The hydrophilic phosphatriazaadamantane ligand in the development of H2 production electrocatalysts: iron hydrogenase model complexes

As functional biomimics of the hydrogen-producing capability of the dinuclear active site in [Fe]H(2)ase, the Fe(I)Fe(I) organometallic complexes, (mu-pdt)[Fe(CO)(2)PTA](2), 1-PTA(2), (pdt = SCH(2)CH(2)CH(2)S; PTA = 1,3,5-triaza-7-phosphaadamantane), and (mu-pdt)[Fe(CO)(3)][Fe(CO)(2)PTA], 1-PTA, were synthesized and fully characterized. For comparison to the hydrophobic (mu-pdt)[Fe(CO)(2)(PMe(3))](2) and [(mu-H)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)](+) analogues, electrochemical responses of 1-PTA(2) and 1-(PTA.H(+))(2) were recorded in acetonitrile and in acetonitrile/water mixtures in the absence and presence of acetic acid. The production of H(2) and the dependence of current on acid concentration indicated that the complexes were solution electrocatalysts that decreased over-voltage for H(+) reduction from HOAc in CH(3)CN by up to 600 mV. The most effective electrocatalyst is the asymmetric 1-PTA species, which promotes H(2) formation from HOAc (pK(a) in CH(3)CN = 22.6) at -1.4 V in CH(3)CN/H(2)O mixtures at the Fe(0)Fe(I) redox level. Functionalization of the PTA ligand via N-protonation or N-methylation, generating (mu-pdt)[Fe(CO)(2)(PTA-H(+))](2), 1-(PTA.H(+))(2), and (mu-pdt)[Fe(CO)(2)(PTA-CH(3)(+))](2), 1-(PTA-Me(+))(2), provided no obvious advantages for the electrocatalysis because in both cases the parent complex is reclaimed during one cycle under the electrochemical conditions and H(2) production catalysis develops from the neutral species. The order of proton/electron addition to the catalyst, i.e., the electrochemical mechanism, is dependent on the extent of P-donor ligand substitution and on the acid strength. Cyclic voltammetric curve-crossing phenomena was observed and analyzed in terms of the possible presence of an eta(2)-H(2)-Fe(II)Fe(I) species, derived from reduction of the Fe(I)Fe(I) parent complex to Fe(0)Fe(I) followed by uptake of two protons in an ECCE mechanism.     

Molecular chemisorption at well-defined Pd(111) electrode surfaces: hydroquinone sulfonate studied by UHV-EC-STM

The chemisorption of 2,5-dihydroxybenzenesulfonate (hydroquinone sulfonate, HQS) from dilute aqueous solutions, onto a well-defined Pd(111) electrode surface has been studied by a combination of Auger electron spectroscopy, high-resolution electron energy loss spectroscopy, scanning tunneling microscopy and electrochemistry. The results indicate that HQS is oxidatively chemisorbed and exists on the surface as benzoquinone sulfonate (BQS); it is oriented essentially parallel to the surface with a slight tilt due to the bulky SO₃⁻ group. The H⁺ counter-ions in the ionic adlayer can be exchanged reversibly and quantitatively by K⁺ or Cs⁺ ions without changes in the structure and coverage of the surface-anchored species.     

Inclusive and exclusive measurements in the projectile breakup of 7Li

The inclusive and exclusive measurements were carried out for ⁷Li projectile breakup on ²⁷Al target at 48 MeV. In the inclusive data we have observed a broad peak around the beam velocity for alphas and tritons. The exclusive data for alpha-triton coincidences show good agreement with the post-form DWBA theory of breakup reactions.