Efficient photocatalytic H2 evolution catalyzed by an unprecedented robust molecular semiconductor {Fe11} nanocluster without cocatalysts at neutral conditions

Ordered Mesoporous Polyoxometalate–Organosilica Frameworks as Efficient Photocatalysts of the Hydrogen Evolution Reaction

“…Of particular note, the H 2 evolution activity of SiW 11 /MES was comparably higher than that obtained for [{Ni 4 (OH) 3 AsO 4 } 4 ( B ‐α‐PW 9 O 34 )4] 28− (2.88 μmol h −1 , TOF=72 h −1 ), [Mn 4 (H 2 O) 2 (VW 9 O 34 ) 2 ] 10− (0.35 μmol h −1 , TOF=7.6 h −1 ), Pt‐loaded K 11 H[Sn 4 (SiW 9 O 34 ) 2 ] (0.43 μmol h −1 , TOF=0.025 h −1 ), and [Ni(H 2 O)GeW 11 O 39 ] 6− (1.4 μmol h −1 , TOF=31 h −1 ) complexes, and is comparable to the activity achieved with Pt‐loaded K 7 [Co III Co II (H 2 O)W 11 O 39 ] (171.4 μmol h −1 , TOF=42.8 h −1 ), Ni 2+ ‐substituted Na 8 HPW 9 O 34 (234 μmol h −1 , TOF=5 h −1 ), and Na 27 [Fe 11 (H 2 O) 14 (OH) 2 (W 3 O 10 ) 2 (α‐SbW 9 O 33 ) 6 ] (78 μmol h −1 , TOF=13 h −1 ) compounds and Cs 3 [PW 11 O 39 {cis‐Pt(NH 3 ) 2 } 2 ]/TiO 2 (P25) (28.5 μmol h −1 , TOF=71 h −1 ) composite materials. However, most of these previous studies involved the use of either precious metals as co‐catalysts, such as Pt, or additional photosensitizers, such as [Ru(bpy) 3 ] 2+ and [Ir(ppy) 2 (dtbbpy)] + (ppy=2‐phenylpyridine, dtbbpy=5,5′‐di‐ tert ‐butyl‐2,2′‐bipyridine) complexes and fluorescein and Eosin Y dyes.…”

Recent Advances in First‐Row Transition Metal Clusters for Photocatalytic Water Splitting

“…Song et al . reported a molecular cluster of Na 27 [Fe 11 (H 2 O) 14 (OH) 2 (W 3 O 10 ) 2 (α‐SbW 9 O 33 ) 6 ] (Figure ) . The cluster was constructed by six [α‐SbW 9 O 33 ] 9− and a [Fe 11 (H 2 O) 14 (OH) 2 (W 3 O 10 ) 2 ] 27+ cluster unit.…”

“… Polyhedral and ball‐and‐stick view of [Fe 11 (H 2 O) 14 (OH) 2 (W 3 O 10 ) 2 (α‐SbW 9 O 33 ) 6 ] 27− . Color Code: Fe, green; Sb, black; O, red.…”

Efficient photocatalytic water oxidation catalyzed by polyoxometalate [Fe11(H2O)14(OH)2(W3O10)2(α-SbW9O33)6]27− based on abundant metals

“…Quantum mechanical calculations were also employed to obtain the electronic properties of 1. The calculated energies 11 for the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are -7.05 and -5.70 eV, respectively. The HOMO-LUMO energy gap is 6 ]·85H 2 O < compound 1.…”