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Sustainable Carbon Materials from Biomass
Hydrothermal Processes
Magda Titirici Queen Mary University of London
Materials Research Institute
Conferinţa „D i a spora în Ce rcetarea Ştiinţifică şi Învăţământul Superior din Ro mâ nia
- Diaspora şi prietenii săi” 2016
Workshop: Perspective în sinteza, investigarea şi ap l ica ţiile materialelor
Locaţie: Universitatea Politehnica Timisoara Biblioteca Centrala UPT, Bd.Vasile Parvan nr.2b, Sala K1
Marţi, 26 aprilie 2016
8.45-9.00 Inregistrarea participantilor la Workshop
Chairman: Prof. Vasile I. Parvulescu 9.00-9.30 Narcis Avarvari, Chiral molecular electroactive precursors and
conductors 9.30-10.00 Cristian Silvestru, Orgnometallic Compounds as Building Blocks
for Supramolecular Arhitectures
10.00-10.30 Floriana Tuna, Molecular Nanomaterials for quantum
information technologies 10.30-11.00 Niculina Hadade, A short journey through the geometrical and
thermodynamical space of Supramolecular and Dynamic
Adaptive Chemistry
11.00 –11.30 PAUZA DE CAFEA 11.30-12.00 Lucian Pintilie, Polar Materials from Physical Phenomena to
Applications
12.00-12.30 Valeria Harabagiu, Complex supramolecular architectures
12.30-13.00 Ionut Enculescu, Functional nanostructures
13.00-15.00 PAUZA DE PRANZ (Complexul Studentesc - Restaurant Universitar,
Aleea FC Ripesnia Nr.3)
Chairman: Dr. Lucian Pintilie
15.00-15.30 Isabela Man, Density functional theory with application in
catalysis for renewable energy production
15.30-16.00 Mihai A. Gîrțu, Molecular modeling of materials used in hybrid
organic-inorganic photovoltaics
16.00-16.30 C. Balogh, F. Riobé, L. Veyre, C. Thieuleux, O. Maury, New luminescent
materials based on lanthanide complexes
16.30-17.00 PAUZA DE CAFEA
17.00-17.30 Loredana Protesescu, Nanocristale de perovskit CsPbX3:
structura, proprietati si aplicatii
28 April 2016, Timisoara
My Scientific Journey
1995-1999 Bucharest, Romania: Organic Chemistry
2001-2005 Mainz & Dortmund, Germany: Imprinted Polymers
2005-2006 Berlin Germany: Discover Hydrothermal Carbonization
2006-2013 Berlin Germany: Consolidate Hydrothermal Carbonization
BSc
Research Stage
PhD
PostDoc
Group Leader
Assistant Professor
Full Professor
1999-2001: INFIM Magurele & Rostock, Germany: Sol-Gel Ferroelectrics
2013-2014 London: Reader in Materials Science
2014-now London, Full Professor in Sustainable Materials Chemistry
Queen Mary University of London
20,000 students and over 4,000 staff
Three faculties:
Humanities and Social Sciences
Medicine and Dentistry
Science and Engineering
25% international students – 151 nationalities
£300 million of infrastructure
investment in past 5 years
Ranked 6 in the UK for general engineering
(REF2014)
QMUL Location
World Energy Consumption: 500 EJ/year
• Making materials & chemicals consumes about 35% of the global energy
• Materials & chemicals today are derived from fossil fuels
• Energy today is from fossil fuels
• To build renewable energy we need materials & chemicals
Materials & Chemicals
Energy
Conflict: Energy vs Materials
Critical Materials
http://ec.europa.eu/growth/sectors/raw-materials/specific-interest/critical/index_en.htm
Economic Importance
Su
pp
ly R
isk
Critical Materials: Geographical Distribution
http://ec.europa.eu/growth/sectors/raw-materials/specific-interest/critical/index_en.htm
Renewable Energy and Critical Materials
http://energy.gov/sites/prod/files/DOE_CMS2011_FINAL_Full.pdf
Materials and Chemicals from Biomass
Liquid: Chemicals
Solid: Carbon
Basic chemicals Liquid fuels Green Solvents Polymers
Functional materials Catalysts Electrode materials Adsorbents Solid fuels
HMF
LA
FA
HTC
Titirici et al, Chem. Soc. Rev., 2015, 44, 250-29 Titirici et al, Sustainable Carbon Materials via Hydrothermal processes, Wiley, 2013 Titirici et al, Energy and Environmental Science, 2012, 5, 6796
200-300 C
self-generated
pressure
• RENEWABLE • CHEAP • LOW ENERGY IMPUT • NO CO2 EMISSIONS
6
The Carbon Biorefinery Concept
Abundant Resources
Materials Design
Characterisation
Modelling
Processing
Reactivity
Structure-Function
Nanoscale
Assessment
Energy Storage
PEM Electrocatalysis
Carbon Capture
Carbon Quantum Dots
Biomass to Chemicals
Metals Recovery
Abundant Resources
Energy Storage
PEM Electrocatalysis
Carbon Capture
Carbon Quantum Dots
Biomass to Chemicals
Platinum Recovery
Hydrothermal Carbonisation
Outline
2h 4h
8h 12h
2h 4h
8h 12h
Carbohydrates: Glucose
10%wt Glucose, HTC @180°C
2h
20h
2h
20h
GC-MS of the residual liquid
glucose -3H2O
HMF
glucose solutionpolymerisation/
nucleation
HTC formation/
growth
glucose solutionpolymerisation/
nucleation
HTC formation/
growth
Time
2µm
4h-solid fraction
2µm 12h
12h-solid fraction
Carbohydrates: Glucose
Glucose Solution 10%wt, 180°C
Carbohydrates: Glucose
Concentration
Glucose 5% wt
Glucose 3% wt
Problem: Low Carbon Yield
180°C, 12h
13C-Solid State NMR
CHx C=C-C C=C-O
COOH C=O
• INEPT • 1H-13C CP experiments • 1H-13C IRCP experiments • 13C homonuclear DQ-SQ
HTC Structure
J. Phys. Chem. C, 2010, 2009, 113, 9644
cross-linked
furanic species
connections with
functional groups
HTC Structure
HTC Structure
Chemical Analysis 69% C - 4.5% H - 26.5% O
Glucose, 180°C
-3H2O + 2H2O
Glucose dehydration
HMF levulinic acid formic acid
HTC Chemistry
HMF polymerization-aromatisation
Diels–Alder
HMF
HRTEM
HTC 180°C
HTC 550°C
0 20 40 60 80 100
(110)
HTC-G-950
HTC-G-750
HTC-G-550
HTC-G-350
Inte
nsi
ty
2
HTC-G
(002)
(100)
a)
0 20 40 60 80 100
HTC-Su-950
HTC-Su-750
HTC-Su-550
HTC-Su-350
Inte
nsi
ty
2
HTC-Su
(110)
(002)
(100)
b)
0 20 40 60 80 100
HTC-St-750
HTC-St-950
HTC-St-550
HTC-St-350
Inte
nsi
ty
2
HTC-St
(110)
(002)
(100)
c)
0 20 40 60 80 100
HTC-X-950
HTC-X-750
HTC-X-550
HTC-X-350
Inte
nsi
ty
2
HTC-X
(110)
(002)
(100)
d)
XRD
13 C- Solid State NMR
Langmuir, 2011, 27, 14460
Heat Treatment
HTC 950°C
Graphitization
+ FeCl2
Fe2+
Fe2+
Fe2+
Fe3C@Graphitic Carbon
HCl
Fe2+
Fe2+
Fe2+
Fe2+
Fe2+
Fe2+
Graphitic Carbon
1000°C
XRD
Raman
RAMAN
D
G D+G
Exfoliation to Graphene
2D
G
200 nm 500 nm
either transform into the final spherical carbon particles or
they can be used for nanocoating of other structures.21,19
Transmission electron micrographs of the resulting materi-
als reveal the perfect replication of the hexagonal order of the
silica pores into the resulting carbonaceous material (Fig. 1). I t
can be clearly observed that the Comp-OHC-25 material has a
much higher remaining porosity than the completely filled
composite, although some pores can still be detected in Comp-
OHC-100. This is in good agreement with nitrogen sorption
experiments which also show some remaining pores (see
Fig. 3a, later). Nevertheless, in both cases, the filling is
sufficiently uniform to provide a stable carbon replica.
The hexagonal order in the silica, composites and resulting
carbon materials was also determined by SAXS. The SAXS
curves are shown in Fig. 2. The typical three Bragg reflections
(100), (110) and (200) for a 2D hexagonal arrangement are
present in the SAXS patterns of the templated carbons as well
as in their corresponding composites. Independent of the
method, complete (OHC-100) or just partial pore filling
(OHC-25), the higher order reflections can still be observed
in the composites proving a good replication of the silica
template. Both resulting ordered carbon materials exhibit
patterns similar to that of the SBA-15 template; their unit cell
parameters ao are presented in Table 1.
Fig. 1 TEM micrographs of A, D: SBA-15 silica template, B: composite obtained by total pore filling with furfural (Comp-OHC-100), C: carbon
replica obtained by silica removal from B (OHC-100), E: composite obtained by filling 25% of the SBA-15 pores (Comp-OHC-25), F: carbon
replica obtained by dissolut ion of silica from E (OHC-25).
Table 1 Physical properties of the obtained materials
M aterial %C %N a/nma SBETb/m2 g2 1 Vmic
c/mL g2 1 Vtotd/mL g2 1 Pd/nme
SBA-15 — — 11 793 0.04 1.02 7.0Comp-OHC-25 22.42 — 9.7 404 0.03 0.73 5.9Comp-OHC-100 42.35 — 9.8 130 0.01 0.15 3.5OHC-25 68.06 — 9.8 577 0.07 1.55 6.8OHC-100 69.05 — 9.9 350 0.02 1.03 4.5OHC-25-NH2 65.14 4.6 9.7 405 0.03 1.40 6.8OHC-100-NH2 67.17 4.4 9.8 275 0.04 0.98 4.5a Lattice parameters calculated from d100 spacing in SAXS patterns. b Surface areas calculated with BET method. c M icroporous volumecalculated by DFT model. d Total pore volume calculated at p/po = 0.99. e Pore sizes obtained from nitrogen adsorption isotherms at maximaof PSDs.
Fig. 2 SAXS patterns of the silica template, corresponding compo-
sites and ordered hydrothermal carbon materials.
3414 | J. Mater. Chem., 2007, 17, 3412–3418 This journal is ß The Royal Society of Chemistry 2007
A B
C D
E F
A- Mesoporous Carbon Spheres: Adv. Funct.
Mater, 2007, 17, 1010
B- Ordered Mesoporous Carbon: J. Mater.
Chem, 2007, 17, 3412
C- Hierarchically Porous Carbon Monoliths-
Carbon, 2013, 61, 245
D- Carbon Nanotubes: Chem. Mater, 2010, 2,
6590
E- Inverse Opal-like Carbons, Chem Mater,
2013,
F -Carbon Hollow Spheres: JACS, 2010, 132,
17360
Hard Templating
Pluroinic Block-Copolymers (F127)
Chem. Mater, 2011, 23, 4882
Soft Templating
Hard & Soft Templating
Chemistry of Materials, 2013 vol. 25, (23) 4781
Hard & Soft Templating
Macropores
Mesopores Micropores
SAXS
Hg-intrusion
N2 Adsorption CO2 Adsorption
Carbon-Inorganic Hybrids
200nm
2µm
A B
C D
E F
A: Pt/C-catalysts for selective
hydrogenation of phenol to cyclohexanone
(Chem. Commun. 2008, 999–1001)
B: Yolk-like Au@C particles-catalysts for
CO oxidation
C: LiFePO4/C-cathode in Li Ion batteries
(Small, 2011, 1,1127)
D: Si/C-anode ín Li ion batteires (Angew.
Chem. Int. Ed, 2008, 47, 1645 –1649)
E: TiO2/C- visible light photocatalyst (Adv.
Mater, 2010, 22, 3317–3321)
F: SnO2/C- anode in Li Ion Batteries-
(Chem. Mater, 2008, 20, 1227–1229)
Abundant Resources
Energy Storage
PEM Electrocatalysis
Carbon Capture
Carbon Quantum Dots
Biomass to Chemicals
Platinum Recovery
Hydrothermal Carbonisation
Outline
Na Ion Batteries
US$/t
Increase in the price of Li2CO3
Li around the globe
Glucose HTC
180°C Δ
Δ = 1000°C; 1300°C and 1600°C
Glucose HTC 1600°C
Glucose HTC 1600°C
200 nm
Figure S2. TEM image of S-1100 material.
Figure S3. TEM image of S-1400 material
5 nm
2 nm
Treatment@ High Temperature
1300°C
Figure S4. TEM image of S-1600 material.
2 nm
1600°C
D = ~0.5 nm
CO2 adsorption: HTC from pure carbohydrates is non-porous
HTC Porosity
0.000 0.005 0.010 0.015 0.020 0.025 0.030
0
10
20
30
40
50
60
70
80
VC
O2
ad
s / c
m3 g
-1 S
TP
Relertive pressure, P/P0
G180
G350
G550
G750
G950
1600°C 0.216 cm3/g
1000°C-0.190 cm3/g
550°C- 0.146 cm3/g
300°C-0.068 cm3/g 180°C- 0.066 cm3/g
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
dV
(D)
/ cm
3 n
m-1 g
-1
Pore width / nm
G180
G350
G550
G750
G950
XRD
002
100
1000°C
1300°C 1600°C
∼0.375 nm
∼0.371 nm
∼0.370 nm
Raman
D-band G-band
1000°C 1300°C
1600°C
1.44
1.84
2.09
ID/IG
• Coin cells
• Active material and PVDF binder in N-methyl-2- pyrrolidone (NMP) at a
weight ratio of 9.5 : 0.5
• Loading mass of hard carbon electrode between 1.5–2.5 mg/cm2.
• 1 M NaClO4 in ethylene (EC) and diethyl carbonate (DEC) (1 : 1)
• Sodium foil counter electrode
• Glass fiber separator
Na Ion Batteries
Electrochemical testing conditions:
1st, 2nd and 10th discharge–charge profiles at 0.1 C (30 mA/g).
1000°C 1300°C
1600°C
Anodes in Na Ion Batteries
Anodes in Na Ion Batteries
1000°C 1300°C
1600°C
Cycling performance at 0.1 C (30 mA/g) for 100 cycles
Figure S2. Discharge and charge curves for the 1st cycle of HCS1000 without soft carbon coating.
Figure S3. Rate performance of HCS electrodes.
Anodes in Na Ion Batteries
Rate Performance
Anodes in Na Ion Batteries
1600°C
Asymmetric current rate test: discharging (Na insertion) at a constant current rate
of 0.1 C and charging (Na extraction) at different rates.
20 C (3 min charge), a reversible charge capacity of 270 mA h/g was achieved
Na extraction is quite fast while Na insertion into hard carbon is the limiting step
Perspectives
Materials Design-Advanced Characterization-Electrochemical Performance
N
N N
N N N
N
N
N
N
v
20 nm
200nm
Sn/Sb
200nm
Sodiation-Desodiation in Hard Carbons
Alloys/Carbon Synergies
Abundant Resources
Energy Storage
PEM Electrocatalysis
Carbon Capture
Carbon Quantum Dots
Biomass to Chemicals
Platinum Recovery
Hydrothermal Carbonisation
Outline
PEM FUEL CELL
H2 → 2H+ + 2e- ½O2 + 2H+ + 2e- → H2O
Cathode
O2 + 4H+ + 4e- 2H2O
O2 + 4H+ + 2e- H2O2
H2O2 + 2H+ + 2e- 2H2O
Oxygen Reduction Reaction
O2 + 4H+ + 4e- 2H2O
Pt particles supported on Carbon
slow ORR kinetic
low durability/stability
low availability and high cost
Oxygen Reduction Reaction
Platinum Availability
Platinum Availability
Pt
DEPLETION
Platinum Availability
H2O
180 oC
Ovalbumin (Alb)
+
t = 5.5 h
D-Glucose
2o Biomass (i.e. Glycoprotein)
Maillard chemistry
Surface stabilising agent(s)
ScCO2
SBET > 250 m2g-1
3D Pore System
Vpore > 0.4 cm3g-1
Green.Chem, 2011, 13, 2428
51
N-doped Carbogels
Calcination@1000°C, Conductivity ≈ 80 S/m
50 nm 5 nm
N-doped Carbogels
N-doped Carbogels
XRD
RAMAN
N-doped Carbogels
Tp, oC
SBET,
m2g-1
Vtotal,
cm3g-1
Vmeso,
cm3g-1
PD,
nm
%C
(EA/XPS)
%N
(EA/XPS)
180 276 0.49 0.41 3.2 57.6 / 72.3 7.5 / 6.8
350 247 0.42 0.40 3.1 65.0 / 78.4 8.0 / 7.3
550 476 0.57 0.40 3.4 79.6 / 90.4 7.3 / 5.4
750 300 0.73 0.62 3.3 83.8 / 92.4 6.0 / 5.3
900 308 0.68 0.65 3.2 84.8 / 93.2 6/ 6.11
• Large Vmeso !!!
• Broad PSD – nature of continuous network
• Variation – system condensation??
• Scope for increasing N content.
N-doped Carbogels
1000 800 600 400 200 0
396 398 400 402 404
N-ON-Q
Inte
nsity (
a.u
.)
Binding Energy (eV)
N-6
C1s: 89.16 %
O1s: 4.73 %
N1s: 6.11 %
O1s N1s
C1s
Inte
nsity (
a.u
.)
Binding Energy (eV)
• 398.6 eV-pyridinic-N (N-6, 40.4%)
• 400.9 eV-quaternary-N (N-Q; 53.7%)
• 402.7 eV-pyridine-N-oxides (N-O; 5.9
%)
XPS
N-doped Carbogels
-0.8 -0.6 -0.4 -0.2 0.0 0.2-5
-4
-3
-2
-1
0
Curr
ent
(mA
cm
-2)
Potential (V vs. Ag/AgCl)
N-CC
Pt/C
-0.2 0.0 0.2 0.4 0.6 0.8-4
-3
-2
-1
0
Curr
ent
(mA
cm
-2)
Potential (V vs. Ag/AgCl)
N-CC
Pt/C
RDE, LSV 1600 rmp
0.1 M KOH 0.5 M H2SO4
ORR Performance
0.2 V to -1 V 1 V to -0.2 V
scan rate of 10 mV s-1
-0.2 0.0 0.2 0.42
3
4
Potential (V vs. Ag/AgCl)
(n) Pt/C
(n) N-CC
(%) H2O
2 Pt/C
(%) H2O
2 N-CC
num
ber
of
ele
ctr
ons t
ransfe
rred (
n)
0
5
10
15
20
Hydro
gen p
ero
xid
e y
ield
(%
)
-1.0 -0.8 -0.6 -0.4 -0.22
3
4
Potential (V vs. Ag/AgCl)
(n) Pt/C
(n) N-CC
(%) H2O
2 Pt/C
(%) H2O
2 N-CC
num
ber
of
ele
ctr
ons t
ransfe
rred (
n)
0
10
20
30
40
Hydro
gen p
ero
xid
e y
ield
(%
)
Number of electrons transferred and peroxide yield
ORR Performance
RRDE 0.1 M KOH 0.5 M H2SO4
0 200 400 600 800 10000
20
40
60
80
100
Rela
tive c
urr
ent
(%)
time (s)
N-CC
Pt/C
a) b)
c) d)
-0.9 -0.6 -0.3 0.0
-5
-4
-3
-2
-1
0
Curr
ent
(mA
cm
-2)
Potential (V vs. Ag/AgCl)
Pt/C
Pt/C (after 3500 cycles)
N-CC
N-CC (after 3500 cycles)
0.0 0.3 0.6 0.9-4
-3
-2
-1
0
Curr
ent
(mA
cm
-2)
Potential (V vs. Ag/AgCl)
Pt/C
Pt/C (after 3500 cycles)
N-CC
N-CC (after 3500 cycles)
0.0 0.3 0.6 0.9
-3
-2
-1
0
Curr
ent
(mA
cm
-2)
Potential (V vs. Ag/AgCl)
0.5 H2SO
4
0.5 H2SO
4+2 M CH
3OH
LSV 1600 rmp
Chronoamperometric
response
Polarization Curves
0.1 M KOH 0.5 M H2SO4
Perspectives
Understand the individual role of:
• Amount of N-doping
• Type of N sites (i.e. pyridinic, quaternary)
• Surface Area
• Pore Size
• Structural Order
• Electrical Conductivity
From Waste to Wealth via Advanced Materials
Acknowledgements
MATERIALS RESEARCH INSITUTE
China
Prof. Qiang Zhang-Tsinghua, Beijing
Prof. Yong Sheng Hu-CAS, Beijing
Prof. Dangsheng Su-Dalian
Prof. Shu Hong Yu
Cheng Tang
Dr Yuesheng Wang
UCL
Prof Dan Brett
Prof Xiao Guo
Money:
Collaborators: Spain
Dr. Marta Sevilla
Guilermo Alvarez
Germany
Dr Robin White
Production of materials or the properties or applications of
materials related to energy storage and conversion,
sustainability or living.
IF= 7.5