Enhanced Light‐Driven Hydrogen‐Production Activity Induced by Accelerated Interfacial Charge Transfer in Donor–Acceptor Conjugated Polymers/TiO₂ Hybrid

Abstract

Donor-acceptor (D-A) conjugated polymers have proved to be desired candidates to couple with inorganic semiconductors for enhanced photocatalytic activity.H erein, the matched energy levels between polymerB FB and TiO 2 make them form BFB-TiO 2 composites with moderate photocatalytic H 2 evolution rate (HER). To further enhancet he interfacial interaction, BFB was modified with ac arboxylic acid end group,w hich reactedw ith surface OH ofT iO 2 to form an ester bond.A saresult, the functionalized BFBA-TiO 2 compositese xhibited superior photocatalytic activity.E specially, HER of 4% BFBA-TiO 2 can reachu pt o2 28.2 mmol h À1 under visiblel ight irradiation (l > 420 nm), which is about 2.02 times higher than that of BFB-TiO 2 .T he enhanced photocatalytic activity originated from the formed ester bond betweenp olymer andT iO 2 ,a nd photogenerated electrons injectionf rom lowestu noccupied molecularo rbital (LUMO) of the exited polymert oc onduction band of TiO 2 were accelerated. Therefore, based on an intermolecular interaction mechanism, more suitable D-A conjugated polymers with anchoring groups could be designedt oc ouple with other semiconductors for enhancing photocatalytic activity.

Hydrogen Evolution Prediction for Alternating Conjugated Copolymers Enabled by Machine Learning with Multidimension Fragmentation Descriptors

“…54−56 Instead, several high-performance materials (such as fluorobenzene-containing copolymers) only contain weak acceptor fragments. 57 To solve the contradictions, it is highly meaningful to develop new models and rationalize these phenomena in a more comprehensive manner. The new venue opened by the ML method, an important descriptor, LUMO_D-LUMO_A, reflects the relative population of the excited electron on D/A fragmentations and has been considered as a descriptor of the electron distribution in the excited states (Figure 4b).…”

Nanoporous and nonporous conjugated donor–acceptor polymer semiconductors for photocatalytic hydrogen production

“…Consequently, the average HERs of P82/TiO 2 and P83/TiO 2 with Pt as cocatalyst dramatically increased to 11.3 and 3.9 times, respectively, as high as that of using TiO 2 only. Chen et al attempted to incorporate several CPs, that is, P37, P40, and P84 (Figure 5 and Figure 10), with TiO 2 and formed binary composites [98][99][100]. Compared with pristine CPs as photocatalysts, the photocatalytic activities of the heterojunctions increased by around 18, 7, and 2 times, respectively.…”

Electronic Properties and Photocatalytic Hydrogen Evolution Rates for Alternating Conjugated Copolymers: Predictions and Insights by Data-Driven Models

“…This, however, is not in line with the results of many more recent studies, where co-polymer with strong charge transfer (such as thiadiazolembedded materials) cannot achieve high-performance (HER > 1,000 μmol/hg). Instead, many high-performance materials (such as fluorobenzene-containing copolymers) do not show strong CT features [37]. To resolve the contradictions, it is highly meaningful to develop new models and rationalize these phenomena in a more comprehensive manner.…”

“…many high-performance materials (such as fluorobenzene-containing copolymers) do not show strong CT features[37]. To resolve the contradictions, it is highly meaningful to develop new models and rationalize these phenomena in a more comprehensive manner.…”