In the field of material chemistry, it is of great significance to develop abundant and sustainable materials for solar energy harvesting and management. Herein, after evaluating the energy band characteristics of 13 kinds of polyoxometalates (POMs), the trisubstituted POM compound K6H4[α-SiW9O37Co3(H2O)3]·17H2O (SiW9Co3) was first studied due to its relatively smaller band gap (2.23 eV) and higher lowest unoccupied molecular orbital (LUMO) level (-0.63 V vs NHE). Additionally, the preliminary computational modeling indicated that SiW9Co3 exhibited the donor-acceptor (D-A) structure, in which the cobalt oxygen clusters and tungsten skeletons act as the electron donor and electron acceptor, respectively. By employing SiW9Co3 to modify the TiO2 film, the visible photovoltaic and photocurrent response were both enhanced, and the light-induced photocurrent at 420 nm was improved by 7.1 times. Moreover, the highly dispersive and small sized SiW9Co3 nanoclusters loading on TiO2 were successfully achieved by fabricating the nanocomposite film of {TiO2/SiW9Co3}3 with the layer-by-layer method, which can result in the photovoltaic performance enhancement of dye-sensitized solar cells (DSSCs), of which the overall power conversion efficiency was improved by 25.6% from 6.79% to 8.53% through the synergistic effect of POMs and Ru-complex.

Three new inorganic-organic hybrid compounds based on Strandberg-type anions and Zn(ii)-H2biim/H2O subunits, namely {H4(H2biim)3}[Zn(H2biim)(H3biim)(H2O)(HP2Mo5O23)]2·3H2O (1), {H9(H2biim)7}[(μ-biim){(Zn(H2O)2)0.5(HP2Mo5O23)}2]·7H2O (2) and {H7(H2biim)7}[Zn(H2biim)(H2O)2(HP2Mo5O23)][H2P2Mo5O23]·8H2O (3) (H2biim = 2,2'-biimidazole), have been synthesized in aqueous solutions and characterized. They were also used as efficient and reusable catalysts for the protection of carbonyl compounds. Their fascinating structural features are that mono Zn(ii)-supporting biphosphopentamolybdate ({P2Mo5}) clusters exist in their crystal structures, and the nitrogen donor ligand H2biim exhibits three different coordination modes in these three compounds, respectively: for 1, two 2,2'-biimidazole molecules, as mono- and bidentate ligands coordinate to the same Zn(ii) ion; for 2, one bi-negative tetradentate ligand μ-biim bridges two Zn(ii) ions, while for 3, one neutral bidentate H2biim ligand links one Zn(ii) ion. Most importantly, compounds 1-3 represent the first example where Strandberg-type POMs are used as acid-catalysts in an organic reaction.

A novel sandwich-type germanotungstate [C(NH2)3]10[Mn2{Sn(CH2)2COOH}2(B-α-GeW9O34)2]·8H2O (1) represents the first single crystalline polyoxometalate (POM) functionalized by open chain carboxyethyltin, which was designed and synthesized in aqueous solution and applied to a dye-sensitized solar cell (DSSC) for the first time. Its photosensitivity was explored through a fluorescence spectrum (FL), surface photovoltage spectrum (SPV), electrochemical method, and solid diffuse spectrum. 1 displays the primary features of sensitizers in DSSCs, and the efficiency of the solar cell is 0.22%. Delightedly, when 1 was employed to assemble a cosensitized solar cell configuration by preparing a 1-doped TiO2 electrode and additionally adsorbing N719 dyes, a considerably improved efficiency was achieved through increasing spectral absorption and accelerating electron transport, which is 19.4% higher than that of single N719 sensitization. This result opens up a new way to position different dyes on a single TiO2 film for cosensitization.

Highly dispersed and small sized POM nanoclusters that were fabricated using MOF materials can result in a significant performance enhancement of QDSCs.