No abstract

N-type XNiSn (X ¼ Ti, Zr, Hf) half-Heusler (HH) compounds possess excellent thermoelectric properties, which are believed to be attributed to their relatively high mobility. However, p-type XNiSn HH compounds have poor figures of merit, zT, compared to XCoSb compounds. This can be traced to the suppression of the magnitude of the thermopower at high temperatures. E g ¼ 2eS max T max relates the band gap to the thermopower peak.However, from this formula, one would conclude that the band gap of p-type XNiSn solid solutions is only one-third that of n-type XNiSn, which effectively prevents p-type XNiSn HHs from being useful thermoelectric materials. The study of p-type HH Zr 1Àx Sc x NiSn solid solutions show that the large mobility difference between electrons and holes in XNiSn results in a significant correction to the Goldsmid-Sharp formula. This finding explains the difference in the thermopower band gap between n-type and p-type HH. The high electron-to-hole weighted mobility ratio leads to an effective suppression of the bipolar effect in the thermoelectric transport properties which is essential for high zT values in n-type XNiSn (X ¼ Ti, Zr, Hf) HH compounds.

Inspired by the promising thermoelectric properties of phase-separated half-Heusler materials, we investigated the influence of electron doping in the n-type Ti 0.3Àx Zr 0.35 Hf 0.35 NiSn compound. The addition of Nb to this compound led to a significant increase in its electrical conductivity, and shifted the maximum Seebeck coefficient to higher temperatures owing to the suppression of intrinsic carriers. This resulted in an enhancement of both the power factor a 2 s and figure of merit, zT. The applicability of an average effective mass model revealed the optimized electron properties for samples containing Nb.There is evidence in the literature that the average effective mass model is suitable for estimating the optimized carrier concentration of thermoelectric n-type half-Heusler compounds.

Nickel-containing superoxide dismutase (NiSOD) is a mononuclear cysteinate-ligated nickel metalloenzyme that catalyzes the disproportionation of superoxide into dioxygen and hydrogen peroxide by cycling between Ni(II) and Ni(III) oxidation states. All of the ligating residues to nickel are found within the first six residues from the N-terminus, which has prompted several research groups to generate NiSOD metallopeptide-based mimics derived from the first several residues of the NiSOD sequence. To assess the viability of using these metallopeptide-based mimics (NiSOD maquettes) to probe the mechanism of SOD catalysis facilitated by NiSOD, we computationally explored the initial step of the O2(-) reduction mechanism catalyzed by the NiSOD maquette {Ni(II)(SOD(m1))} (SOD(m1) = HCDLP CGVYD PA). Herein we use spectroscopic (S K-edge X-ray absorption spectroscopy, electronic absorption spectroscopy, and circular dichroism spectroscopy) and computational techniques to derive the detailed active-site structure of {Ni(II)(SOD(m1))}. These studies suggest that the {Ni(II)(SOD(m1))} active-site possesses a Ni(II)-S(H(+))-Cys(6) moiety and at least one associated water molecule contained in a hydrogen-bonding interaction to the coordinated Cys(2) and Cys(6) sulfur atoms. A computationally derived mechanism for O2(-) reduction using the formulated active-site structure of {Ni(II)(SOD(m1))} suggests that O2(-) reduction takes place through an apparent initial outersphere hydrogen atom transfer (HAT) from the Ni(II)-S(H(+))-Cys(6) moiety to the O2(-) molecule. It is proposed that the water molecule aids in driving the reaction forward by lowering the Ni(II)-S(H(+))-Cys(6) pK(a). Such a mechanism is not possible in NiSOD itself for structural reasons. These results therefore strongly suggest that maquettes derived from the primary sequence of NiSOD are mechanistically distinct from NiSOD itself despite the similarities in the structure and physical properties of the metalloenzyme vs the NiSOD metallopeptide-based models.