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Developing two‐dimensional (2D) and single atomic layered materials is a fascinating challenge. Here we successfully synthesize porphyrin‐based monoatomic layer (PML), a freestanding 2D porphyrin‐based material of monomer‐unit thickness (2.8 Å). The solvothermal method provides a bottom‐up approach for tailoring the monoatomic layer from the nanoscale to the milliscale. PMLs containing accurately tailorable M‐N4 units (M=Cu and Au) were synthesized, which present metal center‐dependent performance for CO2 electrocatalysis. PML with Cu‐N4 centers performs high faradaic efficiencies of HCOO− and CH4 (80.86 % and 11.51 % at −0.7 V, respectively) while PML with Au‐N4 centers generates HCOO− and CO as major products (40.90 % and 34.40 % at −0.8 V, respectively). Irreversible restructuring behavior of Cu sites is also observed. Based on the graphene‐like properties and metal center‐selectivity relationships, we believe that PML will play a distinct role in various applications. [ABSTRACT FROM AUTHOR]

Utilizing sustainable energy for chemical activation of small molecules, such as CO2, to produce important chemical feedstocks is highly desirable. The simultaneous production of CO/H2 mixture (syngas) from photoreduction of CO2 and H2O is highly promising. However, the relationships between structure, composition, crystallinity, and photocatalytic performance are still indistinct. Here, amorphous ultrathin CoO nanowires and polyoxometalate incorporated nanowires with even lower crystallinity were synthesized. The POM‐incorporated ultrathin nanowires exhibit high photocatalytic syngas production activity, reaching H2 and CO evolution rates of 11555 and 4165 μmol g−1 h−1 respectively. Further experiments indicate that the ultrathin morphology and incorporation of POM both contribute to the superior performance. Multiple characterizations reveal the enhanced charge–hole separation efficiency of the catalyst would facilitate the photocatalysis. [ABSTRACT FROM AUTHOR]

Utilizing sustainable energy for chemical activation of small molecules, such as CO2, to produce important chemical feedstocks is highly desirable. The simultaneous production of CO/H2 mixture (syngas) from photoreduction of CO2 and H2O is highly promising. However, the relationships between structure, composition, crystallinity, and photocatalytic performance are still indistinct. Here, amorphous ultrathin CoO nanowires and polyoxometalate incorporated nanowires with even lower crystallinity were synthesized. The POM‐incorporated ultrathin nanowires exhibit high photocatalytic syngas production activity, reaching H2 and CO evolution rates of 11555 and 4165 μmol g−1 h−1 respectively. Further experiments indicate that the ultrathin morphology and incorporation of POM both contribute to the superior performance. Multiple characterizations reveal the enhanced charge–hole separation efficiency of the catalyst would facilitate the photocatalysis. [ABSTRACT FROM AUTHOR]