Pseudo-single atom Pt catalysts have achieved an excellent selectivity to branched paraffins and cycloalkanes in n-hexane reforming here. Highly dispersed platinum in single-atom and small clusters made up of several separated atoms was produced under the inducement of Sn or Zr as promoting components. The Sn or Zr oxides were topologically transformed from layered double hydroxides as precursors, and thus homogeneously dispersed owing to the confinement of the brucite-like lattices. The lattice confinement also caused the promoter sites charge-transferred, affording electron-rich (Sn) or electron-defected (Zr) sites on the surface, thereby facilitating the inducement to Pt sites. This strategy provides an effective and feasible alternative for the facile preparation of highly dispersed metal catalysts. In n-hexane reforming, a selectivity of up to 95 % to branched paraffins and cycloalkanes was obtained with the pseudo-single-atom Pt catalysts.

Effectively enhancing the enantioselectivity is a persistent challenge in heterogeneous asymmetric catalysis. Here, the validity of a layered double hydroxides (LDH) nanosheet as an efficient planar substituent to enhance the enantioselectivity has been investigated theoretically; first in vanadium-catalyzed asymmetric epoxidation of allylic alcohols, and then in zinc-catalyzed direct asymmetric aldol addition. The computational predication is further confirmed experimentally in zinc-catalyzed direct asymmetric aldol addition by controlling the location of catalytic sites.

An efficient ligand design strategy towards boosting asymmetric induction was proposed, which simply employed inorganic nanosheets to modify α-amino acids and has been demonstrated to be effective in vanadium-catalyzed epoxidation of allylic alcohols. Here, the strategy was first extended to zinc-catalyzed asymmetric aldol reaction, a versatile bottom-up route to make complex functional compounds. Zinc, the second-most abundant transition metal in humans, is an environment-friendly catalytic center. The strategy was then further proved valid for organocatalyzed metal-free asymmetric catalysis, that is, α-amino acid catalyzed asymmetric aldol reaction. Visible improvement of enantioselectivity was experimentally achieved irrespective of whether the nanosheet-attached α-amino acids were applied as chiral ligands together with catalytic Zn^II centers or as chiral catalysts alone. The layered double hydroxide nanosheet was clearly found by theoretical calculations to boost ee through both steric and H-bonding effects; this resembles the role of a huge and rigid substituent.

The use of suitable chiral ligands is an efficient means of producing highly enantioselective transition-metal catalysts. Herein, we report a facile, economic, and effective strategy for the design of chiral ligands that demonstrate enhanced enantioselectivity and catalytic efficacy. Our simple strategy employs naturally occurring or synthetic inorganic nanosheets as huge and rigid planar substituents for, but not limited to, naturally available α-amino-acid ligands; these ligands were successfully used in the vanadium-catalyzed asymmetric epoxidation of allylic alcohols. The crucial role of the inorganic nanosheets as planar substituents in improving the enantioselectivity of the reaction was clearly revealed by relating the observed enantiomeric excess with the distribution of the catalytic centers and the accessibility of the substrate molecules to the catalytic sites. DFT calculations indicated that the LDH layer improved the enantioselectivity by influencing the formation and stability of the catalytic transition states, both in terms of steric resistance and H-bonding interactions.