Tailoring Porosity in Copper-Based Multinary Sulfide Nanostructures for Energy, Biomedical, Catalytic, and Sensing Applications

Abstract

Copper-based multinary sulfides (CMSs) have been the subject of intense research over the past decade due to the numerous outstanding properties that emerge when they are synthesized on the nanoscale. CMS compounds (e.g., CuInS 2 , Cu 2 SnS 3 , Cu 12 Sb 4 S 13 , and Cu 2 ZnSnS 4 ) are best known for their immense potential in energy-related disciplines. Through nanoscale engineering, new and exciting opportunities have opened up for these materials to be used in a wider range of applications. This review accords particular attention to nanostructured CMS materials with porous morphological features to be used in energy, biomedical, catalytic, and sensing applications owing to their large, tunable, and accessible surface area. Although the construction of porous nanostructures of metals and binary materials has already been well established, tailoring porosity in multinary materials like CMSs remains a big challenge due to their multiple elemental components. Herein, we provide useful discussions on the different modes of pore formation that are fundamental to the construction of CMS nanostructures with tailor-made porosity. These pore-forming strategies are classified into three types: (1) Kirkendall effectinduced hollowing, (2) aggregation-based pore formation, and (3) template-assisted pore engineering. The ability to craft porous features in CMS nanomaterials has proven to be beneficial in advancing their properties and expanding their application domains, and thus, future efforts should be devoted to furthering our understanding of the various pore formation mechanisms as this could lead to the construction of more sophisticated porous CMS architectures with optimal performance for desired applications. We anticipate that the design concepts discussed here can be extended to other emerging classes of multinary materials.

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries

“…But since binary copper sulfides have already been examined extensively, it may be worth looking into their multinary derivatives, which are vast in number given that a myriad of combinations is possible when other metals are incorporated into the Cu–S system. Some of these multinary copper sulfide derivatives (e.g., Cu 2 SnS 3 , Cu 2 NiSnS 4 , CuCo 2 S 4 ) have already been studied as electrode materials for other energy storage systems, [ 89 ] but they remain unexplored as RMB cathodes except for Cu 2 MoS 4 . [ 46,98 ]…”

“…[27,88] Recent reports indicate that multinary compositions have the potential to dramatically outperform binary systems as electrodes for energy storage applications. [89] Aside from having higher electronic conductivity than binary compounds, richer redox chemistry and better charge redistribution can be realized in multinary compounds where more than one metal component are present. Thus, the use of multinary metal chalcogenides as cathodes for RMBs has also been explored lately.…”

“…Incorporating void spaces in nanostructured electrodes has been known to impart additional benefits that can lead to impressive electrochemical performance. [ 89 ] For one, the empty spaces can mitigate the structural strain during the charge–discharge cycling. Furthermore, the presence of pores allows for efficient electrolyte penetration, accelerates transport of ions and electrons, and provides richer electroactive sites for redox reactions.…”

Selective CO2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring

“…Previous experimental and theoretical studies demonstrated that Cu(100) is the most favorable crystal orientation for the C−C coupling process . However, the surface of Cu electrodes under electrochemical environments often undergoes reconstructions induced by applied potentials, the intermediates formed during CO 2 RR, as well as specifically adsorbed anions . On the other hand, some anions either present in the electrolyte or adsorbed on the electrode surface, have been shown to play a vital role in the dynamic evolution of the catalyst structure under reaction conditions as well as the activity and selectivity of CO 2 RR.…”

“…[21][22][23] However,t he surface of Cu electrodes under electrochemical environments often undergoes reconstructions induced by applied potentials, [24][25][26] the intermediates formed during CO 2 RR, [27] as well as specifically adsorbed anions. [28][29][30] On the other hand, some anions either present in the electrolyte [12,31,32] or adsorbed on the electrode surface, [33] have been shown to play av ital role in the dynamic evolution of the catalyst structure under reaction conditions as well as the activity and selectivity of CO 2 RR. These important findings might be used in the design and development of new electrodes via electrochemical modifications.…”