Solid state electroanalytical chemistry (SSEAC) deals with studies of the processes, materials, and methods specifically aimed to obtain analytical information (quantitative elemental composition, phase composition, structure information, and reactivity) on solid materials by means of electrochemical methods. The electrochemical characterization of solids is not only crucial for electrochemical applications of materials (e.g., in batteries, fuel cells, corrosion protection, electrochemical machining, etc.) but it lends itself also for providing analytical information on the structure and chemical and mineralogical composition of solid materials of all kinds such as metals and alloys, various films, conducting polymers, and materials used in nanotechnology. The present report concerns the relationships between molecular electrochemistry (i.e., solution electrochemistry) and solid state electrochemistry as applied to analysis. Special attention is focused on a critical evaluation of the different types of analytical information that are accessible by SSEAC.

Sub-nanometric Cu clusters formed by endogenous reduction of Cu salts and Cu nanoparticles are active and selective catalysts for C-N, C-C, C-O, C-S, and C-P bond-forming reactions. Sub-nanometric Cu clusters have also been generated within a polymeric film and stored with full stability for months. In this way, they are ready to be used on demand and maintain high activity (TONs up to 10(4)) and selectivity for the above reactions. A potential mechanism for the formation of the sub-nanometric clusters and their electronic nature is presented.

Herein, a general protocol for the preparation of a broad range of valuable N-heterocyclic products by hydrogenation of quinolines and related N-heteroarenes is described. Interestingly, the catalytic hydrogenation of the N-heteroarene ring is chemoselectively performed when other facile reducible functional groups, including alkenes, ketones, cyanides, carboxylic acids, esters and amides, are present. The key to successful catalysis relies on the use of a nanolayered cobalt-molybdenum sulfide catalyst hydrothermally synthesized from earth abundant metal precursors. This heterogeneous system displays a tunable composition of phases that allows for catalyst regeneration. Its catalytic activity depends on the composition of the mixed phase of cobalt sulfides, being higher with the presence of Co3S4, and could also be associated to the presence of transient Co-Mo-S structures that are mainly vanished after the first catalytic run.

An electrochemical methodology for discriminating monetary emissions, a recurrent problem in much archaeological studies, is introduced. The method is based on the record of voltammetric signatures of cuprite and tenorite corrosion products in the patina using a minimally invasive nanosampling following the voltammetry of immobilized particles methodology. A model for the depth variation of voltammetric electrochemical parameters characterizing the composition of the corrosion patinas is presented. This model permits to rationalize electrochemical data and discriminate different monetary emissions. The application of this technique, corroborated by electrochemical impedance spectroscopy (EIS) and focusing ion beam-field emission scanning electron microscopy (FIB-FESEM-EDX), to a series of 10 cash copper coins produced around the Kuang Hsu and Hsüan T'ung last Chinese emperors permits to discern different provincial mints and reveals that the monetary unification developed in this period was not uniform.

Voltammetry of microparticles is applied to the identification of lead corrosion products by means of an essentially non-invasive one-touch technique based on the use of graphite pencil. This methodology permits the mechanical attachment of few nanograms of sample from the surface of lead archaeological artefacts to a paraffin-impregnated graphite electrode, which, upon immersion in aqueous electrolytes, provides distinctive voltammetric responses for litharge and cotunnite-anglesite-, cerusite-based corrosion products. The reported method is applied to the identification of corrosion products in archaeological lead pieces from different Iberian sites in Valencia (Spain).