Highly Crystalline Hollow Toroidal Copper Phosphosulfide via Anion Exchange: A Versatile Cation Exchange Nanoplatform.

Postmodification of nanocrystals through cation exchange has been very successful in diversifying nanomaterial compositions while retaining the structural motif. Copper compound nanoparticles are particularly useful as templates because of inherent defects serving as effective cation diffusion routes and excellent cation mobility. Therefore, the development of shape-controlled multianion systems, such as copper phosphosulfide, can potentially lead to the formation of diverse metal phosphosulfide nanomaterials that have otherwise inaccessible compositions and structures. However, there is, to the best of our knowledge, no report on the shape-controlled synthesis of copper phosphosulfide nanoparticles because the introduction of the second anion to the metal compound might destroy the nanoparticle morphology and crystallinity due to the required high energy for anion diffusion and mixing. Herein, we report that it is feasible to transfer the structural motif of copper sulfide to copper phosphosulfide using tris(diethylamino)phosphine. The anion-mixed copper phosphosulfide in the form of a hollow toroid could provide a pathway to previously inaccessible phases and morphologies. We verified the versatility of a copper phosphosulfide hollow toroid as a cation-exchange template by the successful synthesis of cobalt, nickel, indium, and cadmium phosphosulfides as well as bimetallic cobalt-nickel phosphosulfide (Co2-xNixP1-ySy) with a retained structural motif.

Reactive nanotemplates for synthesis of highly efficient electrocatalysts: beyond simple morphology transfer.

Efficient electrocatalysts for energy conversion in general, and fuel cell operation and water electrolysis in particular, are pivotal for carbon-free hydrogen production. While the requirements of successful electrocatalysts include a high number density of catalytically active sites, high surface-to-volume ratio, inherently high catalytic activity, and robustness of the catalyst surface structure under harsh operating conditions, it is extremely difficult to synthesize nanocatalysts that could possess all these structural characteristics. Nanotemplate-mediated synthesis, namely, the coating or filling of a template with a desired material phase followed by the removal of the template, has captured the interest of researchers because of the ease of creating hollow-structured nanocatalysts with a high surface to volume ratio. Recent studies, however, have revealed that nanotemplates could be more than just passive supports because they greatly affect catalytic performance by creating an unusual synergy between the substrate and catalyst and by providing dopants to the actual catalyst phase owing to their reactive nature. In this review, we discuss the most notable recent advances in the nanotemplate-based synthesis of electrocatalysts as well as the unusual effects of nanotemplates on the performance of nanocatalysts. We also provide an outlook for this fledgling field so that future research efforts could be focused on the development of practically useful electrocatalysts that could shape the future of energy technologies.