Atomically dispersed M-N-C (M refers to transition metals) materials represent the most promising catalyst alternatives to the precious metal Pt for the electrochemical reduction of oxygen (ORR), yet the genuine active sites in M-N-C remain elusive. Here, we develop a two-step approach to fabricate Cu-N-C single-atom catalysts with a uniform and well-defined Cu 2+ -N 4 structure that exhibits comparable activity and superior durability in comparison to Pt/C. By combining operando X-ray absorption spectroscopy with theoretical calculations, we unambiguously identify the dynamic evolution of Cu-N 4 to Cu-N 3 and further to HO-Cu-N 2 under ORR working conditions, which concurrently occurs with reduction of Cu 2+ to Cu + and is driven by the applied potential. The increase in the Cu + /Cu 2+ ratio with the reduced potential indicates that the low-coordinated Cu + -N 3 is the real active site, which is further supported by DFT calculations showing the lower free energy in each elemental step of the ORR on Cu + -N 3 than on Cu 2+ -N 4 . These findings provide a new understanding of the dynamic electrochemistry on M-N-C catalysts and may guide the design of more efficient low-cost catalysts.

Chinese bayberry (Myrica rubra) is a fruit crop with cultivars producing fruit ranging from white (Shuijing, SJ) to red (Dongkui, DK) and dark red-purple (Biqi, BQ), as a result of different levels of anthocyanin accumulation. Genes encoding the anthocyanin biosynthesis enzymes chalcone synthase, chalcone isomerase, flavanone 3-hydroxylase (F3H), flavonoid 3'-hydroxylase (F3'H), dihydroflavonol 4-reductase (DFR), anthocyanidin synthase (ANS) and UDPglucose: flavonoid 3-O-glucosyltransferase (UFGT), as well as MrMYB1, a R2R3 MYB transcription factor homologous to known activators of anthocyanin biosynthesis, were isolated from ripe fruit of BQ. Differences in mRNA abundance of MrF3H, MrF3'H, MrDFR1, MrANS and MrUFGT were highly correlated with differential accumulation of anthocyanins between cultivars, suggesting coordinated regulation by transcription factors. The transcript level of MrMYB1 was strongly associated with the anthocyanin content in ripe fruit of the three cultivars, as well as different anthocyanin containing tissues of BQ fruit. Fruit bagging strongly inhibited anthocyanin accumulation in fruit as well as the expression of all anthocyanin biosynthetic genes and MrMYB1. Overexpression of MrMYB1 stimulated both anthocyanin accumulation and activated an Arabidopsis-DFR promoter in tobacco (Nicotiana tabacum). MrMYB1d, an allele with a 1 bp deletion at nucleotide 30 of coding sequence, was observed in SJ and DK fruit, suggesting that a nonsense mutation of the MYB1 protein may be responsible for no or low expression of MYB1 in the white and red fruit. These results show that coordinated expression of multiple biosynthetic genes is involved in anthocyanin accumulation in Chinese bayberry fruit, and this is regulated by MrMYB1.

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