Shvo-Catalyzed Hydrogenation of CO2 in the Presence or Absence of Ionic Liquids for Tandem Reactions.

Ionic liquids (ILs) have been widely used in transition metal-catalyzed processes, but the precise behavior of ILs and catalysts in these reactions is unknown. Herein, the role of ILs and the interaction pattern between Shvo's catalyst and ILs have been revealed with characterization by 1H NMR and crystallography based on the catalytic hydrogenation of CO2. ILs promote the dissociation of Shvo's catalyst and enhance the rate of production of CO. The CO that is produced is subsequently used in the tandem hydroformylation-reduction of alkenes to produce valuable alcohols. In the absence of ILs, formamides can be obtained by N-formylation of most primary or secondary amines.

Polyoxometalate-Based Catalysts for CO2 Conversion.

Polyoxometalates (POMs) are a diverse class of anionic metal-oxo clusters with intriguing chemical and physical properties. Owing to unrivaled versatility and structural variation, POMs have been extensively utilized for catalysis for a plethora of reactions. In this focused review, the applications of POMs as promising catalysts or co-catalysts for CO2 conversion, including CO2 photo/electro reduction and CO2 as a carbonyl source for the carbonylation process are summarized. A brief perspective on the potentiality in this field is proposed.

Recent advances of polyoxometalate-catalyzed selective oxidation based on structural classification.

The structural diversity and tenability observed in POMs has encouraged extensive investigations into their catalytic activity. Based on the structural classification of POMs, this review summarizes recent advances relating to POM-catalyzed selective oxidation and places most emphasis on dynamic developments from 2015 onwards. Work which contributes to comparing the catalytic performance of POMs with delicate structural differences (e.g. the same type of POM structure with differences of the heteroatom, addenda, protonated state or counter-ion) and in elucidating the origin/distinction of catalytic activity, as well as reasonable mechanisms, are especially highlighted.