A scientific investigation of a useful catalyst .

By Jakob Engbk
1/19

Acid Rain
SO2 + H2SO4 NOx + HNO3

The big question: What happened to the Acid Rain?

2/19

A catalyst for removing Sulphur from crude oil was invented and used
SO2 emissions from fuels Natural Sulphur contens

New Sulphur regulations world wide EU :

Year 2000 2005 2010 ppm S in diesel 350 50 10(?)

S-polluted crude oil + H2(g)

300-400 C 10-50 bar

Desulfurized oil + H2S(g)

3/19

How is it done?

4/19

Different levels of investigation

Traditional studies

New studies Atomic level

5/19

An early example: Mssbauer

The Co-Mo-S phase Co at Mo sites. CoxMo1-xS2 Activity of Co-Mo/Al2O3 proportional with Co concentration.
S Mo S S Co S
6/19

Geometry on the surface is still unknown Reactive part or sites still unknown, has something to do with Co

Traditional studies
A lot has been found. Problems: From this it is believed: Low signals Co most likely at Complex system corners or edges. Average over large Active sites are area vacancies connected to Advantages: Co sites. Practical knowledge (Closer to plant conditions) Result from average over large area likely local structure 7/19

New Studies with an STM

But first: What is an STM? And how does an STM work?

8/19

New Studies with an STM

Properties: Conducting substrate Atomic scale Real space UHV conditions

9/19

New Studies with an STM

Properties: Conducting substrate Atomic scale Real space UHV conditions

(2 k)2
10/19

Model system for MoS2 catalyst

Morphology
?

Molecular Adsorption

Nanoparticle Edge Structure

Hydrodesulfurization catalysis Active Sites

Promoters
Co Ni MoS2

Synthesize a model system under UHV conditions and use STM to explore the atomic details.

11/19

The Herringbone reconstructed Au(111) surface

Nucleation site at elbows for Ni, Co, Fe, Ru, Pd and Mo
(a) (b)
(23x 3) unit cell Nucleation Site

[11 2]

FCC

3000 x 3000

2,

[110]

bulged
[11 2]

HCP
[112]

pinched
[110]

[110] (23x 3) unit cell

802 x 795 2,

141 x 135 2,

12/19

Mo Deposition on Au(111)
Mo coverage ~10 % High degree of

dispersion.
Self-assembled Mo

nanoclusters, size 2030.

Well-defined nanometer

spacing.
500

4035 x 4090 2,, insert 890 x 920 2

13/19

Sulphating Mo on Au(111)

High degree of dispersion MoS2 nanoclusters,size 20-30 Triangular morphology

41 42
807 x 818 2

Mo deposited in H2S (10-6 mbar), Postannealing to 673K

Good model system for HDS catalysts

41 42
14/19

MoS2 Nanocrystal :

Edge Structure of MoS2 Triangles

One-dimensional Electronic Edge States

Protrusions at edges imaged out of registry with basal plane S atoms.

15/19

What is seen on the surface

Mo edge with S dimers in MoS2 reproduced by STM simulation Mo edge with S dimers

S Mo S S

S S

Nanosized, metallic, closed wire Protrusions reflect interstitial region

16/19

Simulation (DFT)

Thiophene on MoS2 Nanoclusters Low Temperature Substrate Temperature < 200K

Thiophene (C4H4S)

Size ~ 4 5 2

Thiophene on Au substrate towards perimeter of cluster Thiophene adsorbed on bright brim (edge state II)
40 x 43 2 The desorbtion temperature for both species is below room temperature

17/19

S Vacancies at the Mo-edge - Catalytically Active Sites

Side view

Top view

Energy barrier for vacancy formation surmounted with pre-dissociated hydrogen atoms at 673 K. The S covered edges are stable, vacancies are active.
18/19

MoS2 nanoparticles promoted by Co

Cobalt S edge Mo edge

MoS2 Mo Edge Co inclusion

CoMoS S Edge

19/19

References:
Hydrotreating catalysis, Science and technology. H. Topse, B. S. Clausen, F. E. Massoth Infrared Spectroscopic Investigations of enviromental DeNOx and Hydrotreating catalysts. Nan-Yu Topse. (Doctor Technices thesis) Atomic-scale study of a Hydrodesulfurizations Model catalyst. J. V. Lauritzen (PhD Thesis) Hydrodesulfurization catalysts. Line S. Byskov (PhD Thesis) Structure and electronic properties of MoS2 and metallic nano-scale systems. Mikkel V.Bollinger (PhD Thesis)
20/19

S. Mrup et al. Journal of catalysis 1981