Synthesis of ordered carbonaceous frameworks from organic crystals

Abstract

Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni–porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873–1073 K. In addition, the porphyrin’s Ni–N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.

Recent Advances in Electrochemical CO2‐to‐CO Conversion on Heterogeneous Catalysts

“…In line with earlier homogeneous reports on metal–porphyrin and metal–cyclam systems, M‐N 4 moieties with four neighboring nitrogen is also widely recognized as active site for reducing CO 2 to CO. Still taking Ni, for example, Ni–N 4 moieties within nickel porphyrin carbonaceous frameworks and/or supported over carbon substrates have been reported for selective CO 2 RR. Figure a shows a molecular optimization of covalent organic frameworks (COFs), by using cobalt porphyrin as building units, to prepare a heterogeneous catalyst for aqueous electrochemical reduction of CO 2 to CO .…”

Partially Pyrolyzed Binary Metal–Organic Framework Nanosheets for Efficient Electrochemical Hydrogen Peroxide Synthesis

“…[32] In comparison with MOF NSs, the partially pyrolyzed MOF NSs-300 displays a similar pattern, confirming the retention of the MOF structure after controlled pyrolysis. [33] However, unlike MOF NSs, the weaker FT amplitude and longer radial distance of the main peak in MOF NSs-300 suggest a lower first coordination number and longer bond length owing to partially pyrolysis effects, [34] which are verified by EXAFS fitting analysis. The best-fitting results in Figure S16 and Table S2 reveal that the Ni À O coordination numbers are 5.8 and 3.2 for MOF NSs and MOF NSs-300, respectively.…”

Metal-organic frameworks for electrochemical reduction of carbon dioxide: The role of metal centers

“…MOF derivatives materials have also attracted increasing interest due to the promising electrocatalytic properties [16,89,93,95,118] . Previous reports have pointed out that the metal nodes of MOFs materials act as the active centers for electrocatalytic reduction of CO 2 , and the electrochemistry performance of MOFs can be regulated by tailoring the structure of catalytic active sites and organic ligands.…”