Achmatowicz rearrangement enables hydrogenolysis-free gas-phase synthesis of pentane-1,2,5-triol from furfuryl alcohol

Article abstract of DOI:10.1039/c9gc02888a

Highly efficient synthesis of pentane-1,2,5 triol, a promising member of biorenewable C5 alcohols, has been achieved by gas-phase hydrogenation of the Achmatowicz intermediate derived from furfuryl alcohol. The hydrogenation was carried out on monocomponent or bicomponent Ni and/or Pt modified mesoporous silica catalysts. The process features the absence of hydrogenolysis of the furan ring and rendered 100% selectivity together with additional green chemistry benefits, such as mild and simpler solvent free technology that operates at atmospheric pressure. The bicomponent Ni/Pt modified mesoporous silica catalysts exhibited the highest catalytic activity, with 10Ni1Pt/KIT-6 being the most active, providing up to 100% conversion.

Full text of DOI:10.1039/c9gc02888a

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Please Gd roe en no tC ha ed mj u iss tt r my argins
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DOI: 10.1039/C9GC02888A
ARTICLE
Achmatowicz rearrangement enables hydrogenolysis–free gas–
phase synthesis of pentane-1,2,5-triol from furfuryl alcohol.
a
a
a
a
Svilen P. Simeonov,* Hristina I. Lazarova, Maya K. Marinova and Margarita D. Popova
Received 00th January 20xx,
Accepted 00th January 20xx
Abstract: Highly efficient synthesis of pentane-1,2,5 triol, a promising member of the biorenewable C5 alcohols, has
been achieved by gas-phase hydrogenation of the derived from furfuryl alcohol Achmatowizc intermediate. The
hydrogenations were carried out on monocomponent or bicomponent Ni and/or Pt modified mesoporous silica catalysts.
The process features the absence of hydrogenolysis of the furan ring and rendered 100 % selectivity together with additional
green chemistry benefits, such as mild and simpler solvent fee technology that operates at atmospheric pressure. The
bicomponent Ni/Pt modified mesoporous silica catalysts exhibited the highest catalytic activity, with 10Ni1Pt/KIT-6 being
the most active, providing up to 100% conversion.
DOI: 10.1039/x0xx00000x
1
1
25PTO is a homolog of the industrially produced butane-
1
. INTRODUCTION
,2,4-triol thus is a promising target for technological
7
Recently, driven by the uncertain availability of fossil exploration. 125PTO has been observed as a side product in
resources and the related environmental concerns, substantial 19% yield from the hydrogenation of furfural to 1,2-
8
steps towards the transition to a bio-based economy have pentanediol in the presence of Rh-Ir alloy. Later, it has been
been taken. Due to their large availability from the detected in up to 6.2% conversion and 48.7% selectivity during
9
carbohydrates fraction of the biomass, the furanics quickly the hydrogenolysis of THFA over Ni catalysts. Our group
emerged as the privilege candidates for technological recently reported the synthesis of 125PTO from furfuryl
exploration. Currently, two major platforms, namely 5- alcohol in outstanding 92% yield.10 In that work we harnessed
1
hydroxymethyl furfural (HMF) derived from hexoses and the improved reactivity of intermediate 1 (Figure 1), which was
2
furfural derived from pentoses are considered the most conveniently achieved by Achmatowicz rearrangement of
promising. However, despite the intense research, the HMF furfuryl alcohol and bypassed the problematic C-O bonds
platform is still in its industrial infancy and is considered a hydrolysis or hydrogenolysis. Notwithstanding the high yield of
3
“
Sleeping Giant” that has to be awakened. In contrast, the 125PTO and the implementation of flow chemistry
furfural platform is currently one of the notable examples of an methodology, several drawbacks remained namely, the high
4
industrialized biorefinery process. Apart from furfural, many price of the Pt and Ru catalysts, the very high
of its derivatives, for instance, furfuryl alcohol,2a catalysts/substrate ratios and the large influence of the solvent
2
b
tetrahydrofurfuryl alcohol (THFA), , etc. have also reached and the concentration of the feeding solution over the reaction
industrial stage, while others, such as C5 alcohols, are still outcome.
challenging targets.
With the idea to overcome those drawbacks, we envisaged
The biorenewable C5 alcohols have been recognized as that the hydrogenation of the Achmatowicz intermediate 1 in
important commodity chemicals for the production of gas instead of liquid phase will render higher catalytic activity
polyesters, polyurethanes, polyethers, and fuel additives.5 and simultaneous use of cheap metal catalysts. On the other
However, the upgrade of the existing portfolio of furfural hand, the solvent-free approach may provide additional green
derived C5 alcohols usually relies on catalytically challenging chemistry credits. Given the aforementioned considerations,
hydrolysis or hydrogenolysis of the furan ring.6 These herein we report the first highly efficient synthesis of 125PTO
transformations usually suffer from harsh conditions and low by gas-phase hydrogenation of 1 over mono or bicomponent
atom efficiency, which goes against the major principles of transition metal modified mesoporous silica catalysts.
green chemistry. In particular, the synthesis of pentane-1,2,5-
triol (125PTO) has been rarely achieved from the furfural
platform (Figure 1). This observation is intriguing because
a.
Institute of Organic Chemistry with Centre of Phytochemistry
Bulgarian Academy of Sciencies
Acad. G. Bontchev str. Bl. 9, 1113 Sofia, Bulgaria
E-mail: svilen@orgchm.bas.bg
†
Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Pleas eG dr eo e nn oC th ae dm j ui s st tr ym argins
Page 2 of 9
ARTICLE
Journal Name
Selected examples of 125PTO synthesis from the furfural platfom
2. EXPERIMENTAL SECTION
View Article Online
DOI: 10.1039/C9GC02888A
Rh-Ir alloy
H2
2.1. General
O
O
Unless otherwise stated, all reagents were purchased from
commercial sources and were used without further
purification. The NMR spectra were recorded on Bruker
Avance II+ 600 ( H at 600.13 MHz; 13C at 150.92 MHz)
up to 19%
Ref. 25
Furfural
OH
Ni/HZSM-5
HO
OH
1
7
4
.6 % convertion
1.1 % selectivity
Ref. 9a
O
1
25PTO
OH
spectrometer using CDCl as a solvent.
3
THFA
Ni/SAPO–34
X-ray patterns were recorded on Philips PW 1810/3710
6
4
.2 % convertion
8.7 % selectivity
Ref. 9b
diffractometer applying monochromatized CuKα radiation (40
kV, 35 mA). Crystallite sizes of the metal oxides were
determined by the Sherrer equation evaluating the FWMH
values with full profile fitting methods.
Our previous work
3
0% aq. H2O2
.2 equiv
Ru/C
O
O
H2
OH
1
OH
O
OH
HO
OH
Nitrogen physisorption measurements were carried out at
77 K using Quantachrome NOVA Automated Gas Sorption
Instrument. Samples were pretreated at 623 K in a vacuum.
The pore-size distributions were calculated from the
desorption isotherms by the BJH method.
TS1
EtOH in Flow
EtOH in Flow
up to 0.05M
1
125PTO
furfuryl
alcohol
up to 92% from
furfuryl alcohol
This work
The
temperature-programmed
reduction-
1
0Ni1Pt/KIT-6
OH
OH
O
H2
HO
thermogravimetric analysis (TPR-TGA) investigations were
performed on Setaram TG92 instrument. The sample (40 mg)
was placed in a microbalance crucible and heated in a flow of
0 vol. % H in Ar (100 cm /min) up to 600 C at 5 C/min and a
2
final hold-up of 1h. Prior to the TPR experiments the samples
O
OH
gas phase, 120°C
TOF = 0.9 s-1
1
25PTO
1
1
1
00% conversion
00% selectivity
3
o
o
5
Figure 1. Overview of the 125PTO synthesis from the furfural
platform
o
were treated in situ in air flow (10 C/min) up to 600°C,
followed by a hold-up of 1 h.
Supported noble metals and metal oxides have been
explored in many catalytic processes.11 Gas-phase
hydrogenation reactions have been carried over a large
number of mono- and bimetallic catalysts, for instance, Pt, Ni,
Diffuse reflectance spectra in the UV-Vis region were
detected at ambient using Jasco V-670 UV-Vis
spectrophotometer equipped with NV-470 type integrating
4
sphere using a BaSO disk as reference. The data were
2 3 2
Pd, Cu, Co and Fe on various supports, such as Al O , SiO ZrO2,
collected between 900 and 200 nm wavelengths with 100
nm/min speed, and with 2 nm bandwidth at 1 nm data pitch.
The TEM images were taken on JEOL JEM 2100 ТЕМ (200
kV). The samples were suspended in a small amount of ethanol
and a drop of the suspension was deposited onto copper grid
covered by carbon supporting film and dried at ambient.
and active carbon have been explored.12 Among those
supports mesoporous silica materials are of particular interest
due to their uniform mesoporous channel structure and high
specific surface area. A variety of metal ions (Fe, Ti, V, Cr, Cu,
Mn, etc.) has been introduced into silica matrix and the
tuneable catalytic properties of the obtain materials have been
demostrated.11a, 13 Several parameters such as the preparation
method, type of salt precursors and supports strongly
influence the state (localization, dispersion, and oxidative
state) of the loaded metal species.12a, 14 The modification of
mesoporous materials by two metals have been used to obtain
catalysts owning higher activity and thermal stability as
compared to the single oxides. Furthermore, the appropriate
ratio between two metals and their amount could facilitate the
stabilization of metals as finely dispersed nanoparticles on the
silica mesoporous support.11d, 15
Given the enormous utility of the mesoporous silica
materials as catalyst support in gas phase hydrogenation
reactions for our studies we explored KIT-6 and SBA-15 silicas
2.1.1.
Synthesis of 6-hydroxy-(2H)-pyran-3(6H)-one
Achmatowicz intermediate)
1
(
Freshly distilled furfuryl alcohol (20 g) was dissolved in
acetonitrile (200 mL) than the catalyst TS-1 (2 g) was slowly
added followed by dropwise addition of aq. H O (37%, 30 mL).
2 2
The reaction mixture was heated under stirring at 40°C for 5 h
The progress was monitored by TLC (EtOAc/Hexane = 1:1) until
full consumption of the starting material. The crude mixture
was filtered, the filtrate was evaporated under vacuum,
dissolved in CH
21.62 g), without further purification. The product was
isolated as pale-yellow oil that crystallized in the freezer (-
2°C).
2 2 4
Cl and dried over MgSO to give 1 in 94%
(
1
as supports for Ni and/or Pt nanoparticles formed by incipient 2.2. Synthesis of the catalysts
wetness impregnation. The catalysts have been fully
characterized and their catalytic behaviour is demonstrated.
2
.2.1. Synthesis of TS-1 catalyst
TS-1 was prepared according to a previously described
procedure16 with modifications. Tetraisopropyl orthotitanate
2
| J. Name., 2012, 00, 1-3
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Pleas eG dr eo e nn oC th ae dm j ui s st tr ym argins
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(0.93 g) and tetraethyl orthosilicate (22.5 g) were dissolved in give 1Pt/KIT-6 or 1Pt/SBA-15, respectively. ThVieewnAr0tic.l2e7O5nlinge
5
0 mL 20 wt% aqueous solution of tetrapropylammonium Ni(NO .6H O was dissolved in 2 mL
3
)
2
2
D
E
O
tOI:
H
10
,
.1
a
0
d
39
d
/
e
C
d
9G
t
C
o
02
0 g
.588A
8
hydroxide (TPAOH) under vigorous stirring. The resulting 1Pt/KIT-6 or 1Pt/SBA-15 and stirred till dry. Then the samples
mixture was kept at 60°C for 3h. The final molar ratios in the were dried at 80°C for 18 h. The precursor salts were
solution were: SiO
2
/TiO
2
= 32.7, TPAOH/SiO
2
2
= 0.46, H O/SiO
2
decomposed in air at 450°C at a rate of 1°C/min for 3 hours.
=
35. The mixture was transferred into a stainless steel The samples were denoted as 10Ni1Pt/SBA-15 and
autoclave and heated in an oven at 175°C, under autogenous 10Ni1Pt/KIT-6.
pressure, in static conditions for 24h. After cooling to room 2.4. Catalytic activity measurements
temperature, the crystalline product was filtered, washed
several times with water, dried at 100°C for 2 h, and finally 1 h in H (60 mL/min) up to 400 C. The hydrogenation of 6-
2
Prior to the catalytic tests, the samples were pretreated for
o
calcined at 550°C in air for 5 h.
.2.2. Synthesis of SBA-15
Pluronic P123 (12.0 g) was dissolved under vigorous stirring (30 mL/min). 50 mg sample (particle size 0.2-0.8 mm) diluted
at 35°C in a solution of 37.1 g 37 % HCl in 365.8 g distilled H
O.17 with 50 mg glass beads of the same diameter, previously
hydroxy-(2H)-pyran-3(6H)-one 1 was studied at atmospheric
2
pressure using a fixed-bed flow reactor with H as carrier gas
2
2
After the surfactant was completely dissolved, 24.0 g TEOS was checked to be inactive, was tested in each reaction. The reactor
added and the stirring was continued for 24 h. The obtained itself was a quartz tube of 15 mm inner diameter, with the
gel was transferred into an autoclave and kept at 100°C for catalyst bed in the middle. For accurate measurement of the
another 24 h followed by filtration, washing with distilled catalyst’s temperature a thermocouple was positioned in the
water and drying at room temperature. For template removal, catalyst bed. All gas lines of the apparatus were heated
o
the obtained powder sample was calcined with a temperature continuously at 110 C in order to minimize reactant and
increase of 1°C/min up to 550°C and dwelling times of 2 h at products adsorption on the tube walls because of the high
o
2
90°C and 6 h at 550°C.
boiling temperature of 6-hydroxy-(2H)-pyran-3(6H) 1 (298 C).
2
.2.3. Synthesis of KIT-6
The H
2
stream was passed through a saturator filled with 6-
o
Pluronics P123 (12.0 g) was dissolved under vigorous hydroxy-(2H)-pyran-3(6H)-one 1 and equilibrated at 80 C,
stirring at 35°C in a solution of 37.1 g 37 % HCl in 365.8 g ensuring 0.68 g/h reactant content in the H
2
flow. The reactant
O. Then 12.0 g of 1-butanol was added and stirred was fed into the reactor by bubbling through it H flow at 30
for an additional 1 h. Then, 24.0 g of TEOS was added and the mL/min rate. The catalytic tests were carried out in the
1
7
distilled H
2
2
o
-1
stirring was continued for 24 h. The formed gel was transferred temperature range of 50-400 C and WHSV=1.1 h . The
in a teflon autoclave and heated at 140°C for 24 h. After reaction steady state was established after 30 min at each
filtration, washing and drying at room temperature, the temperature. On-line analysis of the reaction products was
obtained powder was calcined in a muffle furnace by heating performed using HP-GC-FID/TCD with a 30 m HP 5MS capillary
at a rate of 2°C/min to 550°C for 6 h.
column. The catalytic activity of all the studied samples was
2
.3. Preparation of mesoporous silicas transition metal represented as 6-hydroxy-(2H)-pyran-3(6H)-one conversion
modified analogs.
(%) and TOF (calculated using the amount of the metallic sites
o
An incipient wetness impregnation technique with Ni and at 120 C).
Pt was applied for loading of 10 wt. % and 1 wt. % metals,
respectively. The supports were heated at 160°C for 2 h before
3. RESULTS AND DISCUSSION
the impregnation procedure.
.3.1. Preparation of monocomponent-modified silicas:
.275 g Ni(NO .6H O was dissolved in 2 mL EtOH, added
2
The XRD data of the Ni and Pt modified silica materials in the
low two theta region (not shown) confirmed the preservation of the
mesoporous structure after the impregnation process. The
observed reflections with low intensity in the higher two theta
region for the monocomponent Pt supported catalysts indicated the
formation of Pt particles with high dispersion whereas reflections
with high intensity were registered for Ni-containing catalysts
showing the formation of bigger NiO particles. For the bicomponent
Ni and Pt supported materials, wide reflections with low intensity,
typical for Pt nanoparticles and an intensive peak, typical for NiO
0
3
)
2
2
to the silica support (0.5 g KIT-6 or SBA-15) and stirred till dry.
Then the sample was dried at 80°C for 18 h.
0
.105 g Pt(II) acetyl acetonate was dissolved in 20 mL EtOH
and added to the silica support (0.5 g KIT-6 or SBA-15) under
stirring at room temperature for 1 h. The solvent was removed
under vacuum. Then the sample was dried at 80°C for 18 h. The
precursor salts were decomposed in air at 450°C at a rate of
1
1
2
°C/min for 3 hours. The samples were denoted as 10Ni/SBA-
5, 10Ni/KIT-6, 1Pt/SBA-15 and 1Pt/KIT-6.
.3.2. Preparation of bicomponent-modified silicas:
(Figure 2), were registered. The formation of smaller NiO particles
was evident for the mono- and bicomponent KIT-6 supported
catalysts. Peaks with higher intensity were detected for the SBA-15
supported samples thus suggesting the formation of bigger NiO
particles.
0
.105 g Pt(II) acetyl acetonate was dissolved in 20 mL EtOH
and added to the silica support (0.5 g KIT-6 or SBA-15) under
stirring at room temperature for 1 h. The solvent was removed
under vacuum. Then the sample was dried at 80°C for 18 h to
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Journal Name
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DOI: 10.1039/C9GC02888A
1
0Ni/SBA-15
1
Pt10Ni/SBA-15
1
Pt/SBA-15
SBA-15
20
40
60
80
Figure 3. TEM images of 1Pt/KIT-6 (A, C) and 10Ni1Pt/KIT-6
Bragg angle/°2
samples (B, D)
The nitrogen physisorption isotherms of the metal-containing
silica materials are shown in Figure 4, while the corresponding
calculated parameters are summarized in Table 1.
1
0Ni1Pt/KIT-6
9
8
7
6
00
00
00
00
SBA-15
10Ni/SBA-15
1
0Ni/KIT-6
1
1
0Ni1Pt/SBA-15
Pt/SBA-15
1
Pt/KIT-6
KIT-6
500
00
300
4
2
0
40
60
80
Bragg angle/°2
2
1
00
00
0
Figure 2. XRD of the KIT-6 and SBA-15 supported samples
The crystallite sizes of the Ni and Pt nanoparticles after ex-situ
reduction determined by the Scherrer method are summarized in
Table 1. The reduction of the Ni-containing samples led to the
formation of metallic nanoparticles with sizes in the interval 10-18
nm whereas smaller Ni nanoparticles (8 nm for 10Ni1Pt/KIT-6 and
0
,0
0,2
0,4
0,6
0,8
1,0
relative pressure, p/p0
The
9
00
1
1
0Ni1Pt/KIT-6
0Ni/KIT-6
800
1
5 nm for 10Ni1Pt/SBA-15) were detected on Ni-Pt bicomponent
7
6
00
00
KIT-6
Pt/KIT-6
materials. This phenomenon is possibly due to the effects of
redispersion of Pt on the Ni nanocrystals on the surface of the silica
matrix.
1
500
The obtained TEM data was in a good accordance with the XRD
observations. The TEM images of 1Pt/KIT-6 (A, C) and 10Ni1Pt/KIT-
4
3
2
00
00
00
6
(B, D) (Figure 3) showed that the predominant particle sizes of Pt
in 1Pt/KIT-6 are around 6 nm however some clusters of around 12
nm were also observed. The Pt and Ni particles in 10Ni1Pt/KIT-6
were around 5 and 10 nm, respectively.
100
0
0
,0
0,2
0,4
0,6
0,8
1,0
relative pressure (p/po)
Figure 4. N
2
physisorption of the KIT-6 and SBA-15 supported
samples
The isotherms were of type IV (IUPAC classification), with a
sharp capillary condensation step at about 0.7 and 0.6 relative
pressures, characteristic of KIT-6 and SBA-15 type mesoporous
4
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materials, respectively. On SBA-15 catalysts a parallel, H1 type and 700-760 nm preserving the absorption bands aVtie2w6A0rt-i2cl9e5Onnlinme
hystereses loop was observed.17-18 This is a characteristic of narrow which suggests some modification of thDeONI: i1O0x.10s3p9e/Cci9eGsCo0n288th8Ae
pore size distribution, indicating the preservation of the catalyst.
mesoporous structure. The impregnation procedure resulted in a
decreased BET surface area of the modified KIT-6 and SBA-15
materials (Table 1). Upon impregnation the average pore diameter
in KIT-6 samples slightly decreased, whereas in SBA-15 a bimodal
pore structure was formed with 6 and 4.7-4.4 nm pore diameters
(Table 1). This indicates that some pores were not affected by the
impregnation procedure, while other pores are partly blocked by
the metal nanocrystals.
Table 1. Physico-chemical properties of the samples
Size of the
metallic
particles
PDa
Pore
Extent of TOF at
reductionb 120 C,
S
BET
2
o
Sample
(nm) volume
(
m /g)
3
s-1
(
cm /g)
(%)
(nm)
KIT-6
660
610
430
490
760
680
460
7.9
7.9
7.8
7.9
6.0
6.0
4.6
4.8
1.2
1.1
0.9
1.0
0.9
0.9
0.7
0.5
-
-
-
0.53
-
1
Pt/KIT-6
4c
100
80.8
77.2
-
Figure 5. UV Vis spectra of the KIT-6 and SBA-15 supported
1
0Ni/KIT-6
10d
samples
c
d
1
0Ni1Pt/KIT-6
SBA-15
(4 ) 8
-
0.90
-
TPR-TG profiles of the Ni and/or Pt-modified materials are
shown in Figure 6. TPR curves of 1Pt/KIT-6 and 1Pt/SBA-15 samples
exhibit a low intensive peak at a high reduction temperature. The
TPR curve of the 10Ni//KIT-6 sample is characterized by several
overlapping peaks between 440 and 534 K and one low intensive
peak at 723 K. The first reduction step could be probably related to
the reduction of finely dispersed NiO particles. The higher
temperature peak could be associated with the reduction of the Ni
species incorporated into the wall of the silica matrix during the salt
decomposition procedure by reaction with the surface silanol
groups.12a The TPR curve of 10Ni/SBA-15 was characterized by two
reduction peaks at 565 and 677 K, the latter being more intensive.
Bicomponent samples supported on KIT-6 and SBA-15 were reduced
1
Pt/SBA-15
4c
100
96.4
78.8
0.46
-
1
0Ni/SBA-15
18d
c
d
1
0Ni1Pt/SBA-15 307
(4 ) 15
0.81
a
Pore diameter calculated by BJH method (desorption branch); b total
weight loss related to the calculated theoretical weight loss for the reduction
of the corresponding ion to metallic state; sizes of Pt particles determined
by XRD using the Debye-Scherrer method; sizes of Ni particles determined
by XRD using the Debye-Scherrer method.
c
d
The oxidation and coordination state of the Ni species in the
modified KIT-6 and SBA-15 samples were characterized by DR UV-
Vis spectra (Figure 5) recorded at room temperature. As was
expected no UV–Vis absorbance was evident in the spectra of
o
in one step at low temperature (the peaks’ maximum is at 177 C for
o
1
0Ni1Pt/KIT-6 and at 252 C for 10Ni1Pt/SBA-15). The high-
1
Pt/SBA and 1Pt/KIT-6. The Ni-containing samples present a broad
temperature peak which was registered for Ni-containing samples
disappears in the case of bicomponent ones. Compared to the
monocomponent the low-temperature peak for the both
bicomponent samples was shifted down by 40-80°C. More
adsorption band, which exhibits a maximum at 245-260 nm with a
shoulder at 295 and then a long tail towards longer wavelengths.
This zone is typically associated with the O (2p) → Ni (3d) charge
transfer transition of octahedral Ni2+ species, although the first
maximum at 260 nm could also be attributed to isolated Ni
incorporated in the structure.19 Several adsorption bands at 430 and
2
-
2+
o
prominent shift by 80 C was registered for 10Ni1Pt/SBA-15 with a
o
reduction peak maximum centered at 177 C (Figure 6). The
presence of Pt nanoparticles in bicomponent samples facilitated the
5
10 nm, and an adsorption zone in the 700-800 nm range, were
2
H dissociation and nucleation thus enabling the reduction of NiO at
a lower temperature.21
registered for the 10Ni1Pt/SBA-15. The latter bands are not
registered for the 10Ni1Pt/KIT-6 material. These bands in the visible
The overall reduction rates of the NiO nanoparticles supported
on KIT-6 and SBA-15 (Table 1), were lower than the theoretically
required, which can also be explained by the formation of hardly
reducible NiO species.
region are associated with several kinds of d-d transitions,
superimposed with each other, of Ni2+ ions in octahedral local
environment in NiO.20 The observed red-shift in the interval 410-580
nm can be ascribed to the well-known quantum size effect,
demonstrating the presence of smaller NiO particles in the Ni- and
Pt-containing samples as compared to the monocomponent
1
1
0Ni/SBA-15 and 10Ni/KIT-6.19b The presence of Pt in the
0Ni1Pt/SBA-15 and 10Ni1Pt/KIT-6 catalysts significantly decreased
the broad absorption bands in the regions between 410–580 nm
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Pleas eG dr eo e nn oC th ae dm j ui s st tr ym argins
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Journal Name
View Article Online
DOI: 10.1039/C9GC02888A
1
Pt/SBA-15
1
0Ni/SBA-15
2
92
2
52
1
0Ni1Pt/SBA-15
4
04
T=const
1
00
350
Temperature, C
600
o
1
Figure 7. H NMR spectra of 1 A) authentic sample; B) 80°C, 20 min
under Argon.
1
Pt/KIT-6
1
67
4
50
2
17
1
0Ni/KIT-6
2
60
1
77
1
0Ni1Pt/KIT-6
T=const
1
00
350
600
o
Temperature, C
Figure 6. TPR of the KIT-6 and SBA-15 supported samples
Figure 8. Hydrogenation of 1 to 125PTO vs. reaction temperature
The catalytic activity was dominated by the metal components,
while the type of mesoporous silica support exhibited a strong
effect on the state and dispersion of the active sites.
Monocomponent Pt-modified 1Pt/KIT-6 and 1Pt/SBA-15 catalysts
exhibited much higher catalytic activity as compared to
monocomponent Ni- modified 10Ni/KIT-6 and 10Ni/SBA-15 (Figure
With a set of fully characterised catalysts in hand we focused on
the gas phase synthesis of 125PTO. To our delight, the use of 1 as
an intermediate in this process was beneficial. In contrast with the
previous reports .(Figure 1) on the synthesis of 125PTO from the
furfural platform,8-9 the exclusion of the hydrogenolysis of the
parent furan ring and the ease reduction of the olefin and carbonyl
moieties in 1 render 100% selectivity in all cases with no evidence
of side reactions. In order to validate these results, we studied the
stability of 1 by simulating the conditions in the saturator. To this
end, we heated 1 under inert atmosphere at 80°C for 20 min. The
8
). The ability of the metallic Pt to activate hydrogen causing high
activity in hydrogenation reactions is well known.20 The
simultaneous modification by Ni and Pt resulted in significantly
higher activity for 10Ni1Pt/KIT-6 and 10Ni1Pt/SBA15 which was
more pronounced in case of the former (Figure 8). In order to clarify
the role of the obtained metallic sites in the catalytic process, the
1
comparison of the collected H NMR spectra with an authentic
sample showed no evidence of decomposition (Figure 7).
Furthermore, for the entire set of experiments, we have never
observed side peaks by FID neither formation of light gases, such as
CO or CO , by TCD analysis (all the samples were analysed by
2
GC/FID/TCD). These observations prompt us to believe that indeed
the process is highly selective.
o
turnover frequency (TOF) data at 120 C was calculated for the
catalysts which were active at this temperature (Table 1).
1
0Ni1Pt/KIT-6 catalyst rendered the highest TOF value thus
demonstrating the beneficial synergistic effect of the simultaneous
modification with Pt and Ni particles and the pore structure of the
KIT-6 material. Moreover, a drop in the activity was registered for
the monocomponent Pt-modified 1Pt/KIT-6 and 1Pt/SBA-15
catalysts with time on stream (3 h) whereas the bicomponent
6
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Pleas eG dr eo e nn oC th ae dm j ui s st tr ym argins
Journal Name
ARTICLE
samples exhibited stable activity. This could be explained by Achmatowicz rearrangement as a platform transfVoierwmAartitciloe nOnflioner
preservation of metallic nanoparticles’ dispersion (both Pt and Ni) biorefinery.
which was validated by the lack of changes in the particle sizes (XRD)
of the spent catalysts. Additionally, we performed catalytic tests on
DOI: 10.1039/C9GC02888A
Conflicts of interest
2
0Ni/KIT-6 and 20Ni1Pt/KIT-6 samples containing bigger Pt (8 nm)
and Ni (43 nm for mono component and 35 nm for bicomponent)
nanoparticles (XRD). The catalytic data (Figure 9) showed a decrease
of the catalytic activity in comparison to their 10%Ni-containing
mono- and bicomponent KIT-6 analogues that feature smaller
nanoparticles. Moreover, the significantly lower catalytic acidity
“There are no conflicts to declare”
Acknowledgements
The authors would like to acknowledge the financial support
from National Science Fund of Bulgaria (grant КП-06-OПР-01/2) and
partial support by the Bulgarian Ministry of Education and Science
under the National Research Programme E+: Low Carbon Energy for
the Transport and Households, grant agreement D01-214/2018. H.
Lazarova acknowledges the partial support by the Bulgarian
Ministry of Education and Science under the National Research
Programme “Young scientists and postdoctoral students” approved
by DCM # 577/17.08.2018.
2 2
was registered on 10Ni1Pt/SiO prepared with nonporous SiO
carrier (Figure 9) indicating the significant role of the particles’
dispersion.
References
1
2
(a) R.-J. van Putten, J. C. van der Waal, E. de Jong, C. B.
Rasrendra, H. J. Heeres and J. G. de Vries, Chem. Rev.,
2
013, 113, 1499-1597; (b) A. A. Rosatella, S. P.
Simeonov, R. F. M. Frade and C. A. M. Afonso, Green
Chem., 2011, 13, 754-793.
(a) X. Li, P. Jia and T. Wang, ACS Catal., 2016, 6, 7621-
7
640; (b) R. Mariscal, P. Maireles-Torres, M. Ojeda, I.
Sádaba and M. López Granados, Energy Environ. Sci.,
016, 9, 1144-1189.
K. I. Galkin and V. P. Ananikov, ChemSusChem, 2019, 12,
976-2982.
2
3
4
5
6
2
Figure 9. Hydrogenation of 1 to 125PTO on 10Ni/SiO , 20Ni/KIT-6
2
and 20Ni1Pt/KIT-6 vs 10Ni/KIT-6 and 10Ni1Pt/KIT-6
C. M. Cai, T. Zhang, R. Kumar and C. E. Wyman, J. Chem.
Technol. Biotechnol., 2014, 89, 2-10.
D. Sun, S. Sato, W. Ueda, A. Primo, H. Garcia and A. Corma,
Green Chem., 2016, 18, 2579-2597.
(a) S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau and
S. Royer, Chem. Rev., 2018, 118, 11023-11117; (b) Y.
Nakagawa, M. Tamura and K. Tomishige, ACS Catal., 2013,
4
. CONCLUSIONS
In conclusion, we demonstrated high-yield synthesis of
pentane-1,2,5-triol by gas-phase hydrogenation of the derived
from furfuryl alcohol Achmatowicz intermediate. A range of
newly prepared mono or bicomponent mesoporous SBA-15
and KIT-6 catalysts modified with Pt and/or Ni were fully
characterised and explored in a hydrogenolysis-free process
that rendered up to 100% conversion and selectivity.
Furthermore, we demonstrated that the variation of the pore
structure of the supports influences the nature and the
dispersion of the formed metal nanoparticles as well as their
catalytic activity. The successful penetration of the metal
precursors into the bimodal pore structure of KIT-6 led to the
formation of more finely dispersed metal nanoparticles than in
the open pore structure of SBA-15. The bicomponent catalysts
3
, 2655-2668; (c)
Y. Nakagawa, M. Tamura and K.
Tomishige, Catal. Surv. Asia., 2015, 19, 249-256.
(a) Y. Cao, W. Niu, J. Guo, M. Xian and H. Liu, Sci. Rep.,
7
2
015, 5, 18149; (b) G. Wang, B. Guo and R. Li, J. Appl.
Polym. Sci., 2012, 124, 1271-1280.
8
9
S. Liu, Y. Amada, M. Tamura, Y. Nakagawa and K.
Tomishige, Catal. Sci. Technol., 2014, 4, 2535-2549.
(a) E. Soghrati, C. Choong, C. K. Poh, S. Kawi and A.
Borgna, ChemCatChem, 2017, 9, 1402-1408; (b) E.
Soghrati, T. K. C. Ong, C. K. Poh, S. Kawi and A. Borgna,
Appl. Catal. B Environ., 2018, 235, 130-142.
1
0
S. P. Simeonov, M. A. Ravutsov and M. D. Mihovilovic,
ChemSusChem, 2019, 12, 2748-2754.
exhibited higher catalytic activity, showing the beneficial effect 11
of the presence of a second metal. Furthermore, our studies
provided additional green chemistry benefits, such as mild and
simpler solvent free technology that operates at atmospheric
pressure. Therefore, we believe that this highly efficient and
greener process further highlights the potential of
(a) S. Singh, R. Kumar, H. D. Setiabudi, S. Nanda and D.-
V. N. Vo, Appl. Catal., A, 2018, 559, 57-74; (b) B.
Fotoohi, M. Kazemzad and L. Mercier, Ceram. Int., 2018,
4
4, 20199-20210; (c) M. Popova, Á. Szegedi, Z.
Cherkezova-Zheleva, A. Dimitrova and I. Mitov, Appl.
Catal., A, 2010, 381, 26-35; (d) Á. Szegedi and M.
Popova, J. Porous Mat., 2010, 17, 663-668; (e) S. Song,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Pleas eG dr eo e nn oC th ae dm j ui s st tr ym argins
Page 8 of 9
ARTICLE
Journal Name
S. Yao, J. Cao, L. Di, G. Wu, N. Guan and L. Li, Appl. Catal.
View Article Online
B Environ., 2017, 217, 115-124.
(a) Á. Szegedi, M. Popova, V. Mavrodinova, M. Urbán, I.
Kiricsi and C. Minchev, Micropor. Mesopor. Mat., 2007,
DOI: 10.1039/C9GC02888A
1
2
9
9, 149-158; (b) D. Sun, A. Ohkubo, K. Asami, T. Katori, Y.
Yamada and S. Sato, Molecular Catalysis, 2017, 437, 105-
13; (c) V. V. Kumar, G. Naresh, M. Sudhakar, C.
1
Anjaneyulu, S. K. Bhargava, J. Tardio, V. K. Reddy, A. H.
Padmasri and A. Venugopal, RSC Adv., 2016, 6, 9872-9879;
(
1
d) L. Liu, H. Lou and M. Chen, Appl. Catal., A, 2018, 550,
-10; (e) K. Tie, X. Pan, T. Yu, P. Li, L. He and X. Bao, J.
Energy Chem., 2019, 31, 154-158.
(a) A. Taguchi and F. Schüth, Micropor. Mesopor. Mat.,
1
1
3
4
2
005, 77, 1-45; (b) J. Liang, Z. Liang, R. Zou and Y. Zhao,
Adv. Mater., 2017, 29, 1701139; (c) P. Sudarsanam, E.
Peeters, E. V. Makshina, V. I. Parvulescu and B. F. Sels,
Chem. Soc. Rev., 2019, 48, 2366-2421.
(a) V.-C. Niculescu, G. Paun and V. Parvulescu,
Materials Today: Proceedings, 2019, 7, 443-448; (b) J.
Grams, N. Potrzebowska, J. Goscianska, B. Michalkiewicz
and A. M. Ruppert, Int. J. Hydrog. Energy, 2016, 41, 8656-
8
667; (c) S. Chen, C. Ciotonea, A. Ungureanu, E. Dumitriu,
C. Catrinescu, R. Wojcieszak, F. Dumeignil and S. Royer,
Catal. Today, 2019, 334, 48-58.
1
1
1
1
1
5
6
7
8
9
P. C. Rath, M. Mishra, D. Saikia, J. K. Chang, T.-P. Perng and
H.-M. Kao, Int. J. Hydrog. Energy, 2019, 44, 19255-19266.
M. G. Clerici, G. Bellussi and U. Romano, J. Catal., 1991,
1
29, 159-167.
D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B.
F. Chmelka and G. D. Stucky, Science, 1998, 279, 548.
M. Grün, K. K. Unger, A. Matsumoto and K. Tsutsumi,
Micropor. Mesopor. Mat., 1999, 27, 207-216.
(a) P. Dai, T.-t. Yan, X.-x. Yu, Z.-m. Bai and M.-z. Wu,
Nanoscale Res. Lett., 2016, 11, 226; (b) Y. Volokitin, J.
Sinzig, L. J. de Jongh, G. Schmid, M. N. Vargaftik and I. I.
Moiseevi, Nature, 1996, 384, 621-623.
2
2
0
1
S. A. Karakoulia, E. Heracleous and A. A. Lappas,
Catal.Today, 2019, DOI: 10.1016/j.cattod.2019.04.072
C. M. N. Yoshioka, T. Garetto and D. Cardoso, Catal.
Today, 2005, 107-108, 693-698.
8
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Page 9 of 9
Green Chemistry
View Article Online
DOI: 10.1039/C9GC02888A
Hydrogenolysis-free gas-phase hydrogenation of an Achmatowicz intermediate provided pentane-
,2,5-triol in 94% overall yield from furfuryl alcohol
1