title: Enhanced Visible Photovoltaic Response of TiO₂ Thin Film with an All-Inorganic Donor-Acceptor Type Polyoxometalate.
abstract: 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.
authors.affiliation: †Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
authors.forename: Jian-Sheng
authors.initials: JS
authors.lastname: Li
authors.affiliation: †Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
authors.forename: Xiao-Jing
authors.initials: XJ
authors.lastname: Sang
authors.affiliation: †Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
authors.forename: Wei-Lin
authors.initials: WL
authors.lastname: Chen
authors.affiliation: ‡School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China.
authors.forename: Lan-Cui
authors.initials: LC
authors.lastname: Zhang
authors.affiliation: ‡School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China.
authors.forename: Zai-Ming
authors.initials: ZM
authors.lastname: Zhu
authors.affiliation: †Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
authors.forename: Teng-Ying
authors.initials: TY
authors.lastname: Ma
authors.affiliation: †Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
authors.forename: Zhong-Min
authors.initials: ZM
authors.lastname: Su
authors.affiliation: †Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, China.
authors.forename: En-Bo
authors.initials: EB
authors.lastname: Wang
keywords: TiO2; donor−acceptor; photovoltaic; polyoxometalate; visible