Precisely Precisely ccontrolled ontrolled ssynthesis of ynthesis of PVPPVP--ccapped Ni and Co metal nanoparticlesapped Ni and Co metal nanoparticles

Yu. Demidova1,2, I. Simakova*1,2, I. Prosvirin1, J. Glaesel3, B. Etzold3, T. Schubert4, A.

Simakov5, D.Yu. Murzin61Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia, 2Novosibirsk State University, Novosibirsk, 630090, Russia

3Friedrich-Alexander Universität Erlangen-Nürnberg, Erlangen, 91058, Germany, 4FutureCarbon GmbH, Bayreuth, 95448, Germany5Centro de Nanociencias y Nanotecnología, UNAM, Ensenada, 22860, México, 6Åbo Akademi University, PCC, Turku/Åbo, 20500, Finland

*simakova@catalysis.ru, demidova@catalysis.ruIntroductionIntroductionDevelopment of effective approaches for controlled synthesis of metal nanoparticles (NPs) is of great fundamental and practical interest due to a wide range of applications in different fields, including electronics, optics, magnetic devices and catalysis. Ni is widely used as an industrial hydrogenation/hydrotreating catalyst, while Co exhibits appreciable activities for C–C bond scission, water–gas shift reaction, and Fischer–

Tropsch synthesis [1]. Supported Ni and Co metal NPs are anticipated also to be of potential interest as inexpensive catalytic materials

for aqueous phase reforming (APR) of bioderived sugar and sugar alcohols resulting in a mixture of hydrogen and alkanes [2]. In the present work it is demonstrated that Ni and Co NPs with controllable sizes can be prepared in bench scale quantities by a facile modified polyol method utilizing sodium borohydride (NaBH4

) as a reducing agent and polyvinylalcohol as a capping agent with a high metal/PVP ratio.

Synthesys of Ni NPsSynthesys of Ni NPs

Synthesys of Co NPsSynthesys of Co NPs

Effect of atmosphere• Polyol method

Precursor: NiCl2·6 H2OStabilizer: PVP Reductant: NaBH4/ethylene glycolArgon or air 23-170°C

[1] R.R. Davda, J.W. Shabaker, G.W. Huber, R.D. Cortright, J.A. Dumesic, Appl. Catal. B.

43 (2003) 13-26.[2] A.V. Kirilin, A.V. Tokarev, H. Manyar, C. Hardacre, T. Salmi, J.-P. Mikkola, D.Yu. Murzin, Cat. Tod.

223

(2014) 97-107.

Acknowledgment Acknowledgment The SusFuelCat project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement No 310490 (www.susfuelcat.eu).

T=23°C, Ar T=140°C, Ar T=140°C, air

• Polyol method

Precursor: CoCl2·6 H2OStabilizer: PVP Reductant: NaBH4/ethylene glycolAr atmosphere7-100°C

T=7°C, Ar T=23°C, Ar T=100°C, Ar

A series of Co and Ni NPs with the average particle sizes 1.8-2.8 and 2.6-9.8 nm, respectively, were synthesized by the modified polyol method. The influence of reduction temperature and gas atmosphere was studied. Parameters determining formation of Co and Ni NPs by the polyol method with a controlled size were found. Increase of the reduction temperature and application of an oxidative atmosphere increased nanoparticles size favouring NPs growth versus nucleation.

Effect of temperature

850 860 870 880 890

Ni-3

Ni-2

Ni2p

Ni-1

856.1 - Ni2+

Binding energy (eV)

Effect of temperature

0 10 20 30 40 500

5

10

15

20

25

Ni-4mean - 9.8 nmSD 6.85

size, nm

Cou

nt

T=170°C, air

0 5 10 15 20 25 300

2

4

6

8

10

12

Ni-3mean - 5.4 nmSD - 2.72

size, nm

Cou

nt

1 2 3 4 5 6 7 8 90

10

20

30

40

50

60

70

Cou

nt

size, nm

Ni - 2mean - 3.2 nmSD - 0.9

1 2 3 4 5 60

20

40

60

80

Cou

nt

size, nm

Ni - 1mean - 2.6 nmSD - 0.6

0 2 4 6 8 100

5

10

15

20

Co-5mean - 1.80 nmSD - 0.49

Cou

nt

size, nm1 2 3 4 5 6

0

20

40

60

80

Cou

nt

size, nm

Co-6mean - 2.6 nmSD - 0.6

2 3 4 50

10

20

30

40

50

60

70

80

Cou

nt

size, nm

Co-7mean - 2.8 nmSD - 0.5

300 400 500 600 7000.0

0.5

1.0

Abs

Wavelength, nm

CoCl2 in EG

Co- 5

UV-visUV-vis

ConclusionsConclusions

XPSXPS

Optimizing the controlled synthesis of PVPOptimizing the controlled synthesis of PVP--based based carbon supported Ru nanoparticles: carbon supported Ru nanoparticles:

synthesis approaches and characterizationsynthesis approaches and characterization

IntroductionIntroductionA precise control over size and shape of NPs at the nanometer scale by varying the synthesis conditions is expected to allow prediction of their catalytic performance as well as to give possibility to

tune material properties with high accuracy and reproducibility.

The purpose of the current work is to explore regularities of ruthenium NPs formation via polyol reduction and to determine key parameters for the synthesis of Ru NPs with a controllable particle size allowing further preparation of heterogeneous catalysts for different catalytic application, e.g. aqueous phase reforming (APR) of bioderived sugar and sugar alcohols.

Synthesys of Ru NPsSynthesys of Ru NPsPrecursor: RuCl3·n H2OStabilizer: PVPRu/PVP = 1/1÷1/50Reductant: ethylene glycol (EG) or NaBH4/EGArgon atmosphere 170-198°C or microwave irradiation (m/w)

Effect of Ru/PVP ratio Effect of Ru/PVP ratio

UV-Vis

Acknowledgment Acknowledgment The SusFuelCat project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement No 310490 (www.susfuelcat.eu).

Color change during reduction under heating (reflux conditions)

red yellow green dark brown

Effect of scaling Effect of scaling (10 ml 10 ml →→

100 ml)100 ml)Effect of temperature Effect of temperature

Ru-EG-4Ru-EG-4

Ru-EG-3Ru-EG-3

Ru-EG-2Ru-EG-2

Ru:PVP=1:5 Ru:PVP=1:10

0 2 4 6 8 100

2

4

6

8

10

12

14

16

18

Statistical Function Base Unit nmCount 236Mean 2.76Median 2.70Minimum 1.38Maximum 4.59St. Deviation 0.55

size, nm

Rel

ativ

e Fr

eque

ncy

0 2 4 6 8 100

5

10

15

20Statistical Function Base Unit nmCount 252Mean 2.59Median 2.57Minimum 1.38Maximum 3.99St. Deviation 0.40

Rel

ativ

e Fr

eque

ncy

size, nm

198°C

0 2 4 6 8 100

2

4

6

8

10

12

14

16

18

Statistical Function Base Unit nmCount 236Mean 2.76Median 2.70Minimum 1.38Maximum 4.59St. Deviation 0.55

size, nm

Rel

ativ

e Fr

eque

ncy

0 2 4 6 8 100

5

10

15

20

Statistical Function Base Unit nmCount 216Mean 2.36Median 2.32Minimum 1.28Maximum 3.87St. Deviation 0.43

size, nm

Rel

ativ

e Fr

eque

ncy

170°C

Different strategies to prepare Ru NPs of different size with narrow particle size distribution were applied. Stable Ru NPs with

mean diameters 1.7-2.8 nm and a narrow distribution were prepared by reduction of RuCl3

with EG as well as PVP as a stabiliser in the temperature range 170-198oC. As an effective alternative approach synthesis of Ru NPs using microwave assistance along with NaBH4

reduction at room temperature was developed. The effect of heating conditions, Ru/PVP ratio, reducing agent and initial Ru precursor concentrations on the particle size was studied.

I. Simakova*1,2, Yu. Demidova1,2, I. Prosvirin1, J. Glaesel3, B. Etzold3, T. Schubert4, A.

Simakov5, D.Yu. Murzin61Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia, 2Novosibirsk State University, Novosibirsk, 630090, Russia

3Friedrich-Alexander Universität Erlangen-Nürnberg, Erlangen, 91058, Germany, 4FutureCarbon GmbH, Bayreuth, 95448, Germany5Centro de Nanociencias y Nanotecnología, UNAM, Ensenada, 22860, México, 6Åbo Akademi University, PCC, Turku/Åbo, 20500, Finland

*simakova@catalysis.ru

ConclusionsConclusions

Sample T, ºC Reducing agent

Ru conc.,mol/L

Ru/PVP, mol/mol

dn

, nm

SD, nm

Ru-1 198 EG 1.0·10-2 1/1 1.7 0.31Ru-2 198 EG 1.0·10-2 1/2 2.0 0.29Ru-3 198 EG 1.0·10-2 1/5 2.1 0.40Ru-4 198 EG 1.0·10-3 1/10 1.7 0.20Ru-5* 198 EG 1.0·10-2 1/50 1.7 0.30Ru-6* 198 EG 1.0·10-2 1/1 agglomeratesRu-7* 198 EG 1.0·10-2 1/5 2.1 0.31Ru-8 198 EG 1.0·10-1 1/5 2.5 0.47Ru-9 170 EG 1.0·10-1 1/5 2.4 0.43Ru-10 198 EG 1.0·10-1 1/5 2.8 0.55Ru-11 198 EG 1.0·10-1 1/10 2.6 0.40Ru-12 RT NaBH4 1.0·10-1 1/5 1.8 0.3

* reduction under microwave irradiation at reflux conditions

300 400 500 600 700 8000,0

0,5

1,0

1,5

Abs

Wavelength, nm

RuCl3 Ru-1 Ru-2 Ru-3 Ru-7 Ru-4

350

STRUCTURE SENSITIVITY IN HYDROGENATION OF STRUCTURE SENSITIVITY IN HYDROGENATION OF GALACTOSE AND ARABINOSE OVER Ru/C CATALYSTSGALACTOSE AND ARABINOSE OVER Ru/C CATALYSTS

I.

Simakova*1,2, Yu. Demidova1,2, D.Yu. Murzin3

1Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia, 2Novosibirsk State University, Novosibirsk, 630090, Russia3Åbo Akademi University, PCC, Turku/Åbo, 20500, Finland

*simakova@catalysis.ruIntroductionIntroductionSugar alcohols can be used as alternative sweeteners, intermediates in pharmaceutical production and as humectants in cosmetics.

Hydrogenation of glucose or other sugars to corresponding sugar alcohols has been extensively studied over Ni and Ru catalysts. Application of Raney-type Ni catalysts has a range of disadvantages such as metal sintering and poisoning as well as nickel leaching [1-3]. As an alternative to nickel glucose hydrogenation to sorbitol over ruthenium catalysts has been actively studied [3, 4] and was shown recently [4] to be structure sensitive. In this work, the influence of ruthenium nanoparticle size on the catalyst activity was studied in order to find an optimal Ru catalyst for hydrogenation of another sugar-

galactose, which is an epimer of glucose and can be derived from hemicelluloses. In addition experiments were performed with a C5 sugar -

arabinose.

ResultsResults

Catalytic experiments

[1] B.W. Hoffer, E. Crezee, F. Devred, et al., Appl. Catal. A 2003, 253, 437–452.[2] J.-P. Mikkola, H. Vainio, T. Salmi, et al., Appl.Catal. A 2000, 196, 143–155.[3] K. van Gorp, E. Boerman, C.V. Cavenaghi, P.H. Berben, Catal.

Today 1999, 52, 349–361.[4] A. Aho, S. Roggan, O.A. Simakova, T. Salmi, D.Yu. Murzin, Catal. Today 2015, 241, 195-199.

Acknowledgment Acknowledgment The SusFuelCat project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement No 310490 (www.susfuelcat.eu). The authors are grateful to E.Murzina for performing the catalytic tests.

Catalysts synthesis

ConclusionsConclusions

0 5 10 15 20 250

20

40

60

80

100

Cou

nt

size, nm

Sample Ru-133-1size - 327mean - 7.6 nmSD - 4.4

0 5 10 15 200

20

40

60

80

100

Cou

nt

size, nm

Sample Ru - 133-2size - 319mean - 7.6 nmSD - 2.8ds - 9.7 nmdm - 10.9 nm

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.40

10

20

30

40

50

60

70

80

Cou

nt

size, nm

Sample Ru 133-3size - 233mean - 1.3 nmSD - 0.2dS - 1.3 nmdm - 1.4 nm

0.5 1.0 1.5 2.00

20

40

60

80

100

120

140

Cou

nt

size, nm

Sample Ru-133-4size - 261mean - 1 nmSD - 0.2ds - 1.1 nmdm - 1.1 nm

0 50 100 150 200 2500,00

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

0,09

Con

cent

ratio

n, m

ol/l

time, min

Ru-133-1 Ru-133-2 Ru-133-3 Ru-133-4

Parr 4561 autoclave 110ºC P(H2) = 20 barHLPC (Biorad HPX-87C carbohydrate column)

equipped with an RI detector

Catalyst treatmentair H2

Ru-133-1 300ºC, 1.5 h 430ºC, 6 hRu-133-2 400ºC, 1.5 h 430ºC, 6 hRu-133-3 150ºC, 1.5 h 430ºC, 6 hRu-133-4 150ºC, 1.5 h

200ºC, 6 h430ºC, 6 h

3 wt.% Ru/CPrecursor RuCl3·nH2O Mesoporous carbon material SibunitIncipient wetness impregnation (IWI)Catalysts treatment under oxidizing atmosphere

prior to reductionGalactose

Arabinose

Ru/C catalysts with the different particles size and distributions were synthesized and were used to explore their catalytic behavior. Ru/C with monomodal and bimodal distribution showed different activity in hydrogenation of galactose, with the bimodal sample being more active than its monomodal counterpart probably due to presence of rather smaller nanoparticles in the former (Fig. 2). The catalysts with narrow particle size distribution and similar average particle size 1.0-1.3 nm showed the same catalytic activity.

Aqueous phase reforming of biomass compounds Aqueous phase reforming of biomass compounds over Pt and Ru containing catalystsover Pt and Ru containing catalystsA.K.K. Vikla1, I.L. Simakova2, Yu.S. Demidova2, L. Calvo3, M.A. Gilarranz3,

D.Yu. Murzin4, L.

Lefferts1

1Catalytic Processes and Materials, University of Twente, Netherlands2Boreskov Institute of Catalysis, Novosibirsk, Russia

3Facultad de Ciencias, Universidad Autónoma de Madrid, Spain4Process Chemistry Centre, Åbo Akademi University, Turku/Åbo, Finland

*simakova@catalysis.ru

IntroductionIntroductionBiomass can be regarded as a renewable source of platform chemicals, biofuels and energy-rich materials [1-4]. Aqueous phase reforming (APR) has attracted a lot of attention, since this process is efficient and tunable in terms of hydrogen and light hydrocarbons production from biomass-derived compounds. The catalysts based on VIII group metals were

shown to be effective for APR with Pt being the most active for APR of polyols among the monometallic catalysts [5]. At the same time, Ru was shown recently to be a more suitable catalyst due to its higher activity for C-C cleavage in the case of light oxygenates such as acetic acid [6]. In the current work catalytic behavior of Ru and Pt as well as mixed RuPt carbon-supported catalysts was studied with the general aim to relate activity/selectivity with the catalyst parameters.

ResultsResultsCatalytic experiments

[1] D.A. Simonetti, J.A. Dumesic, Catal. Rev. 2009, 51, 441.[2] J.C. Serrano-Ruiz, R. Luque, A. Sepulveda-Escribano, Chem. Soc. Rev. 2011, 40, 5266.[3] C.-H. Zhou, X. Xia, C.-X. Lin, D.-S. Tong, J. Beltramini, Chem. Soc. Rev. 2011, 40, 5588. [4] D.Yu. Murzin, I.L. Simakova, Catalysis in biomass conversion, in Comprehensive Inorganic Chemistry II, vol. 7, From Elements

to Applications, 2013, 7, 559-586. [5] R.R. Davda, J.W. Shabaker, G.W. Huber, R.D. Cortright, J.A. Dumesic, Appl. Catal. B: Environ. 2005, 56, 171.[6] D.J. M. de Vlieger, L. Lefferts, K. Seshan, Green Chem. 2014, 16, 864.

Acknowledgment Acknowledgment The SusFuelCat project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement No 310490 (www.susfuelcat.eu).

Catalysts synthesis

ConclusionsConclusions

Continuous flow reactor equipped with total organic carbon analyzer (TOC) and GC (Micro-GC, MS5 and PPQ columns)

T = 225-250°C P(H2) = 35-60 barAnalysis of the liquid phase by HPLC (RID-10A detector and Aminex

HPX-87H (300x7.8mm) column)

0.5 1.0 1.5 2.0 2.5 3.00

20

40

60

80

Cou

nt ()

size, nm

Sample pt-114size - 261mean - 1.4 nmSD - 0.3ds - 1.5 nmdm - 1.6 nm

2 3 4 5 6 70

20

40

60

80

100

Cou

nt ()

size, nm

Sample Pt-105k-2-bsize - 316mean - 3.6 nmSD - 0.6ds - 3.8 nmdm - 3.9 nm

1 wt.% Pt/C and PtRu(1:1)/CPrecursor H2PtCl6 and RuCl3·nH2O Mesoporous carbon material SibunitMethods:

1. Incipient wetness impregnation (IWI)2. Colloidal method Colloid synthesis by polyol methodColloidal NPs immobilization on carbon material

IWIIWI Colloidal methodColloidal method

The catalytic activity of Ru and Pt deposited on mesoporous carbon Sibunit by different methods was explored in APR of light oxygenates, including acetic acid, hydroxyacetone, and ethylene glycol. Comparable activity was observed in APR of hydroxyacetone

over Pt/C and PtRu/C synthesized by incipient wetness impregnation, whereas higher

selectivity to hydrogen was achieved with Pt/C.

1 wt. % Pt/C1 wt. % Pt/C

Liquid phase

Ethylene glycol

Ethylene glycol

HydroxyacetoneAfter 7 h