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

Abstract

An eleven iron-containing nanoscale inorganic polyanionic oxide cluster was reported as the first example for exceptional photocatalytic water oxidation. Under optimal conditions, a remarkable turn-over number (TON) of 1815 ± 50 and a turn-over frequency (TOF(initial)) of 6.3 s(-1) over were achieved for water oxidation.

Catalysts Based on Earth‐Abundant Metals for Visible Light‐Driven Water Oxidation Reaction

“…We designed and obtained a novel Fe‐based POM [Fe 11 (H 2 O) 14 (OH) 2 (W 3 O 10 ) 2 (α‐SbW 9 O 33 ) 6 ] 27− ( 4 ) as photocatalytic WOC in 2015 . This POM possesses multiple intriguing structural feature.…”

Homogeneous and Heterogeneous Photocatalytic Water Oxidation by Persulfate

“…The initial reaction rate of 7.9 mmol min −1 (the oxygen evolution rate in the first 60 s of light illumination) and TOF initial (TON 1 min/60 s) of 6.3 s −1 in the photocatalytic oxidation with the Fe‐POM are the largest among the data in Table . The quantum yield [(initial O 2 formation rate)/(photon flux)] of 47 % is also the highest value ever reported for the homogeneous photocatalytic water oxidation because the quantum yield of 50 % corresponds to 100 % quantum efficiency (two photons are required to produce four equivalents of [Ru(bpy) 3 ] 3+ , which oxidize water to O 2 with WOC) . Isotope‐labeling water oxidation experiments using 18 O‐enriched water instead of H 2 16 O demonstrated that the evolved oxygen comes from water‐derived oxygen atoms .…”

“…[ www.chemasianj.org quantum yield [(initialO 2 formation rate)/(photonflux)] of 47 % is also the highest value ever reportedf or the homogeneous photocatalytic water oxidation because the quantum yield of 50 %c orresponds to 100 %q uantum efficiency (two photons are required to produce four equivalents of [Ru(bpy) 3 ] 3 + ,w hich oxidize water to O 2 with WOC). [41] Isotope-labeling water oxidation experiments using 18 O-enriched water instead of H 2 16 O demonstrated that the evolved oxygen comesf rom water-derived oxygen atoms. [41] In catalytic water oxidation, homogene-ous metal complexes are often claimed as precatalysts,w hich decompose under oxidizing conditions to insoluble metal oxides that are the real catalysts as discussed in the next section.…”

Crystal structure of poly-[tetraaquabis(μ8-benzene-1,2,4,5-tetracarboxylato-1κ3 O 4:O 6:O 8:2κ4 O 2:O 2:O 5:O 5:3κ4 O 1:O<

“…[1][2][3][4][5][6]. The most e ective and facile approach for constructing new CPs is the judicious choice of various organic linkers such as benzenecarboxylates and N-donor ligands.…”