In situ preparation of a Co4S3-based electrocatalyst by taking advantage of the controllable components of metal–organic frameworks†
Abstract
In order to give full play to the advantages in structure tailoring and quantitative assembly, metal–organic frameworks (MOFs) with different topological structures formed by the self-assembly of inorganic ligands containing sulfur, cobalt ions and large-size ligands were used to prepare electrocatalyst materials for hydrolysis with controllable composition and performance. According to the synthesis proposition, we can not only avoid using additional doped sulfur sources to reduce waste but also make it very convenient for Co and sulfur elements to be uniformly and controllably distributed in the whole material, and enhance the overall synergistic effects. Based on the above considerations, two-dimensional layered and three-dimensional MOFs, Co-MOF-1, and Co-MOF-2, with the same chemical compositions were utilized as the templates, and a series of Co/S-based materials with variable compositions and properties were obtained only by controlling the pyrolysis temperature. For each MOF series, it can be observed that with the increase in the pyrolysis temperature, the derivatives gradually change from Co4S3 to Co9S8 composites, which could be proven by PXRD studies. The electrocatalytic properties of two series of derivatives were also investigated, and the results indicate that the materials containing Co4S3 can indeed show better water-splitting performance than Co9S8 ones. Furthermore, the macroscopic stacking form of the MOF template also plays an important role in determining the electrocatalytic performance of the derived materials. Through an overall comparison, it is found that the electrocatalytic performance of the Co-MOF-1 series is better than that of the Co-MOF-2 series at various temperatures, which should be only caused by the natural packing modes of the pristine MOF template. For Co-MOF-1 derivatives, the retention of the two-dimensional layered structure is favorable to form an electrostatic charge separation layer and electron transport channel, which is beneficial to the intercalation and delamination of hydroxide ions, thus improving the storage capacity of materials, promoting electron transfer, and producing less electron transfer resistance. Therefore, based on the research results, the reasonable design of layered MOF materials containing the specific sulfur-containing linker as water-splitting catalysts is an applicable route for the preparation of economical, environmentally friendly, and low energy consumption electrocatalysts, which should receive increasing attention in the future.