The First Catalytic Synthesis of an Acrylate from CO2 and an Alkene—A Rational Approach

For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C₁ building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO₂, ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.     

Synthesis and Self‐Association of Double‐Helical AADD Arrays

The design and syntheses of four self‐complementary oligomers that contain an underlying AADD hydrogen bond sequence are presented, and their self‐association was examined in the solution and solid state. The molecular recognition between the two strands is highly sensitive to substitutions of their component heterocycles. Substitution with electron‐donating and ‐withdrawing groups and the influence of preorganization has a large effect on the overall stabilities of the complexes studied. In particular, a wide range (>10⁵ M ^?1) of stabilities with respect to substitutions at various positions in the AADD oligomers was demonstrated. In the most extreme case, the dimerization constant measured (K_dimer≥4.5×10⁷ M ^?1) is comparable to the most stable homodimers of neutral AADD arrays reported to date.     

Does a Photocatalytic Synergy in an Anatase–Rutile TiO2 Composite Thin‐Film Exist?

It has often been suggested that anatase–rutile mixtures/composites synergistically enhance photocatalysis. However, in the case of dense thin‐films containing an intimate mix of both anatase and rutile phases, such an effect has not been observed. In synthesising combinatorial films with graded film thickness and phase, and applying established photocatalytic mapping methods, we were able to assess how dense thin‐films of intimately mixed anatase–rutile mixtures affect photocatalytic performance. We found that no photocatalytic synergy between anatase–rutile composites (29≤rutile %≤83) within such dense thin‐film systems exists. In fact, an increased presence of rutile caused the photocatalytic activity to fall. This was explained by the unfavourable energetics in the multiple electron transfers required between several neighbouring rutile and anatase sites for the photo‐generated electron to reach the material’s surface; encouraging the trapping of electrons within the bulk and increasing the likelihood of charge recombination. The decrease in photocatalytic activity was found to vary linearly with rutile component.