Bridging oxidase catalysis and oxygen reduction electrocatalysis by model single-atom catalysts

【摘要】 Nanocatalysts with enzyme-like catalytic activities,such as oxidase mimics,are extensively used in biomedicine and environmental treatment.Searching for enzyme-like nanomaterials,clarifying the origins of catalytic activity and developing activity assessment methodologies are therefore of great significance.Here,we report that oxidase catalysis and oxygen reduction reaction(ORR) electrocatalysis can be well bridged based on their identical activity origins,which makes facile electro catalytic ORR activity measurements intrinsically applicable to oxidase-like activity evaluations.Inspired by natural heme-copper oxidases,Gu/Fe-doped single-atom catalysts(SACS) were first synthesized and used as model catalysts.Chromogenic reactions,electro chemical voltammetric measurements and density functional theory calculations further verified the linear relationship between the oxidase-like and ORR catalytic activities of the catalysts;thus,an effective descriptor(|jn|) is proposed for rapid enzymatic catalyst evaluation.Evidence suggests that the enhanced tumour therapeutic efficacy of SACs is a result of their oxidase-like/ORR activities,which proves that numerous ORR electrocatalysts are promising candidates for oxidase mimics and tumour therapy.The synergistic catalytic effect of the biomimetic heterobinuclear Cu-Fe centres has also been thoroughly probed.更多还原

【Abstract】 Nanocatalysts with enzyme-like catalytic activities,such as oxidase mimics,are extensively used in biomedicine and environmental treatment.Searching for enzyme-like nanomaterials,clarifying the origins of catalytic activity and developing activity assessment methodologies are therefore of great significance.Here,we report that oxidase catalysis and oxygen reduction reaction(ORR) electrocatalysis can be well bridged based on their identical activity origins,which makes facile electro catalytic ORR activity measurements intrinsically applicable to oxidase-like activity evaluations.Inspired by natural heme-copper oxidases,Gu/Fe-doped single-atom catalysts(SACS) were first synthesized and used as model catalysts.Chromogenic reactions,electro chemical voltammetric measurements and density functional theory calculations further verified the linear relationship between the oxidase-like and ORR catalytic activities of the catalysts;thus,an effective descriptor(|jn|) is proposed for rapid enzymatic catalyst evaluation.Evidence suggests that the enhanced tumour therapeutic efficacy of SACs is a result of their oxidase-like/ORR activities,which proves that numerous ORR electrocatalysts are promising candidates for oxidase mimics and tumour therapy.The synergistic catalytic effect of the biomimetic heterobinuclear Cu-Fe centres has also been thoroughly probed.更多还原