Maalaoui Ahlem, Toumi Baya, Agwamba Ernest C, Okon Gideon A, Rzaigui Mohamed, Akriche Samah
Laboratory of Chemical Materials LR13ES08, Faculty of Sciences of Bizerte, Carthage University, Zarzouna, Bizerte 7021, Tunisia.
Laboratoire des Ressources en Eau et Environnement, INRAP Technopole, Sidi Thabet 2020, Ariana-Tunis.
ACS Omega. 2024 Aug 28;9(36):38066-38079. doi: 10.1021/acsomega.4c05150. eCollection 2024 Sep 10.
In this paper, we employ density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches to predict the solvatochromism and light-harvesting properties of a newly synthesized hybrid hexamine () vanadium-substituted Lindqvist-type ( ) polyoxometalate (POM), (CHNO)(CHN)[VWO]·6HO, ( ) for application in dye-sensitized solar cells (DSSCs). Single crystal X-ray diffraction (XRD) and noncovalent interaction (NCI) analyses show a 3D-supramolecular packing stabilized by means of hydrogen bonds and van der Waals (vdW) and ionic interactions between highly nucleophilic cage-like surfactant, lattice water, and electrophilic polyanions. Experimental and theoretical UV/vis absorption spectra show large absorption in the visible region, which is strongly solvent polarity dependent. This solvatochromic behavior can be attributed to hydrogen bonding interactions between the polyanion and protic solvents. Furthermore, the energy level of semiconductor-like nature of with high LUMO level matches well with the conduction band (CB) of TiO, which is beneficial for the photovoltaic device performance. The photovoltaic empirical parameters are theoretically predicted to demonstrate a remarkably high open-circuit voltage (Voc) value (1.805 eV) and a photoelectric conversion efficiency (PCE) value up to 8.7% (FF = 0.88) along with superior light-harvesting efficiency (LHE) (0.7921), and therefore, the studied compound is expected to be a potential candidate as a photosensitizer dye for applications in DSSCs. The aim of this work was to broaden the range of applications of POMs, owing to their low-cost fabrication, leveraging and flourishing optoelectronic properties, and ever-improving efficiency and stability for use in future technology pointed to the development of clean and green renewable energy sources to solve the current energy crisis.
在本文中，我们采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）方法来预测一种新合成的杂化六胺（）钒取代的Lindqvist型（）多金属氧酸盐（POM），即(CHNO)(CHN)[VWO]·6HO，（）在染料敏化太阳能电池（DSSC）中的溶剂化显色和光捕获特性。单晶X射线衍射（XRD）和非共价相互作用（NCI）分析表明，通过高亲核性笼状表面活性剂、晶格水和亲电多阴离子之间的氢键、范德华（vdW）和离子相互作用，形成了三维超分子堆积。实验和理论紫外/可见吸收光谱表明，在可见光区域有较大吸收，且强烈依赖于溶剂极性。这种溶剂化显色行为可归因于多阴离子与质子溶剂之间的氢键相互作用。此外，具有高LUMO能级的类半导体性质的能级与TiO的导带（CB）匹配良好，这有利于光伏器件性能。理论预测的光伏经验参数显示出非常高的开路电压（Voc）值（1.805 eV）和高达8.7%的光电转换效率（PCE）值（填充因子FF = 0.88）以及优异的光捕获效率（LHE）（0.7921），因此，所研究的化合物有望成为用于DSSC的潜在光敏染料候选物。这项工作的目的是拓宽POMs的应用范围，这是由于它们低成本制造、利用和蓬勃发展的光电特性，以及在未来技术中不断提高的效率和稳定性，这些都指向了开发清洁和绿色可再生能源以解决当前能源危机。
