D layered MOF, in particular, usually has a lot of precipitate and was then filtered. The filtrate was trans-
interlayer electrons and intermediate adsorption/desorp- ferred to a rigid test tube, defined as layer A (Fig. 1(a)),
tion pathways, making it a good template for water followed by the slow addition of methanol solution (5
splitting catalysis [42–48]. To promote the application of mL), as layer B (Fig. 1(a)), finally the addition of
MOF-based electrocatalysts, it is critical to create an methanol solution containing L (0.005 mol/L) placed in
MOF with high efficiency and large-scale production. layer C (Fig. 1(a)). After leaving the reaction for a few
The two-dimensional (2D) MOF can be created in a days, shiny pink crystals (35% in L) appeared at the
variety of ways, such as solvothermal reaction, bottom of the test tube. L represents tetrakis (3-
mechanical grinding, and diffusion technique. Therein, pyridyloxymethylene) methane which was produced in
the reaction conditions of the diffusion method are mild, accordance with Wang et al. [57]. The X-ray diffraction
and the solvent can be changed to tailor the structure of (XRD) pattern of the Co0.6Fe0.4-MOF precursor is
MOF [49–55]. As a result, the cost of MOF-based consistent with the original Co-MOF, which determined
electrocatalysts can be lowered from the initial step, and successfully to synthesize by powder X-ray diffraction
large-scale preparation would be achieved by using the (PXRD), as shown in Fig. S1 in Electronic
diffusion method. Supplementary Material (ESM). In addition, Co and Fe
In this work, a 2D CoFe-MOF constructed via the contents were measured by inductively coupled
diffusion method was selected as self-sacrificing template plasma−mass spectrometry (ICP/MS) to further confirm
to explore the viability of making Se-containing electroca- the above results, which are shown in Table S1.
talysts via two methods. In the first method, CoFe-MOF
is used as raw material, the selenium source is introduced 2.1.2 Synthesis of Co/Fe/S/Se-400
by SeO2 solution etching, and then the CoFe-MOF is
calcined. In the second method, SeCN− is used as the The pristine Co0.6Fe0.4-MOF was submerged in the aqua
construction unit to prepare Se-containing MOF, and then solution of SeO2 for 5 h. The solid samples were dried
the Se-containing MOF is calcined. It is found that the for later use after being filtered, then washed three
calcination obviously enhances the activity of MOF for times with water. Then the solid samples (named as
HER. Co/Fe/Se-400 displays an overpotential of 270 mV CoFe/Se-MOF-5h) were placed in the tubular furnace
(10 mA/cm2) for OER and 235 mV (10 mA/cm2) for at N2 atmosphere, and then heated at 400 °C for 2 h, and
HER, and a remarkable stability over the course of a 24-h the calcinated derivative is named as Co/Fe/S/Se-400.
consecutive test. The current findings may provide a For comparison, CoFe/Se-MOF-1h, CoFe/Se-MOF-3h,
simple and feasible way to manufacture metal selenides and Co/Fe/S/Se-500 were fabricated and their structures
as catalysts for HER and OER. and electrocatalytic properties were also characterized to
380 Front. Energy 2024, 18(3): 378–389

Fig. 1 Schematic diagram for preparation of materials.

(a) Co0.6Fe0.4-MOF (the pristine 2D MOF in the etching method) and Co/Fe/S/Se-400 (the calcinated derivative in the etching method); (b)
CoFe-MOF-Se (the pristine 2D MOF in the replacing method) and Co/Fe/Se-400 (the calcinated derivative in the replacing method).

determine the optimal temperature and SeO2 etching ESCALAB 250XI spectrometer was used to collect the
times. The detailed results are shown in ESM. singles of X-ray photoelectron spectroscopy (XPS)
spectra. N2 adsorption–desorption isotherms were
2.1.3 Synthesis of CoFe-MOF-Se determined by Micromeritics ASAP2020 PLUS HD.
Electrochemical tests were conducted with CHI 760E
The precise synthesis method and reagent amount were (Shanghai Chenhua Science Technology Corp., Ltd.,
the same for Co0.6Fe0.4-MOF, with the exception that China) electrochemistry workstation operating at room
KSeCN (0.2 mmol) was employed in place of KSCN. A temperature. The apparatus employed has three
sparkling pink crystal was obtained after several days electrodes, including a saturated calomel electrode, a
(30% depending on L). For comparison, a series of CoFe- graphite rod counter electrode, and a working electrode.
MOF-Se based on different amount of SeCN− were The reversible hydrogen electrode (RHE) was widely
synthesized and the electrocatalytic results are shown in used for potential conversion in this work, and the
ESM. specific procedure for electrode preparation is described
in ESM.
2.1.4 Synthesis of Co/Fe/Se-400

The pristine pink crystal named as CoFe-MOF-Se was 3 Results and discussion
placed in the tubular furnace at N2 atmosphere, and then
heated at 400 °C for 2 h and the last calcinated product is 3.1 Structural analysis of materials
named as Co/Fe/Se-400.
A 2D MOF layer (Co0.6Fe0.4-MOF) was successfully
2.2 Characterizations constructed via the diffusion method by utilizing the
teterpyridyl ligand, Co2+, Fe2+, and SCN−, according to
PXRD was detected by using a Panalytical X’pert Fig. 1 [56]. Subsequently, there are two methods to
Powder Diffractometer at 40 kV and 40 mA, in which the introduce the Se element into the material, i.e., the
Cu Kα radiation source (λ = 1.5406 Å). A Sigma HD etching of Co0.6Fe0.4-MOF (the pristine 2D MOF in the
thermal field emission scanning electron microscope etching method) by SeO2 solution (process as shown in
(SEM) was performed to observe the morphologies of 2D Fig. 1(a)) and synthesizing Se-containing MOFs (named
MOFs and their derivatives. Meanwhile, the Thermo as CoFe-MOF-Se, the pristine 2D MOF in the replacing
 Zhao-ting SHANG et al. 2D MOFs and their derivatives as electrocatalysts for overall water splitting 381

method) by replacing SCN− with SeCN− (process as on different amount of SeCN− (Figs. 2 and S4) are
shown in Fig. 1(b)), both are calcined to obtain the final comparable to those of Co0.6Fe0.4-MOF except that the
materials, Co/Fe/S/Se-400 (the calcinated derivative in diffraction intensity is significantly increased,
the etching method) and Co/Fe/Se-400 (the calcinated demonstrating that the replacement of SCN− by SeCN−
derivative in the replacing method), respectively. for the synthesis of Se-containing MOFs is successful.
For the first method, Se-containing MOF was prepared After calcination of CoFe-MOF-Se at 400 °C, Co/Fe/Se-
by etching 2D Co0.6Fe0.4-MOF in a SeO2 solution. The 400 was fabricated. The diffraction peaks belonging to
intermediate products are named CoFe/Se-MOF-1h, pristine MOFs vanished completely, and new peaks
CoFe/Se-MOF-3h, and CoFe/Se-MOF-5h after etching appeared (Fig. 2). The diffraction peaks at 30.8°, 34.7°,
for 1, 3, and 5 h. XRD images also demonstrate that the 36.3°, 47.8°, and 57.2° can be ascribed to CoSe2
etched materials can still maintain the original crystalline (PDF#10-0408), while peaks at 44.3°, 57.4°, and 77.7°
structure with the pristine Co0.6Fe0.4-MOF even after coming from FeSe2 (PDF#48-1881). The presence of
etching for 5 h, which can be seen from Fig. S2(a). The FeSe2 may be attributed to the higher doping amount of
peaks at 9.81° and 12.09° show a rightward shift with selenium in CoFe-MOF-Se than that of CoFe/Se-MOF-
increasing etching time, accompanied by an increase in 5h, which allows the formation of FeSe2.
the lattice spacing as determined by Bragg calculation The morphology of materials is characterized by SEM.
(Fig. S2(b)). Furthermore, CoFe/Se-MOF-5h was utilized As for the samples prepared by the etching method, the
as a self-sacrificial template to prepare MOF-derived 2D MOF, i.e., the Co0.6Fe0.4-MOF shows as a lamellar
materials by calcination. The thermogravimetric measure- stacking structure as shown in Figs. 3(a) and 3(b). As for
ment of MOF demonstrates that its structure is stable the corresponding calcinated derivative, Co/Fe/S/Se-400
until 380 °C [56]. As a result, the calcination temperature presents a fragmented flake-like structure with many
is restricted to 400 and 500 °C, and the Co/Fe/S/Se-400 small particles on the surface (Figs. 3(c), 3(d), and S5(a)).
derived from CoFe/Se-MOF-5h by calcination at 400 °C The relatively smaller sheet size of Co/Fe/S/Se-400 is
shows diffraction peaks (30.7°, 35.2°, and 47.2°) ascribed conducive to exposing more active sites. The
to CoSe2 (PDF#10-0408) in addition to Co1−xS (PDF#42- transmission electron microscope (TEM) images of
0826) (Fig. 2). As the calcination temperature increased Co/Fe/S/Se-400 (Figs. S5(c) and S5(e)) clearly show the
to 500 °C, the main diffraction peaks (30.8° and 34.7°) of fragmented structure, which is in consistent with the
Co/Fe/S/Se-500 were matched with CoSe2 (PDF#10- SEM image.
0408) (Fig. S3), and the other diffraction peaks were When it comes to the replacing method, the SEM
matched with Co1−xS. Comparably, the characteristic image of CoFe-MOF-Se shows a flower-like lamellar
peaks of CoSe2 are more obvious and sharper in structure which is slightly different from that of
Co/Fe/S/Se-400, indicating that the calcination Co0.6Fe0.4-MOF as presented in Figs. 3(e) and 3(f). After
temperature of 400 °C is more favorable for the calcination, the surface of Co/Fe/Se-400 becomes rough,
formation of CoSe2. However, no diffraction peaks of as can be observed from Figs. 3(g), 3(h), and S5(b). The
FeSe2 could be detected by XRD (Fig. 2), indicating that irregular layered structure consists of randomly
the calcination does not promote the formation of FeSe2. assembled nanosheets stacked close to each other. The
thinner lamellar structure, with significantly smaller
particle size and gaps between layers, can provide more
marginal active sites. The TEM images of Co/Fe/Se-400
(Figs. S5(d) and S5(f)) clearly show a 2D lamellar
structure, which is in agreement with the SEM image.
The energy dispersive spectrometer (EDS) mapping
images (Fig. S6) show that the Co, Fe, and Se
compositions in Co/Fe/S/Se-400 and Co/Fe/Se-400 are
uniformly distributed, including the presence of S within
Co/Fe/S/Se-400. The specific surface area of the as-
synthesized calcinated derivatives was characterized
through N2 adsorption–desorption measurements. The N2
adsorption–desorption isotherms of Co/Fe/S/Se-400 and
Co/Fe/Se-400 display typical type I isotherms (Fig. S7),
Fig. 2 XRD patterns of Co0.6Fe0.4-MOF, CoFe-MOF-Se,
Co/Fe/S/Se-400, and Co/Fe/Se-400.
indicating the presence of microporous structures in both
materials (Table S2). The Brunauer–Emmett–Teller
The second method to introduce Se into 2D MOF is the (BET) surface area of Co/Fe/Se-400 was 178.72 m2/g
replacement of SCN− by SeCN−, and the corresponding compared to 102.44 m2/g of Co/Fe/S/Se-400.
product obtained is named CoFe-MOF-Se. The Figure 4 illustrates the XPS analysis findings applied to
characteristic diffraction peaks of CoFe-MOF-Se based investigate the elements content and surface valence
382 Front. Energy 2024, 18(3): 378–389

Fig. 3 SEM images.

(a, b) Co0.6Fe0.4-MOF; (c, d) Co/Fe/S/Se-400; (e, f) CoFe-MOF-Se; (g, h) Co/Fe/Se-400.

states of Co/Fe/S/Se-400, CoFe-MOF-Se, and Co/Fe/Se- In the XPS spectrum of Se 3d, Se 3d5/2 exhibits the peaks
400. Regarding Co/Fe/S/Se-400, the overall spectrum at 56.0 eV, along with the peak of Se 3d3/2 at 55.2 eV,
exhibits distinct peaks corresponding to O 1s, C 1s, Co indicating the existing metal-Se species [62,63], and the
2p, S 2p, Fe 2p, and Se 3d (Figs. S2 and S3). In the Co peak with binding energy at 61.1 eV allocated for Se
2p spectrum observed from Fig. 4(a), Co 2p splits into oxide [63]. The formation of S and Se oxide is attributed
two spin orbits of Co 2p3/2 (781.8 eV) and Co 2p1/2 to the thin surface oxide layer formed by exposure to air.
(794.5 eV), and two satellite peaks (at 785.5 and The XPS spectra of CoFe-MOF-Se are exhibited in
802.4 eV), which indicates the existence of Co2+ [58,59]. Figs. 4(d)–4(f). The peaks at 796.6 and 780.8 eV are
In the Fe 2p spectrum, the peaks around 711.6 and linked to Co 2p1/2 and Co 2p3/2. The high intensity of
713.9 eV might be originated from Fe2+ 2p3/2, and the satellite peaks at 785.5 and 802.4 eV indicates the
peak at 724.8 eV from Fe2+ 2p1/2 [60,61]. In the S 2p presence of Co2+ [58,59]. The two peaks of Fe 2p which
spectrum (Fig. S8), the peaks which centered on 168.7 appeared around 711.3 and 721.4 eV correspond to Fe
and 164.1 eV belong to SO42− and metal-S bond, 2p3/2 and Fe 2p1/2. The peak at 54.8 and 55.1 eV of Se 3d
respectively, indicating the existence of metal-S species. is assigned to Se 3d5/2 and Se 3d3/2. Like CoFe-MOF-Se,
 Zhao-ting SHANG et al. 2D MOFs and their derivatives as electrocatalysts for overall water splitting 383

Fig. 4 XPS spectra.

(a–c) Co/Fe/S/Se-400: (a) Co 2p, (b) Fe 2p, (c) Se 3d; (d–f) CoFe-MOF-Se: (d) Co 2p, (e) Fe 2p, (f) Se 3d; (g–i) Co/Fe/Se-400: (g) Co 2p,
(h) Fe 2p, (i) Se 3d.

the Co 2p and Fe 2p spectrum of Co/Fe/Se-400 in HER regulated by the etching time is the lowest. Thus,
Figs. 4(g)–4(i) also demonstrates that the Co and Fe the corresponding CoFe/Se-MOF-5h was utilized as a
element exist in the form of Co2+ and Fe2+ state. The self-sacrificial template and calcined at a high
peaks which centered at 54.4 and 55.4 eV should be temperature, and the derived materials were also
ascribed to Se 3d5/2 and Se 3d3/2, indicating that there characterized by electrocatalysis. The results reveal that
exists a metal–Se bond in the sample [64]. there exists calcination at 400 and 500 °C, that the HER
The related XPS spectra of carbon and oxygen in performance of the derived materials has been improved,
different samples are shown in Figs. S8 and S9. All the and that the overpotential of Co/Fe/S/Se-400 is the
peaks of carbon which occur around 285 eV are assigned smallest, which may be due to the exposure of more
to the binding energy of C 1s [65]. Meanwhile, the active sites of co-doped Co, S, and Se at 400 °C as
related peaks of oxygen are presented around 531 eV illustrated in Figs. S11(a) and S11(b). Both the OER and
[66]. HER polarization curves of CoFe-MOF-Se (based on
different amounts of SeCN−) are essentially the same
3.2 Electrocatalytic performances (Fig. S12), suggesting that Se-containing MOFs formed
with different amounts of SeCN− has no effect on
The electrocatalytic behaviors of MOF materials etched improving the OER and HER performance.
by SeO2 reveal that HER performances have been Comparing the electrochemical characteristics of the
improved to some extent, as shown in Figs. S10(a) and materials obtained by the two selenisation methods, the
S10(b). When the etching time is 5 h, the overpotential of OER and HER performance of the original 2D MOFs
384 Front. Energy 2024, 18(3): 378–389

including Co0.6Fe0.4-MOF and CoFe-MOF-Se, as well as the lowest, which could be due to the fact that as time
the corresponding calcinated derivatives including passes, Se becomes more complete, exposing more active
Co/Fe/S/Se-400 and Co/Fe/Se-400, were evaluated sites, hence improving the HER performance.
systematically. The values of the electrocatalytic results Secondly, the linear sweep voltammetry (LSV) and
are shown in Table S3. Tafel curves were obtained to further evaluate the
First, the OER polarization curves and Tafel slopes of electrochemical performance, and the corresponding
Co/Fe/S/Se-400 are close to that of the original results for CoFe-MOF-Se and Co/Fe/Se-400 are shown in
Co0.6Fe0.4-MOF, as shown in Figs. 5(a) and 5(b), Fig. 5. The OER performance of CoFe-MOF-Se is
indicating that the calcination has no effect on the activity inferior to that of Co0.6Fe0.4-MOF, while the HER
of the OER. The overpotential of Co/Fe/S/Se-400 for performance of CoFe-MOF-Se is similar to that of
OER is comparable to that of Co0.6Fe0.4-MOF, such as Co0.6Fe0.4-MOF, suggesting that the replacement of
their overpotential comparison at a specific current SCN− with SeCN− cannot increase the electrochemical
density: Co/Fe/S/Se-400 (273 mV) and Co0.6Fe0.4-MOF performance of CoFe-MOF. In contrast, the calcination at
(260 mV) at 10 mA/cm2. 400 °C (Co/Fe/Se-400) leads a significant enhancement
In contrast, as presented in Figs. 5(c) and 5(d), HER is in the catalytic activity. When the current density is
obviously improved after calcination. Co/Fe/S/Se-400 dis- 10 mA/cm2 for OER, the overpotential of CoFe-MOF-Se
plays a considerably lower overpotential than Co0.6Fe0.4- and Co/Fe/Se-400 are 300 and 270 mV, respectively. The
MOF (381 mV@10 mA/cm2), 225 mV at 10 mA/cm2. Tafel slopes are 55.2 and 49.7 mV/dec, respectively. The
After SeO2 etching and calcination, the overpotential of overpotential of Co/Fe/Se-400 is 30 mV less than that of
the final Co/Fe/S/Se-400 in HER is reduced by 156 mV, CoFe-MOF-Se, which may be due to the synergistic
which is a great improvement compared to the original impact of CoSe2 and FeSe2 (according to XRD and XPS
sample. The improved HER activity is probably accoun- results) to enhance the performance of OER.
ted for the formation of CoSe2 and Co1−xS (according to As presented in Figs. 5(c) and 5(d), the overpotential of
XRD and XPS results) in Co/Fe/S/Se-400, which are HER is 235 mV for Co/Fe/Se-400 and 360 mV for CoFe-
active species for HER catalysis. The comparison reveals MOF-Se at 10 mA/cm2, and the Tafel slopes are 134.5
that following SeO2 etching, HER performances to some and 174.4 mV/dec, respectively. The final calcination
extent has been improved. When the etching time is 5 h, Co/Fe/Se-400 indicates an overpotential reduction of
the overpotential of HER regulated by the etching time is 125 mV in HER, which is an improvement in comparison

Fig. 5 LSV and Tafel curves (( log j and log |j| in horizontal coordinates represents the logarithmic value of current density, bottoming
at 10) of Co0.6Fe0.4-MOF, CoFe-MOF-Se, Co/Fe/S/Se-400, and Co/Fe/Se-400.
(a, b) OER; (c, d) HER.
 Zhao-ting SHANG et al. 2D MOFs and their derivatives as electrocatalysts for overall water splitting 385

with the original MOF. The associated findings indicate CoSe2-30 (287 mV) [71], 6%Se–Co3O4 (281 mV) [72],
that the calcination increases the OER and HER activities Co0.8Fe0.2Se2 (345 mV) [73], CoSe2/CNT (300 mV) [74],
of Co/Fe/Se-400, and the effect on HER is more commercial IrO2 (331 mV) [75] for OER, proving that
significant, which may be due to fact that the CoSe2 the synthetic method is feasible and effective for the
formed during calcination is the active species for HER. synthesis of metal selenides as water splitting catalysts.
The overpotential values of Co/Fe/S/Se-400 and Aside from the above evaluation index for electroche-
Co/Fe/Se-400, which has been synthesized after calcina- mical performance, the electrochemical double layer
tion by the two selenide methods, are lower than those of capacitance (CDL) is regarded as another properties
the previously reported metal selenides derivative characterization to indirectly reflect the activity of the
(Table S4) from MOF at 10 mA/cm2, such as FeSe2 catalyst [76]. The cyclic voltammetry (CV) curves of
(240 mV) [67], CoSe2/C (253 mV) [68], 30%FeSe2/GO four materials at different scanning rates are shown in
(250 mV) [69] for HER, and CoSe2-450 (330 mV) [70], Fig. 6. The CDL is 7.9, 4.2, 3.9, and 12.0 mF/cm2 for

Fig. 6 CV curves.
(a) Co0.6Fe0.4-MOF; (b) Co/Fe/S/Se-400; (c) CoFe-MOF-Se; (d) Co/Fe/Se-400 at the scan rates of 10, 20, 40, 60, 80, and 100 mV/s;
(e) electrochemical double-layer capacitance of different materials; Δj represents the difference between the two current densities
corresponding to a fixed voltage of 0.05 V at each scan speed. (f) Nyquist plots of different materials during OER. Z' represents the real
part of the impedance value; Z" represents the imaginary part of the impedance value.
386 Front. Energy 2024, 18(3): 378–389

Co0.6Fe0.4-MOF, CoFe-MOF-Se, Co/Fe/S/Se-400, and that. The LSV curve after the 24-h testing is close to the
Co/Fe/Se-400, respectively, of which, the CDL of Co/Fe/ pristine one, indicating that Co/Fe/Se-400 displays a
Se-400 is much larger than that of Co/Fe/S/Se-400, good durability for OER.
indicating that the number of active sites is the largest. However, it should be noted that the electrochemical
However, for Co/Fe/S/Se-400, the smallest CDL value properties of Co/Fe/S/Se-400 and Co/Fe/Se-400 are
might be caused by the random etching in the solution of similar, which suggests that the two methods of
SeO2, which sacrifices the effective area. Comparably, introducing Se into MOF have similar effects on the
the introduction of SeCN− might be appropriate to electrochemical properties. According to the relaxed
preserve the effective electrochemical active area for the experimental results, the second method, i.e., the
electrocatalytic performance. Electrochemical impedance replacement of SCN− with SeCN−, is a simpler process,
spectroscopy (EIS) has been used to further demonstrate easier to control the amount of doped Se, which
the electrocatalytic performance for these materials [77]. contributes to the formation of bimetallic selenides
It can be found that CoFe-MOF-Se has the highest charge (CoSe2/FeSe2) while improving the OER and HER
transfer resistance for OER (Fig. 6(f)), while the other activity. It provides a new idea for designing 2D MOF
three materials have a lower and similar charge transfer materials for doping.
resistance, which is consistent with the OER electroca- The results of the related experiments show that both
talytic performance results. However, the Nyquist plots the pristine MOF (Co0.6Fe0.4-MOF) and (CoFe-MOF-Se)
of various materials demonstrate that calcined derivatives exhibit an unsatisfactory OER and HER catalytic activity,
such as Co/Fe/S/Se-400 and Co/Fe/Se-400 exhibit a but the calcined samples both show a great improvement
lower charge transfer resistance for HER (Fig. S13 and in HER. The high electrochemical performance of CoFe-
Table S5), which is compatible with the results of HER MOF derivatives may be resulted from the following
electrocatalytic performance. factors: First, the two similar electron intrinsic
The turnover frequency (TOF) has been used for the configurations of Co2+ and Fe2+ and their synergistic
evaluation of the intrinsic activity of the catalyst [78]. In effects are the foundation for achieving efficient catalytic
general, the efficiency of a catalyst increases with a activity and long-term stability. Next, the unique 2D
higher TOF value. According to calculation (see ESM), hierarchical structure provides a high porosity feature
the TOF values of Co/Fe/Se-400 and Co/Fe/S/Se-400 at a (i.e., adequate gaps) that allows for an effective contact of
potential of 270 mV are 5.6 s−1 and 5.3 s−1 higher than electrolyte and active sites, as well as a quick release of
those of pristine (CoFe-MOF-Se) (3.8 s−1) and Co0.6Fe0.4-
H2/O2 gas bubbles. Finally, direct integration of
MOF (2.2 s−1) for HER, respectively, which represents
CoSe2/FeSe2 or CoSe2/Co1−xS nanosheets ensures the
the superior HER reactivity of the calcined selenides.
effective charge transport between the catalyst and the
The morphology and crystalline phase composition of
substrate, considerably lowering the charge transfer
Co/Fe/Se-400 and Co/Fe/S/Se-400 after cycling reaction
resistance.
have been characterized. Irregular agglomeration of the
nanosheets of Co/Fe/S/Se-400 after cycling for HER can
be observed from Figs. S14(a), S14(c), and S14(e),
forming agglomerated particles, indicating that some of
4 Conclusions
the active sites will be blocked, which is detrimental to
the inter-transfer of electrolyte ions. The nanosheets of In this work, two strategies are utilized to introduce Se
Co/Fe/Se-400 (Figs. S14(b)–S14(f)) are not completely element into the 2D CoFe MOF to form the final
destroyed after cycling for HER, but the edges of the calcinated derivatives for catalyzing HER and OER in
nanosheets are corroded and passivated. The alteration of overall water splitting. One is the etching of as-prepared
the nanosheet layer facilitates the full contact of the MOF by SeO2 solution, and the other is the replacing
electrolyte with the reactants and the exposure of more SCN− with SeCN− as the construction unit. As a
active sites, which is responsible for the better stability. consequence, it is found that both two Se introducing
The nanosheets are severely agglomerated and approaches can obviously improve the HER performance,
aggregated and changed significantly after OER cycles, and the HER electrocatalytic activity of the final
as shown in the morphologies of Co/Fe/S/Se-400, and calcinated derivatives from those two methods are
Co/Fe/Se-400 (Fig. S15). The results of XRD (Fig. S16) comparable during overall water splitting. The high
also show that the crystalline phase of CoSe2/FeSe2 are electrochemical performance of 2D CoFe MOF
also retained in Co/Fe/Se-400. derivatives may be resulted from the unique 2D
The stability of the electrocatalyst is a crucial factor in hierarchical porous structure and strong synergistic effect
the evaluation of high-performance catalysts. As shown between different components in the material. Based on
in Fig. S17, during the 24-h chronopotentiometry testing, the results, the rational design of layered MOFs with
Co/Fe/Se-400 only has a little step at the 4th hour from S- or Se-containing linkers as water splitting catalysts is a
1.49 to 1.50 V, and there is no obvious attenuation after feasible option for the development of economical and
 Zhao-ting SHANG et al. 2D MOFs and their derivatives as electrocatalysts for overall water splitting 387

low-energy-consuming electrocatalysts, which provides water splitting. ACS Applied Materials & Interfaces, 2020,
an innovative approach for the synthesis of MOF-based 12(46): 51437–51447
metallic selenides. 11. Li Y, Zhang W, Wu T, et al. Segregation induced self-assembly
of highly active perovskite for rapid oxygen reduction reaction.
Acknowledgements This work was supported by the National Natural Advanced Energy Materials, 2018, 8(29): 1801893
Science Foundation of China (Grant No. 22250710676), the Excellent 12. Xiao M, Wu C, Zhu J, et al. In situ generated layered NiFe-
Discipline Cultivation Project of Jianghan University, China (No. LDH/MOF heterostructure nanosheet arrays with abundant
2023XKZ039), the Fundamental Research Funds for State Key Laboratory
of Precision Blasting of Jianghan University, China (No. PBSKL2022202),
defects for efficient alkaline and seawater oxidation. Nano
and the Minjiang Scholar Program of Fujian Province, China. Research, 2023, 16(7): 8945–8952
13. Zheng Y, Li Y, Wu T, et al. Controlling crystal orientation in
Electronic Supplementary Material Supplementary material is multilayered heterostructures toward high electro-catalytic
available in the online version of this article at https://doi.org/10.1007/ activity for oxygen reduction reaction. Nano Energy, 2019, 62:
s11708-024-0924-x and is accessible for authorized users.
521–529
14. Li F, Li Y, Chen H, et al. Impact of strain-induced changes in
Competing interests The authors declare that they have no competing
interests.
defect chemistry on catalytic activity of Nd2NiO4+δ electrodes.
ACS Applied Materials & Interfaces, 2018, 10(43): 36926–36932
15. Li X, Deng C, Kong Y, et al. Unlocking the transition of
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