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Extending photoresponse ranges of semiconductors to the entire ultraviolet-visible (UV)-shortwave near-infrared (SWIR) region (ca. 200-3000 nm) is highly desirable to reduce complexity and cost of photodetectors or to promote power conversion efficiency of solar cells. The observed up limit of photoresponse for organic-based semiconductors is about 1800 nm, far from covering the UV-SWIR region. Here we develop a cyanide-bridged layer-directed intercalation approach and obtain a series of two viologen-based 2D semiconductors with multispectral photoresponse. In these compounds, infinitely π-stacked redox-active N-methyl bipyridinium cations with near-planar structures are sandwiched by cyanide-bridged Mn-Fe or Zn-Fe layers. Radical-π interactions among the infinitely π-stacked N-methyl bipyridinium components favor the extension of absorption range. Both semiconductors show light/thermo-induced color change with the formation of stable radicals. They have intrinsic photocurrent response in the range of at least 355-2400 nm, which exceeds all reported values for known single-component organic-based semiconductors.
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http://dx.doi.org/10.1038/s41467-020-14986-7 | DOI Listing |
J Am Chem Soc
March 2025
Department of Chemistry, University of Pennsylvania, 231 S 34th St. Philadelphia, Pennsylvania 19104, United States.
While redox polymer-mediated catalysis at silicon photoelectrodes has been studied since the 1980s, there have been few detailed studies of these materials in photoelectrochemical CO reduction. Here, we develop silicon photoelectrodes functionalized with a viologen-based polymer that mediates the formation of catalytic gold nanoparticles. The presence of gold was confirmed by X-ray photoelectron spectroscopy (XPS), and the nanoparticles were imaged with high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM).
View Article and Find Full Text PDFAdv Sci (Weinh)
April 2025
Ministry-of-Education Key Laboratory for Green Preparation and Application of Functional Materials, School of New Energy and Electrical Engineering, Hubei University, Wuhan, 430062, P. R. China.
Solar thermal technology offers a promising solution to water scarcity; however, the continuous operation of solar evaporators remains challenging due to sunlight's intermittent availability. Herein, an alternative strategy is proposed to achieve dual-functional energy management of photo-thermoactivated viologen T semiconductors for enhanced solar water evaporation, water-enabled electricity generation, and electrothermal evaporation. A sequential cyanide-bridged layer-directed intercalation approach is developed, where infinitely π-stacked, redox-active N-methyl bipyridinium cations with near-planar structures are sandwiched between cyanide-bridged Mn-Fe.
View Article and Find Full Text PDFFundam Res
March 2024
State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Centre on Molecular Devices, Institute for Energy Science and Technology, Dalian University of Technology, Dalian 116024, China.
The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical (PEC) H production devices. Coupling TiO with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation. However, the band position of TiO could not perfectly match with all p-type semiconductors.
View Article and Find Full Text PDFChem Commun (Camb)
June 2021
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
A new design strategy through the synergy of Mo(vi)-Mo(v) intervalence charge transfer and π(radical)-π(radical/cation) interactions is proposed to obtain semiconductors with photoresponsive ranges covering the whole UV-SWIR (ultraviolet-shortwave near-infrared; ca. 250-3000 nm) region. With this strategy, a viologen-based molybdate semiconductor with a UV-SWIR photoresponsive range was obtained through UV/X-ray irradiation or thermal annealing.
View Article and Find Full Text PDFInorg Chem
April 2021
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
Photoresponse ranges of commercially prevailing photoelectric semiconductors, typically Si and InGaAs, are far from fully covering the whole solar spectrum (∼295-2500 nm), resulting in insufficient solar energy conversion or narrow wave bands for photoelectric detection. Recent studies have shown that infinite π-aggregation of viologen radicals can provide semiconductors with a photoelectric response range covering the solar spectrum. However, controlled assembly of an infinite π-aggregate is still a great challenge in material design.
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