Acetylene-linked conjugated polymers for sacrificial photocatalytic hydrogen evolution from water

Abstract

Conjugated organic polymers have shown potential as photocatalysts for hydrogen production by water splitting. Taking advantage of a high throughput screening workflow, two series of acetylene-linked co-polymers were prepared and...

Linear Conjugated Polymers for Solar-Driven Hydrogen Peroxide Production: The Importance of Catalyst Stability

“…DE7 shows poor activity for photocatalytic hydrogen (H 2 ) evolution, 17 and more broadly, sacrificial H 2 production and H 2 O 2 generation are somewhat contraindicated ( Figure S9 ), although several catalysts (e . g., DE3, TE2, TE3, TE9, TE10, TE12) are poor catalysts for both reactions.…”

“…As such, we do not believe that variable Cu contents in these polymers account for their variable catalytic performances. Microwave heating was also used to synthesize DE7-M (that is, DE7 synthesized under microwave conditions), shortening the synthesis time from 2 days 17 to 2 h along with enhanced photoelectric properties ( Figures S17 and S18 ). The optical gap of DE7-M was calculated from the UV–visible spectrum to be 2.34 eV ( Figure 2 a).…”

“…We found no simple correlation between the H 2 O 2 production rate and any single physical property such as band gap, fluorescence lifetime, particle size, or water contact angle (Figure S8), much as for sacrificial hydrogen evolution. 15,16 DE7 shows poor activity for photocatalytic hydrogen (H 2 ) evolution, 17 and more broadly, sacrificial H 2 production and H 2 O 2 generation are somewhat contraindicated (Figure S9), although several catalysts (e.g., DE3, TE2, TE3, TE9, TE10, TE12) are poor catalysts for both reactions. DE7 was synthesized by Pd-catalyzed Sonogashira coupling of 1,4diethynylbenzene and 2,5-dibromopyridine (Figures S10− S15).…”

Linear multiple-thiophene-containing conjugated polymer photocatalysts with narrow band gaps for achieving ultrahigh photocatalytic hydrogen evolution activity under visible light

“…Among the reported acceptors, sulfone-based aromatic compounds are some of the most efficient acceptor units that enable the D–A polymer photocatalysts to show high photocatalytic activity, due to their strong electron-withdrawing capability and coplanar structure with extended conjugation. 30–32 A representative sulfone-based acceptor is dibenzothiophene- S , S -dioxide (BTDO), which has been coupled with different donor units to design various D–A polymers with encouraging photocatalytic performance (Scheme S1†). For example, Cooper and colleagues first reported the BTDO-based polymer photocatalyst by using benzene as the donor, which exhibited hydrogen evolution rates (HERs) of 3.68 and 5.80 mmol h −1 g −1 under visible light and full arc light, respectively.…”

Why do sulfone-containing polymer photocatalysts work so well for sacrificial hydrogen evolution from water?

“…Since then, numerous research groups have synthesised series of photocatalysts in which sulfone-containing materials have outperformed sulfone-free materials [30][31][32][33][34][35][36][37][38][39][40][41][42] . Sulfone-containing photocatalysts have rapidly reached impressive apparent quantum efficiencies of 29.3% at 420 nm 43 , 18% at 500 nm 44 and 13.6% at 550 nm 40 when paired with hole scavengers.…”