Comparison of Penta and Tetra-pyridyl Cobalt-based Catalysts for Water Reduction: H2 Production Cycle, Solvent Response and Reduction Free Energy
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Tarih
2020
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Wiley-V C H Verlag Gmbh
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
Understanding water reduction towards H-2 generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H-2 production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H-2 production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H-2 production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H-2 production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV.
Açıklama
Anahtar Kelimeler
ab-initio molecular dynamics, cobalt-bipyridine-pyridine based catalysts, density functional theory, reduction free energy, water reduction
Kaynak
Chemphyschem
WoS Q Değeri
Q2
Scopus Q Değeri
Q2
Cilt
21
Sayı
24
