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We present here a novel strategy based on the covalent grafting of a C-functionalized Ni–cyclam complex onto glassy carbon to achieve heterogeneous electrocatalytic CO2 reduction in neutral water at low overpotential (−500 mV vs. NHE), with moderate turnover number (TON = 454), high selectivity (85% CO produced) and good faradaic efficiency (56% CO). Direct comparison with the N-functionalized Ni–cyclam analogue highlights the benefits of this approach in terms of CO2 electroreduction.

Copper (Cu) sensing in the nanomolar range is an important challenge for marine water monitoring, especially with eco-friendly materials and reagents. For this purpose, electrochemical Cu(II) sensors appear as fully suitable because of their relatively high sensitivity, selectivity and adaptability for in situ measurements. So far, one of the usual electrochemical methods for Cu(II) sensing is adsorptive anodic stripping voltammetry (AdASV), since it offers a good selectivity, accumulation at open circuit potential and a reliable analytical response for concentrations above 10 nmol.L−1. Surprisingly, no work has ever addressed an electrocatalytic procedure to enhance the electrochemical copper sensing and allowed detection below 10 nM. Thus, we have developed an original two-step strategy based on the surface modification of pencil graphite electrodes (PGE) with p-aminobenzyl-C-functionalized cyclam, a strong chelating ligand for Cu(II), as well as the use of a simple reaction which can be electrocatalyzed by Cu such as HER (Hydrogen Evolution Reaction) to finally determine the accumulated amount of copper catalyst on the PGE. We show here that i) a well-defined diffusion-limited catalytic peak can be obtained from cyclic voltammetry (CV) experiments with Cu(II)-cyclam-modified PGE, ii) this HER peak potential is correlated to copper surface concentration, which can be sensed at the same time by adsorptive anodic stripping voltammetry and iii) peak shift analysis (SA) of the voltammetric curves is a more sensitive method than the commonly used stripping voltammetry to reveal copper accumulation at modified PGE. Indeed, the limit of detection (LOD) reached with this method is one order of magnitude lower compared to AdASV (LOD = 1.1 nM and 16 nM, respectively). These results illustrate the ability of electrocatalysis to be a relevant tool under certain conditions for metal trace detection through SA.

The deliberate surface modification of nanocatalysts with organic ligands has recently emerged as a promising strategy to boost their efficiency, durability, and/or selectivity in key electrocatalytic processes. The interface between the metallic interface and the immobilized ligands promotes high electrocatalytic activity. Herein, the oxygen reduction reaction activity of gold nanoparticles functionalized with a covalently bound monolayer of calix[4]arenes is compared with commercially available gold nanoparticles, classically stabilized through electrostatic adsorption of citrates onto the gold surfaces. Nanocatalysts coated by calix[4]arenes show enhanced selectivity and stability compared to their citrate-stabilized counterparts. These nanohybrids exhibit excellent activity with a dominant 4-electron reduction of O2 with good electrocatalytic performances along with a high robustness under operation as revealed by X-ray photoelectron spectroscopy analyses., SCOPUS: ar.j, info:eu-repo/semantics/published

A water-soluble calix[6]arene-based azacryptand was synthesized. The corresponding tren [tris(2-aminoethyl)amine] cap grafted at the small rim coordinates strongly a copper(II) ion over a wide range of pH. The host-guest properties of the complex were explored by EPR spectroscopy. Due to second coordination sphere effects and the hydrophobic effect ascribed to the calixarene cavity, this funnel complex selectively binds neutral molecules (alcohols, nitriles, amines) versus anions in water near physiological pH. Among the coordinating guests, hydrophobic primary amines are preferentially recognized thanks to the combined effect of the better metal-ligand interaction and hydrogen bonding to the oxygen atoms present at the small rim. Hence, this Cu(II) calix[6]arene-based funnel complex behaves as a sensitive and selective EPR probe for primary amines, including biologically important molecules such as tyramine and tryptamine, in water, over a large pH window., SCOPUS: re.j, info:eu-repo/semantics/published

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A new "two-story" calix[6]arene-based ligand was synthesized, and its coordination chemistry was explored. It presents a tren cap connected to the calixarene small rim through three amido spacers. X-ray diffraction studies of its metal complexes revealed a six-coordinate ZnII complex with all of the carbonyl groups of the amido arms bound and a five-coordinate CuII complex with only one amido arm bound. These dicationic complexes were poorly responsive toward exogenous neutral donors, but the amido arms were readily displaced by small anions or deprotonated with a base to give the corresponding monocationic complexes. Cyclic voltammetry in various solvents showed a reversible wave for the CuII/CuI couple at very negative potentials, denoting an electron-rich environment. The reversibility of the system was attributed to the amido arms, which can coordinate the metal center in both its +II and +I redox states. The reversibility was lost upon anion binding to Cu. Upon exposure of the CuI complex to O2 at low temperature, a green species was obtained with a UV-vis signature typical of an end-on superoxide CuII complex. Such a species was proposed to be responsible for oxygen insertion reactions onto the ligand according to the unusual and selective four-electron oxidative pathway previously described with a "one-story" calix[6]tren ligand., SCOPUS: ar.j, info:eu-repo/semantics/published