Synthesis,characterization and electrocatalysis of mono- and di-nickel tetraiminodiphenolate macrocyclic complexes as active site models of [NiFe]-hydrogenases

A series of mononuclear Ni^II and binuclear Ni^IINi^II macrocyclic complexes were investigated as functional models of the active site of [Ni–Fe]-hydrogenase. The electrocatalytic properties of the compounds were assessed and their efficiency was correlated with the availability of donor atoms in the structure of the macrocycle to accept the proton. The catalysts exhibited a regular activity for proton reduction. Redox levels and plausible electrochemical mechanisms for H₂ production are presented as well.     

DFT investigation of the TiO2 band shift by nitrogen-containing heterocycle adsorption and implications on dye-sensitized solar cell performance

A density functional theory (DFT) method (periodic DMol³) with full geometry optimization was used to investigate the adsorption of nitrogen-containing heterocycles such as 4-t-butylpyridine (TBP) and imidazole on a TiO₂ anatase (1 0 1) surface. Negative shifts of the TiO₂ Fermi level by N-containing heterocycle adsorption were observed. Imidazole adsorption shifted the Fermi level of TiO₂ more negatively than TBP. This shift corresponded to the enhancement of the open-circuit photovoltage (V_oc) and the reduction of the short-circuit photocurrent density (J_sc) in a dye-sensitized TiO₂ solar cell. We are the first to theoretically discover a TiO₂ band shift upon N-containing heterocycles adsorption, and have successfully related this shift to the effect as an additive in an electrolyte solution on dye-sensitized solar cell performance.     

DFT study of the oxygen reduction reaction on iron,cobalt and manganese macrocycle active sites

The best performing non-precious metal based catalysts for polymer electrolyte membrane fuel cells are manufactured by incorporation of nitrogen into a carbon structure in the presence of iron and cobalt. Herein, density functional theory (DFT) calculations have been performed to investigate the oxygen reduction reaction on catalyst active sites modelled as transition metal macrocycles with iron, cobalt or manganese central atoms. The effects of the transition metal and macrocycle structure have been investigated. The structure of the most promising active sites has been proposed, and the detailed potential energy profiles of the oxygen reduction reaction have been obtained over the active sites, including all intermediate steps with corresponding activation barriers. The efficiency of the active sites depends primarily on the transition metal nature, and the central iron atom accounts for the higher catalytic activity than cobalt and manganese. The central manganese atom can favour the two-electron oxygen reduction pathway and thus yielding hydrogen peroxide.     

A polyene-based polymer functionalized with a model of [FeFe]-hydrogenase and film electrodes assembled from the polymer via spin-coating

A diiron hexacarbonyl complex possessing an alkynyl group as a model complex of the diiron sub-unit of [FeFe]-hydrogenase was polymerized under the catalysis of WCl₆-SnPh₄. The polymer (Poly-{Fe₂}) functionalized with {Fe₂(CO)₆} units which is dominated by cis-form was fully characterised using FTIR, NMR, SEM, TEM, and TGA techniques. Through modifying the monomer, the properties, for example, solubility, of the resultant polymer could be tuned and much larger molecule weight, which was estimated as 7.93 × 10⁵ g mol⁻¹ using static light scattering technique was achieved without compromising its solubility. Spin-coating the functionalized polymer onto the surface of vitreous carbon electrode with or without multi-wall carbon nanotubes (MWCNTs) produced film electrodes which show electrochemical responses. Adding MWCNTs into the film enhances significantly the electrochemical response probably via not only improving the conductivity of the film, but also the increase in its effective surface area after being doped with MWCNTs.     

Photoelectrochemical splitting of water with nanocrystalline Zn1−xMnxO thin films: First-principle DFT computations supporting the systematic experimental endeavor

Photoelectrochemical splitting of water with nanocrystalline Zn_1−xMn_xO thin films was investigated. ZnO thin films with 1, 3, 5 and 7% at. Mn incorporation were synthesized by sol–gel method and characterized by X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray Photoelectron spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM) and UV–Vis spectroscopy. Mn incorporation coupled with variation in sintering temperature led to significant microstructural changes, which tentatively influenced the magnitude of optical absorption and charge carrier mobility, thereby impacting the performance of such systems towards photoelectrochemical splitting of water. Electronic structure computations based on first principle density functional theory (DFT) revealed electronic states of Mn being responsible for the marginally recorded red shift in bandgap energy. Photoelectrochemical measurements using thin films of 1% at. Mn:ZnO sintered at 600 °C yielded 3 times enhanced photocurrent at zero bias due to improved optical absorption. Plausible explanations for the effect have also been offered.     

Development and application of a functional CE-SSCP fingerprinting method based on [Fe–Fe]-hydrogenase genes for monitoring hydrogen-producing Clostridium in mixed cultures

A Capillary Electrophoresis Single Strand Conformation Polymorphism (CE-SSCP) method based on functional [Fe–Fe]-hydrogenase genes was developed for monitoring the hydrogen (H₂)-producing clostridial population in mixed-culture bioprocesses. New non-degenerated primers were designed and then validated on their specific PCR detection of a broad range of clostridial hydA genes. The hydA-based CE-SSCP method gave a specific and discriminating profile for each of the Clostridium strains tested. This method was validated using H₂-producing mixed cultures incubated at temperatures ranging from 25 °C to 45 °C. The hydA CE-SSCP profiles clearly differed between temperatures tested. Hence, they varied according to variations of the H₂ production performances. The HydA sequences amplified with the new primer set indicated that diverse Clostridium strains impacted the H₂ production yields. The highest performances were related to the dominance of Clostridium sporogenes-like hydA sequences. This CE-SSCP tool offers highly reliable and throughput analysis of the functional diversity and structure of the hydA genes for better understanding of the H₂-producing clostridial population dynamics in H₂ dark fermentation bioreactors.     

Unveiling the mechanistic landscape of formic acid dehydrogenation catalyzed by Cp1M(III) catalysts (M = Co or Rh or Ir) with bis(pyrazol-1-yl)methane ligand architecture: A DFT investigation

The production of dihydrogen via formic acid dehydrogenation (FAD) has been gaining remarkable attention and advancement as an alternative, sustainable and clean energy source. Density functional theory (DFT) calculations have been utilized to probe the reaction mechanism of FAD catalyzed by a Cp1Rh(III) complex reported by Fink and Laurenczy with bis(pyrazol-1-yl)methane ligand system. The calculated energetics show that the rate-limiting step is the β-hydride elimination step and protonation by hydronium ion was calculated to be the most favourable route requiring relatively less activation energy than the conventional process which entails formic acid as the proton source. The Co and Ir congeners of the chosen Rh catalyst were computationally designed and they were also found to follow the same mechanism. Interestingly, the three metal centres (Co, Rh and Ir) were estimated to possess nearly the same activation barrier of c.a. 14 kcal/mol at the rate determining step. Thus, the proposed Co complex with such a small rate determining activation barrier, could be considered as a cheap and propitious earth-abundant transition metal-based catalyst for FAD.