Hungarian Mössbauer Forum, 20181Somechemicalapplicationsof Mössbauer spectroscopyErnőKuzmann

(1)

Some chemical applications of Mössbauer spectroscopy

Ern ő Kuzmann

(2)

CURRENT ACTIVITY OF LABORATORY OF NUCLEAR CHEMISTRY IN 2017/18

Topic Publication

Characterization of nanomagnetites co- precipitated in inert gas atmosphere for plant nutrition

A Lengyel, Z Homonnay, K Kovács, Z Klencsár, Sz Németh, R Szalay, V Kis, F Fodor, Á Solti, M Ristic, S Music, E Kuzmann, Hyperfine Interactions 239 (1), 38 (2018)

Mössbauer spectroscopy control of the preparation of citric-and mandelic acid functionalized nanomagnetites

A Lengyel, VK Garg, AC de Oliveira, SW da Silva, LR Guilherme, Z Klencsár, Z Homonnay, JAH Coaquira, Gy Tolnai, E Kuzmann, Hyperfine Interactions 239 (1), 17 (2018)

The effect of carboxylic acids on the oxidation of coated iron oxide

nanoparticles

A Lengyel, G Tolnai, Z Klencsár, V K Garg, A C Oliveira, L HSingh, Z Homonnay, R Szalay, P Németh, B Szabolcs, M Ristic, S Music, E Kuzmann, Journal of Nanoparticle Research 20 (5), 137 (2018) Synthesis and properties of 1D

manganese-doped hematite particles

M Ristić, E Kuzmann, Z Homonnay, S Musić

Journal of Alloys and Compounds 767, 504-511(2018) Washing effect on the structural and

magnetic properties of NiFe2O4

nanoparticles synthesized by chemical sol-gel method

J Mantilla, L León Félix, MA Rodriguez, FH Aragon, PC Morais, JAH Coaquira, E Kuzmann, AC de Oliveira, I Gonzalez, WAA Macedo, VK Garg Materials Chemistry and Physics 213, 295-304 (2018)

119Sn Mössbauer study of Sn-

containing radiopharmaceutical kits

E Kuzmann, Z Homonnay, S Keresztes, M Antalffy, J Környei Hyperfine Interactions 239 (1), 32 (2018)

Improving the visible-light photocatalytic activity of SnOx·SiO2 glass systems by introducing SnOx nanoparticles

B Kobzi, E Kuzmann, Z Homonnay, S Krehula, M Ristic, S Kubuki Journal of R adioanalytical and Nuclear Chemistry 316 (2), 579-586 (2018)

Mössbauer study of novel iron (II) complexes synthesized with Schiff bases

Cs Várhelyi, A Lengyel, Z Homonnay, R Szalay, Gy Pokol, I-M Szilágyi, P Huszthy, J Papp, F Goga, L-M Golban, M Várhelyi, M Tomoaia-Cotisel, Á Szőke, E Kuzmann Hyperfine Interactions 238 (1), 87 (2017)

(3)

an Outstanding Member of Mössbauer Community

is

70 years old

(4)

In our present case however we knew a more important goal this conference. This is to celebrate Professor Dr Károly Lázár on the occasion of his 70th birthday since Károly Lázár is 70 years old.

We know that it is generally said that the age is a stage of the life and to reach an age is not a merit. However in the case of Professor Károly Lázár there are several merits.

-Károly is an outstanding scientist and great personality

- He is an outstanding Mössbauer spectroscopist who

-has more than 250 publications in the field of Mössbauer spectroscopy

- he established and headed the Mössbauer Laboratory at the Institutes of Isotopes, HAS for decades

- transferred his knowledge to others

- He is still an active enthusiastic researcher as emeritus professor

(5)

16.06. 1948.

in BUDAPEST

He was born

(6)

6 Hungarian Mössbauer Forum, 2018

Basic education:

he attended a Secondary School named after Petrik Lajos in Budapest (Hungary), belonging to special education in chemistry, in where he deeply interested in understanding of chemical problems, therefore after

finishing this school he decided to enter the Eötvös

University, Budapest to study chemistry.

(7)

University years (1967-1971) at the Eötvös Loránd University

Budapest

Graduation

Eötvös Loránd University Budapest

During these years he became familiar with the

theoretical and practical basic of Mössbauer

spectroscopy. Prof. Attila Vértes taught him the basic

and how to record the Mössbauer spectra.

(8)

He prepared his diploma work using the Mössbauer spectroscopy in 1970-71 at the Laboratory of Nuclear Chemistry at Department of Physical Chemistry and Radiology, Eötvös University

supervised by Prof. Attila Vértes

Graduation at the Eötvös University

M.S. degree in Chemistry in 1971

(9)

He was affiliated as research associate at the Central Research Institute for Physics, HAS, Budapest, between 1971-1979

There he dealt with high-temperature metal-gas reactions, carburization of iron, nickel and

alloys, studied by resistivity relaxation and thermopower

(10)

Károly Lázár received the

Candidate of Science (PhD) degree from the Hungarian Academy of

Sciences in 1984

(11)

He has been affiliated as research associate at the Institute of Isotopes, HAS, Budapest, from 1982

where he started to study catalysts by in-situ Mössbauer measurements: studies of carbide formation of iron in CO + H ₂ reaction, and study

of bimetallic (PdFe, CoFe, RhFe. etc.) supported

catalysts

(12)

Between 1982-84 he worked there as a post-doc fellow at the Department of Chemistry with Prof. William Reiff

Hungarian Mössbauer Forum, 2018

Research Years

at the Northeastern University, Boston, USA

Performing magnetic and Mössbauer spectroscopic

studies of layered and two-dimensional complexes

(13)

Between 1985-87 he worked there as a research fellow

Research Years

at the at the Institut de Recherches sur la Catalyse, CNRS, Villeurbanne, France

Performing in situ

¹¹⁹

Sn Mössbauer spectroscopy studies on

SnIr bimetallic catalysts

(14)

Hungarian Mössbauer Forum, 2018 14

Between 1987-1992 he

performed a variety of in situ Mössbauer studies, as research fellow in the Institute of Isotopes

He developed a

Mössbauer laboratory suitable for the in-situ

57 Fe and ¹¹⁹ Sn Mössbauer

measurements

(15)

This makes possible that the catalyst sample should be heated, and treated

among reaction conditions (with gaseous reactants). An advantage is if the catalysts can be measured at lower temperatures (cooling preferably with liquid nitrogen or even with liquid helium) at the very same place where the preceding treatments had been performed. Another important condition can be that the catalytic process

and analysis of the reaction products can be performed on the very same sample

which is measured by the Mössbauer analysis

(16)

Upon using

¹¹⁹

Sn Mössbauer spectroscopy the active

participation of tin in Sn–Pt/SiO

₂

catalysts was demonstrated in the low temperature CO oxidation.

Journal of Catalysis 203, 94–103 (2001)

The oxidation of CO takes place at the Sn

⁴⁺

–Pt ensemble sites

(i) Tin oxide phase (ii) Free platinum sites (FTIR);

(iii) Highly mobile

Sn

⁴⁺

(sf) phase and

(iv) New alloy phase,

Pt–Sn (1 :1)

(17)

In Fe-ZSM-5 zeolite catalysers it was evidenced changes in iron microenvironments by the Mössbauer spectra before and after the use of the catalyser. The occurrence of Fe(II) is well visible in the spectra of the sample after use.

before use

after use

A closer look of the analyis of spectra of the evacuated and heat treated samples showed that

framework (FW) and extraframework (EFW) Fe(III)

microenvironments transforms partially to

superparamagnetic hematite and

magnetite

microenvironments after use.

it was also established that contrary to fully inactive

hematite, magnetite retains about 50% original activity in

the direct oxidation of benzene to phenol (oxidant N

₂

O)

because it exposes [Fe(III)]

_Th

–O – [Fe(III)]

_Oh

linkages

responsible for oxidation

(18)

ISIAME 1988 PARMA

(19)

He was a co-editor of the Proceedings (6 volumes of the Hyperfine Interactions, 2780 pages)

ICAME 1989

BUDAPEST

(20)

(21)

Károly Lázár received the title

Doctor of Sciences of the Hungarian Academy of Sciences

in 1992

Hungarian Academy

of

Sciences

(22)

1993 - 2008 - Head of the Department of Catalysis and

Tracer Studies and the Mössbauer Laboratory

(23)

2009 - 2011 Head of the Department of Application of

Radioisotopes and the Mössbauer Laboratory

(24)

ICAME RIMINI

1995

(25)

Eötvös Workshop in Science, Budapest, 1994

(26)

1st FEZA conference

"Porous materials in Environmentally Friendly Processes", was organized in Eger, Hungary, from September 1st to 4th,

1999.

Károly Lázár was the co-chairman of

the 1st FEZA

conference

(27)

University of Technology

Budapest

He received Prof. Dr. Habil.

title from the University of Technology and Economy,

Budapest, in 2001

(28)

1999 - 2011 Prof Dr Károly Lázár served as Deputy Director

of the Institute of Isotopes, Hungarian Academy of Sciences

(29)

ISIAME 2000 Virginia Beach

(30)

ISIAME 2004 MADRID

(31)

ISIAME 2004 MADRID

(32)

Celebration of the 70th birthday of Attila Vértes at the

ELTE

(33)

ICAME 2005

MONTPELLIER

(34)

Károly Lázár was the co-chairman of the

ISIAME 2008,

Budapest

(35)

ISIAME 2008 Budapest

(36)

(37)

(38)

He was a key person in the realization of the in-beam Mössbauer spectroscopy station at the Budapest Research Reactor, when simultaneously the

¹⁹⁷

Au

Mössbauer spectroscopy was also installed which gave meaningful results related

to the gold nanoparticles and catalysers, too.

(39)

AMONG HIS COLLEAGUES IN THE INSTITUTE IN BUDAPEST

(40)

He presented a very nice comprehensive

invited talk about the Mössbauer spectroscopy

in catalysis at the

ISIAME 2012 in Dalian

(41)

International – multilateral:

·Project coordinator :PHARE ACCORD H-9112-0338(1993-1996, Novel methods for the preparation of nanostructured systems: their characterization and evaluation as heterogeneous catalysts , Budget: 70,000 ECU)

·Participant: COST CIPE CT 92 6107: (1995- 1998, Non-conventional preparation of novel uniform zeolite and supported catalysts).

·Team coordinator: IAEA CRP(1995 – 2000, Extrapolation of short term observations to time periods relevant to the isolation of long lived radioactive waste)

·Team coordinatorin the FUNMIG EU FP6 - 516514integrated project (Fundamental processes of radionuclide migration, 2005 - 2008),

·Team coordinatorin the ReCosy EU FP7 - 212287collaboratory project ( Redox Phenomena Controlling Systems, 2008 - 2012)

International - bilateral(Hungarian coordinator)

· 1998-2000, CAV – HAS (J. Heyrovsky Institute – Location of iron in molecular sieve matrices),

· 2000-2001, CNRS – HAS(with LACCO UMR C6503 at Poitiers University, Study of Ir base catalysts with different crystallite size of different preparations),

· 2006-2009Cooperation in Science and Technology (with Slovenia, topic: Characterization of iron modified nanoporous silicates)

· 2016-2018 MOST - HASBilateral Chinese Hungarian Cooperation on studying supported gold catalysts

National grants- coordinator

· 1993-1995(Preparation and stabilization of ultradisperseous metallic particles - OTKA T07364),

· 1996-1999(Synthesis and study of nanostructured heterogeneous catalytic centres - OTKA T021131)

· 2000-2003(Study of change in oxidation states on framework substituted ions in zeolites, OTKA T32249)

· 2007-2010(Synthesis and characterisation of micro/mesoporous ferrisilicate composites, OTKA K68414)

PROJECTS

(42)

Professor Lázár authored/co-authored nearly 300 scientific papers partly in international journals on topics of catalysis, radiochemistry, solid-state chemistry and materials chemistry as well as other areas of the applications of Mössbauer spectroscopy. He also made around 100 presentations at international conferences.

In 2003 he became a member of the Mössbauer Century Club. He has over 3000 citations and a Hirch index of 31.

(43)

MTMT general evaluating table of publications and citations Károly Lázár 's data (2018.10.22.)

Type of publications Number Citations

Total scientific Total detailed Independent Total

I. Scientific journal paper 192 --- --- ---

in international journal --- 177 2042 2965

in domestic journal in foreign language --- 9 43 60

in domestic journal in Hungarian --- 6 4 5

II. Books 7 --- --- ---

a) Book as author 5 --- --- ---

in foreign language --- 5 0 0

in Hungarian --- 0 0 0

b) Book as editor 2 --- --- ---

in foreign language --- 2 ³--- ---

in Hungarian --- 0 --- ---

III. Part of book 5 --- --- ---

IV. Conference publications in journal or proceedings 22 --- --- ---

Total scientific 226 --- 2114 3063

Other scientific --- 6 0 0

Number of citations --- --- 2114 3063

(44)

2000 - 2006 (IBAME, International Board on the Applications of the Mössbauer Effect), 2003 - Mössbauer Century Club

2018 - Affiliate to the Mössbauer Effect Data Center National:

1995 – 1999, Expert's Committee for Chemistry I., Scientific Qualifying Board 1996 – 2000, Council for Ethics of Science, Hungarian Academy of Sciences 1998 – , Hungarian Zeolite Association

1999 –, Catalysis Club of Hungary

2000 - , Committee for Radiochemistry, Hungarian Academy of Sciences

2010 - 2016 Representative to the General Assembly of the Hungarian Academy of Sciences 2018 - , Doctoral Committee of the Section of Chemical Sciences,

Hungarian Academy of Sciences

2008 Niveau Prize of Hungarian Chemical Society 2017 Albert Nelson Lifetime Achievement Award

MEMBERSHIPS AND AWARDS

(45)

He likes the tennis, hiking and boating

Károly loves and takes care

about his family. He is a

loving husband to his wife

Vera and a good father and

grandfather of his children

(46)

MECAME 2015 ZADAR

(47)

ICAME 2015 HAMBURG

(48)

ICAME 2015 HAMBURG

(49)

AUTUMN RADIOCHEMISTRY DAYS 2015

BALATONSZÁRSZÓ

(50)

HUNGARIAN MÖSSBAUER FORUM 2016

(51)

MECAME 2016 CAVTAT

(52)

Hungarian-Chinese meeting in the Kaltenberg Restaurant

in Budapest, 2016

(53)

MECAME 2017 JERUSALEM

(54)

MECAME 2017 JERUSALEM

(55)

MECAME 2017 JERUSALEM

(56)

MECAME 2017 JERUSALEM

(57)

AUTUMN RADIOCHEMISTRY DAYS 2017

BALATONSZÁRSZÓ

(58)

MSMS

2018

PRAGA

(59)

In 2018 he became a visiting professor at the

Dalian Institute of Chemical Physics, Chinese

Academy of Sciences, Dalian, China

(60)

Hungarian Mössbauer Forum, 2018

60

Professor Emeritus

From 2018 Károly Lázár is Professor emeritus

at the Centre for Energy

Research, Hungarian

Academy of Sciences

(61)

Hungarian Mössbauer Forum, 20181Somechemicalapplicationsof Mössbauer spectroscopyErnőKuzmann

Some chemical applications of Mössbauer spectroscopy

Ern ő Kuzmann

CURRENT ACTIVITY OF LABORATORY OF NUCLEAR CHEMISTRY IN 2017/18

an Outstanding Member of Mössbauer Community

is

70 years old

In our present case however we knew a more important goal this conference. This is to celebrate Professor Dr Károly Lázár on the occasion of his 70th birthday since Károly Lázár is 70 years old.

We know that it is generally said that the age is a stage of the life and to reach an age is not a merit. However in the case of Professor Károly Lázár there are several merits.

-Károly is an outstanding scientist and great personality

- He is an outstanding Mössbauer spectroscopist who

-has more than 250 publications in the field of Mössbauer spectroscopy

- he established and headed the Mössbauer Laboratory at the Institutes of Isotopes, HAS for decades

- transferred his knowledge to others

- He is still an active enthusiastic researcher as emeritus professor

16.06. 1948.

in BUDAPEST

He was born

Basic education:

he attended a Secondary School named after Petrik Lajos in Budapest (Hungary), belonging to special education in chemistry, in where he deeply interested in understanding of chemical problems, therefore after

finishing this school he decided to enter the Eötvös

University, Budapest to study chemistry.

University years (1967-1971) at the Eötvös Loránd University

Budapest

Graduation

During these years he became familiar with the

theoretical and practical basic of Mössbauer

spectroscopy. Prof. Attila Vértes taught him the basic

and how to record the Mössbauer spectra.

He prepared his diploma work using the Mössbauer spectroscopy in 1970-71 at the Laboratory of Nuclear Chemistry at Department of Physical Chemistry and Radiology, Eötvös University

supervised by Prof. Attila Vértes

Graduation at the Eötvös University

He was affiliated as research associate at the Central Research Institute for Physics, HAS, Budapest, between 1971-1979

There he dealt with high-temperature metal-gas reactions, carburization of iron, nickel and

alloys, studied by resistivity relaxation and thermopower

Károly Lázár received the

Candidate of Science (PhD) degree from the Hungarian Academy of

Sciences in 1984

He has been affiliated as research associate at the Institute of Isotopes, HAS, Budapest, from 1982

where he started to study catalysts by in-situ Mössbauer measurements: studies of carbide formation of iron in CO + H 2 reaction, and study

of bimetallic (PdFe, CoFe, RhFe. etc.) supported

catalysts

Between 1982-84 he worked there as a post-doc fellow at the Department of Chemistry with Prof. William Reiff

Research Years

at the Northeastern University, Boston, USA

Performing magnetic and Mössbauer spectroscopic

studies of layered and two-dimensional complexes

Between 1985-87 he worked there as a research fellow

Research Years

at the at the Institut de Recherches sur la Catalyse, CNRS, Villeurbanne, France

Performing in situ

Sn Mössbauer spectroscopy studies on

SnIr bimetallic catalysts

Between 1987-1992 he

performed a variety of in situ Mössbauer studies, as research fellow in the Institute of Isotopes

He developed a

Mössbauer laboratory suitable for the in-situ

57 Fe and 119 Sn Mössbauer

measurements

This makes possible that the catalyst sample should be heated, and treated

and analysis of the reaction products can be performed on the very same sample

which is measured by the Mössbauer analysis

Upon using

Sn Mössbauer spectroscopy the active

participation of tin in Sn–Pt/SiO

catalysts was demonstrated in the low temperature CO oxidation.

Journal of Catalysis 203, 94–103 (2001)

The oxidation of CO takes place at the Sn

–Pt ensemble sites

(i) Tin oxide phase (ii) Free platinum sites (FTIR);

(iii) Highly mobile

Sn

(sf) phase and

(iv) New alloy phase,

Pt–Sn (1 :1)

In Fe-ZSM-5 zeolite catalysers it was evidenced changes in iron microenvironments by the Mössbauer spectra before and after the use of the catalyser. The occurrence of Fe(II) is well visible in the spectra of the sample after use.

before use

after use

A closer look of the analyis of spectra of the evacuated and heat treated samples showed that

framework (FW) and extraframework (EFW) Fe(III)

where he started to study catalysts by in-situ Mössbauer measurements: studies of carbide formation of iron in CO + H ₂ reaction, and study

57 Fe and ¹¹⁹ Sn Mössbauer