pyrolytic conversion of structured polymeric materials to ... · pyrolytic conversion of structured...
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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: [email protected]
Carbon Materials for Today and FutureTurkish-Japanese Joint Carbon Symposium
March 18 - 19, 2010 Istanbul Technical University
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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)
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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
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(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
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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
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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.
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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
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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
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(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
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(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.
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Synthesis of starting polymersR
O2 / Cu-TMEDA cat.
Hay method
O O
n
Soluble PmPB
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(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
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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
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SDBS
H2O
Cu cat., O2
Freeze-dry
(2)-1. Preparation of PM1 and C-PM1
PM1
carbonization
C-PM1
Micelle formationpolymerization
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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
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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
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(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 ℃
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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]
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OR CuCl-TMEDA cat
O2 in THF
OR
H
H
Hn
HP1: R= -(CH2)17CH3HP2: R= -(CH2)4OPhHP3: R= -CH2Cy
(3) Synthesis of HP
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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
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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
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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 )
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(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
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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.
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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
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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
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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
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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
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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
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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
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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
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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
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(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
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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)
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Conjugated microporous polymers
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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
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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
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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
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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)
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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
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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
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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)