Computational Catalysis Lab
Salient aspects on synergistic effects of
guaiacol HDO to aromatic hydro carbons
Group meeting
31/01/2020
Catalysts synthesis and characterization
Reduction and
(NH4)6W12O39.2H2O Dissolution in Evaporation (55 C) and
0
carburization
water drying (100 0C) Passivation
and (Temperature
programmed)
(NH4)6Mo7O24
• 1: 1 mole ratio of the precursors is taken
15 vol% CH4/H2 1% O2/N2 at room
• The formed carbide is mentioned as MoWC
• The same strategy is extended to other monometallic carbides 350 0C – 650 0C temperature
1. X-ray diffraction (XRD) 2. N2 physisorption 3.X-ray photoelectron spectroscopy (XPS)
2. 4.H2-chemisorption 5. (NH3-TPD)
• Diffractograms display sharp and narrow peaks
• The peaks did not show any peaks related to oxide phase
• The prepared molybdenum carbide sample shows orthorhombic β-
Mo2C phase (JCPDS 00-011-0680).
• XRD pattern of WC-600 shows only one phase of metallic tungsten
(JCPDS 040806)
• WC-700 sample displayed the characteristic peaks of hexagonal
monocarbide WC
• For Bimetallic Mo–W catalyst, the characteristic peaks can be well
indexed to the β-Mo2C and/or W2C phases
• Three sharp peaks at 2θ values of 40.4, 58.3 and 73.2° ascribed to
metallic W in MoWC
• The specific surface areas of the catalysts are determined to be less
than 10 m2 g−1
Catal. Sci. Technol.,2019, 9,1387
Catalyst characterization (contd.) --- XPS results
Table-1: Binding energy values (eV) of Mo 3d, W 4f, and C 1s of the prepared samples Table-2: Atomic ratios of the samples derived from peak
deconvolution of the XPS spectra Catalysts
Mo 3d W 4f C 1s
Metallic
Catalysts Mo2C O-MoCx W W2C WC W oxide Carbide C-C
Mo2C 227.9 228.4- - - - 283 284.5
MoWC 227.8 228.3 31.4 32.1- 37 283 284.5
WC-600 - - 31.1- - 35.5- 284.5
WC-700 - - - - 33.9- 282.7 284.5
Mo2C+WC 227.9 228.5 31.1- - - 283 284.5
• C/(Mo + W) atomic ratio is close to the theoretical value.
• This value demonstrates that formula of X2C
Fig:2 - Chemical shifts of the Mo2C state and metallic W state
for MoWC, Mo2C, and WC-600 samples
Catal. Sci. Technol.,2019, 9,1387
Catalyst characterization (contd.) and activity for HDO of guaiac
Fig. 3 A) Ammonia temperature-programmed desorption (NH 3-TPD) profiles of carbide samples
and B) density of H-sites of carbide samples determined via H 2-chemisorption.
Table-3: Surface area, crystal sizes, and H 2-activating sites of carbide samples
Fig:5 Arrhenius plot for guaiacol conversion over Fig:4 Proposed reaction scheme
monometallic and bimetallic carbides
Catal. Sci. Technol.,2019, 9,1387
HDO of guaiacol transformation and summary
Table-4: Catalyst activity of carbides on the HDO of guaiacol at 350 °C, p =400 psig,WHSV= 1.8h−1,and TOS=2–4h
• The synergistic effect between Mo and W is due
Table-5: Product distribution of the stability test over MoWC at 350 °C,
p = 400psig, and WHSV = 1.8 h−1 to the interaction of Mo–W atoms.
• The presence of metallic W in molybdenum
carbide reduced significantly the density of acid
sites
• Mo-based carbide catalysts displayed high
activity to the HDO of phenolic compounds
• High carburization temperature (≥700 °C) in-
duce carbon deposition on the metal surface.
• The less expensive bimetallic carbide material is
helpful in upgrading bio-oils to higher-value
products
Catal. Sci. Technol.,2019, 9,1387
