On-surface manipulation of atom substitution between cobalt phthalocyanine and the Cu(111) substrate

Abstract

An on-surface atom substation has been manipulated by thermal annealing which transmetalizes CoPc to CuPc for various applications.

On-surface transmetalation of metalloporphyrins

“…The very low barrier that can be surmounted also at low temperature separates our approach from previous studies, in which Cu adatoms were used to replace cations in porphyrins. 25,26 The high annealing temperatures needed for these reactions are presumably due to the different starting configuration, in which the replacing metal centre starts from underneath the molecule, which is, as shown above, accompanied by a larger barrier.…”

“…Two studies describe the replacement of Ni and Co by Cu, which is supplied through the adatom gas on the Cu(111) surface in ultra-high vacuum. 25,26 A third study describes the exchange of Zn by Cu at the solid/ liquid interface. 27 No clear trends can be extracted from the existing literature: on the one hand Franke et al 27 report Zn substitution by Cu in a tetraphenylporphyrin network at the solid-liquid interface.…”

Identification of On-Surface Reaction Mechanism by Targeted Metalation

“…Note that some directly metalated molecules with symmetric appearance are also found in pure 2HPyr samples, which suggests that the approaching Fe atom is directly incorporated to some degree. 33 Mild annealing (433 K, 1 h) leads to the case that all molecules appear bright and symmetric, i.e. complete metalation to FePyr ( Figure S7).…”

N‐Doped Hierarchical Porous Carbon Embedded Synergistic Bimetallic CoCu NPs with Unparalleled Catalytic Performance

“…Additionally, the N content of Cu@NHPC‐800 and Co 0.7 Cu 0.3 @NHPC‐800 is evidently lower than Co@NMC‐800 (Table S2), further proving the possible etching effect of Cu species, which could be the origination of hierarchical porosity. The high‐resolution Co2p and Cu2p spectra are deconvoluted to confirm the surface chemical state of the as‐prepared Co 0.7 Cu 0.3 @NHPC‐800 catalyst (Figure ) . The binding energy at 932.9 eV and 952.7 eV are ascribed to Cu2p 3/2 and Cu2p 1/2 of Cu (0), respectively.…”

“…The high-resolution Co2p and Cu2p spectra are deconvoluted to confirm the surface chemical state of the as-prepared Co 0.7 Cu 0.3 @NHPC-800 catalyst (Figure 3). [18] The binding energy at 932.9 eV and 952.7 eV are ascribed to Cu2p 3/2 and Cu2p 1/2 of Cu (0), respectively. It should be noticed that the binding energy has a slight shift to higher values compared with Cu/C (932.5 eV and 952.5 eV), revealing possible electron transfer from Cu to Co to equilibrate the Fermi level.…”