This study solves a more than two-decades-long "MoS 2 Nanotubes" synthetic enigma: the futile attempts to synthesize inorganic nanotubes (INTs) of MoS 2 via vapor−gas−solid (VGS) reaction. Among them was replication of the recently reported pure-phase synthesis of the analogous INT-WS 2 . During these years, successful syntheses of spherical nanoparticles of WS 2 and MoS 2 were demonstrated as well. All these nanostructures were obtained by VGS reaction of corresponding oxides with H 2 /H 2 S gases, at elevated temperatures (>800 °C), in a fluidized bed reactor (FBR) and a one-pot process. This success and apparent similarity between the two compounds "hid" from us the option of looking for the INT-MoS 2 reaction parameters in entirely different regimes. The main challenge in the synthesis of INT-MoS 2 via VGS was the instability of the in situ prepared suboxide nanowhiskers against over-reduction and recrystallization at high temperatures. The elucidated growth mechanism dictates separation of the reaction into five steps, as properties of the intermediate products are not consistent with a single process and require individual conditions for each step. A horizontal reactor with a porous-quartz reaction cell, which creates proper quasi-static (contrary to the FBR) conditions for the reaction involving sublimation, was imperative for the effective nanofabrication of INT-MoS 2 . These findings render a reproducible synthetic route for the production of highly crystalline pure-phase MoS 2 nanotubes via a multistep VGS process, without the assistance of a catalyst and in a scalable fashion. Being a semiconductor, flexible, and strong, INT-MoS 2 offers a platform for much research and numerous potential applications, particularly in the field of optoelectronics and reinforcement of polymer composites.

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INTRODUCTIONNanostructured transition metal oxides have been extensively studied during the past few years. 1 Among them, vanadium oxide based compounds received significant attention, due to their structural flexibility combined with chemical and physical properties. They find a wide range of potential applications in high energy density lithium ion batteries, 2 catalysis, 3 electrochromic devices, 4 actuators, 5 and sensors. 6 Vanadium oxides exhibit a layered structure and are wellknown for their intercalation properties. A large variety of vanadium oxide based compounds have been described, in which cations, transition metal complexes, organic

Unlike cation substitution, anion substitution in inorganic materials such as metal oxides and sulfides would be expected to bring about major changes in the electronic structure and properties. In order to explore this important aspect, we have carried out first-principles DFT calculations to determine the effects of substitution of P and Cl on the properties of CdS and ZnS in hexagonal and cubic structures and show that a sub-band of the trivalent phosphorus with strong bonding with the cation appears in the gap just above the valence band, causing a reduction in the gap and enhancement of dielectric properties. Experimentally, it has been possible to substitute P and Cl in hexagonal CdS and ZnS. The doping reduces the band gap significantly as predicted by theory. A similar decrease in the band gap is observed in N and F co-substituted in cubic ZnS. Such anionic substitution helps to improve hydrogen evolution from CdS semiconductor structures and may give rise to other applications as well.