Pyrolytic Conversion of Structured Polymeric Materials to Porous Carbons

Transcription

1 Carbon Materials for Today and Future Turkish-Japanese Joint Carbon Symposium March 18-19, 2010 Istanbul Technical University Pyrolytic Conversion of Structured Polymeric Materials to Porous Carbons Masashi Kijima Institute of Materials Science, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki , Japan

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3 Organic Starating materials Pitches, Polymer, Wastes etc Thermo plastic Gas Carbonization process of organic materials aromatization evolution -elimination Thermo setting Fluidity Viscosity eating rate Viscosity Softening eating rate high slow high slow low fast Carbonized materials Closed pores Porous Open pores Graphitizable Nonporous Non(hard)- graphitizable

4 Approaches to prepare porous carbons by pyrolytic methods From poly(m-phenylenebutadiynylene)s, PmPB, a rigid conjugated polymer From lignin-cellulose composites, wooden biomass materials From synthetic organic zeolites: Coordination polymers = Metal organic frameworks (MOFs), Covalent organic frameworks (COFs), and microporous polymers

5 (1) Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C (2) Pyrolytic conversion of structured Lignin-Cellulose composites to porous C (3) Pyrolytic conversion of MOFs and COFs to porous C

6 Classification of C C bonded materials having different hybrid orbitals and dimensions C C C C C C C C C C C C C C

7 Some conjugated polymeric materials for preparation of carbon materials n n PPP polyacene PPV n Good starting materials for Carbons PPE n PPB n igh content of C igh yield carbonization behavior (>90% yield) To prepare one of the models of amorphous C E. Fitzer et al., igh Temp. igh Press., 3 (1971) 53. A. E. Newkirk, et al., J. Polym.Sci., Part A, 2 (1964) 2217.

8 Thermal conversion of PmPB to microporous carbons in high yield T exo 100 variation of 1,2- and 1,4-additions TG(%) TG/DTA DTA(a.u.) PPB abstraction recombination cross-linked polymer network Temperature( ) = 200 Amount Ads. (ml(stp)/g) 100 N 2 adsorption Isotherm S BET =470 m 2 /g P/P 0 aromatization and condensation > elimination graphitic crystallite formation sp 2 -C network microporous carbonized material M. Kijima et al., Carbon, 45(2007)

9 Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C Polymer blocks Rigid backbone strong interaction 1. ow to increase the surface area. 2. ow to regulate the porosity. Polymer gel method Porous carbon block with closed surfaces Three Approaches Microporous surface Swelled polymer gel Dried polymer gel (low density) Carbonized polymer gel consisting of Thin carbon blocks

10 Microporous surface Conventional case: polymer particles are carbonized together to form large carbon blocks consisting of nano-scale basic structural units with cross linking reactions (2) Micellar method Meso & Macroporous spaces Polymer particles are isolated each other by micelle formation. The carbonized blocks must be smaller than the conventional cases.

11 (3) Selective elimination of leaving group from hyperbranched polymer (rigid frame works) N. Kobayashi, M. Kijima, J. Mater.Chem., 17 (2007) Porous carbon (microporous) 900

12 Synthesis of starting polymers R O 2 / Cu-TMEDA cat. ay method O O n Soluble PmPB

13 (1) Preparation of PG O C C O CuCl,TMEDA,O 2 C C C C m C C C C n C C C C C C C C TF,1,4-dioxane C C C-PG carbonization Freeze dry PG (net-like structure)

14 TG (%) DTA (a.u.) exo PmPB PG V ads [ml/g(stp)] r.t (3),900(3) Temperature ( ) Relative Pressure P/P 0 polymer Conditions Y (%) S BET (m 2 /g) Sα s (m 2 /g) V micro (ml/g) w (nm) V meso (ml/g) V total (ml/g) PmPB PG

15 (2)-1. Preparation of PM1 and C-PM1 SDBS 2 O Micelle formation Cu cat., O 2 polymerization Freeze-dry carbonization PM1 C-PM1

16 TG/DTA of PM1 and N 2 adsorption isotherm of C-PM1 Degradation and elimination of SDBS 100 TG (%) DTA (a.u.) exo PmPB PM Amount Ads. (ml(stp)/g) CPmPB CPM Temperature ( ) P/P 0

17 Surface analysis results of C-PM1 water (ml) C-PmPB C-PM C-PM C-PM1-10* Diethynylbenzene (0.2 ml, 1.6 mmol), CuCl-TMEDA (0.34 mmol), SDBS (35 mg, 0.1mmol) *: without freeze-drying process

18 (2)-2. Preparation of PM2 and C-PM2 O O Soluble PmPB n Fused & non-porous C Micelle formation Polymer 50 mg SDBS 300 mg CCl 3 1 ml 2 O 6 ml 40 Precipitation from MeO PM2 2 SO 4 tretment Dispersed image Packed image Micro&mesoporous C C-P1 C-PM2 Carbonization (r.t. 900 [10 /min] under Ar)

19 N 2 -Adsorption isotherms and pore distribution of C-PM2 600 Amount Ads. (ml(stp)/g) C-sol.PmPB(C-P1) C-PM2 C-PM1 C-PmPB dvp/drp[mm 3 /(g nm)] D method P/P Pore Radius Rp[nm] Sample C-yield (%) S BET (m 2 /g) S s (m 2 /g) w micro (ml/g) V micro (ml/g) V meso (ml/g) V total (ml/g) C-P C-PM

20 (3) Synthesis of P OR CuCl-TMEDA cat OR P1: R= -(C 2 ) 17 C 3 P2: R= -(C 2 ) 4 OPh P3: R= -C 2 Cy O 2 in TF n

21 P3(cyclohexylmethyl) OR n DTA (a.u.) exo. TG (%) PmPB P Elimination of R Amount Ads. (ml(stp)/g) CPmPB P(450) CP Temperature ( ) TG/DTA P/P 0 N 2 -adsorption isotherm

22 Surface analysis data of P and CP Material Y (%) CPmPB P1(450) CP P2(450) CP P3(450) CP

23 Electrical Double Layer Capacitances of C-PmPBs (three-electrode system in 1M 2 SO 4 ) 500 C-P1 (S=700 m 2 /g) Capacitance (F/g) Current density (A/g) C-PM2 ( S=800 m 2 /g) C-PmPB (S=470 m 2 /g) activated C-PmPB (S=950 m 2 /g) activated C-PmPB (S=1400 m 2 /g) Activated C (S=1350 m 2 /g) Capacitance (F/m 2 ) Current density (A/g)

24 (1) Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C (2) Pyrolytic conversion of structured Lignin-Cellulose composites to porous C (3) Pyrolytic conversion of MOFs and COFs to porous C

25 Purpose of our research Synthesis of functional carbon-rich materials from wooden biomass without production of CO 2 Organic materials Semiconducting Conducting materials carbonized materials 300ºC 800ºC 1500ºC Carbon materials Cellulose & Lignin Low content of C Various functional groups in the material Possible to restructurize Structured C-rich Materials igh-c content: uniform & homogeneous composition Application: thermoelectric-conversion, Photovoltaic & sollar cells, electrodes for batteries, fuel cell, EDLC, Stable porous Energy-source ( 2 etc) storage material etc.

26 Lignin aromatic structural unit O O (a) (b) (c) O a possible structure O O OC 3 3 CO OC 3 O (a) p-coumaryl alcohol (b) coniferyl alcohol (c) sinapyl alcohol Advantage of lignin to convert into carbon materials: Lignin has the phenolic components: high C fixation ability on anaerobic pyrolysis There has been reported several results on carbonization of lignin and preparation of activated carbon

27 Alkaline Lignin Black powder Water soluble Elemental analysis C: % : 5.12 %, N: 0.13 % (Nacalai), C: %, : 4.78 %, N: 0.11 % (Tokyo Kasei) Reagent grade (available) 350 g/mol (cryoscopic method) TG [%] DTA[a.u.] Tokyo Kasei Nakalai Temperature[ ] exo

28 Carbonization of alkaline lignin Argon gas inlet Furnace r.t ~ 900 ºC Sample Carbonization conditions CL1 r.t ~ 900 ºC 10 ºC/min (annealing time) CL2 r.t ~ 900 ºC 4 ºC/min CL3 r.t ~ 900 ºC 2 ºC/min CL4 r.t ~ 900 ºC 1 ºC/min CL5 r.t ~ 300 ºC 10 ºC/min 300 ºC (1) 300 ºC ~ 900 ºC 10 ºC/min CL6 r.t ~ 350 ºC 10 ºC/min 350 ºC (1) 350 ºC ~ 900 ºC 10 ºC/min CL7 r.t ~ 350 ºC 10 ºC/min 350 ºC (2) 350 ºC ~ 900 ºC 10 ºC/min CL8 r.t ~ 350 ºC 10 ºC/min 350 ºC (3) 350 ºC ~ 900 ºC 10 ºC/min

29 SEM 10 m 10 m 10 m Alkaline lignin CL4 CLW CL4 deposition on the surface was a Na salt confirmed by PS CLW After washing CL4 with water, the deposition was cleaned off Carbonization results and N 2 adsorption data s D sample Yield (%) S BET (m 2 /g) S total (m 2 /g) V micro (ml/g) W micro (nm) V total (ml/g) V meso (ml/g) V meso / V total (%) CL CLW

30 Control of structure and morphology of carbonized materials Particles in nano-micron scale carbonization Microporous C-particles Aims: 1) Increase of effective surface area. 2) Generation of new pore space (external) between the particles Typical conditions ML3 Water (ml) 5 SDBS (mg) 50 Benzene (ml) 45 SO 3 - Na + Sodium Dodecylbenzenesulfonate(SDBS) benzene water SDBS Reverse micelle Preparation of micellar lignins and the carbonization

31 Preparation of micellar lignins ML) and their carbonization (in solution) (freeze-dried) ML3 CML3 10 m Freeze-dried carbonization Fine-structured ML Particle samples could not be obtained in this case. In order to obtain particle lignins, (3) rigid lignin gels are synthesized

32 Toward synthesis of carbonized lignin particles Preparation of alkaline lignin gel and the carbonization Under basic aqueous conditions, alkaline lignin was reacted with formaldehyde to give a swelled polymer gel, which was carbonized after freeze drying. L CO L Freeze-dried, carbonization L L LG L L CLG Swollen polymer gel Preparation of lignin-gel particles and their carbonization Freeze-dried carbonized MLG Swollen lignin gel Lignin+CO+NaO Carbon particles CMLG

33 Carbonization and N 2 adsorption results s D sample Yield (%) S BET (m 2 /g) S total (m 2 /g) V micro (ml/g) W micro (nm) V total (ml/g) V meso (ml/g) V meso / V total (%) CL CML CLG CMLG Surface area [m 2 /g] SBET Sαs Vtotal CL4 CML3 CLG CMLG CL4 CML3 CLG CMLG Sample

34 (1) Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C (2) Pyrolytic conversion of structured Lignin-Cellulose composites to porous C (3) Pyrolytic conversion of MOFs and COFs to porous C

35 Porous materials Adsorbent, Catalyst, Catalyst support, Electrode(carbon) Inorganic materials Zeolite, porous silica Corroded metals Coordination polymers Metal organic frameworks (MOFs) Organic zeolite, COF, Microporous polymers Carbon materials Activated carbons Template carbons Pyrolytic carbons Chemically, physically Stable, electrical conductive MOF-177 (4500 m 2 g -1, Langmuir) MIL-101 (5900 m 2 g -1, Langmuir), COF-103 (4210 m 2 g -1, BET) PAF-1 (5600 m 2 g -1,BET)

36 Conjugated microporous polymers

37 Organic Linkers TPEB Good carbonization yields and high S BET N. Kobayashi, M. Kijima, J. Mater. Chem. 18 (2008) % 495 m 2 /g

38 Image of MOF constructing from the organic linker(tpeb) and metal ion M M M M M M M M M M M M TPEB + Metal ion 2D image

39 N 2 adsorption desorption isotherms of the mesoporous coordination polymers and their carbonised samples COOK K 3 7= KOOC COOK 7b = K Cu(OAc) 2 in dioxane S BET = 37 m 2 /g C7b S BET = 584 m 2 /g 7c = K 3 7 +Cu(OAc) 2 in MeO 105 carbonization C7c d = K CuCl O in MeO 104 C7d 736

40 Organic linkers having triphenylene(tp) and tetraphenylmethane(tpm) structures TP TPM TP(=O) TPM (=COC2Br) TPM (=COCl)

41 Summary of the surface parameters of COF and carbonized COF Organic Linker Connectors Network material C Yield % Carbonized material Yield % S BET m 2 /g V total ml/g S BET m 2 /g V total ml/g V meso /V total % TP(O) Ph(C 2 Cl) TP(O) BrC 2 C CC 2 Br TPM(C 2 COCl) Ph(N 2 ) TPM(COC 2 Br) OC 2 C CC 2 O TPM(COC 2 Br) Ph(COOK)

42 Summary and Conclusions (1)Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C Structuration Increase external surface high specific surface area + mesoporosity (2)Pyrolytic conversion of structured lignin-cellulose composites to porous C. The soluble C(C1,C2) showed good carbonization yields. The L-C composites have a good processability to make thin films and particles. The structuration results in increase of S. (3)Pyrolytic conversion of MOFs and COFs to porous C The organic linkers showed high fixation of C on the pyrolysis. The network materials can be converted to microporous C

43 Acknowledgement The author is grateful to : (Theme I) Mr. Y. Ichikawa, Mr. M. Suzuki (University of Tsukuba) (Theme II) Cooperative Research of RIS, Kyoto University Prof. T. ata, Research Institute for Sustainable umanosphere(ris) Kyoto Univ. Mr. T. irukawa, Mr. F. anawa (University of Tsukuba) (Theme III) Dr. N. Kobayashi, and Mr. T. Ishida (University of Tsukuba)