Using nature's resources more effectively is a central tenet of sustainability. While the carbon-based resources upon which many of our industries rely have been sourced from fossil reserves, there is a crucial need to move towards clean energy. As part of this energy transition and looking ahead to the future, we need to 'close the carbon cycle' and create a circular economy by recycling and reusing the carbon already 'in play'. Our industries thus need to move to Net Zero Emissions. When carbon is permanently removed from the carbon cycle, Negative Emissions are created - see more about the work of our Sydney Sustainable Carbon team with industry partner Southern Green Gas. Read our recent articles for The Conversation (article 1, 2).

In our Carbon Capture, Use & Conversion project, we investigate the development of more efficient processes for carbon removals, use and conversion which are considered a key to the reduction of atmospheric carbon dioxide which has been implicated in global warming. The cornerstone of these projects is highly porous three-dimensional solids known as Metal-Organic Frameworks which have an enormous capacity and selectivity for sorbing gases such as carbon dioxide.

Watch the You Tube video here: Mopping up Gases


The development of more efficient processes for carbon removals is considered key to the reduction of atmospheric carbon dioxide which has been implicated as a major cause of global warming. Highly porous three-dimensional solids known as Metal-Organic Frameworks (MOFs) will be developed for carbon removals and will be characterised using a barrage of techniques (X-ray and neutron diffraction, thermogravimetric analysis and gas sorption measurements). The ultimate goal is the development of industrially-viable materials which can be readily integrated into industrial processes.

While traditional methods for adsorbing carbon dioxide in nanoporous materials such as MOFs rely on physisorption or chemisorption mechanisms, we are particularly interested in relatively less well-studied electrochemical mechanisms. Here, a reversible electrochemical reaction in a molecule allows it to 'react' with carbon dioxide. The process is fully reversible, and potentially more highly selective and efficient than the aforementioned processes.


Carbon dioxide is an important feedstock with uses ranging from accelerating algae growth to the synthesis of polymers and the manufacture of concrete. Carbon dioxide can also be converted into a range of other important feedstocks; however, doing so requires a significant energy input. To provide this energy, light or electricity can be used in processes called photo- or electro-catalysis. Over the past decade, we have been investigating the design of MOFs that incorporate photo- and electro-catalytically active centres.


(1) MOFs based on Electrochemical Swing Carbon Removal

(2) 3D Printed MOFs for Electrocatalytic Conversion of Carbon Dioxide

(3) Direct Air Capture: Removal of carbon dioxide from air as a Negative Emissions Technology


Our team's research has made inroads to new technologies that reduce the energy penalties associated with CO2 capture from large point sources. In work that commenced with Prof. Jeff Long at UC Berkeley, a major achievement was the first successful design and synthesis of air and water stable alkylamine-based MOFs for postcombustion CO2 capture. We hold an international patent on new capture materials with colleagues at UC Berkeley (PCT/WO2013/059527) and have published a number of highly cited critical reviews. Our team's research has continued to make inroads to this area within Australia, including in the development of redox-active MOFs and porous organic polymers (POPs) with stable radical states, where CO2 can be selectively sorbed as the redox state of the material is varied. We played a major role in a highly collaborative 5-year project which was granted $6M by the Science & Industry Endowment Fund in 2011, enabling the development of novel adsorbents for the capture and utilisation of CO2.

Our recent work has involved the development of MOFs for Negative Emissions Technologies that involve carbon removal from ambient air. Over the past 3 years we have built a partnership with Australian renewables start-up Southern Green Gas Ltd., with whom we are developing materials for direct capture of carbon dioxide from air. This work has significant potential environmental impact in reducing atmospheric carbon dioxide levels. In addition to a number of invited presentations, our research has also resulted in presentations to school students and the general public, as well as publications we have written to engage the public in discussion on carbon capture (e.g., our recent article for The Conversation). Further key achievements include:

  • Publication of critical review articles in the field, including an authoritative article on new materials for CO2 capture technologies which has received over 3500 citations to date.

  • The first spiropyran-functionalised MOF has been developed as a new material for light-induced gas separations processes. The new zirconium MOF was found to be more robust than those typically reported in the literature (based on azobenzenes) for light-activated processes, and the physical properties including the surface area, pore volume and CO2 uptake were dependent on the isomerisation state of the spiropyran.

  • The activation of CO2 for reduction to higher energy commodity chemicals represents a long-standing challenge. Our group has started to tackle this problem through the strategic development of MOFs and POPs incorporating transition metal photo- and electrocatalysts such as [Re(dcbpy)(CO)3Cl] {dcbpy = 5,5'-dicarbonyl-2,2'-bipyridine} and salen-based metalloligands. Our initial work focused on tuning the optical bandgap of a series of zirconium-based MOFs into the visible region of the electromagnetic spectrum. This underpins the future examination of these materials as tunable bandgap photocatalysts for CO2 reduction.


Press & You Tube Presentations


“Carbon Dioxide Capture via Alkylamine Functionalized Metal-Organic Frameworks,” J.R. Long, D. M. D'Alessandro, T. McDonald, PCT WO 2013/059527 Published 25 April 2013; US 10,137,430 B2 Published 27 November 2018. See the review in Chemical & Engineering News at

“Multi-stimuli Responsive Metal-Organic Frameworks,” D.A. Sherman, R. Murase, Q. Gu, E. Kearns, L. Hall, D. M. D'Alessandro, The University of Sydney, PCT/AU2021/050527, Filed 28 May 2021.

Book Chapters

1. V. K. Peterson, A. Das and D. M. D'Alessandro, "CO2 Separation, Capture and Storage in Porous Materials", in Neutron Applications in Materials for Energy, Ed. G.J. Kearley and V.K. Peterson, Springer International Publishing, Switzerland, pp. 33-60 (2015).

Peer-Reviewed Journal Articles (total 4742 citations at 29 September 2021)

2. P. W. Doheny, R. Babarao, C. J. Kepert and D. M. D'Alessandro, "Tuneable CO2 Binding Enthalpies by Redox Modulation of an Electroactive MOF-74 Framework", 2021, Materials Advances, accepted 8/2/2021.

3. B. Ding, B. Chan, N. Proschogo, M. B. Solomon, C. J. Kepert and D. M. D'Alessandro, "A Cofacial Metal-Organic Framework Based Photocathode for Carbon Dioxide Reduction", Chemical Science, 2021, DOI: 10.1039/D0SC04691D.

4. M. B. Solomon, T. L. Church and D. M. D'Alessandro, "Perspectives on metal-organic frameworks with intrinsic electrocatalytic activity", CrystEngComm, 2017, 19, 4049-4065. {Front Cover, Invited contribution in special edition on MOFs for Catalysis}

5. W. B. Liang, C. J. Coghlan, F. Ragon, M. Rubio-Martinez, D. M. D'Alessandro and R. Babarao, "Defect engineering of UiO-66 for CO2 and H2O uptake - a combined experimental and simulation study", Dalton Transactions, 2016, 45, 4496-4500.

6. K. Healey, W. B. Liang, P. D. Southon, T. L. Church and D. M. D'Alessandro, "Photoresponsive spiropyran-functionalised MOF-808: postsynthetic incorporation and light dependent gas adsorption properties", Journal of Materials Chemistry A, 2016, 4, 10816-10819. {Selected as a ‘Hot paper’ for 2016}

7. A. Das and D. M. D'Alessandro, "A linear fluorescence-quenching response in an amidine-functionalised solid-state sensor for gas-phase and aqueous CO2 detection", Dalton Transactions, 2016, 45, 6824-6829.

8. W. B. Liang, T. L. Church, S. S. Zheng, C. L. Zhou, B. S. Haynes and D. M. D'Alessandro, "Site Isolation Leads to Stable Photocatalytic Reduction of CO2 over a Rhenium-Based Catalyst", Chemistry-a European Journal, 2015, 21, 18576-18579.

9. W. B. Liang, R. Babarao, T. L. Church and D. M. D'Alessandro, "Tuning the cavities of zirconium-based MIL-140 frameworks to modulate CO2 adsorption", Chemical Communications, 2015, 51, 11286-11289.

10. S. Kanehashi, G. Q. Chen, C. A. Scholes, B. Ozcelik, C. Hua, L. Ciddor, P. D. Southon, D. M. D'Alessandro and S. E. Kentish, "Enhancing gas permeability in mixed matrix membranes through tuning the nanoparticle properties", Journal of Membrane Science, 2015, 482, 49-55.

11. A. Das and D. M. D'Alessandro, "Tuning the functional sites in metal-organic frameworks to modulate CO2 heats of adsorption", CrystEngComm, 2015, 17, 706-718. {Invited contribution; Front cover}

12. H. Chevreau, W. B. Liang, G. J. Kearley, S. G. Duyker, D. M. D'Alessandro and V. K. Peterson, "Concentration-Dependent Binding of CO2 and CD4 in UiO-66(Zr)", Journal of Physical Chemistry C, 2015, 119, 6980-6987.

13. M. J. Murphy, D. M. D'Alessandro and C. J. Kepert, "A porous Mn(v) coordination framework with PtS topology: assessment of the influence of a terminal nitride on CO2 sorption", Dalton Transactions, 2013, 42, 13308-13310.

14. C. F. Leong, T. B. Faust, P. Turner, P. M. Usov, C. J. Kepert, R. Babarao, A. W. Thornton and D. M. D'Alessandro, "Enhancing selective CO2 adsorption via chemical reduction of a redox-active metal-organic framework", Dalton Transactions, 2013, 42, 9831-9839. {Front Cover; Top 10 most accessed articles in March 2013}

15. A. Das, M. Choucair, P. D. Southon, J. A. Mason, M. Zhao, C. J. Kepert, A. T. Harris and D. M. D'Alessandro, "Application of the piperazine-grafted CuBTTri metal-organic framework in postcombustion carbon dioxide capture", Microporous and Mesoporous Materials, 2013, 174, 74-80.

16. A. Das, P. D. Southon, M. Zhao, C. J. Kepert, A. T. Harris and D. M. D'Alessandro, "Carbon dioxide adsorption by physisorption and chemisorption interactions in piperazine-grafted Ni2(dobdc) (dobdc=1,4-dioxido-2,5-benzenedicarboxylate)", Dalton Transactions, 2012, 41, 11739-11744.

17. T. M. McDonald, D. M. D'Alessandro, R. Krishna and J. R. Long, "Enhanced carbon dioxide capture upon incorporation of N,N '-dimethylethylenediamine in the metal-organic framework CuBTTri", Chemical Science, 2011, 2, 2022-2028.

18. D. M. D'Alessandro and T. McDonald, "Toward carbon dioxide capture using nanoporous materials", Pure and Applied Chemistry, 2011, 83, 57-66.

19. D. M. D'Alessandro, B. Smit and J. R. Long, "Carbon Dioxide Capture: Prospects for New Materials", Angewandte Chemie-International Edition, 2010, 49, 6058-6082.

20. A. Demessence, D. M. D'Alessandro, M. L. Foo and J. R. Long, "Strong CO2 Binding in a Water-Stable, Triazolate-Bridged Metal-Organic Framework Functionalized with Ethylenediamine", Journal of the American Chemical Society, 2009, 131, 8784.