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3
5000 scans were recorded by a recycle time of 4 ms. The excita-
chromatography (Agilent 7890A GC equipped with HP-5MS 25 m
tion pulse had a length of 5 ms, with a relaxation delay between
transients of 0.5 s. The chemical shifts are reported relative to an
external standard of adamantane (d=29.472 ppm).
0.25 mm i.d. column, coupled with Agilent 5975C MS).
In situ IR spectroscopic study of phenol HDO
In situ IR spectra were recorded on the ReactIR 45 m device (Met-
tler Toledo) connected to the sentinel probe through the conduit
K4. The sentinel probe is coupled to a Parr reactor (150 mL), where
a diamond probe is used to collect the in situ IR spectra in the
liquid phase (Figure S9 in the Supporting Information). Before mea-
surement, the background was collected at reaction conditions
Raman spectroscopy
Raman spectra were collected with a Renishaw Raman spectrome-
ter 1000 equipped with a CCD detector using a 514 nm diode laser
for excitation and Si(111) wafer as an external standard.
(
5
473 K, 3 MPa H ) with 1.0 g catalyst (Ni/C
0 mL hexadecane. Then the autoclave was loaded with the reac-
-SO H) dispersed in
2
GlꢀZn 3
Thermal gravimetric analysis (TGA)
The thermal gravimetric analysis was performed on a Setaram TG-
DSC 111 thermo analyser connected to a high-vacuum system.
About 30 mg of the carbon sample was placed in a quartz sample
holder and the measurement was started at 273 K under vacuum
tant phenol (5.0 g) and H (3 MPa) was charged at ambient temper-
2
ature. The reactor was heated and the stirring was started once
the temperature reached 463 K. The spectra were collected every
ꢀ
1
1 min for a total duration of 180 min, with 8 cm spectral resolu-
tion and 256 scans per spectrum.
ꢀ
4
ꢀ1
(p<10 mbar) with an incremental heating rate of 1 Kmin to
reach 1000 K. The SO release from the sample was measured in
2
a Pfeiffer Vacuum PrismaPlus mass spectrometer.
Catalytic measurements
Cyclohexanol dehydration
X-ray absorption spectroscopy
In a typical experiment for cyclohexanol dehydration, a mixture of
The near-edge structure (XANES) and extended X-ray absorption
fine-structure (EXAFS) measurements were performed at the Pacific
Northwest Consortium/X-ray Science Division (PNC/XSD) bending-
magnet beamline at Sector 20 of the Advanced Photon Source
cyclohexanol (0.10 mol), hexadecane (60mL), and C-SO H (0.5g)
3
was first charged into the reactor (Parr, Series 4843, 300mL). After
flushing the reactor with H three times, it was heated to 473 K at
2
5
1
MPa H while being stirred at 700 rpm; this was continued for
h at reaction temperature. After the reactor was cooled to room
2
(
APS) at Argonne National Laboratory (ANL). The experiments were
performed in transmission mode with a focused beam (0.7ꢄ
1
0
temperature, the H pressure was released and an aliquot of 2 mL
2
0
.6 mm) sending 10 photons through the sample with a harmonic
was analysed by gas chromatography (GC, Shimadzu 2010) with
a HP-5 capillary column (30mꢄ250 mm) and flame ionization de-
tector (FID). Additionally, a gas chromatograph-mass spectrometer
rejection of 5.6 mrad and 8100 eV to decrease the effects of har-
monics. An Ni foil was placed downstream of the sample cell, as
a reference to calibrate the photon energy of each spectrum. A
continuous series of Ni-K edge spectra were acquired throughout
(GC-MS, Shimadzu QP 20105) was used to identify the organic
ꢀ1
compounds. The gas phase was determined by GC (HP 6890)
equipped with a plot Q capillary column (30mꢄ250 mm) with ther-
mal conductivity detector (TCD).
the entire reaction sequence using either 4 min (k=12 ꢃ ) or
ꢀ
1
1
2 min (k=18 ꢃ ) acquisition times. The quantitative analysis al-
lowed the evaluation of bond lengths and Debye–Waller factors
2
Phenol HDO was studied on Ni/C-SO H catalysts to evaluate the ki-
(
structural disorder; s ) up to 6 ꢃ from the core Ni atom. The data
3
[41,42]
netic data in separated batches: a) phenol (6.4 mmol), hexadecane
were processed with the ATHENA program
analysed with the ARTEMIS program. The Fourier transform of
and subsequently
[43]
(
60 mL), Ni/C-SO H (0.12 g), 473 K, 4 MPa H , and b) same condi-
3
2
tions with physically admixed C-SO H (12, 25 and 60 mg). A typical
reaction was performed in an autoclave batch reactor (Parr, Series
the k-space EXAFS data [both real and imaginary parts of c˜ (R)]
3
[44]
were fitted to the FEFF9 theoretical model. Reference standards
used in the analysis included bulk (fcc) NiO, bulk (hcp) a-Ni(OH)2,
and bulk (fcc) Ni. Their lattice parameters were obtained from the
4
843, 300 mL). After loading the reactant, catalyst, and hexade-
cane, the reactor was flushed three times with H . At reaction tem-
2
[45,46]
perature, H was charged to a total pressure of 4.0 MPa and the
literature.
In situ measurements were performed using the microreactor cell
2
mixture was allowed to react for 60, 120, 180, 240, 300 and
360 min while stirring at 700 rpm. After reaction, the work-up pro-
cedure was similar to that described above.
[35]
and procedures described by Chase et al. with a few modifica-
ꢂ
ꢁ
tions. HiP medium pressure Hastelloy tees with an internal
volume of 2 mL were used as reactor cells. Glassy-carbon discs,
0
.75 mm thick by 3 mm in diameter, were used as windows. The
Acknowledgements
discs were affixed to through-bore plugs which had been ma-
chined such that the distance between the windows was approxi-
mately 1 mm. Samples containing approximately 30 mg catalyst
were pressed into a pellet, 0.4 mm thick by 3.5 mm in diameter,
and held between the windows by a polyether ether ketone (PEEK)
This work was supported by the US Department of Energy
(DOE), Office of Basic Energy Sciences (BES), Division of Chemi-
cal Sciences, Geosciences and Biosciences. Pacific Northwest
National Laboratory is a multiprogram national laboratory op-
erated for DOE by Battelle through Contract DE-AC05-
2
mesh (35 mm ). Typically, the reactor was charged with 0.9 mL of
0
.56m phenol solution and then purged with H at room tempera-
2
ture using five fill/purge cycles, then filled to a pressure of approxi-
mately 4.9 MPa. (In some experiments water or no liquid at all was
used.) A spectrum was recorded and then cell was heated to 473 K
while repeatedly recording spectra. The reaction conditions (T=
7
6L01830. PNC/XSD facilities at the Advanced Photon Source,
and research at these facilities, are supported by DOE/BES, the
Canadian Light Source and its funding partners, the University
of Washington, and the Advanced Photon Source. Use of the
Advanced Photon Source, an Office of Science User Facility op-
erated for the DOE Office of Science by Argonne National Lab-
4
73 K, ptotal ~5 MPa) were maintained for periods of up to 12 h
during acquisition of the X-ray spectra. The liquid contents of the
cell were removed after reaction and analysed by capillary gas
Chem. Eur. J. 2015, 21, 1567 – 1577
1576
ꢂ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim