Facile and Large-Scale Fabrication of Sub-3 nm PtNi Nanoparticles Supported on Porous Carbon Sheet: A Bifunctional Material for the Hydrogen Evolution Reaction and Hydrogenation

Article abstract of DOI:10.1002/chem.201900320

Facile and large-scale preparation of materials with uniform distributions of ultrafine particles for catalysis is a challenging task, and it is even more difficult to obtain catalysts that excel in both the hydrogen evolution reaction (HER) and hydrogena

Full text of DOI:10.1002/chem.201900320

A Journal of
Accepted Article
Title: Facile and Large-Scale Fabrication of Porous Carbon Sheet
Supported Sub-3 nm PtNi Nanoparticles: A Bifunctional Material
for HER and Hydrogenation
Authors: Hong-bin Sun, Jifan Li, Lei Liu, Yongjian Ai, Zenan Hu, Liping
Xie, Hongjie Bao, Jiajing Wu, Haimeng Tian, Rongxiu Guo,
Shucheng Ren, Wenjuan Xu, Qionglin Liang, and Gang
Zhang
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To be cited as: Chem. Eur. J. 10.1002/chem.201900320
Link to VoR: http://dx.doi.org/10.1002/chem.201900320
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ARTICLE
Facile and Large-Scale Fabrication of Porous Carbon Sheet
Supported Sub-3 nm PtNi Nanoparticles: A Bifunctional Material
for HER and Hydrogenation
Jifan Li1,2†, Lei Liu1† , Yongjian Ai2, Zenan Hu1, Liping Xie3, Hongjie Bao1, Jiajing Wu1, Haimeng Tian1,
Rongxiu Guo1, Shucheng Ren1, Wenjuan Xu1, Hongbin Sun1,*, Gang Zhang1,* and Qionglin Liang2,*.
Dedication ((optional))
Abstract: Facile and large-scale preparation of materials with uniform
distribution of ultra-fine particles is a challenging work for catalysis,
and it is even more difficult that the catalyst is excellent in both
hydrogen evolution reaction (HER) and hydrogenation, which are
corresponding merge and split procedure of hydrogen, respectively.
Here, we report the fabrication of ultra-fine bimetallic PtNi
nanoparticles embedded in the carbon nanaosheets by means of in-
situ self-polymerization and annealing. It is a bifunctional catalyst
possessing excellent performance in HER and hydrogenation of p-
Nitrophenol. Remarkably, the low-loading PtNi bimetallic catalyst
(PtNi2@CNS-600, 0.074 wt% Pt) exhibited outstanding HER activity
with an overpotential as low as 68 mV at a current density of 10 mA
cm−2 when platinum loading was only 0.612 μg Pt/cm2 and Tafel slope
of 35.27 mV decade−1 in a 0.5 M H2SO4 aqueous solution, which is
comparable to those values for the 20% Pt/C catalyst (31 mV
decade−1). Meanwhile, it also shows the more excellent long-term
electrochemical durability for at least 30 h with negligible degradation
than 20% Pt/C. In addition, the material with increased loading
(mPtNi2@CNS-600, 2.88% Pt) displayed robust catalytic activity for
hydrogenation of p-Nitrophenol in ambient pressure and temperature.
The serious energy crisis and environmental issues caused by the
consumption of fossil fuels have prompted numerous efforts to
explore sustainable energy source,[1] such as solar energy, wind
power, electro/photochemical water splitting, etc.[2] Hydrogen, a
zero emission energy source and the most promising durable
energy carrier, has been deemed as a perfect substitute to the
traditional fossil fuel-based energy on account of its high
gravimetric energy density, carbon footprints and environmental-
friendly properties.[3] Differ from the water gas shift reaction that
consumes carbon resource, the electro production of hydrogen
concern, and it is primarily produced by chloro-alkali industry or
water splitting.[4] The hydrogen evolution reaction (HER), as an
important half-reaction involved in electrochemical water
electrolysis process,[5] has been emerging as a promising
approach for hydrogen production among various routes of
hydrogen supply owing to its low cost, high efficiency and
environment benign.[6] It is generally accepted that the catalytic
mechanism of HER in acid media includes the Volmer reaction
(H3O+ e− →Had + OH−), the Heyrovsky reaction (H+ + Had + e−
→H2) and the Tafel reaction (2Had → H2).[7] However, hydrogen
evolution reaction (HER) is thermodynamically impeditive for the
hydrogen binding energy.[8] Therefore, academic researchers
have been trying to explore the efficient and sustainable HER
catalysts,[9] which is designed and prepared to reduce
overpotential () value and increase the reaction rate for more
economical utilization of energy in the sustainable hydrogen
generation.[10]
The catalytic activity towards the split of hydrogen give
a
circumstantial evidence that agrees the path of Volmer-Tafel reaction
in HER in turn.
Introduction
To date, platinum (Pt) and Pt-based materials,[11] exhibiting the
high-performance (activity and durability) as the‘Holy Grail’of
HER electro-catalysts, are considered the most efficient HER
catalysts with a near-zero overpotential in acid solution, a small
Tafel slope and excellent long-term stability. However, their
widespread implementation are hindered greatly by their scarcity
and high cost.[12] Recent trends in nanomaterial catalysts have
proposed the use of bimetallic NPs, which comprise two distinct
metal atoms in various configurations.[13] The bimetallic alloy NPs
can provide more potent electrocatalytic activity and superior
stability than their monometallic counterparts owing to the
synergistic effects that arise from the interaction of two distinct
metals,[14] as well as allow one to minimize the use of expensive
noble metals.[15] Thus the incorporation of functional non-noble 3d
transition metals (TMs) (e.g., Co, Fe, Ni, Cu, etc.) is an effective
strategy to improve the elcctrocatalytic activity.[16] At present, Pt-
based binary alloys: PtNi-Ni,[17] PtNi,[18] PtNi nanocage,[19]
PtCo,[20] Pt3Co,[21] PtPd,[22] and ternary alloys: Pt-Ni-Co,[23] CNTs-
PdAu/Pt,[24] Pt-Cu-Ni,[25] Pt-Ni-Cu[26] have been widely designed
[a]
[b]
J Li, Dr. L Liu , Dr. Z Hu, H Bao, J Wu, H Tian, R Guo, S Ren, W Xu,
Prof.Hb Sun and Prof.G Zhang
Department of Chemistry
Northeastern University
Shenyang 110819, People’s Republic of China
E-mail: sunhb@mail.neu.edu.cn; gangzhang99@126.com
Dr. Y Ai, Prof.Ql Liang
Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical
Biology (Ministry of Education), Department of Chemistry, Center for
Synthetic and Systems Biologsy
Tsinghua University
Beijing 100084, People’s Republic of China
E-mail: liangql@mail.tsinghua.edu.cn
Prof. Liping Xie
School of Sino-Dutch Biomedical and Information Engineering,
Northeastern University,
[c]
Shenyang 110169, People’s Republic of China
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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by academics for electrochemistry research. Those
electrocatalysts have wonderful HER performance, such as: low
overpotential, small Tafel plot and long-time stability, etc. Among
such efficient catalysts, the 3-D transition metal-Ni is commonly
utilized and especially prominent due to its low price, high
abundance, good corrosion resistance and excellent electrical
TGA measurement is conducted to study the thermal
decomposition behavior of the precursor: PtNi2@3DP, which is
shown in Figure 1. The characteristic thermal response of
precursor shows three obvious mass loss processes: (I) the
removal of the surface adsorbed and internal water molecule
takes place from room temperature to 100 °C (20% weight loss),
conductivity. This results are cheering, however, in the meanwhile, (II) the loss of some small organic molecules, combined water and
most of them are not satisfactory as a result of the complex
processes for catalyst preparation, extremely low yield and lavish
most oxygen-containing functional groups occurs in the range
from 210 °C to 500 °C with a sharp decrease starting from 245 °C,
and (III) the decomposition of the precursor arise from 500 °C to
1000 °C. Therefore, we decide to adopt a calcined temperature
ranges from 400 °C to 800 °C to prepare carbon-based catalysts.
loading of Pt. Therefore, designing
a highly active HER
electrocatalyst with environment-friendlies, facile and large-scale
preparation as well as low cost is desperately desired but still
remains a key challenge.
Following these demands and basing on our interest in advanced
material,[11c, 27] we designed a catalyst with the ultrafine sub-3 nm
PtNi bimetallic nanoparticles embedded on porous carbon
materials and ultralow Pt content (0.074 wt%) confirmed by ICP-
MS via in situ polymerization and annealing in Ar, which modified
the previously reported procedures.[28] As expected, ultralow
noble Pt content, easiness and high production of catalyst
preparation, the low overpotential and excellent stability of HER
were combined in our material. It is worth mentioning that the
material with increasing Pt loading (2.88 wt%) also presented
robust catalytic activity for hydrogenation of p-Nitrophenol in
ambient pressure and temperature, which evidences the path of
Volmer-Tafel reaction in HER in turn.
Results and Discussion
The synthesis route of the electrocatalyst involves mainly four
steps as shown in Scheme 1. A certain amount of Hacac,
Pt(acac)2 and Ni(acac)2 were polymerized and subsequently
converted to PtNix@3DP nanocomposites under normal
temperature and alkaline conditions. Hereafter, the polymer was
carbonized in the tube furnace with Ar atmosphere. The
mechanism of the reaction are systematically descript in the
Scheme S1 and Scheme S2. In the process of synthesizing the
precursor, a C-C bond is formed by simple Aldol condensation
and the small molecules are uniformly connected into a carbon
framework in the presence of NaOH. The carbon anion
intermediate first formed from Hacac immediately attacked the
nearby carbonyl carbon atoms of Hacac, Pt(acac)2 and Ni(acac)2,
which contribute to continuous dehydration of the monomer and
cross-linking. Finally, Pt and Ni nanaoparticals are uniformly
supported on the carbon skeleton in the carbonization process.
Figure 1. TGA curve of the PtNi2@3DP.
The morphology and microstructure of PtNi2@CNS-600
nanocatalyst are described by scanning electron microscopy
(SEM), HAADF-STEM and HRTEM measurements. The SEM
images (Figure 2a–c) of PtNi2@CNS-600 indicate that the
structure of this composite is flaky.
Figure 2. SEM images of PtNi2@CNS-600.
The deeper understanding for catalyst structure is realized via
HAADF-STEM (Figure 3a-c) and HRTEM (Figure 3d-e)
characterization. As in Figure 3a-c, the microscopic appearance
of PtNi2@CNS-600 is composed of extremely thin carbon sheets
and ultra-small nanoparticles, which is in line with SEM results.
From the Figure 3c, we can conclude that the ultra-fine PtNi
bimetal alloy nanoparticals with the average size of 3 nm exist in
this material. Besides, we can observe that massive porous
structure in the carbon substrate, which can further improve
electrocatalytic performance via increasing the quantity of active
sites and accelerating the transfer of mass.[29] Figure 3d highlights
a typical PtNi alloy nanoparticle with crystal lattice of 0.215 nm,
Scheme 1. Schematic representation for the preparation process of
PtNix@CNS-600 electrocatalyst.
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which is between single metal Pt (111) of 0.2256 nm and single
metal Ni (111) of 0.2034 nm, indicating the formation of alloy.[30]
Besides, the selective area electron diffraction (SAED) pattern
inserted in Figure 3d shows the crystal lattice of 0.2123 nm, which
is almost identical to the above result, the crystal lattice of 0.1832
nm, which is between single metal Pt (200) of 0.1962 nm and
single metal Ni (200) of 0.1762 nm, and the crystal lattice of
0.1114 nm, which is between single metal Pt (311) of 0.1183 nm
and single metal Ni (311) of 0.1062 nm (Pt PDF#04-0802, Ni
PDF#04-0850), suggesting the polycrystalline characteristic of
the prepared PtNi2@CNS-600. In addition, the element mapping
in Figure 3e point out that the ultrafine PtNi alloy nanoparticles
are uniformly distributed in the nanosheets. Combined with the
lattice fringe, SAED and EDS results, we consider that Pt and Ni
existed as alloy in the electrocatalyst.
PtNi2@CNS-600. The survey XP spectrum (Figure 4a) confirms
that the existent elements of catalyst contained platinum, nickel,
carbon and oxygen. The two main binding energies of 71.4 eV
and 74.9 eV corresponds to Pt 4f7/2 and 4f5/2 of metallic state
(Figure 4b). The chemical states of Ni and C were also presented
in Fig 4(c-d). As shown in Figure 4c, the BEs at 852.1 eV and
869.2 eV were attributed to Ni 2p3/2 and Ni 2p1/2, confirming the
presence of Ni0. However, the 855.1 eV XPS peaks of Ni in Figure
4c illustrates that the some component of Ni was probably in the
way of the oxidized state in the surface.[31] Figure 4d, the carbon
spectrum embodies C1s (284.8 eV) and COOR (289.2 eV). The
negative shift occurred for Ni 2p3/2(~0.5 eV) and the positive shift
appeared for Pt 4f7/2(~0.4 eV) compared with their benchmark
values, which indicates the electron transfer process and alloy
formation.
Figure 5. (a) X-ray diffraction pattern, (b) Raman spectra of PtNi2@CNS-600
nanocatalyst
The XRD pattern of the PtNi2@CNS-600 catalyst shows three
main peaks in Figure 5a, which are assigned to the typical (111),
(200) and (220) facets of the face centered cubic phase of the
PtNi alloy. That indicates the high crystallinity of the as-synthetic
PtNi2@CNS-600. Additionally, the structural information about the
carbon substrate of the acquired material is obtained by Raman
spectroscopic measurement. Apparently, the Raman spectra of
the catalyst in Fig 5b presents two characteristic absorption bands,
which were assigned to D band (∼1345 cm−1) and G band (∼1595
cm−1) respectively. The D band is attributed to the existence of
substantial defects or structural disorder in the composite,[32]
whereas the G band refers to the ordered graphitic structure,[33]
which is associated with the (002) diffraction peak of the XRD
pattern. ID/ IG, the ratio of the D peak intensity to the G peak
intensity,[34] is usually employed as an indicator for evaluating the
graphitization degree of the synthesized carbon materials. From
the Raman spectra, the calculated ID/IG ratio for PtNi2@CNS-600
catalyst is as high as 0.8577, which combines with a broad D peak
and a sharp G peak suggests the strong electronic conduction
and corrosion resistance contributed by the interaction between
Pt, Ni and carbon during carbonization process. This result was
in accordance with the above discussions on EDS and HRTEM
data, suggesting that PtNi2@CNS-600 catalyst has a high degree
of graphitization and considerable conductivity.
Figure 3. (a-c) HAADF-STEM, (d) HRTEM images and (e) EDS mapping of
PtNi2@CNS-600. The corresponding SAED pattern is inserted in Figure 3d
The N2 adsorption-desorption isotherms of PtNi2@CNS-600 and
CNS-600 (Figure 6) can be divided into IV-type with a H3
hysteresis loop according to IUPAC’s classification, which are
attributed to the crevice formed by the accumulation of
nanosheets. The pore distribution curve of PtNi2@CNS-600 in
Figure 4. XPS spectra of PtNi2@CNS-600. (a) Survey, (b) Pt 4f, (c) Ni 2p and
(d) C 1s
The X-ray photoelectron spectroscopy (XPS) was further
conducted to analyze the surface chemical composition of the
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Figure 6a indicates that the existence of micro pores, confirmed
by the apparently vertical rise of quantity adsorbed at the relative
low pressure of p/p0 < 0.05. The specific surface area from the
adsorption isotherms of PtNi2@CNS-600 was calculated to be
99.65 m2 g-1, which were lower than that of CNS-600 (118.14 m2
g-1) as shown in Figure 6b. For this phenomenon, we consider
that the alloy particles may block a part of the pores. Thus, with
high surface area and pore volume, the electrocatalyst will be
favorable for the accessibility of electrolyte and provide more
tunnels as well as sufficient active sites for hydrogen evolution.[35]
activity was optimal. The accurate composition of Pt and Ni in
PtNi2@CNS-600 catalyst verified by the inductively coupled
plasma mass spectrometry (ICP-MS) analysis are only 0.074%
and 0.043%, which are closely to theoretical value of 0.068% and
0.038%, indicating that there is no lossing of active metal in the
preparation process. Besides, the accurate composition of Pt and
Ni in PtNi1@CNS-600, PtNi1.5@CNS-600, PtNi3@CNS-600 and
mPtNi2@CNS-600 catalyst verified by the ICP-MS analysis are
0.069% and 0.019%, 0.072% and 0.030%, 0.070% and 0.057%,
2.88% and 1.57% ,which are closely to theoretical value of
0.068% and 0.019%, 0.068% and 0.028%, 0.067% and 0.056%,
2.72% and 1.52% respectively.The high overpotentials of
Pt@CNS-600 (348 mV) and Ni@CNS-600 (816 mV) were caused
by the ultralow single metal content and less active sites. The
more excellent HER activity of bimetallic catalyst than single-
metals’ could be attributed to the synergistic effect of the addition
of a non-noble metal Ni into the noble metal Pt, namely the
enhanced charge transfer efficiency as well as modified electronic
structure, and both of which can reduce the energy barrier and
accelerates the reaction kinetics.[37] In order to research the
dominant reaction mechanism in the HER process, the Tafel plots,
as another fundamental criterion, were obtained from the Linear
scan curve (LSV). In general, the catalytic mechanism of HER
including the Volmer reaction, the Heyrovsky reaction and the
Tafel reaction, and the Tafel slope are 120 mV dec−1, 40 mV dec−1
and 30 mV dec−1, respectively.[38] As shown in Fig 7b, the
outstanding electrocatalytic activity of PtNi2@CNS-600 and
mPtNi2@CNS-600 electrocatalyst could also be confirmed by a
small Tafel slope of 35.27 mV dec−1 and 29.00 mV dec−1 , which
Figure 6. N2 adsorption-desorption isotherms of (a) PtNi2@CNS-600, (b) CNS-
600. The inset is their corresponding pore size distribution.
was close to the Tafel slope of commercial 20% Pt/C (31 mV dec-
1 [36]
)
but much lower than the PtNi1@CNS-600(60.19 mV dec-1),
PtNi1.5@CNS-600 (45.06 mV dec-1), PtNi3@CNS-600 (47.71 mV
dec-1), Pt@CNS-600 (72.25 mV dec-1), Ni@CNS-600 (146.82 mV
dec-1) and CNS-600 (158.90 mV dec-1), respectively. The
comparisons with other representative Pt-based HER
electrocatalysts recently reported were shown in Table S1,
suggesting that the PtNi2@CNS-600 electrocatalyst with lowest
Pt content (0.074 wt%) had smaller overpotential and Tafel plot.
The exceedingly small Tafel plot of PtNi2@CNS-600 shows that
HER is possibly controlled by Volmer-Tafel mechanism, where
recombination of absorbed H is the rate-limiting step[39], implying
more favorable kinetics and faster reaction rate, which is highly
corresponding to the above results and proved by Nyquist plot.
The Nyquist plots of the control samples with iR correction were
researched at 0.238 V (vs. RHE) (Figure S1). Similarly, the
comparison of impedance value show the same trend as the
result of Tafel slop: the smaller Tafel slope and impedance indicat
smaller kinetic hindrance and faster electron transfer, making the
reaction kinetics more favorable and the reaction rate faster.
Figure 7. (a) HER polarization curves of PtNi1@CNS-600, PtNi2@CNS-600,
PtNi3@CNS-600, PtNi1.5@CNS-600, mPtNi2@CNS-600, Pt@CNS-600,
Ni@CNS-600 and CNS-600, carbonized under Ar, acquired with 5 mVs-1 in N2-
saturated 0.5 M H2SO4 at 25 °C.
In order to investigate the electrocatalytic performances of
PtNi2@CNS-600, HER experiment of the as-prepared samples
were conducted in 0.5 M H2SO4 solution (Figure 7a-c). As
expected, the polarization curves in Figure 7a show that the
overpotential of PtNi2@CNS-600 was only 68 mV at the current
density of 10 mA·cm−2 comparable to 20% Pt/C (40 mV),[36] which
is much lower than that of PtNi1@CNS-600 (113 mV),
PtNi1.5@CNS-600 (95 mV), PtNi3@CNS-600 (115 mV) and other
Pt-based HER electrocatalysts (Table S1). The results indicated
that when the proportion of Pt to Ni reach to 2, the electrocatalytic
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overpotential.[41] In addition to the catalytic activity, another
significant criterion for evaluating a HER catalyst is the long-term
stability and durability in practical applications. In order to assess
the stability of PtNi2@CNS-600 catalyst in 0.5 M H2SO4 solution,
long-term cyclic voltammetry (CV) cycles was carried out between
-0.1 and 0.1 V (vs RHE) at a scan rate of 100 mV s−1. As shown
in Figure 9a, the linear scanning voltammetry (LSV) curves
showed negligible shift after 2,000 cycles, exhibiting the
outstanding stability of PtNi2@CNS-600 catalyst in acidic media.
Subsequently, the chronoamperometric experiment was also
conducted to evaluate the long-term durability of PtNi2@CNS-600
catalyst at a constant potential in 0.5 M H2SO4, as shown in Figure
9b. The i-t curve showed that the current density maintained 10
mA cm-2 and almost unchanged during 30 h test, displaying the
more robust stability of the PtNi2@CNS-600 catalyst than 20%
Pt/C[42] , which was in good agreement with the above results.
The number of active sites was measured via electrochemical
active surface area (ECSA),[43] which could be calculated from the
double-layer capacitance (Cdl) corresponding to the catalytic
surfaces by means of the following equation.[44]
dl (mF cm2 )
1.7mF cm2 per cm2ECSA
Figure 8. (a) HER polarization curves (b) Tafel plots in 0.5 M H2SO4 for the
PtNi2@3DP annealed at different temperature under Ar atmosphere.(c) Data
histogram obtained from (a) and (b) for convenient comparison.
C
ECSA 
From the Figure 8a-c, we can observe that the HER activity of the
electrocatalysts along with the carbonization temperature showed
the Volcanic type. The most excellent HER activity was achieved
for the sample annealed under 600 °C, which could presumably
be attributed to the balance of electrical conductivity, active site
and porosity.[40] The activity of the electrocatalyst enhanced with
the increase of annealing temperature below 600 °C, and reduced
with the increase of annealing temperature above 600 °C. The
trend in overpotential were as the following: PtNi2@CNS-600 (68
mV) < PtNi2@CNS-700 (297 mV) < PtNi2@CNS-800 (423 mV) <
PtNi2@CNS-500 (512 mV) < PtNi2@CNS-400 (867 mV) in Figure
8a. This phenomenon was analyzed as follows: the degree of
charring was insufficient and the metals were not completely
reduced at lower temperatures, however, when the temperature
was too high, the alloy might be aggregated, which can also be
proved by Figure S1 (Nyquist plots). Therefore, the optimum HER
activity was obtained when keep the annealing temperature at
600 °C and the molar ratio of Pt to Ni was 2, as shown in Figure
7 and 8.
The excellent electrocatalytic performance of PtNi2@CNS-600
was attributed to ultra-fine sub-3 nm PtNi nanoparticles
embedded in porous carbon sheet, which provides a large surface
area for electrochemical reactions. As we can observe, the
appearance of the Cdl presented a regular rectangle, which is the
nature of carbon (Figure 10a-c). The value of Cdl of PtNi2@CNS-
600 (4.16 mF cm−2) was bigger than those of Pt@CNS-600 (0.49
mF cm−2) and Ni@CNS-600 (0.34 mF cm−2) shown in Figure 10d,
suggesting the more active sites on the surface owing to the
synergism of bimetal. The Cdl of PtNi1@CNS-600 (1.38 mF cm−2),
PtNi1.5@CNS-600 (1.41 mF cm−2), PtNi2@CNS-600(4.16 mF
cm−2), and PtNi3@CNS-600(1.34 mF cm−2) were represented in
Figure S2, which also proved that the proportion of Pt to Ni was 2
can achieve the optimum HER activity with the ultralow Pt loading.
Therefore, such high Cdl suggests that PtNi2@CNS-600 exhibited
more exposed surface reactive sites and potential site than
others,[38] which contributes to excellent HER electrocatalytic
performance.
Figure 9. (a) Durability test for PtNi2@CNS-600 in 0.5 M H2SO4 before and after
2000 cycle (b) The current-time curve of PtNi2@CNS-600 for 30 h.
The exploitation of high-performance electrocatalysts are critical
for efficient and economical production of hydrogen from water,
which is designed to drive fast HER reaction with lower
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the product increased sharply, and the yield of p-Aminophenol is
> 99% after 5.5 h of monitor.
This reaction did not only prove that the mPtNi2@CNS-600 had
excellent catalytic activity, but also confirmed that H2 could be
dissociated to Had (Hydrogen adsorption) under the presence of
catalyst, which would further reduce the nitro compound to an
amino compound. This was the first proof to reveal that the
electrocatalyst underwent a chemical desorption to generate Had
through the Volmer-Tafel pathway in the process of electrolyzing
water by adopting such a method.
Conclusions
In conclusion, we have successfully developed a facile approach
to synthesize the sub-3 nm PtNi bimetallic embedded on porous
carbon nanosheet in large-scale, which as a bifunctional catalyst
precede in HER and hydrogenation. The PtNi bimetallic material
with ultra-low Pt content (0.074 wt%), which was verified by ICP-
MS, possesses high number of exposed active sites and superior
intrinsic activities for HER. Remarkably, the electrocatalyst
exhibited excellent HER activity with an overpotential as low as
68 mV at a current density of 10 mA cm−2 and extremely small
Tafel slope of 35.27 mV decade−1 in 0.5 M H2SO4 aqueous
solution, which is comparable to those values for the 20% Pt/C
catalyst (31 mV decade−1). It is worth noting that the PtNi
bimetallic alloy shows splendid long-term electrochemical stability
and durability for 2000 CVs and at least 30 h with negligible
degradation. Last but not the least, the mPtNi bimetallic catalyst
(2.88% Pt) also displayed the catalytic activity for hydrogenation
of p-Nitrophenol in ambient pressure and temperature, which was
employed to prove the Volmer-Tafel path in HER for the first time,
by the way, the electrocatalyst has robust catalytic hydrogenation
activity. The excellent bifunction and the low content of noble
metals render the material a good prospect for practical
application.
Figure 10. The CV curves at different scan rates of (a) PtNi2@CNS-600, (b)
Pt@CNS-600, (c) Ni@CNS-600. (d) Cdl values of the nanocatalysts.
Reduction of p-Nitrophenol:
Experimental Section
Figure 11. a) Reaction equation for the reduction of p-Nitrophenol to p-
Aminophenol. b) The reactive extent tests with time of mPtNi2@CNS-600
nanaocatalyst for the hydrogenation of p-Nitrophenol.
Synthesis of the precursors PtNi2@3DP (3D Polymer)
We prepared the high content PtNi electrocatalyst (named as
mPtNi2@CNS-600) following the same procedure except that the
additive amount of Ni(acac)2 and Pt(acac)2 were 266.4 mg and
200 mg respectively. The microscopic appearance of
mPtNi2@CNS-600 is showed in Figure S3. As shown in Figure
11a, 1 mmol of p-Nitrophenol, 40 mg of catalyst were add to 3 mL
of isopropanol in a 25 mL round bottom flask. The reaction
proceeded under normal pressure hydrogen without heating.
Evidently, the color of the reaction solution changed from yellow
to colorless and transparent after 5.5 h, illustrating that the
hydrogenation of p-Nitrophenol was completed. The completion
of reaction was also verified by HPLC. The plot of p-Nitrophenol
conversion with time is shown in Figure 11b. With the reaction
proceeded, the reactant concentration descended rapidly while
First and the foremost, 66.6 mg Ni(acac)2 and 50 mg Pt(acac)2 were
completely dissolved in 40 mL Hacac under the ultrasonic condition, 16 g
NaOH was then added rapidly under vigorous magnetic stirring. After
stirred for 50 min, the compound was converted to a pastry, then put at
room temperature without further treatment to grow up with a long chain.
After 6 days, the blends turned into a dry, granular and fluffy polymeric
compound. The PtNi1@3DP, PtNi1.5@3DP and PtNi3@3DP were
synthesized via similar procedures for the PtNi2@3DP but with 33.3, 50
and 97.8 mg Ni(acac)2 in the first step, respectively. The 3DP was
synthesized with the same procedures as PtNi2@3DP, except for the
adding Pt(acac)2 and Ni(acac)2.
Synthesis of the PtNi2@CNS
The as-prepared polymer precursor of PtNi2@3DP sample were annealed
at various temperatures (400 °C、500 °C、600 °C、700 °C、800 °C) and
held at the setting temperature for 3 h with a heating rate of 2 °C min-1
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10.1002/chem.201900320
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ARTICLE
under Ar atmosphere to obtain the ultimate carbon-supported bimetal
catalyst: bimetallic PtNi2 carbon nanosheets (PtNi2@CNS-400, 500, 600
or others). After cooling to room temperature, the products were washed
with ethanol and deionized water until pH=7. Ultimately, the
nanocomposites were filtrated under reduced pressure and dried at 120 °C
overnight. 3DP, PtNi1@3DP，PtNi1.5@3DP, PtNi3@3DP were also dealt
with the same procedures as PtNi2@3DP to obtain CNS, PtNi1@CNS,
PtNi1.5@CNS, PtNi3@CNS, respectively.
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Electrochemical study
The electrochemical measurement was conducted at room temperature
(25 ± 1 °C) with a standard three-electrode system controlled by a
CHI660E Electrochemical Workstation (Shanghai CH Instrument, China).
A modified glassy carbon electrode (GCE, 3 mm in diameter) using Pt-
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mg) with 40 L of 5 wt% Nafion solution (Alfa Aesar) , 500 L of ethanol
and 460 L of deionized water, following by a strong ultrasonic treatment
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electrode. Hence the loadings of Pt on the electrode were about 0.612 μg
cm-2 for PtNi2@CNS-600. The catalyst layer was allowed to dry under
ambient conditions before an electrochemical measurement. All the
polarization curves were iR-corrected as well as the presented potentials
in our work were converted to a commonly used reversible hydrogen
electrode (ERHE) with Nernst equation using 0.5 M H2SO4 as the electrolyte
solution. The conversion formula for the SCE reference electrodes as
follows: ERHE = E (SCE) + 0.2412 + 0.0594 * pH. For the HER test, the
Linear scanning curves were measured between 0 V and -0.6 V (vs. RHE)
at a scan rate of 5 mV s-1 in a 0.5 mol L−1 H2SO4 aqueous solution. The
Tafel plot is assigned to the equation η = b log (j) + a (where η is the
overpotential, b represents the Tafel slope, and j refers to the current
density). The double-layer capacitance (Cdl) was determined by cyclic
voltammetry in the voltage ranged between –0.1 and 0.1 V vs. RHE and
the i–t curves were measured at a constant potential of 0.3 V (vs. RHE).
EIS was conducted by SP-150, Bio-Logic SAS.
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This work was financially supported by the National Natural
Science Foundation of China (Nos. 21872020, 81872835,
81501556 and 21621003), the Ministry of Science and
Technology (Nos.2017YFC0906902 and 2017ZX09301032),
Macau Science and Technology Development Fund
(129/2017/A3 and 089/2013/A3). The China Scholarship Council
(No. 201806085012) is also acknowledged.
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DECLARATION OF INTERESTS
The authors declare no competing interests.
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Keywords: Ultra-fine bimetallic PtNi nanoparticles • Ultra-low Pt
content • Excellent HER and hydrogenation performance •
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Entry for the Table of Contents (Please choose one layout)
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ARTICLE
A facile method of fabricating carbon
nanosheet supported sub-3nm
bimetallic PtNi nanoparticles in large-
scale was developed.
Jifan Li1,2†, Lei Liu1† , Yongjian Ai2,
Zenan Hu1, Liping Xie3, Hongjie Bao1,
Jiajing Wu1, Haimeng Tian1, Rongxiu
Guo1, Shucheng Ren1, Wenjuan Xu1,
Hongbin Sun1,*, Gang Zhang1,* and
Qionglin Liang2,*.
This bifunctional material preceded in
both hydrogen split and combination.
Page No. – Page No.
Ultra-low content of Pt (0.074 wt%)
based electrocatalyst with excellent
HER activity was obtained.
Facile and Large-Scale Fabrication of
Porous Carbon Sheet Supported Sub-
3 nm PtNi Nanoparticles: A
Bifunctional Material for HER and
Hydrogenation
Excellent stability, durability and low
power consumption were confirmed.
Layout 2:
ARTICLE
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
Text for Table of Contents
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