Jovanovic- VILNUS-E2a.pptx Kinetics of fularene polyhydroxylation

Presentation at COST Action CA1517, Vilnus 2018

1. Kinetics of fulerene polyhydroxylation Jelena Jovanović 1 , Mihajlo Gigov 2 , Borivoj Adnađević 1 1- University of Belgrade - Faculty of Physical Chemistry, Studentski trg 12-16, 11001 Belgrade, Serbia 2- Mining institute Ltd. Belgrade, Batajnički put 2, 11080 Belgrade, Serbia Cost Action, MultiComp CA1517 Vilnus , 8-9 march 201 8 .

2. Fulerenes The discovery of fullerene ( 1985, R.Curl , M.Kroto , R.Smalley ) Nobel prize in chemistry 10-years later. Fullerene family, ( backyball ) with its unique structure consisting of sp 2 C-atoms form highly symmetric caged molecules with different sizes (C 20 -… C 60 - C 70 -C 80 …..) …. C 540 -) – Fullerene represent the new allotrope of C along with graphite and diamond Fullerene C 60 – the most abundant and explored

3. Fullerene, is the most symmetrical molecule in the world with unique properties: can behave as superconductor through to semi-conductor exceptional radical scavengers super antioxidant (170x higher than C-vitamin) can be easily modified to tailored properties - (modification of electronic structure, solubility and physical properties ) enable a range of applications from electronic to medicine organic photovoltaics, photoresists, Photodetectors… Lack of solubility in water and water solutions

4. Extraordinary physico -chemical properties: solubility in water , high biological activity ability of free radical scavenging, antioxidant properties, photo-toxic , photo-catalytic anti-microbial activity …… C 60 (OH) n , n = 2,..., 4 Fulerenols ( Fullerols ) it could be expected that fullerol should found extensive application in various fields of chemistry , elecrochemistry fuel cells solar energ y storage biochemistry , pharmacy medicine….. Ful l erol s - water soluble pol y h y dro x ila ted derivat es of fuleren e Most frequently, fullerols are denoted as C 60 (OH) n , where “ n ” should be from 2 to 44. HIV protea ses inhibition , Lipid es pero x sida tion , N euron s d egenera tion in Alzha i mer , DNA sequencing …. .

5. Extraordinary physico -chemical properties: solubility in water, ability of free radical scavenging, antioxidant properties, photo-catalytic anti-microbial activity …… C 60 (OH) n , n = 2,..., 4 Fulerenols ( Fullerols ) it could be expected that fullerol should found extensive application in various fields of chemistry , biochemistry , pharmacy medicine ….. Ful l erol s - water soluble pol y h y dro x ila ted derivat es of fuleren e Most frequently, fullerols are denoted as C 60 (OH) n , where “ n ” should be from 2 to 44. In the literature are presented various methods of fullerol synthesis with a defined number of hydroxyl groups The most famous ones: hy drol yses of ( C+i on )* intermedi er formed with n itronium i on, under H+ media , with oleum, r eac t i on with azotdioksida, h y drol yses of pol y c yc losulfat e pre c ursor s .

6. Li . et al- using t etrabutil-amonijum h y droksid (TBAH), phase-transfer c ataly st , T –ambient . C hiang et al- procedure for ful l erol s with hemiketal gr o up s , C 60 reacting with oleum (28 %) under mixing in an inert atmos ph er e , T- 65 °C. L . Y. Chiang et al- C 60 nitr ation or sul phuration – nu c leofil c su b stitu tion of the nitro , o r , sul pho group s, which than hydrolyses in water solution of NaOH and are easily su b stit e with OH gr o up s. 3 Lu et al- by heating the C60 toluene solution with 30 mg of sodium (Na), with constant stirring. Chen et al- described the method of forming fulerol in the reaction of the C60n lithium salt with a methanol / water solution in the presence of O2. 5 Djordjevic et al- preparation o f fulerol C60(OH)24 by complete substitution of bromine atoms C60Br24 with OH groups. Zhang et al- the process of forming fullerol by the technique of vibratory grinding at high speed at room T in the presence of air, by grinding C60 and sodium hydroxide ( NaOH ). Zhang et al- the synthesis in the presence of PEG 400 as an intermediate catalyst. Husebo et al. described a process for the formation o f fullerole from C60 at room-T in the presence of NaOH and TBAH as an intermediate catalyst . [9] Wang et al. - by grinding a mixture of fullerene (C60), a solid NaOH and 30 % of H2O2 in glass mortar in the presence of air at room T [10], Alves et al . - complex hydrolysis of the fulerene derivative in the presence of NaOH and PEG 400 as an intermediate catalyst in an O2 atmosphere . [11] State-of-the-art: Methods of fullerol synthesis

7. State-of-the-art: Kinetics of fullerol synthesis B Adnadjevic , M Gigov , Sindjic M ., J Jovanovic , Comparative study on isothermal kinetics of fullerol formation under conventional and microwave heating , Chemical Engineering Journal 140 (2008) 570–577. B Adnadjevic , J Jovanovic M Gigov , Effect of Ultrasonic Field on Isothermal Kinetics of Fullerene Polyhydroxylation , Science of Sintering 48 (2), 259-272 (2016). M Gigov , J Jovanović , B Adnadjević ,, Isothermal kinetics of C 60 polyhydroxylation in a two-phase system in the presence of tetrabutylammonium hydroxide, Reaction Kinetics, Mechanisms and Catalysis ,122 (2) 741-755 (2017). B Adnadjević , M Gigov , J Jovanović , The effects of external physical fields on the isothermal kinetics of fullerol formation , Reaction Kinetics, Mechanisms and Catalysis DOI : 10.1007/s11144-017-1326-4 REAC-D-17-00458.1 (2018).

8. By examining the state- of-the-art, it was found that the isothermal kinetics of the reaction of the formation of fullerol in the presence of phase-transfer catalyst is not thoroughly investigated . The isothermal kinetics of fullerol formation,- determine the kinetic model of the process and the kinetic parameters of the fullerol formation ; The effects of reaction parameters on the fullerol formation kinetics : Temperature Change in co ncentra tion of fuleren e C 60 phase-transfer c atal yst – cetyltrimethylammonium bromide ( CTAB) (for the first time used) [( C 16 H 33 )N(CH 3 ) 3 ]Br; NaOH H2O2 The aim:

9. Experimental Decolouration of the organic layer of the reaction mixture - VIS spectrophotometry Precipitation of formed product in the inorganic layer by the addition of ethanol to the complete removal of NaOH and CTAB Drying precipitate for 6h at 60 0C. The final product of the reaction – a dark brown color . Termostat ed water bath T : 20 C ; 25 C ; 30 C; 35 C , 40 C ( ±1 C ) . Mixing rate : 500 o/min Organ ic phase : C 60 in toluen e Water phase : NaOH + CTAB +H 2 O 2 (30%)

10. Elemental analysis of the reaction product Infrared spectroscopy of the reaction product T [K] C con [%] H con [%] 293 64,0 2,13 298 64,0 2,15 303 63,9 2,13 308 63,8 2,14 313 63,9 2,17 The effect of temperature on the results of elemental analysis of the final reaction product Determination of the content of carbon [ C(%)] and hydrogen [ H(%)] , in the final product , using instrument Carlo Erba Elemental Analyzer, t y p e EA 1108, Ital y KBr pellet technique (1 mg sample per 100 mg KBr ) Bomem MB100 Fourier transform infrared spectrometer, Hartmann & Braun, Canada. The FTIR absorption spectrum of fullerols (ν and δ denote extensible and folding vibration modes, respectively) C 60 (OH) 24

11. λ 1 = 540 nm λ 2 = 598 nm Determination of the degree of transformation of fullerene into fullerol in reaction time, by Eq : Where: C initial conc. Of C 60 in toluene solution, C i conc. of fullerene C 60 i n the organic layer of the reaction mixture, at a specific reaction time t The absorption spectra of different fullerene conc. in toluene Calibration plot for the determination of the C 60 conc. in the organic layer Spectrophotometric method for determining the concentration of C60 in a solution with a UV / VIS UV / VIS spectrometer "UV mini 1240", Szhimadzu , Japan.

12. Eksperimentalno ispitivanje kinetike reakcije podrazumeva analizu opšte empirijske kinetičke jednačine: Diferencijalne metode određivanja kinetičkih parametara The m et hod of initial rates Gra fical presentation for the determination the reac tion order by the initial rate met h od A, B, C reaktanti stepenovani brojem koji predstavlja red u odnosu na odgovarajući reaktant

13. The effect of initial fuleren e C 60 c oncentra tion Conditions: The initial f ulleren e c onc . : C 60 : 1 g/L; 0,8 g/L; 0,6 g/L; 0,4 g/L i 0,2 g/L. C NaOH = 210 g/L; C CTAB = 1,5 g/L; C H2O2 = 15 g/L; Slope =1 First order reaction against the C 60 Ratio organ ic phase / water phase: 5: 1 Mixing rate: 500 rpm /min T = 25 ±1 C R e sults

14. The effect of changes in phase- transpher c atal yst (CTAB) concentration T= 25 ±1 C Initial c oncentra tion : CTAB: 1,5 g/L; 1,0 g/L , 0,5 g/L C C60 = 0,8 g/L; C NaOH = 210 g/L; C H2O2 = 15 g/L; Slope =1 First order reaction against the CTAB Ratio organ ic phase / water phase: 5: 1 Mixing rate 500 rpm /min [(C 16 H 33 )N(CH 3 ) 3 ]Br

15. The effect of changes in H 2 O 2 c onc entration : Initial conditions T= 25 ±1 C H 2 O 2 : 5 g/L; 10 g/L , 15 g/L C C60 = 0,8 g/L; C NaOH = 210 g/L; C CTAB = 1,5 g/L; Slope =1 First order reaction against the H 2 O 2 Ratio organ ic phase / water phase: 5: 1 Mixing rate: 500 rpm /min

16. Initial conc entra t i on NaOH : 50 g/L; 100 g/L i 210 g/L T = 25 ±1 C C C60 = 0,8 g/L ; C H202 = 15 g/L; C CTAB = 1,5 g/L; Slope =1 Reac tion of ½ order against the NaOH The effect of changes in c oncentra tion of NaOH Ratio organ ic phase / water phase: 5: 1 Mixing rate: 500 rpm /min

17. The expression for the reaction rate can be presented by the equation : v = k [C 60 ] 1 [CTAB] 1 [H 2 O 2 ] 1 [NaOH] 0,5 The overall K ineti c process – 1 ST order chemical reaction against C 60 , CTAB and H202, and 0.5 against NaOH

18. The effect of temperature on fullerene polyhydroxylation C C60 = 1 g/L; C NaOH = 100 g/L; C CTAB = 0,5 g/L; C H202 = 5 g/L Fig. The isothermal kinetic curve of fulerol formation at different T Ratio organ ic phase / water phase: 5: 1 Mixing rate: 500 rpm /min T [K] k, [min -1 ] Kinetic parameters [kJ/ mol ] 293 0.047   48 ± 2 13.1 ± 0.2 298 0.066 303 0.080 308 0.106   313 0.135 T [K] k, [min -1 ] Kinetic parameters 293 0.047   48 ± 2 13.1 ± 0.2 298 0.066 303 0.080 308 0.106   313 0.135 The k e x ponen tialy ↑ with T Arrhenius- Equation The values of KP ( Ea and lnA ) calculated

19. Thank You for the attention

20. Possible Mechanisms of fullerole formation Fig. Posible mechanism of oxidation with O2 in alkali medium Fig . Suggested mechanism of fulerol form ation with high number of OH groups using H2O2

21. Međufazna kataliza Međufazna kataliza - proces koji omogućava prenos jednog od reaktanata, najčešće nukleofilnog anjona iz neorganske faze u organsku fazu, gde se reakcija odigrava, dodavanjem supstance koja se naziva međufazni katalizator. Međufazni katalizator - supstanca bipolarane strukture (najčešće bipolarna so), koja je u određenoj meri rastvorljiva u organskoj i u neorganskoj fazi. Osnovni zahtevi koja mora da ispunjava međufazni katalizator su: 1. Katjonski deo rastvorljiv u organskoj fazi 2. Međujonska veza lako raskida usled visoke reaktivnosti anjona Kvaternarne amonijum soli, Q + X - ispunjavaju optimalne uslove u pogledu aktivnosti, stabilnosti, dostupnosti i niske cene. Slika x. Mehanizam procesa međufazne katalize

22. Starks-ov ekstrakcioni mehanizam za reakciju nukleofilne supstitucije: Kvaternarna so (Q + X - ) u vodenoj fazi disosuje na kvat (Q + ) i anjon (X - ). (Q + ) katjon vezuje nukleofilni anjon (Y - ). Reakcija jonske izmene između međufaznog katalizatora i nukleofila transfer reaktivnog jonskog para (Q + Y - ) u organsku fazu, gde se reakcija odigrava. Anjon (Y - ) u organskoj fazi interaguje sa reaktantom (RX) dajući produkt (RY) i kvaternarnu so (Q + X - ). Ciklus se završava kada reaktivni anjoni u potpunosti izreaguju sa reaktantom u organskoj fazi. Slika x. Mehanizam međufazne katalize za slučaj kada je katjon Q + rastvorljiv u vodenoj fazi

23. F izičkohemijska svojstva fulerola C 60 (OH) n Fulerol Boja Rastvorljivost C 60 (OH) 26-28 tamno braon - crna voda C 60 (OH) 16-18 braon - crna voda / DMF C 60 (OH) 12-14 crna DMF / voda / metanol C 60 (OH) 2 tamno crna Aromatični rastvarači / metanol nukleofilnost hidroksilnih grupa, koja zavisi od elektrofilnosti fulerena, opada sa porastom hidroksilnih grupa. Ovo ima direktan uticaj na fizičkohemijska svojstva fulerola. Zbog toga je veoma važno da se precizno odredi broj hidroksilnih grupa u sintetisanom fulerolu.

24. Dobra rastvorljivosti fulerola omogućuje sprovođenje reakcija u rastvorima, najčešće u vodi, ili u heterogenom medijumu korišćenjem faznih katalizatora. Kombinacija funkcionalnosti poliola i sferični oblik fulerola omogućava primenu fulerola kao molekularno jezgro za sintezu dendritskih makromolekula i polimera. Kovalentno vezane i nasumično raspoređene hidroksilne grupe fulerola ponašaju se kao nukleofili i obezbeđuju veću gustinu reaktivnih centara za stvaranje hiper-razgranatih polimernih mreža i kompozita.