Development of Nickel Molybdenum Based Bimetallic Nanocatalyst

for Transfer Hydrogenation of 5-Hydroxymethylfurfural

Thesis Supervisor - Prof. Sri Sivakumar

Presented by – Mukesh Kumar Meena

DEPARTMENT OF CHEMICAL ENGINEERING

IIT KANPUR
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 Content

• Introduction to Biomass
Conversion

• Hydrogenation of HMF

• Catalyst Synthesis

• Catalyst Characterization

• Catalyst Activity Test

• Conclusion and Future work

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 Introduction to Biomass Conversion

Biomass is the biodegradable fraction of waste, products and

residues from biological origin, agriculture, forestry and the Method of biomass conversion:
biodegradable fraction of industrial and municipal waste.

Composition of Lignocellulosic Biomass:

• Cellulose (40-50%)
• Lignin (15-20%)
• Hemicellulose (25-35%)

• Chemical conversion method requires low

temperature comparison to thermal and
thermochemical conversion technologies.

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 Chemical Conversion of Biomass

• This method convert bio-based platform molecules

(eg. Furfural, HMF) into valuable chemicals and fuels
using various catalysts.

• HMF is an organic compound which is produced by

dehydration of cellulose.

Production route of HMF and Furfural

Products of HMF transformation
 Catalytic Hydrogenation of HMF

• Hydrogenation is the removal of oxygen or addition of hydrogen to a molecule.

• H2 gas is extremely expensive and flammable.

• Catalytic Transfer hydrogenation (CTH) is the addition of hydrogen to a molecule

from solvent such as alcohol, formic acid etc.

• Catalyst is a substance that speeds up a chemical

reaction, but is not consumed by the reaction.

Products of HMF hydrogenation

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 Catalytic Hydrogenation of HMF

Hydrogenation of HMF

• Several transition metals or their combinations can be used as catalyst for hydrogenation of HMF:
o Noble metals - Pt, Pd, Ru, Au, Rh, etc.
o Non-noble metals - Ni, Cu, Co, Mo, Fe etc.

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 Why NiMo@Silica ?
• Ni-based catalysts with low-cost are attractive for hydrogenation of biomass-derived molecules, as they exhibit high activity under
conditions using both gaseous H2 and alcohol as H-donor.

• Synergistic effects between the two metals are highly desirable because they usually offer enhanced activity, selectivity and stability
relative to their monometallic counterparts.
• Previously reported Ni based bimetaliic catalyst – NiFe , NiPd , NiCu etc.
• We can synthesis NiMo bimetallic catalyst.

• Encapsulation of metal particles into a nanoporous shell to form a core−shell nanostructure is a effective strategy to solve the
problems of particle aggregation and detachment from the support.
• We can stabilize catalyst against sintering by encapsulating metal particles within a porous oxide shell such as silica.

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 Synthesis of NiMo Metal Oxide Nanocluster

Nickel Acetylacetonate (16 mg) Centrifuge at 8000 rpm Final

Mixer was heated to 230 0C
Molybdenum Hexacarbonyl (42mg) for 5 minutes precipitate
under Stirring condition Added
Olylamine (15ml) dried
Acetone
Triocylphosphine (0.5 ml) Kept it for 15 minutes and overnight
Oleic Acid (0.5 ml) cooled at room temp.

• Oleylamine acts as a solvent, surfactant as well as a reducing agent.

• Oleic acid and TOP used as co-surfactants to control the growth of metal oxide nanocluster.
• Size of NiMo metal oxide nanoparticle depends on reaction time.

• Synthesis of NiMo bimetallic metal oxide nanoclusters by colloidal synthesis

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 Silica Coating on NiMo
TMAH - Tetramethylammonium
Precipitation-Redispersion to separate excess free ligands – hydroxide
Final
Washing with acetone Precipitate Washing with ethanol precipitate ODTMS -Octadecyltrimethoxysilane
600 mg NiMo
+ dissolved in
2 ml Toluene 9000 rpm for 4 min
9000 rpm for 4 min 2 ml Toluene 2 ml Toluene

• Silica Coating on NiMo –

Precipitate dissolved in 2 ml toluene Precipitate dissolved
Final
+ 80 0C for 1 hour in 2 ml toluene 80 0C for 1 hour precipitate
0.5M ODTMS-Toluene (2 ml) +
Cooled for 15 min Cooled for 15 min dried
+ 0.5M TMAH-Ethanol
and centrifuged and centrifuged overnight
0.5M TMAH-Methanol (2ml) (2ml)

Silica Coating on NiMo Silane conjugation chemistry 9

 Catalyst Characterization
TEM Images of Synthesized Catalyst -

SEM Images of Synthesized Catalyst -

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EDX Spectrum and Elemental Analysis -
Element Weight% Atomic%

OK 24.91 52.00

Si K 8.50 10.11

Ni K 66.59 37.89

Totals 100.00

Element Weight% Atomic%

OK 26.98 56.34

Si K 3.95 4.70

Ni K 67.53 38.43

Mo L 1.54 0.53

Totals 100.00

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XRD Pattern of Synthesised Catalyst -

NiMo@Silica

Intensity

NiO(JCPDS-012-1216)

15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
2 Theta

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 Catalyst Activity Test

HMF (63mg, 0.5mmol)

2-Propanol (10ml)
HMF
Catalyst (20mg) BHMF

Centrifuge to
separate catalyst
150 0C
5 hrs
500 rpm
In Autoclave

Possible Reaction Mechanism – Catalytic Transfer Hydrogenation

Product Analysis
using GC

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 Conclusion and Future Work
• Catalyst with particle size 60-80nm has been prepared. Multicore inside silica shell may be the reason behind large particle size.
• XRD shows that NiO present in the catalyst but oxides of Mo is not present. Silica shell formed is amorphous nature.
• For safety purpose I have used 2-propanol as solvent for H-doner in the place of H2 gas in hydrogenation of HMF reaction.

• Now I will analyse product using GC.

• BET has not done . So I will do BET to find catalyst surface area and pore size.

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 References
• Rupesh Singh, Deepak Kunzru and Sri Sivakumar "Monodispersed Ultrasmall NiMo Metal oxide Nanoclusters as Hydrodesulfurization Catalyst" , Applied
Catalysis B : Environmental, 185 , 163–173 (2016)
• Nikhil R. Jana, Christoher Earhart, and Jackie Y. Ying “Synthesis of Water-Soluble and Functionalized Nanoparticles by Silica Coating”, Chem.
Mater., 2007, 19 (21), pp 5074–5082

• Jian He, Leonhard Schill, Song Yang, and Anders Riisager“Catalytic Transfer Hydrogenation of Bio-Based Furfural with NiO Nanoparticles” ACS Sustainable
Chemistry & Engineering 2018 6 (12), 17220-17229

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