New BImetallic nanoparticles with applications in

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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

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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

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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

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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.

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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
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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)
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Etapa I 2012

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

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Rezumat etapa I 2012

• Raportul stiintific descrie prepararea
  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 realizat in
  prezenta
• polivinil pirolidonei care a jucat atat rol de
  agent de directionare a structurii cat 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.

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Obiectivele generale ale etapei I

• 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 (CO)
• Caracterizarea complexa a nanoparticulelor
  bimetalice prin metode fizico-chimice, activitate
  realizata de intregul consortiu (CO, P1, P2)
• Stabilirea citotoxicitatii si genotoxicitatii
  nanoparticulelor bimetalice, activitate realizata
  de Institutul National De Cercetare-Dezvoltare
  pentru Stiinte Biologice Bucuresti (P2).

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Rezultate estimate etapa I 2012

• Raport stiintific care sa contina rezultatele
  obtinute
• O comunicare prezentata la o conferinta
  internationala

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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.

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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.

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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 I-a
• 1 publicatie ISI
• 2 articole in faza de pregatire.

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• Diseminarea rezultatelor
• Lucrari publicate
• 1.Platinum-modified SiO2 with tubular morphology
  as efficient membrane
• type microreactors for mineralization of formic
  acid
• Crina Anastasescu, Mihai Anastasescu, Maria
  Zaharescu, Ioan Balint
• Journal of Nanoparticle Research 14(10),
  1198-1209, 2012)
• Conferinte si prezentari orale
• 1.Synthesis and characterization of bimetallic
  nanoparticles Au-M (M Pd, Pt,Rh) byalkaline
• Polyol method , Autori Razvan State, F. Papa, A.
  Miyazaki, M.Scurtu,G. Dobrescu, I.Balint,
• ICOSECS 8 ,Belgrad, 27-29 iunie 2013
• 2. 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

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• Conferinte si prezentari orale
• 4. 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
• 5. 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
• 6. Fractal Analysis of Pt-Cu Nanoparticles,
• Autori Gianina Dobrescu, Florica Papa, Iudit
  Fangli, Ioan Balint
• ROMPHYSCHEM XV-2013, 11-13 september Bucharest

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Etapa II 2013

• Sinteza alumimei mesoporoase Asamblarea
  materialelor support (Al2O3, TiO2 , folie titan)
  cu nanoparticule bimetalice .Caracterizarea
  sistemelor realizate
• Buget etapa II 414 000

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Obiectivele generale ale etapei II

• Sinteza si caracterizarea aluminei mezoporoase
  (CO)
• Caracterizarea aluminei mezoporoase prin XPS, XRD
  si TEM ( P1)
• Asamblarea controlata a nanoparticulelor
  bimetalice cu alumina mesoporoasa, TiO2 (Degusa)
  si Titan folie (CO)
• Testarea citotoxicitatii si genotoxicitatii
  materialelor asamblate (P2)
• Evaluarea si diseminarea rezultatelor
  experimentale
• Publicare articole si participare la conferinte
  internationale si vizite de lucru