Highly Selective and Sharp Volcano-type Synergistic Ni2Pt@ZIF-8-Catalyzed Hydrogen Evolution from Ammonia Borane Hydrolysis

Article abstract of DOI:10.1021/jacs.8b06511

Ammonia borane hydrolysis is considered as a potential means of safe and fast method of H₂ production if it is efficiently catalyzed. Here a series of nearly monodispersed alloyed bimetallic nanoparticle catalysts are introduced, optimized amon

Full text of DOI:10.1021/jacs.8b06511

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Article
Highly Selective and Sharp Volcano-type Synergistic Ni2Pt@ZiF-8-
Catalyzed Hydrogen Evolution from Ammonia Borane Hydrolysis
Fangyu Fu, Changlong Wang, Qi Wang, Angel M. Martinez-Villacorta, Ane Escobar, Hanbao
Chong, Xin Wang, Sergio E. Moya, Lionel Salmon, Eric Fouquet, Jaime Ruiz, and Didier Astruc
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 11 Jul 2018
Downloaded from http://pubs.acs.org on July 11, 2018
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Highly Selective and Sharp Volcano-type Synergistic Ni Pt@ZIF-8-
2
Catalyzed Hydrogen Evolution from Ammonia Borane Hydrolysis
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a
a,b
a
c
c
a
Fangyu Fu, Changlong Wang, Qi Wang, Angel M. MartinezꢀVillacorta, Ane Escobar,
d
e
c
b
a
Hanbao Chong, Xin Wang, Sergio Moya, Lionel Salmon, Eric Fouquet, Jaime Ruiz,
Didier Astruc
*a
a
º
ISM, UMR CNRS N 5255, Univ. Bordeaux, 33405 Talence Cedex, France.
b
c
Laboratoire de Chimie de Coordination, UPR CNRS 8241, Toulouse 31077 Cedex, France.
Soft Matter Nanotechnology Lab, CIC biomaGUNE, Paseo Miramón 182. 20014.
DonostiaꢀSan Sebastián, Gipuzkoa, Spain.
d
Institute of Physical Science and Information Technology, Anhui University, No. 111
Jiulong Avenue, Hefei, 230601, China.
e
Department of Chemistry, iChEM (Collaborative Innovation Center of Chemistry for
Energy Materials), University of Science and Technology of China, Hefei, 230026, China.
Abstract
Ammonia borane hydrolysis is considered as a potential means of safe and fast method of H
2
production if it is efficiently catalyzed. Here a series of nearly monodispersed alloyed
bimetallic nanoparticle catalysts are introduced, optimized among transition metals, and
found to be extremely efficient and highly selective with sharp positive synergy between 2/3
Ni and 1/3 Pt embedded inside a zeolitic imidazolate framework (ZIFꢀ8) support. These
catalysts are much more efficient for H
2
release than either Ni or Pt analogues alone on this
Pt@ZiFꢀ8 achieves a TOF of 600
support, and for instance the best catalyst Ni
2
ꢀ1
ꢀ1
ꢀ1
ꢀ1
molH2 · molcatal. · min and 2222 mol · molPt · min under ambient conditions, which
H2
overtakes performances of previous Ptꢀbase catalysts. The presence of NaOH boosts H2
evolution that becomes 87 times faster than in its absence with Ni
2
Pt@ZiFꢀ8, whereas NaOH
decreases H evolution on the related Pt@ZiFꢀ8 catalyst. The ZIFꢀ8 support appears
2
outstanding and much more efficient than other supports including graphene oxide, active
carbon and SBAꢀ15 with these nanoparticles. Mechanistic studies especially involving
kinetic isotope effects using D O show that cleavage by oxidative addition of an OꢀH bond
2
of water onto the catalyst surface is the rateꢀdetermining step of this reaction. The
remarkable catalyst activity of Ni
catalytic hydrogenation reactions using ammonia borane as H
2
Pt@ZiFꢀ8 has been exploited for successful tandem
source. In conclusion the
2
selective and remarkable synergy disclosed here together with the mechanistic results should
allow significant progress in catalyst design towards convenient H generation from
2
hydrogenꢀrich substrates in the close future.
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Introduction
One of the critical issues involving the increasing worldwide demand for clean energy
sources is the development of new hydrogenꢀstorage materials that would be used in
automotive applications. Ammonia borane (NH
content of ca. 19.6 wt%, is highly stable in the solid state and solution under ambient
conditions, nontoxic, and highly water soluble. AB is a promising hydrogen storage material
attracting tremendous research efforts. The hydrolysis of AB was initially shown to produce
4 2
ammonium borate NH BO , but the borate appears to be hydrated, i.e. the overall
hydrolysis reaction produces NH
1
3
BH
3
, AB in short), with a high hydrogen
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+
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+
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B(OH) (equation 1).
+
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H NꢁBH + 4 H O
ꢀ
NH B(OH) + 3 H
(1)
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2
In the past decade, intensive efforts have been achieved to investigate the hydrolytic
dehydrogenation of AB generating 3 mol of H per mole of AB using efficient, economical,
and durable catalysts. In this regard, singleꢀmetal and bimetallic nanoparticles (NPs), metal
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8
NPs deposited on supports, transitionꢀmetal complexes, metal phosphide NPs, and organic
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molecules have been used in catalyzed AB hydrolysis. Many efforts have recently been
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devoted to the design of highꢀperformance noble metalꢀfree nanocatalysts. H
2
release was
recently obtained from AB hydrolysis by Ni NPs supported on ZIFꢀ8
metalꢀorganicꢀframeworks (MOFs) reaching a turnover frequency (TOF) of 85.7 mol H mol
2
ꢀ1
ꢀ1
molH2 · molcatal. · min at ambient temperature. Hou et al synthesized bimetallic NiꢀCoꢀP
NPs on graphene oxide (GO) for hydrolysis of AB reaching a high initial turnover frequency
ꢀ1
ꢀ1
8b
(TOF) of up to 154 molH2 · molcatal. · min at ambient temperature, which is an
unprecedented value for firstꢀraw transition metal NP catalysts.
Earlier results involved molecular catalysts with sophisticated ligands for AB hydrolysis, but
supported metal NPs appeared much more practical, efficient and ligandless catalysts. The
NP support seems to play a key role, however, and therefore MetalꢀOrganic Frameworks
(MOFs) are an intriguing and important class of inorganicꢀorganic hybrids with intrinsic
porous structures that are used as versatile precursors or sacrificial templates for the
preparation of numerous functional nanomaterials. Indeed abundant works employing
MOFs as precursors to access metal/MOF nanostructures have been reported.
have permanent porosities (large Langmuir surface areas) and tunable pore sizes ensuring
good NP dispersion. This allows exposing active sites and facilitates the accessibility of
1
0
6a,6f,11
MOFs
1
2
substrates to the active NP surface by reducing diffusion resistance. Attention has in
particular been attracted to the ZIF family due to their ease of synthesis and extraordinary
high thermal stability and remarkable chemical resistance to boiling water and organic
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solvents.
Pt, Ru, and Rhꢀbased noble metals NPs are ideal catalysts for fast hydrogen evolution from
AB, but the high prices and global reserve scarcities of these precious metals limit their
extensive usage. Developing robust and nobleꢀmetalꢀfree catalysts with high and controllable
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f, 8b, 14
activities is expected.
It has not been possible, however, to obtain really high TOF
values under ambient conditions with nobleꢀmetalꢀfree catalysts. The two disadvantages
might be escaped by the use of bimetallic NPs between a precious metal and an
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earthꢀabundant metal that activate substrates with a highly positive synergy between the two
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metals, especially if the content of the earthꢀabundant metal is large. The bimetallic NPs
ranging from coreꢀshell structures to alloys often have excellent physical and chemical
properties because of their structures and electronic properties caused by the introduction of
16
the foreign metal. Therefore the bimetallic NPs may disclose unusual functionality utilizing
the synergistic effects between two different metals.
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In this work the coꢀreduction method is used to synthesize a series of nearlyꢀmonodispersed
NiPt NPs with tunable compositions using ZIFꢀ8 as NP support. These new nanostructures
are characterized by HighꢀResolution Transmission Electron Microscopy (HRTEM),
Transmission Electron Microscopy (TEM), Highꢀangle Annular Darkꢀfield Scanning
Transmission Electron Microscopy (HADDFꢀSTEM), Energyꢀdispersive Xꢀray Spectroscopy
(EDS), Xꢀray photoelectron spectra (XPS), Xꢀray powder diffraction (XRD),
BrunauerꢀEmmettꢀTeller (BET) and inductively coupled plasma atomic emission
spectrometer (ICPꢀAES). These NiPt@ZIFꢀ8 nanoalloy catalysts are shown to be highly
active and selective as catalysts for AB hydrolysis, and scrutiny of the optimized
composition will prove highly beneficial. In addition Kinetic isotope effects (KIEs) are used
for the mechanistic study of this reaction, allowing the proposition of a viable reaction
mechanism. The efficiency of the best catalyst will finally also be probed for several
regioselective tandem hydrogenation reactions.
Results and discussion
Synthesis and Characterizations of the Nanocatalysts.
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f
The synthesis of ZIFꢀ8 was efficiently conducted as described in a previous report. The
STEM and TEM figures (Figure S2) show that the ZIFꢀ8 NPs are polyhedron nanocrystals,
and that their average size is 56.7 nm. ZIFꢀ8 is very easy synthesized in water, and it is stable
even in refluxing in either methanol or water during 1 day without change of the framework
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f
structure. As shown by the Xꢀray powder diffraction (XRD) patterns in Figure 3, the sample
discloses the typical crystal pattern of ZIFꢀ8.
A series of NiPt@ZIFꢀ8 NP catalysts with tunable compositions were successfully prepared
by the depositionꢀprecipitation (DP) method. First the mixture of metal cations was
incorporated in ZIFꢀ8 by mixing an aqueous solution of NiCl
proportions with an aqueous ZIFꢀ8 suspension under ambient conditions for two hours. Then
fast coꢀreduction by NaBH in water was conducted under N , and the nanomaterial was
collected by centrifugation, washed with water, and dried at 60°C in vacuo overnight
Scheme 1 and Experimental Section).
2 4
and PtCl in preꢀdetermined
4
2
(
Scheme 1. Synthesis of the NiPt@ZIFꢀ8 NPs.
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The compositions of the catalysts NiPt@ZIFꢀ8 NPs were adjusted by varying the molar
ratios of the precursors. Nearlyꢀmonodispersed NPs were obtained under our experimental
conditions as further indicated by the physical characterization. HADDFꢀSTEM (Figure 1a)
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and TEM (Figure 1b) show that the asꢀprepared Ni Pt NPs are packed in the ZIFꢀ8
framework with an average size of 2.0 nm (see the size distribution in Figure S3). Clear
lattice fringes are observed by HRTEM (Figure 1b insert), which indicates that a good
crystallinity is achieved. The lattice spacing is about 2.2 Å, assuming that the
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crystallographic plane of the Ni Pt nanoalloy is {111}. EDS of the single Ni Pt NPs
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shows that the Pt, Ni and Zn elements are present in both 010 and 011 areas (Figure 2),
which leads to conclude that the Ni Pt NPs have an alloy structure in ZIFꢀ8 and not a
coreꢀshell structure. Even thought the percentages of Ni and Pt in 010 and 011 are about
6:74 and 30:70 respectively, the ICPꢀAES result is 2.7:1, which justifies the Ni Pt
2
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composition.
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Figure 1. (a) HAADFꢀSTEM and (b) TEM (insert is the HRTEM) images of Ni Pt@ZIFꢀ8;
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Figure 2. EDS of single Ni Pt NP in ZIFꢀ8, showing that Pt, Ni and Zn are present in both the
010 and 011 areas.
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The metal oxidation states are identified by XPS (Figure S4). Binding energies of 71.3 and
74.7 eV are observed for Pt(0) 4f7/2 and Pt(0) 4f5/2 (Figure S4a). Moreover the binding
energy value detected at 852.9 eV shows that metallic Ni(0) is present in the Ni Pt@ZIFꢀ8
2
NPs (Figure S4b). TEM images and histograms of the other NiPt@ZIFꢀ8 NPs are shown in
Figure S5ꢀ9, and the average particle sizes are smaller than 3 nm except Pt@ZIFꢀ8 (3.4 nm).
No diffractions were detected for the NiPt alloys or NiNPs in ZIFꢀ8 from PXRD patterns
after reduction (Figure 3), which indicates that the metal loadings in ZIFꢀ8 are too low or
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that the NPs are too small, a feature that has precedents in the literature. The formation of
Pt NPs in Pt@ZIFꢀ8 is shown in the PXRD patterns, the diffraction peaks being composed of
the standard Pt peak (JCPDS 04ꢀ0802, Figure S10). This is due to the fact that the Pt loading
is high (14.8 wt%, Table S2) in ZIFꢀ8, and the Pt NPs are larger than in the other cases.
Importantly, the exact atomic ratios in the NiPt@ZIFꢀ8 NPs were further determined by
ICPꢀAES (Table S2), and they confirm that the exact Pt/Ni ratios in the nanoalloys in ZIFꢀ8
follow the trend of the designed compositions. The ZIFꢀ8 NPs show a type I isotherm in the
2
−1 6f
N adsorption measurement, and the BET surface area of ZIFꢀ8 is 1663.3 m g . The BET
2
surface area decreases as a consequence of the presence of the packing of the NPs. Indeed
2
2
the BET surface area of Ni Pt@ZIFꢀ8, that is the best catalyst in AB hydrolysis, is 938.4 m
g (Table S1).
−
1
Figure 3. PXRD patterns of the prepared nanocatalysts.
Sharp volcano-type synergistic and highly selective catalysis of very efficient H
evolution from ammonia borane. The Pt@ZIFꢀ8, Ni@ZIFꢀ8 and NiPt@ZIFꢀ8 described
above were used for catalytically releasing H from AB in water with 1 mol% of the various
2
2
late transitionꢀmetal nanocatalysts (measured by ICPꢀAES). The oxidation of Pt(0) and Ni(0)
in the NPs were avoided upon carrying out the reactions without exposure to air. The
reaction rate and TOF curve in the presence of the nanocatalysts NiPt@ZIFꢀ8 are shown in
Figure 4 and Table S2. The volumes of gas collected represent nearly 3 equiv. of H per AB
2
4
with no detectable NH
3
(Supporting Information). It is known that Pt is an efficient metal
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ꢀ
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ꢀ1
for this reaction, but Pt@ZIFꢀ8 only leads to a TOF value of 16.6 molH2 · molcatal. · min to
attain 61.1% H . On the other hand there is a dramatic rise in the TOF value from 16.6 to
61.4 (Ni Pt@ZIFꢀ8) upon increasing the Ni proportion in the NiPt alloy. Indeed the TOF
value related to the NP surface atoms of Ni Pt@ZIFꢀ8 reaches 669.3 mol · molcatal. · min
2
3
2
ꢀ1
ꢀ1
2
H2
(Supporting Information). The catalyst Ni
this NP series, and when the Ni proportion in the NiPt alloy is higher than 2/3 the TOF value
decreases. For instance in the alloy Ni Pt@ZIFꢀ8 the TOF value only is 256.4
2
Pt@ZIFꢀ8 appears to be the best catalyst among
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molH2 · molcatal. · min for this reaction. All the alloyed NPs give better results than the
pure Pt@ZIFꢀ8 or Ni@ZIFꢀ8 catalysts. These results show that the NiPt@ZIFꢀ8 NPs present
excellent synergistic effects between these two metals.
Figure 4. (a) Kinetics of the AB hydrolysis reaction catalyzed by various NiPt@ZIFꢀ8 at 20
± 0.5 °C with 1 mol% nanocatalysts; (b) Variation of the TOF obtained from various NiPt
nanocatalysts in ZIFꢀ8 as a function of Ni content (%) in the NiPt alloys.
High selectivity of Ni
Ni Pt@C and Ni Pt@SBAꢀ15 were synthesized using the same method as that used for the
synthesis of Ni Pt@ZIFꢀ8 (Experimental Section) in order to understand if this obvious
2 2
Pt@ZIF-8 in ZIF-8 compared to other supports. Ni Pt@GO,
2
2
2
synergistic effect between Ni and Pt also exists with other common supports (GO, C and
SBAꢀ15). Figure 5 shows the comparison between various supports concerning the synergy
effect between Ni and Pt in Ni
synergistic activity measured by the TOF values in the supported NiPt nanocatalysts is by far
obtained with Ni Pt@ZIFꢀ8. In addition various supports were examined and compared for
this catalyst. Figures S19ꢀ21 show the compared AB hydrolysis reactions catalyzed by Ni Pt
2
Pt NPs. This comparison demonstrates that the best
2
2
NPs, Ni NPs and Pt NPs on GO, C and SBAꢀ15 respectively. Ni Pt NPs presents the largest
2
synergistic effects in the ZiFꢀ8. The TOF ratio (Ni
is much higher than the TOF ratio on other supports. This shows that ZIFꢀ8 exhibits high
selectivity for Ni Pt NPs among all supports for the AB hydrolysis reaction. Thus in sum
2
Pt/noble metal Pt) on ZiFꢀ8 is 21.8, which
2
there is a highly selective triple synergy between Ni, Pt and the ZIFꢀ8 nanomaterials in the
catalytic activation of the substrates.
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Figure 5. (a) Hydrolysis of AB catalyzed by Ni
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Pt on various supports at 20 ± 0.5 °C with 1
mol% nanocatalysts; (b) TOF ratio (Ni
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Pt/Pt) on various supports.
High selectivity of Ni Pt@ZIF-8 compared to other bimetallic NPs in ZIF-8. A series of
2
bimetallic lateꢀtransitionꢀmetal NPs, Co
2
Pt@ZIFꢀ8, Cu
Ru@ZIFꢀ8 have been synthesized by the same method as that used for the synthesis of
Pt@ZIFꢀ8 (Experimental Section). The ICPꢀAES analysis indicates that the metal
2 2
Pt@ZIFꢀ8, Ni Rh@ZIFꢀ8 and
Ni
Ni
2
2
loadings are 8.6 wt%, 5.9 wt%, 6.1 wt% and 4.6 wt% and the atomic ratios are 3:1, 2.1:1,
.1:1 and 1.5:1 respectively. The comparison shows that Ni Pt@ZIFꢀ8 exhibits the best
1
2
efficiency among these five catalysts, followed by the Ni
2
Rh@ZIFꢀ8 and Ni
Pt@ZIFꢀ8 and Cu
2
2
Ru@ZIFꢀ8.
Pt@ZIFꢀ8
Only 55.6% and 19.1% H are captured by 1 mol% Co
2
2
respectively in 6 min at 20 ± 0.5 °C, however. Figures S22 and S23 illustrate AB hydrolysis
catalyzed by pure Rh@ZIFꢀ8 and Ru@ZIFꢀ8 NPs respectively. Among all the bimetallic
NPs, again Ni Pt shows the strongest synergistic effects in the ZIFꢀ8 according to the TOF
2
2
ratio (bimetal/noble metal) (Figure 6b). Since ZIFꢀ8 exhibits a high selectivity of Ni Pt NPs
among various bimetallic nanoparticles, support, and Ni/Pt ratio for AB hydrolysis, this
catalytic system was chosen for further studies.
Figure 6. (a) Hydrolysis of AB catalyzed by various bimetallic NPs in ZIFꢀ8 at 20 ± 0.5 °C
with 1 mol% nanocatalysts; (b) TOF ratio (bimetal/noble metal) in ZIFꢀ8.
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Mechanistic Studies for AB hydrolysis catalyzed by Ni
time plots of H evolution vs. various concentration of AB with 1 mol% Ni
Interestingly the reaction time is exactly the same (50 s), and the logarithmic plot of H
generation rate vs. concentration AB is shown in Figure 7b, with a nearly horizontal line
(slope is 0.06) indicating that hydrolysis of AB catalyzed by Ni Pt@ZIFꢀ8 is zeroꢀorder in
AB. This rules out AB activation alone in the rateꢀdetermining step (vide infra). The slope of
the logarithmic plot of H generation vs. concentration of Ni Pt@ZIFꢀ8 NPs is 0.82 (Figure
c and 7d), leading to the result of a firstꢀorder reaction in catalyst concentration. The
measure of the time dependence of H generation at various temperatures indicates that the
2
Pt@ZIF-8. Figure 7a shows the
2
2
Pt@ZIFꢀ8 NPs.
2
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a
activation energy (E ) of AB hydrolysis is low (approximately 23.3 kJ/ mol) with the catalyst
Ni Pt@ZIFꢀ8 (Figure 7e and 7f and calculation) showing the strong implication of the
2
catalyst in the transition state.
Figure 7. Kinetic studies: (a) time plots of the catalytic dehydrogenation of AB by 1 mol %
Ni Pt@ZIFꢀ8 with various AB concentrations; (b) plot of H generation rate vs. the
2
2
concentration of AB both in natural logarithmic scale; (c) time plots of the catalytic
dehydrogenation of AB with various catalytic amounts; (d) plot of H generation rate vs. the
2
concentration of catalyst both in natural logarithmic scale; (e) time plots of the catalytic
dehydrogenation of AB at various temperatures; (f) Arrhenius plots obtained from the kinetic
data
.
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2 2
Kinetic studies were conducted using an isotopic experiment with D O instead of H O. The
kinetic isotope effect (KIE) gives an indication concerning the role of H O in the
2
3,6f,14e,f
rateꢀdetermining step of this reaction.
The results with Ni Pt@ZIFꢀ8ꢀcatalyzed AB
2
hydrolysis are shown in Figure 8a. A large KIE of 4.95 is observed, strongly indicating
cleavage of a water OꢀH bond in the rateꢀdetermining step.
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7
Another series of experiments has been conducted with various amounts of NaOH in order to
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6f, 19
investigate the role of OH on the AB hydrolysis rate in the presence of the catalyst
is eventually beneficial.
that
NaOH appears to be the best candidate among various bases.
The catalytic performance of the Ni Pt@ZIFꢀ8 NPs towards AB hydrolysis in the presence of
various amounts of NaOH (0.1 Mꢀ0.4 M) has been tested, and the results are shown in Figure
b. The H evolution rates are improved compared to those found in the absence of NaOH.
8
b,14e,f,18
2
8
2
The H generation rate increases with the increased NaOH concentrations to the optimum
2
level of 0.3 M, and the best result is obtained with 1 mol% Ni Pt@ZIFꢀ8 reaching a TOF
2
value of 600 molH2/molcatal./min and 2222 molH2/molPt/min, which surpasses that of the
Ptꢀbase NPs systems at 20 ± 1°C (Table S3). The results then decrease with higher NaOH
concentration (0.4 M). No H release are observed for AB hydrolysis in the NaOH (0.3 M)
2
solution in the absence of the Ni Pt@ZIFꢀ8 NPs, indicating that NaOH acts as a catalyst
2
ꢀ
promoter, not as a catalyst for the hydrolytic dehydrogenation of AB. The favorable OH
effect is consistent with coordination of OH to the NP surface, making the NP more
ꢀ
electronꢀrich, which favors the rateꢀlimiting oxidative addition of water. NaOH has a
negative effect on Pt@ZIFꢀ8 NPꢀcatalyzed H evolution upon AB hydrolysis, however. With
2
Pt@ZIFꢀ8 NPs that are the most electronꢀrich NP surfaces, the hydrogen bonding between
AB and H O appears to be sufficient to favor OꢀH oxidative addition by the Pt NP surface
2
ꢀ
ꢀ
without the need to further enriching the Pt NPs by OH coordination. Coordination of OH
to the Pt NP surface possibly partly inhibits the oxidative addition of the water OꢀH bond by
occupying the surface active sites, explaining why Pt@ZIFꢀ8 shows negative effect with 0.3
ꢀ1
ꢀ1
M NaOH (Figure 9). Indeed the TOF decreases from 16.6 to 6.9 molH2 · molcatal. · min
after adding 0.3 M NaOH. It is interesting to see that the synergistic effect between Pt and Ni
in the NiPt alloy in ZIFꢀ8 is more marked in the presence of 0.3 M NaOH, whereas the
opposite in found with Pt@ZIFꢀ8 alone (Figure S24). Figure 9 shows the comparison of the
TOF variation obtained for various catalysts NiPt@ZIFꢀ8 with and without 0.3 M NaOH.
This comparison indicates that the catalyst presents an enhanced synergistic effect between
Ni and Pt in the NiPt alloy in the presence of NaOH. Very remarkably the TOF obtained with
2
Ni Pt@ZIFꢀ8 is around 87 times higher than that of the noble metal catalyst Pt@ZIFꢀ8 in the
presence of 0.3 M NaOH.
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2 2 2
Figure 8. Hydrolysis of AB catalyzed by Ni Pt@ZIFꢀ8 (a) in H O (red) or D O (black), (b)
in the presence of 0.1Mꢀ0.4M NaOH in water, at (20 ± 0.5 °C) with 1 mol% nanocatalyst.
Figure 9. Comparison of the TOF variation obtained for various NiPt@ZIFꢀ8 catalysts
activities with and without 0.3 M NaOH.
Several mechanisms have been proposed for hydrolysis of AB catalyzed by late
2
b, 2c, 6e
ꢀ
+
transitionꢀmetal NPs.
suggested its attack by H
was suggested by Xu who proposed cleavage of the BꢀN bond, then NH
The intermediate BH
3
OH NH
4
was proposed by Fu who also
O on the activated complex
hydrolysis to yield
8
a
2
O for H
2
production. Reaction of H
2
3
20
ꢀ
H
2
. Attack of H
2 2 4
O on a transient MꢀH bond to produce H by analogy with BH hydrolysis
was suggested by Jagirdar and also by Ma. Cleavage of a water OꢀH bond in the
rateꢀdetermining step was proposed by Chen’s goup and Wang et al. A mechanistic
proposal based on the present results is shown in Scheme 2. Here it is likely that H O forms
a hydrogen bond [H NBH H]…HꢀOH, because the BꢀH bond presents a hydridic character.
The very large KIE obtained with D O shows that oxidative addition of the OꢀH bond of
2
1
22
2
3
6f
2
3
2
2
water occurs in the rateꢀdetermining step. This step appears to be water oxidative addition of
ꢀ
an OꢀH bond. The rate increase provoked by 0.3 M OH is taken into account by a bond of
ꢀ
OH to the NP surface. This effect increases the electron density on the NP surface, which
favors oxidative addition of water that is proposed to be the rateꢀlimiting step. Pt@ZIFꢀ8 is
the most electronꢀrich NP surface, which explains that the NP surface already is sufficiently
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electron rich to induce OH oxidative addition on the NP surface in the hydrogen bonded
species [H NBH H]…HꢀOH. In this case only of Pt@ZIFꢀ8 it does not need OH
3 2
ꢀ
coordination, and on the contrary it is probable that the occupation of surface coordination
ꢀ
site by OH inhibits further surface activity.
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Scheme 2. Proposed mechanism for the hydrolysis of AB catalyzed by NiPt@ZIFꢀ8.
Tandem reactions for hydrogenation with H generated from AB. The H produced from
2
2
24
AB catalyzed by Ni
and benzonitrile with the same catalyst whose optimization was shown above and conducted
in a sealed twoꢀchamber system (Figure 10, detail in Supporting Information). Following H
2
Pt@ZIFꢀ8 was used for the hydrogenation of 4ꢀnitrophenol, styrene
2
evolution, the reaction was performed using this nanocatalyst at 30 °C, and the yellow color
of 4ꢀnitrophenol disappeared after 2 h. The isolated yield is 99%. The hydrogenation of
styrene with the generated H also occurred successfully and was complete (quantitative)
2
after 12 h at 50 °C. Moreover, even the more difficult complete hydrogenation the CꢀN bond
of benzonitrile was selectively achieved in 90% isolated yield at 50 °C for 24h. This means
2
that H produced from AB is conveniently used for hydrogenation reactions and that the
catalyst Ni Pt@ZIFꢀ8 is an efficient and versatile catalyst for these and presumably many
2
other organic reactions.
2
Figure 10. Tandem reaction for hydrogenation with H generated from AB catalyzed by
Ni Pt@ZIFꢀ8.
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Concluding remarks
A coꢀreduction method has been established here for the synthesis of ligandꢀfree
nearlyꢀmonodispersed NiPt alloy NPs with tunable compositions using the ZIFꢀ8 MOF as
template. These new catalysts provoke the evolution of 3 mol H
the reaction is zero order in AB and first order in NP catalyst.
Upon scrutinizing the optimal amount of each metal proportion in the bimetallic catalyst, a
very remarkable sharp volcanoꢀtype positive synergistic effect is disclosed for Ni Pt. This
catalyst gives much better results than other compositions and other transition metal
bimetallic catalysts.
The ZIFꢀ8 support also appears extremely selective for this catalyst compared to the supports
GO, C, SBAꢀ15. The highest catalytic activity for H evolution is shown to be that of
2
upon AB hydrolysis, and
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ꢀ1
ꢀ1
Ni Pt@ZIFꢀ8 with a TOF value of 600 mol
· molcatal. · min and 2222.2
H2
2
ꢀ1
ꢀ1
molH2 · molPt · min at 20 ± 1°C. This value is around 87 times higher than the TOF of the
noble metal catalyst Pt@ZIFꢀ8.
2
It is also found that NaOH much enhances the reaction rate with the catalyst Ni Pt@ZIFꢀ8,
whereas on the contrary it decreases that of the reaction catalyzed by Pt@ZIFꢀ8. These
results are taken into account by OH anion coordination to the NP surface enriching its
electron density, thereby facilitating the crucial oxidative addition of a water OꢀH bond. With
Pt@ZIFꢀ8 the electronꢀrich Pt NP seems not to need additional electron density, and OHꢀ
coordination is proposed to inhibit further substrate activation, causing a decrease of catalyst
activity.
ꢀ
A large kinetic isotope effect of 4.95 upon replacing H O by D O indicates that cleavage of
2
2
the OꢀH bond of water appears to be the rateꢀdetermining step. In this mechanism water is
part of the source of dihydrogen production. The high proportion of Ni in the catalysts shows
excellent results obtained using such a “green” approach, yet benefitting from unprecedented
synergistic activation boosting efficiency and selectivity.
Tandem reactions were successfully conducted for hydrogenation with H generated from
2
AB with the catalyst Ni Pt@ZIFꢀ8 showing that it is also a very efficient and versatile
general catalyst. These remarkable performances and results not only enrich the family of
highly efficient catalysts for hydrolysis of AB, but also provide significant and promising
insights into the optimization of the electronic structure design of the alloy surface involving
heteroatom bonding. The principles shown here might be applicable to progress in catalyst
2
2
design in general including for suitable and convenient H generation systems in the future.
Experimental Section
Synthesis of the nanocatalysts (Ni Pt@ZIF-8 as example): A Schlenk flask was charged
2
with 100 mg ZIFꢀ8 NPs under N
sonicated for 5 min and allowed to stir for 30 min under N
PtCl (6.4 mg) (the molar ratio of the Pt: Ni precursor were 1:2, totally 5.68 × 10 mol)
2
. Then 5 mL water was injected, and the mixture was
2
. The precursors NiCl (9 mg) and
2
ꢀ5
4
dissolved in 2 mL water were injected. This mixture was stirred continuously at room
temperature for 2 h. Then 1 mL aqueous solution of fresh prepared NaBH (21 mg, 5.5 × 10
mol) was quickly added after degassing with N for 5 min. The mixture was allowed to
2
ꢀ4
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further stir for another 30 min, and the resulting nanocatalyst was collected by centrifugation,
washed with water and dried at 60°C in vacuo overnight. The metal content was quantified
by inductively coupled plasma atomic emission spectroscopy (ICPꢀAES). A similar synthetic
process was used for various other Ni/Pt ratios, other bimetallic nanoparticles and supports
(C, GO and SBAꢀ15).
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ASSOCIATED CONTENT
Supporting Information
.
The Supporting Information is available free of charge on the ACS Publication website at
DOI:
General data, details of the synthesis, hydrolysis of AB reactions, detection of NH gas,
3
hydrogenation of substrates with hydrogen generated from AB hydrolysis, characterizations of
the nanocatalysts, and calculation of the NP surface atom numbers and TOFs related to the
surface atom numbers (PDF).
AUTHOR INFORMATION
Corresponding Author
didier.astruc@uꢀbordeaux.fr
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Financial support from the China Scholarship Council (CSC) of the People’s Republic of
China (grants to F. F. and Q. W.), the Universities of Bordeaux and Toulouse 3, CIC
bioMAGUNE, and the CNRS are gratefully acknowledged.
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