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Journal of The Electrochemical Society, 2022 169 063513

Review—The Oxygen Reduction Reaction on MXene-Based


Catalysts: Progress and Prospects
Ray Yoo,1 Eugenie Pranada,2 Denis Johnson,1,* Zhi Qiao,1 and Abdoulaye Djire1,2,z,*
1
Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States
of America
2
Department of Materials Science & Engineering, Texas A&M University, College Station, Texas 77843, United States of
America

The oxygen reduction reaction (ORR) is a critical, but sluggish reaction used for various applications, including fuel cells and
metal-oxygen batteries. Currently, the benchmark catalysts for ORR are Pt-based catalysts. However, due to these catalysts being
scarce and very expensive, alternative catalysts that are more abundant and less expensive are urgently in demand. MXenes, a new
two-dimensional (2D) material based on transition metal carbides and nitrides, have advanced the performance of many existing
technologies, including batteries, supercapacitors, sensors, etc. Owing to their unique electronic structure, physical and chemical
properties, and tunable morphology, MXenes are expected to thrive in the ORR electro- and photo-catalytic systems. Recent
studies reported better-performing ORR catalysts with MXenes as supports, which holds promise in the significant reduction of Pt
loading for efficient catalysts. Furthermore, MXenes exhibit wide applicability and stability in a range of pH values, from acidic to
basic. In this work, we carefully review the most pertinent works on ORR using MXenes. We first discuss the catalytic
performance of MXenes in alkaline and acidic environments, followed by their application in metal-air batteries. We investigate
the gaps and challenges in the field, identify key areas that need further attention, and provide directions for future research.
© 2022 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ac766e]

Manuscript submitted March 19, 2022; revised manuscript received May 23, 2022. Published June 17, 2022. This paper is part of
the JES Focus Issue on Electrochemical Separations and Sustainability.

Technological applications involving electrochemical storage and ORR catalyst should possess the following characteristics: high
energy conversion have revolutionized the energy field and shaped electrical conductivity, stability under high electrode potential and
the lives of billions. From batteries and capacitors to fuel cells and harsh electrolyte environment, porous morphology for mass trans-
electrolyzers, materials advancement plays an essential role to port, and high durability of active sites. Currently, the benchmark
accelerate electrochemical processes and enable the development catalysts for ORR are carbon-supported Pt and Pt-based alloy
of novel, life-changing devices. Particularly, oxygen-involved elec- nanoparticles. Their relatively high activity and ORR stability
trocatalytic reactions, including the oxygen reduction reaction make them viable for fuel cell technology, especially in electric
(ORR) and the oxygen evolution reaction (OER), are commonly vehicles.8 However, the key downside to these catalyst systems is
explored in many applications ranging from batteries to catalysis.1 their exorbitant price and accessibility. In addition, the unsatisfac-
ORR is extensively studied at the fuel cell cathode and at the tory long-term durability caused by Pt dissolution, methanol cross-
oxygen-metal battery cathode to analyze its behavior in cathodic over, and CO poisoning are other notable issues. These limitations
reactions and in the closure of the circuit of electron transfer.2 have motivated researchers to look for other alternatives using
Typically, ORR consists of multiple adsorption/desorption processes nonmetal and non-precious metal-based materials. This review
and reaction steps involving oxygen-containing species such as O, article focuses on MXene-based catalysts. The readers are referred
OH, O2–, HO2–, and H2O2. However, ORR is often the slowest to the following review articles for insights about carbon-based
reaction in fuel cells and oxygen batteries due to the high bond materials and noble-metal-free catalysts for ORR.3,9
energy of the O2 molecule, thus calling for the use of catalysts. The When considering the available options for alternatives, transi-
possible reaction pathways of O2 involve the reduction to hydrogen tion metal-based catalysts show more promise than nonmetal-based
peroxide by a 2-electron pathway and the reduction to water or and non-precious metal-based catalysts due to their higher surface
hydroxide by a direct 4-electron pathway. The ORR via 2-electron energy and multiformity.10–12 Currently, the state-of-the-art pla-
pathway, O2 + H2O + 2e− → HO2− + OH− (alkaline media) and tinum group metal (PGM)-free catalyst for ORR is the metal-
O2 + 2H+ + 2e− → H2O2 (acidic media), is studied to potentially nitrogen-carbon (M-N-C) catalyst, in which M usually refers to iron
replace the anthraquinone process for the industrial synthesis of (Fe), cobalt (Co), or manganese (Mn). This type of catalyst is
H2O2.3–5 Producing concentrated H2O2 requires an energy-intensive equipped with single-atom metal sites coordinated with N, which are
distillation process and thus involves a large capital investment.3 immobilized in the carbon substrate. The coordinated FeN4, CoN4,
Though direct synthesis of H2O2 from H2 and O2 is possible, it or MnN4 moiety is considered to be the active site for ORR, and a
imposes a great risk of explosion and suffers from low selectivity carbon support with a porous structure plays a favorable role in
due to dilution to lessen safety hazards.4,6 These are enough reasons facilitating the electron and mass transfer.9,13 Plenty of works have
to prompt scientists to resort to a greener, faster way to produce demonstrated the tremendous improvement of their activity for
peroxides. However, in terms of electrochemical energy conversion ORR.9,14–16 Unfortunately, the harsh conditions posed by acidic
using fuel cells or batteries, the more desirable pathway is the 4- environments lessen the stability of both the active sites and the
electron pathway as it involves more electrons being transferred, carbon substrate, significantly hindering their further application in
according to the pathway equations denoted by O2 + 2H2O + 4e− devices. Other non-Pt catalysts that have attracted a great deal of attention
→ 4OH− (alkaline media) and O2 + 4H+ + 4e− → 2H2O (acidic include monometallic, bimetallic, and multimetallic catalysts,17–21 transi-
media).7 Therefore, a catalyst with a high selectivity of the 4- tion metal oxides,22,23 nitrides,24,25 chalcogenides,26,27 carbides,28 and
electron pathway over the 2-electron one is crucial. In general, an oxynitrides.29
Notably in particular, the discovery of two-dimensional (2D)
carbide and nitride materials, MXenes, has since redefined the role
*Electrochemical Society Member. of carbides and nitrides in ORR. Since its first report in 2011,
z
E-mail: adjire@tamu.edu various MXene applications in energy storage,30 wireless
Journal of The Electrochemical Society, 2022 169 063513

communication,31 catalysis,32 sensing,33 optoelectronics,34 and adsorption energies of anions, which enables faster ORR kinetics,
medicine35 have been proposed. MXene materials are synthesized and provides a less corrosive environment to the catalysts.46
through selective etching of the “A” element from the parent MAX Various non-Pt metal-based catalysts have demonstrated great
phase. With Mn+1XnTx as the general formula of a MXene, in which performance of ORR in alkaline electrolytes. For example, manga-
M, X, and Tx represent early d-block transition metals, C and/or N nese oxides (MnOx) are known for their sufficient activity towards
atoms, and the surface termination groups (–F, –OH, and/or –O–), H2O2 decomposition.47 Related studies have pointed out that the
respectively, the most fascinating facet of a MXene is its structural catalytic activity of MnOx toward ORR follows the sequence:
diversity. The favorable 2D structure of MXenes provide high Mn5O8 < Mn3O4 < Mn2O3 < MnOOH,48 and β-MnO2 <
surface area, high density of active sites, fluent mass transport, λ-MnO2 < γ-MnO2 < α-MnO2 ≈ δ-MnO2,48 indicating the catalytic
and unique electronic properties.36,37 Insofar, the MXene family has process is sensitive to chemical composition and crystallographic
more than 30 stoichiometric compositions that have been experi- structure. In another work, copper was doped on titanium dioxide
mentally synthesized and many more theoretically determined, each (Cu-TiO2) to improve H2O2 selectivity of TiO2.49 It was found that
with its own distinct electronic, physical, and (electro)chemical doping Cu not only improved the electrical conductivity of TiO2 but
properties38 that provide a tremendous chance for leveraging also increased its oxygen vacancies and reduced the adsorption
MXenes to improve upon specific applications.34 The ease of energy of HO2− active sites, thereby favoring the production of
tunability for the termination groups offer a facile method to modify hydrogen peroxide. Metal organic frameworks (MOFs) have also
the surface energy and structure, which can be applied to further been exploited as ORR catalysts due to their high specific surface
manage the catalytic performance. To the best of our knowledge, area, adjustable pore size, and simple pyrolysis preparation.9,50 A 1D
there has only been one study on the use of MXenes as the sole ORR MOF, manganese tetracyanoquinodimethane (Mn-TCNQ), was
electrocatalyst, which was conducted by Shi’s group.39 Among the tested for 2e– ORR in alkaline media.51 DFT calculations revealed
members of the Ti3C2 MXene family (Ti3AlC2 MAX, Ti3C2 that HO2− adsorbed on the Mn sites of the Mn-TCNQ which boosted
multilayer (Ti3C2 ML), Ti3C2 single-layer (Ti3C2 SL)), only the H2O2 selectivity to 98%. Metal carbides are also being investigated
Ti3C2 SL exhibits reasonable ORR activity in 0.1 M KOH with an for ORR in alkaline media. For example, tungsten carbides (WC)
onset potential of 0.85 V and a Tafel slope of 64 mV dec−1. The have attracted great attention as supporting materials or promoters
higher ORR activity compared to the other members of the family is due to their Pt-like electronic behavior, high chemical stability, and
attributed to the higher exposed surface area and improved con- high corrosion resistance.52 Contrary to expectations, however, the
ductivity. It is worth noting that when compared to some of the other intrinsic ORR activity of WC directly applied in alkaline media is
nonmetal and non-precious metal-based catalysts, the Ti3C2 MXene extremely low.53
exhibits a lower performance. Further studies on MXenes are Emerging materials and composites have shown great promise
expected to result in overcoming this drawback. Nevertheless, the for ORR catalysis. Among these materials, MXenes have proven to
versatility of MXenes as good supporting materials ensure their be conducting fortifiers to composites as they demonstrate strong
future in the field of ORR. interfacial coupling interaction and fast charge transfer.54 Thus, the
To date, there have been a number of review papers40–42 detailing integration of MXenes could effectively improve the electroche-
the progress and development of MXenes for ORR. These works mical properties of composite materials, which would then benefit
highlight MXene-support catalysts and discuss the effects of ORR performance. Generally, transition metal nanoparticles act as
different catalyst-support coupling interactions on the resulting active catalysts for ORR in alkaline media, and so MXenes could
electronic structure of the catalyst. Comparisons are made with the potentially behave as scaffolds or supports due to their abundant
benchmark ORR catalysts in terms of durability and electrocatalytic embedding sites.
activity. While these papers provide a strong starting point on the
promising capabilities, they, however, lack critical evaluation of the MXenes as supports to Co-N-C catalysts.—Zhang’s group
mentioned works. Through this paper, we bridge the gap by prepared a binary ORR catalyst consisting of non-precious-metal
providing a critical review on the fundamental concepts of using iron-cobalt (Fe-Co) nanoparticles within Ti3C2 MXene.55 Through
MXenes as electrocatalysts/supports for ORR and revisit key incorporating ethylenediamine (EDA) to form FeCoEDA chelate
fundamental theoretical and experimental works on MXene-based nanoparticles, the authors claimed that these nanoparticles can be
catalysts as alternatives. We then suggest future considerations to successfully grafted onto the Ti3C2 MXene nanoflake substrates. The
extend upon andadvance the present knowledge. We emphasize the agglomeration of nanoparticles can be avoided, leading to higher
different types of systems, including alkaline and acidic media, as activity and stability. From Peng and Zhang’s group, MXene-Ag
well as batteries, to give the readers an organized full picture of this composites were prepared through in situ reduction of AgNO3 on
field. Finally, we provide a clear extension to the field of metal- intercalated Ti3C2(OH/ONa)2 MXenes.56 These analogous urchin-
oxygen batteries in order to better provide a picture on the shaped MXene-Ag0.9Ti0.1 bimetallic nanowire composites exhibited
applicability to real fuel systems. In a thorough perspective, we promising activity for ORR. Notably, the alkalization of the Ti3C2
conclude this review with the existing issues and the future MXene plays a critical role in the successful synthesis of the
challenges along with some possible approaches to them. composites. In 2018, Zhang and coworkers combined cobalt
deposited carbon nanotube with Ti3C2 MXene (Co-CNT/Ti3C2) for
ORR catalysis in alkaline media.57 The metal organic framework
ORR in Alkaline Electrolytes
ZIF-67 was used as a precursor to synthesize carbon nanotubes
ORR in alkaline electrolytes is a critical aspect to consider in through a pyrolysis process, which was further integrated with
direct methanol fuel cells (DMFC) and other fuel cell applications. Ti3C2. The composite achieved a half-wave potential of 0.82 V vs
As a favorable competitor to polymer electrolyte membrane fuel RHE, which is comparable to the performance of Pt/C. Additionally,
cells (PEMFCs), alkaline fuel cells have demonstrated better higher stability was observed for Co-CNT/Ti3C2 when compared
theoretical performance43 and lower costs.44 In the 4-proton transfer with Pt/C. It was speculated that the abundant Co–N/C, located on
mechanism, the standard reduction potential changes by 0.828 V, the tip of the carbon nanotubes, performed as the active sites.
from 1.229 V to 0.401 V vs SHE, as the pH value increases from 0 to However, there is a lack of sufficient evidence, such as scanning
14. This shift in the standard reduction potential leads to a significant electron microscope (SEM) images, to confirm the tipped cobalt
decrease in the overpotential for the first electron transfer in alkaline structure. In addition, the function of integrated MXenes was not
media.45 Alkaline electrolytes are used to enable surface-indepen- clearly revealed regarding the improvement of electrical conduc-
dent outer-sphere electron transfer processes during the first stage of tivity. Other means of synthesizing Co-CNT/Ti3C2 could possibly
ORR (O2/O2−).45 Additionally, the alkaline media confers lower involve the oxidation of Ti3C2, as MXenes are known to be
Journal of The Electrochemical Society, 2022 169 063513

precursors of oxides and/or oxide hybrid materials in the proper a decrease in the local electron density of Fe centers caused by
atmosphere. For example, Li et al. reported a Ti3C2 MXene-derived the electron transfer between FePc and Ti3C2Tx. Furthermore, the
Ti3C2/TiO2 nanoflowers by a synchronous oxidation and alkalization ultraviolet photoelectron spectroscopy (UPS) revealed that the
of Ti3C2 MXene precursor followed by ion exchange and heat electron density of FeN4 active sites become lower at the Fe(II)
treatment.58 The Ti3C2/TiO2 nanoflower-structure catalyst calcined center while accumulating at the nitrogen ligands, inducing an Fe 3d
at 500 °C exhibited significant improvement in photocatalytic water electron delocalization (Fig. 1f). The authors attributed this to the
splitting compared with pristine TiO2. This nanoflower-structured support effects of Ti3C2Tx MXene, which contains abundant
catalyst offered more active sites and possessed enhanced charge hydroxyl and fluorine termination groups with high electronega-
separation. It is of interest to see how utilization of MXene-based tivity. The reduced local electron density and higher spin state of the
catalysts will make an impact on the electrocatalytic activity. For Fe(II) centers significantly enhanced the ORR performance, as
example, a MXene hybrid, Ti3C2/TiO2 with Co-CNT, could be shown in Figs. 1g–1i. A more positive half-wave potential E1/2 of
tested to determine if there is improvement in the ORR activity. the MXene (≈0.88 V vs RHE) corresponds to its higher intrinsic
Song and coworkers developed a pyrolysis method for the ORR activity (Fig. 1g). Figure 1h presents the comparison of the
synthesis of a new composite consisting of nitrogen-doped multi- kinetic current densities (Jk) of the three tested catalysts at two
walled CNTs with cobalt nanoparticles encapsulated and Ti3C2Tx potentials and FePc/Ti3C2Tx exhibited the highest current density in
MXene as a bifunctional electrocatalyst toward ORR and OER.59 both potentials. As seen in Fig. 1h, the calculated electron transfer
Dicyandiamide (DCD) was applied as a source of both C and N for numbers through H2O2 yield are close to 4, indicating a 4-electron
the formation of multiwalled N-CNTs under the catalytic effect of reduction pathway. Therefore, in terms of MXene composites with
cobalt species during the pyrolysis process. The SEM and transmis- single atom metal coordinated sites like FeN4, the vacancy/defect
sion electron microscopy (TEM) images shown in Figs. 1a and 1b engineering of the MXene could enable rational designs with high
exhibit that Co nanoparticles encapsulated N-CNTs (Co/N-CNTs) catalytic performance.65 For future studies on the use of Fe-N-C
are rooted and directly grown on the surface of Ti3C2Tx MXene (red MXenes in ORR, there should also be evaluation on the stability of
circles), demonstrating that Co/N-CNTs are tightly coupled with the these catalysts for long term applications.
Ti3C2Tx MXene. With regards to the ORR activity, there was a Iron-cluster-directed cationic Fe−N−C nanosheets (Zeta poten-
slightly lower performance of Co/N-CNTs@Ti3C2Tx compared with tial of 30.4 mV) have been assembled with anionic Ti3C2 MXene to
benchmark Pt/C (Fig. 1c). But, the Co/N-CNTs@Ti3C2Tx signifi- produce a superlattice-like heterostructure for ORR in alkaline
cantly outperformed the one without the MXene matrix, indicating a media by Zhu and Chen’s group.66 The electrically-driven assembly
potential synergistic role that the MXene matrix plays in promoting method is shown in Fig. 2a. From results that show promising ORR
electron transfer. In addition, through the analysis of the electron activity and stability, this work provides a new strategy to
transfer number (n) and the peroxide production yield (H2O2%), a incorporate Fe-N-C catalysts with MXene materials.
quasifour-electron pathway with a low H2O2 production yield over
the potential range of 0.2–0.8 V vs RHE was observed (Fig. 1d), MXenes as supports to defected carbon materials.—Aside from
suggesting favorable catalytic reaction kinetics. Although the higher transition metal-based catalysts, defected carbon materials attached
ORR performance of MXene-metal nanoparticle composites has to the MXene also behave as catalytically active materials for ORR
been successfully identified, there is a significant lack of clarity on in alkaline media.68 For example, Lei and Zhang’s group synthe-
the function of MXenes in terms of catalytic performance. Detailed sized a porous and N-rich carbon/MXene composite as an ORR
experimental studies coupled with theoretical investigations are catalyst.67 Polypyrrole was used as a precursor for N doping, leading
urgently needed to validate the promising capabilities of MXene to high N content up to 9.6 wt%. As shown in Figs. 2b–2e, Ti3C2
materials in this field. MXene is observed to be well incorporated into the amorphous
carbon structure. The formed N-containing voids and pores, shown
MXenes as supports to Fe-N-C catalysts.—A catalyst group in Fig. 2f, are proposed to be the active site of the ORR. However,
considered to be the most promising alternative to Pt for the ORR in the function of the MXene in accelerating the ORR in this composite
aqueous media is iron–nitrogen–carbon (Fe–N–C) catalysts. Carbon- is not discussed in detail, and the overall enhancement of electrical
based materials are usually applied as a matrix for Fe-N-C as they conductivity is yet to be evaluated. Future work in this area should
can provide abundant defects to incorporate FeN4 active sites.14,61,62 also involve the long-term stability of the catalyst in aqueous media.
With regards to the carbide MXene, abundant access to the C atoms A summary of the MXene catalysts used for ORR in alkaline media
could be provided by both basal plane cation vacancies and through is presented in Table I.57,63,69–72
the edge sites. These exposed C atoms are possibly able to capture
the FeN4 moieties and thus could be integrated as Fe-N-C catalysts. Future considerations of MXene-based catalysts for alkaline
In addition, the various termination groups on MXenes can also offer ORR.—It is important to note that most of the MXene ORR works in
viability to immobilize FeN4-containing molecules to form new alkaline electrolytes covered in this review are based on the titanium
active composites. Li and coworkers developed a FeNC/MXene MXene phases. For long-term operation of this specific electro-
hybrid nanosheet through the pyrolysis of an iron–ligand complex catalytic fuel system, oxidative stability of these MXenes in alkaline
and Ti3C2 MXene nanosheets.63 The authors claimed that FeNC/ media should be taken into account, in addition to the electro-
MXene provides better performance over Pt/C in both activity and chemical durability. A work by Lutkenhaus, Radovic, and Green73
stability of ORR. However, an excessively low performance of the demonstrates that Ti3C2Tx MXene undergoes a loss of conductivity
benchmark Pt/C catalyst, relative to other studies, questions the and significant oxidation when stored in aqueous solution for
reliability of the electrochemical measurement in this work. 1–2 weeks. Another work by the groups74 shows that MXene
Additionally, a detailed discussion about the nature of the active oxidation is accelerated in basic media (such as KOH) by their
sites is missing, as there is a significantly lower content (2.7 at%) of reaction with hydroxyl anions, offsetting the reduction in the over-
N in FeNC/MXene when compared with the state-of-the-art Fe-N-C potential provided by alkaline electrolytes. Specifically, the aqueous
ORR catalysts.64 In another work led by Chen, Mai, and Guo, a close dispersions were shown to undergo rapid decreases in pH values after
interaction of FeN4 moiety and Ti3C2Tx MXene can lead to a the first two days due to the rapid uptake of hydroxyl anions. XPS
twofold activity improvement of pristine Fe–N–C.60 The researchers data for Ti3C2Tx show that the MXenes stored in KOH exhibit a
achieved a self-assembly of iron phthalocyanine (FePc) and Ti3C2Tx higher atomic percentage of Ti(IV) component than those stored in
MXene in dimethylformamide solution under ultrasonication. As HCl, indicating a faster transition from MXene nanosheets to TiO2 in
indicated in Fig. 1e (Fe 2p3/2 and Fe 2p1/2 peaks obtained from X-ray alkaline media. It is unknown to what extent these findings will apply
photoelectron spectroscopy (XPS)), narrow scans shifted toward specifically to MXene-supported catalysts and its specific coupling
higher energy after incorporating FePc with Ti3C2Tx, suggesting interaction. Therefore, all of the MXene electrocatalytic alkaline
Journal of The Electrochemical Society, 2022 169 063513

Figure 1. (a). SEM image and (b). TEM image of Co/N-CNTs@Ti3C2Tx. (c). Linear sweep voltammetry (LSV) curves for different samples at a rotation rate of
1600 rpm in O2-saturated 0.1 M KOH solution (d). Peroxide yield (black) with regard to the total oxygen reduction products and the electron-transfer number (n)
(red) of Co/N-CNTs@Ti3C2Tx in O2-saturated 0.1 M KOH at 1600 rpm. Reproduced with permission from Ref. 59. Copyright (2018) WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim. (e). Fe 2p XPS and (f). UPS spectra of pristine FePc and FePc/Ti3C2Tx (g). LSV curves and (h). kinetic current density (Jk) at
0.9 and 0.85 V vs RHE of pristine FePc, FePc/Ti3C2Tx, and Pt/C (i). Percentage of H2O2 released and electron transfer numbers (n) of pristine FePc and
FePc/Ti3C2Tx. Reproduced with permission from Ref. 60. Copyright (2018) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ORR works should be tested for their long-term oxidative stability. MXene-based catalyst affects the overall electrocatalytic perfor-
Also, many previous studies discussed in the review from Singh’s mance and selectivity. While a work by Sun’s group demonstrates
group42 have mentioned the problem of carbon supports on catalyst the performance of TiO2 as 2e− electrocatalyst involved in the
particles in terms of erosion. If the MXene supports become eroded due production of H2O2 in 0.1 M KOH, there is a considerably low
to oxidation, then they are hypothesized to fall into the aforementioned electrocatalytic performance.75 Thus, the issue concerning the
problem. All of the provided benefits, including proper catalyst selectivity of the 4e− ORR path over the 2e− ORR path is not
particle dispersion, modified electronic structure, enhanced charge deemed to be of great importance. From the aforementioned finding,
transfer, strong coupling interaction, and enhancement of active the oxidation of the Ti3C2Tx MXene to form TiO2 and C signifies
electrochemical surface area, are hypothesized to be nullified. material degradation.
Regardless of the actual effect, a future direction concerning
Ti3C2Tx MXene-based ORR catalysts in alkaline media could be
ORR in Acidic Electrolytes
on the attempts in successfully incorporating antioxidants that slow
down the oxidation process.74 The ORR in acidic electrolytes is considered to be the main
An important aspect to mention in regards to the oxidation of bottleneck preventing the large-scale application of PEMFCs. As
Ti3C2TX MXene is the simultaneous formation of TiO2 as a previously mentioned, the standard reduction potential of ORR is up
byproduct of the oxidation reaction mechanism in aqueous media.5 to 1.229 V vs SHE in acidic media (when pH approaches zero),
Because TiO2 is reported to be an effective 2e− ORR electrocatalyst, which is much higher than that in alkaline media. Due to the high
there is postulation of how this simultaneous formation on the overpotential required for the O2/O2− redox couple in acidic media,
Journal of The Electrochemical Society, 2022 169 063513

Figure 2. (a). Scheme of Fe-cluster-directed synthesis of 2D/2D Fe−N−C/MXene superlattice-like heterostructure. Reproduced with permission from Ref. 66.
Copyright (2020) American Chemical Society. (b). HR-TEM micrograph, (c). inverse FFT image of the selected area, (d). auto-correlation image of the inverse
FFT image and (e). of the selected area for the of the MXene@PPy composite. (f). Structure and position of the pores and voids in N-doped C. Reproduced with
permission from Ref. 67. Copyright (2020) IOP Publishing Limited.

only certain specific catalyst surfaces, such as Pt which offers facile M-N-C catalysts being determined as one of the most promising
adsorption for O2, are able to catalyze the ORR. Therefore, there are PGM-free catalysts for ORR in acidic media.15,16,62 For example,
grand challenges and limitations encountered for the development of NiS2 nanosheets were synthesized and tested as an ORR catalyst and
non-Pt ORR catalysts in acidic media. More importantly, for all attained 98% H2O2 selectivity.6 Even though they have shown a
known catalysts synthesized thus far, the harsh acidic environment promising initial activity of ORR in aqueous electrolytes or even in
brings upon long-term stability issues. Even for the state-of-the-art membrane electrode assemblies (MEA), they exhibit a lower
Pt/C or PtCo/C catalysts, the dissolution of Pt or the loss of Co in the stability compared with that of commercial Pt/C. Therefore, the
PtCo alloy/intermetallic during operation of the fuel cell is a critical engineering and synthesis of other types of catalysts for the ORR in
hindrance.8,76 In the last decade, extensive investigation has led to acidic media is required.
Table I. Summary table of the different types of MXene-based ORR electrocatalysts as they are investigated in the 0.1 M KOH alkaline electrolyte.

# e– per O2

Journal of The Electrochemical Society, 2022 169 063513


MXene-Based Catalyst Onset Potential (V vs RHE) Half- Wave Potential (V vs RHE) H2O2 yield (%) ORR Electrocatalyst Performance References

Pt/Ti3C2Tx 0.95 0.853 3.7 — 99.4% retention of current density after 1,500 ADT 69
cycles at 0.6 V
8.0% decrease of half-wave potential after 1500
ADT cycles
Co-CNT/Ti3C2Tx — 0.82 3.9 <5 10% decay in current after 10,000 s chronoam- 57
perometry test
Co/N-CNTs@Ti3C2Tx 0.936 0.815 3.8 < 15 11 mV loss of half-wave potential after 5,000 cycles 70
7.6% decay in current after 20,000 s chronoam-
perometry test
Fe-N-C/Ti3C2Tx 1.0 0.814 3.9 − 4.0 — 2.6% current loss after 20,000 s 63
11 mV loss of half-wave potential after 10,000
cycles
FePc/Ti3C2Tx 0.97 0.88 4 <1 74% of current density remains after 5,000 s 71
N-doped C/Ti3C2 0.85 0.71 — — 13.8% activity loss after 8,000 s continuous ORR 72
test
Journal of The Electrochemical Society, 2022 169 063513

MXenes as supports to Pt-based catalysts.—Owing to their detailing, the PDOSs of the three bottom Pt atoms and tipped Pt
unique properties, MXenes are able to address the aforementioned and Au atoms of Pt4/v-Ti2CO2 and Pt3Au/v-Ti2CO2, a critical role
problems, and play a revolutionizing role in this application. emerges for the bottom Pt3 layer in promoting the adsorption
MXenes have been theoretically investigated as a support for capability of the tipped metal Pt (or Au). Through confirmation by
different active sites for ORR, specifically in acidic media. Yang the geometric structures, Mulliken charge analysis, and the density
and coworkers systematically investigated a series of MXene of states, the adsorption strength of O-containing intermediates
supported Pt catalysts using density functional theory (DFT) increases with more Pt atoms in the clusters. In this manner, the
calculations, regarding their physical properties, structural stability, Pt3Au/v-Ti2CO2 surface is predicted to be a promising ORR catalyst
and ORR/OER catalytic activity.77 Strong metal-support interactions in acidic media with a low overpotential of 0.46 V. In another work
were demonstrated to lead to high structural stability, in which the by Yang and Wu, a series of composites of transition-metal (TM)
lattice parameters of MXenes play a critical role for controlling the monolayers (Ni, Pd, Pt, Cu, Ag, and Au) on V2C MXene were
morphology and stability of these composites. Wei and coworkers designed and analyzed as potential catalysts for ORR using DFT
reported a systematic screening of single-atom Pt ORR/OER (Fig. 3e).81 As shown in Figs. 3f–3k, a significant amount of electron
catalysts supported by MXene materials, demonstrating that the transfer from V2C to the TM monolayer due to strong metal-support
vanadium (V), titanium (Ti), niobium (Nb), and chromium (Cr) interactions (SMSI) is observed through Mulliken charge analysis.
based MXenes are promising supports for single-atom Pt.78 The transferred electrons are proposed to fill the TM d-orbitals and
Particularly, fluorine (F)-terminated ones exhibit ORR/OER bifunc- cause strong hybridizations between the d orbitals of TM and V
tional catalytic performance. Liu and Li studied the termination atoms, as evidenced by the DOSs plotted in Figs. 3f–3k. As a result,
effects of Pt/v-Tin+1CnT2 (where v- denotes Ti vacancy) single- Pd, Pt, Ag, and Au deposited V2C all exhibited promising activity
atom/MXene surfaces for their overall ORR performance.79 Similar and high chemical stability during ORR, which are attributed to the
results are observed for F-terminated surfaces, which are proposed to modified electronic structure of these composites coming from
show a better performance for ORR but have a lower durability than SMSI.
the O-terminated counterparts because of the weaker chemical Due to the corrosive environment and higher overpotential in
bonding. Yang and coworkers proposed a method to tune the ORR acidic media, Pt is one of the few favorable materials for the ORR.
performance of Ti2CO2 MXene-supported Pt catalysts through Wei and coworkers applied Ti3C2X2 (X = OH, F) nanosheets as
controlling the cluster size of Pt nanoparticles.80 Ptn (n = 1–4) and supports to produce Pt catalysts.82 When compared with Pt/C, an
Pt3Au alloy subnano-clusters supported on a defective Ti2CO2 enhanced stability during ORR operation in acidic media was
monolayer with oxygen vacancies (denoted as v-Ti2CO2) are used observed through accelerated durability tests (ADT) between 0.6
as the model catalysts. Figures 3a–3d depicts the projected density of to 1.1 V vs RHE. Another means of enhanced stability was observed
d-states (PDOSs) of different Pt/MXene (or PtAu/MXene) surfaces, through the possibility of electron transfer between the MXene
and it can be seen that an increasing number of d-band states of Pt is support and Pt nanoparticles, as evidenced by the XPS spectra. In a
observed with the increase of Pt atoms, suggesting a gradually similar work by Zhou’s group,69 the researchers compared the
increased binding strength of the adsorbates. Furthermore, the activity and stability of Ti3C2Xx supported- Pt catalysts for the
introduction of Au causes a lower d-band center of Pt in ORR in both the acidic and alkaline media. Their results indicated
Pt3Au/v-Ti2CO2, leading to a weaker binding strength of the that the Pt/Ti3C2Xx catalyst shows better ORR performance under
oxygenated intermediates during ORR process. With further the alkaline media than under the acidic media, raising the concern

Figure 3. The PDOS of (a). Pt/v-Ti2CO2, (b). Pt3/v-Ti2CO2, (c). Pt4/v-Ti2CO2 and (d). Pt3Au/v-Ti2CO2. The positive and negative values represent the PDOSs
of the spin-up and spin-down channels, respectively. The total PDOSs are denoted by the black full lines; the PDOSs of the three bottom Pt atoms in
Pt4/v-Ti2CO2and Pt3Au/v-Ti2CO2are denoted by the orange full lines; the PDOSs of the tipped Pt and Au atoms are denoted by the blue and green full lines,
respectively. The d-band center of supported Pt atoms connected to O is also shown in units of eV. The Fermi level is denoted by a black vertical dotted line.
Reproduced with permission from Ref. 80. Copyright (2020) The Royal Society of Chemistry (e). A schematic of MXene-supported transition metals with strong
metal–support interactions. Partial DOSs and average Mulliken charge populations (in ∣e∣/atom) for f. NiML/V2C, (h). PdML/V2C, (j). PtML/V2C, (g).
CuML/V2C, (i). AgML/V2C, and (k). AuML/V2C, respectively. The dotted line at zero represents the Fermi level. Reproduced with permission from Ref. 81.
Copyright (2020) American Chemical Society.
Journal of The Electrochemical Society, 2022 169 063513

of its structural stability under such harsh conditions. Kasak and performance. Through DFT calculations, the authors attributed the
coworkers designed a spontaneous reduction method to synthesize role of the carbon nanotube to two aspects. First, it could facilitate
Pt/MXene composites, and highlighted the important role of NaBH4 the O2 dissociation on the catalyst composite, improving the overall
in reducing the Pt precursor gently without compromising the ORR performance. Additionally, the distortion of the Pt cluster
structure of the MXene supports.83 could be alleviated by introducing CNTs to Ti3C2Tx (Figs. 4c and
Restacking is a common problem for many 2D materials, 4d), benefitting the catalytic stability.
including ML MXene supports for the deposition of metal nano-
particles, particularly for Pt/Ti3C2Tx. However, it is only of concern MXenes as supports to non-precious metal-based catalysts.—
with the MXene material when it is in the ML morphology rather Non-precious metal single-atom catalysts are yet to be explored in
than the SL morphology. Complete delamination of the ML MXene MXene ORR research. Cu single atom catalysts immobilized on
can help in the application of MXenes as supports, as it results in the Ti2CO2 as an efficient ORR catalyst was proposed by Zhou and
exposure of the sub-surface for deposition, and an increased number Sun’s group.86 Tian and Yang’s group doped a zeolitic imidazolate
of layers for surface metal deposition. Simultaneously, intermediate framework-8 (ZIF-8) with Fe then incorporated it with Ti3C2Tx
products could also be trapped between the layers of the ML MXene for ORR catalysis.87 ZIF-8, a type of metal organic frame-
structure, resulting in a mix of 2e− and 4e− processes occurring, work (MOF), contains ZnN4 active moieties, which act as a
leading to a lowered selectivity. For example, Pt/Ti3C2Tx involves precursor to synthesize M-N-C catalyst for ORR. However, the
3.71 e− transferred per O2 molecule in alkaline media but 3.13 in size of ZIF-8 ranges from 20 nm to 500 nm, which makes it difficult
acidic medium.69 Xu et al. designed and synthesized MXene and to incorporate with multilayer MXenes. Thus, single layer MXenes
carbon nanotube hybrid-supported Pt catalysts, in which the CNTs are required for this type of catalyst design. Additionally, it is
are known to mitigate restacking.84 As shown in Fig. 4a, a uniform important to note that the catalyst was produced through a strategy
dispersion and narrow size distribution of Pt nanoparticles were involving the separate pyrolysis of the Fe-N-C. The Fe-N-C was
observed on the MXene-carbon nanotube hybrid supports. presynthesized from ZIF-8 through pyrolysis at 1100 °C and then
Electrochemical characterizations demonstrated that the introduction further subjected to a second carbonization treatment at 350 °C
of carbon nanotube could significantly improve the ORR involving the Fe-N-C and Ti3C2Tx. This distinct process is important

Figure 4. (a). TEM image and particle size distribution and (b). HRTEM image of Pt/CNT-Ti3C2Xx catalyst (c). Projected DOS of d-electrons of surface Pt
atoms on MXene and CNT-MXene, excluding the edge Pt atoms. (d). Optimized geometric structures of Pt clusters on MXene and CNT-MXene, where the green
spheres represent the surface Pt atoms. Reproduced with permission from Ref. 84. Copyright (2020) American Chemical Society. (e). Aberration‐corrected
HAADF-STEM image. f-i. HAADF‐STEM image and the corresponding EDS elemental mapping. (j). WT-EXAFS plots (k). EXAFS fitting curve of
Ru-SA/Ti3C2Xx. (Inset: schematic model.) (l). High-resolution Ru 3d XPS spectrum. Reproduced with permission from Ref. 85. Copyright (2020) WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim.
Journal of The Electrochemical Society, 2022 169 063513

in that typical involvement of high temperature will lead to MXene unexpected side reactions. Therefore, future experimental studies
decomposition. In spite of the lower activity compared to Pt/C, the that take careful consideration of these issues are required.
Fe-N-C/Ti3C2Tx catalyst exhibited excellent durability with no Similar to the ORR catalysts applied to fuel cell technology,
attenuation after 10,000 cycles. MXene materials are usually first hybridized with other active
Another trifunctional single-atomic Ru catalyst supported by species, and the resulting composite functions as a cathode for
Ti3C2Tx MXene (Ru-SA/Ti3C2Tx) was reported by Liu, Xin, and metal-oxygen batteries. Long’s group deposited oxygen vacancy-
cowerkers,85 who claimed that this catalyst can accelerate the HER, rich SnO2 on a Ti3C2Tx MXene for lithium-oxygen batteries.96 The
ORR, and OER. As shown in Figs. 4e–4i, an abundant single atom resulting modulation of electronic structure provided by the oxygen
site can be identified in the HAADF-STEM image, with uniformly vacancies is favorable for optimizing the adsorption energy of the
distributed Ru species over the catalyst demonstrated by the composite towards various intermediate species. Additionally, the
corresponding energy dispersive spectroscopy (EDS) elemental oxygen vacancy-rich SnO2 and Ti3C2Tx helps induce electronic
mapping. In order to reveal the local atomic and electronic structure interaction through the heterogeneous interfaces, enhancing the
of the Ru-SA/Ti3C2Xx, extended X-ray absorption fine structure interfacial charge transfer and thus leading to a lower overpotential
(EXAFS) measurements were applied. As presented in Fig. 4j, for both ORR and OER. Similarly, Chen’s group deposited nitrogen-
wavelet transform (WT)-EXAFS signals corresponding to the Ru-Ru doped cobalt selenide nanocrystals on Ti3C2Tx MXenes for Zn-air
contribution were observed in the plots of the Ru foil and RuO2, but batteries.97 Wang, Zhu, and other coworkers reported a NiCo2O4
not in Ru-SA/Ti3C2Tx. This provides the evidence of an exclusive nanocrystal/MXene hybrid for Zn-air batteries, which are strongly
existence of single-atomic Ru sites. Furthermore, the authors coupled through in-situ Ni/Co-F bonds.98 The F terminations on the
proposed that the single-atomic Ru sites in Ru-SA/Ti3C2Tx are MXene were demonstrated to stabilize the NiCo2O4 nanoparticles.
captured and immobilized by oxygen-containing termination groups XPS and near-edge X-ray absorption fine structure (NEXAFS) were
through Ru–O bonds. Further EXAFS fitting was performed as applied to investigate the electronic structure and coordination
shown in Fig. 4k, which is in agreement with the proposed structure environment of the material. The Ni/Co−F bond was found in the
of Ru-O2 (inset of Fig. 4l). The further XPS spectra confirmed that F 1s spectrum as shown in Fig. 5a. In addition, a negative shift of
the valence for the Ru species is approximately Ru3+. Although the the photoenergy peak L3 for both Co and Ni was observed in
ORR performance of this catalyst is not impressive, this work Figs. 5b and 5c. This indicates the existence of a strong coupling
introduces a starting strategy to synthesize MXene supported single effect between the MXene and NiCo2O4, thus resulting in the
atom catalysts and provides insights into their expected structures. A enhancement of charge transport and electrocatalytic activity.
summary of the MXene catalysts used for ORR in acidic media is Regarding the battery performance, the NiCo2O4 loaded Zn-air
presented in Table II.87,88–90 battery exhibited a high peak power density up to 277 mW cm−2
(Fig. 5d), suggesting a high activity of the engineered cathode at a
Future considerations of MXene-based catalysts for acidic large current density. Promising rechargeability and cyclic durability
ORR.—For all of the hybrid catalyst systems studied, they involved were also demonstrated with minimized degradation after 1000
carbide MXenes, either in the form of Ti3C2Tx or Ti2CTx. The work cycles and 333 h (Fig. 5e). On another work by Zhi’s group, a
by Lutkenhaus, Radovic, and Green74 shows that both MXenes Mn3O4-Ti3C2 composite was also studied for efficient ORR and Zn-
under acidic media (HCl) undergo oxidative losses, although not to air battery performance.99
the extent under storage in alkaline media (KOH). Importantly, It has been reported by Lutkenhaus, Radovic, and Green that after
unlike the case for alkaline media, there is no change in pH of the exposure to air for 27 days, Ti3C2Tx loses ∼93% of its original
electrolyte for both types of MXenes. Therefore, existing and future conductivity and forms TiO2-x,73 which is known to be an effective
works concerning the aforementioned ORR catalysts under acidic 2e− ORR bifunctional catalyst for H2O2.5 While there is a possibility
electrolytes should take into account the oxidative loss and methods of this conversion forming an effective 2e- ORR catalysis, such a
of successfully implementing antioxidants that slow down the promise is downplayed by the fact that the aforementioned catalytic
oxidation. As with the case for alkaline electrolytes, the hypothe- activity of TiO2-x is only observed under alkaline media (0.1 M
sized potential effects from the erosion of MXene support due to KOH).102 Because it is uncertain how TiO2-x will react and perform
oxidation and restacking of the multilayer Ti3C2Tx should be electrocatalytically in air, the exact nature of the effect of oxidation
considered. Finally, more research should be devoted to non-carbide of Ti3C2Tx MXene into TiO2-x should be investigated. There is
MXenes such as nitrides, which appear to be more stable in aqueous greater uncertainty in how this oxidation effect will apply to Ti3C2Tx
environments. MXene-supported catalyst cathodes in metal-air batteries. Further
investigations regarding Ti3C2Tx MXenes as cathodes in metal-air
MXenes for Metal-Oxygen Batteries batteries will need to look more into this aspect by evaluating the
electrocatalytic performance over time.
The ORR plays a crucial role in the technological development of
metal-oxygen battery cathodes.91,92 MXenes have shown to be Pristine MXenes.—Pristine MXenes have also demonstrated to
potential candidates for these cathodes. be active in catalyzing the ORR in metal-oxygen batteries. Zhang,
Han, and Dang’s group developed a uniform O-terminated Nb2C
Heterogenous MXenes.—Xu and coworkers designed a compo- MXene cathode material for lithium–oxygen batteries.101 A large
site consisting of MXene and two-dimensional organic framework capacity of 19785.5 mAh g−1 at 200 mA g−1 (Fig. 5g), attributed to
for Na−O2 batteries,93 in which lower overpotentials for both OER the lamellar structure of MXenes and their abundant O termination
and ORR were proposed. It was determined that the potential charge active sites, was obtained. Comparing the galvanostatic first-cycle
transfer between the layer structures was proposed to promote the profiles between few-layer (F-Nb2C) and multilayer (M-Nb2C)
electrical conductivity and adsorption energy to Na+. In another MXenes (Fig. 5f), the F-Nb2C MXene cathode shows significantly
work by Ihme,94 Alireza and coworkers concluded that controlling higher first discharge/charge capacity, lower discharge/charge over-
the vacancy concentration on the MXene surface could help in potentials for ORR/OER process, and greater round-trip efficiency.
enhancing the ORR performance. When analyzing surface termina- Additionally, through DFT calculations, the reaction mechanism was
tion groups, a higher O:F ratio on the functionalized Ti4N3 catalyst discussed. As shown in Fig. 5h, there are two reaction pathways on
can reduce the overpotential significantly. A similar work of Yao the Nb2CO2 surface, both with a two-electron ORR and the same
and Huang’s group also reported on the Ti2C MXene for Li-O2 ΔG = −5.39 eV. The effect of MXene termination groups on the
batteries.95 Although all of these works show promising results of reaction performance and the mechanism of the lithium-oxygen
the MXene, it is of importance to consider the complicated system battery, both experimentally and theoretically, were also carefully
involving the electron/mass transfer, product management, and investigated. Although this work provides future insights for detailed
Table II. Summary table of the different types of MXene-based ORR electrocatalysts as they are investigated in the 0.1 M HClO4 acidic electrolyte.

Journal of The Electrochemical Society, 2022 169 063513


MXene-Based
Catalyst Onset Potential (V vs RHE) Half- Wave Potential (V vs RHE) # e– per O2 H2O2 yield (%) ORR Electrocatalyst Performance References

Pt/Ti3C2Tx — 0.847 — — 15.66% loss in initial ECSA after 10,000 ADT 88


cycles
Pt/CNT-Ti3C2Tx — 0.876 3.7 — 9 mV loss of half-wave potential after 2,000 89
cycles
8.7% decay in current after 15,000 s chronoam-
perometry test
6% drop in ECSA after 2,000 ADT cycles
Fe-N-C/Ti3C2Tx — 0.777 3.8 − 4.0 — 11 mV loss of half-wave potential after 10,000 87
cycles
Ru/Ti3C2Tx 0.87 0.75 3.82 — 10 mV loss of half-wave potential after 2,000 90
cycles
7% decay in current after 9,000 s chronoampero-
metry test
Journal of The Electrochemical Society, 2022 169 063513

Figure 5. (a). Deconvoluted XPS spectra of F 1 s for NiCo2O4/MXene catalyst. NEXAFS spectra of (b). Co L-edge, (c). Ni L-edge for various catalysts (d).
Charge and discharge polarization curves and the corresponding power density (e). Galvanostatic discharge−charge cycling curves at 5.0 mA cm−2 of the liquid
Zn-air batteries. Reproduced with permission from Ref. 100 Copyright (2020) American Chemical Society (f). Comparison of the initial discharge/charge
profiles of the lithium-oxygen batteries from 2.35 to 4.35 V for M, F-Nb2C MXene at 500 mA g−1 and M-Nb2C MXene at 200 mA g−1. (g). Initial discharge/
charge plots of F-Nb2C MXene cathode with different current density (h). Two pathways for ORR with zero electrode potential (U = 0 V), equilibrium potential
(U0) and discharge potential (UDC). Reproduced with permission from Ref. 101 Copyright (2020) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

engineering of MXene materials as the cathode material, future the deeper understanding of the physical and electronic properties of
studies related to this field should take into consideration the MXenes through state-of-the-art characterization methods. With
oxidative stability of the MXenes. For example, Nb2C is known to rational control of the crystal facets, size, and morphology of the
undergo a rapid oxidation in air at room temperature and seems to catalyst materials, it is possible to maximize the exposure of active
have the least oxidative stability out of all the MXenes in the sites, facilitate electron/mass transfer, and tailor the activity and
Nbn+1CnTz family. Future work in remedying this stability issue selectivity during electrocatalysis. For MXene-based composites,
should involve using an antioxidant such as ascorbic acid.103 the electrocatalytic efficiency could potentially be maximized if
Another route is to implement more stable MXene phases, such as the basal plane of these materials serve as the platform to capture the
Nb4C3, as the cathode in lithium-oxygen batteries. It is hypothesized active phase. In conclusion, the various electronic, structural, and
that lithium-oxygen batteries could successfully implement ascorbic chemical properties of MXenes offer abundant space for material
acid on the MXene cathode and operate at different temperatures. In and structural engineering, and knowledge advancement in electro-
the case of battery systems that have such successful implementa- catalysis.
tions, oxidative durability analysis should be conducted. Even with the several types of MXenes currently available,
almost all of the current works primarily focus on Ti3C2 materials.
Summary and Prospects Therefore, future works should involve finding facile and cost-
efficient methods to reliably produce other types of carbide and
MXene materials hold promise in various electrocatalytic and nitride MXenes. For example, nitride MXenes show great potential
energy storage applications because of their high-surface, 2D in different applications, including electrocatalysis. By possessing
morphology, and tunable electronic interaction with reactants, higher electrical conductivity than carbide MXenes,104 nitride
intermediates and products. Great progress has been achieved from MXenes could be even more promising to behave as an
Journal of The Electrochemical Society, 2022 169 063513

electrocatalyst with enhanced electron transfer. However, there are 17. S. N. Goubert-Renaudin and A. Wieckowski, “Ni and/or Co nanoparticles as
currently only few reports on nitride MXenes due to its difficulty in catalysts for oxygen reduction reaction (ORR) at room temperature.”
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