李纪红AFM NiFeB

Research Article
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Design of a Multilayered Oxygen-Evolution Electrode with

High Catalytic Activity and Corrosion Resistance for Saline
Water Splitting
Jihong Li, Yipu Liu, Hui Chen, Zhankai Zhang, and Xiaoxin Zou*
the Pourbaix diagram of aqueous chloro-

The realization of seawater electrolysis requires high-performing anode chemistry for the OER-relevant environ-
materials that should possess good catalytic activity, stability, and specificity ment.[19] In an artificial alkaline seawater
for the oxygen evolution reaction (OER) as well as high resistance toward system (pH > 7.5; cNaCl = 0.5 m), the equi-
chloride corrosion. Herein, the design of a multilayered oxygen-evolution librium potential of OER (EOER0) is nega-
electrode is reported to meet the multiple needs of anode material for saline tive than that of chlorine evolution reaction
(CER) (ECER0). In such a catalytic environ-
water splitting. The multilayered electrode is synthesized through direct
ment, the OER is thermodynamically prefer-
thermal boronization of commercially available NiFe alloy plate with boron able over the CER for seawater electrolysis,
powder, followed by electrochemical oxidation. And this electrode is composed and there is a thermodynamic potential
of the surface oxidized NiFeBx alloy layer, the NiFeBx alloy interlayer, and the window of 480 mV (ECER0-EOER0) at the equi-
NiFe alloy substrate. The boron species are present in the form of metaborate librium state, in which a 100% OER selec-
tivity can be realized (Figure 1a, case i).[20]
in the outermost oxidized NiFeBx layer, and their existence is conductive to
When the OER and CER occur at the inter-
the generation and stabilization of the catalytic active phase γ-(Ni,Fe)OOH. face between electrode and electrolyte, a
The introduction of NiFeBx interlayer effectively prevents the excessive oxidative deviation of the equilibrium potential, also
corrosion of the anode material in the electrolyte containing chloride ions. known as overpotential (η), appears due
to the involvement of activation polariza-
tion.[21] The overpotentials are originated
1. Introduction from activation barriers present in the OER and CER, and their
magnitudes are actually correlated with the electrode material.[22]
Transforming the main energy structure from fossil fuels into In general, the OER is kinetically more sluggish than the CER due
renewable energies (solar, wind, etc.) is the key step to achieve to the intrinsic difference of involved electron number during the
sustainable energy utilization without harming our ecosystem.[1–6] two reactions (four-electron reaction for OER vs two-electron reac-
Electrochemical water splitting is considered an attractive solution for CER).[23] As a result, the actual OER-only range of poten-
tion to convert and store these renewable energy sources with tial is quite narrow (e.g., ≈200 mV for IrO2),[23–25] as demonstrated
hydrogen as a high-energy-density energy carrier.[7–13] Highly puri- in Figure 1a, case ii. However, the ideal situation for seawater
fied water is demanded for current electrolysis technologies, but in electrolysis is that the actual OER-only potential range should be
fact 96.5% of the total water on the planet is reserved in the form broadened as much as possible by designing active electrode mate-
of oceans.[14,15] Thus, it would be very tempting to realize effec- rials with a catalytic ability for promoting the OER and inhibiting
tive electrochemical water splitting using seawater as feedstock the CER simultaneously (Figure 1a, case iii). This objective is fur-
directly. However, achieving this goal is a quite challenging task. ther complicated by having to enhance the corrosion resistance of
One of the difficulties lies in higher requirements on anode mate- oxygen-evolution electrodes at the same time.
rial, which mediates the oxygen evolution reaction (OER).[16–19] Herein, we report, for the first time, the design of a multi-
Besides good catalytic activity, the anode material requires high layered oxygen-evolution electrode (denoted as MOEE) to meet
resistance toward chloride corrosion and high catalytic specificity the multiple needs of anode material for saline water splitting,
for the OER over a wide range of potential in seawater electrolysis. which consists of the oxidized NiFeBx alloy layer on the sur-
Recently, a guideline on the selection of catalytic environment face, the NiFeBx alloy interlayer, and the NiFe alloy substrate
for specific OER in seawater electrolysis was proposed based on (Figure 1b). This oxygen-evolution electrode exhibits excellent
catalytic activity and stability for water splitting in the electrolyte
J. Li, Dr. Y. Liu, Dr. H. Chen, Z. Zhang, Prof. X. Zou containing chloride ions, and shows a significantly improved
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry resistance toward chloride corrosion.
College of Chemistry
Jilin University
Changchun 130012, P. R. China
E-mail: [email protected]
2. Results and Discussion
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202101820. We first performed density functional theory (DFT) calculations
DOI: 10.1002/adfm.202101820 to assess the catalytic properties for the OER and CER of the
Adv. Funct. Mater. 2021, 31, 2101820 2101820 (1 of 9) © 2021 Wiley-VCH GmbH
16163028, 2021, 27, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202101820 by Jilin University, Wiley Online Library on [20/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.afm-journal.de
Figure 1. a) Schematic of OER-only potential windows (light blue region) under i) equilibrium state and ii,iii) polarized state in chloride-involved
system. The dark blue region represents the potential difference between the equilibrium potential of OER (EOER0) and equilibrium potential of CER
(ECER0). The blue region represents the OER-only range of potential. b) Structural illustration of a multilayered alloy electrode for seawater electrolysis.
c) The theoretical overpotentials of OER (blue bars) and CER (yellow bars) for IrO2, Fe-doped γ-NiOOH, and γ-NiOOH.
three model catalysts, IrO2, γ-NiOOH and Fe-doped γ-NiOOH. (e.g., ηOER: 0.80 eV vs 1.56 eV). The higher catalytic activity of
γ-NiOOH, and Fe-doped γ-NiOOH are the well-accepted active Fe-doped γ-NiOOH is consistent with the previous reports.[28]
phases for Ni-based and NiFe-based OER catalysts, respectively. The above results overall suggest that it is theoretically feasible
In our calculations, the typical adsorbate evolution mechanism to enlarge the actual OER-only potential range in seawater elec-
is adopted for the OER,[26] and the Volmer–Heyrovsky mecha- trolysis by using NiFe-based anode materials that enable effi-
nism is chosen for the CER[27] (please check calculation details cient and selective OER catalysis.
in the Experimental Section). As presented in Figure 1c, the Inspired by the above theoretical results, we next synthesized
theoretical overpotentials of OER and CER for IrO2 are 0.59 a NiFe-based multilayered oxygen-evolution electrode (labeled as
and 0.28 eV, respectively. This result indicates that IrO2 is MOEE), which consists of the oxidized NiFeBx alloy layer on the
such a catalyst that mediates the CER more readily than the surface, the NiFeBx alloy interlayer, and the NiFe alloy substrate
OER. Additionally, γ-NiOOH gives a theoretical overpotential (Figure 1b). Such a multilayered design of electrode material
of 1.56 eV for the OER (Figure 1c and Figure S1, Supporting is also for the improved resistance toward chloride corrosion.
Information), which is smaller than the theoretical overpoten- The synthesis of MOEE involves two main steps (see details in
tial (1.99 eV) for the CER. Although γ-NiOOH possesses lower Experimental Section): i) direct thermal boronization of com-
catalytic activity for both the OER and the CER than IrO2, the mercially available NiFe alloy plate with boron powder and
former inclines to catalyze the OER. The potential-determining ii) electrochemical oxidation of boronized NiFe plate by cyclic
step (PDS) of CER in the presence of γ-NiOOH as the catalyst is voltammograms (CVs) from 1.23 to 1.63 V versus reversible
the Cl− adsorption process (i.e., the Volmer reaction), whereas hydrogen eectrode (RHE) (Figure S2, Supporting Information).
the PDS for IrO2-catalyzed CER is the recombination process The photographs of MOEE before and after being stretched
between adsorbed chlorine species (M-Cl, M represents the (Figure 2a inset) reveal that the material can bend as the
active site) and the Cl− anion (i.e., the Heyrovsky reaction). normal metal plates do. Scanning electron microscopy (SEM)
This comparison demonstrates that the weak Cl− adsorption image (Figure 2a) shows that unlike the smooth surface of
on the surface of γ-NiOOH effectively hinders the subsequent normal metal plates, the surface of MOEE is composed of
elementary reaction step of CER. Furthermore, Fe-doped micron-scale chunks that are tightly connected with each other,
γ-NiOOH adopts a similar catalytic mechanism for the CER and cross-section elemental mapping images (Figure 2b) show
with γ-NiOOH, and Fe-doped γ-NiOOH also has a weak ability that there is a surface region of ca. 5 µm thickness that con-
to adsorb Cl− anion (Figure S1, Supporting Information). But sists of micron-scale chunks and uniformly-distributed B, Ni
Fe-doped γ-NiOOH exhibits significantly higher intrinsic cata- and Fe elements. The high-resolution transmission electron
lytic activity for both OER and CER compared with γ-NiOOH microscopy (HRTEM) image (Figure 2c) presents two different
Figure 2. a) Top-view SEM image and photographs (inset) of MOEE. b) Cross-section elemental mapping images and c) HRTEM image of MOEE.
d) B 1s XPS spectra for MOEE as well as several boron-containing compounds as the references.
lattice fringes with interplanar distances of 0.201 and 0.212 nm, (342 mV) in the presence of NiFe alloy plate as the electrode.
which correspond to (220) and (211) crystallographic planes At the overpotential of 350 mV, the MOEE achieves a current
of the (Ni,Fe)3B phase, respectively. The crystal structure of density of 122 mA cm−2, which is around 10 times higher than
NiFeBx interlayer is further confirmed by the X-ray diffraction the current density obtained by the NiFe alloy plate. Further-
(XRD) result (Figure S3, Supporting Information). More impor- more, the better activity of the MOEE can also be supported
tantly, the HRTEM image (Figure 2c), coupled with additional by its lower Tafel slope (47.1 mV decade−1) than that of NiFe
HRTEM images (Figure S4, Supporting Information), shows (68.6 mV decade−1) (Figure S6, Supporting Information). In
that there is an amorphous layer of ca. 2 nm thickness outside the case of MOEE, a Tafel slope near 40 mV decade−1 indicates
the NiFeBx interlayer as a result of electrochemical oxidation. the rate-determining step (RDS) for OER should be the second
The outermost amorphous layer of MOEE is further charac- electron transfer step (M-OH + OH– → M-O + H2O + e–, where
terized by X-ray photoelectron spectroscopy (XPS). Figure 2d M represents active site). And for NiFe, a Tafel slope around
presents B 1s XPS spectra of MOEE as well as several boron- 60 mV decade−1 suggests a chemical step followed by the first
containing compounds as the references. The B 1s single peak electron transfer step may limit the OER catalysis, which can
located at 191.8 eV for MOEE is very close to the binding energy be expressed as M− OH →M− OH* with no electron involved.
of boron in sodium metaborate (NaBO2), indicating that the These results infer that MOEE can effectively interact with OH*
existing form of boron in the outermost amorphous layer of intermediates during the catalytic reaction, and thus exhibits
MOEE is likely to be metaborate. Additionally, Ni 2p and Fe 2p faster reaction kinetics.[33–35]
XPS spectra (Figure S5, Supporting Information) reveal that To better access the catalytic activity of MOEE, its electro-
both Ni and Fe show oxidized states (i.e., Ni2+ and Fe3+) in the chemically active surface area (ECSA) is calculated and used to
outermost amorphous layer.[29–31] normalize the currents (Figures S7 and S8, Supporting Infor-
We investigated the electrocatalytic property of MOEE for mation). The results demonstrate that the MOEE has a larger
OER (see detailed electrochemical measurements in Experi- ECSA (3.26 cm2) than the NiFe alloy plate (1.39 cm2). But the
mental Section). For comparison, the catalytic property of NiFe higher ECSA is not the main reason behind the significantly
alloy plate is also studied. As shown in Figure 3a, the MOEE improved catalytic activity of MOEE, as revealed by its better
displays significantly higher apparent electrocatalytic activity, specific catalytic activity (Figure 3b). The specific catalytic
which is reflected by the currents normalized with a geo- activity of MOEE is further compared with some representative
metric area of the electrode, for OER in 1 m KOH electrolyte. electrode materials in a benchmarking study on oxygen evolu-
In particular, the MOEE gives 10 mA cmgeo−2 current density tion catalysts conducted by McCrory et al.[32] The overpotential
at an overpotential of 263 ± 14 mV, which is smaller than that at 10 mA cmECSA−2 current density was used as the criterion for
Figure 3. a) Polarization curves for OER by using MOEE and NiFe as the electrode in 1 m KOH electrolyte with (dash line) and without (solid line)
0.5 m NaCl under 85% iR-compensations. b) The ECSA-normalized specific activities for MOEE and some representative electrode materials at a cur-
rent density of 10 mA cm−2. These reference data are originated from a benchmarking study on oxygen evolution catalysts reported by McCrory et al.[32]
c) Chronopotentiometric curves with NiFe and MOEE as the electrode in 1 m KOH solution containing 0.5 m NaCl. The photographs of the electrodes
after OER electrocatalysis are provided in the insets. d) Polarization curves for OER by using MOEE as the electrode in 30 wt% KOH electrolyte with
0.5 m NaCl under 85% iR-compensations. e) Chronopotentiometric curves of MOEE as an electrode in 30 wt% KOH electrolyte with 0.5 m NaCl at
current densities of 100 and 500 mA cm−2 for 100 h. f) Electrocatalytic efficiency of MOEE toward the OER in 30 wt% KOH electrolyte with 0.5 m NaCl
at 500 mA cm−2 current density.
the comparison. As shown in Figure 3b, among the catalyst mate- ions (Figure 3a), but their catalytic stabilities are greatly influ-
rials the MOEE requires the lowest overpotential (317 ± 10 mV) to enced (Figure 3c). As shown in Figure 3c, when the electro-
get a current density of 10 mA cmECSA−2, and particularly, it has chemical reaction is in process in the presence of NiFe alloy
a better specific activity than some representative materials, electrode, the applied voltage drops rapidly within 10 h. This
such as NiMoFe, RuO2, and IrO2 catalysts.[32] The above results phenomenon is accompanied by the appearance of a number of
overall demonstrate that the MOEE is one of the most active black solid powders on the surface of the electrode (Figure 3c,
catalytic electrodes for the OER. inset and Figure S9, Supporting Information). These results
In order to simulate a catalytic environment of seawater indicate that the NiFe alloy electrode is corroded seriously in
electrolysis, a 1 m KOH solution containing 0.5 m chloride ions the electrolyte containing chloride ions. By contrast, the MOEE
was employed as the electrolyte for further catalysis study. The can electrocatalyze stably the OER for over 70 h (Figure 3c), with
results show that the catalytic activities of MOEE and NiFe elec- the almost unchanged electrode surface (Figure 3c, inset and
trodes are not largely affected by the introduction of chloride Figure S10, Supporting Information). Additionally, the MOEE
also remains a ≈100% Faradaic efficiency for oxygen evolution corrosion-proof layer, which can effectively limit undesired cor-
(Figure S11, Supporting Information), and the concentration of rosion involved by the Cl– participation.
chloride ions in electrolyte remained almost constant during The catalytic performance of MOEE was further studied in
electrolysis (Table S1, Supporting Information). All the above 30 wt% KOH electrolyte with 0.5 m NaCl, a more application-rele-
results suggest that the existence of NiFeBx interlayer effec- vant electrolyte. Figure 3d presents the linear sweep voltammetry
tively prevents the deep oxidative corrosion of the MOEE, and (LSV) curve toward OER with the MOEE as the anode electrode.
the MOEE is such an oxygen evolution electrode that is highly The result demonstrates that the MOEE possesses an excellent cat-
active and corrosion resistant even in the electrolyte chloride alytic activity for OER, and it delivers 100, 500, and 1000 mA cm−2
ions. at overpotentials of 328, 400, and 470 mV, respectively. Addi-
We further used the typical potentiodynamic curves, elec- tionally, the MOEE can maintain its surface morphology
trochemical impedance spectroscopy (EIS) measurements and (Figure S14, Supporting Information) and the catalytic activities
open circuit potential (OCP) tests to investigate the corrosion at current densities of both 100 and 500 mA cm−2 for more than
behaviors of MOEE and NiFe under Cl– containing medium. 100 h (Figure 3e). At either current density, the MOEE can give
Figure S12a, Supporting Information, shows that the corrosion 100% oxygen production efficiency (Figure 3f and Figure S15,
potential in MOEE (1.46 V vs RHE) is higher than that in NiFe Supporting Information). This is further supported by the
(1.41 V vs RHE), and MOEE exhibits a smaller corrosion cur- absence of hypochlorite in the electrolyte (Figure S16, Supporting
rent (5.30*10−7 A) compared with NiFe (9.59*10−6 A). The above Information), which is qualitatively detected with o-Tolidine as
results demonstrate that MOEE has higher corrosion resistance the indicator (see details in Experimental Section).[23]
than NiFe in the Cl– containing condition, and this conclusion In situ Raman spectroscopy is performed in order to unravel
is further supported by the impedance data (Figure S12b, Sup- the interfacial electrocatalytic behavior of MOEE during the
porting Information, other relevant explanations are also pre- electrochemical process. A series of in situ Raman spectra
sented in the Supporting Information), in which the semicircle are recorded when a class of constant voltages is applied on the
of the Nyquist plots for MOEE is larger than that of NiFe. Addi- MOEE from 1.23 to 1.52 V (vs RHE) for 600 s in 1 m KOH solu-
tionally, from Figure S12c, Supporting Information, the OCP of tion. Figure 4a presents a dynamic phase change taking place
MOEE (1.39 V vs RHE) is higher than that of NiFe. According on the electrode surface, which can be reflected from Raman
to the previous reports,[36,37] the higher value of OCP should characteristics from 300 to 600 cm−1. Specifically, at low poten-
be attributed to a more compact and stable passive film. Com- tials (1.23–1.34 V), a pair of Raman bands located at 457 and
pared with NiFe, such a positive OCP value for MOEE indicates 526 cm−1 are assigned to A1g stretching vibration of NiOH
the important role of NiFeBx interlayer in MOEE as the actual and NiO bands for Ni(OH)2.[38–41] At the middle potentials
Figure 4. a) In situ Raman spectra collected at different potentials (from 1.23 to 1.52 V vs RHE) in 1 m KOH electrolyte with MOEE as the anode.
b) Schematic of the structural transformation of surface layer of MOEE under electrocatalytic conditions. c) Band intensities of the 473 and the 553 cm−1
and the corresponding ratio of band intensity (I553/I473) obtained from in situ Raman spectra at 1.35, 1.38, 1.43, and 1.45 V in five continuous cycles.
(1.35–1.36 V), two characteristic bands at 473 and 553 cm−1 ΔGO*−ΔGOH* is 1.51 eV, which is far from the optimized value.
appear with two bands mentioned earlier disappearing. The These results demonstrated metaborate-modified γ-(Ni,Fe)OOH
Raman bands at 473 and 553 cm−1 can be indexed to the Eg has higher intrinsic catalytic active sites compared with γ-(Ni,Fe)
Ni-O bending vibration mode and A1g Ni-O stretching vibration OOH. For further analysis, the charge density difference image
in NiOOH.[42] Therefore, there is a phase transformation from of metaborate-modified γ-(Ni,Fe)OOH is present in Figure S20,
Ni(OH)2 to NiOOH under such potential conditions. Besides, Supporting Information, which exhibits the electron transfers
when the applied potential reaches above 1.37 V, the position from B atoms to Ni atoms and Fe atoms, and from Ni atoms to
of Raman bands no longer changes, but the band intensity at Fe atoms. This charge redistribution results in an increase in
553 cm−1 increases obviously. It should be also noted that no the electron density of iron atoms and a slight depletion of elec-
iron-related Raman features are observed during this process, trons on nickel atoms, as confirmed by bader charge analysis
inferring that iron mainly serves as dopants existing in the (Table S2, Supporting Information), and which explains why
framework of Ni-based active phases.[43–45] These phenomena the presence of metaborate can modify the property of surface
are similar to the observation in the Bell group’s reports.[38] oxygen adsorption. Moreover, it is found that in optimized struc-
The above results, coupled with some previous reports, sug- tures of adsorbed O* on γ-(Ni,Fe)OOH and metaborate-modified
gest that the main active phase should be γ-NiOOH, rather than γ-(Ni,Fe)OOH (Figure S21, Supporting Information), the bond
β-NiOOH. The key structural difference between γ-NiOOH and length (1.777 Å) for the latter is longer than that (1.766 Å) for
β-NiOOH lies in the existence or the absence of intercalated spe- the former. And correspondingly, the covalency of Ni-O* is also
cies in its interlayers.[28] Due to the involvement of Fe dopants, found to be increased for metaborate-modified γ-(Ni,Fe)OOH
intercalated ions together with water molecules should exist in (Figure S22, Supporting Information). The above results dem-
the interlayers of Ni(OH)2 to balance the positive charge, and onstrate that the introduction of metaborate finely tunes the
the Ni(OH)2 would preferably transform to γ-NiOOH with electronic structure of Ni sites in metaborate-modified γ-(Ni,Fe)
hydrated ions during OER. This consideration is also supported OOH, and further optimizes their surface oxygen adsorption
by Trotochaud’s work,[46] which suggests that the presence of Fe and catalytic ability for OER. Additionally, the slight increase
in Ni-Fe oxides inhibits the formation of β-NiOOH. of valence state for Ni species in metaborate-modified γ-(Ni,Fe)
Besides active phase identification, we also observed that the OOH also contributes to the fast generation and stabilization
Raman characteristics of γ-NiOOH can spontaneously go back of the catalytic active phase, as observed by the in situ Raman
to those of Ni(OH)2 after around 6 h when the applied poten- results. This higher oxidation state of Ni species, induced by
tial is taken off (Figure S17, Supporting Information). With the metaborate-involvement, may lead to easier oxidation from
changes of applied potentials, such a structural evolution of (Ni,Fe)(OH)2 to γ-(Ni,Fe)OOH during OER, further stabilizing
surface-active phase, as illustrated in Figure 4b, can be repeated the γ-(Ni,Fe)OOH after removing the applied potential.
for at least five times (Figure 4c), indicating that the formation
of surface catalytic active phase (i.e., γ-(Ni,Fe)OOH) is dynamic
and reversible. 3. Conclusions
For comparison, in situ Raman spectra of NiFe alloy elec-
trode are also recorded under the same conditions (Figures S18 In summary, a multilayered oxygen-evolution electrode
and S19, Supporting Information). We found that the NiFe alloy (denoted as MOEE) has been designed to meet the multiple
electrode also goes through similar phase transformation as needs of anode material for saline water splitting, including
MOEE, and the surface-active phase γ-(Ni,Fe)OOH appears at good catalytic activity, stability, and specificity for OER as well
an applied potential of 1.35 V, which is 30 mV higher than that as high resistance toward chloride corrosion. The MOEE has
in the presence of MOEE as the electrode (Figures S18, Sup- been synthesized through direct thermal boronization of com-
porting Information). Moreover, when the applied potential on mercially available NiFe alloy plate, followed by electrochemical
the NiFe alloy electrode is removed, the time that γ-(Ni,Fe)OOH oxidation. The multilayered electrode consists of the surface
takes to spontaneously go back to (NiFe)(OH)2 is about 1 h oxidized NiFeBx alloy layer as the catalytic active layer, the
(Figures S19, Supporting Information), which is much shorter NiFeBx alloy interlayer as the corrosion-proof layer, and the
than that in the existence of MOEE as the electrode. The above NiFe alloy substrate as structural support. The results reported
comparison suggests that the presence of metaborate in the herein could light a path toward a more sustainable water-split-
outermost oxidized NiFeBx layer of MOEE should benefit the ting technology by using unpurified water as feedstock.
generation and stabilization of the catalytic active phase, further
boosting the catalytic activity for OER of MOEE.
In order to further understand the roles of metaborate in cat- 4. Experimental Section
alytic activity, DFT calculations are performed by constructing Computation Details: All the DFT computations were carried
two theoretical models, γ-(Ni,Fe)OOH and metaborate-modified out using the Vienna ab initio simulation package (VASP).[47] The
γ-(Ni,Fe)OOH. According to the scaling relation of OER, exchange-correlation energy was evaluated using generalized gradient
ΔGO*−ΔGOH* as a well-accepted descriptor is used to evaluate approximation (GGA) with the Perdew–Burke–Ernzerhof (PBE)
the intrinsic catalytic activity of materials, and the optimized functional,[48] and the projector augmented wave (PAW) method was
used to describe the electron-ion interactions.[49] The energy cutoff
value is around 1.6 eV.[22] Our results show that metaborate- for plane wave expansions was set to 600 eV, and the convergence
modified γ-(Ni,Fe)OOH can achieve a relatively optimized threshold was set as 10−5 eV in energy and 0.02 eV Å−1 in force,
adsorption with intermediates, and the value of ΔGO*−ΔGOH* is respectively. For the calculations on the slab models, a vacuum space
calculated as 1.644 eV. In the case of γ-(Ni,Fe)OOH, the value of of 15 Å was added to avoid the interaction between periodic images. In
addition, the dipolar correction was adopted for slab models with the Highly purified water (>18 MΩ cm resistivity) was provided by a PALL
symmetrization switching off, and the DFT-D3 method was included PURELAB Plus system.
to improve the description of the long-range weak van der Waals Synthesis of MOEE: MOEE was synthesized via a facile two-step
(vdW) interaction for all DFT calculations.[50] Bader charge analysis method. NiFe plate was first boronized with boron powder. In detail, 2.0 g
was performed to decompose the charge density into volumes around of boron powder was placed in a quartz tube with a diameter of 1 cm and
each atom.[51] a height of 10 cm, and a clean NiFe plate (5 cm × 0.5 cm × 0.3 mm) was
Theoretical Methods for OER and CER: The typical adsorbate evolution inserted into the boron powder. Then the quartz tube was thermally treated
mechanism proposed by Nørskov et al. was chosen to evaluate the OER at 900 °C for 30 min in Ar atmosphere with a heating rate of 3 °C min−1.
performance for slab models.[26] Briefly, the reaction free energy of each After the quartz tube was cooled to room temperature, the boronized
step could be expressed as follows: NiFe plate was taken out from the quartz tube, cleaned using both water
and ethanol, and dried at room temperature. Next, the boronized NiFe
∆G1 = E (HO ∗ ) − E (∗) − E H2O + 1/ 2E H2 + ( ∆ZPE − T∆S )1 − eU (1) plate was electrochemically oxidized by CV measurements at a potential
range from 1.23 to 1.63 V (vs RHE) in alkaline media for 20 segments
(see the first three CV curves in Figure S2, Supporting Information, and
∆G 2 = E ( O ∗ ) − E (HO ∗ ) + 1/ 2E H2 + ( ∆ZPE − T∆S ) 2 − eU (2)
the detailed test parameters in electrochemical measurements section),
resulting in a multilayered oxygen-evolution electrode. The as-obtained
∆G3 = E (HOO ∗ ) − E ( O ∗ ) − E H2O + 1/ 2E H2 + ( ∆ZPE − T∆S )3 − eU (3) material was labeled as MOEE.
Characterizations: The powder XRD patterns were obtained from a
∆G 4 = E (∗) − E (HOO ∗ ) + E O 2 + 1/ 2E H2 + ( ∆ZPE − T∆S ) 4 − eU (4) Rigaku D/Max 2550 X-ray diffractometer with Cu Kα radiation (λ = 1.5418 Å).
The XPS was performed on an ESCALAB 250 X-ray photoelectron
spectrometer with a monochromatic X-ray source (Al Kα hυ = 1486.6 eV).
where E(*), E(HO*), E(O*), and E(HOO*) are the total energy of the
The Raman spectra of the materials were obtained with a Renishaw
clean surface and the adsorbed surface with three intermediates,
Raman system model 1000 spectrometer operating with a 20 mW air-
respectively. EH2O, EH2, and EO2 are the computed energies for the H2O,
cooled argon-ion laser (532 nm) as the excitation light source. The SEM
H2, and O2 molecules, respectively. The values of ΔZPE were determined
images were recorded on a JEOL JSM 6700F electron microscope at an
by the computed vibrational frequencies and the -eU term represents the
accelerating voltage of 5 kV. The Energy dispersive X-ray (EDX) analysis
external bias U imposed on each step. For the total reaction H2O →
was carried out using an EDX system attached to JEOL JSM-7800F SEM.
1/2O2 + H2, the free energy change was fixed at the experimental value
The transmission electron microscope (TEM) images were collected on a
of 2.46 eV per water molecule to avoid the calculation of O2 using DFT.
Philips FEI Tecnai G2S-Twin microscope equipped with a field emission
The theoretical reaction overpotential can be obtained by evaluating the
gun operating at 200 kV. Inductively coupled plasma atomic emission
difference between the minimum voltage needed for the OER and the
spectroscopy (ICP-OES) was performed on a Perkin-Elmer Optima
corresponding voltage needed for changing all the free-energy steps into
3300DV ICP spectrometer. The concentration of chloride ions in the
the downhill.
electrolyte during electrolysis was measured using ion chromatography
As for CER, the well-accepted Volmer-Heyrovsky mechanism was
(PIC-10A ion chromatograph from Qingdao Puren Instrument Co., Ltd.,
used to conduct corresponding DFT calculations. The Volmer-Heyrovsky
China).
mechanism is presented as follows,
Electrochemical Measurements: All electrochemical measurements
Volmer step: were conducted on a standard three-electrode configuration with a CH
Instrument (Model 650E). 1 m KOH, 1 m KOH with 0.5 m NaCl, and
M + 2Cl − → M − Cl + e − + Cl − (5) 30 wt% KOH with 0.5 m NaCl solutions were used as electrolytes.
A plastic cell with a diameter of 4 cm and a height of 8 cm acted as
Heyrovsky step: the electrochemical cell. The materials (MOEE, etc.) were used
as working electrodes and the working surface area was fixed as
0.2 cm2. Hg/HgO electrode and Pt wire were used as reference and
M − Cl + Cl − → M + Cl2 + e − (6)
counter electrodes, respectively. The LSV was recorded at a scan
rate of 1 mV s−1 and compensated by 85% iR-drop unless otherwise
Where M represents the catalytic active sites on the surface of stated. Chronopotentiometric measurements were performed to
catalysts, and in this case, M is always O site because Cl– tends to evaluate the stability of the electrode without iR-compensations. The
adsorb on O site to form adsorbed chlorine specie O-Cl. It should also potentiodynamic polarization curves were carried out in the potential
be noted that the potential relative was referenced to the standard range of 0.73–1.63 V (vs RHE) and the potential sweep rate was set
hydrogen electrode (SHE) according to Rossmeisl’s work.[27] Based on as 2 mV s−1. EIS measurement was carried out at 1.48 V (vs RHE) and
computational SHE, the correction ΔGref was regarded as 1.36 eV for the frequency ranged from 100 kHz to 0.01 Hz. The Hg/HgO electrode
CER, which was related to the reversible potentials of the chlorine and was calibrated according to previous work.[35] The relation between the
hydrogen electrodes. Therefore, the reaction free energy of each step Hg/HgO reference and RHE in 1 m KOH solution and 30 wt% KOH can
could be expressed as follows: be established by the followed equations:
∆G1 = E ( Cl∗ ) − E (∗) − 1/ 2E Cl2 + ( ∆ZPE − T∆S )1 + ∆Gref − eU (7) For 1 m KOH electrolyte,
E RHE = E Hg/HgO + 0.918 V (9)

∆G 2 = E (∗) − E ( Cl∗ ) + 1/ 2E Cl2 + ( ∆ZPE − T∆S ) 2 + ∆Gref − eU (8)
For 30 wt% KOH electrolyte,
Chemicals and Reagents: NiFe plate (thickness: 0.3 mm, atomic
ratio of Fe:Ni = 1:1) was purchased from Chang’an Mingshang Metal E RHE = E Hg/HgO + 0.975 V (10)
Materials. Before using, the NiFe plate was cleaned several times with
acetone and deionized water. Ethyl alcohol, potassium hydroxide (KOH), The ECSA of the electrode was calculated based on the reported
and sulfuric acid (H2SO4) were purchased from Beijing Chemical Factory. methods. CV parameters were set as follows: the voltage range was
Nafion perfluorinated resin solution was purchased from Sigma-Aldrich. 1.018–1.118 V (vs RHE), the scanning rates were 10, 20, 30 mV s−1,
Amorphous boron powder, sodium chloride (NaCl), and ο-Tolidine were etc., and the sweep segments were 20. Faradic efficiency for OER was
purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. determined according to reported literature.[3,35]
Methods for Detecting OCl–: o-Tolidine indicator was used to detect [5] Z.-P. Wu, X. F. Lu, S.-Q. Zang, X. W. Lou, Adv. Funct. Mater. 2020,
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by dissolving 0.1 g o-Toluidine in 15 mL concentrated hydrochloric acid [7] L. Han, S. Dong, E. Wang, Adv. Mater. 2016, 28, 9266.
followed by diluting the solution to 100 mL. 200 µL of electrolyte was [8] Z. Ye, T. Li, G. Ma, Y. Dong, X. Zhou, Adv. Funct. Mater. 2017, 27,
taken from the working electrocatalytic system (the total volume of 1704083.
electrolyte is always fixed at 40 mL unless otherwise mentioned), then [9] R. Zhang, P. A. Russo, A. G. Buzanich, T. Jeon, N. Pinna, Adv. Funct.
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of the solution would change from colorless to yellow when ClO- is [10] Y. Li, H. Zhang, M. Jiang, Q. Zhang, P. He, X. Sun, Adv. Funct.
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[11] L. Yan, L. Cao, P. Dai, X. Gu, D. Liu, L. Li, Y. Wang, X. Zhao,
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Research Article

Design of a Multilayered Oxygen-Evolution Electrode with

the Pourbaix diagram of aqueous chloro-

E RHE = E Hg/HgO + 0.918 V (9)

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