Central site regulation of cobalt porphyrin conjugated polymer to give highly active and selective CO2 reduction to CO in aqueous solution

Tuning the Metal Electronic Structure of Anchored Cobalt Phthalocyanine via Dual‐Regulator for Efficient CO2 Electroreduction and Zn–CO2 Batteries

“…Recently, homogeneous molecules modified via peripheral functionalization with different substituents (e.g., F, CN, N + (CH 3 ) 3 [21][22][23] ) has been demonstrated as can tune the electronic structure of the metal centers to reduce CO poisoning, [22] facilitate the active sites accessible, [22,23] and favor the formation of *COOH intermediate, [23] however, the complex synthesis procedure, harsh reaction conditions, lower yield, and surging cost of catalysts, [24,25] resulting in the application of this strategy still being suffered from economic viability. To further exert the application of M-Pc, combining with conductive carbon materials, such as, graphene, [26,27] carbon nanotube, [21,24,28] hollow carbon spheres, [29,30] etc., endowed M-Pc with homo-heterogeneous property and optimized reaction performance. Tuning metal electronic structure via carbon matrix would shed the light on the optimizing the active sites of heterogeneous molecules.…”

Optimizing the Electrocatalytic Selectivity of Carbon Dioxide Reduction Reaction by Regulating the Electronic Structure of Single‐Atom M‐N‐C Materials

“…[56] At an overpotential of 550 mV, the Ni monatomic catalyst showed high CO selectivity (FE = 95%) and good stability. [112] Copyright 2021, Elsevier B.V.…”

“…Peng et al designed a highly conjugated system to facilitate electron transfer, using in situ Sonogashira coupling reaction to support acetylene-linked Co(II) porphyrin conjugated polymer (PCP) onto ornament functionalized carbon nanotubes(CoCoPCP/CNTs). [112] By adjusting the central site of the porphyrin unit to optimize the electrocatalytic performance, the FE CO reached 94% with a TOF of 2.4 s −1 at an overpotential of 0.44 V. The experimental results verified that the high CO partial current density of CoCoPCP/CNTs was due to the exposure of more CO active sites and the promotion of electron transfer by hybridization with CNTs, which enhanced the conductivity and inherent electrocatalytic activity of CO 2 RR (Figure 11a-d). The two Co centers differed slightly in the charge of Mulliken and Hirshfield, and the spin densities of Mulliken and Hirshfield were very close.…”

“…b) Proposed mechanism for the CO 2 RR on CoCoPCP/CNTs. Reproduced with permission [112]. Copyright 2021, Elsevier B.V.…”

Boosting CO2 electroreduction towards C2+ products via CO* intermediate manipulation on copper-based catalysts

“…Sargent's group 27 proposed to solve this problem by appropriately modifying the surface of copper with molecular catalysts. Many molecular catalysts such as Fe-porphyrin, 201 Co-porphyrin, 202,203 and Cuphenanthroline 204 exhibit excellent performances for the production of CO via 2-electron transfer reactions. Based on the principle of tandem catalysis, when porphyrin catalysts were combined with Cu catalysts to construct the molecularmetal interface, the required intermediate species (CO) were enriched, finally achieving high selectivity in the CO 2 RR to produce ethanol.…”