Li-Heng Han

A high conductive 2D COF polyporphyrin (TThPP) linked by 4-thiophenephenyl groups was synthesized through an in situ chemical oxidative polymerization on the surface of copper foil. The TThPP films were used as the anode of lithium-ion battery, which exhibited high specific capacities, excellent rate performances, and long cycle lives due to the alignment of 2D polyporphyrin nanosheets, and they (i) can highly efficiently adsorb Li atoms, (ii) have short-ended paths for the fast lithium ion diffusion, and (iii) open nanopores holding electrolyte. The reversible capacity is up to 666 mAh/g. This is the first example of an organic 2D COF for an anode of lithium-ion battery and represents an important step toward the use of COFs in the next-generation high-performance lithium-ion battery.

The electronic structures and excitation properties of dye sensitizers determine the photon-to-current conversion efficiency of dye sensitized solar cells (DSSCs). In order to understand the different performance of porphyrin dye sensitizers YD2 and YD2-o-C8 in DSSC, their geometries and electronic structures have been studied using density functional theory (DFT), and the electronic absorption properties have been investigated via time-dependent DFT (TDDFT) with polarizable continuum model for solvent effects. The geometrical parameters indicate that YD2 and YD2-o-C8 have similar conjugate length and charge transfer (CT) distance. According to the experimental spectra, the HSE06 functional in TDDFT is the most suitable functional for describing the Q and B absorption bands of porphyrins. The transition configurations and molecular orbital analysis suggest that the diarylamino groups are major chromophores for effective CT excitations (ECTE), and therefore act as electron donor in photon-induced electron injection in DSSCs. The analysis of excited states properties and the free energy changes for electron injection support that the better performance of YD2-o-C8 in DSSCs result from the more excited states with ECTE character and the larger absolute value of free energy change for electron injection.