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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• 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

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• 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

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Etapa 1 2012

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

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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.

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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).

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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 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.