Alan Le Goff

From Hydrogenases to Noble Metal–Free Catalytic Nanomaterials for H2 Production and Uptake

Electrolysis at Nickel One drawback of solar and wind power is the need for an efficient storage system to release accumulated energy when neither source is readily available (during still nights, for example). Hydrogen derived from electrolysis of water is potentially a useful medium for this purpose, but catalyzing the interconversion efficiently at large scale would currently require a substantial amount of the scarce precious metal platinum. An alternative approach would be to mimic natural enzymatic reactions, which accomplish the interconversion using hydrogenases that incorporate the more abundant metals iron and nickel. In this vein, Le Goff et al. (p. 1384; see the Perspective by Hambourger and Moore) have lightly modified a hydrogenase-inspired nickel complex in order to append it to a conductive carbon nanotube support. The resulting hybrid material shows promising catalytic efficiency for reversible aqueous electrolysis in a standard apparatus. A nickel electrocatalyst supported on carbon nanotubes shows promising activity for proton-hydrogen interconversion in water. Interconversion of water and hydrogen in unitized regenerative fuel cells is a promising energy storage framework for smoothing out the temporal fluctuations of solar and wind power. However, replacement of presently available platinum catalysts by lower-cost and more abundant materials is a requisite for this technology to become economically viable. Here, we show that the covalent attachment of a nickel bisdiphosphine–based mimic of the active site of hydrogenase enzymes onto multiwalled carbon nanotubes results in a high–surface area cathode material with high catalytic activity under the strongly acidic conditions required in proton exchange membrane technology. Hydrogen evolves from aqueous sulfuric acid solution with very low overvoltages (20 millivolts), and the catalyst exhibits exceptional stability (more than 100,000 turnovers). The same catalyst is also very efficient for hydrogen oxidation in this environment, exhibiting current densities similar to those observed for hydrogenase-based materials.

Mediatorless high-power glucose biofuel cells based on compressed carbon nanotube-enzyme electrodes

Enzymatic fuel cells use enzymes to produce energy from bioavailable substrates. However, such biofuel cells are limited by the difficult electrical wiring of enzymes to the electrode. Here we show the efficient wiring of enzymes in a conductive pure carbon nanotube matrix for the fabrication of a glucose biofuel cell (GBFC). Glucose oxidase and laccase were respectively incorporated in carbon nanotube disks by mechanical compression. The characterization of each bioelectrode shows an open circuit potential corresponding to the redox potential of the respective enzymes, and high current densities for glucose oxidation and oxygen reduction. The mediatorless GBFC delivers a high power density up to 1.3 mW cm−2 and an open circuit voltage of 0.95 V. Moreover, the GBFC remains stable for 1 month and delivers 1 mW cm−2 power density under physiological conditions (5×10−3 mol l−1 glucose, pH 7). To date, these values are the best performances obtained for a GBFC.

Nanomaterials for biosensing applications: a review

A biosensor device is defined by its biological, or bioinspired receptor unit with unique specificities toward corresponding analytes. These analytes are often of biological origin like DNAs of bacteria or viruses, or proteins which are generated from the immune system (antibodies, antigens) of infected or contaminated living organisms. Such analytes can also be simple molecules like glucose or pollutants when a biological receptor unit with particular specificity is available. One of many other challenges in biosensor development is the efficient signal capture of the biological recognition event (transduction). Such transducers translate the interaction of the analyte with the biological element into electrochemical, electrochemiluminescent, magnetic, gravimetric, or optical signals. In order to increase sensitivities and to lower detection limits down to even individual molecules, nanomaterials are promising candidates due to the possibility to immobilize an enhanced quantity of bioreceptor units at reduced volumes and even to act itself as transduction element. Among such nanomaterials, gold nanoparticles, semi-conductor quantum dots, polymer nanoparticles, carbon nanotubes, nanodiamonds, and graphene are intensively studied. Due to the vast evolution of this research field, this review summarizes in a non-exhaustive way the advantages of nanomaterials by focusing on nano-objects which provide further beneficial properties than “just” an enhanced surface area.

Noncovalent Modification of Carbon Nanotubes with Pyrene‐Functionalized Nickel Complexes: Carbon Monoxide Tolerant Catalysts for Hydrogen Evolution and Uptake

Hydrogen production through the reduction of water appears to be a very attractive solution for the long-term storage of renewable energy. However, economically viable processes require platinum-free catalysts, since this expensive and scarce metal is not a sustainable resource. We recently showed that the combination of a bioinspired molecular approach with nanochemical tools, through the covalent attachment of mimics 3] of the active site of hydrogenase enzymes onto carbon nanotubes (CNTs), results in a noblemetal-free electrocatalytic nanomaterial with low overpotential and exceptional stability for H2 evolution or uptake. [4,5] In this initial study, we used the electroreduction of a diazonium salt to decorate multiwalled carbon nanotubes (MWCNTs) deposited on the electrode support with a polyphenylene layer bearing amino groups. These amino groups were then used to attach an activated ester derivative [Ni(P2N Ar 2)2] 2+

Enzymatic biosensors based on SWCNT-conducting polymer electrodes

This short review is focused on recent advances in the combination of conducting polymers and SWCNTs for the fabrication of electrochemical biosensors. The different properties of conducting polymers and SWCNTs are discussed in respect of their use in immobilizing and wiring biomolecules on electrode surfaces. We further describe the functionalization techniques used in the fabrication of these devices and their associated biosensing performances.

Electrocatalytic Oxidation of Glucose by Rhodium Porphyrin-Functionalized MWCNT Electrodes: Application to a Fully Molecular Catalyst-Based Glucose/O2 Fuel Cell

This paper details the electrochemical investigation of a deuteroporphyrin dimethylester (DPDE) rhodium(III) ((DPDE)Rh(III)) complex, immobilized within a MWCNT/Nafion electrode, and its integration into a molecular catalysis-based glucose fuel cell. The domains of present (DPDE)Rh(I), (DPDE)Rh-H, (DPDE)Rh(II), and (DPDE)Rh(III) were characterized by surface electrochemistry performed at a broad pH range. The Pourbaix diagrams (plots of E(1/2) vs pH) support the stability of (DPDE)Rh(II) at intermediate pH and the predominance of the two-electron redox system (DPDE)Rh(I)/(DPDE)Rh(III) at both low and high pH. This two-electron system is especially involved in the electrocatalytic oxidation of alcohols and was applied to the glucose oxidation. The catalytic oxidation mechanism exhibits an oxidative deactivation coupled with a reductive reactivation mechanism, which has previously been observed for redox enzymes but not yet for a metal-based molecular catalyst. The MWCNT/(DPDE)Rh(III) electrode was finally integrated in a novel design of an alkaline glucose/O(2) fuel cell with a MWCNT/phthalocyanin cobalt(II) (CoPc) electrode for the oxygen reduction reaction. This nonenzymatic molecular catalysis-based glucose fuel cell exhibits a power density of P(max) = 0.182 mW cm(-2) at 0.22 V and an open circuit voltage (OCV) of 0.64 V.

Label-free impedimetric thrombin sensor based on poly(pyrrole-nitrilotriacetic acid)-aptamer film

A label-free and highly sensitive impedimetric aptasensor was developed based on electropolymerized film for the determination of thrombin. The first step is the electrogeneration of a poly(pyrrole-nitrilotriacetic acid) (poly(pyrrole-NTA)) film onto the surface of electrodes followed by complexation of Cu(2+) ions. Then, the histidine labeled thrombin aptamer was immobilized onto the electrode through coordination of the histidine groups on the NTA-Cu(2+) complex. The aptamer sensor was applied for the detection and quantification of thrombin via impedimetric detection without a labeling step. A linear quantification of thrombin was obtained in the range 4.7×10(-12)-5.0×10(-10) mol L(-1) with a sensitivity of 2838 Ω/log unit (R(2)=0.9984). The impedance modulus at 0.3 Hz as a function of thrombin concentration was used to elaborate a similar linear relationship from 4.7×10(-12) to 5×10(-10) mol L(-1). In addition, aptamer-poly(pyrrole-NTA) electrodes incubated for 40 min in aqueous solutions of bovine serum albumin (BSA), lysozyme and IgG (5×10(-7) mol L(-1)) did not exhibit non-specific adsorption of proteins. Moreover, it has been demonstrated that the selective sensor can be regenerated several times with a good reproducibility.

Covalent grafting onto self-adhesive surfaces based on aryldiazonium salt seed layers

The chemistry of aryldiazonium salts has been thoroughly used in recent years to graft in a very simple and robust way ultrathin polyphenylene-like films on a broad range of surfaces. We show here that the same chemistry can be used to obtain “self-adhesive surfaces”. This target was reached in a simple way by coating various surfaces with chemisorbed organic films containing active aryldiazonium salts. These “self-adhesive surfaces” are then put into contact with various species (molecules, polymers, nanoparticles, nanotubes, graphene flakes, etc.) that react either spontaneously or under activation with the immobilized aryldiazonium salts. Our self-adhesive surfaces were synthesized following a simple aqueous two-step protocol based on p-phenylenediamine diazotisation. The first diazotisation step results in the robust grafting of thin polyaminophenylene (PAP) layers onto the surface. The second diazotisation step changed the grafted PAP film into a “poly-aryldiazonium polymer” (PDP) film. The covalent grafting between those self-adhesive surfaces and the target species was achieved by direct contact or by immersion of the self-adhesive surfaces in solution. We present in this preliminary work the grafting of multi-wall carbon nanotubes (MWCNTs), flakes of highly oriented pyrolytic graphite (HOPG), various organic compounds and copper nanoparticles. We also tested these immobilized aryldiazonium salts as electropolymerization initiators for the grafting-to process.

Supramolecular Immobilization of Laccase on Carbon Nanotube Electrodes Functionalized with (Methylpyrenylaminomethyl)anthraquinone for Direct Electron Reduction of Oxygen

An efficient way of immobilizing and wiring a large amount of laccase on non-covalently-functionalized multi-walled carbon nanotube (MWCNT) electrodes is reported. 1-(2-anthraquinonylaminomethyl)pyrene and 1-[bis(2-anthraquinonyl)aminomethyl]pyrene were synthesized and studied for their capability to non-covalently functionalize MWCNT electrodes and immobilize and orientate laccase on the nanostructured electrodes. This led to high-performance biocathodes for oxygen reduction by direct electron transfer with maximum current densities of (1±0.2) mA cm(-2). The performance of the resulting bioelectrodes could be doubled simply by using the bis-anthraquinone compound. The bioelectrodes show excellent stability over weeks and can thus be envisioned in enzymatic biofuel cells.

Fully Oriented Bilirubin Oxidase on Porphyrin-Functionalized Carbon Nanotube Electrodes for Electrocatalytic Oxygen Reduction

The efficient immobilization and orientation of bilirubin oxidase from Myrothecium verrucaria on multi-walled carbon nanotube electrodes by using π-stacked porphyrins as a direct electron-transfer promoter is reported. By comparing the use of different types of porphyrin, the rational effect of the porphyrin structure on both the immobilization and orientation of the enzyme is demonstrated. The best performances were obtained for protoporphyrin IX, which is the natural precursor of bilirubin. These electrodes exhibit full orientation of the enzyme, as confirmed by the observable non-catalytic redox system corresponding to the T1 copper center associated with pure Nernstian electrocatalytic behavior with high catalytic currents of almost 5 mA cm(-2) at neutral pH.