Achieving High Photo/Thermocatalytic Product Selectivity and Conversion via Thorium Clusters with Switchable Functional Ligands

Abstract

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.

Spatial Decoupling of Redox Chemistry for Efficient and Highly Selective Amine Photoconversion to Imines

“…At the same time, NH 3 forms along with NBI production, as suggested by the appearance of N–H bending and stretching vibrations for NH 3 (1597 and 3309 cm –1 ). Notably, no characteristic IR peak of CO bond is resolved (e.g., the stretching vibration at ∼1700 cm –1 ), which suggests that BA photoconversion to NBI on CoP@ZnIn 2 S 4 photocatalysts does not involve the benzaldehyde intermediate. − Isotope-labelling in situ DRIFTS experiment using benzyl-α,α-d2-amine (BA-D2) as the reactant further corroborates the above photoconversion mechanism of BA to NBI. Due to the isotope effect, C–H stretching vibrations of BA (2942 and 2866 cm –1 ) and benzyl imine intermediate (2889 cm –1 ) shift to the lower wavenumber region (2211 and 2095 cm –1 for BA-D2; 2160 cm –1 for deuterium-containing benzyl imine intermediate), while the CN stretching vibrations of the benzyl imine intermediate and the NBI product shift from 1640 and 1665 to 1627 and 1649 cm –1 , respectively (Figure d).…”

Modulating the Electronic Structure of α-Fe2O3 by Doping Atomically Dispersed Ce for the Transfer Hydrogenation of Nitroaromatics Using Stoichiometric Hydrazine Hydrate

“…Based on these results, we were able to exclude AOB and AB as intermediates. Moreover, NSB can quickly react with PHA to form AOB (Table , entry 16). , The kinetic experimental result of NB (Figure a) proved that a certain amount of PHA exists in the reaction process. Therefore, if AN was produced via intermediate NSB, AOB should be detected during the reduction process of NB.…”

Layered Co–O Cluster Applied to Photocatalytic CO2 Reduction

“…The rapid development of the global economy demands abundant energy consumption . Most of that energy is derived from burning fossil fuels. , The behavior of uncontrolled use of fossil fuels has created serious energy challenges due to their nonrenewable and limited reserves and also posed environmental threats owing to the release of excess CO 2 . − Therefore, there is an urgent call for prompt action to the catalytic conversion of CO 2 to various clean energies or valuable chemicals. − Among various strategies, photocatalytic CO 2 RR has attracted much attention from researchers. − It has lived up to its reputation as a ponderable and sustainable method of converting CO 2 for the reason that it can availably make use of solar power to reduce CO 2 to value-added chemicals. − Nevertheless, the reduction process is considerably demanding because of the tardy reaction kinetics of CO 2 . As a consequence, developing photocatalysts that are economical, high-performance, and environmentally friendly is the top priority.…”