Unique Catalysis of Nickel Phosphide Nanoparticles to Promote the Selective Transformation of Biofuranic Aldehydes into Diketones in Water

Article abstract of DOI:10.1021/acscatal.9b05120

Although the development of metal nanoparticle catalysts for organic synthesis has been widely studied, the catalytic potential of "metal phosphide nanoparticles" has little been studied. Herein, we describe that nickel phosphide nanoparticles (Ni₂P NPs) act as a highly efficient heterogeneous catalyst for the selective transformation of biofuranic aldehydes into diketones, which is a useful biorefining technology. The biofuranic aldehydes are hydrogenated in water without any additives, giving the corresponding diketones in high yields. The catalytic performance of Ni₂P NPs demonstrated here is significantly different from conventional Ni(0) and NiO NPs, and other metal phosphide NPs, which show no activity, indicating the unique catalysis of Ni₂P NPs. Spectroscopic analyses showed that bifunctional Ni₂P NP catalysis combining their hydrogen-activating ability and surface acidity plays a crucial role, leading to the transformations of selective biofuranic aldehydes.

Full text of DOI:10.1021/acscatal.9b05120

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Article
Unique Catalysis of Nickel Phosphide Nanoparticles to Promote the
Selective Transformation of Biofuranic Aldehydes into Diketones in Water
Shu Fujita, Kiyotaka Nakajima, Jun Yamasaki, Tomoo Mizugaki, Koichiro Jitsukawa, and Takato Mitsudome
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b05120 • Publication Date (Web): 04 Feb 2020
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ACS Catalysis
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Unique Catalysis of Nickel Phosphide Nanoparticles to Promote the
Selective Transformation of Biofuranic Aldehydes into Diketones in
Water
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Shu Fujita,† Kiyotaka Nakajima,‡ Jun Yamasaki,§ Tomoo Mizugaki,† Koichiro Jitsukawa,†
and Takato Mitsudome*,†
†Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3
Machikaneyama, Toyonaka, Osaka 560-8531, Japan
‡Institute for Catalysis, Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo 001-0021, Japan
§Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, 7-1, Mihogaoka, Ibaraki, Osaka 567-0047,
Japan
KEYWORDS: nickel phosphide, heterogeneous catalyst, hydrogenation, biofuranic aldehydes, diketones.
ABSTRACT: Although the development of metal nanoparticle catalysts for organic synthesis has been widely studied, the catalytic
potential of ‘metal phosphide nanoparticles’ has little been studied. Herein, we describe that nickel phosphide nanoparticles (Ni2P
NPs) act as a highly efficient heterogeneous catalyst for the selective transformation of biofuranic aldehydes into diketones, which is
a useful biorefinery technology. The biofuranic aldehydes are hydrogenated in water without any additives, giving the corresponding
diketones in high yields. The catalytic performance of Ni2P NPs demonstrated here is significantly different from conventional Ni(0)
and NiO NPs, and other metal phosphide NPs, which show no activity, indicating the unique catalysis of Ni2P NPs. Spectroscopic
analyses showed that bifunctional Ni2P NP catalysis combining their hydrogen-activating ability and surface acidity plays a crucial
role, leading to the selective biofuranic aldehydes transformations.
The integration of additional metals into metal nanoparticles
(NPs) to obtain nanoalloys represents a promising method for
producing novel catalysis or achieving significant improve-
ments that are not possible using single metal NPs.1–3 Nanoalloy
catalysts have been broadly employed in diverse areas, such as
oil refineries, automobile exhaust gas cleaning, petrochemical
manufacturing, fine chemical synthesis, and electrocatalytic
and photocatalytic hydrogen evolution reactions.4–6 Many stud-
ies on metal–metal nanoalloy catalysts have been reported.
However, the catalytic functions of metal–nonmetal or metal–
metalloid nanoalloys have not been widely explored.7 In this
context, metal phosphide NPs, such as Ni2P and Co2P NPs, are
less common metal–nonmetal nanoalloys that have recently at-
tracted attention as a new family of electrocatalysts for the hy-
drogen evolution reaction.8–10 These nanoalloys have also been
applied in hydrotreating reactions in the petroleum industry.11–
14 However, the study of metal phosphide catalysts in fine and
bulk chemical synthesis is extremely rare, despite their high cat-
alytic potential.15–20 Therefore, exploring the unique catalytic
functions of metal phosphide nanoparticles is of great interest
in the field of organic synthesis.21
and heterogeneous36-42 catalysts have been reported for this
transformation. However, these catalyst systems inevitably re-
quire expensive and rare metals, such as Ir, Pd, Ru, and Au, and
the addition of toxic acids, such as hydrochloric acid and phos-
phoric acid.29,32,35,39 The difficulty of catalyst reuse is also prob-
lematic.32,40 Therefore, the development of a cost-effective and
efficient catalytic system for diketone production from the
HMF derivatives using highly active nonprecious metals in the
absence of organic solvents and additives, which will be a
promising and powerful tool for future biorefinery processes,
remains highly challenging.
In this study, we report that well-ordered nickel phosphide
nanoparticles (Ni2P NPs) showed high catalytic activity and se-
lectivity for the transformation of HMF derivatives to 2,5-
diketones in water without any additives. This is the first exam-
ple of nonprecious metal catalysts for the production of 2,5-
diketones from HMF derivatives. The outstanding catalytic per-
formance of Ni2P NPs was very different to those of other metal
phosphide NPs and conventional Ni NPs, such as Raney Ni,
Ni(0) and NiO, which showed almost no activity. Furthermore,
Ni2P NPs were easily recoverable after the reaction and could
be reused without a significant loss in activity and selectivity.
The transformation of 5-(hydroxymethyl)furfural (HMF) de-
rivatives to give 2,5-diketones has attracted much attention as
an important biorefinery technology, because HMF derivatives
can be produced from the dehydration of glucose and fructose,
and 2,5-diketone products are valuable intermediates for surfac-
tants, polymers, and solvents.22–28 Several homogeneous29–35
The Ni2P NPs were synthesized by adding NiCl2 to 1-octade-
cene in the presence of hexadecylamine and triphenylphosphite.
This mixture was stirred at 120 C for 1 h in vacuo before in-
creasing the temperature to 300 C, which was held for 2 h with
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stirring under an argon atmosphere to give a black colloidal so-
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86% yield under the optimized conditions, which is the highest
yield among those previously reported (see SI for details, Table
S3). In a control experiment, conventional non-phosphide Ni
catalysts, such as Raney Ni, mordenite-supported Ni(0) NPs
and NiO NPs (see SI for details), and commercially available
bulk Ni2P were tested in the hydrogenation of 1. In sharp con-
trast to the high activity of Ni2P/mordenite, Raney Ni,
Ni(0)/mordenite and NiO/mordenite did not produce 2, and
bulk Ni2P was almost inactive in the reaction. These results
clearly confirmed that the Ni2P NPs showed high catalytic ac-
tivity distinguishable from bulk Ni2P and conventional Ni cata-
lysts. These above results strongly suggested that both phos-
phidation and nanosizing of the Ni play vital roles in generating
the unique catalytic activity of Ni for the transformation of 1
into 2.
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lution. After cooling to room temperature, the precipitate was
recovered by centrifugation. The obtained precipitate was then
washed with chloroform–acetone (1:1, v/v), to afford the Ni2P
NPs.43 Other metal phosphide NPs, namely, Fe2P NPs and Co2P
NPs, and nickel phosphide NPs with different compositions,
such as Ni5P4 NPs and NiP2 NPs, were also synthesized using a
similar method (see Supporting Information (SI) for details). In
the X-ray diffraction (XRD) pattern of the prepared Ni2P NP,
the peak positions are consistent with those of bulk Ni2P, and
weak and broad diffraction peaks that suggested the formation
of nanosize Ni2P (Figure 1a). A high-angle annular dark field
scanning transmission electron microscopy (HAADF-STEM)
image of Ni2P showed that NPs with a mean diameter of 5.4 nm
with narrow size distribution (±1.4 nm) were regularly formed
(Figure 1b). Energy-dispersive X-ray (EDX) line scan analysis
and elemental mapping of Ni2P NPs confirmed the presence of
nickel and phosphorus elemental components distributed homo-
geneously within each Ni2P NP (Figure 1c–1f). The correspond-
ing EDX spectrum also revealed the atomic ratio between Ni
and P was close to 2:1. These results clearly demonstrated the
successful synthesis of uniform Ni2P NPs.
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Figure 2. (a) Catalytic performance of various metal phosphide
NPs in the hydrogenation of 1. (b) Catalytic performance of
Ni2P NPs supported on different supports, Raney Ni, mor-
denite-supported Ni(0) NPs, mordenite-supported NiO NPs,
and bulk Ni2P. Reaction conditions: Catalyst (metal: 6 mol%),
1 (0.25 mmol), H2O (10 mL), H2 (20 atm), 130 C, 2 h.
Figure 1. (a) XRD pattern of Ni2P NPs. The reference JCPDS
pattern of Ni2P (03-0953) is also included in the XRD graph.
(b) HAADF-STEM image of Ni2P NPs with (c) EDX line scan
analysis and elemental mapping images of (d) Ni and (e) P. (f)
Composite overlay image formed from (d) and (e).
The present simple catalyst system using Ni2P/mordenite in
water without additives was also applicable to a gram-scale re-
action, with 2 g of 1 converted into 2 in 74% isolated yield
(Scheme 1a). Furthermore, Ni2P/mordenite promoted the trans-
formation of platform biomass derivative molecule HMF, af-
fording 1-hydroxy-2,5-hexanedione in 84% yield (Scheme 1b).
The reusability of Ni2P/mordenite was also investigated, be-
cause facile catalyst recovery and reuse are the major ad-
vantages of heterogeneous catalysts over homogeneous cata-
lysts. After the reaction, the spent Ni2P/mordenite catalyst was
easily recovered by simple centrifugation and reused.
Ni2P/mordenite was found to maintain its high activity and se-
lectivity over several recycling experiments without requiring
any catalyst pretreatment (Figure 3a). The transmission electron
microscopy (TEM) images of the spent Ni2P/mordenite (Figure
S3) showed that the average diameter of the Ni2P NPs was 5.7
nm, similar to that of the fresh catalyst, which thus confirmed
the high durability of the Ni2P/mordenite. To determine whether
the leached Ni species from Ni2P NPs participated in the reac-
tion, Ni2P/mordenite was filtered from the reaction mixture at
30% conversion of 1 and the filtrate was treated again under the
same reaction conditions. No additional products were formed,
as shown in Figure 3b, proving that the reaction occurred on the
surface of Ni2P/mordenite. This result was also consistent with
the high reusability of Ni2P/mordenite, demonstrating its high
Initially, the catalytic potential of metal phosphide NPs was
investigated in the hydrogenation of 5-methylfurfural (1) under
20 atm of H2 at 130 C in water without any additives. The re-
sults are shown in Figure 2a. Interestingly, Ni2P NPs gave 2,5-
hexanedione (2) in 38% yield with high selectivity. Nickel
phosphide NPs with different compositions, such as Ni5P4 and
NiP2, also afforded 2. Although Ni5P4 NPs exhibited slightly
lower activity than Ni2P NPs, NiP2 NPs gave poor yield of 2.
Other metal phosphide NPs, Fe2P and Co2P NPs, hardly showed
any activity, indicating the unique catalysis of nickel phosphide
NPs. To our knowledge, this is the first example of the direct
conversion of 1 into 2 using a nonprecious metal catalyst.
Next, to improve the catalytic activity of Ni2P NPs and allow
easy handling of the catalyst, Ni2P NPs were dispersed on sev-
eral supports, including SiO2, mordenite, and ZSM-5 (Figure
2b). The support effect provided improved yields of 2, with
Ni2P/mordenite showing the highest activity, affording 2 in
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Scheme 1. (a) Gram-scale experiment using Ni2P/mordenite.
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(b) Transformation of HMF to 1-hydroxy-2,5-hexanedione us-
ing Ni2P/mordenite.
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Figure 4. (a) Ni K-edge XANES spectra of Ni foil, NiO, Ni2P
NPs, Ni5P4 NPs, and NiP2 NPs. (b) Fourier transform k3-
weighted EXAFS of Ni foil, NiO, Ni2P NPs, Ni5P4 NPs, and
NiP2 NPs, and fitting results for Ni2P, Ni5P4, and NiP2 NPs.
Figure 3. (a) Ni2P/mordenite reuse experiments in the transfor-
mation of 1 to 2. (b) Hot filtration experiment of Ni2P/mordenite
in the transformation of 1 to 2. Reaction conditions: Ni2P/mor-
denite (50 mg), 1 (0.25 mmol), H2O (10 mL), H2 (20 atm), 130
C, 6 h.
Figure 5. XPS spectra of (a) Ni 2p and (b) P 2p for Ni2P NPs.
870.1 eV, respectively, which were close to those of metallic Ni
2p3/2 (852.8 eV) and Ni 2p1/2 (870.0 eV) (Figure 5a). These data
were consistent with the XANES results (Figure 4a). The P 2p
spectrum showed two peaks, indicating the coexistence of phos-
phorus atoms with different electronic states on the surface of
the Ni2P NPs (Figure 5b). The first peak at 129.5 eV was close
to that of P0 (130.0 eV) and assigned as P (0 <  < 1),46, 47 while
the other peak at 134.4 eV was assigned to unreduced phosphate
durability. These results show that the Ni2P NP catalyst system
is a cost-effective, efficient, and reusable catalytic system for
diketone production from HMF derivatives.
To investigate the origin of the specific activity of Ni2P NPs,
X-ray absorption fine structure (XAFS) analysis was performed
under ambient temperature and atmosphere. The X-ray absorp-
tion near-edge structure (XANES) spectra of Ni foil, NiO refer-
ences, Ni2P, Ni5P4, and NiP2 NPs are shown in Figure 4a. The
absorption edge energies of NixPy NPs (Ni2P, Ni5P4, and NiP2
NPs) were located between Ni foil and NiO standards, indicat-
ing that the average oxidation state of Ni species in NixPy NPs
ranged from 0 to 2.18 In particular, the absorption edge energies
of Ni2P and Ni5P4 NPs were close to that of Ni foil, which sug-
gested that the Ni species in Ni2P and Ni5P4 NPs represented
metal-like states in air. Fourier transform Ni K-edge extended
X-ray absorption fine structure (EXAFS) spectra were also
shown in Figure 4b. Ni2P and Ni5P4 NPs showed two peaks at
distances of 1.7 Å and 2.3 Å, corresponding to Ni–P and Ni–Ni
bond distances, respectively.44,45 In contrast, no Ni–Ni bond was
detected in the NiP2 NPs. The catalytic activities of Ni2P and
Ni5P4 NPs were superior to that of NiP2 NPs, as shown in Figure
2a, indicating that the Ni–Ni bond in NixPy NPs played an im-
portant role in promoting the transformation of 1 to 2.
3
species PO4 arising from the superficial oxidation of Ni2P
NPs.48
To elucidate the reaction pathway from 1 to 2, several control
experiments were conducted (Scheme 2). First, the reaction was
conducted using 5-methylfurfuryl alcohol as the starting mate-
rial in the presence of Ni2P NPs in water under pressurized H2,
similar to the conditions shown in Figure 2. This resulted in
96% conversion of 5-methylfurfuryl alcohol into 2 (Scheme 2a).
Furthermore, 5-methylfurfuryl alcohol was transformed into 3-
hexene-2,5-dione under a N2 atmosphere instead of under H2
(Scheme 2b). This ring-opening reaction is known to occur us-
ing acid catalysts.32 We also confirmed that 3-hexene-2,5-dione
was hydrogenated to 2 by Ni2P NPs (Scheme 2c). These results
suggested that 1 transformed into 2 through the formation of 5-
methylfurfuryl alcohol and 3-hexene-2,5-dione as intermediates.
It is reported that the Ni–Ni site of Ni2P NPs is important for in
the activation of H2.49 which is well consistent with our experi-
mental and XAFS results where Ni2P and Ni5P4 NPs having the
Ni–Ni site showed high activity for the hydrogenation of 1. We
The electronic states of surface Ni and P in the Ni2P NPs were
also investigated by X-ray photoelectron spectroscopy (XPS).
The Ni 2p spectrum of Ni2P NPs showed Ni 2p3/2 and Ni 2p1/2
binding energy peaks, located predominantly at 853.1 eV and
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also confirmed that Ni2P NPs have acidic properties by temper-
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acidity derived from P–OH, played a key role, leading to the
highly efficient transformation of 1 into 2 without any additives.
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ature-programmed desorption of ammonia (Figure S4 and Ta-
ble S2). The presence of Brønsted acid in the surface of N2P
NPs is reported, which is formed with the reaction of phosphate
species with water and H2.50-52
In conclusion, we found that less common Ni2P NPs showed
high catalytic activity for the selective transformation of biofu-
ranic aldehydes to 2,5-diketones. This study represents the first
example of a nonprecious metal catalyst promoting this reaction.
Although conventional Ni catalysts and other metal phosphides
showed poor activity, the Ni2P catalyst efficiently promoted the
transformation in water as solvent under additive-free condi-
tions. Furthermore, the Ni2P/mordenite catalyst was easily re-
coverable and reusable without losing activity and selectivity.
Spectroscopic analyses showed that the Ni2P NPs had an intrin-
sic metal-like nature, with Ni–Ni species as H2 activation sites
and P–OH as surface acid sites. Bifunctional catalysis of Ni2P
NPs, combining its hydrogenation ability and acidity, was key
to the successful transformation of 1 into 2, providing a new
cost-effective and efficient method for diketone synthesis from
biofuranic aldehydes.
Based on the results of these control experiments, we pro-
posed a possible reaction pathway for the transformation of 1
to 2 using Ni2P NPs, as shown in Scheme 3. First, 1 is hydro-
genated into 5-methylfurfuryl alcohol at the Ni–Ni site of Ni2P
NPs. Subsequently, 5-methylfurfuryl alcohol intermediate is
transformed into 3-hexene-2,5-dione through hydrolysis, fol-
lowed by a ring-opening reaction promoted by surface acid sites
of PO–H.53 Finally, successive hydrogenation of the C=C bond
of 3-hexene-2,5-dione proceeds to give desired product 2. In
the above catalytic cycle, bifunctional catalysis of Ni2P NPs,
involving the H2-activating ability of Ni–Ni sites and surface
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Scheme 2. Control experiments under various conditions over
Ni2P NPs.
ASSOCIATED CONTENT
Supporting Information.
The Supporting Information is available free of charge on the
xxx.
Experimental details, characterization of catalysts and
NMR data. (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: mitsudom@cheng.es.osaka-u.ac.jp
ORCID
Kiyotaka Nakajima: 0000-0002-3774-3209
Tomoo Mizugaki: 0000-0001-5701-7530
Koichiro Jitsukawa: 0000-0002-4893-5863
Takato Mitsudome: 0000-0002-0924-5616
Notes
Scheme 3. Plausible reaction pathway for the conversion of 1
into 2 over Ni2P NPs.
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by JSPS KAKENHI Grant Nos.
26289303, 26105003, 24246129 and 17H05224. This study was
partially supported by the Cooperative Research Program of In-
stitute for Catalysis, Hokkaido University (19A1002). A part of
this work was conducted at Hokkaido University, supported by
"Nanotechnology Platform" Program of the Ministry of Educa-
tion, Culture, Sports, Science and Technology (MEXT), Japan.
We thank Dr. Ina (SPring-8) for XAFS measurements.
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