No abstract

Cobalt-promoted molybdenum sulfide (CoMoS) is known as a promising catalyst for H2 evolution reaction and hydrogen desulfurization reaction. This material exhibits superior catalytic activity as compared to its pristine molybdenum sulfide counterpart. However, revealing the actual structure of cobalt-promoted molybdenum sulfide as well as the plausible contribution of a cobalt promoter is still challenging, especially when the material has an amorphous nature. Herein, we report, for the first time, on the use of positron annihilation spectroscopy (PAS), being a nondestructive nuclear radiation-based method, to visualize the position of a Co promoter within the structure of MoS at the atomic scale, which is inaccessible by conventional characterization tools. It is found that at low concentrations, a Co atom occupies preferably the Mo-vacancies, thus generating the ternary phase CoMoS whose structure is composed of a Co-S-Mo building block. Increasing the Co concentration, e.g., a Co/Mo molar ratio of higher than 1.12/1, leads to the occupation of both Mo-vacancies and S-vacancies by Co. In this case, secondary phases such as MoS and CoS are also produced together with the CoMoS one. Combining the PAS and electrochemical analyses, we highlight the important contribution of a Co promoter to enhancing the catalytic H2 evolution activity. Having more Co promoter in the Mo-vacancies promotes the H2 evolution rate, whereas having Co in the S-vacancies causes a drop in H2 evolution ability. Furthermore, the occupation of Co to the S-vacancies leads also to the destabilization of the CoMoS catalyst, resulting in a rapid degradation of catalytic activity.

Manganese dioxide nanomaterials have wide applications in many areas from catalysis and Li−ion batteries to gas sensing. Understanding the crystallization pathways, morphologies, and formation of defects in their structure is particularly important but still a challenging issue. Herein, we employed an arsenal of X-ray diffraction (XRD), scanning electron microscopy (SEM), neutron diffraction, positron annihilation spectroscopies, and ab initio calculations to investigate the evolution of the morphology and structure of α-MnO 2 nanomaterials prepared via reduction of KMnO 4 solution with C 2 H 5 OH prior to being annealed in air at 200−600 °C. We explored a novel evolution that α-MnO 2 nucleation can be formed even at room temperature and gradually developed to α-MnO 2 nanorods at above 500 °C. We also found the existence of H + or K + ions in the [1 × 1] tunnels of α-MnO 2 and observed the simultaneous presence of Mn and O vacancies in α-MnO 2 crystals at low temperatures. Increasing the temperature removed these O vacancies, leaving only the Mn vacancies in the samples.

The variation of lamellar structures of poly(styrenesulfonic acid)-grafted poly (ethylene-co-tetrafluoroethylene) proton exchange membranes dependence on preparation procedures and grafting degree (GD) was investigated by small angle X-ray scattering. The detail structures of lamellar including lamellar period L, thickness of lamellar crystal Lc, thickness of lamellar amorphous La, and linear crystallinity Lc/L were examined by a 1D correlation function. The lamellar structures were recognized at the grafting step and did not change under the sulfonation process. With GD  79 %, Lc significantly decreased (corresponding to the increase of La) and then retained in the GDs of 79-117 %. Note that the retained values of Lc, La, and linear crystallinity in the GDs of 79-117 % are the origin of high conductivity and mechanical strength of membranes under severe operation conditions for fuel cell applications.