ARTICLE

DOI: 10.1038/s41467-017-01259-z OPEN

Bottom-up precise synthesis of stable platinum

dimers on graphene
Huan Yan1, Yue Lin2, Hong Wu1, Wenhua Zhang3, Zhihu Sun4, Hao Cheng4, Wei Liu4, Chunlei Wang1, Junjie Li1,
Xiaohui Huang1, Tao Yao 4, Jinlong Yang1,2, Shiqiang Wei4 & Junling Lu 1,2,3,5

Supported metal clusters containing only a few atoms are of great interest. Progress has been
made in synthesis of metal single-atom catalysts. However, precise synthesis of metal dimers
on high-surface area support remains a grand challenge. Here, we show that Pt2 dimers can
be fabricated with a bottom–up approach on graphene using atomic layer deposition, through
proper nucleation sites creation, Pt1 single-atom deposition and attaching a secondary Pt
atom selectively on the preliminary one. Scanning transmission electron microscopy, x-ray
absorption spectroscopy, and theoretical calculations suggest that the Pt2 dimers are likely in
the oxidized form of Pt2Ox. In hydrolytic dehydrogenation of ammonia borane, Pt2
dimers exhibit a high specific rate of 2800 molH2 molPt−1 min−1 at room temperature, ~17- and
45-fold higher than graphene supported Pt single atoms and nanoparticles, respectively.
These findings open an avenue to bottom–up fabrication of supported atomically precise
ultrafine metal clusters for practical applications.

1 Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China. 2 Hefei National Laboratory for Physical

Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China. 3 CAS Key Laboratory of Materials for Energy
Conversion, University of Science and Technology of China, Hefei, Anhui 230026, China. 4 National Synchrotron Radiation Laboratory, University of Science
and Technology of China, Hefei, Anhui 230029, China. 5 Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science
and Technology of China, Hefei 230026, China. Huan Yan and Yue Lin contributed equally to this work. Correspondence and requests for materials should
be addressed to S.W. (email: [email protected]) or to J.L. (email: [email protected])

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z

S
upported metal catalysts are among the most important anchor sites atom-by-atom in a sequential manner using Pt ALD.
categories of heterogeneous catalysts in many reactions The dominant presence of isolated Pt1 single atoms and Pt2
including chemical upgrading, automobile exhaust treat- dimers in the corresponding samples were confirmed by both
ment, Fischer-Tropsch synthesis, biomass conversions, and many aberration-corrected high-angle annular dark-field scanning
other processes1–7. Decreasing metal particle size is desirable for transmission electron microscopy (HAADF-STEM) and X-ray
improving metal utilization, since catalytic reactions take place on absorption fine structure spectroscopy (XAFS). Their structures
the surface of metal nanoparticles (NPs). When a metal cluster were determined through a combination of density function
contains only a few metal atoms, it could have a discrete energy theory (DFT) calculations and XAFS spectra simulations. In
band structure, tightly correlated with the number of metal hydrolysis of ammonia borane (AB) for hydrogen generation,
atoms. Changing one atom in the ultrafine cluster might largely graphene supported Pt2 dimers (Pt2/graphene) exhibited a strik-
alter the electronic structure and drastically change its catalytic ing activity, which is ~17- and 45-fold higher than that of gra-
properties. Such atom-dependent catalytic behaviors have been phene supported Pt1 single atoms and Pt NPs, respectively.
successfully demonstrated by the model catalysts of mass-selected Compared to Pt1 single atoms and Pt NPs, the decreased
metal clusters, which were fabricated by soft landing of mass- adsorption energies of both AB and H2 molecules on Pt2 dimers
selected ions from their physical vapor under ultrahigh vacuum are likely the major reason for the high activity. More impor-
conditions8–14. However, such complicated approach is only tantly, the Pt2 dimers were stable under the current reaction
limited to model catalyst studies and is not applicable to high- condition and in the inert environment at below 300 °C.
surface area supports for practical applications.
Recently, synthesis of supported metal single-atom catalysts
(SACs) has been extensively explored and a number of successful Results
examples have been demonstrated15–23. Nonetheless, synthesis of Synthesis and morphology of Pt1/graphene and Pt2/graphene.
atomically precise ultrafine metal clusters, such as dimers, on Based on our recent strategy22, the nucleation sites of isolated
high-surface area supports, remains a grand challenge. The phenols or phenol–carbonyl pairs suggested by Shenoyl et al40.
decisive limitation is the lack of precise control over the aggre- for Pt ALD were first created on pristine graphene nanosheets
gation process, which often causes metal NPs formation with a through acid oxidation followed by high-temperature thermal
broad size distribution. Protecting metal clusters with a strong reduction, as illustrated in the schematic model in Fig. 1. The
ligand can certainly inhibit metal aggregation to a large extent, such reduced graphene oxide support was defect-rich multilayered
as in the case of thiolate-protected Au magic clusters24. However, graphene films with a thickness of about a few nanometers
these strong protective ligands typically poison the metal clusters, (Supplementary Fig. 1). It had a surface area of 570 m2/g. Next, Pt
and decrease their catalytic activities considerably25–30. Alter- ALD was performed on the graphene support by alternately
natively, Gates et al. demonstrated that precisely defined iridium exposing trimethyl(methylcyclopentadienyl)-platinum(IV)
and rhodium clusters were achieved by grafting the corresponding (MeCpPtMe3) and molecular O2 at 250 °C. The self-limiting
carbonyl complexes with a specific number of metal atoms onto surface reactions between MeCpPtMe3 and the support ensure
oxide supports31–33. But the success is limited. As a consequence, a nucleation of one MeCpPtMe3 molecule on one phenol-related
general bottom–up approach to synthesize atomically precise metal nucleation site during the saturated MeCpPtMe3 exposure
clusters on high-surface area supports is still missing. Atomic layer (Supplementary Fig. 2). It should be noted that Pt nucleation on
deposition (ALD) relies on two sequential self-limiting surface graphene defect sites, such as edges and line defects, was inhibited
reactions at the molecular level, which are separated by inert gas at 250 °C, although it is possible at 300 °C (Supplementary
purging34–36. This unique character makes ALD possible to Table 1)41. A similar temperature effect on inhibiting metal ALD
bottom–up construct catalytic materials on a high-surface area on oxides was also observed by Elam et al42. Next, the ligands
substrate uniformly and precisely37–39. were removed through a combustion reaction during the O2
Here, we show that Pt2 dimers can be bottom–up fabricated on exposure step43–45 and Pt1 single atoms are formed (denoted as
a graphene support by depositing Pt on phenol-related oxygen Pt1/graphene).

MeCpPtMe3

Controlled nucleation Self-limiting

sites creation Pt ALD

Graphene 1st cycle

O2

O3
Self-limiting
Pt ALD
2nd cycle
Pt dimers Pt single atoms

Fig. 1 Schematic illustration of bottom–up synthesis of dimeric Pt2/graphene catalysts. Controlled creation of isolated anchor sites on pristine graphene;
one cycle of Pt ALD on the anchor sites for Pt single atoms formation by alternately exposing MeCpPtMe3 and molecular O2 at 250 °C; second cycle of Pt
ALD on the Pt1/Graphene to selectively deposit the secondary Pt atoms on the preliminary ones for Pt2 dimers formation at 150 °C. The balls in cyan,
white, red, and blue represent carbon, hydrogen, oxygen, and platinum while the ball in gray represents carbon atoms in the graphene support

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NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z ARTICLE

Next, the formed Pt1 single atoms was further utilized as ALD reactor quickly to perform the second cycle (Pt-MeCpPtMe/
nucleation sites for anchoring the secondary MeCpPtMe3 graphene) at 150 °C. In nine independent trials, the ICP-AES
molecule in the following cycle. Again, the steric hindrance results showed that the ratio of the Pt loadings of Pt-MeCpPtMe/
between MeCpPtMe3 molecules restricts chemisorbing one graphene to those of the corresponding MeCpPtMe/graphene
MeCpPtMe3 molecule only on one isolated Pt1 atom. However, were all very close to one (Fig. 2h). Therefore, there was no
we noticed that a considerable amount of Pt NPs were additional Pt deposited on MeCpPtMe/Graphene, reflecting the
formed after two successive cycles of Pt ALD at 250 °C (denoted saturated self-limiting reaction character of ALD34–36. Second, we
as 2cPt/graphene, Supplementary Fig. 3). Therefore, the deposi- found that exposure of pristine graphene to O2 at 250 °C did not
tion temperature was decreased to 150 °C for the second ALD cause any detectable Pt deposition either (Supplementary Table 1).
cycle to avoid any metal aggregation. Meanwhile, ozone (O3), a This is very important to ensure that the oxygen pulse at 250 °C
stronger oxidizing regent was utilized to remove the ligand in the first ALD cycle did not create any additional nucleation
efficiently to form Pt2 dimers (Pt2/graphene) (Fig. 1)46. sites. Taken together, the Pt1 single atoms formed on graphene,
The formed Pt1 single atoms and Pt2 dimers are expected to be confirmed by HAADF-STEM in Fig. 2a–c, are the only nucleation
in the oxidized forms, since they were exposed to O2 and O3 sites for the following ALD cycle. It is worthy to note that Pt1
during synthesis, respectively. single atoms well isolated from each other could be crucial to
Aberration-corrected HAADF-STEM measurements were car- make all the Pt1 single atoms accessible for chemisorbing the
ried out to investigate the morphologies of the single-atom second MeCpPtMe3 molecule in the second ALD cycle without
Pt1/graphene and dimeric Pt2/graphene catalysts. Compared to steric hindrance.
the naked graphene (Supplementary Fig. 1), HAADF-STEM During the second ALD cycle, one MeCpPtMe3 molecule
images illustrated that one cycle of Pt ALD on the graphene anchors on one Pt1 atom in the Pt1/graphene sample due to the
support at 250 °C resulted in a formation of atomically dispersed steric hindrance effect, which doubles the Pt loading.
Pt1 atoms without presence of any visible clusters or NPs This was confirmed by the ratios of two for the Pt loadings of
(Fig. 2a–c, and Supplementary Fig. 4). These Pt1 single atoms Pt2/Graphene to Pt1/graphene in nine independent trials (Fig. 2i
were well isolated from each other with a distance >2 nm in and Supplementary Table 2), hence providing strong evidence of
average, which is significantly larger than the effective diameter of the formation of Pt2 dimers. The Pt1 single atoms observed in
the MeCpPtMe3 molecule of ~0.96 nm47, confirming the steric Fig. 2e and Supplementary Figs. 6–9 were likely formed by
effect during synthesis. Similar to our recent study of Pd1 single- uncoupling of Pt2 dimers under the high flux electron beam
atom growth on graphene22, we found that complete removal of during STEM measurements49. On the other hand, once Pt NPs
other oxygen-contained functional groups, such as carboxyl were formed during ALD, the ratio of Pt loading of the two-ALD
groups, from graphene by carefully tuning the reduction cycle sample to the one-cycle sample was apparently off from the
temperature and time, is the key to eliminate any Pt clusters or stoichiometric value of two (Supplementary Table 2).
NPs formation (Supplementary Fig. 5). These findings suggest Performing an additional cycle on Pt2/graphene to form Pt3
that metal atoms anchored on carboxyl groups have a general trimers might be possible. However, we noticed that the O3 in the
weak interaction with the graphene support, thus aggregate second cycle can create additional nucleation sites on graphene.
aggressively to larger metal NPs under the ALD conditions, in As a consequence, selective deposition was not achieved for the
line with literature48. third cycle and resulted in a mixture of Pt1, Pt2 and Pt3.
After performing another cycle of Pt ALD on Pt1/graphene at Therefore, we mainly focused on the Pt2 dimers in this work.
150 °C (Pt2/graphene), Pt2 dimers were dominantly formed along
with a certain number of Pt1 single atoms (Fig. 2d–f, and
Supplementary Fig. 6), where neither Pt clusters nor NPs were XAFS characterization and DFT calculations. Figure 3a shows
observed. Very interestingly, we noticed that Pt2 dimers the X-ray absorption near-edge structure (XANES) spectra of
frequently rotated by specified angles of 30, 60, and 90° under MeCpPtMe/graphene, Pt1/graphene, and Pt2/graphene at the Pt
the electron beam during STEM measurements and then split L3-edge, along with Pt foil, PtO2, and MeCpPtMe3 as references.
into two isolated Pt1 atoms (see more details in Supplementary Evidently, the XANES white line peaks of these three samples
Figs. 7–9). Such characteristic rotations might be related with the (11,567 eV) located at between Pt foil and PtO2, indicating that
geometry of the graphene support and the size of carbon defect by the Pt in MeCpPtMe/graphene, Pt1 single atoms, and Pt2 dimers
considering the aforementioned Pt2 dimer structure (Supplemen- were all in a similar oxidation state between Pt0 and Pt4+. The
tary Fig. 10). This observation provides strong evidence of the MeCpPtMe3 reference sample exhibits two well-resolved peaks at
presence of Pt2 dimers rather than the projection coincidence of 1.62 and 1.99 Å in the Fourier transformed (FT) k3χ(k) curve in
two isolated Pt1 atoms at different Z positions. Statistical analysis the real-space (R-space) (Fig. 3b), assigned to the shorter Pt–C
of more than 80 pairs of Pt2 dimers showed a Pt–Pt distance of bonds (1.99−2.14 Å) in the three Pt–Me groups and longer Pt–C
0.30 ± 0.02 nm for Pt2 dimers (Fig. 2g), which is significantly bonds (2.26−2.36 Å) in the Pt–MeCp group, respectively (Sup-
longer than the Pt–Pt bond in Pt bulk. This indicates that the Pt2 plementary Fig. 11a)47,50. Apparently, the two split peaks in the
dimers are in the oxidized form as expected. MeCpPtMe/graphene curve suggests that the MeCp group stayed
To step-wise elucidate the selective deposition of secondary Pt on Pt in this sample. This observation is in line with both the
atom onto the preliminary ones for the formation of Pt2 dimers in experimental result of the formation of MeCpPtMe2 surface
the second ALD cycle, a set of control experiments were further species on oxides43,51 and theoretical calculations where
performed using inductively coupled plasma-atomic emission MeCpPtMe3 on epoxydated and hydroxylated graphene surfaces
spectroscopy (ICP-AES). First, the influence of the Pt precursor liberates either one or two methyl groups depending on the
ligand on the second Pt ALD cycle was examined. In this case, available surface groups52.
half cycle of Pt ALD was executed on the graphene support by The first shell FT peak in the Pt1/graphene spectrum had a
performing the MeCpPtMe3 pulse step only (denoted as higher intensity and slightly shifted to 1.65 Å, while the peak at
MeCpPtMe/graphene) at 250 °C. After that, the ALD reactor 1.99 Å disappeared. Clearly, the MeCp ligand was combusted off
was cooled to near room temperature and half amount of the after the O2 exposure step at 250 °C. The first shell peak is
MeCpPtMe/graphene sample was taken out of reactor for ICP- assigned to Pt−O and/or Pt−C coordinations. Similar to
AES analysis; while the rest of the sample was put back to the MeCpPtMe/graphene, a very weak peak at 2.4 Å was visible in

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z

a b c

d e f

g h i
D = 0.30 ± 0.02 nm 1.01 ± 0.03 1.98 ± 0.07
2.5 2.5
30
Ratio of Pt loadings

Ratio of Pt loadings

2.0 2.0
Frequency (%)

20 1.5 1.5

1.0 1.0
10
0.5 0.5

0 0.0 0.0
0.0 0.2 0.4 0.6 0.8 0 2 4 6 8 10 0 2 4 6 8 10
Pt–Pt distance (nm) Trials Trials

Fig. 2 Morphology of the single-atom Pt1/graphene and dimeric Pt2/graphene catalysts. Aberration-corrected HAADF-STEM images of Pt1/graphene
(a–c) and dimeric Pt2/graphene (d, e). Scale bars, 20 nm (a, d), 2 nm (b, e), and 1 nm (c, f). Pt single atoms in b and c and dimers in e and f are
highlighted by white and yellow circles, respectively. g Statistical Pt–Pt distance in the observed Pt2 dimers. h The ratio of Pt loading of in Pt-MeCpPtMe/
graphene to that in MeCpPtMe/graphene, and i the ratio of Pt loading in Pt2/graphene to that in Pt1/graphene in nine independent trials determined by
ICP-AES

the spectrum of Pt1/graphene. However, this peak is significantly support containing a carbon vacancy along with either isolated
different from the Pt–Pt coordination peak (at ~2.62 Å) in Pt foil, phenol group or phenol–carbonyl pairs40 was employed as the
thus assigned to the second nearest C/O neighbors of Pt. This reduced graphene oxide surface. The structural models optimized
suggests the absence of Pt NPs in Pt1/graphene, consistent by DFT calculations were further examined by EXAFS
with our STEM observation (Fig. 2a–c and Supplementary Fig. 4). simulations.
The dimeric Pt2/graphene sample showed a similar FT curve Regarding the previous work52, the structures of MeCpPtMe2
with Pt1/graphene, implying a similar local C/O coordinations in and MeCpPtMe were both considered for the MeCpPtMe/
these two samples. In the Pt2/graphene spectrum, there was no graphene sample (Supplementary Fig. 11). Compared to the
discernible peak for the Pt–Pt coordination, suggesting the Pt2 MeCpPtMe3 molecule, the five Pt–C bonds in the Pt–MeCp
dimers are in the oxidized form after the ozone exposure step at group in these two structures both changed significantly.
150 °C. According to the EXAFS simulations for these two structures,
Considering the difficulties in discriminating the C/O neigh- MeCpPtMe bonded to the graphene support through two
bors by EXAFS fittings, we resorted to the combination of interfacial O atoms might be the promising structure for the
DFT calculations with EXAFS simulations to determine the MeCpPtMe/graphene sample (Fig. 3c and Supplementary
optimized structures of these three samples. Here, a graphene Figs. 11b and 12). Compared to the spectrum of MeCpPtMe3,

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a c
Pt L3-edge MeCpPtMe/graphene

11568 eV Simulation
Pt foil

|FT(k 3χ(k ))| (a.u.)

PtO2
MeCpPtMe3
XANES (a.u.)

11566 eV

MeCpPtMe-
/graphene
11567 eV
Pt1/graphene
A 0 1 2 3 4 5 6
Pt2/graphene
R (Å)
d
Pt1/graphene
Simulation

|FT(k 3χ(k ))| (a.u.)

11,550 11,575 11,600 11,625
E (eV)

b
Pt-O shell Pt-Pt shell
1.65 Å 2.62 Å

1.99 Å 0 1 2 3 4 5 6
Pt foil*1/3 R (Å)
Pt-C shell
e
|FT(k 3χ(k ))| (a.u.)

1.62 Å PtO2*1/2
MeCpPtMe3 Pt2/graphene
Simulation
|FT(k 3χ(k ))| (a.u.)

1.65 Å

3Å
MeCpPtMe-
1.60 Å

3.0
/graphene

Pt1/graphene
Pt2/graphene

0 1 2 3 4 5 6 0 1 2 3 4 5 6
R (Å) R (Å)

Fig. 3 XAFS structural characterization and spectra simulations. a The XANE spectra and b the K2-weighted Fourier transform spectra of MeCpPtMe/
graphene, Pt1/graphene, and Pt2/graphene at the Pt L3-edge. The reference samples of Pt foil, PtO2, and MeCpPtMe3 are also shown for comparison.
Comparison of the EXAFS simulations based on the corresponding DFT calculated structural models (insets) with the experimental EXAFS spectra of
MeCpPtMe/graphene (c), Pt1/graphene (d) and Pt2/graphene (e). The ball in gray, white, red, and dark blue represent carbon, hydrogen, oxygen, and
platinum, respectively

the remarkably attenuated peak at 1.99 Å in the MeCpPtMe/ exposure step. Taking this information into account, a Pt2O6
graphene spectrum is due to the considerable distortion of the chain structure with O atoms alternating between the terminal
MeCp group. and bridge positions was constructed (inset in Fig. 3e). After
When oxygen combusts off the ligand, additional oxygen optimization, our calculations show that the Pt–Pt bond distance
chemisorbs on the Pt1 atom in the Pt1/graphene sample53. in the Pt2O6 chain is 3.03 Å (the inset of Fig. 3e), consistent with
Indeed, Pt1 atom with one chemisorbed O2 molecule at the the experimental results very well (Fig. 2g). The lengths of the
terminal position (the Pt–O bond distance: 2.00 Å) and two O Pt–O bonds in the Pt2O6 chain are very close to each other,
atoms at the interface (the Pt–O bond distance: 2.02 Å) produces ~1.93–2.03 Å. Moreover, XAFS spectrum simulation for this
an EXAFS spectrum in good agreement with the experimental Pt2O6 chain structure also agrees very well with the experimental
result (Fig. 3d and Supplementary Fig. 12). On the contrary, the result (Fig. 3e and Supplementary Fig. 12). This chain structure is
Pt1 atom with one O and one C atom at the interface generates found to be similar to the suggested structure models for PtxOy (x
split FT peaks in the first shell, in contrast with the experimental = 1–3) clusters by Schneider et al. previously54. Interestingly, we
results (Supplementary Fig. 13). Nonetheless, this structure might also noticed that the tilted angle of the Pt2O6 chain could vary
not be completely ruled out. largely from ~8 to ~50°, depending on both the size of carbon
During the second Pt ALD cycle, a secondary Pt atom anchors vacancies and the configurations of two interfacial O atoms
on the preliminary one and then becomes oxidized during the O3 (Supplementary Fig. 14). The largely varied angles tilted from the

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ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z

a 25
The activity of 2cPt/graphene, synthesized by two successive
Pt1/graphene
cycles of Pt ALD on graphene at 250 °C, was rather close to
Pt2/graphene
Pt1/graphene, by generating 7.5 mL H2 in 10.5 min. Obviously,
Pt2/graphene and 2cPt/graphene were distinctly different in
Volume of H2 generation (mL)

20
2cPt/graphene structure. As a comparison, the activities of the Pt NP catalysts of
Pt/graphene-WI Pt/graphene-WI, Pt/carbon, and Pt/SiO2, as well as the
15 Pt/carbon commercial PtO2 were tested. The Pt/graphene-WI catalyst with
Pt/SiO2 a Pt particle size of 1.8 ± 0.5 nm (Supplementary Fig. 15 and
PtO2 Table 3), showed a very poor activity of 6.6 mL H2 release in
10 15.2 min. The commercial Pt/carbon catalyst with a Pt particle
size of 2.3 ± 0.7 nm (Supplementary Fig. 16 and Table 3)
was considerably better, generating 23.4 mL H2 in 9.7 min. The
5 Pt/SiO2 ALD catalyst with a Pt particle size of 1.9 ± 0.3 nm
(Supplementary Fig. 17 and Table 3) was also very active,
releasing 23.4 mL H2 in 6.8 min. The commercial PtO2 powder
0 (Supplementary Fig. 18) generated ~ 21 mL H2 in 15 min. In this
case, a reduction of PtO2 into Pt occurred during the reaction, in
0 3 6 9 12 15 18
Time (min) line with literature56.
b 3000
The specific rates of these samples were calculated based on the
2800 Pt contents. The rates were 160 and 110 molH2 MolPt−1 min−1, for
Pt1/graphene and 2cPt/graphene, respectively (Fig. 4b and
Specific rate (molH2 molPt–1 min–1)

2500 Supplementary Fig. 19). For the Pt NP samples, the rates were
62, 380, and 440 molH2 MolPt−1 min−1, for Pt/graphene-WI, Pt/
2000
carbon, and Pt/SiO2, respectively, close to the values for Pt
catalysts reported in the literature (Supplementary Table 4).
The rate of PtO2 was 197 molH2 MolPt−1 min−1. Obviously,
1500 hydrolytic dehydrogenation of AB on Pt catalysts is a structure
sensitive reaction, the size, and electronic properties of Pt NPs
1000 might both play important roles57,58. In sharp contrast with the
above samples, the Pt2 dimers exhibited the highest rate of
2800 molH2 MolPt−1 min−1 ever reported in literature, which
500 380 440 was ~17 and 45 times higher than the corresponding single-
160 110
197 atom Pt1/graphene and Pt/graphene-WI samples, respectively.
62
0 When the mole ratio of Pt to the AB substrate was increased,
ne ne ne WI arbon Pt2/graphene could preserve the high specific rate to a large
phe phe phe ne- SiO 2 PtO 2
/1 gra /gra t / gra phe Pt/
c Pt/ extent (Supplementary Fig. 20). Note that all the Pt samples
t t P ra
produced a similar product of BO2− in the spent reaction
P P 2
2c g
Pt/

Fig. 4 Catalytic activities of various Pt catalysts in AB hydrolysis. a Plots of

solution, according to the identical 11B resonance at 8.9 ppm
time vs normalized volume of hydrogen gas generated from the AB
(Supplementary Fig. 21)56.
hydrolysis reaction over the single-atom Pt1/graphene and dimeric Pt2/
DFT calculations were further carried out to get a deeper
graphene catalysts. Pt NPs samples of 2cPt/graphene, Pt/graphene-WI,
insight into the vast activity difference between Pt1/graphene and
Pt/carbon, Pt/SiO2, and commercial PtO2 powder were also evaluated as a
Pt2/graphene. Since AB is known as an excellent reducing agent59,
comparison. b The specific rates over these samples based on the mole
and could likely stripe off the terminal dioxygen of Pt1/graphene
of Pt
and Pt2/graphene (the insets of Fig. 3d, e) during the reaction,
partially reduced structures without the terminal dioxygen were
considered for both Pt1/graphene and Pt2/graphene (the insets of
Fig. 5a). The reduced samples are denoted as Pt1/graphene-R and
graphene support, explain well the different Pt–Pt bond distances Pt2/graphene-R, respectively. First, we compared the projected
in the Pt2 dimers observed by STEM (Fig. 2e–g). Again, the density of states of the 5d orbitals of the Pt atom in Pt1/graphene-
structure model of Pt2 dimers with one O and one C atom at the R and the top Pt atom in Pt2/graphene-R. It was found that the
interface might not be completely ruled out. unoccupied 5d states of the top Pt atom in Pt2/graphene-R locates
at a considerably higher energy position of 0.87 eV above Fermi
Catalytic activity. AB with satisfactory air stability and remark- level (Ef) than that of the Pt atom in Pt1/graphene-R (0.40 eV),
ably high hydrogen content of 19.6 wt%, has been regarded as a which indicates that Pt1/graphene-R is more prone to accept
promising hydrogen storage media for portable applications55. electrons than Pt2/graphene-R (Fig. 5a). This result is in line with
Here, hydrolysis of AB for hydrogen production was utilized as a the recent literature where Åstrand et al. reported that Pt1 single
probe reaction to investigate the catalytic properties of Pt1 single atom had a more strong ability to accept electrons than the top Pt
atoms and Pt2 dimers. According to literature, this reaction is atom in Pt2 dimer, thereby showing stronger CO adsorption on
depicted as the following Eq. (1):56 Pt160,61.
NH3 BH3 þ 2H2 O ! NH4 þ þ BO2  þ 3H2 ðgÞ ð1Þ When AB is adsorbed on Pt1/graphene-R, two B–H bonds were
significantly elongated from 1.22 to 1.42 Å, with a strong
As shown in Fig. 4a, the single-atom Pt1/graphene catalyst adsorption energy of −3.20 eV (Fig. 5b). On Pt2/graphene-R,
generated 9.8 mL H2 gas only in 10.8 min, which is ~42% of the the elongation of the two B–H bonds was slightly less, to 1.39 Å,
theoretical volume of 23.4 mL according to the Eq. (1). In and the AB adsorption energy was considerably weaker, about
sharp contrast, the dimeric Pt2/graphene catalyst released 23.4 mL −2.81 eV (Fig. 5c). The adsorption of AB on Pt (111) was also
H2 vigorously in only 0.9 min, indicating the depletion of AB. investigated as a comparison (Supplementary Fig. 22). We found

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NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z ARTICLE

6 (−2.42 eV) is remarkably stronger than that on Pt2/graphene-R

a Pt1/graphene-R
Pt2/graphene-R (−1.29 eV). More interestingly, we found that H2 chemisorbs
5
LPDOS (electron/eV)

Ef dissociatively on Pt1/graphene-R, but molecularly on Pt2/

4 graphene-R, indicated by the H–H bond distance of 2.02 and
0.96 Å, respectively. Such molecular adsorption of H2 on the Pt2
3
0.87 eV dimer with a moderate adsorption energy favors H2 desorption
2 0.40 eV during the AB hydrolysis reaction, thereby further boosting the
catalytic activity. Taken together, compared to Pt1 single atom,
1
the higher energy position of the unoccupied state of the Pt 5d
0 orbital of the top Pt in the Pt2 dimer might play an important role
–6 –4 –2 0 2 4 in weakening the adsorption of both AB and H2 molecules, thus
Energy (eV) facilitating the activity remarkably.
b c
1.39 Å Stability of Pt2 dimers on graphene. In sharp contrast with all
other Pt samples shown in Supplementary Fig. 23, the dimeric
1.42 Å 1.42 Å 1.39 Å Pt2/graphene catalyst exhibited a very high stability in the AB
hydrolysis reaction during the recyclability test for five cycles
(Fig. 6a). STEM measurements showed that there was no any
visible Pt NPs formation and Pt2 dimers remained as the main
features in the used sample (Fig. 6d, g). The Pt1 single atoms
shown in Fig. 6g were likely produced by the electron beam
during STEM measurements (Supplementary Figs. 7–9), since
Ead (AB)= –3.20eV Ead (AB)= –2.81 eV there was no apparent activity decrease. When Pt2/graphene was
d e 0.96 Å
annealed at high temperatures in helium, the activity declined
considerably (Fig. 6b), but rates still remained as high as1670 and
2.02 Å 1037 molH2 MolPt−1 min−1 for the sample annealed at 300 (Pt2/
graphene-300C) and 400 °C (Pt2/graphene-400C), respectively
(Fig. 6c). Obviously, significant amounts of Pt2 dimers were
survived after the high-temperature treatments. Indeed, HAADF-
STEM revealed a mixture of Pt2 dimers, Pt1 single atoms, and Pt
NPs in both Pt2/graphene-300C (Fig. 6e, h) and Pt2/graphene-
400C (Fig. 6f, i). Please keep in mind that these STEM images
might significantly underestimate the portion of Pt2 dimers in the
Ead (H2)= –2.42 eV Ead (H2)= –1.29 eV
samples owing to the possible beam damage during STEM
Fig. 5 Electronic properties as well as AB and H2 adsorptions. a The local measurements (Supplementary Figs. 7–9).
partial density of state (LPDOS) projected on the Pt 5d orbitals of Pt1/ In conclusion, we have successfully demonstrated that Pt2
graphene-R and the top Pt atom in Pt2/graphene-R. The local dimers can be bottom–up constructed on graphene with a high-
configurations for AB adsorption on Pt1/graphene-R (b), Pt2/graphene-R surface area. We found that the type of surface nucleation sites,
(c). The local configurations for H2 adsorption on Pt1/graphene-R (d), Pt2/ selective deposition, the self-limiting nature of ALD, and the high
graphene-R (e). The ball in gray, white, pink, blue, red, and dark blue stabilities of Pt1 single atoms and Pt2 dimers are the keys factors
represent carbon, hydrogen, boron, nitrogen, oxygen, and platinum, for the Pt2 dimers synthesis. The dominant presence of Pt2 dimers
respectively on graphene in the oxidized form of Pt2Ox were confirmed by a
combination of aberration-corrected HAADF-STEM, ICP-AES,
and XAFS and DFT calculations. Rotating and uncoupling of Pt2
that AB could quickly dissociate to three H atoms and BNH3 dimers under the electron beam during STEM measurements,
species without any barrier. The AB adsorption energy is provide direct evidence of the presence of Pt2 dimers on
−3.97 eV, significantly stronger than that on Pt1 single atom graphene. In the AB hydrolysis reaction, the dimeric Pt2/
and Pt2 dimer. The strong AB adsorption on Pt (111) revealed by graphene catalyst exhibited a strikingly high activity, which was
DFT calculations agrees well with the literature57, where Pt NP ~17- and 45-fold higher than graphene supported Pt1 single
catalyst deactivation induced by B poisoning was observed during atoms and Pt NPs, respectively. The lower adsorption energies of
the AB hydrolysis reaction. Bearing this in mind, we further AB and H2 on the Pt2 dimers than that on Pt1 single atoms or Pt
examined the recycling stabilities of the Pt1/graphene, Pt NP, and NPs are likely the major reasons for the high activity.
PtO2 catalysts and measured the B contents in the used samples Importantly, the dimeric Pt2/graphene catalyst showed a high
using ICP-AES. Indeed, catalyst deactivations and considerable stability under the current reaction conditions and in the inert
amounts of B adsorption were observed on all the used samples environment at below 300 °C. Finally, our findings point out a
(Supplementary Figs. 23 and 24), in line with the literature57. In new avenue to bottom–up synthesis of atomically precise ultrafine
addition, sintering and leaching of Pt were also noticed on Pt1/ metal (and/or metal oxide) clusters on high-surface area supports
graphene, Pt/graphene-WI, and Pt/SiO2 (Supplementary Fig. 25). for advanced catalysis.
Therefore, the considerable weaker adsorption of AB on Pt2
dimer could be one key factor for its high activity as shown in Methods
Fig. 4. Materials. Trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtMe3, 98%),
H2 adsorptions on Pt1/graphene-R and Pt2/graphene-R were chloroplatinic acid (H2PtCl6, ≥99.9%, trace metals basis), ammonia borane (97%),
the commercial PtO2 (≥99.9%, 70 m2/g), and Pt/carbon catalysts (the Pt content,
also investigated as a descriptor of hydrogen desorption from the 5.0 wt%) were all purchased from Sigma Aldrich. Silica gel was purchased from
catalyst surface during the AB hydrolysis reaction (Fig. 5d, e). It Alfa Aesar (Brunauer, Emmett, and Teller (BET) surface area 300 m2/g). Pristine
was again found that H2 adsorption on Pt1/graphene-R graphene nanosheet (99.5%) was bought from Chengdu Organic Chemicals Co.

NATURE COMMUNICATIONS | 8: 1070 | DOI: 10.1038/s41467-017-01259-z | www.nature.com/naturecommunications 7

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z

a 25
b 25
c

Specific rate (molH2 molpt–1 min–1)

3000 2800
Volume of H2 genration (ml)

Volume of H2 genration (ml)

20 20

15 15 2000
1670
10
10
1037
5 1000
5 Pt2/graphene
Pt2/graphene-300C
0
Pt2/graphene-400C
1st 2nd 3th 4th 5th 0
0
0 1 2 3 4 5 6 7 0 1 2 3 Fresh 300°C 400°C
Time (min) Time (min)

d e f

g h i

Fig. 6 Stability of the dimeric Pt2/graphene catalyst. a Five recycles in hydrolytic dehydrogenation of AB at room temperature over the dimeric Pt2/
graphene catalyst by adding additional 0.325 mmol of pure AB into the reaction flask after each run. b Plots of time vs volume of hydrogen gas generated
from AB hydrolysis and c the corresponding specific rates at room temperature over the dimeric Pt2/graphene catalysts after different pretreatments: as-
prepared, annealing in helium at 300 and 400 °C for 1 h, respectively. d, g Representative HAADF-STEM images of the used Pt2/graphene catalyst after
the recyclability test, scale bars, 20 nm (d), 1 nm (g). e, h Representative HAADF-STEM images of the Pt2/graphene catalyst after annealing in helium at
300 °C for 1 h, scale bars, 10 nm (e), 2 nm (h). f, i Representative HAADF-STEM images of the Pt2/graphene catalyst after annealing in helium at 400 °C
for 1 h, scale bars, 10 nm (f), 2 nm (i). Pt2 dimers in g–i are highlighted by yellow circles

Ltd., Chinese Academy of Sciences. All materials were used as received without Synthesis of Pt1/graphene. Pt ALD was carried out on a viscous flow reactor
further purification. (GEMSTAR-6 Benchtop ALD, Arradiance) by alternatively exposing to
MeCpPtMe3 precursor and O2 (99.999%) at 250 oC46,63,64. Ultrahigh purity N2
(99.999%) was used as the carrier gas at a flow rate of 200 mL/min. The Pt pre-
Preparation of reduced graphene oxide. Pristine graphene nanosheet was first cursor was heated to 65 °C to get a sufficient vapor pressure. The reactor inlets were
oxidized to graphene oxide according to the procedure described previously62. In held at 110 °C to avoid any precursor condensation. The timing sequence was 90,
brief, 0.6 g graphene nanosheet and 0.3 g sodium nitrate was sequentially added 120, 60, and 120 sec for the MeCpPtMe3 exposure, N2 purge, O2 exposure, and N2
into concentrated sulfuric acid (H2SO4, 15 mL) and stirred at room temperature for purge, respectively (90-120-60-120).
22 h. Then the mixture was cooled down to 0 °C to add 1.8 g potassium per-
manganate (KMnO4). After stirring at room temperature and 35 °C for 2 and 3 h,
respectively, the mixture was heated to 98 °C and kept at this temperature for
Synthesis of Pt2/graphene. The second Pt ALD cycle was performed on the Pt1/
another 30 min. Next, it was cooled down to 40 °C, and 90 mL of water and 7.5 mL
graphene SAC at 150 °C. Here, O3 was used as the oxidant to make sure that the
of hydrogen peroxide (H2O2, 30%) were slowly added into the mixture. After that
precursor ligand can be fully removed65. The timing sequence was 90-120-60-120.
the precipitate was filtered out by washing with HCl (5%) and ultrapure water, it
was dried in a vacuum oven at 45 °C overnight. The dry material was grinded to
obtain graphene oxide powder. Finally, the reduced graphene oxide was obtained
by thermal deoxygenation of graphene oxide powder at 1050 °C for 2 min under Synthesis of 2cPt/graphene. Two consecutive cycles of Pt ALD was also per-
helium at a flow rate of 50 mL/min. formed on the reduced graphene oxide at 250 °C using the same timing sequence.

8 NATURE COMMUNICATIONS | 8: 1070 | DOI: 10.1038/s41467-017-01259-z | www.nature.com/naturecommunications

NATURE COMMUNICATIONS | DOI: 10.1038/s41467-017-01259-z ARTICLE

Synthesis of Pt/SiO2. Pt ALD was performed on the silica gel support for one catalysts was adjusted to keep the same amount of Pt with Pt2/graphene. Typically,
cycle at 250 °C using the same timing sequence. 5 mL aqueous AB solution (6.5 × 10−2 M) were introduced into the glass container
via a syringe. For the commercial PtO2 catalyst, the mole ratio of Pt to AB was kept
as the same with other samples, and the result was normalized to other samples
Synthesis of Pt/graphene-WI. A Pt/graphene NP catalyst was synthesized by the
based the amount of Pt. The AB solution and the catalyst were well-mixed by using
wetness impregnation method (Pt/graphene-WI). In this case, 100 mg graphene
a magnetic stirrer at a speed of 800 r/min to eliminate any mass-transfer issue. The
support was slowly added into a 1.93 × 10−2 M H2PtCl6 aqueous solution (0.9 mL).
generated volume of H2 was measured by a water-filled gas burette, where the
Then, the mixture was stirred for 30 min, and then dried in air at room tem-
volume of water discharged was converted into the volume of hydrogen
perature for 12 h. The dried material was first calcined in air at 120 °C for 12 h, and
generated69.
then reduced in 10% H2 in argon at 300 °C for another 2 h to get the Pt/graphene-
The specific rates (r) of these catalysts were calculated according to the Eq. (2):
WI catalyst.
nH2
r¼ ð2Þ
Catalyst characterization. The Pt loadings in these samples were determined by nPt ´ t
ICP-AES measurements; therein all samples were dissolved in hot fresh aqua regia. Here nH2 is the mole of generated H2, while nPt is the total mole of Pt in the
The BET surface area was measured on a Micromeritics ASAP 2020 system. Raman sample. t is the reaction time in min.
spectra were recorded on a LabRAM HR Raman spectrometer with a 514 nm Ar
laser in backscattering geometry. Aberration-corrected HAADF-STEM measure-
ments were taken on a JEM-ARM200F instrument (University of Science and Data availability. All the relevant data are available from the authors upon
Technology of China) at 200 keV. XAFS measurements at the Pt L3-edge request.
(11,564 eV) were performed in the transmission mode with the Si (111) mono-
chromator at the BL14W1 beamline of the Shanghai Synchrotron Radiation Received: 21 February 2017 Accepted: 4 September 2017
Facility (SSRF), China. The storage ring of SSRF worked at 3.5 GeV with a max-
imum current of 210 mA.

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(2014). This work was supported by the National Natural Science Foundation of China
43. Kessels, W. M. M., Knoops, H. C. M., Dielissen, S. A. F., Mackus, A. J. M. (21473169, 21673215, 21533007, and 21233007), Innovative Research Groups of the
& van de Sanden, M. C. M. Surface reactions during atomic layer deposition of National Natural Science Foundation of China (11621063), the One Thousand Young
Pt derived from gas phase infrared spectroscopy. Appl. Phys. Lett. 95, 013114 Talents Program under the Recruitment Program of Global Experts, the Young Scientists
Fund of the National Natural Science Foundation of China (11404314), Anhui Provincial
(2009).
Natural Science Foundation (1708085MA06), and the Fundamental Research Funds for
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