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Recently, photo switching porous materials have been widely reported for low energy costed CO2 capture and release via simply remoted light controlling method. However, most reported photo responsive CO2 adsorbents relied on metal organic framework (MOFs) functionalisation with photochromic moieties, and MOF adsorbents still suffered from chemically and thermally unstable issues. Thus, further metal free and highly stable organic photoresponsive adsorbents are necessary to be developed. CTFs, because of their high porosity and stability, have attracted great attention for CO2 capture. Considering the high CO2 uptake capacity and structural tunability of CTFs, it suggests high potential to fabricate the photoswitching CTF materials by the same functionalisation method as MOFs. Herein, the first series of photo switching CTFs were developed for low energy CO2 capture and release. Apart from that, the CO2 switching efficiency could be doubled either through the azobenzene numbers adjusting method or through the previously reported structural alleviation strategy. Furthermore, the pore size distribution of azobenzene functionalised PCTFs also could be tuned under UV exposure, which may contribute to the UV light induced decrease of CO2 uptake capacity. These photoswitching CTFs represented a new kind of porous polymers for low energy costed CO2 capture.

Covalent triazine frameworks (CTFs) are a class of porous organic polymers that continuously attract growing interest because of their outstanding chemical and physical properties. However, the control of extended porous organic framework structures at the molecular scale for a precise adjustment of their properties has hardly been achieved so far. Here, we present a series of bipyridine-based CTFs synthesized through polycondensation, in which the sequence of specific building blocks is well controlled. The reported synthetic strategy allows us to tailor the physicochemical features of the CTF materials, including the nitrogen content, the apparent specific surface area, and optoelectronic properties. Based on a comprehensive analytical investigation, we demonstrate a direct correlation of the CTF bipyridine content with the material features such as the specific surface area, band gap, charge separation, and surface wettability with water. The entirety of these parameters dictates the catalytic activity as demonstrated for the photocatalytic hydrogen evolution reaction (HER). The material with the optimal balance between optoelectronic properties and highest hydrophilicity enables HER production rates of up to 7.2 mmol/(h·g) under visible light irradiation and in the presence of a platinum cocatalyst.

Covalent triazine frameworks (CTFs) with polypyridyl ligands are very promising supports to anchor photocatalytic complexes. Herein, we investigate the photophysical properties of a series of ligands which vary by the extent of the aromatic system, the nitrogen content and their topologies to aid in selecting interesting building blocks for CTFs. Interestingly, some linkers have a rotational degree of freedom, allowing both a trans and cis structure, where only the latter allows anchoring. Therefore, the influence of the dihedral angle on the UV‐Vis spectrum is studied. The photophysical properties are investigated by a combined computational and experimental study. Theoretically, both static and molecular dynamics simulations are performed to deduce ground‐ and excited state properties based on density functional theory (DFT) and time‐dependent DFT. The position of the main absorption peak shifts towards higher wavelengths for an increased size of the π‐system and a higher π‐electron deficiency. We found that the position of the main absorption peak among the different ligands studied in this work can amount to 271 nm; which has a significant impact on the photophysical properties of the ligands. This broad range of shifts allows modulation of the electronic structure by varying the ligands and may help in a rational design of efficient photocatalysts., The photophysical properties of various polypyridyl ligands have been investigated by a combined computational and experimental study in order to select interesting building blocks for covalent triazine frameworks. The position of the main absorption peak shifts towards higher wavelengths for an increased size of the π ‐system and a higher π ‐electron deficiency. The shift can amount to 271 nm among the different ligands; which has a significant impact on the photophysical properties.

In this study, a novel fibrous carbon nitride (FCN) was prepared from laminated covalent triazine framework (CTF) via pyrolysis, using functionalized 2,5-thiophenedicarboxylic acid and melamine as the precursors. A carbon vacancy was produced by two-step calcination in argon and air atmospheres. These carbon vacancies further exposed the edges and diffusion channels of the FCN nanofibers, which accelerated photogenerated charge transfer and provided more active sites. The FCN was characterized using various techniques and used for H2 evolution under visible-light irradiation. The as-synthesized FCN exhibited excellent stability, and its photocatalytic activity for H2 evolution under visible-light irradiation was 66 times higher than that of bare C3N4 (BCN), attaining a maximum H2 evolution rate of 102.63 μmol in 6 h. The FCN remained stable following visible-light irradiation at the end of 10 cycles. The FCN benefited from the absorption of solar energy and a large number of active sites. These advantages facilitated the efficient separation of photoexcited electron-hole pairs to hinder charge recombination. This work generates new insights into the preparation of highly effective FCN photocatalysts that may be put to various applications, especially in the fields of energy and environment.

Altres ajuts: RSC Covalent organic frameworks (COFs) are crystalline porous organic polymers built from covalent organic blocks that can be photochemically active when incorporating organic semiconducting units, such as triazine rings or diacetylene bridges. The bandgap, charge separation capacity, porosity, wettability, and chemical stability of COFs can be tuned by properly choosing their constitutive building blocks, by extension of conjugation, by adjustment of the size and crystallinity of the pores, and by synthetic post-functionalization. This review focuses on the recent uses of COFs as photoactive platforms for the hydrogen evolution reaction (HER), in which usually metal nanoparticles (NPs) or metallic compounds (generally Pt-based) act as co-catalysts. The most promising COF-based photocatalytic HER systems will be discussed, and special emphasis will be placed on rationalizing their structure and light-harvesting properties in relation to their catalytic activity and stability under turnover conditions. Finally, the aspects that need to be improved in the coming years will be discussed, such as the degree of dispersibility in water, the global photocatalytic efficiency, and the robustness and stability of the hybrid systems, putting emphasis on both the COF and the metal co-catalyst.

Metal-modified covalent triazine frameworks (CTFs) have attracted considerable attention in heterogeneous catalysis due to their strong nitrogen-metal interactions exhibiting superior activity, stability and hence recyclability. Herein, we report on a post-metalation of a bipyridine-based CTFs with an Ir(I) complex for C H borylation of aromatic compounds. Physical characterization of the Ir(I)-based bipyCTF catalyst in combination with density functional theory (DFT) calculations exhibit a high stabilization energy of the Ir-bipy moiety in the frameworks in the presence of B2Pin2. By using B2Pin2 as a boron source, Ir(I)@bipyCTF efficiently catalyzed the C H borylation of various aromatic compounds with excellent activity and good recyclability. In addition, XAS analysis of the Ir(I)@bipyCTF gave clear evidence for the coordination environment of the Ir.