Visible light-active binary metal ion containing functional triazine metallopolymers as a stable p-type photo-electrocatalyst in protic electrolytes

Abstract

Visible light active metallo-organic coordination systems have versatile opportunities due to their tunable electronic properties. Herein, we report a photocathode based on triazine trithiolate network polymers containing mixed metal...

Bismuth(III) Coordination Linkage with Dimercaptothiadiazole: A p-Type Metallopolymer Photocathode Stable in Protic Electrolytes

“…Furthermore, the post-XPS analysis of c-BiDMcT reveals the presence of N–H units in c-BiDMcT, which could play a crucial role during the proton–electron transfer in the ORR and photocurrent enhancement. Protonation-induced delamination and exposure of more active sites are known for N-containing coordination catalytic systems. ,,, The photocurrent measurements and ORR investigations reveal relatively good acidic stability of this new p-block element-based Bi–S–C–N photoelectrocatalytic system, which is essential for photoinduced PCET electrosynthesis reactions.…”

“…Protonation-induced delamination and exposure of more active sites would improve the photocurrent response, which is known for nitrogen-containing polymeric systems. The sulfur- and nitrogen-rich ligands were shown to improve the photocurrent response in protic electrolytes. ,, The protonatable S and N of DMcT could play a crucial role in tautomeric structural shift to provide a local proton relay for the active sites and enable intra-unit proton transfer in multi-PCET reactions. This enhances and provides long-term photocurrent stability even with prolonged exposure to protic electrolytes.…”

“…Hence, various efforts were made in search of efficient hole/electron transporting materials that can form heterostructures with photoactive metal–organic polymers. This facilitates improving the photoexcitons' charge separation and the interfacial photoelectrochemical stability as an overlayer on the inorganic semiconductors. , …”

“…Recently, coordination molecular complexes, metal–organic polymers, and metallo-organic frameworks have been widely investigated for diverse applications due to their tunable structural and electronic properties. , The coordination structures with two- and three-dimensional networks could provide an efficient charge transfer from metals to ligands and vice versa and utilize the photoredox activity. ,, Notably, the charge trapping and recombination of photogenerated excitons can be minimized while using metal-incorporated coordination polymers. ,,, Recently, functional organic ligands with linker units have been explored for the development of photoactive coordination molecular systems. ,,, Metal ions incorporated with highly functionalized ligands have been explored for various applications. − Especially, the proton relay sites at ligands which are structurally positioned in the secondary coordination sphere of the redox-active metal centers could favor multiple proton–electron transfer in electrocatalytic reactions. , This enables the fast transfer or exchange of protons to the local redox-active sites, which is essential for m-PCET. The polydentate functional ligand systems that are rich in N and S in the backbone have obtained interest in coordination photoelectrocatalysts. ,− In our previous reports, triazine trithiolate and dimercaptothiadiazole being the functional ligands can form highly cross-linked coordination network structures and provide good charge transport. ,, …”

Incorporation of Ruthenium Ions into Nanometer-Thick Films of Copper Sulfide by Anodization for Proton-Coupled Electron Transfer Reactions

“…Incessant efforts have been devoted to the search for acid-stable electrocatalysts that can replace costly and scarce platinum for electrochemical hydrogen production and hydrogen oxidation. Various materials based on transition-metal phosphides, nitrides, carbides, sulfides, metal–organic frameworks, and metallopolymers were explored for hydrogen evolution reactions with relatively good stability in acidic electrolytes. − Among these, transition-metal sulfide (TMS)-based electrocatalysts are extensively investigated for hydrogen evolution reactions due to their high exchange current density, stability in a wide pH range, abundant active sites, and tunable electrochemical properties. ,− …”