Mechanistic insights into photocatalysis and over two days of stable H₂ generation in electrocatalysis by a molecular cobalt catalyst immobilized on TiO₂

Abstract

Molecular and heterogeneous water reduction combined: Over 2 days of electrocatalysis of a cobalt polypyridyl catalyst immobilized on TiO2.

Charge accumulation kinetics in multi-redox molecular catalysts immobilised on TiO2

“… 5,6 Using natural photosynthesis as a blueprint, in artificial photosynthesis employing photo(electro)chemical devices for solar energy conversion and storage, there is an increasing interest in the use of light absorbing molecules or semiconductors coupled to molecular catalysts, as they provide a unique and tuneable active site that can also be mechanistically investigated. 7–10 In these systems, much progress has been made in understanding and optimising light absorption and charge separation, 11–15 but rather little is known about the mechanism of function of the catalysts within such systems. 16–21 …”

“…5,6 Using natural photosynthesis as a blueprint, in articial photosynthesis employing photo(electro)chemical devices for solar energy conversion and storage, there is an increasing interest in the use of light absorbing molecules or semiconductors coupled to molecular catalysts, as they provide a unique and tuneable active site that can also be mechanistically investigated. [7][8][9][10] In these systems, much progress has been made in understanding and optimising light absorption and charge separation, [11][12][13][14][15] but rather little is known about the mechanism of function of the catalysts within such systems. [16][17][18][19][20][21] The mechanism of catalysts in articial photosynthetic devices is usually not well understood, in particular because of the difficulty in characterising the reactive intermediates involved and the kinetics of the individual steps of the catalytic mechanism.…”

Cobalt Complexes of Polypyridyl Ligands for the Photocatalytic Hydrogen Evolution Reaction

“…Synthesis of a di-phosphonated pyrphyrin ligand and its cobalt complex. [36] (H 2 Q) were investigated as excited state quenchers. [37] However, it was rather difficult at that time to incorporate quinone-based relays in an artificial system.…”

About Control: Kinetics in Molecule- based Photochemical Water Reduction Investigated by Transient IR Spectroscopy

“…[9,33,[44][45][46] Immobilization of only the PS or the WRC on a surface has been explored as well. [47,48] An example for a semi-heterogeneous model system is shown in Fig. 1, right, [49] with ZrO 2 as redox-inactive substrate.…”