Porous coordination polymers (PCPs) and metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and geometry-directing metal ion clusters. Since the inception of the field in the late 1990s, these materials have been investigated extensively for applications in gas storage, separations, and catalysis because of their high porosity and chemical tunability. However, high electrical conductivity is rare in PCPs/MOFs, even though this property would enable diverse sustainable technologies in charge (energy) storage and electrocatalysis, among others. Indeed, the electronic properties of MOFs have received comparatively less attention than their physical PCP/MOF properties until recently, driven by renewed commitments to global sustainable energy agenda. However, timely progress in the field still faces potential barriers given that the study of these gateway materials are often siloed to single disciplinary approaches: whether by theoreticians (who model conductivity and transport dynamics), synthetic chemists (who engineer intrinsic electronic properties through bottom-up molecular design) and materials scientists (who measure physical material properties and the performance of MOFs within solid-state applications).
The project aims to establish rational design principles for electrically-conductive and redox-active porous organic framework materials towards achieving sustainable semiconductor and energy storage technologies. By pursuing a holistic experimental and theoretical understanding of fundamental properties, this project will adopt a “model–make–measure” approach via oversight of a single, well-trained SusMat0 PhD researcher led by an expert supervisory team across Chemistry (Avestro) and the School of Physics, Engineering and Technology (McKenna) at the University of York. By positioning the PhD researcher strategically at the heart of both experimental and theoretical activities, we maximise their project oversight and eliminate communication barriers that can hamper traditional cross-disciplinary collaborations between theoretical physicists and experimental chemists, thereby facilitating the vision and potential for research impact.
The ideal candidate for this project will have a mixed interest and background in primarily areas of Chemistry, though Physics candidates with appropriate experience working with functional organic and/or hybrid nanomaterials will also be considered. Skills will involve organic synthesis (to prepare and characterise PCP/MOF ligands), solid-state spectroscopy, microscopy, X-ray diffraction or other materials analysis techniques (to analysis PCP/MOF materials), and DFT and computational modelling (to model PCP/MOF structures for electronic and conductivity properties).
In Year 1, they will immediately undertake training in both Departments to design, prepare and model electrically conductive PCPs/MOFs comprising electrochemically active organic ligands based on well-established aromatic diimide charge acceptors combined with conductive transition metals like Fe, Cu, Co, Mn, Ni, Zn. A central activity of this PhD will be the creative design and synthesis of novel redox-active organic ligands to probe hypotheses regarding the structure porous 3D semiconductor materials — thus, a strength in organic chemistry is essential. Owing to their insolubilities, PCPs/MOFs will be characterised primarily using materials analysis methods such as surface area/porosity analysis (BET), thermal stability analysis (TGA/STA), solid-state NMR, X-ray diffraction (PXRD, SCXRD, microED) and electron microscopy. First-principles modelling approaches will enable the student to identify the predominant conductivity pathways at the molecular/nanoscopic levels for MOFs being simultaneously prepared and optimised. With X-ray results in hand, the student will also utilise Hirschfeld analysis to confirm intramolecular through-space interactions that may be correlated to its structural stability and/or conductivity properties.
As novel materials are generated, first-principles modelling will become further useful in Years 2–3 for correlating grain boundary influence on bulk properties, as determined experimentally by electron microscopy (JEOL Nanocentre), materials analysis (Green Chemistry) thin-film X-ray diffraction (Chemistry), and two-point probe conductivity and battery device testing (Chemistry). Promising project materials to be integrated within rechargeable batteries and electrochemical devices, utilising the expertise of the lead supervisor. As a result, the PhD researcher will gain a broad and diverse skill set in materials synthesis, physical and electronic properties characterisation, device fabrication and testing, and theoretical modelling of intrinsic conduction pathways. This concerted cross-disciplinary effort will ultimately aid our ability to overcome the current limitations in conductive MOF research, raising the probability of innovation in sustainable energy technologies from York.
The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. The Department strives to provide a working environment which allows all staff and students to contribute fully, to flourish, and to excel: https://www.york.ac.uk/chemistry/ed/.
For more information about the project, click on the supervisor's name above to email the supervisor. For more information about the application process or funding, please click on email institution
This PhD will formally start on 1 October 2023. Induction activities may start a few days earlier.
You should hold or expect to achieve the equivalent of at least a UK upper second class degree in Chemistry or a related subject. Please check the entry requirements for your country: https://www.york.ac.uk/study/international/your-country/
We will also consider applicants with a Masters in a closely related field, applicants who have relevant industry experience, and applicants with a BSc at 2:1 or above where sufficient relevant experience can be demonstrated.
To apply for this project, submit an online PhD in Chemistry application: https://www.york.ac.uk/study/postgraduate/courses/apply?course=DRPCHESCHE3
On the postgraduate application form, please select 'CDT in Sustainable Materials for Net Zero' as your source of funding. You do not need to provide a research proposal, just enter the name of the project you wish to apply for. The deadline for applications is 21 July 2023 although applications may close early if a suitable candidate is found.
Shortlisted candidates will be progressed to interview.
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