Effect of linker functionalisation on the catalytic properties of Cu nanoclusters embedded in MOFs in direct CO and CO₂ reduction by H₂

Abstract

Metal-organic frameworks are promising host supporting matrices for catalytically active guest. In particular, their crystallinity renders them desirable as their pores may act as atom-precise templates for the growth of...

Polycationic Rh–JosiPhos Polymers Supported on Phosphotungstic Acid/Al2O3 by Multiple Electrostatic Attractions

“…This catalyst hydrogenated DMI (0.2% Rh, 6.5 atm H 2 , MeOH, 20 °C, ∼15 min/run, TOF ∼ 2000 h –1 ) in 10 batch hydrogenations (ee = 94–90%, total TON = 4930). Noncovalently immobilized catalysts can suffer from metal leaching and subsequent loss in activity. − ,− Immobilized cationic catalysts, for example, may exchange with cationic impurities present during the hydrogenation.…”

“…Heterogeneous catalysis can address these shortcomings by allowing recovery and reuse of the catalyst. Many methods to immobilize chiral catalysts are reported in the literature. − Non-covalent immobilization strategies include electrostatic attraction, adsorption, encapsulation, and solvent systems such as ionic liquids , or supercritical CO 2 . , In enantioselective hydrogenation, a prominent heterogenization approach is to adsorb cationic Rh-diphosphine catalysts onto anionic supports through electrostatic interactions. ,,, Such inorganic supports include Hectorite clay, mesoporous aluminosilicate Al-MCM-41, and AlTUD-1. , The most common, developed by Augustine et al, are heteropoly acids [e.g., phosphotungstic acid (PTA)] adsorbed onto Al 2 O 3 . − ,, …”

Concluding remarks: current and next generation MOFs

“…These include hybrids with organic polymers, composites with metals, hybrids with metal oxides, and COFs. 40 In this Faraday Discussion, graphitic carbon nitride/MOF 41 and nanoclusters/MOF 42 were discussed.…”

Direct CO2 to methanol reduction on Zr6-MOF based composite catalysts: a critical review

“…Most importantly, Zr 6 MOFs have been shown to be excellent templates and supports for catalytically active species, including those for CO 2 reduction to methanol. [37][38][39][40][41][42][43][44][45][46] In this review, we analyse the status of thermocatalytic CO 2 hydrogenation by composite Zr 6 MOFs-based catalysts. Firstly, we briefly provide information regarding the fundamentals of the process including, thermodynamics and possible reaction mechanisms.…”

“…Experimental catalytic performance trends and mechanistic insights for Zr 6 MOF-based catalyst Zr 6 -based MOF structures and incorporated metal particles have been successfully studied as composite catalysts for CO 2 hydrogenation to methanol in the literature. [37][38][39][40][41][42][43][44][45][46][86][87][88] Each study has numerous variables in terms of structural, compositional, and reaction parameters aimed to effectively improve the dispersion of catalytic sites and the adsorption and activation of CO 2 for efficient catalysis of CO 2 hydrogenation at lower temperatures. Furthermore, the inorganic nodes of MOFs may provide Lewis and Brønsted acid sites, which can contribute to activating CO 2 or stabilising certain intermediates.…”