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Article

MOF-Derived CoSe2@NiFeOOH Arrays for Efficient Oxygen Evolution Reaction

by
Yulong Tang
1,2,†,
Jiangning Li
1,2,†,
Zhiyi Lu
2,3,
Yunan Wang
2,3,*,
Kai Tao
1,* and
Yichao Lin
2,3,*
1
School of Materials Science & Chemical Engineering, Ningbo University, Ningbo 315211, China
2
Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
3
University of Chinese Academy of Sciences, Beijing 100049, China
*
Authors to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Nanomaterials 2023, 13(19), 2621; https://doi.org/10.3390/nano13192621
Submission received: 28 August 2023 / Revised: 16 September 2023 / Accepted: 19 September 2023 / Published: 22 September 2023
(This article belongs to the Special Issue Mesoporous and Microporous Materials for Energy and Environmental Applications)
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Abstract

:
Water electrolysis is a compelling method for the production of environmentally friendly hydrogen, minimizing carbon emissions. The electrolysis of water heavily relies on an effective and steady oxygen evolution reaction (OER) taking place at the anode. Herein, we introduce a highly promising catalyst for OER called CoSe2@NiFeOOH arrays, which are supported on nickel foam. This catalyst, referred to as CoSe2@NiFeOOH/NF, is fabricated through a two-step process involving the selenidation of a Co-based porous metal organic framework and subsequent electrochemical deposition on nickel foam. The CoSe2@NiFeOOH/NF catalyst demonstrates outstanding activity for the OER in an alkaline electrolyte. It exhibits a low overpotential (η) of 254 mV at 100 mA cm−2, a small Tafel slope of 73 mV dec−1, and excellent high stability. The good performance of CoSe2@NiFeOOH/NF can be attributed to the combination of the high conductivity of the inner layer and the synergistic effect between CoSe2 and NiFeOOH. This study offers an effective method for the fabrication of highly efficient catalysts for an OER.

1. Introduction

The storage of renewable energy presents a significant challenge to constructing an environmentally friendly energy system [1,2,3,4,5,6]. Water electrolysis has become a promising technology for storing electricity generated from renewable sources by converting it into a clean energy carrier, H2. It involves two distinct half-reactions: an hydrogen evolution reaction (HER) occurring at the cathode and an oxygen evolution reaction (OER) taking place at the anode [7,8,9,10]. Relative to the HER, the OER suffers from much more sluggish kinetics, and so, it requires highly efficient electrocatalysts. Thus far, Ir- and Ru-based materials represent state-of-the-art OER electrocatalysts because of their high activity level and stability [11,12,13,14,15,16,17]. However, the high cost and scarcity of these resources limit their extensive utilization [12,18,19,20]. Therefore, it is crucial to develop alternative, affordable electrocatalysts that are abundant in the Earth’s crust. Transition metal chalcogenides (TMCs) with the formula MxCy (M = Fe, Co, and Ni; C = S and Se) have gained significant interest for their good performance in OER catalysis, as well as their low cost and abundance in the Earth’s crust [21]. Yang Shao-Horn and colleagues conducted the catalytic analysis of perovskite oxide, where they elucidated a correlation between OER activity and the occupancy of 3D electrons with eg symmetry in transition metal cations on the surface. Their findings revealed that an optimized OER electrocatalyst possesses eg occupancy of approximate one [22]. Liu et al. applied this principle to explain the high OER activity of CoSe2, which exhibits a t2g6eg1 electronic configuration, approaching the optimal eg filling [23,24]. However, they overlooked the surface reconstruction or oxidation of CoSe2 under OER catalysis. The surface reconstruction of catalysts was frequently observed in the OER test. For example, Shahid et al. synthesized a catalyst for the OER, which consists of cobalt-containing ester salts of polyoxometalates that are immobilized on carbon nanotube fibers (Co4POM@CNTF). The catalyst showcases an exceptional OER performance and remarkable stability in alkaline solutions, which can be attributed to the efficient transfer of electrons and the enhanced electrochemical active surface area of the self-activating electrocatalyst that is affixed to the highly conductive carbon nanotube fibers [25]. Theoretically, the surface oxidation of CoSe2 would lead to the generation of Co oxides or hydroxides on the CeSe2 surface. This indicates that the actual catalytic phase occurs with the Co oxides/hydroxides rather than CoSe2. Therefore, the inner CoSe2 serves as an electron-transfer conductor and is also probably influenced by the electronic structure of the surface Co oxides/hydroxides. Based on the above analysis, we are inclined to believe that the good OER catalytic performance of CoSe2 may result from the synergistic effect of the surface oxides and the inner CoSe2.
NiFe-layered double-hydroxide (NiFe-LDH) and NiFeOOH species have been recognized as very efficient OER electrocatalysts both in theoretical calculations and experimental investigations [26,27]. For example, Du and coworkers prepared an OER catalyst of NiO/NiFe-LDH, which demonstrated an OER overpotential of only 205 mV at a current density of 30 mA cm−2, with a Tafel slope of merely 30 mV dec−1 in 1 M KOH solution [27].
This good catalytic performance is achieved by adjusting the adsorption energy of each intermediate, which effectively bypasses the scaling relationship. Hu et al. conducted a comprehensive investigation on FeOOH-NiOOH and NiFe LDH, unveiling the distinct electrochemical and spectroscopic characteristics between the two catalysts, despite their similar chemical compositions. Notably, in FeOOH-NiOOH, a significant portion of iron ions were observed to reside within surface γ-FeOOH clusters, contrasting the doping of iron ions within the lattice of Ni(OH)2/NiOOH in NiFe LDH. This discrepancy played a crucial role in the remarkable tenfold enhancement of OER activity witnessed in FeOOH-NiOOH compared to that of NiFe LDH [26].
Based on the above, we proposed to fabricate thin NiFeOOH onto a CoSe2 surface, aiming to achieve an optimized OER performance through the synergistic effect of NiFeOOH and CoSe2. To increase the accessibility of CoSe2, we prepared it via the selenidation of a Co-based metal–organic framework (MOF, ZIF-L) array grown on Ni foam [28,29,30]. ZIF-L is selected as the precursor because it has a thin leaf morphology and can be readily grown on nickel foam, which facilitate the following selenidation. The deposition of NiFeOOH onto CoSe2 was achieved through electrochemical deposition (Figure 1). The CoSe2@NiFeOOH/NF composite exhibited a good performance in alkaline electrolytes for the OER, demonstrating an overpotential of 254 mV at a current density of 100 mA cm−2 and a Tafel slope of 73 mV dec−1. Furthermore, it showed excellent stability with negligible current density decay after 100 h of operation. The high OER activity level can be attributed to the increased exposure of active sites and the synergistic effect of NiFeOOH outer layer and CoSe2 inner layer.

2. Experimental Section

2.1. Materials

Co(NO3)2·6H2O, 2-methylimidazole (2-MeIM, 99%), Ni(NO3)2·6H2O, Fe(NO3)3·9H2O, sodium borohydride (NaBH4), selenium powder (Se), and absolute ethanol were purchased from Aladdin. Ni was obtained from J&K Chemical Technology (San Jose, CA, USA) and subsequently subjected to sonication with acetone, ethanol, and deionized water for 30 min each prior to use.

2.2. Preparation of Cobalt-Based ZIF-L/NF

Initially, a solution of 2 × 10−3 mol Co (NO3)2 and another solution of 1.6 × 10−2 mol 2-MeIM were prepared by dissolving them individually in 40 mL of deionized water in a beaker. Then, the two solutions were combined via stirring. Subsequently, nickel foam (NF) measuring 2 × 3 cm was immersed in the mixture and left at room temperature for 4 h to generate ZIF-L/NF. To prepare it for future use, ZIF-L/NF was subjected to three rounds of rinsing with both ethanol and deionized water. Subsequently, it was dried overnight in an oven at 60 °C.

2.3. Synthesis of CoSe2/NF

The ZIF-L/NF selenidation process was carried out using a hydrothermal method. Initially, 60 mg of NaBH4 was completely dissolved in 25 mL of deionized water. Subsequently, 20 mg of selenium powder was added to the solution. The mixture was continuously stirred for 40 min until a light-yellow solution was formed. The solution was then transferred into a Teflon-lined stainless steel autoclave, and a ZIF-L/NF sample with dimensions of 1 cm × 1.5 cm was immersed in the solution. The autoclave was kept at a temperature of 180 °C for a duration of 8 h. Afterward, the resulting CoSe2/NF product was rinsed with ethanol and water and finally dried in an oven at a temperature of 60 °C for 12 h.

2.4. Synthesis of CoSe2@NiFeOOH/NF

The CoSe2@NiFeOOH/NF composite was synthesized via electrochemical deposition with CoSe2/NF as the working electrode in a solution containing Ni(NO3)2 and Fe(NO3)3 (molar ratio of Ni2+/Fe3+ = 4:1). The electrochemical deposition was conducted at a constant potential of −1.4 V vs. RHE for 8 s.

2.5. Characterization

X-ray power diffraction (XRD) data were recorded on a Bruker D8 ADVANCE DAVINCI. The morphologies and nanostructures were probed using field emission scanning electron microscopy (SEM, Hitachi S-4800, Japan) and transmission electron microscopy (TEM, Tecnai F20, JEM-ARM200F, USA). The surface chemical valences of the samples were analyzed using X-ray photoelectron spectroscopy (XPS) (Axis SUPRA Kratos, UK).

2.6. Electrocatalytic Measurement

The electrochemical measurements were conducted on a CHI760E electrochemical workstation. The as-prepared samples served as the working electrode (geometric area: 1.0 cm2). The counter electrode was a Pt mesh with dimensions of 1 cm × 1 cm, and an Ag/AgCl electrode was used as the reference electrode. A 1.0 M KOH electrolyte was utilized. To convert the measured potentials to the reversible hydrogen electrode (RHE) scale, the following equation was used: ERHE = EAg/AgCl + 0.059 pH + 0.197 V. Linear sweep voltammetry (LSV) curves were measured at a scan rate of 5 mV s−1, while cyclic voltammetry (CV) curves were recorded at scan rates ranging from 10 to 50 mV s−1. Electrochemical impedance spectra (EIS) were measured at 1.52 V vs. RHE. All the polarization curves were IR-corrected. The double-layer capacitances were determined by analyzing the CV curves obtained at different scan rates, ranging from 10 to 50 mV s−1. The stability of the electrocatalyst was evaluated through chrono-amperometry performed at a constant potential. The Faraday efficiency (FE) was determined using the bubbling method following the formula: FE = 4 × F × V/(1000 × Vm × It), where V is the rising volume (mL) of the soap bubble over time t, I is the current density (It representing the total number of charges transferred under constant current), Vm is the molar volume (24.5 L mol−1 at 25 °C), and F is the Faraday constant (96,485 C mol−1).

3. Results and Discussion

ZIF-L was deposited onto NF prepared by facilely immersing NF into a solution of cobalt nitrate and 2-methylimidazole at room temperature. The morphology of the ZIF-L/NF sample was analyzed via SEM, which allows the detailed imaging of the sample surface at high magnification. The crystal structure of the synthesized catalyst was determined using powder XRD. Figure 2a,d,g illustrates the triangular ZIF-L plates with smooth surfaces vertically aligned on the NF. The sharp diffraction peaks at 44.5°, 51.9°, and 76.2° are attributed to the Ni substrate, and the peak at 29.4° belongs to ZIF-L. This confirms the successful fabrication of ZIF-L on NF. After selenization, ZIF-L transformed into the CoSe2 phase while maintaining its morphology, except that the surface became rougher (Figure 2b,e,h). Subsequently, NiFeOOH was electrochemically deposited onto CoSe2, resulting in a morphological change, where CoSe2 formed an array with increased surface roughness and additional folds. The XRD analysis of the CoSe2@NiFeOOH/NF sample showed no visible peaks except those of the Ni substrate, suggesting an amorphous structure in the NiFeOOH layer [31]. The absence of XRD signals for CoSe2 demonstrates that a relatively compact NiFeOOH layer formed on the CoSe2 surface. The three-dimensional CoSe2@NiFeOOH can aid in the transportation of electrolytes and the diffusion of reactive gases, thereby accelerating the reaction process [31].
The detailed morphology of CoSe2@NiFeOOH was further characterized via TEM. Figure 3a shows that CoSe2@NiFeOOH possesses a thin-leaf-like morphology. The weak polycrystalline rings in the selected area electron diffraction (SAED) pattern (Figure 3c) indicate the poor crystallization of these thin leaf structures in the single derived CoSe2@NiFeOOH sample. The structure of CoSe2@NiFeOOH/NF was precisely characterized using high-resolution TEM (HRTEM). On the top surface of CoSe2@NiFeOOH, two fringes with lattice spacings of 0.259 and 0.223 nm were observed, corresponding to the (111) and (210) planes of CoSe2, respectively (Figure 3b). Elemental mapping images demonstrate the homogeneous dispersion of Ni, Fe, Co, Se, and O elements throughout the entire CoSe2@NiFeOOH/NF, with an atomic ratio of Ni:Fe:Co:Se:O = 24:6:29:3:38 (Figure S2).
X-ray photoelectron spectroscopy (XPS) measurements were taken to analyze the elemental composition and chemical valence states of the as-prepared CoSe2@NiFeOOH/NF. As shown in Figure 4a, two peaks centered at 855.7 and 873.5 eV were identified as the main peaks corresponding to oxidized Ni 2p3/2 and Ni 2p1/2, respectively. Another two peaks at 861.2 and 879.3 eV were attributed to the shake-up satellite peak [32]. Figure 4b displays the Co 2p1/2 and Co 2p3/2 peaks, which can be further divided into four peaks located at 796.8/780.8 eV (Co2+) and 783.8/802.2 eV (Co3+). This suggests that the Co atom in CoSe2@NiFeOOH/NF is predominantly in the valence states of +2 and +3 [33]. Due to the overlap of the 2p peak of Fe with the Auger peak of Co, it is impossible to deconvolute the Fe 2p XPS peak. Nevertheless, we can determine the presence of Fe and its oxidation state from the two peaks in the XPS raw data of Fe 2p. In the XPS spectra of Fe 2p (Figure 4c), two characteristic peaks at 711.1 and 724.6 eV correspond to Fe 2p3/2 and Fe 2p1/2, respectively, indicating the presence of Fe3+ [33]. The findings collectively indicate that Ni and Fe exist in Ni and Fe oxidation states in CoSe2@NiFeOOH/NF. In addition, as shown in Figure 4d, Se 3d5/2 (54.7 eV) and Se 3d3/2 (55.4 eV) confirm the existence of selenium–metal bonds, while the peak at 59.2 eV corresponds to a Se-O bond, which is due to the surface oxidation in the air environment [34,35,36,37].
The catalysts’ OER performance was assessed using an electrochemical three-electrode system in 1 M KOH alkaline solution. As shown in Figure 5a, CoSe2@NiFeOOH/NF exhibits an overpotential of 254 mV at 100 mA cm−2, which is significantly lower than those of CoSe2/NF, NiFe-LDH/NF, NF/Selenization, CoSe2@NiOOH/NF, and CoSe2@FeOOH/NF. The OER performance of CoSe2@NiFeOOH/NF is comparable to those of other reported OER electrocatalysts, such as NiSe2-CoSe2 [38], SiO2/CoxP [39], and Ni(OH)2@NiS2 [40] (Table S1). The Tafel slopes of the four samples, namely CoSe2@FeOOH/NF, CoSe2@NiOOH/NF, CoSe2/NF, and CoSe2@NiFeOOH/NF, were calculated to analyze their kinetics. As shown in Figure 5c, CoSe2@NiFeOOH possesses the smallest Tafel slope of 73 mV dec−1, which is much smaller than those of CoSe2@FeOOH/NF (102 mV dec−1), CoSe2/NF (119 mV dec−1), and CoSe2@NiOOH/NF (126 mV dec−1), suggesting faster OER kinetics. To gain further insight into the kinetics of electron transfer, EIS measurements were taken. Figure 5b displays the Nyquist plots of all the samples. Notably, the CoSe2@NiFeOOH/NF sample exhibits the smallest diameter of the semicircle in the high frequency region, which unequivocally confirms the presence of charge transfer resistance (Rct). This resistance facilitates smooth charge transfer, ultimately resulting in excellent oxygen evolution reaction (OER) activity. Additionally, to understand the intrinsic catalytic activity of CoSe2@NiFeOOH/NF for the OER, the electrochemical surface area (ECSA) was estimated by measuring the double-layer capacitance (Cdl) in the potential range of 1.07–1.17 V at scan rates ranging from 10 to 50 mV s−1 (Figure S1). Interestingly, CoSe2@NiFeOOH/NF exhibits the highest Cdl value of 29.0 mF cm−2 among all the samples, surpassing those of CoSe2@NiOOH/NF (23.1 mF cm−2) and CoSe2@FeOOH/NF (20.5 mF cm−2). Furthermore, the electrocatalytic stability of CoSe2@NiFeOOH/NF was evaluated. As depicted in Figure 5h, the current variation is negligible after a 100 h continuous test at 1.54 V. Furthermore, we also probed the morphology and electronic structural characterization of CoSe2@NiFeOOH/NF after a 100 h stability test. As shown in Figures S3 and S4, no visible variation in the XPS spectra and morphology of CoSe2@NiFeOOH/NF after the stability test was observed, demonstrating excellent stability.
The overpotential increase for every 50 mA cm−2 of current density is illustrated in Figure 5f. It is evident from Figure 5a that CoSe2@NiFeOOH/NF has a significantly lower overpotential than those of CoSe2@FeOOH/NF and CoSe2@NiOOH/NF, signifying the higher catalytic activity level of CoSe2@NiFeOOH. Figure 5e illustrates the chrono-potentiometric curve of CoSe2@NiFeOOH, showing multiple steps with the current density incrementing from 10 to 100 mA cm−2 in ten steps. In the initial step, the potential rapidly stabilizes at 1.44 V and remains nearly constant for a duration of 320 s. Similar phenomena are observed in subsequent steps, indicating the exceptional mass transport and electronic conductivity characteristics of CoSe2@NiFeOOH/NF. The Faradaic efficiency of the OER with the CoSe2@NiFeOOH/NF electrodes was evaluated by measuring the O2 produced during a constant current test experiment. According to Figure 5g, the measured amount of O2 is in close agreement with the theoretical yield, resulting in a remarkable Faradaic efficiency of 97.8% for the CoSe2@NiFeOOH/NF electrode.

4. Conclusions

In summary, a three-dimensional CoSe2@NiFeOOH sample supported on nickel foam for efficient OER catalysis was fabricated. The excellent conductivity of CoSe2 and the synergistic effect between CoSe2 and NiFeOOH facilitate OER catalysis on CoSe2@NiFeOOH/NF. The CoSe2@NiFeOOH/NF catalyst demonstrated an excellent performance in the alkaline electrolyte, achieving an overpotential of 254 mV at 100 mA cm−2 and a Tafel slope of 73 mV dec−1. Furthermore, the catalyst demonstrated remarkable stability with minimal decay in the current density, even after 100 h. The findings of this study represent a prototype of a synergistic strategy for creating highly efficient electrocatalysts.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/nano13192621/s1. Figure S1. CV curves of (a) CoSe2@FeOOH/NF. (b) CoSe2@NiFeOOH/NF and c) CoSe2@NiOOH/NF. Figure S2. Elemental mapping images of Co, O, Fe, Ni, and Se. Figure S3. (a) TEM, (b) HRTEM, (c) SAED pattern, and (d) STEM images and the corresponding elemental mapping images of Co, O, Fe, Ni, and Se of CoSe2@NiFeOOH/NF after 100 h durability test. Figure S4. High-resolution XPS spectra of CoSe2@NiFeOOH/NF after 100 h durability test. Table S1. Comparison of the OER activity of CoSe2@NiFeOOH/NF with other non-noble metal electrocatalysts in alkaline solution. References [41,42,43,44,45,46,47,48,49,50,51,52] are cited in the Supplementary Materials.

Author Contributions

Conceptualization, Y.L., Y.W. and K.T.; methodology, Y.L., Y.T., Z.L. and J.L.; formal analysis, J.L., Y.T., Y.W. and Y.L.; investigation, Y.T. and J.L.; data curation, Y.T. and J.L.; writing—original draft preparation Y.T. and J.L.; writing—review and editing, Y.L. and Y.W.; supervision, Y.L. and K.T.; project administration, Y.L., Y.T. and J.L.; funding acquisition, Y.L. and Y.W. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by R&D Program of Zhejiang (No. 2022C01029), National Natural Science Foundation of China (No. 52271232), Bellwethers Project of Zhejiang Research and Development Plan (2022C01158), Natural Science Foundation of Zhejiang Province (No. LY21E020008), Youth Innovation Promotion Association, CAS (No. 2020300), Ningbo S&T Innovation 2025 Major Special Program (2022Z205), and Jiangbei Science and Technology planning project (202301A09).

Data Availability Statement

We would like to share our data upon request from the authors.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Dresp, S.; Ngo Thanh, T.; Klingenhof, M.; Brückner, S.; Hauke, P.; Strasser, P. Efficient direct seawater electrolysers using selective alkaline NiFe-LDH as OER catalyst in asymmetric electrolyte feeds. Energy Environ. Sci. 2020, 13, 1725–1729. [Google Scholar] [CrossRef]
  2. Wang, Y.; Tao, S.; Lin, H.; Wang, G.; Zhao, K.; Cai, R.; Tao, K.; Zhang, C.; Sun, M.; Hu, J.; et al. Atomically targeting NiFe LDH to create multivacancies for OER catalysis with a small organic anchor. Nano Energy 2021, 81, 105606. [Google Scholar] [CrossRef]
  3. Sun, H.; Zhang, W.; Li, J.-G.; Li, Z.; Ao, X.; Xue, K.-H.; Ostrikov, K.K.; Tang, J.; Wang, C. Rh-engineered ultrathin NiFe-LDH nanosheets enable highly-efficient overall water splitting and urea electrolysis. Appl. Catal. B Environ. 2021, 284, 119740. [Google Scholar] [CrossRef]
  4. Alobaid, A.; Wang, C.; Adomaitis, R.A. Mechanism and kinetics of HER and OER on NiFe LDH films in an alkaline electrolyte. J. Electrochem. Soc. 2018, 165, J3395–J3404. [Google Scholar] [CrossRef]
  5. Hunter, B.M.; Hieringer, W.; Winkler, J.R.; Gray, H.B.; Müller, A.M. Effect of interlayer anions on NiFe-LDH nanosheet water oxidation activity. Energy Environ. Sci. 2016, 9, 1734–1743. [Google Scholar] [CrossRef]
  6. Wang, Y.; Yan, D.; El Hankari, S.; Zou, Y.; Wang, S. Recent progress on layered double hydroxides and their derivatives for electrocatalytic water splitting. Adv. Sci. 2018, 5, 1800064. [Google Scholar] [CrossRef]
  7. Tang, Y.; Liu, Q.; Dong, L.; Wu, H.B.; Yu, X.-Y. Activating the hydrogen evolution and overall water splitting performance of NiFe LDH by cation doping and plasma reduction. Appl. Catal. B Environ. 2020, 266, 118627. [Google Scholar] [CrossRef]
  8. Hu, L.; Zeng, X.; Wei, X.; Wang, H.; Wu, Y.; Gu, W.; Shi, L.; Zhu, C. Interface engineering for enhancing electrocatalytic oxygen evolution of NiFe LDH/NiTe heterostructures. Appl. Catal. B Environ. 2020, 273, 119014. [Google Scholar] [CrossRef]
  9. Nayak, S.; Parida, K. Superactive NiFe-LDH/graphene nanocomposites as competent catalysts for water splitting reactions. Inorg. Chem. Front. 2020, 7, 3805–3836. [Google Scholar] [CrossRef]
  10. Yu, J.; Yu, F.; Yuen, M.-F.; Wang, C. Two-dimensional layered double hydroxides as a platform for electrocatalytic oxygen evolution. J. Mater. Chem. A 2021, 9, 9389–9430. [Google Scholar] [CrossRef]
  11. Chen, S.; Huang, H.; Jiang, P.; Yang, K.; Diao, J.; Gong, S.; Liu, S.; Huang, M.; Wang, H.; Chen, Q. Mn-doped RuO2 nanocrystals as highly active electrocatalysts for enhanced oxygen evolution in acidic media. ACS Catal. 2019, 10, 1152–1160. [Google Scholar] [CrossRef]
  12. Hubert, M.A.; Patel, A.M.; Gallo, A.; Liu, Y.; Valle, E.; Ben-Naim, M.; Sanchez, J.; Sokaras, D.; Sinclair, R.; Nørskov, J.K.; et al. Acidic oxygen evolution reaction activity–stability relationships in Ru-based pyrochlores. ACS Catal. 2020, 10, 12182–12196. [Google Scholar] [CrossRef]
  13. Liao, J.; Zaman, S.; Wang, Y.; Yang, M.; Yang, L.; Chen, M.; Wang, H. Improved reversal tolerant properties of IrO(x) as an anode electrocatalyst in proton exchange membrane fuel cells. ACS Appl. Mater. Interfaces 2023, 15, 4092–4100. [Google Scholar] [CrossRef] [PubMed]
  14. Jin, H.; Choi, S.; Bang, G.J.; Kwon, T.; Kim, H.S.; Lee, S.J.; Hong, Y.; Lee, D.W.; Park, H.S.; Baik, H.; et al. Safeguarding the RuO2 phase against lattice oxygen oxidation during acidic water electrooxidation. Energy Environ. Sci. 2022, 15, 1119–1130. [Google Scholar] [CrossRef]
  15. Lin, Y.; Tian, Z.; Zhang, L.; Ma, J.; Jiang, Z.; Deibert, B.J.; Ge, R.; Chen, L. Chromium-ruthenium oxide solid solution electrocatalyst for highly efficient oxygen evolution reaction in acidic media. Nat. Commun. 2019, 10, 162–175. [Google Scholar] [CrossRef] [PubMed]
  16. Retuerto, M.; Pascual, L.; Calle-Vallejo, F.; Ferrer, P.; Gianolio, D.; Pereira, A.G.; Garcia, A.; Torrero, J.; Fernandez-Diaz, M.T.; Bencok, P.; et al. Na-doped ruthenium perovskite electrocatalysts with improved oxygen evolution activity and durability in acidic media. Nat. Commun. 2019, 10, 2041–2050. [Google Scholar] [CrossRef]
  17. Zaman, S.; Wang, M.; Liu, H.; Sun, F.; Yu, Y.; Shui, J.; Chen, M.; Wang, H. Carbon-based catalyst supports for oxygen reduction in proton-exchange membrane fuel cells. Trends Chem. 2022, 4, 886–906. [Google Scholar] [CrossRef]
  18. An, L.; Wei, C.; Lu, M.; Liu, H.; Chen, Y.; Scherer, G.G.; Fisher, A.C.; Xi, P.; Xu, Z.J.; Yan, C.H. Recent development of oxygen evolution electrocatalysts in acidic environment. Adv. Mater. 2021, 33, e2006328. [Google Scholar] [CrossRef]
  19. Li, L.; Wang, P.; Shao, Q.; Huang, X. Recent progress in advanced electrocatalyst design for acidic oxygen evolution reaction. Adv. Mater. 2021, 33, e2004243. [Google Scholar]
  20. Spori, C.; Kwan, J.T.H.; Bonakdarpour, A.; Wilkinson, D.P.; Strasser, P. The stability challenges of oxygen evolving catalysts: Towards a common fundamental understanding and mitigation of catalyst degradation. Angew. Chem. Int. Ed. 2017, 56, 5994–6021. [Google Scholar]
  21. Zhang, T.; Hang, L.; Sun, Y.; Men, D.; Li, X.; Wen, L.; Lyu, X.; Li, Y. Hierarchical hetero-Ni3Se4@NiFe LDH micro/nanosheets as efficient bifunctional electrocatalysts with superior stability for overall water splitting. Nanoscale Horiz. 2019, 4, 1132–1138. [Google Scholar] [CrossRef]
  22. Suntivich, J.; May, K.J.; Gasteiger, H.A.; Goodenough, J.B.; Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 2011, 334, 1383–1385. [Google Scholar] [CrossRef]
  23. Liu, Y.; Cheng, H.; Lyu, M.; Fan, S.; Liu, Q.; Zhang, W.; Zhi, Y.; Wang, C.; Xiao, C.; Wei, S.; et al. Low overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. J. Am. Chem. Soc. 2014, 136, 15670–15675. [Google Scholar] [CrossRef]
  24. Li, J.G.; Sun, H.; Lv, L.; Li, Z.; Ao, X.; Xu, C.; Li, Y.; Wang, C. Metal-organic framework-derived hierarchical (Co,Ni)Se2@NiFe LDH hollow nanocages for enhanced oxygen evolution. ACS Appl. Mater. Interfaces 2019, 11, 8106–8114. [Google Scholar] [CrossRef] [PubMed]
  25. Tariq, I.; Asghar, M.A.; Ali, A.; Badshah, A.; Abbas, S.M.; Iqbal, W.; Zubair, M.; Haider, A.; Zaman, S. Surface reconstruction of Cobalt-Based polyoxometalate and CNT fiber composite for efficient oxygen evolution reaction. Catalysts 2022, 12, 1242. [Google Scholar] [CrossRef]
  26. Bai, L.; Lee, S.; Hu, X. Spectroscopic and electrokinetic evidence for a bifunctional mechanism of the oxygen evolution reaction. Angew. Chem. Int. Ed. Engl. 2021, 60, 3095–3103. [Google Scholar] [CrossRef] [PubMed]
  27. Gao, Z.W.; Liu, J.Y.; Chen, X.M.; Zheng, X.L.; Mao, J.; Liu, H.; Ma, T.; Li, L.; Wang, W.C.; Du, X.W. Engineering NiO/NiFe LDH intersection to bypass scaling relationship for oxygen evolution reaction via dynamic tridimensional adsorption of intermediates. Adv. Mater. 2019, 31, e1804769. [Google Scholar] [CrossRef]
  28. Dong, Q.; Wang, Q.; Dai, Z.; Qiu, H.; Dong, X. MOF-derived Zn-doped CoSe2 as an efficient and stable free-standing catalyst for oxygen evolution reaction. ACS Appl. Mater. Interfaces 2016, 8, 26902–26907. [Google Scholar] [CrossRef]
  29. Muráth, S.; Varga, T.; Kukovecz, Á.; Kónya, Z.; Sipos, P.; Pálinkó, I.; Varga, G. Morphological aspects determine the catalytic activity of porous hydrocalumites: The role of the sacrificial templates. Mater. Today Chem. 2022, 23, 100682. [Google Scholar] [CrossRef]
  30. He, K.; Tadesse Tsega, T.; Liu, X.; Zai, J.; Li, X.H.; Liu, X.; Li, W.; Ali, N.; Qian, X. Utilizing the space-charge region of the FeNi-LDH/CoP p-n junction to promote performance in oxygen evolution electrocatalysis. Angew. Chem. Int. Ed. 2019, 58, 11903–11909. [Google Scholar] [CrossRef]
  31. Yang, R.; Zhou, Y.; Xing, Y.; Li, D.; Jiang, D.; Chen, M.; Shi, W.; Yuan, S. Synergistic coupling of CoFe-LDH arrays with NiFe-LDH nanosheet for highly efficient overall water splitting in alkaline media. Appl. Catal. B Environ. 2019, 253, 131–139. [Google Scholar] [CrossRef]
  32. Liu, J.; Wang, J.; Zhang, B.; Ruan, Y.; Lv, L.; Ji, X.; Xu, K.; Miao, L.; Jiang, J. Hierarchical NiCo2S4@NiFe LDH heterostructures supported on nickel foam for enhanced overall-water-splitting activity. ACS Appl. Mater. Interfaces 2017, 9, 15364–15372. [Google Scholar] [CrossRef]
  33. Zhang, F.S.; Wang, J.W.; Luo, J.; Liu, R.R.; Zhang, Z.M.; He, C.T.; Lu, T.B. Extraction of nickel from NiFe-LDH into Ni2P@NiFe hydroxide as a bifunctional electrocatalyst for efficient overall water splitting. Chem. Sci. 2018, 9, 1375–1384. [Google Scholar] [CrossRef]
  34. Jia, B.; Xue, Z.; Liu, Q.; Liu, Q.; Liu, K.; Liu, M.; Chan, T.-S.; Li, Y.; Li, Z.; Su, C.-Y.; et al. Hierarchical nanotubes constructed from CoSe2 nanorods with an oxygen-rich surface for an efficient oxygen evolution reaction. J. Mater. Chem. A 2019, 7, 15073–15078. [Google Scholar] [CrossRef]
  35. Kwak, I.H.; Im, H.S.; Jang, D.M.; Kim, Y.W.; Park, K.; Lim, Y.R.; Cha, E.H.; Park, J. CoSe2 and NiSe2 nanocrystals as superior bifunctional catalysts for electrochemical and photoelectrochemical water splitting. ACS Appl. Mater. Interfaces 2016, 8, 5327–5357. [Google Scholar] [CrossRef] [PubMed]
  36. Zhao, S.; Jin, R.; Abroshan, H.; Zeng, C.; Zhang, H.; House, S.D.; Gottlieb, E.; Kim, H.J.; Yang, J.C.; Jin, R. Gold nanoclusters promote electrocatalytic water oxidation at the nanocluster/CoSe2 interface. J. Am. Chem. Soc. 2017, 139, 1077–1080. [Google Scholar] [CrossRef]
  37. Zan, G.; Wu, T.; Zhang, Z.; Li, J.; Zhou, J.; Zhu, F.; Chen, H.; Wen, M.; Yang, X.; Peng, X.; et al. Bioinspired nanocomposites with self-adaptive stress dispersion for super-foldable electrodes. Adv. Sci. 2022, 9, e2103714. [Google Scholar] [CrossRef] [PubMed]
  38. Li, M.; Feng, L.G. NiSe2-CoSe2 with a hybrid nanorods and nanoparticles structure for efficient oxygen evolution reaction. Chin. J. Struc. Chem. 2022, 41, 2201019–2201024. [Google Scholar]
  39. Zeng, X.; Zhang, H.; Zhang, X.; Zhang, Q.; Chen, Y.; Yu, R.; Moskovits, M. Coupling of ultrasmall and small Co P nanoparticles confined in porous SiO2 matrix for a robust oxygen evolution reaction. Nano Mater. Sci. 2022, 4, 393–399. [Google Scholar] [CrossRef]
  40. Xu, S.J.; Zhou, Y.N.; Shen, G.P.; Dong, B. Ni(OH)2 derived from NiS2 induced by reflux playing three roles for hydrogen/oxygen evolution reaction. Chinese J. Struc. Chem. 2022, 41, 2208052–2208057. [Google Scholar]
  41. Wang, Z.; Zeng, S.; Liu, W.; Wang, X.; Li, Q.; Zhao, Z.; Geng, F. Coupling molecularly ultrathin sheets of NiFe-layered double hydroxide on NiCo2O4 nanowire arrays for highly efficient overall water-splitting activity. ACS Appl. Mater. Interfaces 2017, 9, 1488–1495. [Google Scholar] [CrossRef] [PubMed]
  42. Song, F.; Hu, X. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat. Commun. 2014, 5, 4477. [Google Scholar] [CrossRef] [PubMed]
  43. Youn, D.H.; Park, Y.B.; Kim, J.Y.; Magesh, G.; Jang, Y.J.; Lee, J.S. One-pot synthesis of NiFe layered double hydroxide/reduced graphene oxide composite as an efficient electrocatalyst for electrochemical and photoelectrochemical water oxidation. J. Power Sources 2015, 294, 437–443. [Google Scholar] [CrossRef]
  44. Yu, X.; Zhang, M.; Yuan, W.; Shi, G. A high-performance three-dimensional Ni–Fe layered double hydroxide/graphene electrode for water oxidation. J. Mater. Chem. A 2015, 3, 6921–6928. [Google Scholar] [CrossRef]
  45. Zhong, H.; Liu, T.; Zhang, S.; Li, D.; Tang, P.; Alonso-Vante, N.; Feng, Y. Template-free synthesis of three-dimensional NiFe-LDH hollow microsphere with enhanced OER performance in alkaline media. J. Electrochem. Soc. 2019, 33, 130–137. [Google Scholar] [CrossRef]
  46. Lin, Y.; Wang, H.; Peng, C.K.; Bu, L.; Chiang, C.L.; Tian, K.; Zhao, Y.; Zhao, J.; Lin, Y.G.; Lee, J.M.; et al. Co-induced electronic optimization of hierarchical NiFe LDH for oxygen evolution. Small 2020, 16, e2002426. [Google Scholar] [CrossRef]
  47. Meng, L.; Xuan, H.; Wang, J.; Liang, X.; Li, Y.; Yang, J.; Han, P. Flower-like Co3O4@NiFe-LDH nanosheets enable high-performance bifunctionality towards both electrocatalytic HER and OER in alkaline solution. J. Alloys Compd. 2022, 919, 165877. [Google Scholar] [CrossRef]
  48. Yang, Z.; Lin, Y.; Jiao, F.; Li, J.; Wang, J.; Gong, Y. In situ growth of 3D walnut-like nano-architecture Mo-Ni2P@NiFe LDH/NF arrays for synergistically enhanced overall water splitting. J. Energy Chem. 2020, 49, 189–197. [Google Scholar] [CrossRef]
  49. Zhang, Y.; Zhang, C.; Guo, Y.; Liu, D.; Yu, Y.; Zhang, B. Selenium vacancy-rich CoSe2 ultrathin nanomeshes with abundant active sites for electrocatalytic oxygen evolution. J. Mater. Chem. A 2019, 7, 2536–2540. [Google Scholar] [CrossRef]
  50. Liu, X.; Liu, Y.; Fan, L.-Z. MOF-derived CoSe2 microspheres with hollow interiors as high-performance electrocatalysts for the enhanced oxygen evolution reaction. J. Mater. Chem. A 2017, 5, 15310–15314. [Google Scholar] [CrossRef]
  51. Du, X.; Li, J.; Tong, K.; Zhang, X. Coupling Co2P/CoSe2 heterostructure nanoarrays for boosting overall water splitting. Dalton Trans. 2021, 50, 6650–6658. [Google Scholar] [CrossRef] [PubMed]
  52. Liu, T.; Liu, Q.; Asiri, A.M.; Luo, Y.; Sun, X. An amorphous CoSe2 film behaves as an active and stable full water-splitting electrocatalyst under strongly alkaline conditions. Chem. Commun. 2015, 51, 16683. [Google Scholar] [CrossRef] [PubMed]
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Figure 1. Schematic illustration of the routes to CoSe2@NiFeOOH/NF.
Figure 1. Schematic illustration of the routes to CoSe2@NiFeOOH/NF.
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Figure 2. SEM images of (a,d) ZIF-L, (b,e) CoSe2, and (c,f) CoSe2@NiFeOOH/NF. XRD patterns of (g) ZIF-L/NF, (h) CoSe2/NF, and (i) CoSe2@NiFeOOH/NF.
Figure 2. SEM images of (a,d) ZIF-L, (b,e) CoSe2, and (c,f) CoSe2@NiFeOOH/NF. XRD patterns of (g) ZIF-L/NF, (h) CoSe2/NF, and (i) CoSe2@NiFeOOH/NF.
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Figure 3. (a) TEM, (b) HRTEM, (c) SAED pattern, and (d) STEM images and the corresponding elemental mapping images of Co, O, Fe, Ni, and Se of CoSe2@NiFeOOH/NF.
Figure 3. (a) TEM, (b) HRTEM, (c) SAED pattern, and (d) STEM images and the corresponding elemental mapping images of Co, O, Fe, Ni, and Se of CoSe2@NiFeOOH/NF.
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Figure 4. High-resolution XPS spectra of CoSe2@NiFeOOH/NF (a) Ni, (b) Co, (c) Fe, (d) Se.
Figure 4. High-resolution XPS spectra of CoSe2@NiFeOOH/NF (a) Ni, (b) Co, (c) Fe, (d) Se.
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Figure 5. (a) LSV curves for CoSe2/NF, CoSe2@FeOOH/NF, CoSe2@NiOOH/NF, NiFe-LDH/NF, NF/selenization, and CoSe2@NiFeOOH/NF. (b) EIS curves, (c) Tafel plots, and (d) Cdl plots. (e) Rate capability evaluation of CoSe2@NiFeOOH/NF. (f) Catalyst overpotentials at different current densities. (g) Faraday efficiency. (h) i–t curve for CoSe2@NiFeOOH at the η = 0.31 V for 100 h.
Figure 5. (a) LSV curves for CoSe2/NF, CoSe2@FeOOH/NF, CoSe2@NiOOH/NF, NiFe-LDH/NF, NF/selenization, and CoSe2@NiFeOOH/NF. (b) EIS curves, (c) Tafel plots, and (d) Cdl plots. (e) Rate capability evaluation of CoSe2@NiFeOOH/NF. (f) Catalyst overpotentials at different current densities. (g) Faraday efficiency. (h) i–t curve for CoSe2@NiFeOOH at the η = 0.31 V for 100 h.
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MDPI and ACS Style

Tang, Y.; Li, J.; Lu, Z.; Wang, Y.; Tao, K.; Lin, Y. MOF-Derived CoSe2@NiFeOOH Arrays for Efficient Oxygen Evolution Reaction. Nanomaterials 2023, 13, 2621. https://doi.org/10.3390/nano13192621

AMA Style

Tang Y, Li J, Lu Z, Wang Y, Tao K, Lin Y. MOF-Derived CoSe2@NiFeOOH Arrays for Efficient Oxygen Evolution Reaction. Nanomaterials. 2023; 13(19):2621. https://doi.org/10.3390/nano13192621

Chicago/Turabian Style

Tang, Yulong, Jiangning Li, Zhiyi Lu, Yunan Wang, Kai Tao, and Yichao Lin. 2023. "MOF-Derived CoSe2@NiFeOOH Arrays for Efficient Oxygen Evolution Reaction" Nanomaterials 13, no. 19: 2621. https://doi.org/10.3390/nano13192621

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