RESUMO
Despite the widespread investigations on the M-N-C type single atom catalysts (SACs) for oxygen evolution reaction (OER), an internal conflict between its intrinsic thermodynamically structural instability and apparent catalytic steadiness has long been ignored. Clearly unfolding this contradiction is necessary and meaningful for understanding the real structure-property relation of SACs. Herein, by using the well-designed pH-dependent metal leaching experiments and X-ray absorption spectroscopy, an unconventional structure reconstruction of M-N-C catalyst during OER process was observed. Combining with density functional theory calculations, the initial Ni-N coordination is easily broken in the presence of adsorbed OH*, leading to favorable formation of Ni-O coordination. The formed Ni-O works stably as the real active center for OER catalysis in alkaline media but unstably in acid, which clearly explains the existing conflict. Unveiling the internal contradiction between structural instability and catalytic steadiness provides valuable insights for rational design of single atom OER catalysts.
RESUMO
Electrochemical hydrogenation of acetonitrile based on well-developed proton exchange membrane electrolyzers holds great promise for practical production of ethylamine. However, the local acidic condition of proton exchange membrane results in severe competitive proton reduction reaction and poor selection toward acetonitrile hydrogenation. Herein, we conduct a systematic study to screen various metallic catalysts and discover Pd/C exhibits a 43.8% ethylamine Faradaic efficiency at the current density of 200 mA cm-2 with a specific production rate of 2912.5 mmol g-1 h-1, which is about an order of magnitude higher than the other screened metal catalysts. Operando characterizations indicate the in-situ formed PdHx is the active centers for catalytic reaction and the adsorption strength of the *MeCH2NH2 intermediate dictates the catalytic selectivity. More importantly, the theoretical analysis reveals a classic d-band mediated volcano curve to describe the relation between the electronic structures of catalysts and activity, which could provide valuable insights for designing more effective catalysts for electrochemical hydrogenation reactions and beyond.
RESUMO
While Ru owns superior catalytic activity toward hydrogen oxidation reaction and cost advantages, the catalyst deactivation under high anodic potential range severely limits its potential to replace the Pt benchmark catalyst. Unveiling the deactivation mechanism of Ru and correspondingly developing protection strategies remain a great challenge. Herein, we develop atomic Pt-functioned Ru nanoparticles with excellent anti-deactivation feature and meanwhile employ advanced operando characterization tools to probe the underlying roles of Pt in the anti-deactivation. Our studies reveal the introduced Pt single atoms effectively prevent Ru from oxidative passivation and consequently preserve the interfacial water network for the critical H* oxidative release during catalysis. Clearly understanding the deactivation nature of Ru and Pt-induced anti-deactivation under atomic levels could provide valuable insights for rationally designing stable Ru-based catalysts for hydrogen oxidation reaction and beyond.