Journal of Materials Chemistry A
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The gas phase products were analyzed by using an online gas This work was supported by the National Key Basic Research
DOI: 10.1039/C7TA03005C
chromatograph (GC, Fuel Cell GC-2014ATF, Shimadzu) and Development (973) Program of China (2013CB632300) and
equipped with a thermal conductivity detector (TCD) and a Natural Science Foundation of Ningbo (No. 2015A610241 and
methanizer assisted flame ionization detector (FID). The liquid- 2016A610109).
products were identified by a nuclear magnetic resonance
(NMR) spectrometer. 2,2,3,3-d(4)-3-(trimethylsilyl)propionic
acid sodium salt (TSP) was used as the internal standard, and
Notes and references
the 0.6 mM TSP standard solution was prepared in D2O. The
sample for H NMR was prepared by depositing 500 µl of the
1
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1
2
3
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KHCO3 solution after electrolysis in NMR tube followed by
adding 100 µl of STP standard solution.
The Faradaic efficiency (FE) of gas phase products at each
applied potential was calculated based on the equation as
follows:32,52
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4
5
6
Where
gas product (
(1.01 × 105 Pa), F is Faraday constant (96500 C mol−1),
gas flow rate (5.67×10−7 m3 s−1),
is the volume concentration
is the number of electrons transferred per mole of
is 2 for CO and H2, z is 8 for CH4), is pressure
is the
5
, 4470.
T. Palaniselvam, M. O. Valappil, R. Illathvalappil and S.
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7
8
9
7
of gas product determined by GC,
is the temperature
is the
W. Ding, L. Li, K. Xiong, Y. Wang, W. Li, Y. Nie, S. Chen, X. Qi
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Angew. Chem. Int. Ed., 2015, 54, 9230-9234.
(298.15 K), and
is the gas constant (8.314 J mol−1 K−1).
current at each applied potential. The partial current density
for CO is determined by calculating the total current density
multiplied by FE of CO.
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,
In summary, we have developed a new self-constructing
protocol to fabricate 3D N,P,Co-doped MPCs frameworks via a
self-growth-templating approach. It is worthy highlighted that
the self-formation and removal of the mesoporous templates,
and in situ incorporation of the N,P,Co functionalities are
achieved simultaneously in an enclosed space-assisted
pyrolysis process. Benefiting from the N,P,Co-induced dopants
as the highly active centers, mesoporous architecture to
increase sites density and to promote mass delivery, and high
surface area to enhance sites exposure, MPCs can serve as the
bifunctional electrocatalysts for the oxygen and CO2 reduction.
The optimized MPCs exhibit the outstandingly intrinsic
activities for the ORR with a positive E1/2 of 0.85 V, a high JK of
51 mA cm−2 at −0.71 V and a low Tafel slope of 53 mV dec−1, as
well as for the CO2RR in terms of a low overpotential of −0.19
V, a maximum FE of 62% for CO and a small Tafel slope of 129
mV dec−1, along with high stability for both reactions. The
palmary performance renders MPCs frameworks promising
electrocatalysts systems in fuel cells and CO2 conversion
technologies. More importantly, the self-growth-templating
concept proposed here represents a major breakthrough in
the development of heteroatoms-functionalized MPCs to gain
the enhanced electrochemical performance, which is also
believed to potentially bring an innovation on the
methodology for synthesizing other mesoporous materials
beyond carbon for the broad applications.
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Acknowledgements
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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