BORESKOV INSTITUTE OF CATALYSIS

Siberian Branch, Russian Academy of Sciences

CATALYSTS WITH NANOSTRUCTURED ACTIVE COMPONENT.

Synthesis, Investigation And Application in Processes of Environmental Protection, Power Production and Refinery

Prof. Dr. Valerii I. Bukhtiyarov

Pr.Akademika Lavrentieva, 5 Novosibirsk, 630090 Russia Tel.: +7-(383)-330-67-71 Fax: +7-(383)- 308-356 E-mail: vib@catalysis.ru

Nanomaterials and Catalysis

Reduction of the size parameters of a substance to nanometer scale causes appearance of unique properties which can be used in practice for development of novel materials and technologies called as NANOMATERIALS and NANOTECHNOLOGIES Not only physical properties, but also reactivity of a substance in nanometer scale will be changed. As consequence, new functional nanomaterials such as chemical sensors, CATALYSTS, adsorbents, membranes, fillers can be produced

Nanomaterials and Catalysis

Size effects are known since the Boudarts discovery of the structure-sensitive and structure-insensitive reactions and have been studied for a long time Turnover number, s-1
Positive size effects

Structural insensitive reaction

Structural sensitive reactions

Abatement of and CHx Reforming of gasoline Hydrogenation of unsaturated CxHy Hydrogen and methanol FC .

10

100

1000

Particle Size,
1. Bukhtiyarov V.I. Chemical Reactivity of Metal Clusters at Solid Surfaces, In: Interfacial Science, Chemistry for the 21st Century Monograph (Ed. M.W.Roberts), Blackwell Science, 1997, 109-128. 2. Bukhtiyarov V.I., Slinko M.G. Metallic nanosystems in catalysis. Russian Chemical Reviews, 2001, v. 70, n.2, 147-159.

Nanomaterials and Catalysts

Systematic investigation of the size effects in catalysis by metallic nanoparticles and, especially, their application in practice require:

1) to develop the methods of synthesis of nanosized metallic particles, which have to provide:
Homogeneous size distribution with the mean particle size which is optimal for catalytic properties; Stability of the supported metallic particles against sintering; Economical practicability 2) to develop the methods of testing of catalytic properties: with application of porous and planar supports; intensification of catalytic activity testing the search of structuresensitive reactions using the testing protocols developed by catalysts producers

Preparation of supported metal nanoparticles with homogeneous size distribution. Colloid formation
Scientific bases of preparation of platinum nanoparticles with the mean sizes of 0.510 nm on -alumina have been developed It has been shown that variation of pH and gas-phase composition during ageing of the solution of Pt metal precursor regulates the sizes of polynuclear platinum hydroxocompomlexes: H H H H H

[Pt(OH)6]2- + nH+

[Pt(-OH)m]y

O
Pt

O
Pt

O
Pt

O
Pt

O O
H

O
H

O
H

O
H

O
H

This provides homogeneous size distribution of [Pt(OH)m]y collodidal particles in impregnated solution (contrary to commercial solutions): SAXS data
Commercial solution
100 80
100 80

0.8-1.2 nm 2.0-2.4 nm

Our solution (lower pH)

100 80

Our solution (higher pH)

Dv(d)

60 40 20 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28

Dv(d)

60 40 20 0

Dv(d)

60 40 20 0

10

10

dPt, nm

dPt, nm

dPt, nm

Size effects in catalysis by metal nanoparticles. Observation and investigation

Application of the prepared solutions for impregnation of alumina allows us to prepare the series of Pt/-Al2O3 catalysts and shows the size effect in CH4 oxidation
TEM images and Pt particle size distribution for the Pt/-Al2O3 catalysts with smallest platinum nanopartices
0.07 0.06 0.05

Size effect in methane oxidation

TEM images and Pt particle size distribution for the Pt/-Al2O3 catalysts with smallest platinum nanopartices

TOF, sec-1

0.04 0.03 0.02 0.01 0.00 0 2 4 6 8 10

50

<d>, nm
35

Nd/Ntotal100, %

Nd/Ntotal100, %

30 25 20 15 10 5 0 0 2 4 6 8 10

Tcalcination = 400

- TOF or turn-over frequency is rate of a catalytic reaction, normalized to the number of surface atoms of active compoment

40 30 20 10 0 0 5 10 15 20 25 30 35 40

Tcalcination = 600

d, nm

d, nm

Preparation of supported metal nanoparticles with homogeneous size distribution. Epitaxial growth
Scientific bases of preparation of gold nanoparticles with the mean sizes of 110 nm on high-surface aluminas have been developed It has been shown, that deposition-presipitation: Aumetal

[AuCl4

]-

+ NaOH
+ Al2O3

Au(OH)3[AuCl4-n(OH)n]-/MOx

O2

results in epitaxial growth of gold nanoparticles, that provides the best results in preparation of the particles with homogeneous size distribution and improved stability against sintering
HRTEM images of gold nanoparticles on Al2O3
The model (molecular dynamics method) of epitaxial growth of gold nanoparticles on Al2O3

Au [111] face Al2O3 [111] face

Au O Al

x 600 000

Size effects in catalysis by metal nanoparticles. Observation and investigation

We have observed the size effect in reaction of low-temperature CO oxidation over Au/Al2O3 catalysts, which is appeared as sharp increase of TOF for the gold supported particles with the mean sizes of 1-2 nm
The particle number
150

140 120
-4

Size distribution of Au nanoparticles

Dl = 1.8 nm Dvs= 2.0 nm
0 2 4 6 8 10 12 14 16 18 20

100

50

TOF (sec )10

100 80

Particle size, nm

-1

TEM images 60 40 20 0 0 5 10 15 dvs (nm) 20 25

Flow reactor = 293 K; 0.05%CO, 2% of H2O, air for balance

Catalysts on the bases of metallic nanoparticles for afterburning of exhaust gases from car engines
We have shown the perspectives of application of the catalysts gold nanoparticles supported on alumina to solve the cold start problem for car engines
The method of preparation of honeycomb catalysts for afterburning of exhaust gases from car engines, front layer of which (Pt) provides standard neutralization of exhaust gases (from CHx and CO at high temperatures), while the deeper layer (Au) burns up CO on cold engine.

CO conversion, %

100

80
60

Au/Al2O3

40 20
0 50

1 run 2 run 3 run

Pt/Al2O3 (commercial)

100 150

200 250 300

Temperature, 0C

Observation and study of the nature of the size effects in practically important catalytic reactions with further development and scaling-up of more effective (nano-)catalysts with lower loading of the noble metals

Preparation of supported metal nanoparticles with homogeneous size distribution.Epitaxial growth

HRTEM study of Pd+Rh/Al2O3+CeO2-ZrO2 automobile catalyst produced by UECP allowed us to identify epitaxial growth of Pd particels on ceria-containing phase

Preparation of supported metal nanoparticles with homogeneous size distribution. MMM as supports
Homogeneous distribution of Ag nanoparticles have been reached with application of mesophase mesoporous silica (SBA-15) data of DICP CAS and FHI der MPG

There is a possibility to vary fluently the pore sizes of these materials (silica, carbon) via variation of the preparation conditions Internal location of metal particles allows limitation of the particle sizes by pore diameters

Nanomaterials and Catalysis

Systematic investigation of the size effects in catalysis by metallic nanoparticles and, especially, their application in practice require: 3) to develop the physical methods for characterization of supported metallic nanoparticles: Transmission electron microscopy with high resolution (HR TEM) Scanning electron (SEM) and probe microscopy (STM, AFM) X-ray absorption and scattering (EXAFS, XANES, SAXS) Surface Science methods for in situ measurement (IRAS, SFG, UV-Vis, XPS, XAS) 4) to elucidate the reasons of unique catalytic properties of nanoparticles and search of the ways for the their practical applications

Combined application of in-situ XPS and MS for operando study of operating nanostructured catalysts
VG photoelectron spectrometer has been reconstructed for operando measurements in millibar pressure range
Photoelectrons (kin = h Eb) Lenses
6 The mean free path of photoelectrons (torrmm)

X-ray tubes

sample X-rays

Gas cell

Sample holder

0 0 200 400 600 800 1000 Kinetic energy of photoelectrons (eV)

To perform in-situ XPS measurements, it is necessary: to decrease the path of photoelectrons in highpressure zone; to provide the differential pumping of X-ray source and energy analyzer.

Bukhtiyarov V.I., Kaichev V.V., Prosvirin I.P. X-ray Photoelectron Spectroscopy as a Tool for In situ Study of the Mechanisms of Heterogeneous Catalytic Reactions. Topics in Catalysis 32 (2005) 3-15

Combined application of in-situ XPS and MS for operando study of operating nanostructured catalysts
Using this spectrometer, the chemical state of platinum nanoparticles in Pt/Al2O3 catalysts for total oxidation of methane were studied
P(CH4) = 0.02; P(O2) = 0.04 mbar T = 430oC +

Pt4f + Al2p
PtO2
Intensity, arb.un.

Pt

Pt4f + Al2p
Ptmet
68
Intensity, arb.un.

72

76

80

84

Binding energy, eV

68

72

76

80

84

68

72

76

80

84

Binding energy, eV

Binding energy, eV

Investigation of the nature of active sites in nanostructured catalysts with physical methods
Identification of active sites in Au/Al2O3 catalysts for low-temperature CO oxidation: XRD and UV-VIS spectroscopy for
Au [3.1.1.] Au/Al2O3
4

Au Au Au

[Au-O-Au]m

Au [2.2.2.]
800oC F(R) 600oC
3

Au, wt.% 0.3%

2

500oC
1

0.13% 0.05% 0.02%

0

Al2O3 72 74 76 78 80 82 84
10000 10000

20000 20000

30000 30000

40000 40000

50000 50000

60000 60000

2q

Wavenumber, cm-1

Investigation of the nature of active sites in nanostructured catalysts with physical methods
Suggestion about the nature of active sites and experiments about influence of water is in agreement with the proposed mechanism of this reaction The influence of water on the activity of gold in CO oxidation
100 80 H2O on
H2O off

The proposed mechanism of CO oxidation over gold nanoparticles

C conversion (%)

60
H2O on

40

20

0 0 50 100 150 200 250

Time-on-stream (min)

M.C. Kung, R.J. Davis, H.H. Kung J. Phys. Chem. C: 111 (2007) 11767

Nanomaterials and catalysis

Industrial catalysis has involved nanoparticles since beginning of the 20-th century Addition of the nano prefix to many technical terms is not simple replacement of the unit of ngstroms

CATALYSIS

NANOSCIENCE
Nanoscience gives a great contribution to a fundamental approach for optimization of the catalyst performance

Scientific bases of the preparation of nanocomposite ()MoS2 phase supported on alumina

Methodology of synthesis of the mixed - sulfide phase with high dispersity and location of cobalt ions on the lateral phase of the layered MoS2 phase has been developed and realized
Preparation of impregnating solutions with bimetallic Co-Mo compounds Preparation of the support (Al2O3) with optimal texture properties and its impregnation with Co-Mo solutions Preparation of bimetallic Co-Mo compound in oxide form of the catalysts
All steps of the catalyst preparation have been studied with a number of physical methods: NMR, EXAFS, IR-spectroscopy, HRTEM
Preparation and physical-chemical characterization of the catalysts

Co-MoS2 Synthesis of the proposed structure of active sites in hydrodesulfurization catalysts:

Catalysts with active component in sulfide form

Mo

Study of catalytic properties of -Mo-S/Al2O3 catalysts in hydrodesulfurization of diesel fraction

Systematic investigation of catalytic activity of - sulfide catalysts in hydrogenolysis of -S bond have been performed depending on the support nature and sulfidation conditions of oxide precursors
Testing the catalytic properties
DBT 3200 406 ppmS

Optimization of the catalyst working conditions

4-MDBT 4,6-DMDBT 3400C 54 ppmS 3600C 14 ppmS

The catalytic data were used to optimize the conditions of catalyst activation (sulfidation) and operation, as well as the procedures of active component supporting on specific types of alumina oxides, prepared by the company (JSC Industrial catalysts), production facilities of which have being apply for industrial production of the catalysts To test the catalytic performance of the synthesized samples, technological set-up for performing the catalytic testing under the representative conditions and unique (for Russia) analytical unit allowing not only definition of total content of the residual sulfur, but also identification of individual sulfur-containing compounds have been created at the Boreskov Institute of Catalysis

Nanocomposite of Co-Mo sulfide catalysts for deep hydrotreating of straight-run gas-oil

Industrial testing of pilot batch (30 tons)* of nanocomposite catalysts in hydrotreating reactor on Saratov oil-refinery plant decreases the sulfur content from S < 1800 ppm to S < 50 ppm (Euro-4 standard)
Scaling up of the catalyst production
500

Independent expertise of the catalytic properties of the synthesized catalyst in comparison with imported catalysts
Product sulphur (ppm wt)
400

300

200

100

0 0 5 10 15 20 25 30 35 40

- preparation of pilot batch of the catalysts were performed by JSC Industrial catalysts

Study of interaction of individual (first of all, very stable) sulfur-containing organic compounds with new series of sulfide catalysts. Optimization of the methods and conditions for sulfidation of active component . Development of the hydrodesulfurization catalysts of diesel fraction to sulfur content in several ppm.

Acknowledgement for financial support

Siberian Branch of RAS:

interdisciplinary project 79 Size effects in catalysis by metals. Development

of preparation methods and study of nano-sized metallic particles

Russian Ministry of Education and Science: state contract 2007-3-1.3-28-03-127 Development of technological bases of application of nanosize effects to produce nanostructured catalysts of new generation Russian Foundation for Basic Research (joint Call with China) project # 07-03-92117-GFEN Size effects in adsorption and catalysis over metals: from individual atoms and nanoparticles to nanostructured catalysts Russian Foundation for Basic Research project # 08-03-01016 The influence of the size effects on activity of Pt nanoparticles in various heterogeneous catalytic reaction