RESUMEN
Solar-driven water electrolysis to produce hydrogen is one of the clean energy options for the current energy-related challenges. Si as a photocathode exhibits a large overpotential due to the slow hydrogen evolution reaction (HER) kinetics and hence needs to be modified with a cocatalyst layer. MoS2 is a poor HER cocatalyst due to its inert basal plane. Activation of the MoS2 basal plane will facilitate HER kinetics. In this study, we have incorporated SnS2 into MoS2 ultrathin sheets to induce defect formation and phase transformation. MoS2/SnS2 composite ultrathin sheets with a Sn2+ state create a large number of S vacancies on the basal sites. The optimized defect-rich MoS2/SnS2 ultrathin sheets decorated on surface-modified Si micro pyramids as photocathodes show a current density of -23.8 mA/cm2 at 0 V with an onset potential of 0.23 V under acidic conditions, which is higher than that of the pristine MoS2. The incorporation of SnS2 into 2H-MoS2 ultrathin sheets not only induces a phase but also can alter the local atomic arrangement, which in turn is verified by their magnetic response. The diamagnetic SnS2 phase causes a decrease in symmetry and an increase in magnetic anisotropy of the Mo3+ ions.
RESUMEN
Metal-CO2 rechargeable batteries are of great importance due to their higher energy density and carbon capture capability. In particular, Na-CO2 batteries are potential energy-storage devices that can replace Li-based batteries due to their lower cost and abundance. However, because of the slow electrochemical processes owing to the carbonated discharge products, the cell shows a high overpotential. The charge overpotential of the Na-CO2 battery increases because of the cathode catalyst's inability to break down the insulating discharge product Na2CO3, thereby resulting in poor cycle performance. Herein, we develop an ultrathin nanosheet MoS2/SnS2 cathode composite catalyst for Na-CO2 battery application. Insertion of SnS2 reduces the overpotential and improves the cyclic stability compared to pristine MoS2. As shown by a cycle test with a restricted capacity of 500 mAh/g at 50 mA/g, the battery is stable up to 100 discharge-charge cycles as the prepared catalyst successfully decomposes Na2CO3. Furthermore, the battery with the MoS2/SnS2 cathode catalyst has a discharge capacity of 35â¯889 mAh/g. The reasons for improvements in the cycle performance and overpotential of the MoS2/SnS2 composite cathode catalyst are examined by a combination of Raman, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure analysis, which reveals an underneath phase transformation and changes in the local atomic environment to be responsible. SnS2 incorporation induces S-vacancies in the basal plane and 1T character in 2H MoS2. This combined impact of SnS2 incorporation results in undercoordinated Mo atoms. Such a change in the electronic structure and the phase of the MoS2/SnS2 composite cathode catalyst results in higher catalytic activity and reduces the cell overpotential.
RESUMEN
Si is regarded as a promising photocathode material for solar hydrogen evolution reaction (HER) because of its small band gap and highly negative conduction band edge. However, bare Si electrodes have high overpotential because of sluggish HER kinetics on the surface. In this study, molybdenum tungsten sulfide (MoS2-WS2) was decorated on Si photocathodes as the co-catalyst to accelerate HER kinetics. The catalytic performance of MoS2-WS2 was further enhanced by introducing phosphate materials. Phosphate-modified molybdenum tungsten sulfide (PO-MoWS) was deposited on Si photoabsorbers to provide an optimal current of -15.0 mA cm-2 at 0 V. Joint characterizations of X-ray photoelectron and X-ray absorption spectroscopies demonstrated that the phosphate material dominantly coordinated with the WS2 component in PO-MoWS. Moreover, this phosphate material induced a large number of sulfur vacancies in the PO-MoWS/Si electrodes that contributed to the ideal catalytic activity. Herein, TiO2 thin films were prepared as the protective layer to improve the stability of photocathodes. The PO-MoWS/2 nm TiO2/Si electrode maintained 83.8% of the initial photocurrent after chronoamperometric measurement was performed for 8000 s.
