CISS efektu dun material kiralen sintesi eta karakterizazioa. Garapen iraunkorraren sustapena

Abstract

[EU] Lan honen helburua, kiraltasunak eragindako spin korronte polarizatuak (Ingelesetik, Chiral Induced Spin Selectivity, CISS) sortzeko gaitasuna duten sare metaloorganiko (ingelesetik, Metal Organic Framework, MOF) eroaleak garatzea da. Material berri hauek, uraren elektrolisiaren bidez erregai fosilen ordezkari den H2 erregaiaren ekoizpenerako beharrezkoa den gain-potentziala gutxitzea dute helburu; horretarako, zelda elektrokimikoaren elektrodoetako batean, lan honetan garatu nahi izan diren material ezorganiko berria estaliz. Garatu nahi izan den material ezorganikoa, elektrolisian zehar anodoan ematen den espin debekaturiko O2 tripletearen (3O2) sorreraren erreakzioaren energia beharrak murrizteko gaitasuna izan behar du. Horretarako, ikerkuntza taldean aurretik garaturiko eta CISS efektudun MOF kiral 3D baten (Dy-D-tar) hainbat ezaugarri hobetu nahi izan dira, eroankortasuna eta jasangarritasuna besteak beste. Eroankortasunari dagokionez, jatorrizko Dy(III)-dun MOF-aren ligando kirala (azido D-tartarikoa, D-tar) komertziala ez den azido D-2,3-dimerkaptosukzinikoarekin (D- DMSA) ordezkatu nahi izan da, aldez aurretik taldean egindako lan teoriko batek, aldaketa honek MOF-aren eroankortasuna hobetuko zuela aurre esan bait zuen. Jasangarritasunari dagokionez, jatorrizko MOF-aren Dy(III) metala Fe(III) metalarengatik aldatzen saiatu gara, aurrekoari isoestrukturala izango litzaiokeen Fe-D-tar MOF 3D sortu nahian. Lanaren erronka nagusia, komertziala ez den D-DMSA ligandoa sintetizatu eta karakterizatzea izan da, horretarako hainbat prozedura garatu behar izan direlarik. Baieztatzeke dagoen arren, eta D-DMSA ligandoa sortu delakoan, MOF isoestruktural berri bat sintetizatu ahal izan da. Honekin guztiarekin, gradu amaierako lan (GrAL) honek gizarteak orokorrean eta UPV/EHU-k bereziki, 2030 agendaren inguruan ezarri dituen Garapen Iraunkorreko Helburuen (GIH) lorpenerako aurrerapauso txiki bat izan nahi du. Bereziki hurrengo bi helburuen lerroan garatu da lan hau: 7. GIH. “Denontzako energia eskuragarria, segurua, iraunkorra eta modernoa bermatzea” eta 13. GHI. “Klima aldaketari eta haren ondorioei aurre egiteko premiazko neurriak hartzea”.

[EN] The objective of this work is to create from chirality polarized spin currents (CISS efect, Chiral Induced Spin Selectivity) electrically conductive metal-organic framework (MOF) materials. These new materials, through the electrolysis of water, will reduce the overpotential necessary for the creation of the fossil fuels substituent, H2; inserting this new inorganic material that has been developed in this work, in one of the electrochemical cells of the electrode. The material to be created must be able to reduce the energy barrier created by the spin forbidden reaction (SFR) of the triplet O2 (3O2) during the electrolysis in the anode. For this purpose, we wanted to improve some characteristics of a 3D chiral MOF with CISS effect (Dy-D-tar) previously created in the research group. The aim was to improve conductivity and sustainability, among others. Regarding the conductivity, we want to change the chiral ligand D-tartaric acid (D- tar) to the non-commercial ligand 2,3-dimercapto succinic acid (DMSA) in the original Dy(III) MOF, since a theoretical study previously performed in the group predicts that this change will improve the conductivity of the whole MOF network. In terms of sustainability, the parent compound has dysprosium (Dy) as a core metal, which is to be replaced by iron. Since this is not a Critical Raw Material (CRM), we want to create a material isostructural to the one described above, the Fe-D-tar. The main challenge of this work is to synthesize and characterize the non- commercial D-DMSA ligand, which will involve several processes. Although it is still to be confirmed, believing that D-DMSA has been synthesized, a new isostructural MOF based on this ligand has been obtained. With all this, this final degree project wants to make a small contribution to society in general, and to the UPV/EHU in particular, with regard to the objectives related to the 2030 agenda. In particular, the work has been developed with the following two objectives: 7. GIH. "Ensure available, safe, sustainable and modern energy for all". 13. GHI. "Urgent measures to face climate change and its consequences".