Solar-CO2 -to-Syngas Conversion Enabled by Precise Charge Transport Modulation.

The rational design of the directional charge transfer channel represents an important strategy to finely tune the charge migration and separation in photocatalytic CO2 -to-fuel conversion. Despite the progress made in crafting high-performance photocatalysts, developing elegant photosystems with precisely modulated interfacial charge transfer feature remains a grand challenge. Here, a facile one-pot method is developed to achieve in situ self-assembly of Pd nanocrystals (NYs) on the transition metal chalcogenide (TMC) substrate with the aid of a non-conjugated insulating polymer, i.e., branched polyethylenimine (bPEI), for photoreduction of CO2 to syngas (CO/H2 ). The generic reducing capability of the abundant amine groups grafted on the molecular backbone of bPEI fosters the homogeneous growth of Pd NYs on the TMC framework. Intriguingly, the self-assembled TMCs@bPEI@Pd heterostructure with bi-directional spatial charge transport pathways exhibit significantly boosted photoactivity toward CO2 -to-syngas conversion under visible light irradiation, wherein bPEI serves as an efficient hole transfer mediator, and simultaneously Pd NYs act as an electron-withdrawing modulator for accelerating spatially vectorial charge separation. Furthermore, in-depth understanding of the in situ formed intermediates during the CO2 photoreduction process are exquisitely probed. This work provides a quintessential paradigm for in situ construction of multi-component heterojunction photosystem for solar-to-fuel energy conversion.

Multicolor Emission from Non-conjugated Polymers Based on a Single Switchable Boron Chromophore.

Multicolor emissive and responsive materials are highly attractive owing to their potential applications in various fields, and polymers are preferred for their good processability and high stability. Herein, we report a series of new polymers based on a methacrylate monomer containing a switchable boron chromophore. In spite of their unconjugated nature, interestingly, the homopolymers from this monomer display rare multicolor fluorescence in solution that is highly dependent on the degree of polymerization (DP). With an increasing DP, the local concentration of the chromophore increases, leading to a higher propensity for switching the blue-emitting tricoordinate boron chromophore to the red-emitting tetracoordinate one. The homopolymers also display temperature- and solvent-dependent emission color change. Furthermore, pure white-light emission could be achieved in various solvents by precisely tuning the homopolymer molecular weight, or in films/solid state by copolymerizing the emissive boron monomer with non-emissive monomers in an appropriate ratio.

Water-soluble polymer dots formed from polyethylenimine and glutathione as a fluorescent probe for mercury(II).

Water-soluble fluorescent polymer dots (PDs) were prepared from polyethylenimine and glutathione and are shown to be viable fluorescent probes for selective and sensitive determination of Hg(II). The PDs possess bright blue fluorescence (with excitation/emission peaks at 340/462 nm) which is quenched on addition of Hg(II). Based on these findings, a fluorometric assay was worked out. Fluorescence linearly drops in the 0.1 to 100 µM Hg(II) concentration range, and the limit of detection is 32 nM. Graphical abstract The fluorescence of polymer dots prepared from glutathione and polyethyleimine (G-PEI PDs) is selectively quenched by Hg2+, and this finding was applied to the determination of Hg2+ in environmental water samples.

Non-Conjugated Polymer as an Efficient Dopant-Free Hole-Transporting Material for Perovskite Solar Cells.

A new non-conjugated polymer (PVCz-OMeDAD) with good solution processability was developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PSCs). PVCz-OMeDAD was simply prepared by the free-radical polymerization of vinyl monomers, which were synthesized from low-cost raw materials through three high-yield synthesis steps. The combination of the flexible non-conjugated polyvinyl main chain and hole-transporting methoxydiphenylamine-substituted carbazole side chains endowed PVCz-OMeDAD with excellent film-forming ability, a suitable energy level, and high hole mobility. As a result, by using an ultra-thin (≈30 nm) PVCz-OMeDAD film as cost-effective dopant-free polymer HTM, the conventional n-i-p-type PSCs demonstrated a power conversion efficiency (PCE) up to 16.09 %, suggesting the great potential of the polymer film for future low-cost, large-scale, flexible PSCs applications.