A novel synthesis approach for silica-based nanotubes (NTs) was discovered in the purely inorganic system containing the molecular compounds OP(NH 2 ) 3 , SP(NH 2 ) 3 and SiCl 4 in evacuated and sealed silica glass ampoules. Without any solvent or structure directing template the amorphous NTs self-organise to form orthogonally ordered, 3D hyperbranched mesocrystals, exhibiting an interesting material for nanofluidic device applications.Silica, the most abundant solid compound on earth, occurs in a multitude of crystalline and amorphous forms and has been used for a diverse range of applications (e.g. as ceramics, quartz oscillators) for a long time.1,2 The discovery of one-dimensional silica nanotubes (NTs) 3 has generated considerable attention towards the search for further functionalities, e.g. in gas storage, drug/gene-delivery, sensing, catalysis or nanofluidic systems.4 Triggered by this high potential, research concerning new synthesis methods for silica-based hollow NTs is a topic of great interest. While two-dimensional, layered compounds exhibit an intrinsic rolling up tendency, 5,6 the preparation of purposeful NTs of three-dimensional, isotropic materials like silica, however, usually requires structure-directing templates.7,8 Therefore, physical templates such as porous alumina membranes or previously fabricated nanowires in combination with atomic layer deposition (ALD), organic surfactants in self-assembled gels or biological templates were drawn into consideration.3,9-14 In principle, these methods allow a precisely controlled growth of silica NTs. In some cases, however, the template-assisted synthesis exhibits laborious multiple-step reactions with partially toxic organic substances involved. Apart from that the process of removal of the template could be a severe problem causing collapse of a newly prepared tubular silica nanostructure.
4Silica (SiO 2 ) is isoelectronic to phosphorus oxonitride (PON) and phosphorus oxonitride imide (PN(NH)) while a structural analogy is consequent. The related compound classes of nitridophosphates and oxonitridophosphates exhibit structural chemistry with many variants including e.g. highly condensed layered as well as openframework structures. [15][16][17][18][19][20] In the course of our systematic investigation of these silicate-analogous compound classes, we discovered a novel approach for a template-and solvent-free synthesis of silicabased NTs. In a purely inorganic reaction, actually trying to synthesise a silicon oxonitridophosphate, we simply performed a reaction of a mixture of phosphoryl triamide OP(NH 2 ) 3 (ref. 21) and thiophosphoryl triamide SP(NH 2 ) 3 (ref. 7 and 22) with silicon tetrachloride SiCl 4 in a closed system of a sealed silica glass ampoule (see ESI †). For systematically exploring the system, we performed the synthesis at different temperatures from 300 to 700 C (in steps of 100 C) while maintaining all other conditions constant. Additionally, some of the syntheses were carried out with an increased amount of SiCl 4 in the ampoule...