Atomic Layer Deposition of Cu Electrocatalysts on Gas Diffusion Electrodes for CO2 Reduction.

Electrochemical reduction of CO2 using Cu catalysts enables the synthesis of C2+ products including C2H4 and C2H5OH. In this study, Cu catalysts were fabricated using plasma-enhanced atomic layer deposition (PEALD), achieving conformal deposition of catalysts throughout 3-D gas diffusion electrode (GDE) substrates while maintaining tunable control of Cu nanoparticle size and areal loading. The electrochemical CO2 reduction at the Cu surface yielded a total Faradaic efficiency (FE) > 75% for C2+ products. Parasitic hydrogen evolution was minimized to a FE of ∼10%, and a selectivity of 42.2% FE for C2H4 was demonstrated. Compared to a line-of-sight physical vapor deposition method, PEALD Cu catalysts show significant suppression of C1 products compared to C2+, which is associated with improved control of catalyst morphology and conformality within the porous GDE substrate. Finally, PEALD Cu catalysts demonstrated a stable performance for 15 h with minimal reduction in the C2H4 production rate.

trans-Platinum planar amine compounds with [N2O2] ligand donor sets: effects of carboxylate leaving groups and steric hindrance on chemical and biological properties.

Replacement of NH3 by a planar amine L to give trans-[PtCl2(L)(L')] (L = NH3, L'= pyridine or substituted pyridine, quinoline, isoquinoline, thiazole; L = L'= pyridine, thiazole), greatly enhances the cytotoxicity of the transplatinum geometry. The "parent" compound trans-[PtCl2(NH3)2] is therapeutically inactive. Modification of the ligands to an [N2O2] donor set, where O represents an acetate leaving group, enhances the aqueous solubility while retaining the cytotoxicity of the parent chloride compounds. The effect of two mutual trans leaving groups with weak trans influence is to impart remarkable chemical stability on the structure. This strategy is analogous to the use of the inert dicarboxylate leaving groups in the clinical compounds carboplatin and oxaliplatin. In this paper, systematic modification of the steric effects of carrier pyridine groups and, especially, carboxylate leaving groups in trans-[Pt(O2CR)2(NH3)(pyr)] is shown to modulate aqueous solubility and hydrolysis to the activated aqua species. The results presented here demonstrate the utility of the "carboxylate strategy" in "fine-tuning" the chemical and pharmacokinetic properties in the design of clinically relevant transplatinum complexes.