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Physical Chemistry Institute Ilie Murgulescu New BImetallic nanoparticles with applications in water CLEANing of chlorinated compounds and BIOSensors – PowerPoint PPT presentation

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Title: New BImetallic nanoparticles with applications in


1
Physical Chemistry Institute Ilie Murgulescu
New BImetallic nanoparticles with applications
in water CLEANing of chlorinated compounds and
BIOSensors Type PCCA-1 / 46/2012 Project
duration 36 months Project directorDr. Balint
Ioan Contact details ibalint_at_icf.ro Total
budget 1 850 000 Contracting Authority UEFISCDI
Program Partnerships
BICLEANBIOS

2
Participants
  • CO-(IPC) Institute of Physical Chemstry Ilie
    Murgulescu
  • belongs to Romanian Academy.
  • Director Dr Ioan Balint
  • P1 (NIRDMP) National Institute of Research and
  • Development of Material Physics
  • Scientific Responsible P1 Dr. Mihai Lazarescu
  • P2 (NIBS) National Institute of Research and
    Development
  • for Biological Science
  • Scientific Responsible P2 Dr. Ioana Vasilescu

3
Project Summary
  • The project proposes the use eco-friendly
    bimetallic nanoparticles with controlled
    composition,
  • morphology (size and shape), structure and
    oxidation state in catalytic and photocatalytic
    abatement
  • of toxic chlorinated compounds in Water via
    dehydrochlorination reaction.
  • The fine tuning of nanoparticle structure
    prepared by alkaline polyol method is expected to
  • bring crucial improvements by increasing the
    catalytic activity and resistance against
    poisoning
  • compared to already existing materials. A
    strategy of improving the catalytic performances
    is
  • proposed by using ordered mesostructured Al2O3 as
    supporting material which will be synthesized
  • by combined microemulsion-hydrothermal
    techniques. In addition, the photocatalytic
  • hydrodechlorination reaction over bimetallic
    nanoparticles assembled in a controlled manner
    with
  • TiO2 will be investigated. All catalytic
    materials will be characterized by a bunch of
    physico chemical
  • techniques (XRD, XPS, fractal analysis, gas
    titration TPO, TPR, Cyclic Voltammetry).
  • The targeted technical goal is to develop a
    laboratory technology for catalytic and
  • photocatalytic degradation of chlorinated
    compounds in polluted waters. Sensitive and
    stable
  • biosensors devoted to TCE assessment and based on
    bimetallic nanoparticles use are also planned
  • to be developed at prototype level.
  • In order to achieve these ambitious objectives,
    in the three years proposed, a well-balanced and
  • multidisciplinary consortium of three partners
    has been created. All the participant Members
    have a
  • well-established reputation in catalysis,
    material science, bio-chemistry and
    physicochemical
  • characterization techniques

4

Project objectives
  • The main concepts of the project are to use
    bimetallic nanoparticles (NPs) with controlled
    composition, morphology (size and shape),
    structure and oxidation state in catalytic
    dehydrochlorination reaction and biosensors.
  • The fine tuning of nanoparticle structure in
    colloidal synthesis stage is expected to bring
    crucial improvements by increasing the catalytic
    activity and resistance against poisoning in
    hydrodechlorination reaction compared to already
    existing materials.
  • The use of the materials that we are proposing in
    this project is enhanced by the fact that they
    will provide low genotoxicity, being highly
    eco-friendly.
  • The core objective is to to develop new
    eco-friendly catalytic materials based on
    bimetallic NPs with a well defined morphology and
    structure and low genotoxic impact, to be applied
    in water de-contamination technologies, based on
    catalytic dehydrochlorination reaction. A very
    important application field of the NPs is to play
    as immobilization support (enhancing sensitivity)
    and/or redox mediators in sensors/biosensors
    development.

5
Phase list
Year Phase title Budget Involved parteners
2012 Synthesis and characterization of Pt-M, Pd- M, Rh-M (MAg, Cu, Au) nanoparticles 460 000 CO, P1,P2
2013 Synthesis of mesoporous alumina assembling the support materials (mesoporous Al2O3, TiO2 and Ti plate) with bimetallic NPs. Characterization of designed systems 414 00 CO, P1,P2
2014 Applications of supported bimetallic nanoparticles (core-shell, alloy) as hydrodechlorination catalysts and photocatalysts biosensing systems design. 736 000 CO, P1,P2
2015 Laboratory technology for water cleaning and prototype biosensors based on bimetallic NPs 240 000 CO, P1,P2
6
Research team
No. Surname and first name Scientific Title Scientific Degree
1. Balint Ioan Senior Researcher Dr (CO)
2. Papa Florica Senior Researcher Dr (CO)
3. Dobrescu Gianina Senior Researcher Dr (CO)
4. Scurtu Mariana Researcher Dr (CO)
5. State Razvan Researcher Dr (CO)
6. Hornoiu Cristian Researcher Dr (CO)
7. Lazarescu Mihai Senior Researcher Dr (P1)
8. Negrila Catalin Senior Researcher Dr (P1)
9. Cotarlan Simionuc Costel Senior Researcher Dr (P1)
10. Ungureanu Florica Researcher Dr (P1)
11. Vasilescu Ioana Researcher Dr (P2)
12. Litescu Simona Senior Researcher Dr (P2)
13. Radu Lucian Senior Researcher Dr (P2)
14. Tache Andreea Researcher Dr (P2)
15. Eremia Sandra Researcher Dr (P2)
7
  • Scientific contributions based on the results
    obtained
  • Published papers
  • 1.Platinum-modified SiO2 with tubular morphology
    as efficient membrane
  • type microreactors for mineralization of formic
    acid
  • Autori Crina Anastasescu, Mihai Anastasescu,
    Maria Zaharescu, Ioan Balint
  • Journal of Nanoparticle Research 14(10),
    1198-1209, 2012)
  • Conferences oral presentations
  • 1. Synthesis and characterization of Cu-M (M
    Pd, Pt, Rh) bimetallic
  • nanoparticles,
  • Autori Razvan State, Florica Papa, Akane
    Miyazaki, Mariana Scurtu, Gianina,
  • Dobrescu,Ioan Balint
  • ROMPHYSCHEM XV-2013, 11-13 september, Bucharest
  • 2.The effect of surface basicity on the C2
    formation yield over an equimolecular

8
  • Scientific contributions based on the results
    obtained
  • Conferences oral presentations
  • 3. Comparative study on the catalytic and
    photocatalytic reduction of NO3- over
  • Pd-Cu nanoparticles supported on Al2O3 and TiO2,
  • Autori Mariana Scurtu, Florica Papa, Razvan
    State, Cornel Munteanu, Catalin
  • Negrila, Ioan Balint, ROMPHYSCHEM XV-2013, 11-13
    september, Bucharest
  • 4. Catalytic denitration over simple and
    alumina-supported Pt-Cu bimetallic
  • nanoparticles,
  • Autori Ioan Balint, Kahori Matsuda,
    Akane,Miyazaki, Florica Papa, Catalin
  • Negrila, Iuliana,Pasuk, ROMPHYSCHEM XV-2013,
    11-13 september Bucharest
  • 5. Fractal Analysis of Pt-Cu Nanoparticles,
  • Autori Gianina Dobrescu, Florica Papa, Iudit
    Fangli, Ioan Balint
  • ROMPHYSCHEM XV-2013, 11-13 september Bucharest

9
Etapa 1 2012
  • Sinteza si caracterizarea nanoparticulelor
  • bimetalice Pt-M, Pd-M, Rh-M (MAg, Cu, Au)
  • Buget etapa 1 460 000

10
Rezumat
  • Raportul stiintific descrie prepararea a
    nanoparticulelor bimetalice bimetalice Pt-M,
    Pd-M, Rh-M (MAg, Cu, Au) prin metoda poliol
    alcalina precum si caracterizarea complexa a
    acestora. Sinteza nanoparticulelor bimetalice in
    faza organica de etilen glicol s-a facut in
    prezenta polivinil pirolidona care a jucat
    rolurile de agent de directionare a structurii si
    de prevenire a aglomerarii. Prin ajustarea
    parametrilor de sinteza s-a incercat obtinerea
    nanoparticulelor bimetalice cu structuri
    core-shell, core-shell invers sau de aliaj.
    Nanoparticulele obtinute au fost caracterizate
    prin microscopie electronica (TEM), XPS, TPR
    (termoreducere programata), TPO (termooxidare
    programata), chemosorptie si voltametrie ciclica.
    Din imaginile TEM s-au determinat histogramele de
    dimensiuni ale nanoparticulelor bimetalice
    folosind programe de analiza a imaginii. TEM,
    porozimetrie (distributie de pori si suprafata
    specifica) si difractie de raze X. Caracterizarea
    electrochimica a nanoparticulelor bimetalice s-a
    facut indeosebi prin tehnici de voltametrie
    ciclica, deoarece caracterizarea riguroasa a
    bimetalelor sintetizate poate conduce la
    imbunatatirea proprietatilor catalitice prin
    ajustarea unora dintre parametrii de sinteza.

11
Obiectivele generale ale etapei I
  • Obiectivul 1 Prepararea nanoparticulele
    bimetalice cu o morfologie controlata de Pt-M,
    Pd-M, si Rh-M (MCu, Ag, Au) protejate cu PVP
    (polivinil pirolidon) prin metoda poliol
    alcalina, activitate realizata exclusiv de catre
    coordonator, ICF Bucuresti
  • Obiectivul 2 Caracterizarea complexa a
    nanoparticulelor bimetalice prin metode
    fizico-chimice, activitate realizata de intregul
    consortiu (CO, P1, P2)
  • Obiectivul 3 Stabilirea citotoxicitatii si
    genotoxicitatii nanoparticulelor bimetalice,
    activitate realizata de Institutul National De
    Cercetare-Dezvoltare pentru Stiinte Biologice
    Bucuresti (P2).

12
Rezultate obtinute in etapa I
  • S-a realizat sintetiza nanoparticulelor
    bimetalice de Pt, Pd, Rh-M (MCu, Ag, Au) prin
    metoda poliol alcalina. Metoda de preparare a
    fost variata astfel incat sa se obtina
    nanoparticule cu morfologii si structuri
    diferite.
  • Nanoparticulele bimetalice au fost caracterizate
    extensiv prin metodele fizico-chimice propuse in
    planul de lucru TEM, XRD, XPS, chemosorptie,
    TPR, TPO, voltametrie ciclica. Pe baza datelor de
    caracterizare s-au tras concluzii importante
    privind morfologia (dimensiune medie, forma),
    structura (core-shell, aliaj sau core-shell
    invers), structura cristalina, stare de oxidare,
    activitate pentru reactia de evolutie a
    hidrogenului.
  • Din rezultatele obtinute la caracterizarea
    fizico-chimica si morfologica a nanoparticulelor
    bimetalice pe baza de platina, paladiu si rodiu
    aliate cu argin , cupru si aur se poate
    concluziona ca acestia pot fi folositi cu succes
    ca si potentiali catalizatori.
  • Datele de caracterizare electrochimica a NP
    Cu-Rh, recomanda utilizarea acestora ca si
    potential mediator redox in constructia viitoare
    de biosenzori.

13
Rezultate obtinute in etapa I
  • La o prima analiza microscopica se pare ca NP de
    tip Pt, Pd, Rh-M nu afecteaza morfologia
    celulelor fibroblast-like (NCTC) in timp ce NP de
    tip M-Pt, Pd, Rh determina o apoptoza celulara
    chiar la concentratii foarte reduse.
  • S-a demonstrat ca un numar de 7 probe din cele 15
    testate prezinta
  • genotoxicitate prin generare de SRO de tip
    lipoperoxid, dar rezultatele nu trebuie privite
    ca alarmante intrucat s-a lucrat cu concentratii
    destul de ridicate de nanoparticule, de 50 mg/mL,
    astfel incat este necesar ca, dupa ce vor fi
    definite intervalele de concentratii la care NP
    sintetizate vor fi utilizate in reactia de
    dehidroclorurare, pe baza protocolului stabilit
    in aceasta etapa sa fie re-testate NP de interes.
  • S-a demonstrat de asemenea ca majoritatea NP
    bimetalice au o buna eficacitate de descompunere
    a apei oxigenate.

14
Indicatori de rezultat
  • Obiectivele au fost realizate in totalitate,
    planul de realizare
  • fiind urmarit si respectat cu
    rigurozitate
  • 25 studii experimentale
  • 1 conferinta
  • 4 seminarii comune coordonator-parteneri pentru a
    urmari
  • progresul cercetarii in vederea realizarii
    obiectivelor Etapei 1-a
  • 1 publicatie ISI
  • (Crina Anastasescu, Mihai Anastasescu, Maria
    Zaharescu,
  • Ioan Balint "Platinum-modified SiO2 with tubular
  • morphology as efficient membrane-type
    microreactors for
  • mineralization of formic acid" Journal of
    Nanoparticle
  • Research, 14(10), 1198-1209, 2012).
  • 2 articole in faza de pregatire.
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