Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion of a singlecluster catalyst is challenging. In this work, for the first time, we present a versatile strategy for uniformly dispersed polyoxometalates (POMs) in covalent organic frameworks (COFs) through confining POM cluster into the regular nanopores of COF by a covalent linkage. These COF-POM composites combine the properties of light absorption, electron transfer, and suitable catalytic active sites; as a result, they exhibit outstanding catalytic activity in artificial photosynthesis: that is, CO 2 photoreduction with H 2 O as the electron donor. Among them, TCOF-MnMo 6 achieved the highest CO yield (37.25 μmol g −1 h −1 with ca. 100% selectivity) in a gas−solid reaction system. Furthermore, a mechanism study based on density functional theory (DFT) calculations demonstrated that the photoinduced electron transfer (PET) process occurs from the COF to the POM, and then CO 2 reduction and H 2 O oxidation occur on the POM and COF, respectively. This work developed a method for a uniform dispersion of POM single clusters into a COF, which also shows the potential of using COF-POM functional materials in the field of photocatalysis.

The precise tuning and multi‐dimensional processing of covalent organic frameworks (COFs)‐based materials into multicomponent superstructures with appropriate diversity are essential to maximize their advantages in catalytic reactions. However, up to now, it remains an ongoing challenge for the precise design of COFs‐based multicomponent nanocomposites with diverse architectures. Herein, a metal organic framework (MOF)‐sacrificed in situ acid‐etching (MSISAE) strategy that enables continuous synthesis of core‐shell, yolk‐shell, and hollow‐sphere COFs‐based nanocomposites through tuning of core decomposition (NH2‐MIL‐125 into TiO2) rate is developed. More importantly, due to the multiple active sites, fast transfer of carriers, increased light utilization ability, et al, one of the obtained samples, NH2‐MIL‐125/TiO2@COF‐366‐Ni‐OH‐HAc (yolk‐shell) with special three components, exhibits high photocatalytic CO2‐to‐CO conversion efficiency in the gas‐solid mode. The MSISAE strategy developed in this work achieves the precise morphology design and control of multicomponent hybrid composites based on COFs, which may pave a new way in devealoping porous crystalline materials with powerful superstructures for multifunctional catalytic reactions.

Structural exploration and functional application of thorium clusters are still very rare on account of their difficult synthesis caused by the susceptible hydrolysis of thorium element. In this work, we elaborately designed and constructed four stable thorium clusters modified with different functionalized capping ligands, Th 6 -MA, Th 6 -BEN, Th 6 -C8A, and Th 6 -Fcc, which possessed nearly the same hexanuclear thorium-oxo core but different capabilities in light absorption and charge separation. Consequently, for the first time, these new thorium clusters were treated as model catalysts to systematically investigate the lightinduced oxidative coupling reaction of benzylamine and thermodriven oxidation of aniline, achieving >90% product selectivity and approximately 100% conversion, respectively. Concurrently, we found that thorium clusters modified by switchable functional ligands can effectively modulate the selectivity and conversion of catalytic reaction products. Moreover, catalytic characterization and density functional theory calculations consistently indicated that these thorium clusters can activate O 2 /H 2 O 2 to generate active intermediates O 2 •− /HOO • and then improved the conversion of amines efficiently. Significantly, this work represents the first report of stable thorium clusters applied to photo/thermotriggered catalytic reactions and puts forward a new design avenue for the construction of more efficient thorium cluster catalysts.

The selective photoisomerization or photocyclization of stilbene to achieve value upgrade is of great significance in industry applications, yet it remains a challenge to accomplish both of them through a one-pot photocatalysis strategy under mild conditions. Here, a sevenfold interpenetrating 3D covalent organic framework (TPDT-COF) has been synthesized through covalent coupling between N,N,N,N-tetrakis(4-aminophenyl)-1,4-benzenediamine (light absorption and free radical generation) and 5,5′-(2,1,3-benzothiadiazole-4,7-diyl)bis[2-thiophenecarboxaldehyde] (catalytic center). The thus-obtained sevenfold interpenetrating structure presents a functional pore channel with a tunable photocatalytic ability and specific pore confinement effect that can be applied for selective stilbene photoisomerization and photocyclization. Noteworthily, it enables photogeneration of cisstilbene or phenanthrene with >99% selectivity by simply changing the gas atmosphere under mild conditions (Ar, Sele Cis . > 99%, Sele Phen . < 1% and O 2 , Sele Cis . < 1%, and Sele Phen . > 99%). Theoretical calculations prove that different gas atmospheres possess varying influences on the energy barriers of reaction intermediates, and the pore confinement effect plays a synergistically catalytic role, thus inducing different product generation. This study might facilitate the exploration of porous crystalline materials in selective photoisomerization and photocyclization.

Realizing simultaneously energy-efficiency improvement and green economic implementation remains a daunting challenge in addressing the low-efficiency issues of CO 2 electroreduction to meet the sustainable development strategy. Here, we propose a series of porphyrin-based COFs (TTCOF-M, M = Co, Ni, and Cu) as model catalysts to study the hybrid CO 2 electrocatalytic full reaction for the first time, during which the catalysts can simultaneously accomplish photoassisted CO 2 electroreduction and 4-nitrophenol (4-NP) mineralization. As model catalysts, the effects of various parameters have been intensively studied from typical tandem electro-reactions to extended photoassisted ones. Specifically, TTCOF-Co can achieve the cathodic reduction efficiency increasing from 90 to 96% (−0.7 V) after illumination and simultaneously 5 times shortened reaction time with a 4-NP degradation efficiency of ∼99%. Notably, the 4-NP mineralization rate is calculated to be ∼93.51% with ∼30.27 mmol/g/h CO 2 production rate, and a rarely investigated mechanism relating to the 4-NP electro-degradation has been intensively studied.