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 305-8573, JapanE-mail: kijima@ims.tsukuba.ac.jp

Carbon Materials for Today and FutureTurkish-Japanese Joint Carbon Symposium

March 18 - 19, 2010 Istanbul Technical University

Carbonization process of organic materials

Gas aromatization

evolution H-elimination

Thermo plastic

Thermo setting

Non-porous

Fluidity ・Viscosity

Heating rate

highslow

high（slow）Viscosity ・

Softening

Heating rate Open pores

Closed pores

200℃ 500℃ 1500℃900℃

Porous

Graphitizable

Non(hard)-graphitizable

OrganicStaratingmaterials

Carbonizedmaterials

Pitches,Polymer,Wastes etc

low（fast）

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

(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

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

hybrid

dimension

orbital 0 1 2 3

sp3 ethane

polyethylene Polymethyne (GIC, GO)

diamond

sp2 ethene

（fullerenes）

polyacetylene graphite

sp ethyne

(Cyclocarbons)

polyethynylene

(carbyne)

C C

HH

H HH

H

H

H

HH

H

H

HH

HH

H

H

H

H

H

HH

H

C C

H

HH

H

H

H

H

H

C CH HC C C C

C C C C

Some conjugated polymeric materials for preparation of carbon materials

n n n

n n

PPP polyacene PPV

PPE PPB

Good starting materials for Carbons

High content of C High yield carbonization behavior (>90% yield)To prepare one of the models of amorphous C

E. Fitzer et al., High Temp. High Press., 3 (1971) 53.A. E. Newkirk, et al., J. Polym.Sci., Part A, 2 (1964) 2217.

variation of 1,2- and 1,4-additions

Texo

cross-linked polymer network200-600℃

> 600℃

microporouscarbonized material

sp2-C network

PPB

=

aromatization andcondensation

H-abstractionrecombination

H2 eliminationgraphitic crystalliteformation

Thermal conversion of PmPBto microporous carbons

in high yield

200 400 600 80040

60

80

100

TG(%

)

DTA

(a.u

.)

Temperature(℃)

0 0.2 0.4 0.6 0.8 10

100

200

P/P0

Am

ount

Ads

. (m

L(S

TP)/g

)

TG/DTA

N2 adsorptionIsothermSBET=470 m2/g

M. Kijima et al., Carbon, 45(2007) 594-601

Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C

1. How to increase the surface area .2. How to regulate the porosity.

Polymer blocksPorous carbon blockwith closed surfaces

Swelled polymer gel Dried polymer gel (low density)

Carbonized polymer gel consisting ofThin carbon blocks

ThreeApproaches

（１）Polymer gel method

Microporoussurface

Rigid backbone

strong interaction

(2) Micellar method

Conventional case: polymer particles are carbonized together to form large carbon blocks consisting of nano-scale basic structural units with cross linking reactions

Polymer particles are isolated each other by micelle formation.The carbonized blocks must be smaller than the conventional cases.

Meso &Macroporousspaces

Microporoussurface

(3) Selective elimination of leaving group from hyper-branched polymer

＞900℃Porous carbon(microporous)

(rigid frame works)

N. Kobayashi, M. Kijima, J. Mater.Chem., 17 (2007) 4289.

Synthesis of starting polymersR

O2 / Cu-TMEDA cat.

Hay method

O O

n

Soluble PmPB

(1) Preparation of PG C

C C

CH

CHHC

+1 40 CuCl,TMEDA,O2

THF,1,4-dioxane

C

C

C

C

CC

CC

nm

CC

O

CHHC

CC

O

Freeze drycarbonization

PG (net-like structure)

C-PG

0 0.2 0.4 0.6 0.8 10

100

200

300

Relative Pressure P/P0

Vad

s [m

L/g(

STP

)]

r.t 450 450(3),900(3)

Vtotal(ml/g)

Vmeso(ml/g)

w(nm)

Vmicro(ml/g)

Sαs(m2/g)

SBET(m2/g)

Y(%)

Conditionspolymer

0.280.030.790.254047092-PmPB

0.410.040.660.34107276461450(3),900(3)

0.020.01―00290450(0)

PG

40

60

80

100

TG (%

)

200 400 600 800

Temperature (℃)

DTA

(a.u

.)ex

o.

PmPB PG

SDBS

H2O

Cu cat., O2

Freeze-dry

(2)-1. Preparation of PM1 and C-PM1

PM1

carbonization

C-PM1

Micelle formationpolymerization

TG/DTA of PM1 and N2 adsorption isotherm of C-PM1

40

60

80

100

TG (%

)

200 400 600 800

Temperature (℃)

DTA

(a.u

.)ex

o.

PmPB PM

0 0.2 0.4 0.6 0.8 10

100

200

300

400

500

CPmPB CPM

P/P0

Am

ount

Ads

. (m

L(S

TP)/g

)

Degradation and elimination of SDBS

3.80.280.030.790.2540470-C-PmPB

42.10.590.250.640.20859674100C-PM1-9

50

50

20

3

water(mL)

46.90.600.280.720.16630538C-PM1-10*

56.40.810.450.710.14727638C-PM1-8

39.30.430.170.680.21721560C-PM1-7

42.60.500.210.690.18693569C-PM1-6

Vmeso/Vtotal

(%)V total

(ml/g)Vmeso

(ml/g)wmicro

(nm)Vmicro

(ml/g)Stotal

(m2/g)Stotal

(m2/g)

DHαsBET

Surface analysis results of C-PM1

Diethynylbenzene (0.2 mL, 1.6 mmol), CuCl-TMEDA (0.34 mmol), SDBS (35 mg, 0.1mmol)

*: without freeze-drying process

(2)-2. Preparation of PM2 and C-PM2Soluble PmPB

Micelle formation

Precipitation from MeOH PM2

H2SO4 tretment

C-P1

O O

n

Fused & non-porousC

Dispersedimage

Packed image

Carbonization (r.t.→900℃ [10℃/min] under Ar)

Micro&mesoporous C

C-PM2

Polymer 50 mg、SDBS 300 mg、CHCl3 1 ml、H2O 6 ml、40 ℃

N2-Adsorption isotherms and pore distribution of C-PM2

0 0.2 0.4 0.6 0.8 10

200

400

600

P/P0

Am

ount

Ads

. (m

L(S

TP)/g

)

C-sol.PmPB(C-P1) C-PM2 C-PM1 C-PmPB

0.920.450.150.5999081851C-PM2

0.40.060.30.62102871451.3C-P1

Vtotal

(ml/g)Vmeso

(ml/g)Vmicro

(ml/g)wmicro

(ml/g)Sαs

(m2/g)SBET

(m2/g)C-yield

(%)Sample

DH method

5 10 150

100

200

dVp/

dRp[

mm

3 /(g×

nm)]

Pore Radius Rp[nm]

OR CuCl-TMEDA cat

O2 in THF

OR

H

H

Hn

HP1: R= -(CH2)17CH3HP2: R= -(CH2)4OPhHP3: R= -CH2Cy

(3) Synthesis of HP

0 0.2 0.4 0.6 0.8 10

100

200

300

400

CPmPB HP(450) CHP

P/P0

Am

ount

Ads

. (m

L(S

TP)/g

)

40

60

80

100

TG (%

)

200 400 600 800

Temperature (℃)

DTA

(a.u

.)ex

o.

PmPB HP

HP3(cyclohexylmethyl)

TG/DTA N2-adsorption isotherm

OR

H

H

Hn

Eliminationof R

Surface analysis data of HP and CHP

67

69

59

69

39

43

92

Y(%)

3.10.180.010.990.10260HP1(450)

3.80.280.010.790.2540CPmPB

260.550.140.750.21820HP3(450)

170.280.050.700.16560CHP3

220.400.090.630.23820CHP2

320.510.160.670.26940HP2(450)

-0.05---2CHP1

Vmeso/Vtotal

(%)V total(ml/g)

Vmeso(ml/g)

wmicro(nm)

Vmicro(ml/g)

Stotal(m2/g)

DHαsMaterial

Electrical Double Layer Capacitances of C-PmPBs(three-electrode system in 1M H2SO4)

0 0.1 0.2 0.3 0.40

100

200

300

400

500

Current density (A/g)

Cap

acita

nce

(F/g

)

C-P1 (S=700 m2/g)

C-PM2( S=800 m2/g)

C-PmPB (S=470 m2/g)

activated C-PmPB (S=950 m2/g)

activated C-PmPB (S=1400 m2/g)

Activated C (S=1350 m2/g)

0 0.1 0.2 0.3 0.4

0.2

0.3

0.4

Current density (A/g)C

apac

itanc

e (F

/m2 )

(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

Purpose of our researchSynthesis of functional carbon-rich materials

from wooden biomass without production of CO2

Organic materials

Semiconducting materials

Conducting carbonized materials

Carbon materials

∆ ∆ ∆

300ºC 800ºC 1500ºC

Cellulose& Lignin

Low content of C Various functionalgroups in the material

Possible to restructurize

Structured C-rich MaterialsHigh-C content: uniform & homogeneous composition

Application: thermoelectric-conversion,Photovoltaic & sollar cells, electrodes for batteries, fuel cell, EDLC, Stable porousEnergy-source (H2 etc) storage material etc.

OH

OH

OH

OH

OCH3

OHH3CO OCH3

OH

(a) p-coumaryl alcohol(b) coniferyl alcohol(c) sinapyl alcohol

(a) (b) (c)

Advantage of lignin to convert into carbon materials:Lignin has the phenolic components: high C fixation

ability on anaerobic pyrolysis

＜aromatic structural unit＞ ＜a possible structure＞

Lignin

There has been reported several results on carbonization of lignin and preparation of activated carbon

0

20

40

60

80

100

TG [%

]

0 200 400 600 800Temperature[℃]

DTA

[a.u

.]

東京化成ナカライテスク

Alkaline Lignin

Elemental analysis

C: 51.72 %，H: 5.12 %, N: 0.13 % (Nacalai),

C: 51.83 %, H: 4.78 %, N: 0.11 % (Tokyo Kasei)

Reagent grade (available)

Ｍ≒350 g/mol (cryoscopic method)

Black powder，Water soluble

Tokyo Kasei

Nakalai

exo

CL1： r.t ~ 900 ºC 10 ºC/min

CL2： r.t ~ 900 ºC 4 ºC/min

CL3： r.t ~ 900 ºC 2 ºC/min

CL4： r.t ~ 900 ºC 1 ºC/minCL5： 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

Carbonization conditions(annealing time)

Furnace r.t ~ 900 ºC

Argon gas inlet

Sample① Carbonization of alkaline lignin

Alkaline lignin CL4 CLW10μm 10μm 10μm

CL4 ：deposition on the surface was a Na salt confirmed by XPSCLW ： After washing CL4 with water, the deposition was cleaned off

270.190.690.650.171031899―CLW

Vmeso/ Vtotal (%)

Vtotal (ml/g)

0.55664

SBET

(m2/g)

46

Yield(%) Vmeso (ml/g)

Wmicro

(nm)Vmicro

(ml/g)Stotal

(m2/g)

0.15

DH

655

αs

280.900.09CL4

sample

Carbonization results and N2 adsorption data

SEM

benzene

water

SDBS

carbonization

Particles in nano-micron scale

② Preparation of micellar ligninsand the carbonizationReverse micelle

Microporous C-particles

Aims: 1) Increase of effective surface area. 2) Generation of new pore space (external) between the particles

Benzene(ml)

SDBS(mg)

Water(ml)

45505ML3

SO3-Na+

Sodium Dodecylbenzenesulfonate(SDBS)

Typical conditions

Control of structure and morphology of carbonized materials

Particle samples could not be obtained in this case.In order to obtain particle lignins, (3) rigid lignin gels are synthesized

CML310μm(in solution) (freeze-dried)

carbonizationFreeze-dried

Preparation of micellar lignins （ML) and their carbonization

ML3

Fine-structured ML

Under basic aqueous conditions, alkaline lignin was reacted withformaldehyde to give a swelled polymer gel, which was carbonizedafter freeze drying.

∆

Swollen lignin gel Carbonparticles

Freeze-dried

Lignin+HCHO+NaOH

④ Preparation of lignin-gel particles and their carbonization

③ Preparation of alkaline lignin gel and the carbonization

L LL

HCHO L LL

Freeze-dried, carbonization

Swollen polymer gel

carbonized

Toward synthesis of carbonized lignin particles

LG

MLG

CMLG

CLG

0200400600800

10001200140016001800

CL4 CML3 CLG CMLG1

Sample

Surf

ace

area

[m2 /g

]

0

0.2

0.4

0.6

0.8

1

1.2

Pore volume [ml/g]

SBETSαsVtotal

CL4 CML3 CLG CMLG

390.451.161.140.19928134017CML3300.230.780.700.17102991542CLG260.301.140.780.281528142329CMLG

Vmeso/ Vtotal (%)

Vtotal

(ml/g)

0.50738

SBET

(m2/g)

45

Yield(%)

Vmeso

(ml/g)Wmicro

(nm)Vmicro

(ml/g)Stotal

(m2/g)

0.06

DH

920

αs

110.700.26CL4

sample

Carbonization and N2 adsorption results

(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

Porous materials

Inorganic materialsZeolite, porous silicaCorroded metals

Organic zeolite, COF,Microporous polymers

Carbon materialsActivated carbonsTemplate carbonsPyrolytic carbons

Chemically, physicallyStable, electricalconductive

Coordination polymersMetal organic frameworks

(MOFs)

Adsorbent, Catalyst, Catalyst support, Electrode(carbon)

MOF-177 (4500 m2 g-1, Langmuir)MIL-101 (5900 m2g-1, Langmuir),

COF-103 (4210 m2 g-1, BET)PAF-1 (5600 m2 g-1,BET)

Conjugated microporous polymers

Good carbonization yields and high SBET

82% 495 m2/g

84 113

70 459

59 840

56 1040

53 67

53 534

77 150

N. Kobayashi, M. Kijima, J. Mater. Chem.18 (2008) 1037

Organic Linkers TPEB

Image of MOF constructing from the organic linker(TPEB) and metal ion

XX

X

MM

M

X

X X

X

X X

XX

X

MM

M

XX

X

MM

M

X

X X

X

X X

XX

X

MM

M

XX

X

TPEB+

Metal ion

2D image

7b = K37 + Cu(OAc)2 in dioxane SBET= 37 m2/g C7b SBET= 584 m2/g

7c = K37 +Cu(OAc)2 in MeOH 105 carbonization C7c 1250

7d = K37 + CuCl2・2H2O in MeOH 104 C7d 736

N2 adsorption–desorption isotherms of the mesoporous coordination polymers and their

carbonised samples

K37=

COOK

COOKKOOC

Organic linkers having triphenylene(TP) and tetraphenylmethane(TPM) structures

X

X

X

X

X

X

X

X

X

X

TP TPM

TP(X=OH) ，TPM (X=COCH2Br) ，TPM (X=COCl)

440.81798400.124290Ph(COOK)3TPM(COCH2Br)

280.51782550.16386HOCH2C≡CCH2OHTPM(COCH2Br)

220.53600400.5818380Ph(NH2)2TPM(CH2COCl)

200.29480570.3622070BrCH2C≡CCH2BrTP(OH)

340.56585560.07285Ph(CH2Cl)2TP(OH)

Vmeso/Vtotal%

Vtotalml/g

SBETm2/g

Vtotalml/g

SBETm2/g

Yield%

Carbonized materialCYield

%

Network materialConnectorsOrganic Linker

Summary of the surface parameters of COF and carbonized COF

Summary and Conclusions

(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 CThe organic linkers showed high fixation of C on the pyrolysis. The network materials can be converted to microporous C

(1)Pyrolytic conversion of structured poly(m-phenylenebutadiynylene)s PmPBs to porous C

Structuration→ Increase external surface→high specific surface area + mesoporosity

AcknowledgementThe author is grateful to :

(Theme I)

Mr. Y. Ichikawa, Mr. M. Suzuki (University of Tsukuba)

(Theme II) Cooperative Research of RISH, Kyoto University

Prof. T. Hata, Research Institute for Sustainable Humanosphere(RISH)

Kyoto Univ.

Mr. T. Hirukawa, Mr. F. Hanawa (University of Tsukuba)

(Theme III)

Dr. N. Kobayashi, and Mr. T. Ishida (University of Tsukuba)