Engineering the Coordination Environment of Single-Atom Platinum Anchored on Graphdiyne for Optimizing Electrocatalytic Hydrogen Evolution

Article abstract of DOI:10.1002/anie.201804817

Two Pt single-atom catalysts (SACs) of Pt-GDY1 and Pt-GDY2 were prepared on graphdiyne (GDY)supports. The isolated Pt atoms are dispersed on GDY through the coordination interactions between Pt atoms and alkynyl C atoms in GDY, with the formation of five-

Full text of DOI:10.1002/anie.201804817

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Accepted Article
Title: Engineering the Coordination Environment of Single-Atom
Pt Anchored on Graphdiyne for Optimizing Electrocatalytic
Hydrogen Evolution
Authors: Xue-Peng Yin, Hong-Juan Wang, Shang-Feng Tang, Xiu-Li
Lu, Miao Shu, Rui Si, and Tong-Bu Lu
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Angewandte Chemie International Edition
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COMMUNICATION
Engineering the Coordination Environment of Single-Atom Pt
Anchored on Graphdiyne for Optimizing Electrocatalytic
Hydrogen Evolution
+
+
Xue-Peng Yin , Hong-Juan Wang , Shang-Feng Tang, Xiu-Li Lu*, Miao Shu, Rui Si* and Tong-Bu Lu*
Abstract: Platinum-based heterogeneous catalysts are widely used
in many important catalytic reactions, and it is highly desirable to
reduce its usage for decreasing the cost of catalysts. Herein, we
report a facile method for the preparation of two Pt single-atom
catalysts (SACs) of Pt-GDY1 and Pt-GDY2 on the support of
graphdiyne (GDY), in which the isolated Pt atoms are dispersed on
GDY through the coordination interactions between Pt atoms and
isolated Pt atoms anchored on the surfaces of FeO
g-C and graphene indeed exhibit much higher catalytic
activity and much lower usage of noble Pt than the traditional Pt-
x 2
, MoS , TiN,
3
N
4
[9-13]
based catalysts, such as Pt/C.
More recently, Pt SACs with
individual Pt atoms anchored on the supports of carbon
nanotube and CoP have also been developed as efficient HER
[14,15]
electrocatalysts.
alkynyl C atoms in GDY, with the formation of five-coordinated C
1
-
For SACs, the coordination environments of metal atoms will
greatly influence their electronic structures, and subsequently
Pt-Cl species in Pt-GDY1 and four-coordinated C -Pt-Cl species in
4
2
2
[16]
Pt-GDY2. Importantly, Pt-GDY2 shows exceptionally high catalytic
activity for hydrogen evolution reaction (HER), with a mass activity
up to 3.3 and 26.9 times more active than Pt-GDY1 and the state-of-
the-art commercial Pt/C catalysts, respectively. Experimental results
and theoretical calculations demonstrate that Pt-GDY2 possesses
higher total unoccupied density of states of Pt 5d orbital and close to
affect their catalytic activity.
For example, Zhang et al. found
species in Fe SACs displays the highest catalytic
activity for selective oxidation of the C-H bond, which is one
III
that Fe N
5
III
order magnitude more active than Fe N
6
species and three
Wu and coworkers
II
[17]
times more active than Fe N
constructed
coordination numbers, and they found that atomically dispersed
4
species.
a
series of Co SACs with different nitrogen
zero value of Gibbs free energy of the hydrogen adsorption (|
Pt
∆
G
H*|) at the Pt active sites, which are responsible for its excellent
Co with two coordinate nitrogen atoms displays the best CO
2
[
18]
catalytic performance. This work can help us to better understand
the ‘structure-catalytic activity’ relationship in Pt SACs, which is
regarded as the most challenge in the investigations on
heterogeneous catalysts.
electroreduction
catalytic
performance.
Though
the
coordination environments of metal atoms are closely related to
their catalytic activity in SACs, there is rare investigation for the
influence of Pt atoms coordination environments on their
catalytic activity of HER in Pt SACs. To better understand the
structure-activity relationship between the ‘coordination
environment’ of Pt atoms and the corresponding HER catalytic
activity in Pt SACs, it is imperative to disperse the individual Pt
Hydrogen evolution reaction (HER) through electrocatalytic
water splitting is considered as a promising approach for the
production of clean hydrogen, which has been regarded as one
atoms on
a stable support with adjustable coordination
[
1-3]
of the most potential energy carriers in the future.
Among the
environments.
developed electrocatalysts, Pt-based catalysts are the most
Herein, we originally put forward a simple method for the
synthesis of two Pt SACs on the support of graphdiyne (GDY).
As a new man-made carbon allotrope, GDY possesses of
uniform 18 C-hexagonal pores formed by three butadiyne
[
4-6]
effective electrocatalysts for HER.
However, the scarcity and
high cost of noble metal Pt limit their large-scale applications.
Notably, the platinum utilization in traditional Pt-based catalysts
is very low, as the active sites only come from Pt atoms on the
surface of the catalysts. Therefore, great efforts have been
devoted to increase the platinum utilization as well as to improve
linkages (-CC-CC-) between the benzene rings (see Figure
[19-21]
1),
which can provide ideal anchoring sites for single Pt
atoms with high stability, as demonstrated by the results of
[
7,8]
the HER activity of Pt-based catalysts.
Compared with
[22a]
theoretical calculations.
More recently, zero valence Ni and
traditional Pt-based catalysts, Pt single-atom catalysts (SACs)
have great advantage with utmost utilization of Pt atoms, which
can dramatically reduce the usage of noble metal Pt and
decrease the cost of catalysts. It has been shown that the
Fe single atoms anchored on the pores of GDY for hydrogen
[22b]
evolution has been reported.
of GDY, we constructed two Pt SACs simply by the reaction of
GDY with K PtCl aqueous solution at 273 K for 8 h (named as
Based on the unique structure
2
4
Pt-GDY1), and subsequently annealing in Ar atmosphere at 473
K for 1 h (named as Pt-GDY2). The results of atomic resolution
high-angle annular dark-field scanning transmission electron
microscopy (HAADF-STEM) images and X-ray absorption fine
structure (XAFS) spectra in R space, as well as the first-
principles calculations verify that the isolated Pt atoms are
anchored on the surface of GDY by the coordination interactions
of Pt with the alkynyl C atoms in GDY, forming a five-
+
+
[*]
X. P. Yin , Dr. H. J. Wang , Dr. X. L. Lu, S. F. Tang, Prof. T. B. Lu
Institute for New Energy Materials & Low Carbon Technologies,
School of Materials Science and Engineering, Tianjin University of
Technology, Tianjin 300384, China
E-mail: luxiuli@email.tjut.edu.cn; lutongbu@tjut.edu.cn
M. Shu, Prof. R. Si
Shanghai Synchrotron Radiation Facility, Shanghai Institute of
Applied Physics, Chinese Academy of Sciences, Shanghai
1 4 2 2
coordinated C -Pt-Cl species and a four-coordinated C -Pt-Cl
2
01204, China
species in Pt-GDY1 and Pt-GDY2, respectively. Interestingly, Pt-
GDY2 shows much higher HER catalytic activity than Pt-GDY1
and commercial Pt/C, with a mass activity up to 3.3 times and
E-mail: sirui@sinap.ac.cn
+
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end
of the document.
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Angewandte Chemie International Edition
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COMMUNICATION
2
6.9 times more active than Pt-GDY1 and Pt/C catalysts,
GDY2 display isolated bright dots, which can be attributable to
the heavy Pt atoms. Furthermore, the elemental mapping
images for Pt-GDY2 reveal the homogeneous spatial
distributions of carbon, platinum and chlorine on GDY (Figure
respectively. The higher HER catalytic activity of Pt-GDY2
originates from its higher total unoccupied density of states of Pt
Pt
5d orbital and close to zero |∆G H*| value.
2c). The energy dispersive spectroscopy (EDS) measurement
(
Figure 2d) confirms the presence of C, Pt and Cl elements in
Pt-GDY2 (other elements derived from Cu grid). The above
results demonstrate that abundant single Pt atoms are
successfully dispersed on GDY support in Pt-GDY1 and Pt-
GDY2. In addition, the Pt loading in both Pt-GDY1 and Pt-GDY2
were measured using inductively coupled plasma-atomic
emission spectroscopy (ICP-AES), with a Pt loading of 4.65
2

g/cm for both Pt-GDY1 and Pt-GDY2, indicating the Pt atoms
anchored on GDY are not lost during the annealing process.
Figure 1. Schematic illustration for the synthesis of Pt-GDY1 and Pt-GDY2.
Atomically dispersed Pt species were anchored on GDY by a
wet-chemical route as shown in Figure 1. Firstly, graphdiyne
was synthesized and grown on the titanium foils by a modified
Hay–Glaser coupling reaction using hexaethynylbenzene as a
[23]
precursor.
The sp-hybridized alkynyl carbon atoms in the 18
C-hexagonal pores in GDY provide ideal anchoring sites for
immobilizing the isolated Pt atoms into the GDY framework. In
the wet-chemical approach, K PtCl was used as a precursor
2 4
and reacted with GDY at 273 K for 8 hours to generate the Pt-
GDY1 sample. The Pt-GDY2 sample was obtained by annealing
Pt-GDY1 at 473 K under Ar atmosphere for 1 h. Notably, Pt-
GDY1 and Pt-GDY2 maintain the morphology of GDY with no
obvious Pt clusters formed, as shown in the SEM and TEM
images in Figure S1. In addition, the XRD patterns for Pt-GDY1
and Pt-GDY2 also demonstrate that no Pt nanoparticles formed
in two Pt SACs (Figure S2).
Figure 3. (a) Raman spectra of GDY, Pt-GDY1 and Pt-GDY2. (b) High-
resolution core level spectra of Pt 4f for Pt-GDY1, Pt-GDY2 and K
2 4
PtCl . (c) Pt
L
3
-edge XANES spectra of Pt-GDY1, Pt-GDY2 and Pt foil. The inset is the
3
3 3
enlarged spectra at Pt L -edge. (d) Pt L -edge k -weighted FT-EXAFS spectra
of Pt-GDY1, Pt-GDY2 and Pt foil (the EXAFS intensity of Pt foil is shown in
half).
The compositions of Pt-GDY1 and Pt-GDY2 were investigated
by Raman spectroscopy and X-ray photoelectron spectroscopy
(
XPS). As shown in Figure 3a, the Raman spectrum of as-
synthesized GDY shows distinct four peaks at 1384.2, 1572.9,
-
1
1
926.4 and 2181.4 cm , respectively, which is consistent with
[
24]
the reported values in the literature,
384.2 cm is due to the breathing vibration of sp carbon
domains in aromatic rings (D band), the peak at 1572.9 cm
in which the peak at
−
1
2
1
−1
corresponds to the first-order scattering of the E2g mode for in-
2
phase stretching vibration of sp carbon domains in aromatic
-1
rings (G band), and the peaks at 1926.4 and 2181.4 cm can be
attributed to the vibration of conjugated diyne linkers. After the
formation of Pt-GDY1 and Pt-GDY2, their G bands have a
hypsochromic shift compared to that of GDY, and the intensities
belonging to the conjugated diyne linkers become weaker
(
Figure 3a), indicating the formation of coordination bonds
Figure 2. Atomic-resolution HAADF-STEM images for Pt-GDY1 (a) and Pt-
GDY2 (b). (c) Elemental mapping for Pt-GDY2. (d) The EDS for Pt-GDY2.
between the single Pt species and the carbon atoms of
conjugated diyne linkers in GDY.
[25]
The valence states of isolated Pt atoms in Pt-GDY1 and Pt-
GDY2 were investigated by XPS. As shown in Figure 3b, the
high-resolution core level spectra of Pt 4f in Pt-GDY1, Pt-GDY2
The abundant isolated Pt atoms on GDY support can be
verified by the HADDF-STEM images. As shown in Figures 2a
and 2b, the HADDF-STEM images for both Pt-GDY1 and Pt-
2 4
and K PtCl display 4f7/2 and 4f5/2 doublets due to the spin-orbital
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COMMUNICATION
splitting. The Pt 4f7/2 and 4f5/2 of K
2
PtCl
4
locate at 73.0 and 76.3
As shown in Figure S7, the ∆Eads is -0.183 eV for Pt-GDY1 and -
2
+
2-
eV, respectively, which are consistent with the values of Pt as
1.142 eV for Pt-GDY2, indicating both the reactions of [PtCl
and PtCl
favorable, and Pt-GDY2 is more stable than Pt-GDY1.
4
]
[
26]
reported in the literatures. While the peaks of Pt 4f7/2 and 4f5/2
in Pt-GDY1 and Pt-GDY2 shift to lower binding energy relative to
2
species with the alkynyl carbons of GDY are thermal
those of K
2 4
PtCl , indicating the electron transfers from the
alkynyl C atoms in GDY to Pt atoms after the formation of Pt-
[
27]
GDY1 and Pt-GDY2. Furthermore, the Pt 4f7/2 and 4f5/2 peaks
at 72.8 and 76.0 eV in Pt-GDY2 are slightly larger than the
corresponding values of 72.6 and 75.8 eV in Pt-GDY1, indicating
the Pt atoms in Pt-GDY2 have a higher valence state than those
in Pt-GDY1. The above results further demonstrate the
formation of coordination bonds between the Pt atoms and the
conjugated alkynyl C atoms of GDY in Pt-GDY1 and Pt-GDY2,
and the Pt atoms in Pt-GDY2 possess of more positive valence
state than those in Pt-GDY1.
To further investigate the electronic structure and coordination
environments of single Pt atoms in Pt-GDY1 and Pt-GDY2, the
Pt L -edge X-ray absorption near edge structure (XANES) and
3
extended X-ray fine structure (EXAFS) were studied. As shown
in Figure 3c, the XANES spectra of Pt-GDY1 and Pt-GDY2 are
much different from that of Pt foil, as the Pt atoms in Pt-GDY1
[
28]
and Pt-GDY2 are individually dispersed on GDY. Furthermore,
the L -edge white-line (WL) intensities increase in a order of Pt
Figure 4. (a) The polarization curves for Pt-GDY1, Pt-GDY2 and commercial
Pt/C in 0.5 M H SO solution, with a scan rate of 5 mV/s. (b) The HER mass
3
2
4
foil < Pt-GDY1 < Pt-GDY2 (inset in Figure 3c). The increase in
the WL intensity means a decrease in the number of electrons in
activity at η = -0.1 V for Pt/C, Pt-GDY1 and Pt-GDY2. (c) Tafel plots of Pt/C,
Pt-GDY1 and Pt-GDY2 for HER. (d) Durability measurements for Pt-GDY2
SAC. The polarization curves of Pt-GDY2 at initial and after 1000 cycles with a
scan rate of 5 mV/s (Inset: the time-dependent current density curve at -95 mV
vs RHE for 10000 s).
[13]
the d orbital. To further understand the unoccupied density of
states of Pt 5d orbital, quantitative WL intensity of Pt-GDY2, Pt-
[
29]
GDY1 and Pt foil were conducted by the reported methods.
As shown in Figure S3 and Table S1, Pt-GDY2 has the highest
total unoccupied density states of Pt 5d character, while metal Pt
has the lowest. As is well known, the vacant d-orbitals of the
isolated atoms play an important role during the catalytic
process, and are responsible for the outstanding catalytic activity
To understand the effect of coordination environments of Pt in
SACs on their HER catalytic activity, we investigated the
electrocatalytic performance of Pt-GDY1 and Pt-GDY2 in 0.5 M
2 4
H SO solution with a three-electrode setup. In the meanwhile,
commercial Pt/C catalyst was used to evaluate the HER catalytic
activity of Pt-GDY1 and Pt-GDY2. As shown in Figure S8a, Pt-
GDY2 shows much better HER catalytic activity than Pt-GDY1
and commercial Pt/C catalyst at an overpotential larger than -
[
13]
of SACs.
3
The Fourier transformations (FT) of k -weighted for EXAFS
oscillations for Pt-GDY1, Pt-GDY2 and Pt foil are shown in
Figure 3d. The Pt foil exhibits a strong peak at ca. 2.8 Å, which
is ascribed to the Pt-Pt bond. In the FT-EXAFS of Pt-GDY1 and
Pt-GDY2, only the peaks in the distances of 1.9~2.3 Å were
observed, while no Pt-Pt contribution was found, further
confirming that Pt has been atomically dispersed on the surface
of GDY in Pt-GDY1 and Pt-GDY2 from macroscopic view, being
consistent with the observations of HADDF-STEM images in
microdomain. The two peaks at ca. 1.9 and 2.3 Å in the FT-
EXAFS curves for Pt-GDY1 and Pt-GDY2 are associated with
Pt-C and Pt-Cl bonds, respectively, and the corresponding
intensities of Pt-C and Pt-Cl in R-space for Pt-GDY1 and Pt-
GDY2 are given in Figure S4. To obtain the coordination
environment around Pt, the FT-EXAFS curves of Pt-GDY1 and
Pt-GDY2 were fitted in R space. The fitting results indicate that
the Pt atoms anchored on GDY by coordinating with one carbon
and four chlorine atoms in Pt-GDY1, and two carbon and two
chlorine atoms in Pt-GDY2 (Table S2). The fitting curves accord
well with the experimental curves in R and k space, respectively
0.05 V. To rationally compare the catalytic performance, their
HER catalytic activity was normalized to the ‘current/Pt loading
mass’ (A/mg). As shown in Figure 4a, the polarization curves for
Pt-GDY1, Pt-GDY2 and commercial Pt/C were recorded from
linear sweep voltammetry (LSV) measurements, with a scan rate
of 5 mV/s at room temperature. Notably, Pt-GDY2 displays
much higher HER catalytic activity than Pt-GDY1 and
commercial Pt/C catalysts. As shown in Figure 4b, the mass
activities for Pt-GDY2, Pt-GDY1 and Pt/C at an overpotential of
100 mV are 23.64, 7.26 and 0.88 A/mg, respectively, in which
Pt-GDY2 shows 26.9 and 3.3 times more active than Pt/C and
Pt-GDY1 catalysts, respectively. Moreover, Pt-GDY2 catalyst
achieved a Tafel slope of 46.6 mV/dec, much smaller than those
of Pt-GDY1 (52.0 mV/dec) and Pt/C (127.5 mV/dec), as
exhibited in Figure 4c.
The long-term CV cycling test and time-dependent current
density curve were tested to examine the stability of Pt-GDY2
catalyst. The polarization curve of Pt-GDY2 after 1000 cycles
maintains similar as the initial curve (Figure 4d). The time-
dependent current density curve at -95 mV for 10000 s also
confirms the superior stability of Pt-GDY2 (inset in Figure 4d).
The platinum contents in Pt-GDY2 before and after HER test are
(
Figures S5 and S6), demonstrating the accurate simulation for
the coordination environments of Pt atoms in Pt-GDY1 (C -Pt-
Cl ) and Pt-GDY2 (C -Pt-Cl ). Furthermore, the adsorption
1
4
2
2
energy (∆Eads) of these two kinds of isolated Pt species on the
surface of GDY was calculated by the first-principles calculations.
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Angewandte Chemie International Edition
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COMMUNICATION
almost the same (Table S3), indicating no Pt atoms lost during
the catalytic process. In addition, the results of atomic-resolution
HAADF-STEM image (Figure S9), XANES and FT-EXAFS
spectra (Figure S10) measurements for Pt-GDY2 after the HER
test indicate the Pt atoms still keep individual dispersion as
those in pristine Pt-GDY2, suggesting its excellent stability. To
eliminate the effect from the Pt counter electrode, graphite rod
was also used to instead of Pt wire as the counter electrode for
HER test. As shown in Figures S8d and S8e, the polarization
curves and the time-dependent current density curves for Pt-
GDY2 by using the graphite rod as the counter electrode are the
similar to those of Pt-GDY2 by using the Pt wire as the counter
electrode. The above results suggest that Pt SACs dispersed on
GDY can efficiently enhance the Pt utilization as well as the
catalytic activity for HER, compared with Pt nanoparticles
counterpart of commercial Pt/C. And the Pt atoms in Pt-GDY2
excellent HER activity. Though Pt-GDY1 has a large negative
∆G H* value of -0.653 eV, it still has a higher mass activity than
Pt
commercial Pt/C due to its utmost Pt utilization. Overall, the
Pt
appropriate |∆G H*| value and higher unoccupied 5d densities of
states of Pt atoms in Pt-GDY2 are responsible for its optimal
HER catalytic activity.
In conclusion, a facile method was reported for the synthesis
of two Pt SACs of Pt-GDY1 and Pt-GDY2 with different Pt
coordination environments. It has shown that the coordination
environments of Pt atoms in Pt SACs greatly affect their HER
catalytic activity, in which Pt-GDY2 SAC with four coordinated Pt
2 2
atoms of C -Pt-Cl shows the highest HER catalytic performance.
The outstanding HER catalytic activity of Pt-GDY2 originates
Pt
from its near to zero |∆G H*| value of 0.092 eV on four-
coordinated Pt atom, as well as its higher unoccupied density of
states of Pt 5d orbital. Our results demonstrate that GDY may
serve as an ideal support for the design and synthesis of other
stable noble metal SACs due to its unique structure, in which the
isolated noble metal such as Pt can be easily anchored on the
surface of GDY by the strong coordination interactions of noble
metal with the alkynyl C atoms in GDY. In the next step, we will
try to construct other noble metal SACs using GDY as a support,
and investigate their unique catalytic properties.
with a C
HER catalytic activity than the Pt atoms in Pt-GDY1 with a C
Cl coordination environment.
2
-Pt-Cl
2
coordination environment show much higher
1
-Pt-
4
Acknowledgements
This work was supported by National Key R&D Program of
China (2017YFA0700104) and the NSFC (21790052 , 21331007
and 21773288).
Figure 5. (a) The configuration of Pt-GDY2 with hydrogen adsorbed on. (b)
The calculated Gibbs free energy diagram for hydrogen evolution on different
catalysts.
Keywords: graphdiyne, Pt single-atom catalyst, coordination
environment, electrocatalyst, hydrogen evolution
To better understand the origin of the enhanced HER catalytic
activity of Pt-GDY2, the Gibbs free energy for hydrogen
adsorption (∆GH*
) on GDY, Pt-GDY1 and Pt-GDY2 were
[
[
1] T. E. Mallouk, Nat. Chem. 2013, 5, 362-363.
calculated (Figures 5 and S11). As is well known, ∆GH* is an
important descriptor for the HER catalytic activity of different
catalysts, which is usually proposed to have an optimal value
being close to zero.
GDY (0.801 eV) is too positive, implying that H cannot be
efficiently adsorbed on the surface of GDY, and its HER catalytic
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Qiao, J. Am. Chem. Soc. 2016, 138, 16174-16181.
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[
30,31]
On the one hand, the ∆GH* for pure
Pt
activity is impeded. On the other hand, the ∆G H* for Pt-GDY1 (-
0.653 eV) is too negative, indicating the adsorption of H on the
[
4] H. Yin, S. Zhao, K. Zhao, A. Muqsit, H. Tang, L. Chang, H. Zhao, Y. Gao,
Pt active site in Pt-GDY1 is too strong, which is also unfavorable
Z. Tang, Nat. Commun. 2015, 6, 6430.
Pt
for HER process. For Pt-GDY2, the ∆G H* is 0.092 eV, which is
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Commun. 2013, 4, 1444.
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[32]
close to that on the surface of Pt metal (∆G H* ≈ -0.09 eV)
,
[
6] R. Subbaraman, D. Tripkovic, D. Strmcnik, K.-C. Chang, M. Uchimura, A.
indicating its excellent HER catalytic activity originates from its
optimal ∆G H* value for the adsorption of H on the individual Pt
active site anchored on GDY with a C -Pt-Cl coordination
2 2
Pt
P. Paulikas, V. Stamenkovic, N. M. Markovic, Science 2011, 334, 1256-
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[
13]
hydride formation,
as Pt 5d orbital could interact with the 1s
orbital of H atom, benefiting to transfer electrons to H atom. The
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an order of Pt metal < Pt-GDY1 < Pt-GDY2, as obtained from
the results of XANES analysis (Table S2). This brings about the
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Angewandte Chemie International Edition
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COMMUNICATION
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1
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201804817
COMMUNICATION
COMMUNICATION
+
+
Xue-Peng Yin , Hong-Juan Wang ,
Miao Shu, Rui Si, Xiu-Li Lu*, Shang-
Feng Tang & Tong-Bu Lu*
Two Pt
single-atom
catalysts
anchored on the support of
graphdiyne with tuned coordination
environments were developed, and
their ‘structure-catalytic performance’
relationship for hydrogen evolution
were investigated.
Engineering the Coordination
Environment of Single-Atom Pt
Anchored on Graphdiyne for
Optimizing Electrocatalytic
Hydrogen Evolution
This article is protected by copyright. All rights reserved.