Influence of the molecular structure of metal-phthalocyanine on electrocatalytic reactions

The demand for new catalysts for renewable energy production has become crucial.As an alternative to metal catalysts for electrocatalysis to produce energy sources,metal-phthalocyanine(MPc)electrocatalysts have shown potential.Their physicochemical and electrochemical properties depend on the chemical structure of the MPc and the central metal atom.Recent reviews of MPcs focused on their electrochemical performance in specific catalytic reactions,such as oxygen reduction reaction and CO_(2)reduction reaction.However,understanding the structure of MPcs in depth is important,since their electrochemical catalytic activity is affected by structural modifications of MPcs.Therefore,this minireview focuses on how the molecular structure of MPcs affects electrochemical catalysis.

Interfacial electronic structure at a metal–phthalocyanine/graphene interface:Copper–phthalocyanine versus iron–phthalocyanine

The energy level alignment of CuPc and FePc on single-layer graphene/Ni（111） （SLG/Ni） substrate was investigated by using ultraviolet and X-ray photoelectron spectroscopy （UPS and XPS）. The highest occupied molecular orbitals （HO- MOs） in a thick layer of CuPc and FePc lie at 1.04 eV and 0.90 eV, respectively, below the Fermi level of the SLG/Ni substrate. Weak adsorbate-substrate interaction leads to negligible interfacial dipole at the CuPc/SLG/Ni interface, while a large interracial dipole （0.20 eV） was observed in the case of FePc/SLG/Ni interface, due to strong adsorbate-substrate coupling. In addition, a new interfacial electronic feature was observed for the first time in the case of FePc on SLG/Ni substrate. This interfacial state can be attributed to a charge transfer from the SLG/Ni substrate to unoccupied orbitals of FePc.

New matrix of MALDI-TOF MS for analysis of small molecules

New matrix, metal-phthalocyanine （MPc）, of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry （MALDI-TOF MS） was used for analysis of small molecules （usually 〈500 Da）. By using MPcs as matrices, small molecular samples were moved to high mass-to-charge region where there was no interference caused by the traditional matrices. The mass of the target analvte was obtained by simple calculation.

Ferroelectric control of single-molecule magnetism in 2D limit

The electric control of magnetic properties based on magnetoelectric effect is crucial for the development of future data storage devices.Here,based on first-principles calculations,a strong magnetoelectric effect is proposed to effectively switch on/off the magnetic states as well as alter the in-plane/perpendicular easy axes of metal-phthalocyanine molecules(MPc)by reversing the electric polarization of the underlying two-dimensional(2D)ferroelectric a-In2Se3 substrate with the application of an external electric field.The mechanism originates from the different hybridization between the molecule and the ferroelectric substrate in which the different electronic states of surface Se layer play a dominant role.Moreover,the magnetic moments and magnetic anisotropy energies(MAE)of OsPc/In2Se3 can be further largely enhanced by a functionalized atom atop the OsPc molecule.The I-OsPc/In2Se3 system possesses large MAE up to 30 meV at both polarization directions,which is sufficient for room-temperature applications.These findings provide a feasible scheme to realize ferroelectric control of magnetic states in 2D limit,which have great potential for applications in nanoscale electronics and spintronics.