Small: Construction of intramolecular D-A heterojunction to enhance the electrocatalytic reduction of carbon dioxide by COF

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The increasing concentration of carbon dioxide in the atmosphere of

leads to the aggravation of greenhouse effect global warming. The efficient conversion of carbon dioxide into high value-added chemicals is a hot research topic of global scientists on carbon neutralization cycle. Among them the electrochemical reduction of carbon dioxide (co2rr) using clean electric energy has the advantages of mild conditions cleanness which is a promising strategy to reduce CO2 to useful chemicals. Covalent organic frameworks (COF) are potential electrocatalyst materials because of their clear structure large specific surface area strong CO2 adsorption enrichment ability good thermal stability. However due to the low conductivity of most co2rr co2rr exhibits limited current density low energy conversion efficiency. Therefore it is still a challenging task to construct functional conductive COF with efficient electron transfer capability for co2rr. In order to solve this problem the State Key Institute of porphyrin chemistry of China Academy of Sciences caoshimer caoshimer Fujian Institute of chemistry have constructed the "cokd 1" heterostructure. Among them thiophene [32-b] thiophene unit (TT) is an excellent electron donor with fast electron transfer. Metalloporphyrin has conjugated electron system which is an excellent electron acceptor or electron transfer carrier. It can realize fast intramolecular charge transfer promote electron transfer to reactants enhance activity. The results of co2rr show that TT por (CO) - COF has high CO selectivity the Faraday efficiency is 91.4% at - 0.7 V vs rhe the current density of CO is 7.28 Ma cm-2 which is higher than that of most reported COFS at the same potential. The carrier mobility electrochemical impedance spectroscopy conductivity measurements show that TT por (CO) - COF has the ability of fast electron transfer. XPS solid state UV Vis show that the introduction of D-A heterojunction in COF can indeed promote the transfer of intramolecular electrons from donor TT to the active center of porphyrin ring. This paper focuses on the introduction of electron rich TT units to construct intramolecular D-A heterocrystalline COF materials with efficient electron transfer which improves the current density of Co. The researchers of

believe that introducing D-A heterojunction into covalent organic framework materials is one of the effective ways to enhance the electrocatalytic activity by improving the intramolecular electron transfer ability conductivity. This also provides a reference for the design of high activity catalytic materials.

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