Exciton binding energy has been regarded as a crucial parameter for mediating charge separation in polymeric photocatalysts. Minimizing the exciton binding energy of the polymers can increase the ...yield of charge‐carrier generation and thus improve the photocatalytic activities, but the realization of this approach remains a great challenge. Herein, a series of linear donor–acceptor conjugated polymers has been developed to minimize the exciton binding energy by modulating the charge‐transfer pathway. The results reveal that the reduced energy loss of the charge‐transfer state can facilitate the electron transfer from donor to acceptor, and thus, more electrons are ready for subsequent reduction reactions. The optimized polymer, FSO‐FS, exhibits a remarkable photochemical performance under visible light irradiation.
Modulating the charge‐transfer pathway in a series of linear donor–acceptor conjugated polymers controls their ability to minimize the exciton binding energy. A low exciton binding energy promotes the photoreaction for artificial photosynthesis
Electron transfer is the rate‐limiting step in photocatalytic water splitting. Viologen and its derivatives are able to act as electron‐transfer mediators (ETMs) to facilitate the rapid electron ...transfer from photosensitizers to active sites. Nevertheless, the electron‐transfer ability often suffers from the formation of a stable dipole structure through the coupling between cationic‐radical‐containing viologen‐derived ETMs, by which the electron‐transfer process becomes restricted. Herein, cyclic diquats, a kind of viologen‐derived ETM, are integrated into a 2,2′‐bipyridine‐based covalent organic framework (COF) through a post‐quaternization reaction. The content and distribution of embedded diquat‐ETMs are elaborately controlled, leading to the favorable site‐isolated arrangement. The resulting materials integrate the photosensitizing units and ETMs into one system, exhibiting the enhanced hydrogen evolution rate (34600 μmol h−1 g−1) and sustained performances when compared to a single‐module COF and a COF/ETM mixture. The integration strategy applied in a 2D COF platform promotes the consecutive electron transfer in photochemical processes through the multi‐component cooperation.
Viologen‐derived electron‐transfer mediators (ETMs) are integrated into a 2,2′‐bipyridine‐containing covalent organic framework (COF) by a controllable post‐synthetic method. The site‐isolated ETM modules cooperate well with photosensitizer modules on the platform of COFs for enhanced electron‐transfer ability, thereby remarkably promoting the photocatalytic H2 evolution performance (34600 μmol h−1 g−1) from water splitting.
Covalent triazine frameworks (CTFs) have attracted a great deal of attention as an attractive new class of visible light-active, metal-free, and polymer-based heterogeneous photocatalysts. CTFs have ...demonstrated promising characteristics such as synthetic diversity, stability, nontoxicity, pure organic nature, and enhanced ordered structure. In this review, we aim to summarize the recent developments in CTFs ranging from novel preparation methods to critical factors that directly impact their photocatalytic efficiency. Various physical and chemical design strategies for morphology, band structure, charge separation, and transfer optimization described in the literature are discussed. Emphasis is placed on the enhancement and maximization of photocatalytic efficiencies of specific applications such as photoredox organosynthesis, water splitting, CO2 photoreduction, H2O2 generation, etc.
Large-scale photochemical synthesis of high value chemicals under mild conditions is an ideal method of green chemical production. However, a scalable photocatalytic process has been barely reported ...due to the costly preparation, low stability of photosensitizers and critical reaction conditions required for classical photocatalysts. Here, we report the merging of flow chemistry with heterogeneous photoredox catalysis for the facile production of high value compounds in a continuous flow reactor with visible light at room temperature in air. In the flow reactor system, polymeric carbon nitrides, which are cheap, sustainable and stable heterogeneous photocatalysts, are immobilized onto glass beads and fibers, demonstrating a highly flexible construction possibility for devices of the photocatalytic materials. As an example of the production of high value chemicals, important chemical structures such as cyclobutanes, which are basic building blocks for many pharmaceutical compounds, like magnosalin, are synthesized in flow with high catalytic efficiency and stability.
Conjugated porous polymers (CPPs) have recently emerged as a new class of visible light-active, organic and heterogeneous photocatalysts for visible light-mediated photoredox reactions. The CPPs have ...been established as a potential alternative to resolve critical drawbacks of traditional molecular and homogeneous photocatalysts due to their structural durability, non-toxicity, low cost due to the absence of noble metals, and high designability. Tremendous attempts have been made toward the design and synthesis of CPPs for a variety of visible light-promoted photocatalytic chemical transformations. Nevertheless, the concomitant design protocols of CPPs have not been well structured so far. Herein, in this review, we aim to summarize the recent developments in controlling the structural, photophysical and electronic properties of CPPs, and thereby extract the underlying design principles. According to the principle of the photocatalytic process, key parameters for the molecular design of CPPs were described in three sections: (1) light absorbance by energy band gap, (2) charge separation and transport, and (3) electron transfer to the target substrate. The macroscopic features,
i.e.
morphology, porosity and chemical functionality, and processibility of CPPs were also presented for the enhancement of their photocatalytic activity.
A review on the recent developments in controlling the structural, photophysical and electronic properties of conjugated porous polymer (CPP) photocatalysts is presented.
Fabrication of nitrogen-doped hollow carbon nanostructures is of great importance for achieving efficient electron and ion transport as a metal-free electrocatalyst. Herein, we report a step-wise ...polymerization and carbonization route to prepare N-doped hollow carbon nanoflowers (N-HCNFs) with a high nitrogen content up to 5.3 at%. A preformed covalent triazine framework (CTF) network assembled on a melamine-cyanuric acid (MCA) supermolecular crystal was achieved
via
a step-wise polymerization. The subsequent carbonization was conducted to obtain hollow and porous carbon materials with a unique flower-shape. Excellent electrochemical oxygen reduction reaction (ORR) performance with a positive half-wave potential of 0.84 V (
vs.
RHE) was achieved with excellent stability and methanol resistance in alkaline media. Furthermore, for the hydrogen evolution reaction (HER), a low overpotential of 243 mV at a current density of 10 mA cm
−2
and a small Tafel slope of 111 mV dec
−1
in acidic media were shown.
N-doped hollow carbon nanoflowers with high nitrogen content up to 5.3 at% were prepared
via
a step-wise polymerization and carbonization route from a covalent triazine framework.
A simple structural design principle and band position alignment of conjugated microporous polymers for enhanced photocatalytic efficiency is presented. The valence and conduction band positions of ...the polymer networks can be fine‐tuned by altering the substitution positions on the centered phenyl unit to match the required redox potential of the catalytic reactions under visible light.
The construction of multiple heteroatom-doped porous carbon with unique nanoarchitectures and abundant heteroatom active sites is promising for reversible oxygen-involving electrocatalysis. However, ...most of the synthetic methods required the use of templates to construct precisely designed nanostructured carbon. Herein, we introduced an ultrasound-triggered route for the synthesis of a piperazine-containing covalent triazine framework (P-CTF). The ultrasonic energy triggered both the polycondensation of monomers and the assembly into a nanoflower-shaped morphology without utilizing any templates. Subsequent carbonization of P-CTF led to the formation of nitrogen, phosphorus, and fluorine tri-doped porous carbon (NPF@CNFs) with a well-maintained nanoflower morphology. The resultant NPF@CNFs showed high electrocatalytic activity and stability toward bifunctional electrolysis, which was better than the commercial Pt/C and IrO2 electrocatalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. As a further demonstration, employing NPF@CNFs as air electrode materials resulted in an excellent performance of liquid-state and solid-state Zn-air batteries, showing great potentials of the obtained multiple heteroatom-doped porous carbon electrocatalysts for wearable electronics.
The search for metal‐free organic photocatalysts for H2 production from water using visible light remains a key challenge. Reported herein is a molecular structural design of pure organic ...photocatalysts, derived from conjugated polybenzothiadiazoles, for photocatalytic H2 evolution using visible light. By alternating the substitution position of the electron‐withdrawing benzothiadizole unit on the phenyl unit as a comonomer, various polymers with either one‐ or three‐dimensional structures were synthesized and the effect of the molecular structure on their catalytic activity was investigated. Photocatalytic H2 evolution efficiencies up to 116 μmol h−1 were observed by employing the linear polymer based on a phenyl‐benzothiadiazole alternating main chain, with an apparent quantum yield (AQY) of 4.01 % at 420 nm using triethanolamine as the sacrificial agent.
Bring to light: Conjugated polybenzothiadiazoles were introduced as a new family of organic photocatalysts for H2 evolution from water in the presence of electron donors with visible‐light irradiation. The molecular engineering of the electron‐withdrawing benzothiadiazole unit on the phenyl unit allows the construction of either one‐ or three‐dimensional polybenzothiadiazoles, and the effect of the structure on the photocatalytic H2 evolution activity was investigated.
Due to the fast inference and good performance, discriminative learning methods have been widely studied in image denoising. However, these methods mostly learn a specific model for each noise level, ...and require multiple models for denoising images with different noise levels. They also lack flexibility to deal with spatially variant noise, limiting their applications in practical denoising. To address these issues, we present a fast and flexible denoising convolutional neural network, namely FFDNet, with a tunable noise level map as the input. The proposed FFDNet works on downsampled sub-images, achieving a good trade-off between inference speed and denoising performance. In contrast to the existing discriminative denoisers, FFDNet enjoys several desirable properties, including: 1) the ability to handle a wide range of noise levels (i.e., 0, 75) effectively with a single network; 2) the ability to remove spatially variant noise by specifying a non-uniform noise level map; and 3) faster speed than benchmark BM3D even on CPU without sacrificing denoising performance. Extensive experiments on synthetic and real noisy images are conducted to evaluate FFDNet in comparison with state-of-the-art denoisers. The results show that FFDNet is effective and efficient, making it highly attractive for practical denoising applications.
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