Manipulating the surface composition of Pt-Ru bimetallic nanoparticles to control the methanol oxidation reaction pathway

Article abstract of DOI:10.1039/c9cc09423g

The rational manipulation of reaction intermediates is crucial for achieving high-performance heterogeneous catalysis. Herein, using in situ Fourier transform infrared-diffuse reflection (FTIR) analysis, we report that the methanol oxidation reaction (MOR) intermediates can be controlled by precisely tuning the location and content of Ru on the Pt-Ru alloy surface.

Full text of DOI:10.1039/c9cc09423g

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Manipulating the Surface Composition of Pt-Ru Bimetallic
Nanoparticles to Control the Methanol Oxidation Reaction
Pathway
Received 00th January 20xx,
Accepted 00th January 20xx
Qingmei Wanga, Siguo Chena*, Jian Jiangb, Jinxuan Liub, Jianghai Denga, Xinyu Pinga, Zidong Weia*
DOI: 10.1039/x0xx00000x
The rational manipulation of reaction intermediates is crucial growth rates owing to the different reduction potential of Pt ([PtCl4]2-
to achieving high performance heterogeneous catalysis. +2e-↔Pt+4Cl-,E0=+0.73V)and Ru (Ru2++2e-↔Ru, E0=+0.45V), which
Herein, using the in-situ Fourier transform infrared-diffuse unavoidably result in alloy inhomogeneity and low alloy degree
reflection (FTIR) analysis, we report that the methanol because of the low temperature synthesis conditions.13,14
oxidation reaction (MOR) intermediates can be controlled by Consequently, further step of high temperature procedure is
precisely tuning the location and content of Ru on PtRu alloy necessarily required to improve the alloy homogeneity and alloy
surface.
degree, which inevitably leads to nanoparticles (NPs) growth,
sintering and aggregation.15 To overcome these elusive challenges
Direct methanol fuel cells (DMFCs) are one of the most promising and achieve both high MOR activity and anti-CO poisoning ability in
electrochemical energy conversion devices for its easy storage, DMFCs applications, therefore, the exploration of simple and cost-
delivery and refueling.1,2 However, the extensive commercialization efficient methodologies for fabricating PtRu alloys with uniform
of DMFCs is appreciably restricted by the sluggish dynamics of the sizes, preferable alloying degree and controlled compositions is
methanol oxidation reaction (MOR) and the suppressed anti-CO highly acceptable.
poisoning ability. Currently, Pt has attracted the most attentions in
Herein, we reported that the pathway of MOR on Pt-Ru alloy can
the field of electrocatalysis as its high kinetic rates of methanol be controlled by precisely manipulating the surface composition of
dehydrogenation.3,4 Unfortunately, pure Pt are severely poisoned by Pt-Ru bimetallic NPs. We tune the location and content of Ru on PtRu
the adsorbed carbon monoxide (ads-CO) intermediate in MOR.5-7 alloy surface through a thermally driven interfacial diffusion route
Therefore, considerable recent research efforts have been devoted that allows for selectively transforming the solid Pt NPs supported on
to the development of high anti-CO poisoning ability electrocatalysts carbon (Pt/C) into Pt-rich PtRu alloy, Ru-rich PtRu alloy and PtRu alloy
for MOR, especially bimetallic Pt-M alloys (M=Ru, Fe, Co, Cu, Ni, etc.) with moderate surface atom ratio of Pt to Ru. As shown in Figure 1,
with various morphologies, composition and structures.8
the high-temperature, in junction with the H2/N2 reduction
Among which, the best-performing anti-CO poisoning catalysts for atmosphere, drives the “reduction” and “diffusion” of absorbed Ru3+
MOR is found to be bimetallic PtRu alloy, in which Pt sites are needed into the Pt to form PtRu alloy. We also correlated their MOR pathway
for methanol dehydrogenation and Ru sites are demanded for water and activity with the location and content of Ru in PtRu alloy by
activation. Since the catalytic process of MOR takes place on only a applying in-situ Fourier transform spectrum (FTIRs) infrared-diffuse
few layers of atoms or near the catalyst surface.9 Achieving the
atomic-level control of the surface composition and atomic
arrangement is of great interest to enhance overall MOR
performance of PtRu catalyst. However, it is not an easy task by the
current and primary traditional wet-chemistry synthesis methods,
such as chemical precipitation, impregnation, colloidal,
microemulsion, polyol method, etc.10-12 The most important
challenges in these synthesis methods are the diverse nucleation and
a The State Key Laboratory of Power Transmission Equipment & System Security and
New Technology, Chongqing Key Laboratory of Chemical Process for Clean Energy
and Resource Utilization, School of Chemistry and Chemical Engineering,
Chongqing University, Chongqing 400044, China.
E-mail: csg810519@126.com; zdwei@cqu.edu.cn
b The State Key Laboratory of Fine Chemical Industry, Dalian University of
Technology, Dalian, China
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx00000x
Figure 1 The synthetic overall concept of the Pt-skin-rich Pt1Ru0.5@NC/C, moderate
Pt and Ru content Pt1Ru1@NC/C and Ru-skin-rich Pt1Ru2@NC/C samples.
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reflection spectrum (FTIRs). Our insights establish that the Pt-rich reduced and diffused into Pt lattice to form bimetallic PtRu alloy. The
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PtRu alloy catalyst featured a MOR pathway through HCOO- induced strain variations of Pt1Ru0.5/C@NC, Pt1Ru1/C@NC and
DOI: 10.1039/C9CC09423G
intermediate, while the Ru-rich PtRu alloy catalyst exhibit a CO Pt1Ru2/C@NC catalysts which based on the Bragg's law and the peak
intermediate pathway. Meanwhile, the PtRu alloy catalyst with position of Pt (111) are 1.49%, 1.66% and 1.13%, respectively (Table
optimal surface atom ratio of Pt to Ru, which possess the best MOR S2). The different crystal lattice shrink degree was also confirmed by
activity and anti-CO poisoning ability, convey a combined pathway of high-resolution TEM (HRTEM), in which the degree of crystal lattice
HCOO- and CO intermediate.
shrinkage on Pt1Ru1/C@NC (Figure S1b) is higher than
The PtRu alloy with different Ru contents was prepared by Pt1Ru0.5/C@NC (Figure S1e) and Pt1Ru2/C@NC (Figure S1h),
integrating the thermal-driven structural evolution and surface respectively. This result means that higher Ru feeding content would
manipulating strategies.16 The resultant PtRu alloy samples not consequently result in higher alloying degree. The possible
were represented as “Pt1Rux/C@NC”, where “X” indicates the reason is due to the inhomogeneity of the distribution of Ru in the
feeding molar ratio of Ru3+ to Pt (Pt1Ru0.5/C@NC, Pt1Ru1/C@NC, whole PtRu NPs. The composition profiles of the as-prepared PtRu
Pt1Ru2/C@NC, respectively). The morphology and structure of alloy were further characterized by atomically resolved aberration-
the as-prepared PtRu alloy were first investigated by corrected high-angle annular dark-field scanning TEM (HAADF-STEM)
transmission electron microscopy (TEM). No noticeable Pt and the energy-dispersive X-ray spectroscopy (EDX) in combination
conglomeration happened in the Pt1Ru0.5/C@NC (Figure S1a),
with the energy loss spectroscopy (EELS) line scan analysis. As shown
Pt1Ru1/C@NC (Figure S1d) and Pt1Ru2/C@NC (Figure S1g), suggesting in Figure 2f, 2g, 2n, the overall elemental mapping images reveal that
that the agglomeration of the PtRu NPs can be effectively prevented most of the Ru are located on the surface of the PtRu NP for thorough
by our reported composite procedure as compared to the of the as-prepared PtRu samples. Further EELS analysis results
commercial PtRu/C catalyst (Figure S2). As shown in Figure S1c, 1f, (Figure 2g, 2k, 2o) show that the lower feeding molar ratios of Ru3+
1i, it is obvious that with the increase in the Ru content, the average to Pt are beneficial to the formation of Pt-skin-rich PtRu alloy phases
particle size of PtRu gradually increased from 2.60 nm for (Pt1Ru0.5/C@NC) with the Ru/Pt molar ratio of 0.2, while the higher
Pt1Ru0.5/C@NC to 2.72 nm for Pt1Ru1/C@NC and 3.04 nm for feeding molar ratios of Ru3+ to Pt led to the formation of a Ru-skin-
Pt1Ru2/C@NC, indicating that more Ru have been diffusion into Pt rich PtRu alloy (Pt1Ru2/C@NC) with the Ru/Pt molar ratio of 0.5. For
due to the increased feeding Ru3+ contents. The Ru contents in the comparison, the medium feeding molar ratios of Ru3+ to Pt prefer to
as-prepared PtRu samples were further confirmed by the inductively form homogenous Ru distribution in whole Pt1Ru1/C@NC alloy
coupled plasma mass spectrometry (ICP-MS) analysis. As shown in (Figure 2h, 2l, 2p). These results are firmly certificating that the
Table S1, the Ru content in PtRu alloy gradually increased from 0.8% location and composition of Ru at PtRu NPs can be exactly
for Pt1Ru0.5/C@NC to 2.1% for Pt1Ru1/C@NC and 3.9% for manipulated by altering the feeding of Ru3+ content, which is
Pt1Ru2/C@NC, further confirming that the Ru content in PtRu alloy consistent with the analysis of XRD and ICP. Additional
can be controlled by tuning the feeding of Ru3+ content. The crystal representative HAADF-STEM and elemental mapping images of
structure of the as-prepared PtRu alloy was investigated by the Pt1Ru1/C@NC are shown in Figure S3 and Figure S4.
powder X-ray diffraction (XRD). As shown in Figure 2a, the peak
The surface composition and chemical status of the PtRu
position of the Pt1Ru0.5/C@NC, Pt1Ru1/C@NC and Pt1Ru2/C@NC samples were further investigated by X-ray photoelectron
shifted to high angles as compared to the pure Pt (PDF#04-0802), spectroscopy (XPS). As shown in Figure S5, the presence and the
further confirming that the pre-adsorbed Ru3+ has been successfully corresponding content of Pt, Ru, C, N and O in PtRu samples were
confirmed by the XPS survey, respectively. The atomic ratio of the
Ru: Pt in the PtRu surface gradually increased from 1.68 for
Pt1Ru0.5/C@NC to 3.02 for Pt1Ru1/C@NC and 19.42 for Pt1Ru2/C@NC,
respectively, further indicating the surface Ru contents in PtRu alloy
consequently increased with the raise of the feeding of Ru3+
contents. The peaks of the N1s signals in PtRu samples could be
deconvoluted into pyridinic-N (398.21 eV), pyrrolic-N (400.54 eV)
and quaternary-N (401.20 eV), demonstrating that dopamine
precursor has been transformed into NC layer (Figure S6). The peak
at 280.6 eV represents the metallic Ru, and the peaks at 281.3 and
281.8 eV indicate the Ru oxides (Figure S7). Moreover, the Pt 4f7/2
and Pt 4f5/2 peaks of the homemade PtRu sample can be split into
predominant metallic Pt and Pt oxides (Figure S8), which can provide
more effective active sites for MOR. The electron transfer degree
from Ru to Pt in Pt1Rux/C@NC samples was determined by the
negative shift value in the Pt 4f7/2 peak as compared with the Pt/C
catalyst (Figure 3a), which followed an order of 0.60eV
(Pt1Ru1/C@NC), 0.34eV (Pt1Ru0.5/C@NC) and 0.24eV(Pt1Ru2/C@NC),
respectively. The lower negative shift in Pt1Ru0.5/C@NC and
Pt1Ru2/C@NC catalysts are owing to the inhomogeneity of the
electronic donor Ru and the electronic acceptor Pt (Figure 3b).17 To
Figure 2 The powder X-ray diffraction of Pt1Ru0.5@NC/C, Pt1Ru1@NC/C and
Pt1Ru2@NC/C catalysts (a) and the Aberration-corrected HAADF-STEM
images, its corresponding EDX elemental mapping and EELS images as well as
the calculated Ru/Pt atomic ratios of the Pt1Ru0.5@NC/C (e-h), Pt1Ru1@NC/C
(i-l) and Pt1Ru2@NC/C (m-p) catalysts, respectively.
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further evaluate the effect of Ru content on anti-CO poisoning ability
of the PtRu sample, the CO-stripping experiment were conducted. As
shown in Figure 3c, the Pt1Ru1/C@NC shows the lowest onset
potential of the CO oxidation as compared with Pt1Ru0.5/C@NC,
Pt1Ru2/C@NC and commercial Pt/C catalysts, suggesting that the
Pt1Ru1/C@NC exhibit accelerated CO oxidation kinetics respect to its
counterpart. As confirmed by XPS, the homogeneity of Ru in
Pt1Ru1/C@NC catalyst can induce more electron transfer from Ru to
Pt as compared with Pt1Ru0.5/C@NC, Pt1Ru2/C@NC, which will
weaken the Pt-CO adsorption energy and facilitate the removal of
ads-CO on Pt sites, resulting in improving the anti-CO poisoning
ability of the catalysts.18 The specific value of electrochemical surface
area (ECSA) based on the CO oxidation charge and Pt mass for the
Pt1Ru0.5/C@NC is estimated to be 49 m2/gPt (Figure 3d), which is
slightly higher than the Pt1Ru1/C@NC (47 m2/gPt) and Pt1Ru2/C@NC
(39 m2/gPt) catalysts. It is suggesting that the more Ru feeding, the
less Pt active sites for MOR in catalyst are exposed.19
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DOI: 10.1039/C9CC09423G
Figure
3
(a) XPS Pt 4f scans of Pt1Ru0.5@NC/C, Pt1Ru1@NC/C and
The MOR activity was further evaluated by the cyclic voltammetry
(CV) in N2-saturated 0.1 M HClO4 solution containing 0.5M CH3OH. As
shown in Figure 3e, the peak currents of MOR are found to be 5.29,
5.31 and 2.20 mA.cm-2 on the Pt1Ru0.5/C@NC, Pt1Ru1/C@NC and
Pt1Ru2/C@NC catalysts, respectively (Figure 3f). The higher forward
peak current on Pt1Ru1/C@NC catalyst indicating that the faster
dynamics rate of C-H cleavage of methanol. To gain further insights
into the MOR activity of PtRu samples, the peak current at 0.7VRHE
correlated with MOR in the forward scan is normalized with respect
to both ECSA and the loading amount of Pt. As shown in Figure 3g
and Table S3, the MOR specific activity firstly increased with the
increase of Ru surface composition from 1.29 mA.cm-2 for
Pt1Ru0.5/C@NC to 1.36 mA.cm-2 for Pt1Ru1/C@NC and subsequently
decreased with further increases of Ru surface composition to 0.59
mA.cm-2 for Pt1Ru2/C@NC. The mass activities gradually increased
from 0.59 mA/ugPt for Pt1Ru0.5/C@NC to 0.67 mA/ugPt for
Pt1Ru1/C@NC and then decreased to 0.23 mA/ugPt for Pt1Ru2/C@NC,
respectively. Except for the peak current, the value of If/Ib (If and Ib
are represent the forward and backward current density) is also very
important factor to evaluate the anti-CO poisoning ability. The
Pt1Ru1/C@NC catalyst exhibits the higher If/Ib value of 7.17 than that
of the Pt1Ru0.5/C@NC (6.86) and Pt1Ru2/C@NC (5.46) catalysts,
respectively. The higher If /Ib ratio and forward peak current propose
that the methanol would be effectively oxidized during the forward
potential scan and there would be generate less ads-CO species
during the backward potential scan, thereby the catalyst of
Pt1Ru1/C@NC maintain superior MOR activity and anti-CO poisoning
ability (Figure S9 and Scheme S2). To the best of our knowledge,
these values including the If /Ib, the mass activity and the specific
activity are advantageous to those of other PtRu catalysts reported
to date as MOR catalysts in an acid surroundings (Table S4). The
stability towards MOR in the Pt1Ru0.5/C@NC, Pt1Ru1/C@NC and
Pt1Ru2/C@NC catalysts was conducted by the chronoamperometric
(CA) on a constant potential of 0.7VRHE for 7500s. The polarization
currents in Pt1Ru0.5/C@NC, Pt1Ru1/C@NC and Pt1Ru2/C@NC are
decrease at the primary stage (Figure 3h), which is mainly owing to
the formation of the by-product and intermediate species (Scheme
S2) during MOR.24 However, the density of the anodic current of the
Pt1Ru1/C@NC is always higher than the Pt1Ru0.5/C@NC and
Pt1Ru2/C@NC during the entire time range (Figure 3i). Moreover,
Pt1Ru2@NC/C catalysts as compared with the primitive Pt/C catalysts and (b)
the corresponding illustration of the electron transfer when CO adsorbed on
the surface. (c) CO stripping curves of the Pt1Ru0.5@NC/C, Pt1Ru1@NC/C,
Pt1Ru2@NC/C and Pt/C catalysts and (d) corresponding ECSA s well as (e) the
CV curves and peak current (f) in 0.1 M HClO4 + CH3OH solution. (g) The mass
and specific activity at peak potential and the chronoamperometric on a
constant potential of 0.75VRHE for 7500s (h) and the current density descend
percentage of the Pt1Ru0.5@NC/C, Pt1Ru1@NC/C and Pt1Ru2@NC/C catalysts
(i).
Figure S10 also indicating that the change in particle size is negligible
in the Pt1Ru1/C@NC samples after long-term cycles, whereas obvious
aggregation occurs on the Pt1Ru2/C@NC catalysts under the same
conditions. These results again confirm that the Pt1Ru1/C@NC
sample with the homogeneity distribution of Ru contents on the
surface possess better anti-CO poisoning ability and improved
stability in MORs (Figure S11). Therefore, combined with the ICP-MS
after the stability test (Table S1), we can conclude that the
appropriative surface Pt and Ru composition can effectively prevent
the PtRu NPs from aggregation and subsequently promote the
electrochemical stability during potential cycling.
To get an insight into how the MOR activity trajectories of
correlate with Pt and Ru compositional changes, the in-situ Fourier
transform infrared-diffuse reflection spectroscopy (FTIRs) was
performed.20-24 For Pt-rich Pt1Ru0.5@NC/C catalyst, the characteristic
adsorbed peak related to methyl formate (HCOOCH3) intermediate
can be clearly observed at 1260 cm-1 with the increasing of scan
potential, while the bands of CO linear molecules (COL) which
represent the CO pathway are not observed, indicating that the
Pt1Ru0.5@NC/C catalyst achieving MOR through HCOO- intermediate
pathway (Figure 4a, 4d). On the contrary, the characteristic adsorbed
peak of COL is evidently viewed at 2050 cm-1 in Ru-rich Pt1Ru2@NC/C
catalyst, while the bands of HCOOCH3 are not observed, indicating
that the Pt1Ru2@NC/C catalyst achieving MOR through CO pathway
(Figure 4c, 4f). Different from the solely MOR pathway in Pt-skin-rich
Pt1Ru0.5@NC/C and Ru-skin-rich Pt1Ru2@NC/C samples, the
Pt1Ru1@NC/C catalyst demonstrate a mixed pathway through HCOO-
and CO intermediate (Figure 4b, 4e), in which both the characteristic
peak of HCOOCH3 and COL are obviously found.25-29 By correlating the
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Research Funds for the Central Universities (2018CDXYHG0028).
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DOI: 10.1039/C9CC09423G
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Acknowledgements
This research work was financially supported by the National Key
Research and Development Program of China (2016YFB0101202),
National Natural Science Foundation of China (Grant No. 91534205,
21436003, 21576031 and 21776023), and by the Fundamental
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TOC
Here we achieve surface composition precisely manipulating of bimetallic PtRu alloy from Pt-skin-rich to
Ru-skin-rich and report that the MOR pathway can be controlled by tuning the location and content of Ru
on PtRu alloy surface.