“Improved Carbon- Based
Sorbent for CO2
Capture”Maha Yusuf1, Habib Nasir1, Wei-Yi-Chen2, Arshad Hussein1, Mohammad
Mujahid1
» Need to improve CO2 capture process; one possible route is to develop new carbon-based
sorbents
» Need to find new routes for disposing captured CO2 ; CO2 fixation on carbonaceous
compounds is the first step of many CO2 utilization processes
» Nano-Carbons have a large surface area for CO2 capture and functionalization – Procedures
for manipulating and functionalizing Nano-Carbons (such as graphene, CNT, GO and GOF) have
been well-established
» CO2 capture on these carbon materials have not been systematically investigated!
Introduction Improved Carbon-Based Sorbent for CO2 Capture
Nano-Graphite Nano-Graphene Nano-Graphene Oxide Nano-Graphene oxide Framework Functionalized Nano-Graphene Oxide, its frameworks CO2 Capture Capacity
Key Concepts
Synthesis of Nano-Graphene Oxide
• Single - Layer Nano-Graphene Oxide (NGO) sheets are prepared from graphite flakes, 450 m by a ‘new method’ which is further modification of the ‘Modified Hummer’s method’, using sonication during the oxidation process and KMnO4 as the only oxidant which was followed by freeze-drying of the product.
4
graphite has an interlayer spacing of 0.335 nm
oxidationby modifiedHummers'method
H2SO4
NaNO3
KMnO4
exfoliation
ultra sonication
graphite oxide has an interlayer spacing about 0.7 nm. It contains three major oxygen functional groups: epoxides, phenolic and carboxylic acids
single-layer graphene oxide (GO) platelets. Nano-sized GO contains a rich population of oxygen functional groups that have emerged as the building blocks for many technologies
Figure 2: Burress et al. (2010) showed that a) boronic ester and b) GOF formation. Idealized graphene oxide framework (GOF) materials proposed in this study are formed of layers of graphene oxide connected by benzenediboronic acid pillars. The resultant GOF can be oxidized and then grafted with an amine (just like GO mentioned in Figure 2) that serves as a potentially potent CO2-chemisorption adsorbent.
Synthesis of Nano-Graphene Oxide Frame-work Preparation of Nano-Graphene Oxide Framework (NGOF) from ‘Methanol Solvothermal synthesis’ using freeze-dried
GO prepared from Asbury Micro 450 as the base material The linker used was: B14DBA (Benzene 1,4-Diboronic Acid)
i. BET with N2 gas• BET Surface Area• Pore Volume
ii. SEMiii. EDAX - SEMiv. XRD v. BET with CO2 gas
RESULTS
BET with N2 Results
Asbury Micro 450 Asbury 4827 Freeze-Dried GO
BET Surface Area m2/g 11.6650 232.0207 102.2141
Adsorption Average Pore Size Width/ Ao 18.9948 18.7232 18.7233
Quantity Adsorbed (cm3/g STP) at relative
pressure of 0.2503.5812 70.2121 30.9314
XRD Spectra of Nano - Graphite
XRD Spectra of Freeze-dried GO
XRD Spectra of Nano-Graphene Oxide Framework
SEM Images
Micro 450 Micro 850
SEM Images
Freeze-Dried GO
Thermally Exfoilated Graphene
SEM Images
Graphene-Oxide Framework
BET with CO2 gas
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.50
5
10
15
20
25
f(x) = 36.5952065911459 x + 4.58372015079742R² = 0.984626749993261
Freeze-Dried GO
Relative Pressure (p/po)
Qua
ntity
Ads
orbe
d (c
m3/
g ST
P)
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.50
0.010.020.030.040.050.060.070.080.09
0.1
f(x) = 0.0343528608783989 x + 0.0658755539223476R² = 0.109990603430659
Asbury Micro 450
Relative Pressure (p/po)
Qua
ntity
Ads
orbe
d (c
m3/
g ST
P)
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.50
2
4
6
8
10
12
f(x) = 8.42112450151645 x + 7.11433165215779R² = 0.425744906286923
Nano-graphene Oxide Framework
Relative pressure (p/po)
Qua
ntity
Ads
orbe
d (c
m3/
g ST
P)
CO2 Adsorption Capacity Data• Calculations: Density of CO2 at 1 atm and 0 C = 1.977 kg/m3Note: these are calculated at p/po = 0.45
Samples Mg CO2 Adsorbed per gram of sample
Nano-Graphite 1.977 kg/m3 * 0.090 cm3/g sample = 0.17793 mg CO2 adsorbed/g sample
Nano-Graphene Oxide 1.977 kg/m3 * 21 cm3/g sample = 41.517 mg CO2 adsorbed/g sample
Nano-Graphene Oxide Framework
1.977 kg/m3 * 9.74 cm3/g sample = 19.255 mg CO2 adsorbed/g sample
Conclusions
Higher O/C ratio for Nano-Graphene Oxide (NGO) with new method of combining oxidation with sonication at the same time
BET Surface area of Asbury 4827 (nano-graphite) highest – possibility of making advanced CO2 sorbent using this as the base material
CO2 Adsorption capacity of single-layer nano-graphene oxide sheets is the highest even higher than the highest reported by the Chinese Group of the functionalized graphitic oxide with 50 wt% EDA = 46.55 mg CO2/g sample!
Goal of CO2 capture CCS technology Improved Gasification Efficiency Waste (including CO2) Utilization Soil fertility New Avenue of CO2 Utilization Possible CO2 Adsorbent in Industry replacing liquid amine CO2 capture membranes
Applications of the Project
Burress, J.W., Gadipelli, S., Ford, J., Simmons, J.M., Zhou, W., Yildirim., T. Graphene oxide framework materials: theoretical predictions and experimental results. Angew. Chem. Int. Ed. 2010, 49, 8902-8904.
Chateauneuf, J.E., Zhang, J., Foote, J., Brink, J., Perkovic, M.W., Photochemical Fixation of Supercritical Carbon Dioxide: the Production of a Carboxylic Acid from a Polyaromatic Hydrocarbon, Advances in Environmental Research, 2002, 6, 487-493.
Stankovich, S., Dikin, D.A., Dommett, G.H.B., Kohlhaas, K.M., Zimney, E.J., Stach, E.A., Piner, R.D., Nguyen, S.T., Ruoff, R.S., Graphene-based composite materials. Nature. 2006, 442, 282-286.
LITERATURE SURVEY/ REFERENCES
Thank You!!!!
Maha Yusuf
CEMP 2013 (NUST)