Institute of Refrigeration and Cryogenics

Department of Mechanical Engineering

Graphene/Metal Organic Framework

Composites as Adsorbents for
Adsorption Chiller Applications

Najam ul Qadir

th
 Contents
Part I. Introduction

Part II. Literature Survey

Part III.Research Methodology

Part IV.Experimental Results and Discussion

Part V. Modeling and Simulation

Part VI. Conclusions 2

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

We are in need of finding alternate

methods for operating electrically
driven household and commercial
processes especially
Refrigeration and Air-conditioning

6
Source: 'Sustainable Aviation CO  Roadmap', December 2008
Solar Adsorption Refrigeration

Nominal Working Conditions

• Max. Desorption Temp: 104 oC

• Min. Adsorption Temp: 28 oC
• Condenser Pressure: 5.6 kPa
• Condensation Temp: 35 oC
• Evaporator Pressure: 1.2 kPa
• Evaporation Temp: 10o C

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

• Conventional Adsorbent Materials

• Drawbacks of Conventional Working
Pairs
• Metal Organic Frameworks (MOFs)
• Advantages of MOFs over conventional
adsorbents for use in adsorption chillers
• Selection of MOFs for current research
• Deficiencies of selected MOFs for use
as adsorbents in adsorption chillers
• Enhancement of properties of selected MOFs
for optimum performance in chiller
applications
12
Conventional Adsorbents for Water-Based
Chillers

Silica gel Zeolite A

Ref:
• http://www.explainthatstuff.com/zeolites.html
13
• http://www.sciencephoto.com/media/684642/view
 Conventional Working Pairs

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

Vapor Compression Refrigeration Systems

Need Better Adsorbent Materials !!!

Conventional Adsorption Chillers

15
 Metal Organic Frameworks

+ =

Inorganic unit Organic unit MOF

(Metal ion) (Linker) Pore
16
https://henkeresearch.wordpress.com/mofs/
 Secondary Building Units
Metal-containing SBUs Organic SBUs

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

MIL-100 (2100 m2g-1) MOF-177 (4500 m2g-1)

PCN-66 (4000 m2g-1)

MIL-101 (4200 m2g-1) MOF-505 (3100 m2g-1) NU-110 (7100 m2g-1)

19

Chap.11 in Nanotechnology and Nanomaterials, Semiconductor Photocatalysis – Materials, Mechanisms and Applications, DOI: 10.5772/63489
MOFs v.s. Conventional Adsorbents

MOFs outclass conventional adsorbents in

water uptake
~130 %
BUT

Very Few are Stable in Water !!!

20
Science, 2013, 341, 974
Performance of Water-Stable MOFs

MIL-100(Fe) and MIL-101(Cr)

show the Highest Water Uptake
and Cyclic Stability amongst all
the Reported Water-Stable MOFs

21
New J. Chem., 2014, 38, 1846
 BUT…
400
Thermal Conductivity (Wm-1K-1)

300 Thermal barrier

200
We Need to Enhance the
100
Thermal Conductivity of
Longer Cycle time
MIL-100(Fe) and MIL-101(Cr) for
0.3 use in Chiller Applications
0.2
0.1
0
MIL-100(Fe) MIL-101(Cr) Heat Exchanger 22
Dalton Trans., 2016,45, 15621
Addition of Second Phase Materials

Multiwalled Carbon Nanotubes and

Graphene Nanoplatelets offer the
Most Affordable Combination of
Thermal conductivity Enhancement
and Cost-Effectiveness !!!

23
Dalton Trans., 2016,45, 15621-15633
 Materials Selection
Host Materials

Second-Phase MIL-100(Fe) MIL-101(Cr)

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

• Preserves the crystal structure of the base MOF

• Preserves the chemical integrity of the base MOF

• Results in the best combination of adsorption capacity and

architectural robustness

• Results in cost-effective and time-efficient synthesis for

commercial use

• Easily reproducible during batch production 25

 Research Methodology

• Synthesis and Characterization

• Acid-treatment of MWCNTs and GNPs
• Synthesis of MWCNT/MIL-100(Fe) composite
• Synthesis of MWCNT/MIL-101(Cr) composite
• Synthesis of GNP/MIL-100(Fe) composite
• Synthesis of GNP/MIL-101(Cr) composite
• Characterization Methods

• 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

• Acid-treatment of MWCNTs and GNPs

• Synthesis of MWCNT/MIL-100(Fe) composite
• Synthesis of MWCNT/MIL-101(Cr) composite
• Synthesis of GNP/MIL-100(Fe) composite
• Synthesis of GNP/MIL-101(Cr) composite
• Characterization Methods
27
 Acid-treatment of MWCNTs and GNPs

3 g MWCNTs in 200 ml conc.

3 g GNPs in 300 ml conc. HNO3
HNO3
Sonication Sonication

Reflux at 120oC for 48 hours Reflux at 60oC for 2 hours

Dilution Dilution

Vacuum filtration Centrifugation

Repeated washing with DI water Repeated washing with DI water

pH ~ 5 pH ~ 5.5

Drying and Deagglomeration Drying and Deagglomeration 28

Synthesis of MWCNT- and GNP/MIL-100(Fe)
composite
4.04 g Fe(NO3)3.9H2O + acid-treated MWCNTs or GNPs

Thorough mixing till uniform color

Addition of 5 ml DI water and sonication for 12 hours

Addition of 1.41 g of 1,3,5 benzenetricarboxylic acid

Hydrothermal synthesis at 160oC for 14 hours

Centrifugation
Till decanted solvent
becomes colorless
Washing with water, ethanol and NH4F solution

Drying and Deagglomeration

29
Synthesis of MWCNT- and GNP/MIL-101(Cr)
composite
4 g Cr(NO3)3.9H2O + acid-treated MWCNTs or GNPs

Thorough mixing till uniform color

Addition of 5 ml DI water and sonication for 12 hours

Addition of 1.66 g of 1,4 benzenedicarboxylic acid

Hydrothermal synthesis at 220oC for 8 hours

Centrifugation
Till decanted solvent
becomes colorless
Washing with water, ethanol and NH4F solution

Drying and Deagglomeration

MWCNT acid-treatment

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

• Brunauer–Emmett–Teller (BET) Surface Area

• Powder X-ray Diffraction (PXRD)
• Fourier Transform Infrared Spectroscopy (FT-IR)
• Scanning Electron Microscopy (SEM)
• Transmission Electron Microscopy (TEM)
• X-ray Photoelectron Spectroscopy (XPS)
• Water sorption isotherms
• Cyclic adsorption-desorption stability

33
Part IV. Results and Discussion

• Acid-treated MWCNTs and GNPs

− FT-IR, PXRD and SEM

• MWCNT- and GNP/MOF composites

− BET Surface Area
− SEM and TEM
− FTIR
− PXRD
− XPS
− Water sorption isotherms
− Cyclic adsorption-desorption test

• 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

• BET Surface Area

• SEM and TEM
• FTIR
• PXRD
• XPS
• Water sorption isotherms
• Cyclic adsorption-desorption test
42
PXRD

13 wt%

5.9 wt%

2.2 wt%

MIL-100(Fe)

Simulated

43
BET Analysis

44
SEM micrographs

45
 TEM micrographs

MIL-100(Fe) 10.7 wt% MWCNTs

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

5.9 wt% 10.7 wt%

MWCNTs MWCNTs

49
 MIL-100(Fe) 2.2 wt% MWCNTs

5.9 wt% MWCNTs 10.7 wt% MWCNTs

50
Part IV – III: MWCNT/MIL-101(Cr) composite

• BET Surface Area

• SEM and TEM
• FTIR
• PXRD
• Water sorption isotherms
• Cyclic adsorption-desorption test

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%

6.9 wt% 8.6 wt%

57
Hydrothermal Cyclic Stability
MIL-101(Cr) 3.5 wt%

5.1 wt% 6.9 wt%

58
Part IV – IV: GNP/MIL-100(Fe) composite

• BET Surface Area

• SEM and TEM
• FTIR
• PXRD
• XPS
• Water sorption isotherms
• Cyclic adsorption-desorption test

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%

12.9 wt% 16.2 wt%

65
Hydrothermal Cyclic Stability
MIL-100(Fe) 6.5 wt%

12.9 wt% 16.2 wt%

66
Part IV – V: GNP/MIL-101(Cr) composite

• BET Surface Area

• SEM and TEM
• FTIR
• PXRD
• XPS
• Water sorption isotherms
• Cyclic adsorption-desorption test

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%

7 wt% 11.6 wt%

71
FT-IR

11.6 wt%

7 wt%

5 wt%

2.7 wt%

MIL-101(Cr)

72
MIL-101(Cr) 2.7 wt%

7 wt% 11.6 wt%

73
Hydrothermal Cyclic Stability
MIL-101(Cr) 2.7 wt%

7 wt% 11.6 wt%

74
Outcome of Experimental Work
5.9 wt%
MWCNT/MIL-100(Fe) 6.9 wt%
MWCNT/MIL-101(Cr)

GNP/MIL-100(Fe) composite with 16 wt%

GNPs offers the best combination of water
uptake and cyclic stability for use in
16.2 wt%
Chiller
GNP/MIL-100(Fe) Applications 11.26 wt%
GNP/MIL-101(Cr)

75
Part IV – VI: Numerical Modeling and Simulation

• Energy Source: Solar

• Adsorbent Material: MIL-100(Fe)

• 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)

x0, D and n: Fitting parameters

Tads: Adsorbent temperature (298 K)

Ps,w (Tr): Saturation vapor pressure of water at refrigerant temperature

Ps,ads (Tads): Vapor pressure at which adsorbent is saturated with water vapor at
77
78
79
Numerical Validation
Reference This work

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

Synthesis of MIL-100(Fe) is more

economical on a commercial scale as
compared to MIL-101(Cr)

Cr(NO3)3.9H2O Fe(NO3)3.9H2O BDC BTC 86

 Summary

1. The GNP/MIL-100(Fe) composite containing almost 16 wt% GNPs

shows the best combination of maximum water uptake and cyclic
stability amongst all the characterized composites
2. The commercial-scale production of MIL-100(Fe) based composites
is found to be more economical and time-efficient as compared to
MIL-101(Cr) based composites
3. Given the environmental toxicity associated with the use of Cr
metal, the GNP/MIL-100(Fe) composite is recommended as the
most appropriate adsorbent material as a result of this work for use
in commercial-scale adsorption chillers using water as refrigerant
4. Numerical modeling results indicate that the cycle time of a two-bed
adsorption chiller cannot be considered as a constant parameter; it
fluctuates every cycle depending upon the temporal variations in
pressures and temperatures inside the beds, the evaporator and the87
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Szokolay), (1984) p. 353
2. Advances in solar energy technology, 3 (1987) 2627–2631
3. Renewable Energy, 26(4) (2002) 611–622
4. Int. J. Refrigeration, 27 (2004) 284–293
5. Int. J. Ref. 28(7) (2005) 1084– 1091
6. Int. Commun. Heat Mass 35(5) (2008) 618–622
7. Appl. Therm. Eng., 28(2-3) (2008) 87–93
8. Energy Convers. Manage., 50(5) (2009) 1157–1162
9. Int. J. Therm. Sci., 48(5) (2009) 1017–1025
10. Appl. Therm. Eng., 30(8-9) (2010) 1039–1046
11. Int. J. Energ. Res., 32(6) (2008) 559–568 88