Freestanding Millimeter‐Scale Porphyrin‐Based Monoatomic Layers with 0.28 nm Thickness for CO₂ Electrocatalysis

Abstract

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). The solvothermal method provides a bottom-up approach for tailoring the monoatomic layer from the nanoscale to the milliscale. PMLs containing accurately tailorable M-N 4 units (M = Cu and Au) were synthesized, which present metal center-dependent performance for CO 2 electrocatalysis. PML with Cu-N 4 centers performs high faradaic efficiencies of HCOO À and CH 4 (80.86 % and 11.51 % at À0.7 V, respectively) while PML with Au-N 4 centers generates HCOO À and CO as major products (40.90 % and 34.40 % at À0.8 V, respectively). Irreversible restructuring behavior of Cu sites is also observed. Based on the graphene-like properties and metal centerselectivity relationships, we believe that PML will play a distinct role in various applications.

Bidirectional Light-Driven Ion Transport through Porphyrin Metal–Organic Framework-Based van der Waals Heterostructures via pH-Induced Band Alignment Inversion

“…However, the in-plane grazing incidence XRD (GIXRD) pattern (Figure 1e), as well as the simulation results, indicates the PMOF layers should adopt an AB stacking mode, that is, the interlayer distance between Page 7 of 28 CCS Chemistry neighboring reticulate layers should be only 4.5 Å (Figure 1a). Considering thickness of the reticulate layer (about 2.7 Å), 37 the interlayer space cannot be the pathway for water and ion transport.…”