Developing highly efficient photocatalyts for water splitting is one of the grand challenges in solar energy conversion. Here, we report the rational design and synthesis of porous conjugated polymer (PCP) that photocatalytically generates hydrogen from water splitting. The design mimics natural photosynthetics systems with conjugated polymer component to harvest photons and the transition metal part to facilitate catalytic activities. A series of PCPs have been synthesized with different light harvesting chromophores and transition metal binding bipyridyl (bpy) sites. The photocatalytic activity of these bpy-containing PCPs can be greatly enhanced due to the improved light absorption, better wettability, local ordering structure, and the improved charge separation process. The PCP made of strong and fully conjugated donor chromophore DBD (M4) shows the highest hydrogen production rate at ∼33 μmol/h. The results indicate that copolymerization between a strong electron donor and weak electron acceptor into the same polymer chain is a useful strategy for developing efficient photocatalysts. This study also reveals that the residual palladium in the PCP networks plays a key role for the catalytic performance. The hydrogen generation activity of PCP photocatalyst can be further enhanced to 164 μmol/h with an apparent quantum yield of 1.8% at 350 nm by loading 2 wt % of extra platinum cocatalyst.
A cluster type of electron acceptor, TPB, bearing four α-perylenediimides (PDIs), was developed, in which the four PDIs form a cross-like molecular conformation while still partially conjugated with the BDT-Th core. The blend TPB:PTB7-Th films show favorable morphology and efficient charge dissociation. The inverted solar cells exhibited the highest PCE of 8.47% with the extraordinarily high Jsc values (>18 mA/cm(2)), comparable with those of the corresponding PC71BM/PTB7-Th-based solar cells.
Self-assembly of monolayers of functional molecules on dielectric surfaces is a promising approach for the development of molecular devices proposed in the 1970s. Substrate chemically bonded self-assembled monolayers of semiconducting conjugated molecules exhibit low mobility. And self-assembled monolayer molecular crystals are difficult to scale up and limited to growth on substrates terminated by hydroxyl groups, which makes it difficult to realize sophisticated device functions, particularly for those relying on n-type electron transport, as electrons suffer severe charge trapping on hydroxyl terminated surfaces. Here we report a gravity-assisted, two-dimensional spatial confinement method for bottom-up growth of high-quality n-type single-crystalline monolayers over large, centimeter-sized areas. We demonstrate that by this method, n-type monolayer molecular crystals with high field-effect mobility of 1.24 cm2 V−1 s−1 and band-like transport characteristics can be grown on hydroxyl-free polymer surface. Furthermore, we used these monolayer molecular crystals to realize high-performance crystalline, gate-/light-tunable lateral organic p–n diodes.
Perylene diimide (PDI) derivatives functionalized at the ortho-position (αPPID, αPBDT) were synthesized and used as electron acceptors in non-fullerene organic photovoltaic cells. Because of the good planarity and strong πstacking of ortho-functionalized PDI, the αPPID and αPBDT exhibit a strong tendency to form aggregates, which endow the materials with high electron mobility. The inverted OPVs employing αPDI-based compounds as the acceptors and PBT7-Th as the donor give the highest power conversion efficiency (PCE) values: 4.92% for αPBDT-based devices and 3.61% for αPPID-based devices, which are, respectively, 39% and 4% higher than that of their β-substituted counterparts βPBDT and βPPID. Charge separation studies show more efficient exciton dissociation at interfaces between αPDI-based compounds and PTB7-Th. The results suggest that α-substituted PDI derivatives are more promising electron acceptors for organic photovoltaic (OPV) components than β-isomers.
Developing
photocatalytic systems for water splitting to generate
oxygen and hydrogen is one of the biggest chemical challenges in solar
energy utilization. In this work, we report the first example of heterogeneous
photocatalysts for hydrogen evolution based on in-chain cobalt-chelating
conjugated polymers. Two conjugated polymers chelated with earth-abundant
cobalt ions were synthesized and found to evolve hydrogen photocatalytically
from water. These polymers are designed to combine functions of the
conjugated backbone as a light-harvesting antenna and electron-transfer
conduit with the in-chain bipyridyl-chelated transition metal centers
as catalytic active sites. In addition, these polymers are soluble
in organic solvents, enabling effective interactions with the substrates
as well as detailed characterization. We also found a polymer-dependent
optimal cobalt chelating concentration at which the highest photocatalytic
hydrogen production (PHP) activity can be achieved.
Developing high-performance polymer donors are highly demanded to fulfil the potential of the layer-by-layer (LBL) processed organic solar cells (OSCs). In this study, we present an effective method to develop...
This paper describes the synthesis and application of βTPB6 and βTPB6-C as electron acceptors for organic solar cells. Compound βTPB6 contains four covalently bonded PDIs with a BDT-Th core at the β-position. The free rotation of PDIs renders βTPB6 with varying molecular geometries. The cyclization of βTPB6 yields βTPB6-C with high rigidity of the molecular geometry and enlarged conjugated skeleton. The inverted solar cells based on βTPB6-C and PTB7-Th as the donor polymer exhibited the highest efficiency of 7.69% with V oc of 0.92 V, J sc of 14.9 mAcm −2 , and FF of 0.56, which is 31% higher than that for βTPB6 based devices. The larger fraction of βTPB6-C and PTB7-Th than that of βTPB6:PTB7-Th in a blend film takes a face-on orientation packing pattern for π-systems that benefits the charge transport and hence higher PCE value than that for βTPB6:PTB7-Th. It was also found that a proper DIO:DPE additive further enhances this trend, which results in an increase of the PCE value for βTPB6-C:PTB7-Th while decreasing the PCE value for βTPB6:PTB7-Th.
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