Synthesis optimisation, characterisation and evaluation of an iron-based oxalate-phosphate-amine

188 Pages·2017·5.47 MB·English

Southern Cross University
ePublications@SCU
Theses
2016
Synthesis optimisation, characterisation and
evaluation of an iron-based oxalate-phosphate-
amine MOF (OPA-MOF) for innovative
application in agriculture
Manuela Anstoetz
Southern Cross University
Publication details
Anstoetz, M 2016, 'Synthesis optimisation, characterisation and evaluation of an iron-based oxalate-phosphate-amine MOF (OPA-
MOF) for innovative application in agriculture', PhD thesis, Southern Cross University, Lismore, NSW.
Copyright 2016 M Anstoetz
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Synthesis optimisation, characterisation
and evaluation of an iron-based oxalate-
phosphate-amine MOF (OPA-MOF) for
innovative application in agriculture

Manuela Anstoetz
Bachelor of Environmental Science (Honours I)

A thesis submitted in fulfilment of the requirements for the degree of Doctor of
Philosophy (PhD) in the School of Environment, Science and Engineering

SOUTHERN CROSS UNIVERSITY
13 May 2016
DECLARATION

I certify that the work presented in this thesis is, to the best of my knowledge and
belief, original, except as acknowledged in the text, and that the material has not
been submitted, either in whole or in part, for a degree at this or any other
university.

I acknowledge that I have read and understood the University’s rules,
requirements, procedures and policy relating to my higher degree research award
and to my thesis.

I certify that I have complied with the rules, requirements, procedures and
policy of the University.

Name: Manuela Anstoetz

Signature:

Date:
I
ABSTRACT

Porous metal-organic framework materials (MOFs) have found exceptional interest in the
engineering and medical communities, due to a large spectrum of valuable properties. These
materials may bring solutions to pressing environmental issues, such as gas storage media, new
type batteries, or carriers for medical drugs. However, not all MOFs fulfil the specific
requirements for these applications, yet may be suitable for alternative applications. In
agriculture, for example, increasing soil acidification requires urgent attention. Use of MOFs
as innovative slow-release fertilisers may contribute to soil alkalinisation, soil fertility and
improved N and P fertiliser use efficiency. This thesis seeks to provide a proof of concept for
optimal production, and mode of action for just such a fertiliser: a structure built by plant
nutrients N, P and Fe, plus oxalate, which is decomposed by soil bacteria, thereby releasing the
nutrients to the soil environment for plant uptake. The structural oxalate provides a source of
carbon and energy for oxalotrophic bacteria through adequate solubility in soil solution, which
enables biomineralisation of carbonate via the oxalate-carbonate pathway, resulting in
increased soil pH. This thesis presents the successful hydrothermal synthesis, with urea as
structure-directing agent (SDA), and synthesis optimisation of a mixed-valence iron-based
oxalate-phosphate-amine framework (OPA-MOF; C Fe N O P ), which crystallizes in a
8 8 16 52 8
Pccm centrosymmetric system. Corner-sharing FeO - and PO - units are connected by the
6 4
oxalate ligand in two directions, forming a macro-porous framework, which carries ammonium
from decomposed urea as guests. Optimal production factors were defined from a full factorial
42+1 design, and response surface method (RSM), which produced a saddle-ridged optimum
function for desirability. Two additional experiments confirmed the robust model. The OPA-
MOF displays all properties required for application as fertiliser: high product yields of
suitable purity, nutrient contents, and oxalate solubility. The material’s fertilising capacities
were tested in a pot trial growing wheat, which showed increased grain yields (compared to
unfertilised controls and urea fertilisation), and an unprecedented long-lasting nitrification
inhibition effect. Due to a short trial period no soil pH increase could be detected, and P
remained limiting for maximum yields. However, microbiological investigations confirmed
presence of oxalotrophic bacteria, and their ability to consume OPA-MOF. Scanning Electron
Microscopy (SEM) reveals that even after 22 weeks exposure to the soil environment the OPA-
MOF particles are almost intact, which suggests that any decomposition of the material is very
slow, affording a long-term presence of the incorporated plant nutrients in the soil. The
successful proof of concept warrants long-term trials to investigate potential soil alkalinising
and P-fertilising effects.
II
ACKNOWLEDGEMENTS

The studies presented here were funded and/or supported by the Grains Research and
Development Council Australia (GRDC), Australian Institute of Nuclear Science and
Engineering (AINSE) Ltd., the Australian Synchrotron, and the New South Wales Department
of Primary Industries (NSW DPI), and Southern Cross University (SCU); without these
financial contributors the research presented here would not have been possible. To make the
specific contributions clear, further acknowledgements are extended at the end of each chapter.
I sincerely thank the people who provided critical reviews on, and editorial inputs to the papers
presented in this thesis. I am very grateful to have received an SCU administered Australian
Postgraduate Award. Also, I thank any person(s) or institution(s) that I might have,
inadvertently, missed below.

I specifically thank my principal supervisor Associate Prof Malcolm Clark (SCU), and my co-
supervisor, Dr Lachlan Yee (SCU), for their continued (life)-teaching, patience and support
throughout my candidature. They both contributed invaluable insights, skills, and assistance,
and helped me greatly to develop and grow on a professional level as a researcher, as well as
on a personal level.

Mrs Maxine Dawes deserves my very special gratitude for her enthusiastic teaching of
microscopy techniques, and her unfailing support in dealing with the presenting difficulties of
the material that is subject of this research — it instilled in me a lasting curiosity and passion
for SEM.

Also sincere thanks to my co-authors: Terry J. Rose for his expert advice on agricultural
matters, always conveyed with humour, patience and uplifting thoughtfulness; Caroline
Raymond for her unfailingly cheerful ways in helping to produce the statistical analyses
presented in Chapter VI; Neeraj Sharma for his friendly initiative and expert support in
characterising the crystallography of the material presented (Chapter IV); Tony Vancov for his
most valuable teaching and insight into the field of microbiology, which inspired me to
embrace the work presented in Chapter VII.
III
I am deeply appreciative to technical and professional staff Michelle Bush, Barbara Harrison,
Peter Bligh-Jones, Mark Rosicky, Craig Taylor and Graeme Palmer for their support over the
years. In particular I would like to express my sincere thanks to SCU Library staff Glenda
Scibilia, Sharon Wheeler and Jeff Smith, and administrative staff at the School of
Environment, Science and Engineering Sonia Weiss and Rosi Brown, who were always
extraordinarily friendly and efficient in their help. A warm thank you to all other staff at SCU,
the Graduate School and EAL, too numerous to list, who assisted me during my candidature.

A heartfelt thank you to my colleagues and friends (Jonathan Parkyn, Jesse Leland, Kirin
Apps, Kerrie Stimpson) who gave me food for thought, and provided lively, inspiring,
challenging and helpful conversations over many years.

Lastly, I thank my dear husband Thomas, and my three girls Johanna, Sonja and Anna-Lena
for their great love, and support. Their ongoing encouragement and patience helped me to
advance myself, and my professional efforts beyond measure; without their unshakeable belief
in me I would not have managed to get this far, and finish this work.

IV
PUBLICATIONS INCORPORATED INTO THESIS

I, Manuela Anstoetz, state that Chapters IV and V in this thesis were peer reviewed prior to
publication in international scientific journals (see links for evidence). Further, I affirm that,
where necessary, I have obtained permission from the copyright owners to use any third-party
copyright material reproduced in this thesis, and to use any of my own published work in
which copyright is held by another party (see Appendix for proof of permission regarding
Chapter V; no permission was required for Chapter VI).

Manuela Anstoetz Date

Chapter V — Anstoetz, M., Clark, M. W., Yee, L. H., 2016. Resolving topography of an
electron beam-sensitive oxalate-phosphate-amine metal-organic framework (OPA-MOF).
Journal of Materials Science 51 (3) pp 1562-1571
http://dx.doi.org/10.1007/s10853-015-9478-y

Chapter VI — Anstoetz, M., Rose, T. J., Clark, M. W., Yee, L. H., Raymond, C. A.,
Vancov, T., 2015. Novel Applications for Oxalate-Phosphate-Amine Metal-Organic
Frameworks (OPA-MOFs): Can an Iron-Based OPA-MOF Be Used as Slow-Release
Fertiliser?. PlosOne, 10 (12) pp e0144169
http://www.plosone.org/article/fetchObject.action?uri=info:doi/10.1371/journal.pone.0144169
&representation=PDF

V
CONTRIBUTION STATEMENT

Chapter I - The general introduction was written fully by Manuela Anstoetz (100 %)

Chapter II - The literature review was written fully by Manuela Anstoetz (100 %)

Chapter III - Manuela Anstoetz participated during all stages of this chapter’s/proposed
paper’s development (including idea development, laboratory experimentation, data analysis,
and writing) and provided a contribution greater than that of any co-author. The specific
authorship percentage contributions are agreed to be: Anstoetz, M (80%), Clark, M.W. (15%),
Yee, L.H. (5%)

Chapter IV - Manuela Anstoetz participated during all stages of this paper’s development
(including idea development, laboratory experimentation, data analysis, and writing) and
provided a contribution greater than that of any co-author. The specific authorship percentage
contributions are agreed to be: Anstoetz, M (60%), Sharma, N (15%), Clark, M.W. (15%),
Yee, L.H. (10%)

Chapter V - Manuela Anstoetz participated during all stages of this paper’s development
(including idea development, laboratory experimentation, data analysis, and writing) and
provided a contribution greater than that of any co-author. The specific authorship percentage
contributions are agreed to be: Anstoetz, M. (75%), Clark, M.W. (15%), Yee, L.H. (10%)

Chapter VI - Manuela Anstoetz participated during all stages of this paper’s development
(including idea development, laboratory experimentation, data analysis, and writing) and
provided a contribution greater than that of any co-author. The specific authorship percentage
contributions are agreed to be: Anstoetz, M. (50%), Rose, T.J. (13%), Clark, M.W. (12%),
Yee, L.H. (10%), Raymond, C.A. (10%), Vancov, T. (5%)
VI
Chapter VII - The chapter was written fully by Manuela Anstoetz (100%)

Chapter VIII - The chapter was written fully by Manuela Anstoetz (100%)

Manuela Anstoetz

Malcolm Clark, principal supervisor

Lachlan Yee, co-supervisor
VII
ADDITIONAL RELEVANT PUBLICATIONS

Listed below are a set of additional publications made by the candidate that are relevant to the
thesis, but not included in it

Anstoetz, M., Clark, M.W., Yee, L.H. (2013) Beam-sensitive materials in conventional HV-
SEM: Simple modification method enables quality imaging. Poster Presentation and Abstract
at Post Graduate Conference of School of Environment, Science and Engineering, Southern
Cross University, Lismore, Australia

Anstoetz, M., Clark, M.W., Vancov, T., Rose, T.J., Yee, L.H. (2014) Post Graduate
Conference Paper: Journey into the unknown - microbiological studies of a novel material with
fertilising capacities. Research in Science, Engineering and Environment (RiSE) Conference,
Southern Cross University, Lismore, Australia, Book of Abstracts p 37

Anstoetz, M., Clark, M.W., Yee, L.H. (2015) Conference Paper: Novel applications for metal-
organic frameworks in agriculture. European Polymer Congress (epf) 2015, Dresden, Germany

VIII