Exploring the Pyrolysis Mechanism towards OER Performance Optimization of Salophen‐ligated Binuclear Cobalt Complex^†

Abstract

Main observation and conclusion Exploring pyrolysis process is an efficient way to study the relationship between molecular level of the precursor structure and electrocatalytic functional materials in practice. Here, the unique semi‐enclosed sector structure of Salophen ligands with highly symmetric N, N, O, O mode was introduced to construct binuclear Co complex [Co2(salophen)(Cl)2(C2H3N)] (compound 1), which provides preliminary theoretical basis for the efficient coreshell structure electrocatalysts obtained by pyrolysis regulation. Moreover, we adopted TG‐MS to real‐time track the pyrolysis process from precursors of binuclear Co complexes with Salophen ligand to efficient catalytic materials with core‐shell nanostructures. As expected, the 1‐600 sample achieves ultra‐low overpotential of 256 mV at 10 mA·cm–2 and high catalytic stability within 10 h in 1 mol/L KOH solution. This work highlights salophen‐ligated complex as excellent precursor material system for the analysis of pyrolysis evolution process, and provides an opportunity for targeted preparation of efficient oxygen evolution reaction (OER) nanocatalysts.

Tuning Carbon Contents and Further Capacitances of Coordination Polymer-Derived Carbonaceous Composites by Annealing Temperatures

“…Comparing with the precursor, the particle sizes of derivatives are much smaller, and obvious invagination is seen owing to the collapse of the precursor skeleton. Moreover, the particles of derivatives look much rougher, and they are composed of many nanograins, which are caused by the cracking of parent spindles during the decomposition of organic components at high temperatures. , Significantly, as the annealing temperature increases, the interspace among derivative grains gradually enlarges because the carbon content becomes fewer, and there is not enough carbon substrate wrapping around the Co 3 O 4 core at higher annealing temperature. Energy dispersive X-ray spectroscopy (EDS) detects the Co, O, and C species, and elemental mapping images illustrate that they are uniformly distributed in Co 3 O 4 @C composites (Figure S4, also taking Co 3 O 4 @C-400 as an example).…”

Pyrolysis of Schiff‐Base Manganese Clusters: Effect of Ligand Modulation on the Performance of Supercapacitor Electrodes

“…Our work system has considerable experience in the design, synthesis and function development of Schiff-base metal organic clusters (MOCs) based on o-vanillin. [14,15] For example, the MnO X /C nanocomposites with excellent capacitive properties prepared by pyrolysis of a salan-ligated manganese cluster. [16] Manganese oxide carbon matrix composites can be directly obtained by high temperature treatment of manganese based metal organic clusters, which can help manganese oxide break through its own limitations and achieve ideal capacitance performance.…”

“…Our work system has considerable experience in the design, synthesis and function development of Schiff‐base metal organic clusters (MOCs) based on o‐vanillin [14,15] . For example, the MnO X /C nanocomposites with excellent capacitive properties prepared by pyrolysis of a salan‐ligated manganese cluster [16] .…”

Nickel–salen as a model for bifunctional OER/UOR electrocatalysts: pyrolysis temperature–electrochemical activity interconnection

“…[19][20][21] Similarly, [Zn 7 (μ 3 -CH 3 O) 6 (L) 6 ][ZnLCl 2 ] 2 and Mn 3 (3-MeOsalophen) 2 (Cl) 2 were synthesized with 3-meosalophen as a ligand and their electrochemical properties as electrode materials for supercapacitors were investigated. 22,23 In this regard, these works inspired us to design organic ligand nickel complexes and realize the pyrolysis process of OER/UOR bifunctional electrocatalysts.…”