Abstract
We propose, supported byab initiocalculations, a possible photocatalytic cycle for hydrogen evolution by a prototypical polymer photocatalyst, poly(p-phenylene), in the presence of a sacrificial electron donor.
Highlights
IntroductionThe role of molecular hydrogen (H2) as an energy carrier has been extensively studied and garnered signi cant interest in recent times because of the high energy content (141.9 MJ kgÀ1) when compared to other known fuels such as methane (55.5 MJ kgÀ1) and gasoline (47.5 MJ kgÀ1).[5] the use of molecular hydrogen has been hindered by the difficulty of nding a renewable, low-cost, synthetic route, as well as a convenient way of subsequently storing the produced hydrogen
A potential photocatalytic cycle for hydrogen evolution by poly(p-phenylene), a prototypical polymer photocatalyst, in the presence of triethylamine as a sacri cial electron donor has been proposed and the thermodynamics of the cycle explored via ab initio calculations, using both density functional theory
In the rst sub-cycle TEA gets oxidized to TEARc, dehydrogenated TEA, with the polymer accepting this hydrogen atom, while in the second sub-cycle TEARc gets oxidized to DEA and MeCHO
Summary
The role of molecular hydrogen (H2) as an energy carrier has been extensively studied and garnered signi cant interest in recent times because of the high energy content (141.9 MJ kgÀ1) when compared to other known fuels such as methane (55.5 MJ kgÀ1) and gasoline (47.5 MJ kgÀ1).[5] the use of molecular hydrogen has been hindered by the difficulty of nding a renewable, low-cost, synthetic route, as well as a convenient way of subsequently storing the produced hydrogen. One possible synthetic route is photocatalytic watersplitting, see eqn (1), rst demonstrated in the form of photoelectrolysis, using a TiO2 photoanode, by Fujishima and Honda in 1972.6. Crystalline inorganic solids such as TiO2, SrTiO3, Ga2O3, GaN, Ge3N4 and Ta2O5 are employed as watersplitting photocatalysts.[7,8,9] organic materials such as carbon nitrides, conjugated linear polymers, conjugated microporous polymers (CMPs) and covalent organic frameworks (COFs) have been shown to be able to drive proton reduction, see eqn (2), and/or water oxidation, see eqn (3), in the presence of sacri cial electron donor (SED) and acceptor (SEA) species, respectively.[10,11,12] Carbon nitride was the rst organic material to evolve both hydrogen and oxygen in the presence of these sacri cial species,[13,14] as well as the rst organic material reported to perform overall water-splitting.[15,16] Compared to their inorganic counterparts, organic photocatalysts have the advantage of facile tunability of the photocatalyst's properties through co-polymerisation and chemical functionalisation,[17,18] as well as being based on generally more earth-abundant elements
Sign-in/Register to view highlights & summary Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
