Home Energy storage analysis of R125 in UIO-66 and MOF-5 nanoparticles: A molecular simulation study
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Energy storage analysis of R125 in UIO-66 and MOF-5 nanoparticles: A molecular simulation study

  • Qiang Wang and Shengli Tang EMAIL logo
Published/Copyright: April 10, 2019
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Open Chemistry
From the journal Open Chemistry Volume 17 Issue 1

Abstract

The efficiency of thermodynamic cycles can be improved by using the optimized working fluid. In the present paper, classic molecular dynamics simulations and grand canonical Monte Carlo were employed to examine the thermal energy storage characteristicsof R125/UIO-66 and R125/MOF-5 nanofluids. The results indicate that the adsorption of R125 in MOF-5 is larger than that in UIO-66. Also, the thermal energy storage capacity of R125 was strengthened by mixing with UIO-66 or MOF-5 nanoparticles. In addition, the R125/UIO-66 mixtures can store less energy than that of R125/MOF-5 mixtures except the temperature difference is 30 K to 50 K.

Keywords: R125; UIO-66; MOF-5; thermal energy storage; molecular simulation

1 Introduction

The energy crisis and environmental issues have become the prominent problems in the fast development of our society. Improving the efficiency of energy resource utilization has become one of the popular approaches of sustainable development [1]. The working fluid serves as the heat-carrier of the thermodynamics cycles which are the important way of energy conversion. Thus, using methods to improve the thermophysical properties of the working fluid can optimize the energy efficiency [2].

Actually, extensive research [3] reported that adding nanoparticles to working fluid will modify the heat and mass transfer properties of the working fluid [4, 5, 6]. In addition, the unique energy storage mechanism has been explored [7]. For instance, the carbon nanotube, metal–organic frameworks (MOFs) and zeolites are the classical micro/nanoporous materials which have been widely used in industry. Compared to the conventional materials with relative low specific surface area, these materials have a very great specific surface area. The fluid molecules are readily adsorbed on the materials’ surface [8]. Since the desorption of fluid from a surface is endothermic, the thermal energy can be stored in the nanofluid by fluid molecules adsorbing and desorbing to materials’ surface [9]. Elsayed et al. [10] experimental studied the characteristics of CPO-27(Ni)MOF and proved its feasibility of energy storage. Rezk et al. [11] studied the ethanol adsorption properties in six kinds of MOFs. Chen et al. [12] studied the energy storage of nanofluids containing carbon nanotube under the fields including heat, force and electric coupling actions. McGrail et al. [13] at Pacific Northwest National Laboratory of US proposed to add the MOFs nanoparticles to refrigerants to form the so-called metal-organic heat carrier nanofluids (MOHCs) to enhance the performance of organic Rankine cycle (ORC). Recently, Zheng et al. firstly reported the adsorption isotherms of R134a in Ni-MOF-74 by experiments [14]. The MOHCs need further research for their great potential applications in the utilization of low grade energy and refrigerating cycles.

MOFs are organic-inorganic hybrid material [15], made of metal clusters (or metal ions) and organic ligands via the coordination bond. With great properties of high specific surface area, good thermal stability and strong adsorption affinity, MOFs have a great prospective in the fields of materials, energy and chemistry and so on [16].

However, due to the pores of MOFs being small, it is still difficult to use conventional experimental and theoretical methods to explore the characteristics of MOFs. Recently, with the developing of computational technology, which is not restricted by the experimental conditions, molecular simulation [17,18] can reveal the micromechanism of the macro phenomenon. As a result, it has been widely used in the designing and researching materials. A large number of articles in literature [19] show that molecular simulation has become a powerful tool in studying nanomaterials. UIO-66 [20] is one of the MOFs, containing Zr, developed by the University of Oslo in Norway in 2008. The material is made up of Zr’s positive eight-hedral and 12 organic ligands to the two formic acids, forming a three-dimensional skeleton with a central hole cage having eight sides and eight tetrahedral cages, which is one of the most stable MOFs. MOF-5 [21] is a kind of MOFs and consists of clusters (Zn4O) connected by the 1,4-benzodicarboxylate ligands. It owns good thermostability whose structure remains stable below 573 K and a specific surface area of 2000 m2/g [22].

Pentafluoroethane (R125 [23]) is a common organic refrigerant with low GWP (Global Warming Potential), zero ODP (Ozone Depletion Potential)and good thermophysical properties. Consequently, here, thermal energy storage properties of R125 in UIO-66 and MOF-5 nanoparticles are analyzed by using molecular simulations.

2 Models and simulation details

Notionally, the thermal energy storage properties of MOHCs (ΔhMOHCs) is primarily composed of [24]: a) Enthalpy difference of pure working fluid (ΔhFluid) at different temperature⍰b) Thermodynamic energy difference of MOFs particles ((∫T0T1CpdT)MOFs)at different temperature⍰c) Desorption heat of working fluid in MOFs (Δhdesorption) at different temperature, which can be calculated by[25]

(1)ΔhMOHCs=(1-a)•ΔhFluid+a•Δhdesorption+a•(∫T0T1CpdT)MOFs

where a is the mass fraction of nanoparticles in MOHCs. And it could be rewritten as follow,

Figure 1 2×2×2 unit cells of UIO-66 structure.
Figure 1

2×2×2 unit cells of UIO-66 structure.

Figure 2 2×2×2 unit cells of MOF-5 structure.
Figure 2

2×2×2 unit cells of MOF-5 structure.

(2)ΔhMOHCs=ΔhFluid+a•(Δhdesorption+(∫T0T1CpdT)MOFs-ΔhFluid)

Thus, more thermal energy can be stored in MOHCs than the pure working fluid while the sum of thermodynamic energy difference of MOFs and desorption heat of working fluid in MOFs is great than the enthalpy difference of the pure fluid.

To compute the value of ΔhMOHCs, ΔhFluid could be easily acquired by experiments or simple thermodynamic calculations. Therefore, the thermodynamic parameters of R125 are searched from the National Institute of Standards and Technology (NIST [26]). As a novel material, the Cp of MOFs is rarely reported, and that could be computed through classic molecular dynamics (MD) by analyzing the energy change curves during heating [27]. The Δhdesorption could be calculated by Grand Canonical Monte Carlo (GCMC) simulations [28].

Figure 3 Molecular structure of R125.
Figure 3

Molecular structure of R125.

2.1 Models of simulation

The computational model of the UIO-66 particle is composed of 8 (2×2×2 in X×Y×Z) unit cells of UIO-66, as presented in Figure 1. The system contains 3648 atoms (including 1536 C, 896 H, 1024 O, and 192 Zr). The computational model of MOF-5 particle is-also comprised of 8 (2×2×2 in X×Y×Z) unit cells, as presented in Figure 2, made of 256 Zn atoms, 1536 carbon atoms, 832 oxygen atoms and 768 hydrogen atoms. And the molecular structure of R125 (CF3CHF2) is presented in Figure 3.

The classic MD and GCMC simulations are using Materials Studio [29]. In the present work, the intra and inter molecular interactions were calculated by COMPASS [30] force field. The long-range Coulombic interactions were described by the Ewald method. Besides, periodic boundary conditions (PBC) are used in all dimensions in the simulations.

2.2 Details of classic MD

The classic MD were simulated in the Forcite component of Materials Studio software. The timestep is chose as 0.01 fs. The total equilibrium time is 200 ps to compute the different thermodynamic energies of UIO-66 and MOF-5 models at 280 K, 300 K, 320 K, 340 K, 360 K, 380 K, 400 K and 420 K, respectively. The simulations are computed in NVT canonical ensemble with Berendsen algorithm to maintain the temperature.

2.3 Details of GCMC

The GCMC computations were simulated in the Sorption component of Materials Studio software. And the adsorption isotherms atthe same temperatures in MD simulations of R125 in UIO-66 and MOF-5 models are computed from 1 to 8,000 kPa. In addition, the Peng-Robinson equation is used to calculate fugacity . For every data of the adsorption isotherms, the equilibrium time is 50,000 cycles with another 100,000 cycles for statistic.

Figure 4 The adsorption isotherms of R125 adsorb in UIO-66 structure.
Figure 4

The adsorption isotherms of R125 adsorb in UIO-66 structure.

Figure 5 The adsorption isotherms of R125 adsorb in MOF-5 structure.
Figure 5

The adsorption isotherms of R125 adsorb in MOF-5 structure.

Ethical approval: The conducted research is not related to either human or animal use.

3 Simulation results and Discussion

3.1 Adsorption isotherms

The adsorption isotherms of R125 in UIO-66 and MOF-5 models are plotted in Figure 4 and Figure 5, respectively. The calculated adsorption isotherms decrease as the temperature rises. Naturally, the fluid molecules have more kinetic energy as the temperature increases. This will result in the decreasing of adsorption for more fluid molecules in overcoming the attractive force from the MOFs. Also, the adsorption capacities of R125 in both UIO-66 and MOF-5 increase as the pressure increases. The adsorption capacity keeps stable until the system reaches its saturation state. Note that the MOF-5 nanoparticle adsorb more R125 than that of UIO-66. This is because the pore size of MOF-5 is larger than that of UIO-66 [14,31].

Figure 6 Thermodynamic energies of MOF-5 and UIO-66 particles at different temperature.
Figure 6

Thermodynamic energies of MOF-5 and UIO-66 particles at different temperature.

Figure 7 The enthalpy difference at different temperature difference (5 MPa).
Figure 7

The enthalpy difference at different temperature difference (5 MPa).

Figure 8 The relative energy change of working fluids at different temperature difference (5 MPa).
Figure 8

The relative energy change of working fluids at different temperature difference (5 MPa).

3.2 Thermal energy storage

The thermodynamic energies of MOF-5and UIO-66 structures are shown in Figure 6, respectively. Thermodynamically, the increment of thermodynamic energies curve at different temperature is the heat capacity, Cp, of the studied material. Here, the Cp of UIO-66 is about 1.744 (kJ/kg•K), while the Cp of MOF-5 is about 1.878 (kJ/kg•K). The difference of heat capacities of UIO-66 and MOF-5 between the simulation results and the reported data [32] is expected to be the result of the different structures and components of MOFs materials.

Then, the thermal energy storage capacity of the studied UIO-66/R125 and MOF-5/R125 MOHCs could be computed based on eq.(2). The thermodynamic energy difference of studied nanoparticles, desorption heat of working fluid in MOFs and the enthalpy difference of pure working fluid R125 are presented in Figure 7. It should be noted the temperature of cold source is assumed as 280 K. And the thermal energy storage characteristics of the studied UIO-66/R125 and MOF-5/R125 MOHCs with different mass ratio of UIO-66 and MOF-5 nanoparticles are shown in Figure 8. The enthalpy difference of pure R125 is considered as the reference working fluid. The results denoted that the R125/UIO-66 and R125/MOF-5 MOHCs can store more thermal energy than the pure R125. This is because that the thermodynamic energy difference of UIO-66 and MOF-5 are much larger than the enthalpy difference of pure R125 as shown in Figure 7. And the thermal energy storage ratio of the studied MOHCs enhance as the mass fraction of MOFs nanoparticle increased. This is in line with the reported results [14,21,32]. Here, the energy storage capacity of the studied MOHCs is enhanced when the temperature difference is less than 80 K.

In addition, the R125/MOF-5 MOHCs can store more energy than that of R125/UIO-66 MOHCs except when the temperature difference is 30 K to 50 K. The reason is that the desorption heat of R125 in UIO-66 structures is larger than that of R125 in MOF-5 structures when the temperature difference is 30 K to 50 K, even though the thermodynamic energy difference of MOF-5 particle is larger than that of UIO-66 particle.

4 Conclusions

In the present research, two molecular simulation methods, including classic MD and GCMC, are used to study the thermal energy storage characteristics by the adsorption of R125 in UIO-66 and MOF-5 nanoparticles. The MOF-5 absorbs more R125 than UIO-66 becauset the pore of MOF-5 is larger than that of UIO-66. Both R125/UIO-66 and R125/MOF-5 MOHCs can enhance the thermal energy storage properties of R125. And the energy storage properties of R125/UIO-66 and R125/MOF-5 MOHCs perform to different abilites due to the difference of thermodynamic changes of MOFs nanoparticles and desorption heat.

Nomenclature

ΔhMOHCs

The enthalpy difference of MOHCs (kJ/kg)

ΔhFluid

The enthalpy difference of pure working fluid(kJ/kg)

Δhdesorption

The enthalpy difference of desorption (kJ/kg)

T

Temperature (K)

Cp

The heat capacity of MOFs particles (kJ/(kg·K))

a

The mass fraction of MOFs in MOHCs (%)

M

Adsorption (mmol/g)

P

Pressure (kPa)

Acknowledgments

The present work is supported under the National Natural Science Foundation of China (Grant No. 51506013). Also, the authors wish to thank Dr. Qibin Li at Chongqing University for the useful discussion.

  1. Conflict of interest: Authors declare no conflict of interest.

Appendix

Table 1

Thermodynamic Energies of MOF-5 and UIO-66.

Temperature (K)MOF-5 (kJ/kg)UIO-66 (kJ/kg)
280-6340.637628-28833.57371
300-6303.646033-28798.27956
320-6267.476843-28764.29193
340-6229.649899-28728.52663
360-6193.184919-28692.75755
380-6154.050674-28659.42097
400-6115.595878-28624.21363
420-6077.80793-28589.42334

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Received: 2018-07-29
Accepted: 2019-01-04
Published Online: 2019-04-10

© 2019 Qiang Wang, Shengli Tang, published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 Public License.

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  81. Enhanced adsorption of sulfonamide antibiotics in water by modified biochar derived from bagasse
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  87. Phytochemistry and toxicological assessment of Bryonia dioica roots used in north-African alternative medicine
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  124. Effect of Electrospinning Process on Total Antioxidant Activity of Electrospun Nanofibers Containing Grape Seed Extract
  125. Effect Of Thermal Treatment Of Trepel At Temperature Range 800-1200˚C
  126. Topical Issue on Agriculture
  127. The effect of Cladophora glomerata exudates on the amino acid composition of Cladophora fracta and Rhizoclonium sp.
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  134. Recovery of phosphates(V) from wastewaters of different chemical composition
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  145. Photocatalytic activity of NiFe2O4 and Zn0.5Ni0.5Fe2O4 modified by Eu(III) and Tb(III) for decomposition of Malachite Green
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  151. Special Issue on 13th JCC 2018
  152. Fluorescence study of 5-nitroisatin Schiff base immobilized on SBA-15 for sensing Fe3+
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  164. Ionic liquids modified cobalt/ZSM-5 as a highly efficient catalyst for enhancing the selectivity towards KA oil in the aerobic oxidation of cyclohexane
  165. Application of Thermal Resistant Gemini Surfactants in Highly Thixotropic Water-in-oil Drilling Fluid System
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  170. Design of SiO2/TiO2 that Synergistically Increases The Hydrophobicity of Methyltrimethoxysilane Coated Glass
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  173. Special Issue on Applied Biochemistry and Biotechnology 2019
  174. Adsorption of copper ions on Magnolia officinalis residues after solid-phase fermentation with Phanerochaete chrysosporium
  175. Erratum
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https://doi.org/10.1515/chem-2019-0026
Keywords for this article
R125; UIO-66; MOF-5; thermal energy storage; molecular simulation
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  140. Special Issue on Chemistry Today for Tomorrow 2019
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  143. Chemomertic Risk Assessment of Soil Pollution
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  145. Photocatalytic activity of NiFe2O4 and Zn0.5Ni0.5Fe2O4 modified by Eu(III) and Tb(III) for decomposition of Malachite Green
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  148. Special Issue on Monitoring, Risk Assessment and Sustainable Management for the Exposure to Environmental Toxins
  149. Soil organic carbon mineralization in relation to microbial dynamics in subtropical red soils dominated by differently sized aggregates
  150. A potential reusable fluorescent aptasensor based on magnetic nanoparticles for ochratoxin A analysis
  151. Special Issue on 13th JCC 2018
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  153. Thermal and Morphology Properties of Cellulose Nanofiber from TEMPO-oxidized Lower part of Empty Fruit Bunches (LEFB)
  154. Encapsulation of Vitamin C in Sesame Liposomes: Computational and Experimental Studies
  155. A comparative study of the utilization of synthetic foaming agent and aluminum powder as pore-forming agents in lightweight geopolymer synthesis
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  160. Production of Biodiesel from Nyamplung (Calophyllum inophyllum L.) using Microwave with CaO Catalyst from Eggshell Waste: Optimization of Transesterification Process Parameters
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  162. Composite Material Consisting of HKUST-1 and Indonesian Activated Natural Zeolite and its Application in CO2 Capture
  163. Topical Issue on Environmental Chemistry
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  165. Application of Thermal Resistant Gemini Surfactants in Highly Thixotropic Water-in-oil Drilling Fluid System
  166. Screening Study on Rheological Behavior and Phase Transition Point of Polymer-containing Fluids produced under the Oil Freezing Point Temperature
  167. The Chemical Softening Effect and Mechanism of Low Rank Coal Soaked in Alkaline Solution
  168. The Influence Of NO/O2 On The NOx Storage Properties Over A Pt-Ba-Ce/γ-Al2O3 Catalyst
  169. Special Issue on the International conference CosCI 2018
  170. Design of SiO2/TiO2 that Synergistically Increases The Hydrophobicity of Methyltrimethoxysilane Coated Glass
  171. Antidiabetes and Antioxidant agents from Clausena excavata root as medicinal plant of Myanmar
  172. Development of a Gold Immunochromatographic Assay Method Using Candida Biofilm Antigen as a Bioreceptor for Candidiasis in Rats
  173. Special Issue on Applied Biochemistry and Biotechnology 2019
  174. Adsorption of copper ions on Magnolia officinalis residues after solid-phase fermentation with Phanerochaete chrysosporium
  175. Erratum
  176. Erratum to: Sand Dune Characterization For Preparing Metallurgical Grade Silicon
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