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Hybridization of binary non‐precious‐metal (Fe‐Co) nanoparticles with d‐

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DOI: 10.1002/celc.201800693

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 DOI: 10.1002/celc.201800693 Articles
1
2
3
4
Hybridization of Binary Non-Precious-Metal Nanoparticles
5 with d-Ti3C2 MXene for Catalyzing the Oxygen Reduction
6
7
Reaction
8
9
Liangguang Chen,[a] Yingxi Lin,[a] Junying Fu,[b] Jian Xie,[a] Rong Chen,[a] and Haiyan Zhang*[a]
10
11
12 In this work, an advanced integrated electrode for high- ity and methanol tolerance can be detected. The outstanding
13 performance electrocatalytic oxygen reduction is designed and activity and stability can be attributed to the fact that the
14 fabricated directly by in-situ hybridization of binary non-pre- FeCoEDA chelate nanoparticles are successfully grafted onto the
15 cious metal (FeCo) ethylenediamine chelate complexes with d-Ti3C2 MXene nanoflake substrate instead of being deposited.
16 multi-layered d-Ti3C2 MXene nanoflakes, in the formation of Thus, aggregation of the particles is prevented and a large
17 FeCo (3 : 1)-N-d-Ti3C2 MXene. The catalyst exhibits outstanding specific surface area is provided, enhancing charge transfer
18 oxygen reduction reaction activity with more positive onset reactions. We conclude that the in-situ hybridization of MXenes
19 potential and half-wave potential than commercial 20 wt.% Pt/C with non-precious metal compounds is a promising candidate
20 and achieves a current density of 5.60 mA · cm2 in O2-saturated for replacing traditional Pt-based catalyst materials for oxygen
21 0.1 M KOH electrolyte solution. Furthermore, remarkable stabil- reduction in fuel cells.
22
23
24 1. Introduction the synergistic effects. It is of vital strategy to make fuel cells,
25 which having high electrical conductivity together with chem-
26 Fuel cells, with the high energy-conversion efficiency, high ical stability at high potentials, economically available, through
27 power density and environmentally friendly, have been consid- expanding the application of heteroatom doped to form some
28 ered to be a promising power source of alternative energy in novel catalytic materials.
29 the future.[1] However, the high cost, mainly caused by the MXene, which is composed of two-dimensional transition
30 using of Pt catalyst, is becoming the biggest problem to metal carbide and/or nitride nanoflakes,[7] have demonstrated
31 obstruct the commercialization of fuel cells. Compared to the versatile electronic properties and potential applications to
32 hydrogen oxidation reaction in the anode of PEMFCs, oxygen energy storage,[8] electromagnetic interference shielding[9] as
33 reduction reaction (ORR) occurring at the cathode has a much well as biosensors,[10] because of their high electrical conductiv-
34 more sluggish kinetic process, resulting in that most of the Pt ity and 2D structure. Recently, few research groups have aimed
35 catalysts are used in the cathode to catalyze the ORR. to exploiting the surface chemistry of MXenes to enhance their
36 Furthermore, the surface area of Pt based materials decreased electrocatalysis. For instance, Xie et al.[11] have prepared Pt
37 gradually along with the electrochemical process, resulting in nanoparticles supported on the MXene for ORR and shown it
38 the inactivation in ORR.[2] To overcome these issues, much effort better stability than the commercial Pt/C catalyst; ORR half-
39 has been devoted to finding alternatives for platinum-based wave potentials did not show any noticeable degradation after
40 electrocatalysts by using nonprecious metals[3] and various the accelerated durability tests. Zhang et al.[12] reported an
41 heteroatom-doped carbonaceous materials.[4] In all non-Pt analogous urchin-shaped MXene-Ag0.9Ti0.1 bimetallic nanowire
42 cathode catalysts, heteroatom-doped carbon materials have composite that exhibited high current density and unexpected
43 received extensive attentions due to their high catalytic electrocatalytic activity for ORR. Zhao et al.[13] in-situ hybridized
44 performance, high tolerant to methanol (as a fuel in fuel cells) 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with Ti3C2Tx nano-
45 and low cost. Especially, binary transition metal, such as iron- flakes via an inter-diffusion reaction-assisted process, which was
46 cobalt (FeCo),[5] iron-copper (FeCu)usw. im Text[6] and et al., applied in the oxygen evolution reaction (OER) and achieved a
47 supported on the N-matrix materials showed higher ORR current density of 10 mA · cm2 at a potential of 1.64 V versus
48 activity and catalytic stability than the single one doped due to reversible hydrogen electrode and a Tafel slope of
49 48.2 mV · dec1 in 0.1 M KOH. Seh et al.[14] reported that the
50 basal plane of Mo2CTx MXene was found to be catalytically
51 [a] L. Chen, Y. Lin, J. Xie, R. Chen, H. Zhang active and stable for the hydrogen evolution reaction (HER) in
School of Materials and Energy, Guangdong University of Technology
52 Guangzhou, Guangdong, 510006, China
acid. In addition, certain kinds of MXenes that was modified by
53 E-mail: hyzhang@gdut.edu.cn some function group, such as methoxy group,[15] p-phenyl-SO3H
54 [b] J. Fu group[16] as well as nitrogen-doped[17] have been examined
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences
55 Guangzhou, Guangdong, 510640, China
recently indicative of significantly improved electrochemical
56 Supporting information for this article is available on the WWW under performance.
57 https://doi.org/10.1002/celc.201800693

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1 All of the above-mentioned studies have indicated that
2 surface modified MXene with some heteroatoms or groups is a
3 promising catalyst for enhancing catalytic activity and improv-
4 ing stability toward the ORR in a fuel cell environment. Thus, in
5 the present work, we report a new class of ORR catalyst that
6 hybridization of binary iron-cobalt (FeCo) non-precious-metal
7 nanoparticles with Ti3C2 MXene. The resulting hybrid catalyst,
8 named FeCo-N-d-Ti3C2 MXene, was applied in an alkaline
9 medium for ORR and its electrocatalytic performance was
10 detected through rotating disk electrode (RDE) and rotating
11 ring-dick electrode (RRDE) tests. For comparison, the no-hybrid-
12 ization FeCoEDA and the FeCo-N-d-Ti3C2 MXene with different
13 Fe : Co ratios catalysts as well as commercial Pt/C were also
14 measured under the same experimental conditions. The ORR
15 stability of various catalysts and the methanol tolerance
16 between FeCo-N-d-Ti3C2 MXene and commercial 20 wt.% Pt/C
17 were also discussed. The results indicated that FeCo-N-d-Ti3C2
18 MXene catalyst with Fe : Co = 3 : 1 had the excellent electro-
19 chemical performance toward ORR and achieved a current
20 density of 5.60 mA · cm2 in 0.1 M KOH at a higher onset
21 potential (Eos = 0.96 V, vs. RHE) and half-wave potential (E1/2 =
22 0.80 V, vs. RHE) compared to that of commercial 20 wt.% Pt/C
23 catalyst. In addition, this hybrid material also showed long-term
24 stability wherein it maintained more than 90 % of its initial
25 current density at 0.60 V (vs. RHE) for 20000 s and excellent
26 tolerance to methanol crossover in ORR. This work may also
27 promote the development of MXene-based hybridized materi-
28 als with potentially enormous family and extensive applications.
29
30
31 Experimental Section
32
All chemicals were purchased commercially and analytical grade, or
33 better, and used without further purification.
34
35
36 Synthesis of Ti3C2 and d-Spacing Increased Ti3C2 (d-Ti3C2)
MXene
37
38 The Ti3AlC2 MAX powder with a particle size of 200 mesh was
39 bought from Forsman Scientific (Beijing) Co.,Ltd. Conventionally,
40 the Ti3C2 MXene was prepared by immersing the Ti3AlC2 MAX
powder into a polytetrafluoroethylene (PTFE) beaker with an
41
aqueous solution of 40 wt.% HF at 60 8C for 24 h to exfoliate Al
42 layers. Then the resulting suspension was centrifuged and washed
43 several times using deionized water. To obtain the d-Ti3C2 MXene
44 nanoflakes, the filtered power was heat treated at 200 8C for 3 h in
45 an Ar atmosphere followed by immersed into the dimethylsulfoxide
(DMSO), and then the mixture was uninterruptedly magnetic stirred
46
for 2 h before being ultrasonicated for over 16 h.[18] After that, the
47 treated powder was washed by deionized water until the pH = 7–8,
48 before being dried under vacuum at 80 8C over 24 h. The single- or
49 few- layer d-Ti3C2 MXene nanoflakes were placed under ambient
50 condition and directly used in the following experiments.
51
52 Synthesis of Different Fe : Co Ratios of FeCo-N-d-Ti3C2 MXene
53
54 A mixture of two transition metal salts [FeCl3 · 6H2O and
Co(NO3)2 · 6H2O] in a total amount of 0.004 mol with different Fe : Co
55
ratios (Fe alone, 3 : 1, 1 : 1, 1 : 3, and Co alone) was first added into
56 200 mL isopropyl alcohol (IPA) solution. Subsequently, 1 g of d-Ti3C2
57
Articles
MXene was mixed with the above solution, followed by continu-
ously stirring for at least 12 h. Then, 2 mL of ethylenediamine (EDA)
in 50 mL of IPA was added and refluxed at 80 8C for 16 h to allow
the chelation reaction to complete. The formed mixture was then
dried under vacuum at 85 8C for 12 h using a rotary evaporator.
After that, the obtained composite powder was annealed at 500 8C
(see Figure S1) for above 3 h at a heating rate of 3 8C · min1 in Ar
flow in order to complete the polymerization reaction. To analysis
the supporting effect of d-Ti3C2 MXene in the ORR catalysis,
FeCoEDA (Fe : Co = 3 : 1) was also synthesized without d-Ti3C2
MXene adjunction. Without notation, the Fe : Co ratio is 3 : 1 for all
FeCoEDA and FeCo-N-d-Ti3C2 MXene catalysts in this work.
Materials Characterization
The X-ray diffraction (XRD) patterns of the nanopowders were
obtained by D/MAX-Ultima IV X-ray diffractometer using Cu Ka
radiation (l = 1.5406 Å) at a voltage of 40 kV and a current of
40 mA with a step scan of 0.028 over the range 2q = 5 ~ 808. Specific
surface areas of the nanopowders were calculated by using the
Brunauere Emmette Teller (BET) method on Micromeritics ASAP
2460 analyzer. Meanwhile, pore size distributions were obtained
from the nitrogen adsorption-desorption branch using the Barrette
Joynere Halenda (BJH) model. Prior to the measurement, the
sample was outgassed under vacuum at 130 8C for 12 h. The
morphology of the samples was observed using field emission
scanning electron microscopy (FE-SEM). Transmission electron
microscope/scanning transmission electron microscope (TEM/
STEM) characterization of the samples were performed on JEOL
JEM-2100 (Japan) with an accelerating voltage of 200 kV. X-ray
photoelectron spectroscopy (XPS) analysis was carried out on
Thermo SCIENTIFIC ESCALAB 250Xi spectrometer with mono-
chromatized Al Ka radiation (hv = 1486.8 eV).
Electrochemical Measurements
All electrochemical properties were evaluated in a standard three-
electrode electrochemical cell by using a PARSTAT Multi-Channel
(PMC, Princeton, U.S.A.) potentiostat in 0.1 M KOH electrolyte
solution which was saturated with pure O2 (99.999 %) for at least
30 min before every measurement at 25 8C. All measured potentials
vs Ag/AgCl in this work are converted to the reversible hydrogen
electrode (RHE) scale based on the Nernst Equation (1) below:[13,19]
VRHE ðVÞ ¼ VAg=AgCl ðVÞ þ 0:0591pH þ Vq Ag=AgCl ð1Þ
where VRHE is the applied potential vs RHE; VAg/AgCl is the applied
potential vs Ag/AgCl reference electrode, pH is the pH of the
electrolyte (pH = 13 at 0.1 M KOH electrolyte solution), and VqAg/AgCl
is the standard potential of Ag/AgCl reference electrode, where
0.1981 V is adopted.
Linear sweep voltammetry (LSV) were recorded using a catalyst-
modified glassy carbon (GC) rotating disk electrode (RDE, 0.196 cm2
area, Princeton Model 636 A, U.S.A.) as the working electrode in the
potential range of 0.55–1.0 V (vs. RHE) with a scan rate of
50 mV · s1. The Ag/AgCl (saturated 3 M KCl) electrode serves as the
reference electrode, a Pt wire as the counter electrode. Moreover,
the GC electrode was typically polished to mirror smoothness using
alumina powder. Additionally, the thin film of the electrocatalyst on
the GC disk were prepared by dispersing 5 mg catalyst material in
1 mL ethanol containing 0.25 wt.% Nafion using ultra-sonication for
30 min, followed by 20 mL catalyst slurry drop-casting onto GC disks
and drying under an infrared lamp. The catalyst loading was
approximately 0.5 mg · cm2.

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1 The electron transfer number per oxygen molecule involved was 2. Results and Discussion
2 calculated based on the following Koutecky-Levich (K-L) Equa-
3 tion (2, 3):[19–20] Figure 1a shows a typical SEM image of pristine Ti3AlC2 MAX
4 1 1 1 1 1 particle. After being exfoliated of Al layers, the periodic
¼ þ ¼ þ 1 ð2Þ
5 j jk jd jk Bw2 accordion-like and nanoflake-like structure of d-Ti3C2 MXene
6 have been clearly exhibited on Figure 1b and Figure 1c (above),
2
1
7 B ¼ 0:2nFC O2 D3O2 1 ð3Þ respectively. However, presumably due to capillary and electro-
v6
8 static force arising after the removal of Al layers and the drying
9 where j is the measured current density; jk and jd are the kinetic of the samples,[7c] nano-arches at the edges of the exfoliated d-
1 1
10 and diffusion limiting current densities, respectively; jk and B are the Ti3C2 planes have been shown in Figure 1c (below). Further-
intercept and slope of the K-L equation, respectively; w ðrpmÞ is
11 more, the crystal structures of the d-Ti3C2 MXene in comparison
the electrode rotation rate; n is the number of transferred electrons
12 in the reduction procedure of one O2 molecule; F is the Faraday with its precursor Ti3AlC2 were characterized by XRD (Figure 1d).
13 constant of 96485 C · mol1; C O2 is the O2 concentration and DO2 is It is obvious that the most intense peak at 2q  398 which
14 the O2 diffusion coefficient in the electrolyte; v is the kinetic corresponds to the (104) peak of Ti3AlC2 is absent in the d-
15 viscosity of the electrolyte. By using the values C O2 = 1.2  Ti3C2Tx MXene XRD pattern, which has been suggested that the
16 103 mol · L1, DO2 = 1.9  105 cm2 · s1, and v = 0.01 cm2 · s1, the Al in the Ti3AlC2 powder had been successfully removed which
electron transfer number (n) was calculated in 0.1 M KOH electro-
17 agreed with the SEM analysis in Figure 1b. Meanwhile, as
lyte solution.
18 shown in the high-resolution transmission electron microscopy
19 For the rotating ring-dick electrode (RRDE) tests of ORR, the disk (HRTEM) image and the corresponding selected-area electron
electrode was scanned at a rate of 50 mV · s1 from 0.55–1.0 V (vs.
20 diffraction (SAED) pattern in Figure 1e, a 2D hexagonal
RHE), and the ring potential was constant at 1.2 V (vs. RHE) to
21 oxidize any peroxide produced in the O2-saturated electrolyte at a structure is arranged on the {100} planes of d-Ti3C2Tx MXene,
22 rotation rate of 2000 rpm. Hydrogen peroxide yield (H2O2%) was which agrees with the previous reports.[21] Interestingly, in
23 determined using the following Equation (4): Figure 1d, the (002) diffraction peak at 2q  9.78 and (004)
24 Ir =N diffraction peak at 2q  19.48 in the Ti3AlC2 XRD pattern have
25 H2 O2 ð%Þ ¼ ð4Þ been broadened and shifted to the lower angles at 2q  8.68
Id þ Ir =N
26 and 2q  18.68 in the d-Ti3C2Tx MXene XRD pattern, respectively,
27 where Id and Ir are the dick and ring current, respectively, and N is resulting in that not only does the c lattice of d-Ti3C2Tx MXene
28 the electrode collection efficiency calibrated at 0.3. increases, but also it becomes less crystallinity and structural
29 The stability and methanol tolerance of the catalysts were order.[8d,22] Typically, it is also indicated that d-spacing values
30 evaluated through chronoamperometric response, which were increases from 9.11 Å of Ti3AlC2 to 10.25 Å of d-Ti3C2 MXene,
31 performed at room temperature in O2-saturated 0.1 M KOH electro- which can be observed in Figure 1f. It is also worth noting that
32 lyte solution at 0.60 V (vs. RHE).
33
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55 Figure 1. a) SEM image of pristine Ti3AlC2. b) SEM image of an accordion-like d-Ti3C2 MXene structure. c) top-view (top) and side-view (bottom) TEM image on
56 the edge of a d-Ti3C2 MXene nanoflake, respectively. d) XRD patterns of the Ti3AlC2 and d-Ti3C2 MXene samples. e) HRTEM image on the {100} planes of d-Ti3C2
57 MXene. The top right inset: SAED pattern of one surface of nanoflake. f) High-magnification TEM image of d-Ti3C2 MXene 2D aisle structure.

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1 via the electrostatic interaction[13] in isopropyl alcohol (IPA)
2 solution. As the EDA was added into the above IPA solution, the
3 Fe and Co ions can combine in-situ with EDA molecules where
4 the segregated graininess FeEDA and CoEDA chelate nano-
5 particles were synthesized. After calcination, the Fe-N and Co-N
6 active centers were highly dispersed between the d-Ti3C2
7 MXene layered-nanoflakes, resulting in the formation of a
8 highly open and interstitial FeCo-N-d-Ti3C2 MXene hybrid
9 (shown in Figure 2b and 2c through SEM). This can also be
10 proved by the nitrogen adsorption-desorption isotherms of the
11 d-Ti3C2 MXene, FeCoEDA and FeCo-N-d-Ti3C2 samples. The
12 specific surface area of FeCoEDA chelate can further increase to
13 185.9 m2 · g1 (Figure 2d) after the hybridizing with d-Ti3C2
14 MXene because the d-Ti3C2 MXene can provide support for
15 FeCoEDA chelate nanoparticles and avoid the aggregation of
16 them and in turn more catalytic active centers can be exposed.
Figure 2. a) XRD patterns of d-Ti3C2 MXene, FeCoEDA, and FeCo-N-d-Ti3C2
17 MXene. b) top-view and c) side-view SEM images of FeCo-N-d-Ti3C2 MXene. To characterize the ORR catalytic performance of FeCo-N-d-
18 d) N2 adsorption-desorption isotherms for d-Ti3C2 MXene, FeCoEDA, and Ti3C2 MXene, the current-potential curves were recorded using
FeCo-N-d-Ti3C2 MXene. The inset: BJH pore size distribution plots for FeCo-N-
19 RDE where the catalysts were severally absorbed in O2-
d-Ti3C2 MXene.
20 saturated solution at a rotation rate of 2000 rpm. For compar-
21 ison, a commercial 20 wt.% Pt/C catalyst (20 wt.% Pt supported
22 the larger space available between a pair of MXene nanosheets on John-Matthey carbon) was subjected to the same potential
23 can make the shuttling electrolyte ions easier.[21a] conditions. As shown in Figure 3a, the ORR activity of the FeCo-
24 The obtained d-Ti3C2 MXene was then used as the synthetic N-d-Ti3C2 MXene catalyst is obviously not only more positive
25 template for the in-situ hybridization of FeCoEDA chelate onset potential (Eos = 0.96 V, vs. RHE) and half-wave potential
26 complex followed by pyrolysis to form FeCo-N-d-Ti3C2 MXene, (E1/2 = 0.80 V, vs. RHE) (see Figure 3a right inset) but also more
27 the crystals of it was analyzed by XRD (Figure 2a). The observed superior current density (5.60 mA · cm2) than that of 20 wt.%
28 diffraction peaks at 2q  44.68 can be matched with that of Fe Pt/C catalyst. Due to non-aggregation of FeCoEDA by the
29 (JCPDS, NO.87-0721) while 2q  12.38, 14.98, 24.88 and 43.68 can hybridizing with d-Ti3C2 MXene mentioned above, much
30 be matched with those of Co (JCPDS, NO.70-2633). Besides, the superior current density of FeCo-N-d-Ti3C2 MXene to FeCoEDA
31 peaks for Fe3O4 (2q  35.58 and 57.08, JCPDS, NO.75-0033) and without d-Ti3C2 MXene supporting. In addition, the ORR activity
32 Co3O4 (2q  36.98, 49.28 and 65.38, JCPDS, NO.76-1802) indicate of the FeCo-N-d-Ti3C2 MXene was further studied by the LSV
33 that transition metal oxides are also generated in FeCo-N-d- wherein the current density increases with increasing rotation
34 Ti3C2 MXene. Meanwhile, according to the XRD data, Fe and Co speeds from 600 rpm to 2000 rpm, which has been illustrated
35 species seems to be segregated from each other, and no in Figure 3c. Hence, the number of electrons transferred per
36 reflexes attributed to FeCo alloy are obvious. This suggests oxygen molecule (n) at the FeCo-N-d-Ti3C2 MXene electrode
37 that the binary non-precious-metal (FeCo) complexes tend to was further determined by the K–L equation (current density1
38 form Fe-N and Co-N nanoparticles during pyrolysis.[5d] Further- 1
vs. w2 ) at various electrode potentials from 0.55 V (vs. RHE) to
39 more, the diffraction peak of d-Ti3C2 MXene at 2q  8.68 shifts to
0.70 V (vs. RHE), which are summarized in Figure 3c. Those
40 the lower angle at 2q  8.08 in FeCo-N-d-Ti3C2 MXene, indicating
corresponding K-L lines in Figure 3c exhibit good linearity and
41 that both the introduction of FeCoEDA chelate nanoparticles
their slopes remain approximately constant, suggesting that
42 and the calcination enlarged the d-spacing of d-Ti3C2 layers for
the electron transfer numbers at different electrode potentials
43 the convenience of the oxygen diffusion and adsorption (the
are similar. For quantitative analysis, the n average value is
44 limiting step of ORR process). It can be explained in Scheme 1
found to be 3.6. It can be inferred that the ORR process for the
45 that the Fe and Co ions were intercalated and absorbed by the
FeCo-N-d-Ti3C2 MXene is achieved via both the 2-electron
46 functional groups on the surfaces of d-Ti3C2 MXene nanoflakes
transfer reduction to generate the H2O2 and the 4-electron
47
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56
57 Scheme 1. Preparation of FeCo-N-d-Ti3C2 MXene hybrid.

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1
2
3
4
5
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8
9
10 Figure 3. a) LSV curves for the ORR on FeCo-N-d-Ti3C2 MXene, FeCoEDA and 20 wt.% Pt/C catalyst in O2-saturated 0.1 M KOH solution at 2000 rpm; The inset:
11 magnification of the LSV curves; b) LSV curves for the ORR on FeCo-N-d-Ti3C2 MXene at varying rotating rate from 600 rpm to 2000 rpm; c) K-L plots of FeCo-
N-d-Ti3C2 MXene.
12
13
14
15 transfer reduction to generate H2O, with the latter is the explained by the migration rate of adsorbed oxygen intermedi-
16 dominant process. ates.[23] FeCo-N-d-Ti3C2 MXene catalysts with the Fe : Co ratios of
17 The above inference is proved in Figure 4. Interestingly, in 3 : 1, 1 : 1, 1 : 3, afford Tafel slopes of 85, 77, 75 mV · dec1,
18 Figure 4a, the current density initially increases with the Fe : Co respectively, lying between both cases, indicating that their
19 ratio from 0 to 3 : 1 and gets maximum of 5.83 mA · cm2 on Fe- ORR rates are primarily determined by both the migration of
20 N-d-Ti3C2 (Fe-alone) catalyst. It can be explained through adsorbed oxygen intermediates and charge transfer.
21 Figure 4b where the H2O2 yields of these catalysts determined In order to explore the ORR activity enhancement mecha-
22 using a RRDE generally correlate with their activity has been nism for FeCo-N-d-Ti3C2 MXene, XPS analysis of the d-Ti3C2
23 illustrated. The Co-N-d-Ti3C2 MXene generates high H2O2 about MXene and FeCo-N-d-Ti3C2 MXene hybrid was carried out. For
24 15 % while about 2 % and 3 % of H2O2 yield for that of Fe-N-d- this, the high-resolution XPS spectra of FeCo-N-d-Ti3C2 MXene
25 Ti3C2 MXene and FeCo-N-d-Ti3C2 MXene, respectively. This is and the deconvolution results of each spectrum are illustrated
26 well consisted with the previous reports[5c,d] that low H2O2 yield in Figure 5a and Figure 5b-h, respectively, while those of d-Ti3C2
27 in ORR is observed to high selectivity of O2 reduction to H2O MXene for comparison are shown in Figure S3. Typically, the
28 through a 4-electron route rather than to H2O2 through a 2- XPS survey spectrum of FeCo-N-d-Ti3C2 MXene shows signifi-
29 electron route in a much less efficiency. It is indicative that the cant signals for Co, Fe, O, Ti, N and C elements in Figure 5a
30 active ORR centers formed by Fe atoms catalyze a 4-electron while this of d-Ti3C2 MXene shows significant signals for the F,
31 ORR, while a 2-electron reduction was produced by Co atoms, O, Ti and C elements in Figure S3a. Further, in the Fe 2p
32 thus the highest current density produced by Fe-N-d-Ti3C2 spectrum (Figure 5b), Fe2 + species[Fe(II)] is observed at
33 MXene can be detected. When a portion of Fe atoms were 711.33 eV (Fe2 + 2p3/2) and 724.09 eV (Fe2 + 2p1/2) while the Fe
34 replaced by Co to form FeCo-N-d-Ti3C2 MXene catalysts with species[Fe(0)] and the Fe3 + species[Fe(III)] are observed at
35 different Fe : Co ratios, the current density performance and 718.18 eV (Fe 2p3/2) and 725.71 eV (Fe3 + 2p1/2), respectively.[24]
36 H2O2 yields of them lie between the plots for single Fe- and Co- Moreover, the Co 2p spectrum (Figure 5c) can be also fitted
37 catalysts shown in Figure 4a and Figure S2a. Furthermore, the with two spin-orbit doublets. The two fitting peaks located at
38 Tafel slopes of ORR on these catalysts were also analyzed in this 782.82 and 797.67 eV are ascribed to Co2 + while another two
39 work (see Figure 4c and Figure S2b). The Tafel slope of Fe-N-d- fitting peaks locate at 781.02 and 796.71 eV are attributed to
40 Ti3C2 MXene (108 mV · dec1) is more close to 120 mV · dec1, Co3 + accompanied by two shakeup satellite peaks (identified as
41 suggesting the rate-determining step associated with the first- sat.) at the binding energy of 786.53 eV and 803.18 eV.[25]
42 electron transfer, while the Tafel slope of Co-N-d-Ti3C2 MXene Furthermore, the N 1s peak which is not found in d-Ti3C2 MXene
43 (69 mV · dec1) is more close to 60 mV · dec1 which has been (Figure S3b) but in FeCo-N-d-Ti3C2 MXene (Figure 5d) can be
44
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56 Figure 4. a) LSV curves for the ORR on FeCo-N-d-Ti3C2 MXene catalyst with different Fe : Co ratios in O2-saturated 0.1 M KOH solution at 2000 rpm; b) The
57 corresponding H2O2 produced for the ORR and c) Tafel plots of ORR catalyzed by FeCo-N-d-Ti3C2 MXene, Fe-N-d-Ti3C2 MXene and Co-N-d-Ti3C2 MXene.

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Figure 5. XPS (a) survey, (b) Fe 2p, (c) Co 2p, (d) N 1s, (e) Ti 2p, (f) C 1s, (g) O 1s and (h) F 1s spectra of FeCo-N-d-Ti3C2 MXene.
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52 deconvoluted into three components, centered near the bind- formed by coupling the iron or cobalt ions with these nitrogen-
53 ing energy of 398.74 eV, 399.97 eV and 401.6 eV, which may be containing groups on the polymer. Besides, quaternary-N can
54 assigned to a pyridinic N, a pyrrolic N and a quaternary N, effectively enhance the ORR activity of the catalyst.[28] Further-
55 respectively.[26] Generally, graphitic, pyrrolic, and pyridinic N are more, interestingly, the doublet peaks belong to Ti-C (at the
56 widely recognized as active N species for N-doped material binding energy of 461.36 and 455.37 eV) of pristine d-Ti3C2
57 catalysts,[27] wherein the Fe-N and Co-N ORR active centers are MXene (Figure S3c) shifted to higher binding energy (at the

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 Articles
1 binding energy of 463.26 and 458.58 eV) in FeCo-N-d-Ti3C2 FeCo-N-d-Ti3C2 MXene electrode, suggesting its excellent toler-
2 MXene (Figure 5e), suggesting the strong interaction and ance to methanol crossover in ORR (see Figure 6b).
3 possible charge transfer between d-Ti3C2 MXene nanoflakes and
4 FeCoEDA chelate.[13,29] Specifically, the FeCo-N-d-Ti3C2 MXene
5 sample shows an additional strong Ti 2p peak contribution at 3. Conclusions
6 454.72 eV representing Ti-N, while it was not found in d-Ti3C2
7 MXene sample, indicating the successful grafting of chelate In summary, a novel hybrid catalytic material for ORR was
8 onto the MXene nanoflakes substrate instead of deposition. It prepared via binary iron-cobalt (FeCo) non-precious-metal
9 would hopefully lead to the FeCo-N-d-Ti3C2 MXene composite ions absorbed and combined in-situ with EDA molecules
10 possessing better electrocatalytic performance for ORR.[30] In between d-Ti3C2 MXene layered-nanoflakes, resulting in the
11 addition, C 1s (Figure 5f) can be deconvoluted into C-Ti-Tx, C=C, formation of FeCo (3 : 1)-N-d-Ti3C2 MXene. The hybridization of
12 CC and C=O peaks, which are corresponding to the binding FeCoEDA with d-Ti3C2 MXene not only increase its specific
13 energy of 281.77 eV, 284.77 eV, 285.87 eV and 288.27 eV. It can surface area but also enhance the possible charge transfer in
14 be identified that the C-Ti-Tx peak (referred to Ti3C2Ox, Ti3C2(OH)x ORR, leading to an improved ORR electrocatalytic activity even
15 and/or Ti3C2Fx) has almost disappeared which compared to the compared to commercial 20 wt.% Pt/C catalyst. It has been also
16 C 1s of pristine d-Ti3C2 MXene sample (Figure S3d). Meanwhile, demonstrated that FeCo (3 : 1)-N-d-Ti3C2 MXene has simulta-
17 the Ti-O and C-Ti-Ox in O 1s peak (Figure S3e) as well as C-Ti-Fx neously enhanced the stability and methanol tolerance of ORR
18 in F 1s peak (Figure S3f) shown in d-Ti3C2 MXene are also absent in alkane electrolytes. Therefore, the d-Ti3C2 MXene hybridized
19 in FeCo-N-d-Ti3C2 MXene sample (see Figure g and h). As a with different non-noble metal nano-catalysts can be excellent
20 result, it is reasonably expected that the functional group (e. g., candidates for fuel cells cathode ORR materials. Besides, a
21 Ox, (OH)x and Fx) on the surfaces of d-Ti3C2 MXene nano- worthy goal and subject of on-going work is to promote the
22 flakes can be displaced by FeCoEDA chelate complex. development of MXene-based hybridized materials with other
23 The stability of various catalysts was evaluated by a transition metal nanoparticles for ORR in order to improve their
24 chronoamperometric approach in O2-saturated 0.1 M KOH performances in acidic condition, as compared to the commer-
25 electrolyte solution at 0.60 V (vs. RHE) for 20000s, the results cial Pt/C catalyst. All those will be discussed in our next paper.
26 were shown in Figure 6a and Figure S4. Although the Co-N-d-
27 Ti3C2 MXene performs a poor current density as above
28 discussion, it retains the highest normalized current among all Acknowledgements
29 the catalysts studied in the stability test. It has been also
30 illustrated that the Fe-N-d-Ti3C2 MXene maintains more than This work is supported by the link project of the National Natural
31 90 % of its initial current density, significantly improved after a Science Foundation of China and Guangdong Province (No.
32 portion of Fe atoms were replaced by Co to form FeCo-N-d- U1401246), by the Science and Technology Program of Guang-
33 Ti3C2 MXene catalysts with different Fe : Co ratios, whereas the dong Province of China (Grant No. 2017B050504004,
34 20 wt.% Pt/C electrode with a current lost more than 15 % 2016 A020221031), by the China Postdoctoral Science Foundation
35 under the same conditions. It is well consisted with the (Grant No. 2018 M633015).
36 previous reports[5c,d,31] that the presence of Co atoms in ORR
37 catalysts can enhance the catalyst stability. In addition, when
38 the methanol was introduced into the electrolyte solution after Conflict of Interest
39 1000s, the ORR performance at the 20 wt.% Pt/C electrode
40 rapidly dropped to about 48 % of its normalized current. In The authors declare no conflict of interest.
41 contrast, almost no apparent change was observed for the
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56 Figure 6. The a) stability of various catalysts and b) methanol tolerance between FeCo-N-d-Ti3C2 MXene and commercial 20 wt.% Pt/C by current-time (i-t)
57 curves.

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1 Keywords: d-Ti3C2 MXene · electrochemistry · in-situ
2 hybridization · oxygen reduction reaction · transition metals
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Manuscript received: May 24, 2018
Version of record online: August 20, 2018

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