Next Article in Journal
Validation of an HPLC–MS/MS Method for the Determination of Plasma Ticagrelor and Its Active Metabolite Useful for Research and Clinical Practice
Next Article in Special Issue
Syntheses and Characterization of Novel Perovskite-Type LaScO3-Based Lithium Ionic Conductors
Previous Article in Journal
Concise Synthesis of Functionalized Cyclobutene Analogues for Bioorthogonal Tetrazine Ligation
Previous Article in Special Issue
Electronic and Magnetic Structures of New Interstitial Boron Sub-Oxides B12O2:X (X = B, C, N, O)
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 26
Issue 2
10.3390/molecules26020277
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions: Nano-Co3O4-Deposited La0.5Sr0.5MnO3 via Infiltration

by
Seona Kim
1,
Guntae Kim
2,* and
Arumugam Manthiram
1,*
1
Materials Science and Engineering Program & Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712, USA
2
Department of Energy Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Korea
*
Authors to whom correspondence should be addressed.
Molecules 2021, 26(2), 277; https://doi.org/10.3390/molecules26020277
Submission received: 5 December 2020 / Revised: 27 December 2020 / Accepted: 5 January 2021 / Published: 8 January 2021
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
Browse Figures
Versions Notes

Abstract

:
For rechargeable metal–air batteries, which are a promising energy storage device for renewable and sustainable energy technologies, the development of cost-effective electrocatalysts with effective bifunctional activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has been a challenging task. To realize highly effective ORR and OER electrocatalysts, we present a hybrid catalyst, Co3O4-infiltrated La0.5Sr0.5MnO3-δ (LSM@Co3O4), synthesized using an electrospray and infiltration technique. This study expands the scope of the infiltration technique by depositing ~18 nm nanoparticles on unprecedented ~70 nm nano-scaffolds. The hybrid LSM@Co3O4 catalyst exhibits high catalytic activities for both ORR and OER (~7 times, ~1.5 times, and ~1.6 times higher than LSM, Co3O4, and IrO2, respectively) in terms of onset potential and limiting current density. Moreover, with the LSM@Co3O4, the number of electrons transferred reaches four, indicating that the catalyst is effective in the reduction reaction of O2 via a direct four-electron pathway. The study demonstrates that hybrid catalysts are a promising approach for oxygen electrocatalysts for renewable and sustainable energy devices.

Graphical Abstract

1. Introduction

Renewable and sustainable energy storage and conversion systems such as fuel cells, electrolysis cells, and secondary batteries have attracted a great deal of attention in recent years to address the environmental challenges we face today [1,2,3,4]. Specifically, metal–air batteries are considered to be promising systems due to their extremely high theoretical energy density [4,5,6,7,8,9]. Metal–air batteries consist of a pure metal (e.g., Li, Na, Zn, Al) anode and an external cathode of ambient air with an aqueous or aprotic electrolyte. To be suitable for rechargeable batteries, the oxygen electrocatalysts should exhibit effective catalytic activity, not only for the oxygen reduction reaction (ORR), but also for the oxygen evolution reaction (OER)—that is, they should exhibit bifunctionality [10,11,12,13,14,15]. However, due to the sluggish reaction kinetics of the ORR and OER (which respectively correspond to the discharge and charge processes), the development of highly efficient and cost-effective oxygen electrocatalysts is considered to be an essential challenge. Although Pt, IrO2, RuO2, and their alloys and composites show superior activities for ORR or OER, they suffer from the drawbacks of poor stability, scarcity, and high cost.
The focus in the literature has been on transition-metal oxides because oxygen electrocatalysts possess bifunctionality due to their operational stability in alkaline solutions and promising catalytic activities for ORR and OER. Among them, Co-containing oxides such as Co3O4, LnxSr1-xCoO3-δ, and BaxSr1-xCoyFe1-yO3-δ have especially been reported as efficient electrocatalysts for OER [13,16,17,18,19,20,21]. Mn-containing oxides (e.g., Mn2O3, NiMnO2, CoMnO2, and La0.5Sr0.5MnO3-δ) have demonstrated excellent catalytic activity for ORR [22,23,24,25,26]. Although the above transition-metal oxides exhibit some bifunctionality, their outstanding catalytic activity is generally specific to either ORR or OER, but not both.
Hybrid catalysts composed of more than two materials have been suggested as an approach to secure the desired bifunctionality. For example, Cu-nanoparticle-loaded Co3O4 microspheres, Co3O4–graphene composite, LaNiO3-Pt/C core–corona structure catalyst, and Co3O4 nanocrystals grown on graphene have been demonstrated [8,17,27,28,29,30,31]. Based on earlier studies, hybrid catalysts (A@B) show enhanced ORR/OER activity compared to the individual catalysts (A or B) and/or their physical mixtures (A + B) due to the synergistic effects between the constituent materials [17,27,32]. Therefore, in this study, a hybrid catalyst consisting of La0.5Sr0.5MnO3-δ (LSM) and Co3O4 was designed to achieve high catalytic activities for both ORR and OER.
Nanosizing fabrications were employed to maximize the performances of each constituent material by endowing enlarged reaction sites and shortened ion-/charge-transport path [33,34,35]. Among the various fabrication techniques, electrospray and infiltration techniques have been used due to their simplicity, effectiveness, and reproducibility. In addition, the stoichiometric ratios can be precisely controlled because the fabrication techniques rely on the precursor mixing at the molecular level.
LSM nanoparticles were prepared through electrospray, and Co3O4 was deposited on the LSM surface through infiltration to synthesize the hybrid catalyst (LSM@Co3O4). We discovered that 20 wt.% Co3O4-infiltrated LSM exhibited a comparable catalytic activity to benchmark bifunctional oxygen electrocatalysts. Furthermore, because the calculated number of transferred electrons is four, it indicates that O2 follows a direct reduction pathway with less thermodynamic reaction potential.

2. Results and Discussion

2.1. Structural and Morphological Characterization

Figure 1a illustrates the electrospray fabrication of La0.5Sr0.5MnO3-δ (LSM) with the precursor solution including La-, Sr-, and Mn nitrates, PVP, and DMF. A syringe needle tip and aluminum foil collector were connected to the anode and cathode of a high-voltage power supply, respectively. After a heat treatment at 850 °C, X-ray diffraction (XRD) was conducted in the range of 20° < 2θ < 60° to identify the crystal structure of the prepared samples. As shown in Figure 1b, LSM was successfully synthesized with a single-phase structure of simple perovskite without any significant impurities. The scanning electron microscopy (SEM) images in Figure 1c, d illustrate that spherical LSM nanoparticles 60–100 nm in size were formed and organically connected.
Employing the infiltration technique for these nanoparticle scaffolds is a new approach and a unique attempt. Typically, micro-scale pore/particles have been used as the scaffold for infiltration technique and the nanoparticles deposited on the scaffold surface have a size of 60 nm or more. However, the nano-sized LSM scaffold has low interactive force with the precursor solution due to the reduced contact area. To overcome this problem and increase the wettability, ethanol was used as the solvent in this study due to its low boiling point, low surface tension (22.3 mN m−1 at 20 °C), and good solubility of cobalt nitrate. The contact angle of the precursor solution was measured to check the wettability by dropping 3 μL of the precursor solution on the polished LSM pellet. The cobalt precursor solution had a low contact angle of 15.8° (inset in Figure 2a), which indicates good wettability, and the use of ethanol facilitated the deposition of precursors on the surface of LSM nanoparticles. Table 1 summarizes the abbreviations for the samples.
To obtain an effective Co3O4 electrocatalyst, the infiltrated powder was sintered at 600 °C and the sintered powder is denoted as LSM@Co3O4. The XRD pattern of LSM@Co3O4 (Figure 2b) shows the phase of LSM and Co3O4 without any detectable impurity phases, indicating the successful synthesis of Co3O4. The broad peak due to Co3O4 can be attributed to the nano size of the deposited particles. The high-magnification SEM images of LSM@Co3O4 in Figure 2c,d confirm that the smaller nanoparticles (~18 nm) of Co3O4 were uniformly deposited on the entire LSM nano-scaffold (~70 nm). Furthermore, LSM@Co3O4 retained the organically connected microstructures, which is effective for the transfer of electrons.

2.2. Rotating Ring-Disk Electrode (RRDE) Test

With different loading amounts of Co3O4, the catalytic activities of LSM@Co3O4 were measured for OER and ORR in 0.1 M KOH. The catalytic activities were compared with the benchmark catalysts IrO2 and Pt/C for OER and ORR to evaluate LSM@Co3O4 as a bifunctional electrocatalyst. For OER, the catalytic activities of LSM, LSM@ Co3O4-20, and LSM@Co3O4-25 were compared with Co3O4 and the benchmark catalyst IrO2 (Figure 3a). LSM has a nano-sized microstructure, but its OER current density showed a low value of 1.85 mA cm−2 at 1.70 V vs. reversible hydrogen electrode (RHE). After conducting Co3O4 infiltration, the current density was significantly enhanced to 13.01 mA cm-2 for LSM@Co3O4-20 and 10.63 mA cm-2 for LSM@Co3O4-25, indicating that the surface material was the dominant factor determining the catalytic activity for the OER. Especially, the current density of LSM@Co3O4-20 was ~7 times, ~1.5 times, and ~1.6 times higher, respectively, than those of LSM, Co3O4, and IrO2. The onset potential was also enhanced, as could be deduced from the voltage at 1 mA cm-2 of LSM@Co3O4-20 (1.55 V) and LSM@Co3O4-25 (1.55 V), compared to those of LSM (1.65 V) and Co3O4 (1.57 V). Moreover, the values are comparable to those of benchmark electrocatalysts such as Pt/C (1.61 V) and IrO2 (1.55 V). To compare OER kinetics, Tafel plots of LSM, LSM@Co3O4-20, and LSM@Co3O4-25 were derived from their OER polarization curves, and are presented in Figure 3c. The Tafel slope of LSM@Co3O4-25 was 73 mV decade-1, which is lower than that of LSM (84 mV decade-1), LSM@Co3O4-20 (89 mV decade-1), and IrO2 (121 mV decade-1). These improved catalytic activities of LSM@Co3O4-20 imply the existence of synergistic effects between LSM and Co3O4 and the potential for the use of LSM@Co3O4-20 as a bifunctional electrocatalyst.
Figure 3b,d presents the polarization curves of LSM@Co3O4 for the ORR with the benchmark samples Co3O4 and Pt/C. LSM on its own exhibited a good limiting current density (−5.30 mA cm-2) compared to Pt/C (−4.90 mA cm-2). However, with the Co3O4 infiltration, the limiting current density was enhanced to −5.45 and −5.30 mA cm-2, respectively, for LSM@Co3O4-20 and LSM@Co3O4-25. The ORR onset potentials at a current density of −0.3 mA cm-2 were observed to be 0.87, 0.87, and 0.89 V vs. RHE, respectively, for LSM, LSM@Co3O4-20, and LSM@Co3O4-25. On its own, Co3O4 showed a lower ORR activity, with the values of −4.45 mA cm-2 for limiting current density and 0.59 V vs. RHE for onset potential. Considering that a hybrid catalyst (A@B) has the properties of both constituent materials (A and B), the reduced activity in the range of 0.10–0.89 V may originate from the low catalytic activity of Co3O4, covering the surface of LSM. In Figure 3d, the Tafel slopes are plotted from the ORR polarization curves near the onset potential. Tafel slopes were obtained from the Koutecky–Levich (K-L) equation: LSM (80 mV decade-1), LSM@Co3O4-20 (114 mV decade-1), and LSM@Co3O4-25 (184 mV decade-1). The lower Tafel slope for LSM@Co3O4 compared to that for LSM indicates that the infiltration of Co3O4 facilitated oxygen diffusion on the catalyst surface and improved the ORR performance.

2.3. Four-Electron Pathway

As shown in Figure 4a,b, the electrochemical reduction of O2 can occur via two pathways, either a direct 4-electron pathway or a 2+2-electron pathway with peroxide intermediates. For oxygen electrocatalysis, the 4-electron pathway is most desirable because the direct pathway requires less thermodynamic reaction potential (Table 2). The 2+2-electron pathway is preferred in the industry for H2O2 production rather than for ORR catalysis.
To verify the ORR catalytic pathways, ring disk current was employed to detect the current of HO2- concomitantly produced via a two-electron pathway. The peroxide yield and electron transfer number (n) were calculated from the following equations with the measured current of the ring electrode and disk electrode for LSM, LSM@Co3O4-20, and LSM@Co3O4-25. The values of commercial Pt/C and Co3O4 were also compared as a benchmark.
% HO2- = 200 × (Ir/N)/(Id + Ir/N)
n = 4 × Id/(Id + Ir/N)
where Id represents the disk current, Ir indicates the ring current, and N is the current collection efficiency of the Pt ring. N was experimentally determined to be 0.41 from the reduction of K3Fe[CN]6.
The measured H2O2 yield was below 3% for LSM, LSM@Co3O4-20, and LSM@Co3O4-25, which is comparable to that for Pt/C and much lower than that for Co3O4 (Figure 4c). The number of electrons transferred for LSM@Co3O4-20 was calculated to be 3.96–4.00 (Figure 4d), which is higher than that for LSM (3.90–3.96) and LSM@Co3O4-25 (3.90–3.97). These results confirm that LSM, LSM@Co3O4-20, and LSM@Co3O4-25 followed a 4-electron reduction pathway rather than the 2+2-electron pathway. Especially, LSM@Co3O4-20 formed a lower quantity of peroxides than Pt/C, allowing the ORR to proceed through an almost ideal 4-electron reduction pathway.

2.4. X-Ray Photoelectron Spectroscopy (XPS) Anaylsis

Based on the RRDE results, LSM@Co3O4 exhibited good catalytic activity for both ORR and OER, comparable to the benchmark catalysts (Pt/C, Co3O4, and IrO2). Since the catalytic activities of LSM@Co3O4-20 and LSM@Co3O4-25 were similar and the n-value of LSM@Co3O4-20 was closer to four, we selected LSM@Co3O4-20 as a representative sample of LSM@Co3O4 for X-ray photoelectron spectroscopy (XPS) characterization.
XPS was performed to analyze the surface electronic state of the catalysts (i.e., LSM, Co3O4, and LSM@Co3O4-20) for O 1s, Co 2p, and Mn 2p. The XPS results were calibrated with the binding energy (BE) of the C 1s peak at 284.3 eV. In Figure 5a–c, the O 1s spectrum can be deconvoluted into three main peaks of lattice oxygen (Olattice, red), surface-adsorbed oxygen species (Oad, green), and adsorbed molecular water (H2Oad, blue). The relative contents of the oxygen species were calculated from the relative area of the three peaks, and are listed in Table 3. The calculated Oad/Olattice ratios were 1.68, 2.02, and 2.39, respectively, for LSM, Co3O4, and LSM@Co3O4-20. Considering that Oad can easily be converted to O2, the higher Oad/Olattice ratio of LSM@ Co3O4-20 is in good agreement with the OER results (i.e., indicating an enhanced catalytic activity of LSM@ Co3O4-20).
According to previous studies, Co3+ cations at the surface play a significant role in the OER due to their unique electronic state, favorable as both an electron donor and an electron acceptor for O2 and electron capturing. The Co3+/Co2+ ratio was 0.45 for Co3O4 and 0.68 for LSM@Co3O4-20, respectively. The highly concentrated Co3+ of LSM@Co3O4-20 indicates the high number of donor–acceptor reduction sites, supporting the enhanced OER catalytic activity. As presented in Figure 5f,g, the Mn3+/Mn4+ ratio was reduced from 0.83 for LSM to 0.77 for LSM@Co3O4-20, indicating ligand effects between LSM and the infiltrated Co3O4 layer. The ligand effect, a type of interfacial effect that leads to synergistic effects on the catalytic activity, refers to the electron transfer derived by the different electronic configurations of two adjacent materials. It has good agreement with the XPS results for Co 2p, in which LSM@Co3O4-20 had a higher Co3+ concentration compared to Co3O4. Based on these results, we speculate that the electrons in the LSM layer were transferred to the infiltrated Co3O4 layer by ligand effects, resulting in an electron-rich state on the surface. Correspondingly, the bond strength between the metal oxide and oxygen species at the surface of an electrocatalyst can be altered and the catalytic activity for ORR and OER can be tuned.

3. Conclusions

In this study, we presented a hybrid catalyst as a bifunctional catalyst for both ORR and OER. To synthesize the hybrid catalyst, 18 nm Co3O4 nanoparticles were uniformly deposited over the entire surface of a ~70 nm LSM nano-scaffold through simple electrospray and infiltration. The hybrid catalysts exhibited comparable OER and ORR performances compared to the benchmarked commercial catalysts. In particular, the hybrid catalysts followed a four-electron pathway, meaning a very effective path to the ORR. Due to differences in the electronic configurations of the ions in Co3O4 and LSM, the concentration of Co3+ and electron-rich phases were increased in the hybrid catalyst, contributing to the enhancement in the catalytic activity of ORR and OER.

4. Materials and Methods

La0.5Sr0.5MnO3-δ nanoparticles were synthesized via electrospray using a precursor solution consisting of La(NO3)3·6H2O (99+%, Sigma Aldrich Co.), Sr(NO3)2 (99+%, Sigma Aldrich Co.), Mn(NO3)2 (98%, Sigma Aldrich Co.), poly-vinylpyrrolidone (PVP, avg. molecular weight ~1,300,000 by LS, Sigma-Aldrich Co.), and N,N-dimethylformamide (DMF, Alfa Aesar Co.). The precursor solution was prepared by mixing the metal nitrates in DMF solvent with continuous stirring. After adding the PVP to the resulting solution, it was stirred for 12 h at 60 °C. The as-prepared LSM/PVP solution was filled into a plastic syringe with a capillary tip (D = 0.5 mm), electrically connected to a high-voltage power supply from Korea switching Co. The needle tip and aluminum collector were connected to the anode and cathode of the power supply, respectively, and were placed horizontally (Figure 2a). The applied voltage was 15 kV, and the distance between the tip and aluminum foil collector was 14 cm. The collected precursor was peeled off and heated at 850 °C for 4 h at a rate of 2 °C min-1 in air.
For the infiltration process, the precursor solution was prepared by dissolving Co(NO3)2·6H2O (98+ %, Sigma Aldrich Co.) in ethanol, which was penetrated into the LSM powder (prepared via electrospray). The resultant product was calcinated at 450 °C for 15 min in air. These penetration–calcination steps were repeated until the loading amount reached 20 and 25 wt.%. The loading amounts of Co3O4 was chosen with the consideration of interfacial effects, investigated in a previous study [12]. The samples with 20 and 25 wt.% Co3O4 are designated hereafter as LSM@Co3O4-20 and LSM@Co3O4-25, respectively. The infiltrated LSM was sintered at 600 °C for 4 h at a ramping rate of 2 °C min-1 in ambient air to obtain Co3O4. The loading amount was calculated using Equation (3):
Loading amount of Co3O4 (wt.%) = (WLSM@Co3O4 − WLSM)/ WLSM × 100
where WLSM is the weight of the LSM before infiltration and WLSM@Co3O4 is the weight of LSM@Co3O4 after sintering at 600 °C.
X-ray diffraction (XRD, Bruker D8 Advance) was performed in the range of 20° < 2θ < 60° for structural analyses. Scanning electron microscopy (SEM) (Nova SEM) was conducted to observe the microstructures of LSM and Co3O4@LSM. X-ray photoelectron spectroscopy (XPS) data were acquired with ESCALAB 250XI (Thermo Fisher Scientific) with a monochromated Al-Kα (ultraviolet He1, He2) X-ray source. To evaluate the electrocatalytic activity for ORR and OER, rotating ring-disk electrode (RRDE) experiments were performed with the prepared ink composed of 20 mg of sample, 0.9 mL of solvent (ethanol: isopropyl alcohol = 1:1), and 0.1 mL of 5 wt.% Nafion solution (Aldrich, 274704). The well-dispersed catalyst ink (5 mL) was spread on the pre-polished glassy carbon (GC) disk electrode (0.1256 cm2). The electrochemical performances with an RRDE-3A rotating disk electrode system were recorded with a Biologic VMP3. A Pt wire, Hg/HgO electrode filled with 1 M NaOH, and 0.1 M KOH solution saturated with oxygen were respectively used as the counter electrode, reference electrode, and electrolyte. To estimate the amount of peroxide from the disk electrode during the ORR, +0.4 V was applied to the ring electrode.
To convert the potential values from vs. Hg/HgO to vs. the reversible hydrogen electrode (RHE), the difference was measured in a cell using Pt wires for the working and counter electrodes under H2-saturated electrolyte 0.1 M KOH with an Hg/HgO reference electrode. The open-circuit potential was −0.89 V at 1 mV s-1 and the relationship between Hg/HgO and RHE was represented as:
EHg/HgO + 0.89 V = ERHE.

Author Contributions

S.K.: Conceptualization, Methodology, Data curation, Visualization, Investigation, Writing. G.K.: Conceptualization, Supervision, Reviewing and Editing. A.M.: Supervision, Reviewing and Editing, Funding acquisition. All authors have read and agreed to the published version of the manuscript.

Funding

Support from the Welch Foundation, grant F-1254, is gratefully acknowledged.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available in manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Goodenough, J.B.; Kim, Y. Challenges for rechargeable batteries. J. Power Sources 2011, 196, 6688–6694. [Google Scholar] [CrossRef]
  2. Fabbri, E.; Bi, L.; Pergolesi, D.; Traversa, E. Towards the next generation of solid oxide fuel cells operating below 600 °C with chemically stable proton-conducting electrolytes. Adv. Mater. 2012, 24, 195–208. [Google Scholar] [CrossRef]
  3. Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 2020, 11, 1550. [Google Scholar] [CrossRef] [PubMed]
  4. Girishkumar, G.; McCloskey, B.; Luntz, A.C.; Swanson, S.; Wilcke, W. Lithium-air battery: Promise and challenges. J. Phys. Chem. Lett. 2010, 1, 2193–2203. [Google Scholar] [CrossRef]
  5. Lee, J.S.; Kim, S.T.; Cao, R.; Choi, N.S.; Liu, M.; Lee, K.T.; Cho, J. Metal-air batteries with high energy density: Li-air versus Zn-air. Adv. Energy Mater. 2011, 1, 34–50. [Google Scholar] [CrossRef]
  6. Cheng, F.; Chen, J. Metal–air batteries: From oxygen reduction electrochemistry to cathode catalysts. Chem. Soc. Rev. 2012, 41, 2172. [Google Scholar] [CrossRef] [PubMed]
  7. Ju, Y.-W.W.; Yoo, S.; Kim, C.; Kim, S.; Jeon, I.-Y.Y.; Shin, J.; Baek, J.-B.B.; Kim, G. Fe@N-Graphene Nanoplatelet-Embedded Carbon Nanofibers as Efficient Electrocatalysts for Oxygen Reduction Reaction. Adv. Sci. 2015, 3, 1500205. [Google Scholar] [CrossRef]
  8. Li, Y.; Gong, M.; Liang, Y.; Feng, J.; Kim, J.E.; Wang, H.; Hong, G.; Zhang, B.; Dai, H. Advanced zinc-air batteries based on high-performance hybrid electrocatalysts. Nat. Commun. 2013, 4, 1805. [Google Scholar] [CrossRef] [Green Version]
  9. Agarwal, S.; Yu, X.; Manthiram, A. A pair of metal organic framework (MOF)-derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for zinc-air batteries. Mater. Today Energy 2020, 16, 100405. [Google Scholar] [CrossRef]
  10. Jung, J.-I.; Park, S.; Kim, M.-G.; Cho, J. Tunable Internal and Surface Structures of the Bifunctional Oxygen Perovskite Catalysts. Adv. Energy Mater. 2015, 5, 1501560. [Google Scholar] [CrossRef]
  11. Zhu, Y.; Zhou, W.; Yu, J.; Chen, Y.; Liu, M.; Shao, Z. Enhancing Electrocatalytic Activity of Perovskite Oxides by Tuning Cation Deficiency for Oxygen Reduction and Evolution Reactions. Chem. Mater. 2016, 28, 1691–1697. [Google Scholar] [CrossRef]
  12. Kim, S.; Kwon, O.; Kim, C.; Gwon, O.; Jeong, H.Y.; Kim, K.-H.; Shin, J.; Kim, G. Strategy for Enhancing Interfacial Effect of Bifunctional Electrocatalyst: Infiltration of Cobalt Nanooxide on Perovskite. Adv. Mater. Interfaces 2018, 5, 1800123. [Google Scholar] [CrossRef]
  13. Lu, Q.; Guo, Y.; Mao, P.; Liao, K.; Zou, X.; Dai, J.; Tan, P.; Ran, R.; Zhou, W.; Ni, M.; et al. Rich atomic interfaces between sub-1 nm RuOx clusters and porous Co3O4 nanosheets boost oxygen electrocatalysis bifunctionality for advanced Zn-air batteries. Energy Storage Mater. 2020, 32, 20–29. [Google Scholar] [CrossRef]
  14. Fujiwara, N.; Nagai, T.; Ioroi, T.; Arai, H.; Ogumi, Z. Bifunctional electrocatalysts of lanthanum-based perovskite oxide with Sb-doped SnO2 for oxygen reduction and evolution reactions. J. Power Sources 2020, 451, 227736. [Google Scholar] [CrossRef]
  15. Sadighi, Z.; Huang, J.; Qin, L.; Yao, S.; Cui, J.; Kim, J.K. Positive role of oxygen vacancy in electrochemical performance of CoMn2O4 cathodes for Li-O2 batteries. J. Power Sources 2017, 365, 134–147. [Google Scholar] [CrossRef]
  16. Suntivich, J.; May, K.J.; Gasteiger, H.A.; Goodenough, J.B.; Shao-horn, Y. A Perovskite Oxide Optimized for Molecular Orbital Principles. Science 2011, 334, 1383–1385. [Google Scholar] [CrossRef] [PubMed]
  17. Liang, Y.; Li, Y.; Wang, H.; Zhou, J.; Wang, J.; Regier, T.; Dai, H. Co3O4 Nanocrystals on Graphene as a Synergistic Catalyst for Oxygen Reduction Reaction. Nat. Mater. 2011, 10, 780–786. [Google Scholar] [CrossRef] [Green Version]
  18. Kim, S.W.; Kim, H.; Yoon, K.J.; Lee, J.H.; Kim, B.K.; Choi, W.; Lee, J.H.; Hong, J. Reactions and mass transport in high temperature co-electrolysis of steam/CO2 mixtures for syngas production. J. Power Sources 2015, 280, 630–639. [Google Scholar] [CrossRef]
  19. Bu, Y.; Gwon, O.; Nam, G.; Jang, H.; Kim, S.; Zhong, Q.; Cho, J.; Kim, G. A Highly Efficient and Robust Cation Ordered Perovskite Oxides as a Bi-Functional Catalyst for Rechargeable Zinc-Air Batteries. ACS Nano 2017, 11, 11594–11601. [Google Scholar] [CrossRef]
  20. Behnken, J.; Yu, M.; Deng, X.; Tüysüz, H.; Harms, C.; Dyck, A.; Wittstock, G. Oxygen Reduction Reaction Activity of Mesostructured Cobalt-Based Metal Oxides Studied with the Cavity-Microelectrode Technique. ChemElectroChem 2019, 6, 3460–3467. [Google Scholar] [CrossRef]
  21. Hong, W.T.; Risch, M.; Stoerzinger, K.A.; Grimaud, A.; Suntivich, J.; Shao-Horn, Y. Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis. Energy Environ. Sci. 2015, 8, 1404–1427. [Google Scholar] [CrossRef] [Green Version]
  22. Hu, J.; Shi, L.; Liu, Q.; Huang, H.; Jiao, T. Improved oxygen reduction activity on silver-modified LaMnO3-graphene via shortens the conduction path of adsorbed oxygen. RSC Adv. 2015, 5, 92096–92106. [Google Scholar] [CrossRef]
  23. Wang, W.; Geng, J.; Kuai, L.; Li, M.; Geng, B. Porous Mn2O3: A Low-Cost Electrocatalyst for Oxygen Reduction Reaction in Alkaline Media with Comparable Activity to Pt/C. Chem. A Eur. J. 2016, 22, 9909–9913. [Google Scholar] [CrossRef] [PubMed]
  24. Lambert, T.N.; Vigil, J.A.; White, S.E.; Delker, C.J.; Davis, D.J.; Kelly, M.; Brumbach, M.T.; Rodriguez, M.A.; Swartzentruber, B.S. Understanding the Effects of Cationic Dopants on α-MnO2 Oxygen Reduction Reaction Electrocatalysis. J. Phys. Chem. C 2017, 121, 2789–2797. [Google Scholar] [CrossRef]
  25. Chowdhury, A.D.; Agnihotri, N.; Sen, P.; De, A. Conducting CoMn2O4—PEDOT nanocomposites as catalyst in oxygen reduction reaction. Electrochim. Acta 2014, 118, 81–87. [Google Scholar] [CrossRef]
  26. Dai, L.; Sun, Q.; Guo, J.; Cheng, J.; Xu, X.; Guo, H.; Li, D.; Chen, L.; Si, P.; Lou, J.; et al. Mesoporous Mn2O3 rods as a highly efficient catalyst for Li-O2 battery. J. Power Sources 2019, 435, 226833. [Google Scholar] [CrossRef]
  27. Sun, C.; Li, F.; Ma, C.; Wang, Y.; Ren, Y.; Yang, W.; Ma, Z.; Li, J.; Chen, Y.; Kim, Y.; et al. Graphene–Co3O4 nanocomposite as an efficient bifunctional catalyst for lithium–air batteries. J. Mater. Chem. A 2014, 2, 7188. [Google Scholar] [CrossRef]
  28. Lee, D.U.; Park, H.W.; Park, M.G.; Ismayilov, V.; Chen, Z. Synergistic bifunctional catalyst design based on perovskite oxide nanoparticles and intertwined carbon nanotubes for rechargeable zinc-air battery applications. ACS Appl. Mater. Interfaces 2015, 7, 902–910. [Google Scholar] [CrossRef]
  29. Zhao, X.; Li, F.; Wang, R.; Seo, J.M.; Choi, H.J.; Jung, S.M.; Mahmood, J.; Jeon, I.Y.; Baek, J.B. Controlled Fabrication of Hierarchically Structured Nitrogen-Doped Carbon Nanotubes as a Highly Active Bifunctional Oxygen Electrocatalyst. Adv. Funct. Mater. 2017, 27, 1–9. [Google Scholar] [CrossRef]
  30. Yang, W.; Salim, J.; Ma, C.; Ma, Z.; Sun, C.; Li, J.; Chen, L.; Kim, Y. Flowerlike Co3O4 microspheres loaded with copper nanoparticle as an efficient bifunctional catalyst for lithium-air batteries. Electrochem. Commun. 2013, 28, 13–16. [Google Scholar] [CrossRef]
  31. Chen, W.F.; Sasaki, K.; Ma, C.; Frenkel, A.I.; Marinkovic, N.; Muckerman, J.T.; Zhu, Y.; Adzic, R.R. Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets. Angew. Chem. Int. Ed. 2012, 51, 6131–6135. [Google Scholar] [CrossRef] [PubMed]
  32. Zhang, H.; Qiao, H.; Wang, H.-Y.; Zhou, N.; Chen, J.; Tang, Y.-G.; Li, J.; Huang, C. Nickel Cobalt Oxide/carbon Nanotubes Hybrid as a High-performance Electrocatalyst for Metal/air Battery. Nanoscale 2014, 6, 10235–10242. [Google Scholar] [CrossRef]
  33. Augustyn, V.; Simon, P.; Dunn, B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ. Sci. 2014, 7, 1597–1614. [Google Scholar] [CrossRef] [Green Version]
  34. Balaya, P. Size effects and nanostructured materials for energy applications. Energy Environ. Sci. 2008, 1, 645–654. [Google Scholar] [CrossRef]
  35. Wang, R.; Lang, J.; Liu, Y.; Lin, Z.; Yan, X. Ultra-small, size-controlled Ni(OH)2 nanoparticles: Elucidating the relationship between particle size and electrochemical performance for advanced energy storage devices. NPG Asia Mater. 2015, 7, e183. [Google Scholar] [CrossRef] [Green Version]
Molecules 26 00277 g001 550
Figure 1. (a) Schematic illustration of the electrospray fabrication of La0.5Sr0.5MnO3-δ (LSM). (b) X-ray diffraction patterns and (c,d) scanning electron microscopy images of LSM sintered at 850 °C for 4 h in air.
Figure 1. (a) Schematic illustration of the electrospray fabrication of La0.5Sr0.5MnO3-δ (LSM). (b) X-ray diffraction patterns and (c,d) scanning electron microscopy images of LSM sintered at 850 °C for 4 h in air.
Molecules 26 00277 g001
Molecules 26 00277 g002 550
Figure 2. (a) Schematic illustration of the infiltration technique for LSM@Co3O4 with the contact angle of the precursor solution (inset). (b) X-ray diffraction pattern and (c,d) scanning electron microscopy images of LSM@Co3O4 sintered at 600 °C for 4 h in air.
Figure 2. (a) Schematic illustration of the infiltration technique for LSM@Co3O4 with the contact angle of the precursor solution (inset). (b) X-ray diffraction pattern and (c,d) scanning electron microscopy images of LSM@Co3O4 sintered at 600 °C for 4 h in air.
Molecules 26 00277 g002
Molecules 26 00277 g003 550
Figure 3. Polarization curves and Tafel slopes according to the loading amount of Co3O4 for (a,c) oxygen evolution reaction (OER) and (b,d) oxygen reduction reaction (ORR) in O2-saturated 0.1 M KOH at a rotation rate of 1600 rpm and a scan rate of 0.01 V s−1.
Figure 3. Polarization curves and Tafel slopes according to the loading amount of Co3O4 for (a,c) oxygen evolution reaction (OER) and (b,d) oxygen reduction reaction (ORR) in O2-saturated 0.1 M KOH at a rotation rate of 1600 rpm and a scan rate of 0.01 V s−1.
Molecules 26 00277 g003
Molecules 26 00277 g004 550
Figure 4. (a) Electron transfer number (n) depending on the loading amount of Co3O4 for the oxygen reduction reaction (ORR). (b) Schematic representation of the ORR mechanism by direct 4-electron and indirect 2+2 electron pathways. (c) Assessment of peroxide yield calculated by the (d) ring current in O2-saturated 0.1 M KOH at a rotation rate of 1,600 rpm and a scan rate of 0.01 V s−1.
Figure 4. (a) Electron transfer number (n) depending on the loading amount of Co3O4 for the oxygen reduction reaction (ORR). (b) Schematic representation of the ORR mechanism by direct 4-electron and indirect 2+2 electron pathways. (c) Assessment of peroxide yield calculated by the (d) ring current in O2-saturated 0.1 M KOH at a rotation rate of 1,600 rpm and a scan rate of 0.01 V s−1.
Molecules 26 00277 g004
Molecules 26 00277 g005 550
Figure 5. (a–c) O 1s, (d,e) Co 2p, and (f,g) Mn 2p XPS peaks of, respectively, LSM, Co3O4, and LSM@Co3O4-20.
Figure 5. (a–c) O 1s, (d,e) Co 2p, and (f,g) Mn 2p XPS peaks of, respectively, LSM, Co3O4, and LSM@Co3O4-20.
Molecules 26 00277 g005
Table
Table 1. Chemical compositions and abbreviations of the samples.
Table 1. Chemical compositions and abbreviations of the samples.
AbbreviationsChemical Composition
LSMLa0.5Sr0.5MnO3-δ
LSM@Co3O4LSM@Co3O4-2020 wt.% Co3O4-infiltrated LSM
LSM@Co3O4-2525 wt.% Co3O4-infiltrated LSM
Table
Table 2. Thermodynamic electrode potential of the O2 reduction pathway.
Table 2. Thermodynamic electrode potential of the O2 reduction pathway.
Reaction ProcessThermodynamic Electrode Potential at Standard Conditions, V vs. SHE
4-electron pathwayO2 + 2H2O + 4e- → 4OH-0.401
2+2-electron pathwayO2 + H2O + 2e- → HO2- + OH-−0.065
HO2- + H2O + 2e- → 3OH-0.867
Table
Table 3. XPS peak deconvolution results of LSM, CO3O4, and LSM@Co3O4-20.
Table 3. XPS peak deconvolution results of LSM, CO3O4, and LSM@Co3O4-20.
SampleSpeciesBE (eV)Ratio (Co3+/Co2+)Ratio (Mn3+/Mn4+)Ratio (Oad/Olattice)
LSMMn2p3/2Mn3+641.49 0.83
Mn4+643.36
2p1/2Mn3+653.26
Mn4+656.21
O 1sOlattice528.77 1.68
Oad528.98
H2Oad530.96
C 1s284.3
Co3O4Co2p3/2Co3+779.320.45
Co2+780.56
2p1/2Co3+794.34
Co2+795.77
O 1sOlattice529.57 2.02
Oad530.48
H2Oad533.08
C 1s284.3
LSM@Co3O4-20Co2p3/2Co3+779.530.68
Co2+780.84
2p1/2Co3+794.58
Co2+796.00
Mn2p3/2Mn3+641.31 0.77
Mn4+643.34
2p1/2Mn3+652.93
Mn4+655.19
O 1sOlattice529.33 2.39
Oad530.40
H2Oad532.44
C 1s284.3
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Kim, S.; Kim, G.; Manthiram, A. A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions: Nano-Co3O4-Deposited La0.5Sr0.5MnO3 via Infiltration. Molecules 2021, 26, 277. https://doi.org/10.3390/molecules26020277

AMA Style

Kim S, Kim G, Manthiram A. A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions: Nano-Co3O4-Deposited La0.5Sr0.5MnO3 via Infiltration. Molecules. 2021; 26(2):277. https://doi.org/10.3390/molecules26020277

Chicago/Turabian Style

Kim, Seona, Guntae Kim, and Arumugam Manthiram. 2021. "A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions: Nano-Co3O4-Deposited La0.5Sr0.5MnO3 via Infiltration" Molecules 26, no. 2: 277. https://doi.org/10.3390/molecules26020277

APA Style

Kim, S., Kim, G., & Manthiram, A. (2021). A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions: Nano-Co3O4-Deposited La0.5Sr0.5MnO3 via Infiltration. Molecules, 26(2), 277. https://doi.org/10.3390/molecules26020277

Article Metrics

Back to TopTop