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We demonstrate an electrostatic confinement-induced charge transfer pathway in a supramolecular photocatalyst comprising of an ionic covalent organic framework (COF) and cationic metal complexes. The dynamic electrostatic interactions not only attract cations around the COF to accept photogenerated electrons, but also allows for a retention of homogeneous catalytic characters of complexes, making a subtle balance. Accordingly, the electrostatic confinement effect facilitates the forward electron transfer from a photoexcited COF to cationic Co complex, realizing a remarkable photocatalytic CO2 reduction performance. Its catalytic efficiency is far superior to the supramolecular counterparts with Van-der-Waals or hydrogen bonding interactions. This work presents an insight for enhancing charge transfer in supramolecular systems, and provides an effective approach for construction of highly efficient photocatalysts., (© 2024 Wiley‐VCH GmbH.)

Metal complex-based photocatalysts are promising for CO2 reduction. Their catalytic performances greatly rely on the synergy of ligands and metal ions. Here, we demonstrate an assembly of covalent organic cage (COC) and metal ions for photocatalytic CO2 reduction. The coordinated metal serves as catalytically active site for CO2 reduction, while the cage not only chelates the metal site, but also enhances the local concentration of CO2 around metal site, and decreases the key intermediate reaction energy barrier, thereby promoting the CO2 reduction reaction kinetically and thermodynamically. Accordingly, a Ni metalized COC exhibited outstanding photocatalytic performance in CO2-to-CO conversion under visible light irradiation. This study highlights the feasibility and advantage of organic cages for the construction of photocatalysts for artificial photosynthesis., (© 2024 Wiley‐VCH GmbH.)

The design of photocatalytic supramolecular systems composing of semiconductors and molecular metal complexes for CO 2 reduction has attracted increasing attention. The supramolecular system combines the structural merits of semiconductors and metal complexes, where the semiconductor harvests light and undertakes the oxidative site, while the metal complex provides activity for CO 2 reduction. The intermolecular charge transfer plays crucial role in ensuring photocatalytic performance. Here, we review the progress of photocatalytic supramolecular systems in reduction of CO 2 and highlight the interfacial charge transfer pathways, as well as their state-of-the-art characterization methods. The remaining challenges and prospects for further design of supramolecular photocatalysts are also presented., (© 2024 Wiley-VCH GmbH.)

Supramolecular systems consisting of covalent organic frameworks (COFs) and Ni complex are designed for robust photocatalytic reduction of CO 2 . Multiple heteroatom-hydrogen bonding between the COF and Ni complex is identified to play a decisive role in the photoexcited electron transfer across the liquid-solid interface. The diminution of steric groups on COF or metal complex can optimize catalytic performance, which is more attributable to the enhanced hydrogen-bond interaction rather than their intrinsic activity. The photosystem with relatively strong strength of hydrogen bonds exhibits remarkable photocatalytic CO 2 -to-CO conversion, far superior to photosystems with supported atomic Ni or metal complex alone in the absence of hydrogen-bond effect. Such heteroatom-hydrogen bonds bridging electron transport pathway confers supramolecular system with high photocatalytic performance, providing an avenue to rationally design efficient and steadily available photosystems., (© 2023 Wiley-VCH GmbH.)

In photocatalysis, reducing the exciton binding energy and boosting the conversion of excitons into free charge carriers are vital to enhance photocatalytic activity. This work presents a facile strategy of engineering Pt single atoms on a 2D hydrazone-based covalent organic framework (TCOF) to promote H 2 production coupled with selective oxidation of benzylamine. The optimised TCOF-Pt SA photocatalyst with 3 wt% Pt single atom exhibited superior performance to TCOF and TCOF-supported Pt nanoparticle catalysts. The production rates of H 2 and N-benzylidenebenzylamine over TCOF-Pt SA3 are 12.6 and 10.9 times higher than those over TCOF, respectively. Empirical characterisation and theoretical simulation showed that the atomically dispersed Pt is stabilised on the TCOF support through the coordinated N 1 -Pt-C 2 sites, thereby induing the local polarization and improving the dielectric constant to reach the low exciton binding energy. These phenomena led to the promotion of exciton dissociation into electrons and holes and the acceleration of the separation and transport of photoexcited charge carriers from bulk to the surface. This work provides new insights into the regulation of exciton effect for the design of advanced polymer photocatalysts., (© 2023 Wiley-VCH GmbH.)

Crystalline covalent organic frameworks (COFs) are porous polymeric semiconductors with network topologies, which are built from the integration of selected organic blocks with covalent bond linkages. They have shown great promise for artificial photosynthesis, owing to broad light harvesting, high crystallinity, and high carrier mobility. This Minireview introduces state-of-the-art COF photocatalysts based on different linkages and discusses the origin of photocatalytic activities for hydrogen evolution. Three typical COF photocatalysts, with linkages including imine (-C=N-), β-ketoenamine (O=C-C=C-NH-), and vinylene (-C=C-), are discussed with a particular focus on the advancements in synthetic methodologies and structural design, as well as photoelectronic properties that are relevant to photocatalytic performance. The Minireview is expected to elucidate their structure-property relationships and the way to design photoactive COFs with enhanced performances., (© 2021 Wiley-VCH GmbH.)

Facile fabrication of nanocatalysts consisting of metal nanoparticles (NPs) anchored on a functional support is highly desirable, yet remains challenging. Covalent organic frameworks (COFs) provide an emerging materials platform for structural control and functional design. Here, a facile one-pot in situ reduction approach is demonstrated for the encapsulation of small Pd NPs into the shell of COF-derived hollow polyamine spheres (Pd@H-PPA). In the one-pot synthetic process, the nucleation and growth of Pd NPs in the cavities of the porous shell take place simultaneously with the reduction of imine linkages to secondary amine groups. Pd@H-PPA shows a significantly enhanced catalytic activity and recyclability in the tandem dehydrogenation of ammonia borane and selective hydrogenation of nitroarenes through an adsorption-activation-reaction mechanism. The strong interactions of the secondary amine linkage with borane and nitroarene molecules afford a positive synergy to promote the catalytic reaction. Moreover, the hierarchical structure of Pd@H-PPA allows the accessibility of active Pd NPs to reactants., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photocatalytic conversion of CO 2 into value-added chemical fuels is a promising approach to address the depletion of fossil energy and environment-related concerns. Tailor-making the electronic properties and band structures of photocatalysts is pivotal to improve their efficiency and selectivity in photocatalytic CO 2 reduction. Herein, a covalent triazine-based framework was developed containing electron-donor triphenylamine and electron-acceptor triazine components (DA-CTF). The engineered π-conjugated electron donor-acceptor dyads in DA-CTF not only optimized the optical bandgap but also contributed to visible-light harvesting and migration of photoexcited charge carriers. The activity of photocatalytic CO 2 reduction under visible light was significantly improved compared with that of traditional g-C 3 N 4 and reported covalent triazine-based frameworks. This study provides molecular-level insights into the mechanism of photocatalytic CO 2 reduction., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photocatalytic CO 2 reduction into carbonaceous feedstock chemicals is a promising renewable energy technology to convert solar energy and greenhouse gases into chemical fuels. Here, a covalent triazine-based framework (CTF) is demonstrated as an efficient cocatalyst to reduce CO 2 under visible-light irradiation. The nitrogen-rich triazine moieties in CTF contribute to CO 2 adsorption, while the periodical pore structure of CTF favors the accommodation of CO 2 and electron mediator. Immobilization of cobalt species onto CTF promotes the photocatalytic activity with a 44-fold enhancement over pristine CTF and the optimal CO production rate of the obtained Co/CTFs was up to 50 μmol g -1 h -1 . The results of solid-state UV-vis diffuse reflectance spectra (UV-vis DRS), CO 2 adsorption and electrochemical impedance spectroscopy (EIS) illustrated that the increased activity was ascribed to the enhanced CO 2 capture capacity, improved absorption of visible-light and facilitated the transfer of charge from CTF to CO 2 molecules. The CTF not only serves as a substrate for active Co species, but also bridges the photosensitizer with cobalt catalytic sites for the efficient transfer of photoexcited electrons. This work highlights the capability and ease of fabricating covalent organic framework-based photocatalytic systems that are potentially useful for energy-conversion applications., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Yolk-shell nanoreactors have received considerable interest for use in catalysis. However, the controlled synthesis of continuous crystalline shells without imperfections or cracks remains challenging. Here, a strategy for the synthesis of yolk-shell metal nanoparticles@covalent organic framework (MNPs@COF) nanoreactors by using MNPs@ZIF-8 core-shell nanostructures as a self-template is designed and developed. The COF shell is formed through an amorphous-to-crystalline transformation process of a polyimine shell in a mildly acidic solution, while the ZIF-8 is etched in situ, generating a void space between the MNPs core and the COF shell. With the protection of the COF shell, multiple ligand-free MNPs are confined inside of the hollow nanocages. Importantly, the synthetic strategy can be generalized to engineer the functions and properties of the designed yolk-shell nanocages by varying the structure of the COF shell and/or the composition of the core MNPs. Representative Pd@H-TpPa yolk-shell nanocages with active Pd NP cores and permeable TpPa shells exhibit high catalytic activity and stability in the reduction of 4-nitrophenol by NaBH 4 at room temperature., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

MoS 2 quantum dots (QDs)-modified covalent triazine-based framework (MoS 2 /CTF) composites are synthesized through an in situ photodeposition method. MoS 2 QDs are well distributed and stabilized on the layers of CTFs by coordination of the frameworks to MoS 2 . The QDs-sheet interactions between MoS 2 and CTFs facilitate interfacial charge transfer and separation. As a consequence, the composites exhibit outstanding photocatalytic activity and stability for hydrogen evolution under visible light irradiation (λ≥420 nm), that exceed those over pristine CTFs and MoS 2 -modified g-C 3 N 4 (MoS 2 /g-C 3 N 4 ) composite, making them promising materials for solar energy conversion., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Covalent organic frameworks (COFs) with hollow structures hold great promise for developing new types of functional materials. Herein, we report a hollow spherical COF with a hierarchical shell, which serves as an effective precursor of B,N-codoped hierarchical hollow carbon spheres. Benefiting from the synergistic effects of hierarchical porosity, high surface area, and B,N-codoping, the as-synthesized carbon spheres show prospective utility as metal-free catalysts in nitroarene reduction. A mechanistic hypothesis is proposed based on theoretical and experimental studies. Boron atoms situated meta to pyridinic N atoms are identified to be the main catalytic active sites. The anti-aromaticity originating from the codoping of B and pyridinic N atoms, not charge distribution and deformation energy, is confirmed to play a pivotal role in the catalytic reaction., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Covalent triazine-based frameworks (CTFs) with a graphene-like layered morphology have been controllably synthesized by the trifluoromethanesulfonic acid-catalyzed nitrile trimerization reactions at room temperature via selecting different monomers. Platinum nanoparticles are well dispersed in CTF-T1, which is ascribed to the synergistic effects of the coordination of triazine moieties and the nanoscale confinement effect of CTFs. CTF-T1 exhibits excellent photocatalytic activity and stability for H2 evolution in the presence of platinum under visible light irradiation (λ ≥ 420 nm). The activity and stability of CTF-T1 are comparable to those of g-C3 N4 . Importantly, as a result of the tailorable electronic and spatial structures of CTFs that can be achieved through the judicial selection of monomers, CTFs not only show great potential as organic semiconductor for photocatalysis but also may provide a molecular-level understanding of the inherent heterogeneous photocatalysis., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The facile synthesis of palladium N-heterocyclic carbene (NHC) particles with spherical, cubic, and honeycomb morphologies is accomplished. The structures of cubic and honeycomb particles are defined as an unprecedented trinuclear palladium-NHC complex. An obvious effect of particle morphologies on catalytic activity and recyclability is observed in hetero-geneous cyanosilylation., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two urea-based porous organic frameworks, UOF-1 and UOF-2, were synthesized through a urea-forming condensation of 1,3,5-benzenetriisocyanate with 1,4-diaminobenzene and benzidine, respectively. UOF-1 and UOF-2 possess good hydrophilic properties and high scavenging ability for palladium. Their palladium polymers, PdII/UOF-1 and PdII/UOF-2, exhibit high catalytic activity and selectivity for Suzuki–Miyaura cross-coupling reactions and selective reduction of nitroarenes in water. The catalytic reactions can be efficiently performed at room temperature. Palladium nanoparticles with narrow size distribution were formed after the catalytic reaction and were well dispersed in UOF-1 and UOF-2. XPS analysis confirmed the coordination of the urea oxygen atom with palladium. SEM and TEM images showed that the original network morphology of UOF-1 and UOF-2 was maintained after palladium loading and catalytic reactions.

Three ionic nitrogen-containing chelating ligands (L1-L3) are synthesized readily through alkylation and quaternization of 2,2'-dipyridylamine. The charge distributions and natural bond orbital analyses of their cations are implemented by using density functional theory calculations. The catalytic performances of their water-soluble palladium complexes are evaluated preliminarily by using the Suzuki-Miyaura cross-coupling reaction, and high catalytic activities of aryl bromides and chlorides are achieved in neat water. The mercury drop test, poison experiments, and TEM analysis are used to demonstrate the formation of palladium nanoparticles (NPs) after the catalytic reaction. The effects of pendant ionic groups in L1-L3 on the catalytic activities and structures of the palladium NPs are disclosed. These NPs are stable in water for several weeks; they are stabilized by synergetic interactions between the chelating coordination of the 2,2'-dipyridylamino group to the surface of the palladium NPs and the electrostatic repulsion of the ionic groups in L1-L3., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The reaction of bis- or tris-chelating nitrogen-containing ligands (L1-L5) with CuI gave rise to five coordination complexes consisting of Cu 2 I 2 dimeric units. L1 in complex 1 adopts a cis conformation and links Cu 2 I 2 into a dinuclear structure. L2 and L3 in complexes 2 and 3 exhibit a trans conformation, and the alternative linkage of L2 or L3 and Cu 2 I 2 results in the formation of a 1D chain. In complex 4, two pyrazolyl-pyridine units of L4 at the same side of the central phenyl ring are connected to Cu 2 I 2 forming a tetranuclear macrocycle, and the third pyrazolyl-pyridine unit at the other side of the central phenyl ring further links the macrocycle into a 1D chain. L5 bridges Cu 2 I 2 in a cis conformation forming a tetranuclear complex, which is very different from 1 owing to the difference of the electronic property between pyrazolyl and triazolyl rings. The coordination nitrogen atoms in two pairs of ortho-positioned nitrogen-containing chelating rings in L1 and L5 are directed toward opposite and the same directions, respectively. Complexes 1-4 containing pyrazolyl-pyridine units showed luminescence whereas no clear emission was observed in complex 5 containing triazolyl-pyridine units, despite the fact that they were investigated under the same conditions. The application of complexes 1-5 in the copper(I)-catalyzed Ullmann cross-coupling reaction and azide-alkyne cycloaddition reaction was preliminarily evaluated., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of click ionic salts 4 a-4 n was prepared through click reaction of organic azides with alkyne-functionalized imidazolium or 2-methylimidazolium salts, followed by metathesis with lithium bis(trifluoromethanesulfonyl)amide or potassium hexafluorophosphate. All salts were characterized by IR, NMR, TGA, and DSC, and most of them can be classified as ionic liquids. Their steric and electronic properties can be easily tuned and modified through variation of the aromatic or aliphatic substituents at the imidazolium and/or triazolyl rings. The effect of anions and substituents at the two rings on the physicochemical properties was investigated. The charge and orbital distributions based on the optimized structures of cations in the salts were calculated. Reaction of 4 a with PdCl(2) produced mononuclear click complex 4 a-Pd, the structure of which was confirmed by single-crystal X-ray diffraction analysis. Suzuki-Miyaura cross-coupling shows good catalytic stability and high recyclability in the presence of PdCl(2) in 4 a. TEM and XPS analyses show formation of palladium nanoparticles after the reaction. The palladium NPs in 4 a are immobilized by the synergetic effect of coordination and electrostatic interactions with 1,2,3-triazolyl and imidazolium, respectively., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)