Iron polypyridyl catalysts assembled on metal oxide semiconductors for photocatalytic hydrogen generation

Abstract

A series of Fe(iii) complexes was recently reported that are active for photocatalytic hydrogen generation when paired with fluorescein and triethylamine. Herein we report an Fe(iii) complex immobilized on TiO2 and SrTiO3 that is significantly more active than the homogeneous system, achieving up to 7800 turnovers in 31 hours.

Computational investigation into intramolecular hydrogen bonding controlling the isomer formation and pKa of octahedral nickel(ii) proton reduction catalysts

“…Homogeneous catalysts based on earth-abundant metals have been shown to be efficient in converting protons to hydrogen gas. [21][22][23][24][25][26][27][28][29][30][31][32][33][34] This work examines the computationally derived structures involved in the catalytic cycle for hydrogen production by tris-( pyridinethiolato)nickel(II), often reported as nickel(II) tris-( pyridinethiolate), [Ni(PyS) 3 ] − , and its derivatives, originally developed by Eisenberg and co-workers. 22,33 The catalytic cycle has been proposed to proceed through a CECE (Chemical-Electrochemical-Chemical-Electrochemical) mechanism, starting with protonation of one of the pyridyl N atoms (Fig.…”

Rational development of molecular earth-abundant metal complexes for electrocatalytic hydrogen production

“…The reorganization energies at different redox states are minimized so that the free energies of the catalytic intermediates are nearly the same, allowing catalytic HER to occur at nearly thermodynamic potentials [20]. Inspired by H2ases, a considerable number of metal catalysts based on Co , Ni , Fe [71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89], Cu [90][91][92], and Mo [93][94][95][96][97] have been developed for electro-and photocatalytic HER [98][99][100][101][102][103][104]. Catalytic systems utilizing metalloproteins or metallopolymers have also been reported for H2 production [81,[105][106][107][108][109][110][111][112].…”