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

November 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:

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

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

indicated and referenced the contributions of others.

• I have explicitly acknowledged all collaborative research and discussions.

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

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

Date: 22 November, 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 have been considered for the
sorption of Uranium from sea water which will be acquired from local beach.
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

3 Proposed Idea 6
3.1 Chemicals Considered . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1 Tuning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2 Expectation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

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

• Theoretical study of Metal-Organic Frameworks.

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

• Synthesis of MOFs with varying network topology.

• Testing of permanent porosity of MOFs.

• 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
(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.
Chapter 2. Literature Review 5

Figure 2.2: Chemical composition of TATAB

Figure 2.3: Chemical composition of BTATB

Chapter 3

Proposed Idea

3.1 Chemicals Considered

UiO MOFs can be used for the current application as they posses high stability in aqueous
solution. The presence of robust Zr6 O4 (OH)4 (CO2 )12 SBUs makes it extremely stable
in an aqueous solution.

3.1.1 Tuning

The open channels can be easily tuned tuned by varying the lengths of the dicarboxylate
bridging ligand. The N-diphenylphosphorylurea (DPPU) functional group has been used
to extract actinides and lanthanides from nitric acid solutions [6].

3.2 Expectation

We expect to obtain promising sorbent materials for actinides by combining the high
porosity and stability of UiO MOFs with the phosphorylurea ligand’s affinity for actinides.

6
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