Delocalizing Excitation for Highly-Active Organic Photovoltaic Catalysts.

Localized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo-induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron-phonon coupling via rational fluoro-substitution. The optimized 2FBP-4F catalyst we develop here exhibits a minimized Huang-Rhys factor of 0.35 in solution, high dielectric constant and strong crystallization in the solid state. As a result, the energy barrier for exciton dissociation is decreased, and more importantly, polarons are unusually observed in 2FBP-4F nanoparticles (NPs). With the increased hole transfer efficiency and prolonged charge carrier lifetime highly related to enhanced exciton delocalization, the PM6 : 2FBP-4F heterojunction NPs at varied concentration exhibit much higher optimized photocatalytic activity (207.6-561.8 mmol h-1 g-1) for hydrogen evolution than the control PM6 : BP-4F and PM6 : 2FBP-6F NPs, as well as other reported photocatalysts under simulated solar light (AM 1.5G, 100 mW cm-2).

Highly-Active Chiral Organic Photovoltaic Catalysts with Suppressed Charge Recombination.

Recombination of free charges in organic semiconductors reduces the available photo-induced charge-carriers and restricts photovoltaic efficiency. In this work, the chiral organic semiconductors (Y6-R and Y6-S with enantiopure R- and S- chiral alkyl sidechains) are designed and synthesized, which show effective aggregation-induced chirality through mainchain packing with chiral conformations in non-centrosymmetric space groups with tilt chirality. Based on the analysis of spin-injection, magnetic-hysteresis loop, and thermodynamics and dynamics of the excited state, we suggest that the aggregation-induced chirality can generate spin-polarization, which suppresses charge recombination and offers more available charge-carriers within Y6-R and Y6-S relative to the achiral counterpart (Y6). Then the chiral Y6-R and Y6-S show enhanced catalytic activity with optimal average hydrogen evolution rates of 205 and 217 mmol h-1 g-1 , respectively, 60-70 % higher than Y6, when they are employed as nanoparticle photocatalysts in photocatalytic hydrogen evolution under simulated solar light, AM1.5G, 100 mW cm-2 .

Organic Photovoltaic Catalyst with σ-π Anchor for High-Performance Solar Hydrogen Evolution.

Efficient in situ deposition of metallic cocatalyst, like zero-valent platinum (Pt), on organic photovoltaic catalysts (OPCs) is the prerequisite for their high catalytic activities. Here we develop the OPC (Y6CO), by introducing carbonyl in the core, which is available to σ-π coordinate with transition metals, due to the high-energy empty π* orbital of carbonyl. Y6CO exhibits a stronger capability to anchor Pt species and reduce them to metallic state, resulting in more Pt0 deposition, relative to the control OPC without the central σ-π anchor. Single-component and heterojunction nanoparticles (NPs) employing Y6CO show enhanced average hydrogen evolution rates of 230.98 and 323.22 mmol h-1 g[OPC] -1 , respectively, under AM 1.5G, 100 mW cm-2 for 10 h, and heterojunction NPs yield the external quantum efficiencies of ca. 10 % in 500-800 nm. This work demonstrates that σ-π anchoring is one efficient strategy for integrating metallic cocatalyst and OPC for high-performance photocatalysis.

Organic Photovoltaic Catalyst with Extended Exciton Diffusion for High-Performance Solar Hydrogen Evolution.

The short exciton diffusion length (LD) associated with most classical organic photocatalysts (5-10 nm) imposes severe limits on photocatalytic hydrogen evolution efficiency. Here, a photovoltaic molecule (F1) without electron-deficient units at the central building block was designed and synthesized to improve the photoluminescence quantum yield (PLQY). With the enhanced PLQY of 9.3% and a large integral spectral overlap of 3.32 × 1016 nm4 M-1 cm-1, the average LD of F1 film increases to 20 nm, nearly twice the length of the control photovoltaic molecule (Y6). Then, the single-component organic nanoparticles (SC-NPs) based on F1 show an optimized average hydrogen evolution rate (HER) of 152.60 mmol h-1 g-1 under AM 1.5G sunlight (100 mW cm-2) illumination for 10 h, which is among the best results for photocatalytic hydrogen evolution.

Two-Dimensional Polycyclic Photovoltaic Molecule with Low Trap Density for High-Performance Photocatalytic Hydrogen Evolution.

Typical organic semiconductors show a high trap density of states (1016 -1018  cm-3 ), providing a large number of centers for charge-carrier recombination, thus hindering the development of photocatalytic hydrogen evolution. Here, we design and synthesize a two-dimensional polycyclic photovoltaic material, named as TPP, to reduce the trap density to as low as 2.3×1015  cm-3 , which is 1-3 orders of magnitude lower than those of typical organic semiconductors. Moreover, TPP exhibits a broad and strong absorption, ordered molecular packing with a large crystalline coherence length and enhanced electron mobility. Then, the bulk heterojunction nanoparticles (BHJ-NPs) based on a blend of polymer donor (PM6) and TPP exhibit an average hydrogen evolution rate (HER) of 64.31 mmol h-1 g-1 under AM1.5G sunlight (100 mW cm-2 ), and 72.75 mmol h-1 g-1 under 330-1100 nm illumination (198 mW cm-2 ) higher than that of the control NPs based on typical PM6 : Y6 (62.67 mmol h-1 g-1 ).