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Perfluorinated covalent triazine frameworks (F‐CTFs) have shown unique features and attractive performance in separation and catalysis. However, state‐of‐the‐art F‐CTFs synthesized via the ZnCl2‐promoted procedure have quite low fluorine contents due to C−F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F‐CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low‐temperature ionothermal approach (275 °C) to prepare F‐CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2)2] without side reactions. With low catalyst loading (equimolar), F‐CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g−1, and micropores around 1.1 nm. The highly hydrophobic F‐CTF‐1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at −0.8 V and high current density (−141 mA cm−2) surpassing most of the metal‐free electrocatalysts. [ABSTRACT FROM AUTHOR]

Progress toward the preparation of porous organic polymers (POPs) with task‐specific functionalities has been exceedingly slow—especially where polymers containing low‐oxidation phosphorus in the structure are concerned. A two‐step topotactic pathway for the preparation of phosphabenzene‐based POPs (Phos‐POPs) under metal‐free conditions is reported, without the use of unstable phosphorus‐based monomers. The synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease. As an example, partially fluorinated Phos‐POPs (F‐Phos‐POPs) were obtained with a surface area of up to 591 m2 g−1. After coordination with Ru species, a Ru/F‐Phos‐POPs catalyst exhibited high catalytic efficiency in the formylation of amines (turnover frequency up to 204 h−1) using a CO2/H2 mixture, in comparison with the non‐fluorinated analogue (43 h−1) and a Au/TiO2 heterogeneous catalysts reported previously (<44 h−1). This work describes a practical method for synthesis of porous organic phosphorus‐based polymers with applications in transition‐metal‐based heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

High‐entropy materials refer to a kind of materials in which five or more metal species were incorporated deliberately into a single lattice with random occupancy. Up to now, such a concept has been only restricted to hard materials, such as high‐entropy alloys and ceramics. Herein we report the synthesis of hybrid high‐entropy materials, polymetallic zeolitic imidazolate framework (also named as high‐entropy zeolitic imidazolate framework, HE‐ZIF), via entropy‐driven room‐temperature mechanochemistry. HE‐ZIF contains five metals including ZnII, CoII, CdII, NiII, and CuII which are dispersed in the ZIF structure randomly. Moreover, HE‐ZIF shows enhanced catalytic conversion of CO2 into carbonate compared with ZIF‐8 presumably a result of the synergistic effect of the five metal ions as Lewis acid in epoxide activation. Give me five: The synthesis of a hybrid high‐entropy material, a polymetallic zeolitic imidazolate framework (also named a high‐entropy zeolitic imidazolate framework, HE‐ZIF), is made possible by entropy‐driven room‐temperature mechanochemistry. HE‐ZIF contains five metals which are dispersed in the ZIF structure randomly and can be used for conversion of CO2 into carbonate. [ABSTRACT FROM AUTHOR]

Visible‐light‐driven photoreduction of CO2 to energy‐rich chemicals in the presence of H2O without any sacrifice reagent is of significance, but challenging. Herein, Eosin Y‐functionalized porous polymers (PEosinY‐N, N=1–3), with high surface areas up to 610 m2 g−1, are reported. They exhibit high activity for the photocatalytic reduction of CO2 to CO in the presence of gaseous H2O, without any photosensitizer or sacrifice reagent, and under visible‐light irradiation. Especially, PEosinY‐1 derived from coupling of Eosin Y with 1,4‐diethynylbenzene shows the best performance for the CO2 photoreduction, affording CO as the sole carbonaceous product with a production rate of 33 μmol g−1 h−1 and a selectivity of 92 %. This work provides new insight for designing and fabricating photocatalytically active polymers with high efficiency for solar‐energy conversion. Let the sunshine in: Eosin Y‐functionalized organic polymers exhibit high catalytic efficiency for CO2 photoreduction in the presence of H2O under visible‐light irradiation, affording CO as the sole carbonaceous product with a rate of 33 μmol g−1 h−1 and a selectivity of 92 %. No metal, sacrifice reagent, or photosensitizer are required. [ABSTRACT FROM AUTHOR]

Cover Picture: Ultrasonication-Induced Strong Metal-Support Interaction Construction in Water Towards Enhanced Catalysis (Angew. Keywords: CO2 Conversion; Encapsulation; Hydrogenation; Strong Metal-Support Interactions; Ultrasonication EN CO2 Conversion Encapsulation Hydrogenation Strong Metal-Support Interactions Ultrasonication 1 1 1 05/05/23 20230508 NES 230508 B A strong-metal support interaction b construction was induced via ultrasonication in water as described by Zhenzhen Yang, Sheng Dai et al. in their Communication (e202214322). CO2 Conversion, Encapsulation, Hydrogenation, Strong Metal-Support Interactions, Ultrasonication. [Extracted from the article]

The synthesis of hierarchically mesoporous polymers with multiple functionalities is challenging. Herein we reported a template-free strategy for synthesis of phenolic azo-polymers with hierarchical porous structures based on diazo-coupling reaction in aqueous solution under mild conditions. The resultant polymers have surface areas up to 593 m2 g−1 with the mesopore ratio of >80 %, and a good ability to complex with metal ions, such as Cu2+, Zn2+,Ni2+, achieving a metal loading up to 26.24 wt %. Moreover, the polymers complexed with Zn showed excellent performance for catalyzing the reaction of CO2 with epoxide, affording a TOF of 2570 h−1 in the presence of tetrabutyl ammonium bromide (7.2 mol %). The polymer complexed with Cu could catalyze the oxidation of alcohol with high efficiency. [ABSTRACT FROM AUTHOR]

The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO2-reactive protic ionic liquid (PIL), [HDBU+][TFE−], was designed by neutralization of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2-aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline-2,4(1 H,3 H)-diones in excellent yields. [ABSTRACT FROM AUTHOR]

Hierarchically mesoporouso‐hydroxyazobenzene polymers with high surface areas can be synthesized without the use of templates in water. In their Communication on page 9685 ff., Z. M. Liu and co‐workers show that these kinds of porous polymers have multiple functions, including excellent dispersity in polar and apolar solvents, good chelation to metal ions (Zn2+, Cu2+, etc.), ultrahigh selectivity for CO2/N2 separation, and excellent performance for catalyzing CO2 conversion. [ABSTRACT FROM AUTHOR]