Extraction of Uranium from seawater

using Metal Organic Frameworks

A report submitted in partial fulfilment of the requirements

for the degree of Dual Degree in MFD

by

ADITYA KUMAR
(Roll No: MFD16I003)

DEPARTMENT OF ELECTRONICS AND COMMUNICATION ENGINEERING

INDIAN INSTITUTE OF INFORMATION TECHNOLOGY,
DESIGN AND MANUFACTURING, KANCHEEPURAM

December 2020
 Certificate

I, Aditya Kumar, with Roll No: MFD16I003 hereby declare that the material
presented in the Design Project Report titled Extraction of Uranium from seawater
using Metal Organic Frameworks represents original work carried out by me in the
Department of Electronics and Communication Engineering at the Indian
Institute of Information Technology, Design and Manufacturing,
Kancheepuram during the year 2020. With my signature, I certify that:

ˆ I have not manipulated any of the data or results.

ˆ I have not committed any plagiarism of intellectual property. I have clearly

indicated and referenced the contributions of others.

ˆ I have explicitly acknowledged all collaborative research and discussions.

ˆ I have understood that any false claim will result in severe disciplinary action.

ˆ I have understood that the work may be screened for any form of academic
misconduct.

Date: 26 December, 2020

In my capacity as supervisor of the above-mentioned work, I certify that the work presented
in this Report is carried out under my supervision, and is worthy of consideration for the
requirements of Design Project work.

Advisor’s Name: Dr. Gowthaman Swaminathan

(Mail forward may be considered equivalent to guide’s signature)

i
 Abstract
There is thousands of times more uranium in seawater than on land, but extracting it
for applications in nuclear power generation is strenuous due to its low concentration
(3 ppb) and the high saline background. Metal organic frameworks(MOFs) have been
considered for the sorption of Uranium from sea water which will be acquired from local
beach. Three MOFs have been considered for this study. UiO-68 network topology using
the amino-TPDC or TPDC bridging ligands containing orthogonal phosphorylurea groups
are considered for the study.
Contents

Certificate i

Abstract ii

Contents iii

1 Introduction 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Metal-Organic Frameworks . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Objectives of the work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2 Literature Review 3
2.1 Metal-Organic Frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1 General Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Extraction of Mercury (Hg) . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3 Extraction of Cadmium (Cd) . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.4 Chemisorption of Actinides and Lanthanides . . . . . . . . . . . . . . . . . 5

3 Process Planning 7
3.1 Selection of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.1 Essential Properties required in the MOFs . . . . . . . . . . . . . . . 7
3.1.2 MOFs considered . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2 Synthesis of MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3 Experimental Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4 Future Work 12
4.1 Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.2 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

iii
Chapter 1

Introduction

1.1 Introduction

Nuclear power is an authentic technology which is capable of generating electricity on

a large scale without emitting greenhouse gases. The growing energy demands present
great opportunities for developing novel porous materials to improve the nuclear fuel cycle.
Particularly, novel porous materials are extensively used to extract uranium from seawater
for nuclear fuel production, as well as for retrieving radionuclides from acid mine drainage.

1.1.1 Metal-Organic Frameworks

Metal-organic frameworks (MOFs) are a class of compounds that consist of metal ions
that are in coordination with organic ligands to form 1D, 2D or 3D structures.
Nowadays, MOFs have been applied in various applications including drug delivery, gas
adsorption/storage, separation, catalysis, carriers for nanomaterials, adsorption of
organic molecules, luminescence, electrode materials, magnetism, polymerization,
imaging, membranes, etc.
MOFs exhibit promising physical and chemical properties. The pore sizes of MOFs are
easily tunable from micro- to meso-scale. This can be achieved by changing the

1
Chapter 1. Introduction 2

connectivity of the inorganic moiety and the nature of the organic linkers. This property
makes it a viable candidate for the above mentioned application.

1.2 Motivation

The motive of this project is to gain a theoretical understanding of Metal-Organic

Frameworks and use them for the extraction of Uranium from sea water. This will help
in developing a strong foundation for further work in applications for Nuclear Power
Plants in India. This will increase the production of electricity at lower costs.

1.3 Objectives of the work

ˆ Theoretical study of Metal-Organic Frameworks.

ˆ Study of the applications of MOFs in extraction of toxic heavy metals.

ˆ Process planning.

ˆ Synthesis of MOFs with varying network topology.

ˆ Testing of permanent porosity of MOFs.

ˆ Comparison of results in order to obtain the best configuration.

Chapter 2

Literature Review

2.1 Metal-Organic Frameworks

A MOF is a coordination compound extending, through repeating coordination entities,

in one dimension, but with cross-links between two or more individual chains, loops, or
spiro-links, or a coordination compound extending through repeating coordination entities
in two or three dimensions; and finally, a coordination polymer is a coordination compound
with repeating coordination entities extending in one, two, or three dimensions. It is a
network with organic ligands containing potential voids [1].

2.1.1 General Synthesis

MOFs are generally produced by hydrothermal or solvothermal techniques, where crystals

are slowly grown from a hot solution [2]. MOFs are constructed by bridging organic ligands
that remain intact throughout the synthesis. In MOFs, the framework is templated by
the SBU (secondary building unit) and the organic ligands [3].

3
Chapter 2. Literature Review 4

2.2 Extraction of Mercury (Hg)

Xiao et. al. [4] observed the reversible adsorption of HgCl2 using an open
metal–carboxylate network containing free-standing methylthio groups
[Zn4 O (H2 O)3 (T M BD)3 ]. They reported a highly robust, 3D porous coordination
network compound featuring microchannels that are extensively functionalized with
methylthio groups.

Figure 2.1: Chemical composition of TMBD

2.3 Extraction of Cadmium (Cd)

Qian-Rong et. al. [5] used Zn4 O (CO2 )6 as secondary building units (SBUs) and two
extended ligands containing amino functional groups, TATAB and BTATB (TATAB =
4,40,400-s-triazine-1,3,5-triyltri-p-aminobenzoate and BTATB = 4,40,400- (benzene-1,3,5-
triyltris(azanediyl))tribenzoate) to synthesize two isostructural mesoporous metal-organic
frameworks (MOFs) with cavities up to 2.73 nm, designated as PCN-100 and PCN-101
Chapter 2. Literature Review 5

(PCN represents porous coordination network). The TATAB ligand that comprises PCN-
100 was employed to capture Cadmium by constructing complexes within the pores with
a possible coordination mode similar to that found in aminopyridinato complexes. This
reveals that mesoporous materials such as PCN-100 can be applied in the elimination of
heavy metal ions from waste liquid.

Figure 2.2: Chemical composition of TATAB

Figure 2.3: Chemical composition of BTATB

2.4 Chemisorption of Actinides and Lanthanides

E. I. Goryunov et. al. [6] pointed out that the key problem of modern nuclear industry is
disposal of acidic liquid radioactive wastes, which are present in large amounts during
processing of irradiated nuclear fuel. These radioactive wastes mainly contain hazardous
actinides and lanthanides. Prior to their study, the most popular method of recovery of
these radionuclides that was proposed liquid extraction with bidentate neutral
organophosphorus compounds (BNOPC). Unfortunately, this method couldn’t be used
Chapter 2. Literature Review 6

for practical purposes as it had extremely low selectivity and was expensive to synthesize.
E. I. Goryunov et. al. [6] noted that in the molecules of the considered
P-phenyl-substituted methylenediphosphine dioxide and carbamoylmethylphosphoryl
compounds, the complexing groups (two phosphoryl or phosphoryl and carbonyl ones)
are separated by a methylene bridge, which does not allow electronic interaction between
these groups. In view of this fact, systems in which both complexing groups are
combined by an imide bridge look in a different way. This structure may ensure
delocalization of the electronic system of the chelating center, which would promote more
efficient concerted binding of cations.
For their study, E. I. Goryunov et. al. [6] chose N-diphenyl- phosphorylureas
(P h2 P (O) N HC (O) N )in which the imide bridge binds the diphenylphosphoryl and
carbonyl complexing groups. They found out that the product is an efficient extractant
capable of extracting actinides and lanthanides from nitric acid solutions with high
distribution coefficients.
Chapter 3

Process Planning

3.1 Selection of MOFs

3.1.1 Essential Properties required in the MOFs

ˆ High stability in aqueous solution.

ˆ Must posses large pore apertures to facilitate the transport of hydrated actinide ions
through the interior of the frameworks.

3.1.2 MOFs considered

For this study, 3 variants of UiO MOFs are considered. They posses high aqueous stability
due to the presence of robust Zr6 O4 (OH)4 (CO2 )12 secondary binding units.
Variants of MOFs considered:

ˆ MOF 1: U iO − 68 − N H2 framework. Schaate et. al. [7] showed that U iO − 68 −

N H2 framework has large tetrahedral pores with apertures that can accommodate
particles of up to 10Å in diameter. It will be used as a control sorbent without the
phosphorylurea group.

7
Chapter 3. Process Planning 8

ˆ MOF 2: U iO − 68 − P (O) (OEt)2 . The amine group in the U iO − 68 − N H2

framework is modified to diethylphosphorylurea group due to its affinity towards
actinide groups.

ˆ MOF 3: U iO − 68 − P (O) (OH)2 .

3.2 Synthesis of MOFs

ˆ MOF 1: U iO − 68 − N H2 framework was synthesized according to the process

mentioned by Schaate et. al. [7].

ˆ MOF 2: Carboni et. al. [8] specially synthesized MOF 2.

Diethoxyphosphorylurea-derived TPDC ligand (H2 L2 ) was prepared in
quantitative yield by condensation of the amino- H2 T P BC with commercially
available diethoxyphosphinyl isocyanate. The new UiO MOF containing the
diethoxyphosphorylurea group [U iO − 68 − P (O) (OEt)2 ] was prepared by heating
a solution of ZrCl4 , H2 L2 , and benzoic acid in DMF at °70C for 3 days. The
resulting light yellow powder was collected by centrifugation and washed with
DMF and ethanol.

ˆ MOF 3: Subsequent deprotection of MOF 2 with M e3 SiBr followed by hydrolysis

with water yielded the isomorphous MOF functionalized with
dihydroxyphosphorylurea groups [U iO − 68 − P (O) (OH)2 ]
Chapter 3. Process Planning 9

Figure 3.1: Schematic showing the preparation of MOFs 1–3 and a structural model of
the new UiO MOF (3) displaying the readily accessible phosphorylurea groups as shown
by Carboni et. al. [8]
Chapter 3. Process Planning 10

3.3 Experimental Procedures

ˆ SEM images: SEM images will be captured in order to determine the dimensions of
the MOFs.

ˆ Permanent Porosity: Ma et. al. [9] demonstrated the permanent porosity of freeze-
dried MOFs by N2 adsorption at 77K. The obtained the Brunauer–Emmett–Teller
surface areas of 3730, 1350, 750 m2 g −1 for MOFs 1, 2 and 3 respectively.

ˆ Relative pore volume: Lin et. al. [10] studied the relative pore volume by measuring
dye uptake by the MOFs. The resulting pore volume hierarchy was obtained as
MOF 1 > MOF 3 > MOF 2.

Figure 3.2: N2 uptake and simulated N2 uptake for MOFs 1–3 at 77 K as shown by Ma
et. al. [9]

ˆ Uranium sorption: Saito et. al. [11] performed experiments to study Uranium
sorption in water and simulated sea water.
Chapter 3. Process Planning 11

– 10mg of MOF will be added to 10 mL of a solution spiked to 50 ppm with

uranyl acetate.

– The resulting solution is shaken for 1 hour at room temperature.

– Afterwards the sorbent will be separated by centrifugation and the supernatant

will be analyzed for U concentration by UV spectroscopy and ICP-MS.

– The sorbent will be washed with 1.0 M HCl aqueous solution to investigate
Uranium removal and determine the affinity of the ligand for the uranyl cation.

– Sorption isotherms at pH 2.5 and 5 will be measured to obtain the saturation

capacity of the MOFs.

– The obtained results are fitted to the Langmuir model. This isotherm is
expressed linearly as:

Ce 1 1
= Ce × +
qe qmax KL qmax

where:

* qe is the sorption capacity at equilibrium.

* qmax is the saturation capacity

* Ce is the Uranium concentration in solution at equilibrium

* KL is a constant related to binding site affinity

qmax and KL can be obtained by plotting Ce /qe vs. Ce .

ˆ DFT calculations of uranyl–sorbent interactions: In order to determine the

sorption efficiency the knowledge of the binding modes for U O22+ with the
phosphorylurea sorbent moiety is required. Density functional theory (DFT)
calculations will be performed to assess optimized geometries and relative
stabilities for a series of U O22+ complexes with carbamoylphosphoramidic acid,
representative of the sorbent in MOFs 2 and 3.
Chapter 4

Future Work

4.1 Experiment

The experiments will be performed according to the process planned. The optimal MOF
topology will be found out in order to maximise sorption rate.

4.2 Application

The results of this study will be considered for applications for Nuclear Power Plants.

12
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