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Titel: Precise Molecular-level Modification of Nafion with Bismuth Oxide

Clusters for High-performance Proton Exchange Membranes

Autoren: Bailing Liu, Bo Hu, Jing Du, Hong-Ying Zang, Dongming

Cheng, xin Ge, Huaqiao Tan, Yonghui Wang, Xiaozheng
Duan, Wei zhang, Zhao Jin, Yangguang Li, and Zhongmin Su

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Zitierweise: Angew. Chem. Int. Ed. 10.1002/anie.202012079

Link zur VoR: https://doi.org/10.1002/anie.202012079

Angewandte Chemie 10.1002/ange.202012079

RESEARCH ARTICLE
Precise Molecular-level Modification of Nafion with Bismuth
Oxide Clusters for High-performance Proton Exchange
Membranes
Bailing Liu,†[a,b] Bo Hu,†[a,c] Jing Du,[a] Dongming Cheng,[a] Hong-Ying Zang,*[a] Xin Ge,[d] Huaqiao Tan,[a]
Yonghui Wang,[a] Xiaozheng Duan,*[e] Zhao Jin,[f] Wei Zhang,[d] Yangguang Li,*[a] Zhongmin Su[a,b]
[a] Bailing Liu, Bo Hu, Jing Du, Dongming Cheng, Hongying Zang, Huaqiao Tan, Yonghui Wang, Yangguang Li, Zhongmin Su
Key Lab of Polyoxometalate Science of Ministry of Education, Key Laboratory of Nanobiosensing and Nanobioanalys
Faculty of Chemistry, Northeast Normal University
Changchun 130024, P. R. China. Fax: +86-431-85684009; Tel: +86-431-85099108

Accepted Manuscript
E-mail: zanghy100@nenu.edu.cn; lig658@nenu.edu.cn
[b] Bailing Liu, Zhongmin Su
Jinlin Provincial Science and Technology Innovation Center of Optical Materials and Chemistry
Changchun University of Science and Technology Changchun
Changchun, Jilin,130024, P. R. China
[c] Bo Hu
School of chemistry and pharmaceutical engineering
Jilin Institute of Chemical Technology
Jinlin 132022, P. R. China.
[d] Xin Ge, Wei Zhang
Electron Microscopy Center
Jilin University
Changchun 130012, China
[e] Xiaozheng Duan
State Key Laboratory of Polymer Physics and Chemistry
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences
Changchun, Jilin, 130022, PR China
E-mail: xzduan@ciac.ac.cn
[f] Zhao Jin
State Key Laboratory of Electroanalytical Chemistry,
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences
Changchun, Jilin, 130022, PR China

Supporting information for this article is given via a link at the end of the document.

Abstract: Fabricating proton exchange membranes (PEMs) with
high ionic conductivity and ideal mechanical robustness through
regulation of the membrane microstructures achieved by molecular-
level hybridization remains essential but challenging for the further
development of high-performance PEM fuel cells. In this work, by
precisely hybridizing nano-scaled bismuth oxide clusters into Nafion,
we have fabricated the high-performance hybrid membrane, Nafion-
−1
Bi12-3%, which showed a proton conductivity of 386 mS cm at 80
ºC in aqueous solution with low methanol permeability, and
conserved the ideal mechanical and chemical stabilities as PEMs.
Moreover, molecular dynamics (MD) simulation was employed to
clarify the structural properties and the assembly mechanisms of the
hybrid membrane on the molecular level. The maximum current
density and power density of Nafion-Bi12-3% for direct methanol fuel
-2 −2
cells reached to 432.7 mA cm and 110.2 mW cm , respectively.
This work provides new insights into the design of versatile
functional polymer electrolyte membranes through polyoxometalate
hybridization.
Introduction
Proton exchange membrane fuel cells (PEMFCs) are widely
used due to their high efficiency, portability, low (or zero)
pollution emission, easy scale-up, and fast start-up capability.[1]
Therefore, there is much current interest in developing desirable
proton exchange membranes (PEMs) used for high-performance
PEMFC.[2,3]
Nafion has been applied as PEMs since the advent due to its
unique hydrophilic/hydrophobic nano-phase structure (shown as
Scheme 1).[4] Despite its advances of considerable conductivity
and ideal mechanical/chemical stabilities, there still remain
several inferiorities for Nafion used as PEMs, including the water
loss at high temperature, excessive swelling, and fuel
penetration, etc.[5] Moreover, given that any alteration to the
chain structure or the assembly environment could cause a
detriment to the bi-continuous nano-phase structure of Nafion, it
is difficult to simultaneously improve the ionic conductivity and
maintain the chemical/mechanical stabilities of the membrane. [6]
Enhancing the comprehensive performance of the Nafion
membrane has become an essential but challenging issue for
the further development of high-performance Nafion-based
PEMs.
The inorganic hybridization serves as a general approach for
altering the membrane micro-structures by dispatching
functional fillers into the Nafion matrix; however, due to its
insufficient accuracy, this approach can hardly achieve the
precise hybridization in nano-phases, which limits its efficacy for
membrane structure optimization. For example, Wang and co-
workers have illustrated that the addition of large-sized
graphene oxide (GO) can disturb the typical nano-phase
structures of Nafion. [7] Particularly, when the scales of the fillers
is 10 times larger than that of the polymers, the incorporation of
these fillers can drastically wreck the original continuous
nanophase.[8] Besides, it is found that the random distribution of
these fillers with weak chemical selectivity can induce a decayed
mechanical strength of the membrane. [9] As shown by Lee et al.,

1
This article is protected by copyright. All rights reserved.
Angewandte Chemie
RESEARCH ARTICLE
the presence of fillers in the backbone nanophase can enhance
the brittleness of the membrane and reduce its elongation at the
break by up to 80%.[10]
In recent years, precisely distributing functional, molecular-
level scaled fillers into the targeted nanophase (also known as
molecular-level hybridization) has been further employed as an
effective strategy to fabricate high-performance PEMs. For
example, Qiao et. al. used two types of nanoscaled (2-5 nm)
quantum dots (QDs) to modify the nanophases of Nafion
membrane, and indicated that the small-sized ones can
automatically recognize and enter the nanophase, leading to
increased proton conduction of the membrane. [11] However, due
to the difficulty in regulating the size and chemical affinity of the
fillers, the effective and precise molecular-level hybridization
remains significantly challenging.
Polyoxometalates (POMs) are an important type of multivalent
ionic molecular inorganic metal-oxide nanoclusters, which are
often used as functional inorganic fillers in PEMs to enhance the
performance of the membrane due to their high-water uptake
ability, dispersity, thermal/chemical stability. [12] Among others,
bismuth oxide clusters {H6 Bi12O16} exhibited a variety of
advantages as molecular-level hybridization fillers. [Bi6 O5(OH)3]2
(NO3)10·6H2O {H6 Bi12 O16} clusters are deca-valent in aqueous
solution, which can act as highly charged cationic fillers with
strong antioxidation capability in the water-containing matrix. In
the previous study, we have demonstrated the ideal proton
conduction of bismuth oxide clusters. [13] More notably, these
nano-scaled clusters exhibit good chemical stability, low toxicity,
low cost, and low water solubility as inorganic fillers.[14]
In this work, we fabricated a hybrid membrane (nominated as
Nafion-Bi12-3%) used as the high-performance PEM, through
molecular-level hybridization of {H6 Bi12O16} clusters into the ionic
phase of Nafion rather than their random distribution into Nafion
matrix. Driven by the electrostatic and hydrogen-bonding
interactions, the cationic {H6 Bi12O16} clusters precisely identify
and assemble with anionic side chains of Nafion, which induces
Scheme 1. Preparation of hybrid Nafion/{H6Bi12O16} composite membranes through the solution-casting technique.
Assembly between Nafion and {H6 Bi12 O16}
Fourier-transformed infrared (FTIR) spectra of recast Nafion
(RN), Nafion-Bi12-3%, Nafion-Bi12-5% in casting solution and dry
membrane were employed to elucidate the molecular-level
interactions in the membrane assembly.[16] As shown in Figure
S1-S2, Compared with the FT-IR spectrum of RN, the Nafion-
Bi12-3% and Nafion-Bi12-5% membranes displayed the
2
This article is protected by copyright. All rights reserved.
10.1002/ange.202012079
the significant optimization of the hydrophilic/hydrophobic nano-
phases in the membrane. In the Nafion-Bi12-3% membrane, the
unique and fundamental physicochemical properties of each
component are naturally incorporated into the hybrid membrane.
In comparison with the recast Nafion (RN) membrane, the
Nafion-Bi12-3% hybrid membrane exhibited a 3-time higher
proton conductivity and a 60% enhancement in fuel cell output
power. Meanwhile, the hybrid membrane showed the ideal
mechanical and chemical stabilities as well as the antioxidation
feature.
Results and Discussion
Accepted Manuscript
A precise molecular-level “targeted assembly” strategy is used
to construct the hybrid Nafion/{H6 Bi12O16} composite membranes
through the solution-casting technique[15] (shown as Scheme 1,
the detailed experimental procedures are provided in the
Supporting Information), in which the {H6Bi12O16} cation clusters
can be hybridized into the ionic nanophase of Nafion
membranes through the electrostatic and hydrogen-bonding
interactions. Given that the bi-continuous nanostructure of the
hybrid Nafion membrane sensitively depends on the additives
and assembly environment, our precise molecular-level
“targeted assembly” strategy can serve as an effective strategy
for the controllable fabrication of hybrid Nafion membrane with
the desired nano-scaled architecture. The assembled
membranes were nominated as Nafion-Bi12-x%, where
([Bi6O5(OH)3]2(NO3)10·6H2O) denotes Bi12 and x (= 3%, 5%)
represents the weight percentage of the inorganic fillers into
Nafion. In order to clearly demonstrate the precise molecular-
level “targeted assembly” strategy, multiple types of techniques
were employed to understand the chemical composition, the
assembly mechanism and the physicochemical properties of the
hybrid membranes.
characteristic vibrations of {H6Bi12O16} clusters, further certifying
the composition of Nafion/{H6Bi12O16} hybrid membranes.
Meanwhile, by comparing the FT-IR spectra results (Figure S3),
it can be also observed that as the content of the added
{H6Bi12O16} cluster increases, the broad peak at 3480 cm-1 (OH
asymmetric stretching vibration) shifts towards a lower
wavenumber, indicating the hydrogen bonding interaction
Angewandte Chemie
RESEARCH ARTICLE
between the Nafion and the bismuth oxygen cluster molecules.
As shown in Figure S4, the Zeta potential measurements
illustrate the existence of electrostatic interaction between the
positively charged {H6Bi12O16} clusters and the negatively
charged Nafion side chains. The above results indicated that
{H6Bi12O16} clusters can be successfully hybridized into the
Nafion membranes through electrostatic and hydrogen-bonding
interactions.
Microscopic Phase Separation of Hybrid Membrane
Figure 1a and S5-S6 exhibited the scanning electron
microscopy (SEM) images of the cross-sectional morphology for
RN, Nafion-Bi12-3%, and Nafion-Bi12-5% membranes,
respectively.[17] The Nafion-Bi12-3% membrane exhibits a fairly
uniform thickness of around 75 μm (Figure 1a). As shown by the
high-resolution SEM images, the cross-section of RN (Figure
S5) is relatively smooth with few cracks; however, with the
addition of the {H6Bi12O16} clusters, the cross-sections of Nafion-
Bi12-3% (Figure 1b), and Nafion-Bi12-5% (Figure S6) become
apparently rough with obvious wrinkles or even pinholes.
This phenomenon indicates that the embedded fillers can
make the composite membranes brittle, which results in the
bulge of the membrane as it is stressed in liquid nitrogen. The
SEM surface images of RN, Nafion-Bi12-3% and Nafion-Bi12-5%
were also shown in Figure S7. It can be seen that the surface of
RN and Nafion-Bi12-3% exhibit relatively uniform without any
wrinkles, which illustrates that the monodispersed nano-sized
{H6Bi12O16} clusters (1-2 nm) have been successfully hybridized
into the internal phase of membranes. The SEM surface image
of the Nafion-Bi12-5% shows slightly rougher than the above two
membranes, which indicates that the excessive {H6Bi12O16}
drastically snatched the -SO3 H groups and wrecked the original
hydrophobic/hydrophilic nano-scaled phases, and the Nafion
matrix separates into large and isolated hydrophilic/hydrophobic
domains.
Tapping-mode atomic force microscopy (AFM) was further
utilized to detect the surface morphology and nanophase
separation structure of hybrid membranes. [18] As seen from
Figure 1c-d and Figure S8-S11, all RN, Nafion-Bi12-3% and
Nafion-Bi12-5% hybrid membranes show typical fingerprint
images of surface morphology with the height of about 0 nm to
4.8 nm, in which the dark and bright districts represent the
hydrophilic ionic nanophase and hydrophobic Nafion-backbone
nanophase, respectively. Compared with RN, the Nafion-Bi12-3%
membrane exhibited the enhanced connectivity for both the
hydrophilic and hydrophobic nano-phases, and the hydrophilic
channels were significantly widened after {H6Bi12O16} addition.
However, for the Nafion-Bi12-5% membrane, the excessively
added {H6Bi12O16} clusters disturb the hydrophobic/hydrophilic
nano-phases, which are also demonstrated by the apparent
irregularity in the surface roughness (Figure 1d and Figure
S10-S11). These results proved that the hybridization between
{H6Bi12O16} clusters and Nafion hydrophobic organic matrix can
promote the hydrophilic/hydrophobic phase separation, which
exhibits more apparent fingerprints.
This article is protected by copyright. All rights reserved.
10.1002/ange.202012079
Accepted Manuscript
Figure 1．(a-b) SEM images of cross-section of Nafion-Bi12-3% membrance;
(c) Tapping mode AFM phase images for Nafion-Bi12-3% membrane. (d) AFM
topography images of Nafion-Bi12-3%.
Transmission electron microscopy (TEM) images are also
used to clarify the nano-scaled morphology of the Nafion-Bi12
and Nafion membranes. As shown in Figure 2a, the dark
regions (surrounded by the red dashed line) represent the
Nafion hydrophobic matrix, which exhibits an ordered lattice
structure (inset of Figure 2a), and the bright regions
(surrounded by the blue dashed line) represent the hydrophilic
ionic nano-phase. Since {H6Bi12O16} is uniformly dispersed in the
Nafion-Bi12-3% membrane on a molecular scale, it is hard to
observe in a routine TEM mode. It is worth noting that compared
with the morphology of RN membrane (Figure S12), the
introduction of {H6Bi12O16} could promote the
hydrophilic/hydrophobic phase separation, in which the diameter
of the nanochannels was widened from 2nm to 5nm, being
consistent with the AFM images. Aberration-corrected STEM is
used to observe the presence of {H6Bi12O16} in Nafion-Bi12-3%
membrane. As shown in Figure 2b-c, the dark and bright
regions represent the hydrophilic ionic nanophase and
hydrophobic Nafion-matrix, respectively. Meanwhile, those
obvious bright dots can be observed at the interfacial region
between the Nafion-matrix and hydrophilic ionic nanophase,
which may indicate the monodisperse {H6Bi12O16} clusters. The
representative high-resolution high-angle annular dark field
(HAADF)-STEM images (Figure. 2d) also reveal that the
majority of bright dots contain a cluster of six or twelve heavy
atoms, as expected for the {H6 Bi12O16} cluster. The various
atomic arrangements of the imaged clusters were detected from
different viewing directions (probably, the electron-beam can
induce the dissociation of partial clusters).[19] Furthermore, the
EDS elemental maps (Figure 2e-h) shows that Bi and S
elements are uniformly distributed in the interfacial region
between the Nafion-matrix and hydrophilic ionic nanophase,
which indicates that the {H6 Bi12O16} cluster can combine with the
-SO3H groups on the side-chains of Nafion matrix through
electrostatic and hydrogen-bonding interactions.
Angewandte Chemie
RESEARCH ARTICLE
Figure 2. (a) TEM image of Nafion-Bi12-3% (inset: HR-TEM image of Nafion-matrix, scale bar: 5 nm), (b-c) STEM-HADDF images of Nafion-Bi12-3%, (d) HR-
STEM-HADDF images of Bi 12 cluster and approximate corresponding orientations (Colors: green: Bi atom; red: O atom, hydrogen atoms are omitted for
clarity,scale bars: 2 Å). (e-h) Corresponding elemental mapping of F, S and Bi of Nafion-Bi12-3%.
Wide-angle X-ray diffraction (WXRD) is used to detect the
distribution of the Nafion/{H6 Bi12O16} nanophase in the
composite membranes.[20,21] WXRD of perfluorosulfonic acid
membranes exhibit broad diffraction spectra at 2θ = 12-22º,
which can be deconvoluted into two peaks, corresponding to the
typical amorphous phase (2θ = 16º) of the hydrophilic species
and crystalline (2θ = 17.5º) scattering from the polyfluorocarbon
backbones of Nafion. Figure S13 indicates the co-existence of
these two phases in RN, Nafion-Bi12-3%, and Nafion-Bi12-5%
membranes. Table S1 represents the ratio between the areas of
the deconvoluted crystalline peak and the amorphous phase, in
which the detailed results prove that the introduction of
{H6Bi12O16} cluster can increase the hydrophobic phase
crystallinity of Nafion.
Small-Angle X-Ray Scattering (SAXS) techniques were
employed to explore the effects of added {H6Bi12O16} clusters on
the microstructure of hybrid membranes. [22] As shown in the
SAXS analysis (Figure S14), the peaks at q = 0.30 nm-1 suggest
the nanophase separation of the RN. The incorporation of
{H6Bi12O16}-3% causes the shift of the peak towards q = 0.32 nm-
1
, indicating the approaching between ionic cluster channels. By
further increasing the amount of {H6Bi12O16} to 5%, the
excessive {H6Bi12O16} significantly wrecked the
hydrophobic/hydrophilic nanophase, which results in the
formation of the widened peak at q~0.37 nm-1. Given that the
scattering intensity is proportional to the electron density of the
backbones and clusters, the intensity reduction of hybrid
membranes can further reflect the cooperation between
electrostatic/hydrogen-bonding interactions of ionic species and
the hydrophobic interactions of Nafion backbones. Compared
with the case of Nafion-Bi12-3%, the stronger scattering intensity
of Naion-Bi12-5% further confirms the fundamental alternations
of the nanophase caused by the addition of excessive
{H6Bi12O16}, which are consistent with the results of AFM and
TEM images.
This article is protected by copyright. All rights reserved.
10.1002/ange.202012079
Accepted Manuscript
Based on the above evidence, we propose the following
mechanisms of the precise molecular-level “targeted assembly”
strategy for the fabrication of Nafion-Bi12-3% membrane: In the
dimethylacetamide (DMAC) solution, the positively charged
deca-valent cationic {H6Bi12O16} and the negatively charged
monovalent anionic sulfonic acid groups of Nafion
spontaneously assembled into the ionic complexations through
the electrostatic interactions. Meanwhile, the {H6 Bi12O16} clusters
contained enriched oxygen atoms and hydroxyl groups on the
surface, which is very conducive to the hydrogen-bonding
interaction between {H6Bi12O16} clusters and -CF2-CF2-
backbones. With the evaporation of the solvent, the -CF2-CF2-
backbones further assemble into the hydrophobic matrix and the
{H6Bi12O16} clusters assembled into the interfacial region
between the Nafion-matrix and hydrophilic ionic nanophase.
During this procedure, the strong electrostatic/hydrogen-bonding
interaction between ionic nanophase and the hydrophobic
interactions between -CF2-CF2- backbones cooperate to cause
the interconnection of hydrophilic domains as well as the
formation of continuous hydrophobic phases. As illustrated by
our previous study, the isolated nanoscaled {H6Bi12O16} clusters
were matched with the ionic nanophase of Nafion in size, [13]
therefore, through our precise molecular-level “targeted
assembly” strategy, the {H6 Bi12 O16} cluster can be compatibly
hybridized into the Nafion membranes.
Thermal, Mechanical and Chemical Stabilities
The thermogravimetric analysis was employed to investigate
the thermal stability of membranes. [23] As shown by the
thermogravimetric curves in Figure S15, all of the RN, Nafion-
Bi12-3% and Nafion-Bi12-5% membranes are thermally stable in
the temperature scope of the proton conduction tests (see
below). Further, in Figure S16, the distribution of {H6Bi12O16} in
ionic nanophase of Nafion was analyzed by differential scanning
calorimetry (DSC) measurement,[24] of which the details are
provided in the Supporting Information. Further, the mechanical
Angewandte Chemie
RESEARCH ARTICLE
properties of the membranes were explored. [25] As shown in
Table S2, the RN shows satisfactory mechanical properties with
a tensile strength of ≈14.8 MPa and elongation at break of
~282%. In general, the inorganic fillers can cause the brittleness
of the polymer membrane and significantly reduce its degree of
elongation; [8] however, our experiments reveal that Nafion-Bi12-
3% displays the ideal mechanical property (with an elongation at
break of ~280% and tensile strength of ~14.6 MPa) similar to
that of RN. The electrostatic and hydrogen-bonding effects
between Nafion and {H6Bi12O16}, which act as “cross-linkers”
enhance the mechanical strength of Nafion-Bi12-3% membrane.
On the contrary, due to the wreck of the Nafion-like nano-phase
caused by the addition of excessive {H6Bi12O16} in Nafion-Bi12-
5%, both Young’s modulus and tensile strength exhibit a
significant decrease, which indicates the weakened mechanical
stability of the membrane.
The radicals (such as HO·, HOO· or H2O2) produced by the
oxygen reduction reaction in PEMFCs can chemically degrade
the internal skeleton structure of Nafion and even cause its
decomposition, which dramatically reduces the cell life. [26]
Therefore, it is essential to explore the chemical stabilities of the
as-prepared membranes. According to the electrochemical
analysis of cyclic voltammetry shown in Figure S17, two well-
defined redox couples can be observed in PBS solution at
pH~7.4. As revealed by the changes in peak current upon the
addition of H2O2, Nafion-{H6 Bi12 O16} shows promising electro-
catalytic activity towards the reduction of H 2O2. Given that most
proton conductor cannot decompose the hydrogen peroxide by
electrocatalysis, Nafion/{H6 Bi12O16} complexations as the PEM
show promising redox properties.
IEC, Water uptake and Swelling Ratio of Hybrid Membrane
The ion exchange capacity (IEC) of the membrane is closely
related to the water uptake (WU) [27,28] and proton conductivity (σ)
of the PEMs. The IEC values of the prepared PEMs are
measured and displayed in Table S2. It is shown that the
Nafion-Bi12-3% hybrid membrane exhibited considerably higher
IEC values (0.95 ± 0.02 mmol g-1) than that of the RN membrane
(0.86 ± 0.01 mmol g-1). Further, the IEC of Nafion-Bi12-5%
membrane increases to (0.98 ± 0.02) mmol g-1, attributed to the
larger amounts of protons dissociated from the added
{H6Bi12O16} clusters. Water molecules within PEMs generally act
as carriers for proton diffusion. Nevertheless, the excessive
water uptake can result in dimensional swelling and decayed
mechanical stability of the PEMs. The water uptake and
dimensional swelling of the as-prepared membranes, obtained
through immersing in water for 48 hours, were displayed in
Table S2-5 and Figure S18-19. It is found that although the
membrane exhibited higher values of water uptake with the
continuous addition of {H6Bi12O16} (which is further confirmed by
the water contact angle test shown in Figure S20-21), the
Nafion-Bi12-3% hybrid membrane exhibits better anti-swelling
ability compared with RN, or Nafion-Bi12-5%. [29] Such anti-
swelling property of Nafion-Bi12-3% hybrid membranes can be
attributed to the Nafion/{H6Bi12O16} interactions and the
maintenance of hydrophobic/hydrophilic nanoscaled phases like
RN, which can enhance the dimensional stability for the
composite membrane and would be favorable for its proton
exchange membrane fuel cells (PEMFCs) applications.
Proton Conductivity
Proton conductivity (σ) is one of the most important properties
employed to evaluate the performance of PEMs applied in fuel
5
This article is protected by copyright. All rights reserved.
10.1002/ange.202012079
cells.[30] We then focus on the study of the proton conductivity for
RN, Nafion-Bi12-3%, and Nafion-Bi12-5% hybrid membranes.
The molecular-level hybridization between Nafion and
{H6Bi12O16} endow the Nafion-Bi12-3% membrane with a
significant breakthrough in its proton conductivity. Figure 3a, 3b,
and Figure S24 show the temperature-dependent proton
conductivity of RN and Nafion-Bi12-3% hybrid membrane in
water solution. Both membranes exhibit a pronounced increase
in proton conductivity under thermal activation. [31] The proton
conductivity of RN rises from 0.102 S cm-1 to 0.132 S cm-1 with
the temperature increasing from 25 ºC to 80 ºC in deionized
water.
Accepted Manuscript
Figure 3. Nyquist plots for RN (a) and Nafion-Bi12-3% (b) in water solution and
various temperatures; (c) RH dependence of the conductivity (σ) for RN and
Nafion-Bi12-3% at different relative humidity at 303K; (d) Arrhenius-type plots
of the conductivity of RN and Nafion-Bi12-3% membranes at various
temperatures and in water solution conditions;
In comparison, the Nafion-Bi12-3% hybrid membrane with higher
ion exchange capacity exhibits a much superior proton
conductivity, ranging from 0.125 S cm-1 at 25 ºC to 0.386 S cm-1
at 80 ºC (Figure S22-24), which is better than most reported
hybrid proton-conducting membrane constructed based on
Nafion (Table S6). Note that the proton conductivity of Nafion-
Bi12-3% at 80 ºC is about 3 times higher than that of RN. The
proton conductivity of Nafion-Bi12-5% rises from 0.135 S cm-1 to
0.150 S cm-1 with the temperature increasing from 25 ºC to 80 ºC
in deionized water (Figure S25).
To investigate the proton conductivity stability of the Nafion-
Bi12-3% membrane, we further measured its proton conductivity
at 80 ºC in water solution for 168 h (Figure S26). The proton
conductivity of Nafion-Bi12-3% remained at 0.38~0.39 S cm-1,
suggesting its long-term durability under high humidity, which is
superior to that of the RN membrane (0.11 S cm -1, 80 ºC, 100%
RH). For the Nafion-Bi12-3% membrane, the ion-exchange
groups ({H6Bi12O16} or -SO3H) tend to form continuous
hydrophilic "channels", which facilitates the transports of protons
within the membrane. Generally, protons can be rapidly
transported in the form of hydronium ions (e.g., H 3O+, H5 O2+,
and H9O4 +) within the hydrophilic ionic channels of the hydrated
PEMs or migrate along the hydrogen-bonded water network
formed by the water molecules and proton conductive groups in
PEMs. [32] The proton conductivity is heavily dependent on water
Angewandte Chemie
RESEARCH ARTICLE
content; that is, the decrease in water content can lead to the
contraction and collapse of the pore structure inside the
membrane, and significantly reduce the proton conductivity. We
then turn to investigate the effect of humidity on the proton
conductivity of the membrane. As shown in Figure 3c, the
proton conductivity of both membranes increased significantly
with increasing the relative humidity. Notably, the conductivity of
the Nafion-Bi12-3% hybrid membrane under low humidity (65%
RH, 0.056 S cm-1) is 20% higher than that of the RN membrane
(65% RH, 0.045 S cm-1). This result indicates that the water
content is not the only factor affecting the proton conductivity of
hybrid membranes. The significant increase in proton
conductivity at low relative humidity is mainly attributed to the
presence of the highly condensed ion clusters (-SO3H-H2O, -
SO3H-{H6Bi12O16}, -SO3H-SO3H) within the hybrid membrane,
and the mechanism for the fast transfer of protons in this
environment is identical to that of the ion transmission in high-
density acid. [33] The protons can pass through the well-
developed water-mediated hydrogen-bonded networks via fast
rotation and reorientation by the Grotthuss mechanism. [34] In the
hydrophilic ionic phase of the Nafion-Bi12-3% membrane, the
acid groups (-SO3H-H2 O-{H6Bi12O16}-, -SO3H-{H6Bi12O16}-, -
SO3H-SO3 H,) act as donors and acceptors for proton
transportation. Since protons cannot exist alone in an aqueous
solution, water plays a key role in proton conduction as the
proton carrier, which can form H3O+, H5O2+; and thereby, the
protons can pass through the waterfilled channels via fast
rotation and reorientation by the Grotthuss mechanism. [34b,c]
Protons move in the water channels according to the Grotthuss
mechanism, which can be decomposed into the following two
procedures: i) “hopping” movement, in which a proton hops from
a proton donor (such as, {H6Bi12O16}) to an acceptor (-SO3 H)
along a hydrogen bond (H-bond), and ii) “reorientation”
movement, in which an H-bond is cleaved and the proton
reorients to another proton acceptor. Water molecules reorient
and reorganize their structures in the second hydration shell
through the fluctuation of the H-bond network formed between
several water molecules. For Nafion-Bi12-5% membranes, as
discussed above, the excessive addition of {H 6Bi12O16} clusters
significantly wrecks the intrinsic micro-phase structure of the
Nafion; consequently, the proton conductivity of the membrane
is significantly decreased. Further, the activation energy (Ea)
was measured to explore proton migration barriers. [35] As shown
in Figure 3d, we proposed that the activation energy values (Ea)
for RN and Nafion-Bi12-3% hybrid membranes are ca. 0.21 eV
and 0.19 eV from Arrhenius plots in the temperature range of
25-80 ºC in water solution, respectively.
We thereby summarized the significant improvement in
conductivity of Nafion-Bi12-3% hybrid membranes as follows: (I)
The added {H6Bi12O16} clusters elevate the concentration of
proton carrier in Nafion-Bi12-3% membrane, which weakens the
energy barrier for the proton (adsorption/dissociation) and
thereby increases the hopping probability of protons at these
sites; (II) The hybridization between {H6Bi12O16} clusters and -
SO3H groups enlarges the size of hydrophilic channels in Nafion
membrane and enhances the connectivity of the water channels,
which offers continuous pathways for proton transportation; (III)
The connected hydrogen-bonded networks between oxygen
atoms (surface oxygen atoms or protonated oxygen atoms) on
the {H6Bi12O16} clusters and sulfonate groups enhance the
This article is protected by copyright. All rights reserved.
10.1002/ange.202012079
water-retention capability, which can further arouse the faster
proton transportation.
Molecular Dynamics (MD) Simulation
Molecular Dynamics (MD) simulation can offer an effective
approach to characterize the water clusters and ionic
aggregates by directly analyzing their morphology on the
molecular level. To fundamentally understand the underlining
mechanisms for the above experimental observations, we
perform the MD simulation to explore the structural properties of
{H6Bi12O16}-containing Nafion/water assemblies. The model we
used is constructed based on the previously well-established
Nafion complex MD model. [36] We coarse-grain the sidechains
and backbones of Nafion, water contents and {H6 Bi12O16} as
Accepted Manuscript
spherical beads, and perform the simulation in a cubic box with
3D periodic boundary conditions in the canonical (NVT)
ensemble using Large-scale Atomic/Molecular Massively
Parallel Simulator (LAMMPS). [37] This classic model can be
employed to probe the physicochemical properties of Nafion
complex in a relatively long time and large length scale; please
see the model schematics (Figure S27), model efficacy, and the
detailed information of the MD simulation in the Supporting
Information.
Figure 4a shows the representative simulation snapshots of
RN, Nafion-Bi12 -3%, and Nafion-Bi12 -5%, respectively. For RN,
the hydrophilic domains of water, hydronium ions, and anionic -
SO3H sidechains form random three-dimensional networks,
which are embedded in a matrix of Nafion backbone aggregated
through hydrophobic interactions. The anionic -SO3 H sidechains
locate at the interfaces between the waterfilled channels and the
hydrophobic domains. For the Nafion-Bi12 -x% membranes, the
added deca-valent cationic {H6 Bi12O16} clusters directly enter the
hydrophilic domain. and combine with the anionic -SO3H
sidechains through electrostatic and hydrogen-bonding
interactions. The structure factors of water contents Sw(q) and
backbones of Nafion Sb(q) are displayed in Figures 4b, c, which
illustrate the typical microscopic phase separation between
hydrophilic and hydrophobic components. We find that with
increasing {H6Bi12O16} concentration that corresponds to x = 0%
~x = 5%, the peak position of Sw(q) exhibits an apparent shift
towards q~0 and the peak width exhibits an increase, which
illustrates the formation of larger water clusters and the
enhancement in the size inhomogeneity of the water clusters,
respectively. Accordingly, the peak shift in Sb(q) towards q~0
with increasing x demonstrates the enhanced aggregation and
weakened framework of the Nafion backbone, which explains
the decayed mechanical strength of the assemblies observed in
our experiments, caused by the {H6Bi12O16} addition. More
specifically, we display the number of neighboring water beads
around each sidechain of Nafion (nsw) and the fraction of
sidechains bound by {H6 Bi12O16} clusters (ϕsb) in Figure 4d. With
x increasing from 0% to 5%, nsw decays and ϕsb exhibits an
apparent growth, indicating that the highly charged cationic
{H6Bi12O16} components snatch away the anionic sidechains of
Nafion from the water molecules, causing the water molecules to
attach to the nearby congeners to form larger clusters. We then
calculate the cluster size distribution f(i) for water contents
(where i denotes the number of water beads contained in each
cluster) in Figure 4e. It shows that with increasing ϕsb, the water
components tend to form larger clusters and the size
inhomogeneity of the clusters enhances significantly. To further
elucidate the variations in water morphology, we calculate the
Angewandte Chemie 10.1002/ange.202012079

RESEARCH ARTICLE

percolation probability (Pw) and the prolateness factor (Fprol) of the prolateness factor at x = 3% indicates that the water clusters
water clusters in Figure 4f. The results illustrate that adding exhibit more elongated structures at such an {H6Bi12O16}
more than 3% {H6 Bi12O16} can cause a 100% probability of concentration (than the case of x = 5%).
percolation for water clusters. Meanwhile, the maximum value of

Figure 4. (a) Simulation snapshots of RN, Nafion-Bi12-3%, and Nafion-Bi12-5% assemblies, in which the pink, green, blue and yellow beads represent the
uncharged hydrophobic backbone of Nafion, grafted anionic sidechains of Nafion, water components and {H 6Bi12O16} clusters, respectively. Structure factors of (b)
water contents [Sw(q)] and (c) backbones of Nafion [Sb(q)] with different amounts (x) of added {H6Bi12O16}, in which the dashed lines correspond to the peak
b
positions. (d) Number of neighboring water beads around each sidechain of Nafion (nsw) and fraction of sidechains around {H6Bi12O16} (ϕs ) at different x. (e)
Accepted Manuscript
Cluster size distribution [f(i)] for water clusters composed of i water beads. (f) Percolation probability (Pw) and prolateness factor (Fprol) of water clusters. (g) Radial
distribution functions of sidechains of Nafion [gss(r)].

Through the above simulations, we can conclude that the
addition of deca-valent cationic {H6Bi12O16} weakens the ion
solvation effect of the monovalent anionic -SO3H sidechains by
‘snatching away’ them from water components through strong
electrostatic interactions, which causes the decrease in the
number of -SO3 H serving as the shell of water-filled channels,
and promotes the phase separation between the hydrophilic and
hydrophobic species (Figure 4a-4c). Therefore, compared to the
case of RN, the Nafion-Bi12 -3% assemblies exhibit improved
ionic conductivity due to the reorganized water-filled channels
with better interconnectivity caused by an appropriate dismantle
of partial channel shells (Figure 4f). However, the successive,
7
excessive addition of {H6Bi12O16} (for x = 5%) causes the over-
break of channel shells by grasping a large majority of the
(Figure 4d and 4f) -SO3H sidechains. The consequential
enlarged hydrophilic and hydrophobic domains lose the network
nature, which turns to be unfavorable for ion conduction and
causes the decay in the mechanical strength of the membrane.
Due to the interplay between these effects, there exists a most
optimized intermediate {H6 Bi12O16} concentration (i.e., x ~ 3% in
this work), at which the assembly conserves its mechanical
strength and achieves the percolation of uniform-
sized/elongated water clusters for the best ionic conductivity.

This article is protected by copyright. All rights reserved.

Angewandte Chemie
RESEARCH ARTICLE
In accordance with the above findings, the variations in the
radial distribution functions (RDF) of sidechains [gss(r) shown in
Figure 4g] and water beads around each sidechain [gsw(r)
shown in Figure S27, 28a], water beads around each water
bead [gww(r) shown in Figure S24b], and backbone beads
around each backbone bead [gbb(r) shown in Figure S27c, d]
demonstrate the enrichment of Nafion sidechains around the
{H6Bi12O16} components through electrostatic interactions, the
aggregation of Nafion backbones through hydrophobic
interactions, as well as the transition in structures of water
clusters, caused by the continuous addition of {H6Bi12O16}.
The electronic modification in the hybrid membrane during the
hybridization may affect the proton conductivity of the
membrane, yet in consideration of the strong electrostatic
interactions between the deca-valent cationic {H6 Bi12O16} and
the anionic sidechains of Nafion, we emphasize that the
alternation in the micro-phase structure of the Nafion membrane
caused by the addition of {H6 Bi12O16} could be the main reason
for the improved proton conductivity in Nafion-Bi12 -3%. We
thereby propose that doping an appropriate amount of
polyoxometalate serves as an effective and easy-operating
strategy to fabricate the high-performance hybrid Nafion
membranes.
Methanol permeability, ionic selectivity and Direct methanol
fuel cell performances of hybrid membranes
Low methanol permeability and high ionic conductivity are
both essential properties for the proton exchange membranes
applied in the direct methanol fuel cell. To explore the
performance of the hybrid membranes, methanol permeability of
the membranes was measured at ambient temperature, in 2 M
and 8 M solution, respectively.[38] As shown in Figure S29,
compared with the case of RN, the methanol permeability for
Nafion-Bi12-3% and Nafion Bi12-5% are reduced by nearly 1.5
orders of magnitude and one order of magnitude, respectively.
The introduction of {Bi12} cations can induce the aggregation of
sulfuric acid groups and increase the steric hindrance of
methanol permeation. On the other hand, the formation of strong
hydrogen bonding networks between the {Bi12} cation and
sulfuric groups benefits the lowering of methanol permeability of
the hybrid membrane.
The changes in methanol permeability for Nafion-Bi12-3%
could be attributed to the structural rearrangement of Nafion
polymer chains caused by the {H6 Bi12O16} hybridization, in which
the continuous hydrophilic phase allows the smooth
translocation of the protons and prohibits the penetration of
methanol molecules. We further calculated the ionic selectivity
as the ratio between ionic conductivity (σ) and methanol
permeability (P) to assess the performance of hybrid
membranes, as shown in Figure S29.[39]
Based on the above results, the comprehensive performance
of RN or Nafion-Bi12 -3% hybrid membranes assembled in situ
and applied in direct methanol fuel cells were evaluated by
single-cell tests. Figure 5 reveals that the maximum current
density and power density of RN were 87 mA cm -2 and 53.9 mW
cm-2, respectively. The Nafion-Bi12 -3% exhibit increases of 200%
in maximum power density compared with that of RN. The open-
circuit voltage of Nafion-Bi12-3% is nearly 0.8 V, demonstrating
the acceptable methanol barrier ability.
As a result, Nafion-Bi12-3% attains enhanced fuel cell
performance, with a maximum current density of 432.7 mA cm -2
and a power density of 110.2 mW cm-2, respectively. Notably,
This article is protected by copyright. All rights reserved.
10.1002/ange.202012079
these fuel cell performances and proton conductivities are
superior to most of the current existing Nafion-based
membranes (Table S6), highlighting the advantages of inorganic
fillers-based PEMs.[40] In addition, we also investigate the current
decay of direct methanol fuel cell under constant voltage. Figure
S30 shows the cell current profile during the durability test. At a
constant voltage of 0.35 V, the current gradually decreased from
1.14 A to 1.11 A. This value corresponds to a total current loss of
17 mA in 50 h, indicating an overall current decay rate of 2.46%.
Although the Nafion-Bi12 -5% membrane might show advantages
in ionic exchange capacity and methanol blocking, no stable
open-circuit voltage was observed by the DMFC texts, which is
probably due to the altered non-phases of the membrane
Accepted Manuscript
electrode assembly (MEA) or the brittleness of the membrane
compared to Nafion-Bi12-3%. [41] Excessive addition of the
inorganic additives and enlargement of the additive sizes could
cause the decay of the mechanical stability (Table S6) and a
rougher surface of the membrane, which is unfavorable for the
internal catalyst in the electrodes.
Figure 5．Direct methanol fuel cell performances of RN, Nafion-Bi12-3%
membranes were tested at 80 ºC under fuel cell operating conditions of 1
M methanol solution.
Conclusion
In summary, we have achieved the molecular-level
hybridization of nano-sized metal oxide clusters into the ionic
phase of Nafion, and fabricated the comprehensively high-
performance hybrid membranes. Driven by the electrostatic and
hydrogen-bonding interactions, the added deca-valent cationic
{H6Bi12O16} clusters spontaneously combine with anionic side
chains of Nafion and significantly optimize the
hydrophilic/hydrophobic nano-phases, which engender high
proton conductivity, ideal mechanical and chemical stability, as
well as low methanol permeability of the hybrid membranes.
Specifically, the Nafion-Bi12-3% hybrid membrane showed a
proton conductivity of 386 mS cm−1 at 80 ºC in aqueous solution,
which is 300% times higher than that of Nafion under identical
conditions. Also, it conserves the ideal mechanical stability and
chemical stability as PEMs used in fuel cells. MD simulations
were employed to clarify the microscopic mechanisms for the
experimentally observed variations in proton conductivity and
mechanical stability of the hybrid Nafion assemblies. The
performance of DMFC single-cell assembled using Nafion-Bi12 -
3% as PEMs are comprehensively enhanced and its maximum
Angewandte Chemie
RESEARCH ARTICLE
current density and power density reached 432.7 mA cm-2 and
110.2 mW cm−2, respectively, which were 200% times higher
compared with recast Nafion. The improvement of the overall
performance indicators of fuel cells based on the newly
designed PEMs is anticipated and the relative studies would be
important. We expect that our strategy for fabricating high-
performance PEMs also applies to other polymers and
polyoxometalates with similar molecular natures, which may
open a new chapter for the development of novel materials for
energy devices.
Acknowledgments
The authors gratefully acknowledge the financial support from
the National Natural Science Foundation of China (No.
21871042, 21471028, 21671036 and 22073094), Changbai
Mountain Scholarship, Natural Science Foundation of Jilin
Province (No. 20200201083JC), Natural Science Foundation of
Department of Education of Jilin Province (JJKH20201169KJ)
We acknowledge the supports from the Jilin Provincial
Department of Education, the Computing Center of Jilin
Province, International Research Centre for Nano Handing and
Manufacturing of China, and the Network and Computing Center
of CIAC, CAS. We thank the supports in experimental testing
from Wei Xing and Changpeng Liu at Laboratory of Advanced
Power Sources, Enyi Chi, Haiying Huang and Jidong Zhang at
State Key Laboratory of Polymer Physics and Chemistry,
Changchun Institute of Applied Chemistry, Chinese Academy of
Sciences.
Keywords: Molecular-level hybridization• bismuth oxide clusters
• Nafion • proton exchange membrane • power density
Author Contributions
[†]
Bailing Liu and Bo Hu contribute equally to this article.
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Angewandte Chemie 10.1002/ange.202012079

RESEARCH ARTICLE
Entry for the Table of Contents

Accepted Manuscript
A hybrid membrane (nominated as Nafion-Bi12-3%) used as the high-performance PEM is fabricated through molecular-level doping
of {H6Bi12O16} clusters into ionic phase of Nafion. Driven by the electrostatic and hydrogen-bonding interactions, the added deca-
valent cationic {H6Bi12O16} clusters spontaneously combine with anionic side chains of Nafion and significantly optimize the
hydrophilic/hydrophobic nano-phases, which endow the hybrid membranes with high proton conductivity, ideal mechanical and
chemical stability, as well as low methanol permeability.

10
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