Proton-gradient-transfer acid complexes and their catalytic performance for the synthesis of geranyl acetate

Special proton-gradient-transfer acid complexes （PGTACs） in which the bonded protons are not equivalent and have gradients in transfer ability, acidity, and reactivity were reported. The acidity gradient of the protons gave the PGTACs excellent catalytic activity and selectivity in the esterifica- tion of terpenols. These PGTACs are ＂reaction-induced self-separation catalysts＂ and can be easily reused. The kinetics with PGTACs as catalyst in the esterification of geraniol were also studied for use in engineering design.

Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO_(2) electrolysis

Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splitting,which is still challenging for developing efficient single-atom catalysts limited by their structural simplicity usually incompetent to handle this task.Incorporation of extra functional units should be viable.Herein,a proton deployment strategy is demonstrated via“atomic and nanostructured iron(A/N-Fe)pairs”,comprising atomically dispersed iron active centers spin-polarized by nanostructured iron carbide ferromagnets,to boost the critical protonation steps.The as-designed catalyst displays a broad window(300 mV)for CO selectivity>90%(98%maximum),even outperforming numerous cutting-edge M–N–C systems.The well-placed control of proton dynamics by A/N-Fe can promote*COOH/*CO formation and simultaneously suppress H2 evolution,benefiting from the magnetic-proximity-induced exchange splitting(spin polarization)that properly adjusts energy levels of the Fe sites’d-shells,and further those of the adsorbed intermediates’antibonding molecular orbitals.