The search for active semiconductor photocatalysts that directly split water under visible-light irradiation remains one of the most challenging tasks for solar-energy utilization. Over the past 30 years, the search for such materials has focused mainly on metal-ion substitution as in In(1-x)Ni(x)TaO(4) and (V-,Fe- or Mn-)TiO(2) (refs 7,8), non-metal-ion substitution as in TiO(2-x)N(x) and Sm(2)Ti(2)O(5)S(2) (refs 9,10) or solid-solution fabrication as in (Ga(1-x)Zn(x))(N(1-x)O(x)) and ZnS-CuInS(2)-AgInS(2) (refs 11,12). Here we report a new use of Ag(3)PO(4) semiconductor, which can harness visible light to oxidize water as well as decompose organic contaminants in aqueous solution. This suggests its potential as a photofunctional material for both water splitting and waste-water cleaning. More generally, it suggests the incorporation of p block elements and alkali or alkaline earth ions into a simple oxide of narrow bandgap as a strategy to design new photoelectrodes or photocatalysts.
Phases of matter are usually identified through the lens of spontaneous symmetry breaking, which particularly applies to unconventional superconductivity and the interactions it originates from. In that context, the superconducting state of the quasi-two-dimensional and strongly correlated Sr 2 RuO 4 is uniquely held up as a solid-state analog to superfluid 3 He-A 1, 2 , with an odd-parity vector order parameter that is unidirectional in spin space for all electron momenta and also breaks time-reversal symmetry. This characterization was recently * These authors contributed equally to this work. 1 called into question by a search for, and failure to find, evidence for an expected "split" transition while subjecting a Sr 2 RuO 4 crystal to in-plane uniaxial pressure; instead a dramatic rise and peak in a single transition temperature was observed 3, 4. NMR spectroscopy, which is directly sensitive to the order parameter via the hyperfine coupling to the electronic spin degrees of freedom, is exploited here to probe the nature of superconductivity in Sr 2 RuO 4 and its evolution under strained conditions. A reduction of Knight shifts K is observed for all strain values and temperatures T < T c , consistent with a drop in spin polarization in the superconducting state. In unstrained samples, our results are in contradiction with a body of previous NMR work 5 , and with the most prominent previous proposals for the order parameter. Sr 2 RuO 4 is an extremely clean layered perovskite, and the superconductivity emerges from a strongly correlated Fermi Liquid. The present work imposes tight constraints on the order-parameter symmetry of this archetypal system. The normal state of Sr 2 RuO 4 is based on three bands crossing the Fermi level 6, 7 , with pronounced strong-correlation characteristics linked to Hund's Rule coupling of the partially filled Ru t 2g orbitals dominating the Fermi surface. The transition to a superconducting ground state at T c =1.5 K 8 , with indirect evidence for proximity to ferromagnetism, led to the suggestion that the pair wave functions of the superconducting state likely exhibit a symmetric spin part, i.e., triplet 1. Crucial support for the existence of a triplet order parameter rested on NMR spectroscopy, which showed no change in Knight shift between normal and superconducting states 5. Later, several experiments produced evidence for time-reversal symmetry breaking (TRSB) 9, 10. Together, these reports aligned well to the above-mentioned proposal that Sr 2 RuO 4 is a very clean, quasi two
We have observed Shubnikov-de Haas oscillations in FeSe. The Fermi surface deviates significantly from predictions of band-structure calculations and most likely consists of one electron and one hole thin cylinder. The carrier density is in the order of 0.01 carriers/ Fe, an order-of-magnitude smaller than predicted. Effective Fermi energies as small as 3.6 meV are estimated. These findings call for elaborate theoretical investigations incorporating both electronic correlations and orbital ordering.
We report measurements of resistance and ac magnetic susceptibility on FeSe single crystals under high pressure up to 27.2 kbar. The structural phase transition is quickly suppressed with pressure, and the associated anomaly is not seen above ∼18 kbar. The superconducting transition temperature evolves nonmonotonically with pressure, showing a minimum at ∼ 12 kbar. We find another anomaly at 21.2 K at 11.6 kbar. This anomaly most likely corresponds to the antiferromagnetic phase transition found in µSR measurements [M. Bendele et al., Phys. Rev. Lett. 104, 087003 (2010)]. The antiferromagnetic and superconducting transition temperatures both increase with pressure up to ∼ 25 kbar and then level off. The width of the superconducting transition anomalously broadens in the pressure range where the antiferromagnetism coexists.
A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.
By a facile solid‐state reaction method with urea as a nitrogen source, HNb3O8 could be successfully doped with nitrogen without destroying its layered structure. It was found that the intercalation of urea not only helps to stabilize the layered structure of HNb3O8 during the heating process, but also facilitates an easier doping of nitrogen into the solid acid. The nitrogen‐doped HNb3O8 photocatalyst so‐obtained shows fairly good activity under visible light irradiation.
or most of its history, the superconductivity of strontium ruthenate (Sr 2 RuO 4) (ref. 1) has been understood in terms of an odd-parity two-component order parameter with equal-spin pairing in the RuO 2 planes: p x ± ip y (refs. 2-5). This order parameter is chiral: the Cooper pairs have angular momentum l = ±1. The evidence for chirality comes from the zero-field muon spin relaxation (ZF-μSR) data 6 , observation of a non-zero Kerr rotation below the critical temperature T c (ref. 7) and signs in the junction experiments of domains in the superconducting state 8,9 , while evidence for equal-spin pairing came from the absence of a change in the Knight shift below T c in nuclear magnetic resonance 10 and polarized neutron scattering 11 measurements. The Knight shift is related to the spin susceptibility; in conventional opposite-spin-pairing superconductors, it is suppressed below T c. However, in new measurements, it has been found that the Knight shift is, in fact, suppressed below T c (refs. 12-14), by a magnitude that is unlikely to be reconcilable with equal-spin pairing. This revision has called into question a number of other results on Sr 2 RuO 4. It raises a particular challenge for experiments that indicate chirality, because opposite-spin pairing implies an even-parity momentum-space gap structure. If the order parameter is constrained to be even parity, chiral, and composed of components that are degenerate on the tetragonal lattice of Sr 2 RuO 4 , the only possibility is d xz ± id yz order 15. Under conventional understanding, this is a highly unlikely order parameter because it
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