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Graphene/Metal Organic Framework Composites As Adsorbents For Adsorption Chiller Applications
Graphene/Metal Organic Framework Composites As Adsorbents For Adsorption Chiller Applications
Najam ul Qadir
th
Contents
Part I. Introduction
• Research Motivation
• Adsorption Refrigeration
• Cooling Production in Adsorption
Refrigeration
• Performance Evaluation of Adsorption
Chiller
3
Household Electricity Breakdown in China
4
http://www.cetdem.org.my/upload_dir/CACCET/CACCET-pic-5.jpg
Worldwide Electricity Generation
5
Source: Energy Information Administration (EIA), 2014
Global CO2 emission sources
6
Source: 'Sustainable Aviation CO Roadmap', December 2008
Solar Adsorption Refrigeration
7
Int. J. Heat Mass Trans. 63 (2013) 171
Lab-scale Two-bed Adsorption Chiller
8
Adsorption Cooling Cycle
Adsorption +
Evaporation
9
Ideal Adsorption Cooling Cycle
Cooling Production 10
Eur. J. Inorg. Chem., 2012, 2625
Coefficient of Performance
Qads Qcond
COP
Qdes
11
New J. Chem., 2014, 38, 1846
Part II. Literature Survey
Silica-gel/Water Zeolite/Water
• Min. desorptionUnresolved
temp. < 50oCissues • Min. desorption temp. > 200oC
• Low adsorption capacity (0.2 gg-1) • Low adsorption capacity (0.15 gg-1)
• evaporating
• Inability to produce • Inability to produce evaporating
High Desorption temperature
temperatures below • C Thermal Conductivity
0 o
Low temperatures below 0oC
•
• Thermal conductivity (0.1 – 0.5 temperatures
Evaporating • Template-assisted
< 0oC synthesis
Wm-1K-1) • Lower Porosity (Low
• Thermal
COP) conductivity (0.2 – 0.4
• Commercial Scalability
Wm-1K-1)
References
1. International Journal of Sustainable Energy,
14 1-17
2. Scientific Reports 6, Article number: 22734 (2016)
Vapor Compression v.s.
Adsorption Refrigeration
15
Metal Organic Frameworks
+ =
17
Chap.11 in Nanotechnology and Nanomaterials, Semiconductor Photocatalysis – Materials, Mechanisms and Applications, DOI: 10.5772/63489
Zn4O(CO2)6
MOF-5
+
Zeolite (ZSM-5)
Ditopic Linker
IRMOF-16 18
Chap.11 in Nanotechnology and Nanomaterials, Semiconductor Photocatalysis – Materials, Mechanisms and Applications, DOI: 10.5772/63489
Other MOF structures
Chap.11 in Nanotechnology and Nanomaterials, Semiconductor Photocatalysis – Materials, Mechanisms and Applications, DOI: 10.5772/63489
MOFs v.s. Conventional Adsorbents
20
Science, 2013, 341, 974
Performance of Water-Stable MOFs
21
New J. Chem., 2014, 38, 1846
BUT…
400
Thermal Conductivity (Wm-1K-1)
23
Dalton Trans., 2016,45, 15621-15633
Materials Selection
Host Materials
MWCNT/MIL-100(Fe) MWCNT/MIL-101(Cr)
MWCNTs
Composite Composite
GNP/MIL-100(Fe) GNP/MIL-101(Cr)
GNPs
Composite Composite
24
Research Objective
Find the most optimum combination of MWCNTs or GNPs with MIL-
100(Fe) or MIL-101(Cr) as an adsorbent material for chiller applications
which
• Numerical Modeling
• Performance prediction of a 2-bed solar adsorption
chiller using MWCNT/MIL-100(Fe) composite as
adsorbent 26
Part III. Synthesis and Characterization
Dilution Dilution
pH ~ 5 pH ~ 5.5
Centrifugation
Till decanted solvent
becomes colorless
Washing with water, ethanol and NH4F solution
Centrifugation
Till decanted solvent
becomes colorless
Washing with water, ethanol and NH4F solution
Dissociation of
precursor salt
Formation of
C–O–Fe bonds
Crystallization of
MOF on MWCNT
31
GNP acid-treatment
Dissociation of
precursor salt
Formation of
C–O–Fe bonds
32
Characterization Methods
33
Part IV. Results and Discussion
• Numerical Simulation 34
Part IV – I: Acid-treated MWCNTs and GNPs
• FT-IR
• PXRD
• SEM
35
SEM of MWCNTs
As-Received Acid-treated
36
PXRD of MWCNTs
Acid-treated
As-received
37
FT-IR of MWCNTs
As-received
Acid-treated
38
SEM of GNPs
As-Received Acid-treated
39
PXRD of GNPs
Acid-treated
As-received
40
FT-IR of GNPs
As-received
Acid-treated
41
Part IV – II: MWCNT/MIL-100(Fe) composite
13 wt%
5.9 wt%
2.2 wt%
MIL-100(Fe)
Simulated
43
BET Analysis
44
SEM micrographs
45
TEM micrographs
46
FT-IR
13 wt%
7.1 wt%
2.2 wt%
MIL-100(Fe)
47
XPS
MIL- 10.7 wt%
100(Fe) MWCNTs/MIL-100(Fe)
Surface Surface
O=C–O C atoms O=C–O C atoms
48
MIL-100(Fe) 2.2 wt%
MWCNTs
49
MIL-100(Fe) 2.2 wt% MWCNTs
50
Part IV – III: MWCNT/MIL-101(Cr) composite
51
PXRD
5.1 wt%
3.5 wt%
1.7 wt%
MIL-101(Cr)
Simulated
52
BET Analysis
Literature
53
SEM micrographs
54
TEM micrographs
5.1 wt%
55
FT-IR
6.9 wt%
5.1 wt%
3.5 wt%
1.7 wt%
MIL-101(Cr)
56
MIL-101(Cr) 5.1 wt%
57
Hydrothermal Cyclic Stability
MIL-101(Cr) 3.5 wt%
58
Part IV – IV: GNP/MIL-100(Fe) composite
59
PXRD
16.2 wt%
14.7 wt%
Intensity (a.u.)
12.9 wt%
6.5 wt%
MIL-100(Fe)
Simulated
5 10 15 20 25 30 35 40 45 50
2q (o) 60
BET Analysis
61
SEM micrographs
62
TEM micrographs
63
FT-IR
16.2 wt%
14.7 wt%
12.9 wt%
MIL-100(Fe)
64
MIL-100(Fe) 6.5 wt%
65
Hydrothermal Cyclic Stability
MIL-100(Fe) 6.5 wt%
66
Part IV – V: GNP/MIL-101(Cr) composite
67
PXRD
11.6 wt%
7 wt%
5 wt%
2.7 wt%
MIL-101(Cr)
Simulated
68
BET Analysis
69
SEM micrographs
70
TEM micrographs
2.7 wt%
71
FT-IR
11.6 wt%
7 wt%
5 wt%
2.7 wt%
MIL-101(Cr)
72
MIL-101(Cr) 2.7 wt%
73
Hydrothermal Cyclic Stability
MIL-101(Cr) 2.7 wt%
74
Outcome of Experimental Work
5.9 wt%
MWCNT/MIL-100(Fe) 6.9 wt%
MWCNT/MIL-101(Cr)
75
Part IV – VI: Numerical Modeling and Simulation
• Refrigerant: Water
76
Adsorption Equilibrium
Dubinin-Ashtakov model
Ps,w Tr
n
Δx* x0 exp D Tads ln
Ps,ads Tads
Δx* : Equilibrium uptake (gg-1)
Ps,ads (Tads): Vapor pressure at which adsorbent is saturated with water vapor at
77
78
79
Numerical Validation
Reference This work
80
Adsorption and Desorption times
81
Preheating switching times
82
Precooling switching time
83
Cycle time
84
Part V: Conclusions
• Cost Analysis
• Summary
85
Cost Analysis