Heptanuclear brucite disk with cyanide bridges in a cocrystal and tracking its pyrolysis to an efficient oxygen evolution electrode

The development of efficient oxygen evolution reaction(OER)catalysts is still lacking in exploration of the mechanism of controlled pyrolysis of precursors among new material platforms.Here,a novel Co-based coordination molecular cluster has been first introduced as precursor to obtain metallic cobalt core shelled by N-doped carbon(Co@NC)structure which operates as an oxygen evolution electrode.Specifically,a new cocrystal compound,[Co7II(l3-CN)6(mmimp)6][CoIICl3N(CN)2]á3CH3OH(Co7+1,mmimp=2-methoxy-6-((methylimino)-methyl)phenol),was isolated consisting of Brucite disks of cobalt where the usual bridging l3-OH is replaced by l3-CN produced by the in-situ decomposition of dicyanamide(NC-N-CNà).The cobalt atoms are bonded through the nitrogen atom of the cyanide.Remarkably,time dependent thermogravimetric-mass spectrometry(TG-MS)analysis was utilized to track its pyrolysis process.It allowed us to propose a possible formation process of the Co@NC structure from Co7+1.Interestingly,an extremely superior OER electrode is optimized for Co@NC-600 having the lowest overpotential of257 m V at 10 m A/cm2in 1 mol/L KOH solution.The present study pins down the importance of clusters of transition metals on realizing distinct nanostructures operating as highly efficient OER electrocatalyst.

Pyrolysis characteristics of Radix Rhizoma Rhei, Cortex Moudan Radicis, and Radix Sanguisorbae and correlations with the carbonizing process of Chinese herbs

AIM： The aim of the work is to study the pyrolysis characteristics of Radix Rhizoma Rhei, Cortex Moudan Radicis, and Radix Sanguisorbae in an inert atmosphere of argon （Ar）, and to investigate the mechanism of the carbonizing process of the three traditional Chinese herbs. METHODS： The pyrolysis characteristics of the crude materials and their extracts were studied by thermogravimetry-mass spectrometry （TG-MS） in a carrier gas of argon, coupled with Fourier transform infrared spectrometry （FTIR） and scanning electron microscopy （SEM） methods. Correlation of the pyrolysis behaviors with the carbonizing process by stir-frying of traditional Chinese medicines was made. RESULTS： Within the temperature range of 200-300 ℃, which is the testing range for the study of the carbonizing process of Chinese herbs, the temperatures indicated by the maximum weight loss rate peak of the above three extracts were taken as the upper-limit temperatures of the carbonizing process of the herbs, and which were 200, 240 and 247 ℃ for Radix Rhizoma Rhei, Cortex Moudan Radicis, and Radix Sanguisorbae, respectively. The ion monitoring signal peaks detected by the TG-MS method corresponded with reports that the level of chemical components of traditional Chinese medicinal materials would decrease after the carbonizing process. It was confirmed by Fourier transform infrared spectrometry （FTIR） and scanning electron microscopy （SEM） methods that better results of ＂medicinal property preservation＂ could be obtained by heating at 200 ℃ for Radix Rhizoma Rhei, at about 250 ℃ for Cortex Moudan Radicis, and Radix Sanguisorbae, as the relative intensity values of the common peaks were among the middle of their three carbonized samples by programmed heating. CONCLUSION： The upper-limit temperatures of the carbonizing process for Radix Rhizoma Rhei, Cortex Moudan Radicis and Radix Sanguisorbae were 200, 240 and 247 ℃ respectively. It is feasible to research the mechanism and technology of the carbonizing process of traditional Chinese medicinal materials using thermogravimetry, Fourier transform infrared spectrometry, and scanning electron microscopy methods.

In-situ evolution process understanding from a salan-ligated manganese cluster to supercapacitive application

The goal of material chemistry is to study the relationship among hierarchical structure,chemical reaction and precision preparation for materials,yet tracking pyrolysis process on multi-dimensional scale is still at primary stage.Here we propose packing mode analysis to understand evolution process in high temperature reaction.As a proof of concept,we first design a salan-ligated Mn3(Mn3(3-MeOsalophen)_(2)(Cl)_(2))cluster and pyrolyze it under an inert atmosphere directly to a mixed valence MnOx embedded in a porous N-doped carbon skeleton(MnOx/C).Meanwhile,combining thermogravimetry-mass spectrometry(TG-MS)with other characterization techniques,its pyrolysis process is precisely tracked real-time and Mn^(2+)/Mn^(3+)ratios in the resulting materials are deduced,ensuring excellent electrochemical advantages.As a result,the as-preferred MnOVC-900 sample reaches 943 F/g at 1 A/g,maintaining good durability under 5,000 cycles with 90%retention.The highlight of packing mode analysis strategy in this work would provide a favorable approach to explore the potential relationship between structure and performance in the future.