Metal Phosphide-Embedded Porous Carbons As Highly Efficient Electrochemical Catalysts For Water Splitting

Organic porous polymers possessing numerous excellent performance and features, causes widespread concern in the field of materials research. Thus the prepared methods for organic porous polymers and design of monomer, as well as the application performance has expended quite rapidly. Molecular hydrogen (H2) is regarded as a promising energy carrier for replacing fossil fuels in the future. At present the main technology for hydrogen production still consumes fossil resource and increases carbon emission. Direct electrochemical water splitting seems to represent one of the most clean and sustainable method of H2 production on a large scale. Typically, transition metal-based catalysts for the hydrogen evolution reaction (HER) are much superior to metal-free catalysts, so it has been hot point. However, most of MetP catalysts suffered from a main limitation:lacking of the more exposed active sites with respect to low specific surface areas. Our topic tries to combine the advantage of Organic porous polymers with the excellent catalytic hydrogen production performance of transition metal. The transition metal-containing anions and phosphorous-based polymer framework serve as metal and phosphorous sources or electron acceptor,(1) Firstly, tris(4-vinylphenyl)phosphane was utilized as key monomer to prepare hyper-cross-linked tri(4-vinylphenyl) phosphine (HC-TVP) through azodiisobutyronitrile (AIBN)-promoted radical polymerization. Afterwards, the resulting HC-TVP was converted to the ionic polymer (HT-I), consisting of cationic framework and iodide counter anions under the treatment of aqueous HI for 24 h. HT-I can be uniformly dispersed in some common organic solvents, such as dimethylformamide (DMF,1.0 mg ml/1) and dioxane. The iodide ions of HT-I can be easily replaced by metal-containing anions, such as tetrathiomolybdate (MoS42-) and hexacyanoferrate (Fe(CN)63’)> by an ion-exchange process in aqueous solution. Of these, MoS42- and Fe(CN)63--loaded cationic porous polymers are denoted as HT-Mo and HT-Fe, respectively.(2) Unlike the previous chapter approach, we prepared the transition metal based porous polymer by using the coordination interaction between phosphorus and transition metals. The, we studied the catalytic hydrogen production performance of the new materials.(3) The porous polymer B-TVP and liner polymer B-BVP were prepared by the Mizoroki-Heck reaction, which successfully introduced the BODIPY into the polymer frame. Then, the donor-acceptor structure of B-TVP and B-BVP were studied.