modification.[6a,b] First, the 1.0 g ZIF-67 particles were mounted in a
ceramic boat and heated to 440 °C with the heating ramp of 2 °C min−1
and held for 8 h under continuous flow of 10 vol% H2/Ar. The obtained
sample was denoted as Co-440. Afterward, the temperature in the
furnace was further raised to 900 °C at a heating rate of 2 °C min−1
and maintained for 2 h in a tube furnace. After the system cooled
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
down naturally,
(denoted as Co-900).
a 0.55 g of product (55% yield) was obtained
Acknowledgements
Synthesis of BTC-Derived Cobalt Catalyst: The Co-BTC was synthesized
according to the reported method described in the reported literature.[11]
The obtained Co-BTC was used as the precursor and subjected to the
same thermal treatment procedure used for Co-900. The obtained
product was denoted as Co-900-B.
Synthesis of Co/AC Catalyst: The commercial activated carbon was
first washed by deionized water and ethanol, followed by drying at 80 °C
in air overnight. Then, 0.5 g of pretreated AC was dispersed into 0.5 mL
of 3.0 m Co(NO3)2 solution, and then dried at 80 °C in air for 12 h. The
obtained AC sample with adsorbed Co was thermally treated at 500 °C
with a ramp rate of 5 °C min−1 for 2 h in N2 atmosphere. The obtained
sample was denoted as Co/AC.
W.G. and Y.L. contributed equally to this work. This work was supported
by the Natural Science Foundation of China (Grant Nos. 51432009 and
51872292) and the CAS Pioneer Hundred Talents Program. The authors
thank the 1W1B station for XAFS measurement in Beijing Synchrotron
Radiation Facility.
Conflict of Interest
The authors declare no conflict of interest.
Characterization: FESEM images of the samples were taken on a
FESEM (SU8020) operated at an accelerating voltage of 10.0 kV. TEM
(JEOL-2010) images were obtained with the instrument operated at
an acceleration voltage of 200 kV. STEM images of the samples were
recorded by a high-resolution TEM (Philips TecnaiG2 F20) operated at
an acceleration voltage of 200 kV. Powder XRD patterns were analyzed
on a Philips X-Pert Pro X-ray diffractometer using the Ni-filtered
monochromatic Cu Kα radiation (λKα1 = 1.5418 Å) at 40 keV and 40 mA.
The surface area and porosity of samples were measured at 77 K using a
surface area and porosity analyzer (Autosorb iQ Station 2). XPS analysis
was performed on an ESCALAB 250 X-ray photoelectron spectrometer
(Thermo, USA) equipped with Al Kα1,2 monochromatized radiation at
1486.6 eV X-ray source. Raman spectra of the samples were recorded
on a LabRAM HR800 confocal microscope Raman system (Horiba Jobin
Yvon) using an Ar ion laser operating at 632 nm. The metal content in the
composite structure was determined by the inductively coupled plasma
spectroscopy after microwave digestion of the samples (ICP 6300,
Thermo Fisher Scientific). The X-ray absorption fine structure spectra
data (Co K-edge) were collected at 1W1B station in Beijing Synchrotron
Radiation Facility (operated at 2.5 GeV with a maximum current of
250 mA). The data were collected in fluorescence excitation mode using
a Lytle detector. All samples were pelletized as disks of 13 mm diameter
with 1 mm thickness using graphite powder as a binder.
Evaluation of the Catalytic Performance for Hydrogenation Reactions:
The catalytic hydrogenation reactions were carried out in a 25 mL
stainless steel autoclave equipped with a mechanical stirrer, a pressure
gauge, and automatic temperature control apparatus. In a typical
experiment, the reaction solutions of reactant (1 mmol), catalyst
(20 mg), and H2O (10 mL) were loaded into the reactor. The reactor
was sealed, purged three times with N2 at 1 MPa, and then pressurized
with H2 to a setting point. The reactor was then heated to the desired
temperature with continuous stirring at 700 rpm, which eliminates the
diffusion effects. After reaction, the autoclave was cooled down quickly.
The autoclave contents were transferred to a centrifuge tube, and the
catalyst was separated by centrifugation. The products were extracted by
ethyl acetate from the liquid and analyzed.
Keywords
biomass-derived molecules, cobalt nanoparticles, Co–Nx, metal–organic
frameworks, selective hydrogenation
Received: December 27, 2018
Revised: January 7, 2019
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