Two-dimensional molecular crystals (2DMCs) are a promising candidate for flexible and large-area electronics. Their large-area production requires both low nuclei density and 2D crystal growth mode. As an emerging type of material, their large-area production remains a case-by-case practice. Here we present a general, efficient strategy for large-area 2DMCs. The method grows crystals on water surface to minimize the density of nuclei. By controlling the interfacial tension of the water/solution system with a phase transfer surfactant, the spreading area of the solvent increases tens of times, leading to the space-confined 2D growth of molecular crystals. As-grown sub-centimeter-sized 2DMCs floating on the water surface can be easily transferred to arbitrary substrates for device applications.

Electrochemically driven carbon dioxide (CO2) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO2; however, this reduction process suffers from tardy kinetics due to low local concentration of CO2 on a catalyst's surface and low density of active sites. Herein, presented is a combination of experimental and theoretical validation of a Ni porphyrin‐based covalent triazine framework (NiPor‐CTF) with atomically dispersed NiN4 centers as an efficient electrocatalyst for CO2 reduction reaction (CO2RR). The high density and atomically distributed NiN4 centers are confirmed by aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy and extended X‐ray absorption fine structure. As a result, NiPor‐CTF exhibits high selectivity toward CO2RR with a Faradaic efficiency of >90% over the range from −0.6 to −0.9 V for CO conversion and achieves a maximum Faradaic efficiency of 97% at −0.9 V with a high current density of 52.9 mA cm−2, as well as good long‐term stability. Further calculation by the density functional theory method reveals that the kinetic energy barriers decreasing for *CO2 transition to *COOH on NiN4 active sites boosts the performance.

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