Abstract
ConspectusMetal chalcogenide quantum dots (QDs) are prized for their unique and functional properties, associated with both intrinsic (quantum confinement) and extrinsic (high surface area) effects, as dictated by their size, shape, and surface characteristics. Thus, they have considerable promise for diverse applications, including energy conversion (thermoelectrics and photovoltaics), photocatalysis, and sensing. QD gels are macroscopic porous structures consisting of interconnected QDs and pore networks in which the pores may be filled with solvent (i.e., wet gels) or air (i.e., aerogels). QD gels are unique because they can be prepared as macroscale objects while fully retaining the size-specific quantum-confined properties of the initial QD building blocks. The extensive porosity of the gels also ensures that each QD in the gel network is accessible to the ambient, leading to high performance in applications that require high surface areas, such as (photo)catalysis and sensing.Metal chalcogenide QD gels are conventionally prepared by chemical approaches. We recently expanded the toolbox for QD gel synthesis by developing electrochemical gelation methods. Relative to conventional chemical oxidation approaches, electrochemical assembly of QDs (1) enables the use of two additional levers for tuning the QD assembly process and gel structure: electrode material and potential, and (2) allows direct gel formation on device substrates to simplify device fabrication and improve reproducibility. We have discovered two distinct electrochemical gelation methods, each of which enables the direct writing of gels on an active electrode surface or the formation of free-standing monoliths. Oxidative electrogelation of QDs leads to assemblies bridged by dichalcogenide (covalent) linkers, whereas metal-mediated electrogelation proceeds via electrodissolution of active metal electrodes to produce free ions that link QDs by binding to pendant carboxylate functionalities on surface ligands (non-covalent linkers). We further demonstrated that the electrogel composition produced from the covalent assembly could be modified by controlled ion exchange to form single-ion decorated bimetallic QD gels, a new category of materials. The QD gels exhibit unprecedented performance for NO(2) gas sensing and unique photocatalytic reactivities (e.g., the "cyano dance" isomerization and the reductive ring-opening arylation). The chemistry unveiled during the development of electrochemical gelation pathways for QDs and their post-modification has broad implications for guiding the design of new nanoparticle assembly strategies and QD gel-based gas sensors and catalysts.