Congreso de Química CR24: Química, una solución para cambios globales

Transcript

1. Strategies to boost electrical conductivity in porous materials: a computational perspective
2. Zn(II), Zr(IV) ⇒ d0 MOF-5 Physical and chemical processes: Gas adsorption & separation, catalysis Electro-inactive porous materials
3. Electroactivation
4. Electroactivation Sensors Photocatalysis Electrocatalysis Batteries Supercapacitors
5. Computational materials design in a nutshell Methodologies Density Functional Theory High-correlated methods Semiempirical methods Molecular Mechanics Big-data Science Properties Geometry Electronic structure REDOX and magnetism Excited states Charge and energy transport
6. Hydrogen-bonded Organic Frameworks H4 TTFTB MUV-20a MUV-20b MUV-21 σ = 6.07 × 10–7 S cm–1 σ = 1.35 × 10–6 S cm–1 σ = 6.23 × 10–9 S cm–1 Guillermo Mínguez (UV) María Vicent (UV)
7. Hydrogen-bonded Organic Frameworks H4 TTFTB MUV-20a MUV-20b MUV-21 σ = 6.07 × 10–7 S cm–1 σ = 1.35 × 10–6 S cm–1 σ = 6.23 × 10–9 S cm–1
8. Hydrogen-bonded Organic Frameworks EPR MUV-20a MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation non-radical
9. Hydrogen-bonded Organic Frameworks EPR MUV-20a MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation non-radical + ‒
10. Hydrogen-bonded Organic Frameworks vacuum dielectric continuum SPIN DENSITY EPR MUV-20a MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation non-radical + ‒
11. Hydrogen-bonded Organic Frameworks vacuum dielectric continuum SPIN DENSITY EPR MUV-20a MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation SPIN DENSITY accumulated charge non-radical + ‒
12. Perylene-based MOFs Perylene
13. Perylene-based MOFs Manel Souto (UA) Gonçalo Valente (UA) Perylene K+ PTC 8.6 Å Per-MOF Mol. Syst. Des. Eng., 2022,7, 1065-1072 σ = 10‒8 S·cm‒1
14. Perylene-based MOFs Manel Souto (UA) Gonçalo Valente (UA) σ = 10‒8 S·cm‒1 Iodine doping Perylene K+ PTC 8.6 Å Per-MOF Mol. Syst. Des. Eng., 2022,7, 1065-1072 Distances in Å
15. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱 = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV Perylene-based MOFs
16. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱 = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV Perylene-based MOFs
17. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱 = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV I3 Spin density Perylene-based MOFs
18. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱 = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV I3 Spin density Perylene-based MOFs Per-MOF: σ = 10‒8 S·cm‒1 I2 -doped Per-MOF: σ = 10‒5 S·cm‒1
19. Iron-based MOFs Chem. Sci., 2017, 8, 4450–4457 Mixed-valency Fe(II)/Fe(III)
20. Iron-based MOFs Chem. Sci., 2017, 8, 4450–4457 Mixed-valency Fe(II)/Fe(III) Fe2 (BDT)3 J. Am. Chem. Soc. 2018, 140, 7411–7414 Fe(II) σ = 10–4 – 1.8 S/cm
21. N N N NH N N N HN H2 BDT Iron-based MOFs BDT2– Fe(II) Fe2 (H0.67 BDT)3 (II) (2–) MOF-2 MOF-3 MOF-1
22. Fe2 (BDT)3 Protonated Deprotonated MOF-1 (Cmmm)
23. Fe2 (BDT)3 Protonated Deprotonated 1.45 0.49 Bandgap: ca. 2 eV 2.52 MOF-1 (Cmmm)
24. Fe2 (BDT)3 Protonated 1.45 80.31 Γ to Z direction VB T to Z direction CB hole transport electron transport Deprotonated MOF-1 (Cmmm)
25. Fe2 (BDT)3 Protonated 1.45 80.31 Γ to Z direction VB T to Z direction CB hole transport electron transport Deprotonated Charge transport pathways MOF-1 (Cmmm)
26. Fe2 (BDT)3 Deprotonated MOF-2 (Fddd) 1.44 0.75 all flat Bandgap: ca. 3.1 eV
27. Fe2 (BDT)3 1.45 80.31 Γ to Z direction VB CB hole transport electron transport Deprotonated Protonated directions MOF-2 (Fddd)
28. Fe2 (BDT)3 1.45 80.31 Γ to Z direction VB CB hole transport electron transport Deprotonated Protonated directions Charge transport pathways MOF-2 (Fddd)
29. Fe2 (BDT)3 MOF-3 (R-3m) Random distribution of protonated ligands 2.46 2.43 2.96 2.46 all flat Bandgap: ca. 2.2 eV
30. Fe2 (BDT)3 1.45 80.31 VB CB hole transport electron transport Random distribution of protonated ligands MOF-3 (R-3m)
31. Fe2 (BDT)3 1.45 80.31 VB CB hole transport electron transport Charge transport pathways Random distribution of protonated ligands h+ MOF-3 (R-3m)
32. Conclusions  Cooperation between experiments and theoretical modelling allows boosting the development of electrically conducting porous materials.  Strategies to enhance conductivity in porous frameworks: o Zwitterion species in a π-stacked assembly o Electroactive guests (charge transfer and carrier formation) o Mixed-valence and appropriate protonation pattern
33. Conclusions  Cooperation between experiments and theoretical modelling allows boosting the development of electrically conducting porous materials.  Strategies to enhance conductivity in porous frameworks: o Zwitterion species in a π-stacked assembly o Electroactive guests (charge transfer and carrier formation) o Mixed-valence and appropriate protonation pattern
34. Guillermo Mínguez (UV) Acknowledgements Manel Souto (UA) María Esteve PID2020-119748GA-I00 funded by MCIN/AEI/10.13039/501100011033
35. Guillermo Mínguez (UV) Acknowledgements Manel Souto (UA) María Esteve PID2020-119748GA-I00 funded by MCIN/AEI/10.13039/501100011033