From filter paper to porous carbon composite membrane oxygen reduction catalyst

Article abstract of DOI:10.1039/c4cc03987d

A novel type of porous carbon composite membrane (PCCM) based on the low-cost common filter paper via a simple route is reported. The obtained material exhibited excellent electrocatalytic activities toward the oxygen reduction reaction, high tolerance of methanol crossover, and durability in alkaline solution.

Full text of DOI:10.1039/c4cc03987d

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From filter paper to porous carbon composite
membrane oxygen reduction catalyst†
Wenxiu Yang,ab Yanling Zhai,ab Xiaoyu Yue,ab Yizhe Wangab and Jianbo Jia*ab
Cite this: Chem. Commun., 2014,
50, 11151
Received 25th May 2014,
Accepted 23rd July 2014
DOI: 10.1039/c4cc03987d
www.rsc.org/chemcomm
A novel type of porous carbon composite membrane (PCCM) based
on the low-cost common filter paper via a simple route is reported.
The obtained material exhibited excellent electrocatalytic activities
toward the oxygen reduction reaction, high tolerance of methanol
crossover, and durability in alkaline solution.
To promote the development and wide application of fuel cells, the
study of efficient, cheap, stable, and green non-precious metal
oxygen reduction reaction (ORR) catalysts is a top priority.1–3 Over
the past few years, tremendous efforts have been made toward
developing a variety of carbon composites that possess relatively
good electrocatalytic ORR activity to substitute the precious metal
catalysts such as Pt and Pt-based materials.4–6 In general, in the
quest of developing high efficient carbon composite catalysts,
several reports are available on different routes such as hydro-
thermal processes,7,8 high-temperature pyrolysis,9,10 microwave,11
and chemical vapor deposition.12 Over the past few decades,
the materials, including carbon nanotubes,13 fullerenes,14
graphene,15,16 mesoporous carbon,17,18 carbon black,19 polymers,20
and organic metal frameworks7 have been widely adopted as the
carbon precursor to prepare carbon composites. However, it is a
cockamamie procedure to prepare the special carbon nano-
structures.21,22 Hence, the batch synthesis of well-controlled and
low-cost carbon composite ORR catalysts becomes one of the
biggest challenges at present in the field of preparation of non-
precious metal ORR catalysts. To date, there has been tremendous
interest in exploring a simple method to prepare stable carbon
composites from renewable biomass resources, including soy
milk, wood, bamboo, fruits, kenaf stem, egg white, and bacteria,
for potential applications in supercapacitors, energy storage,
Scheme 1 Illustration of the preparation process of the PCCM.
electroanalytical chemistry, and electrocatalysts.23–27 In this work,
we attempt to prepare a porous carbon composite membrane
(PCCM) for the first time from low-cost common filter paper (FP)
as the carbon precursor. Meanwhile, the resultant PCCM pos-
sesses efficient electrocatalytic activities for the ORR in an alkaline
environment. The Fe-based nanoparticles formed on the compo-
site surface during pyrolysis may further improve the electro-
catalytic ORR activity of the PCCM, and the porous architecture of
this FP-derived composite is beneficial for O2 adsorption and
transport during the ORR process. Illustration of the preparation
of PCCM is presented in Scheme 1. The fabrication processes are
given in the ESI.† For simplicity, the samples were denoted as the
PCCM900-1% based on pyrolysis temperature (900 1C) and the
concentration of Fe(NO3)3 (1.0%), respectively.
For the purpose of comparing the morphological changes of
the PCCM synthesized at different temperatures, we performed
scanning electron microscopy (SEM) analysis. Fig. 1A clearly depicts
the morphology of the PCCM800-1% after annealing at 800 1C; there
are fewer pores or nanoparticles on the composite surface. The
PCCM900-1% displayed in Fig. 1B possesses relatively homogeneous
morphology with uniformly dispersed nanoparticles near or in the
a State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022,
P. R. China
b University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
E-mail: jbjia@ciac.ac.cn; Tel: +86-431-85262251
† Electronic supplementary information (ESI) available: Experimental details,
TEM, SEM, N2 adsorption isotherms, EDAX, and CVs are included. See DOI:
10.1039/c4cc03987d
Fig. 1 SEM images of (A) PCCM800-1%, (B) PCCM900-1%, and (C)
PCCM1000-1%.
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pores; the diameters of the particles range from 30–100 nm. Fe2O3 (16.49 wt%) as the temperature reached 700 1C (Fig. 2C),
However, Fig. 1C shows that the diameter of the nanoparticles which is similar to that of the EDAX result. Fig. 2D describes the
significantly increased and the nanoparticles aggregated for the XRD patterns of the PCCM900-1% and PCCM900-0%. A typical broad
PCCM1000-1% annealed at 1000 1C. Moreover, the surface of the peak at about 2y = 25 corresponds to amorphous carbon substrates.
PCCM1000-1% is no longer smooth or homogeneous. Transmis- Meanwhile, metallic, oxidized, and carbidic iron, such as Fe (JCPDS
sion electron microscopy (TEM) results (Fig. S1, ESI†) of these file: #894186), Fe3O4 (JCPDS file: #892355), and Fe3C (JCPDS file:
materials are consistent with the SEM images. Fig. S2 (ESI†) #893689) were present in the PCCM900-1%. Recent studies have
shows the high-resolution TEM images obtained from the verified that the encased Fe3C activates the surrounding graphitic
PCCM900-1%. The distances of 0.21 and 0.376 nm correspond to layers, making the outer surface of the carbon layer active towards
the (211) and (011) crystal planes of the Fe3C phase, respectively, the ORR.3 Therefore, the as-prepared PCCM with evenly dispersed
and the Fe3C nanoparticles are surrounded by the carbon Fe3C nanoparticles should find application in the ORR.
shells.3,28 Fig. S3 (ESI†) exhibits the effect of Fe(NO3)3 concen-
To explore the effect of the pyrolysis temperature and concen-
tration on the morphology of PCCMs. Because oxidative gases, tration of Fe(NO3)3 on the electrocatalytic ORR activities of the
such as NO2, O2, and NO, will be released when Fe(NO3)3 melts at PCCMs, a series of catalysts prepared under different conditions
high temperatures,29 more pores appeared on the surface of were examined; the results are given in Fig. S6 and S7 (ESI†).
the PCCM900-1% than on the surface of the PCCM900-0%. To Compared with other modified electrodes, the PCCM900-1% mod-
obtain more information regarding the porous structure of the ified glassy carbon electrode (PCCM900-1%/GCE) displays a superior
PCCM900-1%, the N2 adsorption–desorption isotherm was measured, ORR activity, which has a more positive reduction peak potential,
as exhibited in Fig. S4 (ESI†). The BJH desorption average pore width onset potential, and higher reduction current density in O2-
is 5.9 nm and the BET surface area is 297.1 m2 gÀ1
.
saturated 0.10 M KOH. Meanwhile, Fig. S8 (ESI†) shows that the
As presented in Fig. 2A, X-ray photoelectron spectroscopy (XPS) PCCM900-1%/GCE shows the best electron conductivity among the
analysis indicates that PCCM900-1% is mainly composed of C PCCMs produced with different amounts of Fe(NO3)3. This further
(284.6 eV), O (532.5 eV), and Fe (711.5 eV), confirming that Fe proves that the porous morphology and uniformly dispersed Fe3C
was successfully doped into the carbon composite. In detail, the nanoparticles of the PCCM900-1% play an important role for the
spectra of Fe 2p (Fig. 2B) of the PCCM900-1% reveal the distribution ORR. The kinetics of the ORR of the PCCM900-1%/GCE was further
of Fe 2p into two species: Fe 2p3/2 and Fe 2p1/2 observed at 710.5 investigated and compared to the Pt/C/GCE by linear sweeping
and 723.9 eV, respectively, from which we can deduce that iron voltammograms at 1600 rpm using a rotating ring disk electrode
atoms in the catalyst are either in the metallic, oxidized, or carbidic (RRDE) (Fig. 3A). Note that the number of transferred electron (n) is
state.30 Meanwhile, the energy dispersive X-ray analysis (EDAX) calculated from the ring and disk currents, and is observed to be
spectra (shown in Fig. S5D, ESI†) of the as-synthesized PCCM900-1% B3.82–3.97 in the entire potential range investigated (Fig. 3B). As
displayed the peaks corresponding to C (87.5%), O (5.55%), and Fe shown in Fig. 3C, the H2O2 yield of the PCCM900-1%/GCE is below
(6.95%) elements, which is consistent with the result of XPS. 17.3% over the potential range of À0.2 to À0.65 V in O2-saturated
Furthermore, the PCCM900-1% was also characterized by thermo-
gravimetric analysis (TGA); the result demonstrates an iron content
of 11.54 wt% in the PCCM900-1% based on the remaining mass of
Fig. 3 (A) RRDE voltammograms of (a) PCCM900-1%/GCE and (b) Pt/C/
GCE in O2-saturated 0.10 M KOH at a scan rate of 5 mV sÀ1, a rotation rate
of 1600 rpm; the Pt ring electrode is polarized at 0.2 V (vs. Ag/AgCl).
Fig. 2 (A) XPS survey for the resultant PCCM900-1% and (B) high-
resolution Fe 2p spectra. (C) The TGA curve of PCCM900-1% measured
from 25 to 800 1C in air at a heating rate of 10 1C minÀ1. (D) XRD patterns
of the PCCM900-1% and PCCM900-0%.
(B) Electron transfer number (n) and (C) H2O2 yield of (a) PCCM900-1%/
GCE and (b) Pt/C/GCE. (D) Current–time (i–t) chronoamperometric
responses for the ORR on (a) PCCM900-1%/GCE and (b) Pt/C/GCE in
O2-saturated 0.10 M KOH at À0.3 V at a rotation rate of 400 rpm.
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0.10 M KOH, based on the assumption that oxygen reacts by a protective graphitic layers. Therefore, the successful fabrication of
parallel mechanism.31 All these conclusions indicate that the PCCM not only promotes the development of a new porous
obtained PCCM900-1% possesses superior electrocatalytic ORR acti- carbon ORR catalyst, but this procedure is also more amenable
vity and that a four-electron transfer process predominates.
to large-scale syntheses because of the cheap carbon precursor
For the stability test, the PCCM900-1%/GCE and Pt/C/GCE toward and the simple two-step synthetic process.
ORR was examined chronoamperometrically in O2-saturated 0.10 M
We acknowledge financial supports from the National Natural
KOH (at À0.3 V). As indicated in Fig. 3D, the PCCM900-1%/GCE still Science Foundation of China (No. 21305132), and the National
maintained 91.07% of its original activity after 20 000 s, whereas the Basic Research Program of China (No. 2010CB933603).
Pt/C/GCE showed a decrease with a current loss of approximately
30.96%. Moreover, it could be observed that the addition of 1.0 M
methanol to the O2-saturated 0.10 M KOH has almost no influence
on the electrocatalytic ORR activity of PCCM900-1%/GCE (Fig. S9,
ESI†), whereas the Pt/C/GCE showed a pair of peaks corresponding
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