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Despite the fruitful achievements in the development of hydrogen production catalysts with record-breaking performances, there is still a lack of durable catalysts that could work under large current densities (>1000 mA cm−2). Here, we investigated the catalytic behaviors of Sr2RuO4 bulk single crystals. This crystal has demonstrated remarkable activities under the current density of 1000 mA cm−2, which require overpotentials of 182 and 278 mV in 0.5 M H2SO4 and 1 M KOH electrolytes, respectively. These materials are stable for 56 days of continuous testing at a high current density of above 1000 mA cm−2 and then under operating temperatures of 70 °C. The in-situ formation of ferromagnetic Ru clusters at the crystal surface is observed, endowing the single-crystal catalyst with low charge transfer resistance and high wettability for rapid gas bubble removal. These experiments exemplify the potential of designing HER catalysts that work under industrial-scale current density.

Funding: F.J., A.P.M., and C.W.H. acknowledge the financial support of the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - TRR 288 - 422213477 (project A10). H.S.R. and S.H.S. acknowledge the financial support of the Engineering and Physical Sciences Research Council (UK). H.S.R. acknowledges support from the Aker Scholarship. T.S. acknowledges the support of the Natural Sciences and Engineering Research Council of Canada (NSERC), in particular the Discovery Grant [RGPIN-2020-05842], the Accelerator Supplement [RGPAS-2020-00060], and the Discovery Launch Supplement [DGECR-2020-00222]. N.K. is supported by a KAKENHI Grants-in-Aids for Scientific Research (Grant Nos.17H06136, 18K04715, and 21H01033), and Core-to-Core Program (No. JPJSCCA20170002) from the Japan Society for the Promotion of Science (JSPS) and by a JST-Mirai Program (Grant No. JPMJMI18A3). Applying in-plane uniaxial pressure to strongly correlated low-dimensional systems has been shown to tune the electronic structure dramatically. For example, the unconventional superconductor Sr2RuO4 can be tuned through a single Van Hove point, resulting in strong enhancement of both Tc and Hc2. Out-of-plane (c axis) uniaxial pressure is expected to tune the quasi-two-dimensional structure even more strongly, by pushing it towards two Van Hove points simultaneously. Here, we achieve a record uniaxial stress of 3.2 GPa along the c axis of Sr2RuO4. Hc2 increases, as expected for increasing density of states, but unexpectedly Tc falls. As a first attempt to explain this result, we present three-dimensional calculations in the weak interaction limit. We find that within the weak-coupling framework there is no single order parameter that can account for the contrasting effects of in-plane versus c-axis uniaxial stress, which makes this new result a strong constraint on theories of the superconductivity of Sr2RuO4. Publisher PDF

Despite the fruitful achievements in the development of hydrogen production catalysts with record-breaking performances, there is still a lack of durable catalysts that could work under large current densities (> 1000 mA cm− 2). In the context of this need, we investigated the catalytic behaviors of Sr2RuO4 (SRO) bulk single crystals with well-defined surface crystal structures, which is a benchmark material to explore exotic metallic states and electronic structures. This single crystal has demonstrated remarkable activities under the current density of 1000 mA cm− 2, which require overpotentials of 182 and 278 mV in 0.5 M H2SO4 and 1 M KOH electrolytes, respectively, after ohmic correction. These values slightly increased to 272 and 354 mV even without iR correction, exhibiting high potential for industrial-scale hydrogen production. The high performance is also evidenced by the 56 days of continuous testing at a high current density of above 1000 mA cm− 2 and then under operating temperatures of 70 ℃ for alkaline electrolysis. The in-situ formation of ferromagnetic Ru clusters at the crystal surface is critical for the outstanding catalytic activity, endowing the single-crystal catalyst with low charge transfer resistance and high wettability for rapid gas bubble removal. Density functional theory calculations indicate that SRO gains electrons from the Ru clusters, thus leading to the thermodynamically favorable hydrogen desorption for the rapidly modified catalysts. More generally, our experiment exemplifies the potential of designing novel HER catalysts that work under industrial-scale current density.

Applying in-plane uniaxial pressure to strongly correlated low-dimensional systems has been shown to tune the electronic structure dramatically. For example, the unconventional superconductor Sr

We report on studies of charge carrier plasmon excitations in Sr2RuO4 by transmission Electron Energy-Loss Spectroscopy. In particular, we present results on the plasmon dispersion and its width as a function of momentum transfer. The dispersion can be qualitatively explained in the framework of RPA calculations, using an unrenormalized tight-binding band structure. The constant long-wavelength width of the plasmon indicates, that it is caused by a decay into inter-band transition and not by quantum critical fluctuations. The results from these studies on a prototypical bad metal system show that the long-wavelength plasmon excitations near 1 eV are caused by resilient quasiparticles and are not influenced by correlation effects., Comment: 6 pages, 3 figures

One of the main developments in unconventional superconductivity in the past two decades has been the discovery that most unconventional superconductors form phase diagrams that also contain other strongly correlated states. Many systems of interest are therefore close to more than one instability, and tuning between the resultant ordered phases is the subject of intense research

This work has been financially supported by the Deutsche Forschungsgemeinschaft (GR 4667/1, GRK 1621 and SFB 1143 projects C02 and C09) and the Max Planck Society. Y.M., T.M. and J.S.B. acknowledge the financial support of JSPS Kakenhi (JP15H5852, JP15K21717 and JP17H06136) and the JSPS Core-to-Core Program. N.K. acknowledges the financial support from JSPS Kakenhi (no. JP18K04715) and JST-Mirai Program (no. JPMJMI18A3). A.N. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 701647. Strontium ruthenate (Sr2RuO4) continues to present an important test of our understanding of unconventional superconductivity, because while its normal-state electronic structure is known with precision, its superconductivity remains unexplained. There is evidence that its order parameter is chiral, but reconciling this with recent observations of the spin part of the pairing requires an order parameter that is either finely tuned or implies a new form of pairing. Therefore, a definitive resolution of whether the superconductivity of Sr2RuO4 is chiral is important for the study of superconductivity. Here we report the measurement of zero-field muon spin relaxation—a probe sensitive to weak magnetism—on samples under uniaxial stresses. We observe stress-induced splitting between the onset temperatures of superconductivity and time-reversal symmetry breaking—consistent with the qualitative expectations for a chiral order parameter—and argue that this observation cannot be explained by conventional magnetism. In addition, we report the appearance of bulk magnetic order under higher uniaxial stress, above the critical pressure at which a Lifshitz transition occurs in Sr2RuO4. Postprint

We report resistance and elastoresistance measurements on $({\mathrm{Ba}}_{0.5}{\mathrm{K}}_{0.5}){\mathrm{Fe}}_{2}{\mathrm{As}}_{2}$, ${\mathrm{CaKFe}}_{4}{\mathrm{As}}_{4}$, and ${\mathrm{KCa}}_{2}{\mathrm{Fe}}_{4}{\mathrm{As}}_{4}{\mathrm{F}}_{2}$. The Fe-site symmetry is ${D}_{2d}$ in the first compound but ${C}_{2v}$ in the latter two, which lifts the degeneracy of the Fe ${d}_{xz}$ and ${d}_{yz}$ orbitals. The temperature dependence of the resistance and elastoresistance is similar between the three compounds. Especially, the [110] elastoresistance is enhanced with decreasing temperature irrespective of the Fe-site symmetry. This appears to be in conflict with recent Raman scattering studies on ${\mathrm{CaKFe}}_{4}{\mathrm{As}}_{4}$, which suggest the absence of nematic fluctuations. We consider possible ways of reconciliation and suggest that the present result is important in elucidating the origin of in-plane resistivity anisotropy in iron-based superconductors.

The interplay between spin–orbit coupling and structural inversion symmetry breaking in solids has generated much interest due to the nontrivial spin and magnetic textures which can result. Such studies are typically focused on systems where large atomic number elements lead to strong spin–orbit coupling, in turn rendering electronic correlations weak. In contrast, here we investigate the temperature-dependent electronic structure of [Formula: see text] , a [Formula: see text] oxide metal for which both correlations and spin–orbit coupling are pronounced and in which octahedral tilts and rotations combine to mediate both global and local inversion symmetry-breaking polar distortions. Our angle-resolved photoemission measurements reveal the destruction of a large hole-like Fermi surface upon cooling through a coupled structural and spin-reorientation transition at 48 K, accompanied by a sudden onset of quasiparticle coherence. We demonstrate how these result from band hybridization mediated by a hidden Rashba-type spin–orbit coupling. This is enabled by the bulk structural distortions and unlocked when the spin reorients perpendicular to the local symmetry-breaking potential at the Ru sites. We argue that the electronic energy gain associated with the band hybridization is actually the key driver for the phase transition, reflecting a delicate interplay between spin–orbit coupling and strong electronic correlations and revealing a route to control magnetic ordering in solids.

The cubic Kondo lattice ${\mathrm{YbCo}}_{2}{\mathrm{Zn}}_{20}$ is one of the heaviest known Fermi liquids. We have measured the low-temperature electrical resistivity $\ensuremath{\rho}(T)$, magnetic susceptibility $\ensuremath{\chi}(T)$, and heat capacity $C(T)$ in single crystals of $\mathrm{Yb}{({\mathrm{Co}}_{1\ensuremath{-}x}{\mathrm{Ni}}_{x})}_{2}{\mathrm{Zn}}_{20}$ ($x\ensuremath{\le}0.126$) and $\mathrm{Yb}{({\mathrm{Co}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{y})}_{2}{\mathrm{Zn}}_{20}$ ($y\ensuremath{\le}0.07$). While pure ${\mathrm{YbCo}}_{2}{\mathrm{Zn}}_{20}$ displays maxima in $\ensuremath{\rho}(T)$ and $\ensuremath{\chi}(T)$, ascribed to an enhanced crystal electric field (CEF) degeneracy, the maxima are suppressed by small amounts ($\ensuremath{\approx}6$ at.%) of substitutions of the Co atoms. This goes along with a suppression of superheavy Fermi liquid behavior as manifested in the divergence of $C/T$. We ascribe the observations to local distortions at the Yb site due to the chemical disorder in the environment, rather than to a chemical pressure effect. This fragileness to the local distortion indicates that superheavy Fermion behavior in ${\mathrm{YbCo}}_{2}{\mathrm{Zn}}_{20}$ is closely linked to an enhanced CEF degeneracy.

We report the magnetocaloric effect of the Tsai-type 1/1 quasicrystal approximants Au64Al22R14 (R = Gd, Tb, and Dy) with the space group of Im 3 . These approximants with the electron-per-atom (e/a) ratio of 1.72 exhibit a ferromagnetic transition in bulk at the Curie temperatures of 27, 15, and 9.5 K for R = Gd, Tb, and Dy, respectively, as confirmed by both magnetic susceptibility and specific heat measurements. The magnetic entropy change (ΔSM) of the materials for a field change of 7 T are 6.3, 4.4, and 4.8 J/K mol-R for R = Gd, Tb, and Dy, respectively. Other parameters related to the magnetocaloric effect, the adiabatic temperature change (ΔTad) and the relative cooling power (RCP) are also evaluated. We also discuss the obtained magnetocaloric effect of the approximants with relation to the recently reported unique magnetic order formed on the icosahedral clusters, a building unit of the Tsai-type 1/1 quasicrystal approximants.

Polar distortions in solids give rise to the well-known functionality of switchable macroscopic polarisation in ferroelectrics and, when combined with strong spin-orbit coupling, can mediate giant spin splittings of electronic states. While typically found in insulators, ferroelectric-like distortions can remain robust against increasing itineracy, giving rise to so-called "polar metals". Here, we investigate the temperature-dependent electronic structure of Ca$_3$Ru$_2$O$_7$, a correlated oxide metal in which octahedral tilts and rotations combine to mediate pronounced polar distortions. Our angle-resolved photoemission measurements reveal the destruction of a large hole-like Fermi surface upon cooling through a coupled structural and spin-reorientation transition at 48 K, accompanied by a sudden onset of quasiparticle coherence. We demonstrate how these result from band hybridisation mediated by a hidden Rashba-type spin-orbit coupling. This is enabled by the bulk structural distortions and unlocked when the spin reorients perpendicular to the local symmetry-breaking potential at the Ru sites. We argue that the electronic energy gain associated with the band hybridisation is actually the key driver for the phase transition, reflecting a delicate interplay between spin-orbit coupling and strong electronic correlations, and revealing a new route to control magnetic ordering in solids., Comment: Contains 6+5 pages, including supplementary information

Sr2RuO4 has stood as the leading candidate for a spin-triplet superconductor for 26 years1. However, recent NMR experiments have cast doubt on this candidacy2,3 and it is difficult to find a theory of superconductivity that is consistent with all experiments. The order parameter symmetry for this material therefore remains an open question. Symmetry-based experiments are needed that can rule out broad classes of possible superconducting order parameters. Here, we use resonant ultrasound spectroscopy to measure the entire symmetry-resolved elastic tensor of Sr2RuO4 through the superconducting transition. We observe a thermodynamic discontinuity in the shear elastic modulus c66, which implies that the superconducting order parameter has two components. A two-component p-wave order parameter, such as px + ipy, naturally satisfies this requirement. As this order parameter appears to have been precluded by recent NMR experiments, we suggest that two other two-component order parameters, namely $$\{{d}_{xz},{d}_{yz}\}$$ and $$\{{d}_{{x}^{2}-{y}^{2}},{g}_{xy({x}^{2}-{y}^{2})}\}$$ , are now the prime candidates for the order parameter of Sr2RuO4. Ultrasound measurements show that the superconducting order parameter in strontium ruthenate must have two components.

The authors would like to acknowledge the financial support from the Max-Planck Society. E.H. and M.N. acknowledge support from Deutsche Forschungsgemeinschaft (DFG) through the Project No. 107745057 (TRR80: From Electronic Correlations to Functionality). This work is also supported by JSPS KAKENHI (No. 18K04715). A portion of this work was performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreements No. DMR-1157490 and No. DMR-1644779 and the State of Florida. The delafossite series of layered oxides includes some of the highest conductivity metals ever discovered. Of these, PtCoO2, with a room-temperature resistivity of 1.8 μΩcm for in-plane transport, is the most conducting of all. The high conduction takes place in triangular lattice Pt layers, separated by layers of Co-O octahedra, and the electronic structure is determined by the interplay of the two types of layers. We present a detailed study of quantum oscillations in PtCoO2, at temperatures down to 35 mK and magnetic fields up to 30 T. As for PdCoO2 and PdRhO2, the Fermi surface consists of a single cylinder with mainly Pt character and an effective mass close to the free-electron value. Due to Fermi-surface warping, two close-lying high frequencies are observed. Additionally, a pronounced difference frequency appears. By analyzing the detailed angular dependence of the quantum-oscillation frequencies, we establish the warping parameters of the Fermi surface. We compare these results to the predictions of first-principles electronic-structure calculations including spin-orbit coupling on Pt and Co and on-site correlation U on Co, and hence demonstrate that electronic correlations in the Co-O layers play an important role in determining characteristic features of the electronic structure of PtCoO2. Publisher PDF

This work was supported in part by the Laboratory Directed Research and Development (LDRD) program of Los Alamos National Laboratory under Project No. 20170204ER. Y. L. acknowledges partial support through the LDRD and 1000 Youth Talents Plan of China. N. K. acknowledges the support from JSPS KAKNHI (Grant No. 18K04715). I. I.M. is supported by ONR through the NRL basic research program. This work is supported in part by the National Science Foundation (Grants No. DMR-1410343 and No. DMR-1709304).

Nonequilibrium steady state conditions induced by a dc current can alter the physical properties of strongly correlated electron systems. In this regard, it was recently shown that dc current can trigger novel electronic states, such as current-induced diamagnetism, which cannot be realized in equilibrium conditions. However, reversible control of diamagnetism has not been achieved yet. Here, we demonstrate reversible in situ control between a Mott insulating state and a diamagnetic semimetal-like state by a dc current in the Ti-substituted bilayer ruthenate ${\mathrm{Ca}}_{3}({\mathrm{Ru}}_{1\ensuremath{-}x}{\mathrm{Ti}}_{x}{)}_{2}{\mathrm{O}}_{7}$ ($x=0.5%$). By performing simultaneous magnetic and resistive measurements, we map out the temperature vs current-density phase diagram in the nonequilibrium steady state of this material. The present results open up the possibility of creating novel electronic states in a variety of strongly correlated electron systems under dc current.

We perform de Haas-van Alphen measurements and quasiparticle self-consistent \textit{GW} (QS\textit{GW}) calculations on FeS. The calculated Fermi surface (FS) consists of two hole and two electron cylinders. We observe all the eight predicted FS cross sections experimentally. With momentum-independent band-energy adjustments of less than 0.1 eV, the maximum deviation between the calculated and observed cross sections is less than 0.2\% of the Brillouin zone area for $B \parallel c$. The carrier density is $\sim$0.5 carriers/Fe. The mass enhancements are nearly uniform across the FS cylinders and moderate, $\sim$2. The absence of a third hole cylinder with $d_{xy}$ character is favorable for the formation of a nodal superconducting gap., 7 pages, 3 figures

We report magnetic torque measurements on iron-pnictide superconductors ${\mathrm{Ba}}_{1\ensuremath{-}x}{\mathrm{K}}_{x}{\mathrm{Fe}}_{2}{\mathrm{As}}_{2}$ ($x\ensuremath{\approx}$ 0.69 and 0.76) to an applied field of ${B}_{a}=45$ T. The peak effect is observed in torque-vs-field curves below the irreversibility field. It is enhanced and becomes asymmetric as the field is tilted from the $c$ axis. For field directions close to the $ab$ plane, increasing- and decreasing-field curves peak at markedly different fields and exhibit a sharp jump, suggestive of a first-order phase transition, on the high- and the low-field sides of the peak, respectively. Complicated history dependence of the torque is observed in the peak-effect region. We construct and discuss the temperature-- ($T$) applied-magnetic-field (${B}_{a}$) phase diagram. Since the upper critical field for the $ab$-plane direction is comparable to the Pauli limit, we also consider possible influence of the spin paramagnetic effect on the anomalous peak effect.

Nonequilibrium steady state conditions induced by a dc current can alter the physical properties of strongly correlated electron systems. In this regard, it was recently shown that dc current can trigger novel electronic states, such as current-induced diamagnetism, which cannot be realized in equilibrium conditions. However, reversible control of diamagnetism has not been achieved yet. Here, we demonstrate reversible in situ control between a Mott insulating state and a diamagnetic semimetal-like state by a dc current in the Ti-substituted bilayer ruthenate Ca_{3}(Ru_{1-x}Ti_{x})_{2}O_{7} (x=0.5%). By performing simultaneous magnetic and resistive measurements, we map out the temperature vs current-density phase diagram in the nonequilibrium steady state of this material. The present results open up the possibility of creating novel electronic states in a variety of strongly correlated electron systems under dc current.

To investigate the electronic state of CeRu2Al10, which exhibits an unusual antiferromagnetic order below TN = 27 K, we measured the electrical resistivity ρ, the transverse magnetoresistance (TMR)...

Magnetic properties of an Yb-based semiconductor YbCuS2 with a zigzag chain of Yb3+ ions were studied. The Curie–Weiss behavior of the magnetic susceptibility χ(T) indicates antiferromagnetic inter...

The Ce atoms in CeIrSn form a quasikagome lattice in the hexagonal $c$ plane. Our single-crystal x-ray diffraction analysis has confirmed the absence of superstructure in the ZrNiAl-type structure. Motivated by the recent observation of quantum critical behaviors in the isostructural and isoelectronic compound CeRhSn, we have studied low-temperature properties of single-crystalline samples of CeIrSn by measuring the electrical resistivity, magnetic susceptibility $\ensuremath{\chi}$, magnetization $M$, and specific heat $C$ down to 0.05 K. Our study does not show evidence of a long-range magnetic ordering down to the lowest temperature. The $\ensuremath{\chi}(T)$ data show an Ising character, ${\ensuremath{\chi}}_{c}\ensuremath{\gg}{\ensuremath{\chi}}_{a}$, and power-law behaviors at low temperatures: ${\ensuremath{\chi}}_{c}\ensuremath{\propto}{T}^{\ensuremath{-}0.8}$ and ${\ensuremath{\chi}}_{a}\ensuremath{\propto}{T}^{\ensuremath{-}0.6}$. When external field $B$ is applied along the $a$ axis, both $M(B)$ and $C(B)/T$ exhibit metamagnetic anomalies at 5.5 T, which resemble those observed in CeRhSn at 3.5 T. We attribute the metamagnetic crossover under in-plane magnetic fields to the alleviation of magnetic frustration inherent in the quasikagome Ising Kondo lattice.

Resistance and magnetic torque measurements are reported in a layered organic superconductor, $\ensuremath{\beta}''\ensuremath{-}{(\mathrm{BEDT}\ensuremath{-}\mathrm{TTF})}_{4}[({\mathrm{H}}_{3}\mathrm{O})\mathrm{Ga}{({\mathrm{C}}_{2}{\mathrm{O}}_{4})}_{3}]{\mathrm{C}}_{6}{\mathrm{H}}_{5}{\mathrm{NO}}_{2}$ with ${T}_{c}=4.8$ K, where BEDT-TTF stands for bis(ethylenedithio)tetrathiafulvalene. Because of the large anion between the BEDT-TTF conducting layers, the superconductivity of this salt is highly anisotropic. In magnetic fields parallel to the conducting layers for $T=0.4$ K, the magnetic torque shows a large diamagnetic signal associated with hysteresis up to $\ensuremath{\sim}21$ T, suggesting the upper critical field ${H}_{c2}\ensuremath{\gtrsim}21$ T at 0.4 K. The large reduction of the diamagnetic signal is observed above 16 T, which shows a Fulde and Ferrell and Larkin and Ovchinnikov (FFLO) phase transition. For $T=0.5$ K, the interlayer resistance has nonzero value in a wide field region up to ${H}_{c2}$, arising from the Josephson vortex dynamics. Successive dips in the second derivative curves of the resistance are observed between 16 T and ${H}_{c2}$, which are ascribed to the commensurability effect between the Josephson vortex lattice and the order parameter oscillation of the FFLO phase. The commensurability effect is observed only in nearly parallel fields, showing that the FFLO phase is stable in a very limited field angle region. The temperature-field phase diagram is determined.

The strongly correlated insulator Ca2RuO4 is considered as a paradigmatic realization of both spin-orbital physics and a band-Mott insulating phase, characterized by orbitally selective coexistence of a band and a Mott gap. We present a high resolution oxygen K-edge resonant inelastic x-ray scattering study of the antiferromagnetic Mott insulating state of Ca2RuO4. A set of low-energy (about 80 and 400 meV) and high-energy (about 1.3 and 2.2 eV) excitations are reported, which show strong incident light polarization dependence. Our results strongly support a spin-orbit coupled band-Mott scenario and explore in detail the nature of its exotic excitations. Guided by theoretical modeling, we interpret the low-energy excitations as a result of composite spin-orbital excitations. Their nature unveils the intricate interplay of crystal-field splitting and spin-orbit coupling in the band-Mott scenario. The high-energy excitations correspond to intra-atomic singlet-triplet transitions at an energy scale set by Hund’s coupling. Our findings give a unifying picture of the spin and orbital excitations in the band-Mott insulator Ca2RuO4.

We report single-crystal growth of a perovskite ruthenate SrRuO3 by the floating-zone method using an infrared image furnace. By employing a cold trap for the growth, we prevented the evaporated RuO2 from coating the inner surface of a quartz tube and were thereby able to maintain a stable molten zone during the growth. Powder X-ray and Laue diffraction measurements confirmed the quality of the grown single crystal. The crystal was cut into a 1.4 mm × 1.4 mm × 3.0 mm rectangle that was characterized by magnetic susceptibility, magnetization, and specific heat measurements. The crystal showed a ferromagnetic transition with a Curie temperature of 163.5 K, and the coercive field was as low as 0.004 T. The residual resistivity was 1.05 μΩ cm, corresponding to a residual resistivity ratio of 192. These results indicate that the grown crystal is high-quality. Electrical resistivity measurements show temperature-squared behavior, revealing that a Fermi-liquid-like electron–electron scattering is dominant. Toget...

CeRhSn with a quasikagome lattice of Ce atoms in the hexagonal $c$ plane has been expected to be in close vicinity to a zero-field quantum criticality derived from magnetic frustration. We have studied how the ground state changes with substitution of Pd for Rh in $\mathrm{CeR}{\mathrm{h}}_{1\ensuremath{-}x}\mathrm{P}{\mathrm{d}}_{x}\mathrm{Sn}$ $(x\ensuremath{\le}0.75)$ by measuring the specific heat $C$, magnetic susceptibilities ${\ensuremath{\chi}}_{\mathrm{dc}}$ and ${\ensuremath{\chi}}_{\mathrm{ac}}$, magnetization $M$, electrical resistivity \ensuremath{\rho}, and magnetoresistance. For $x=0$, the field dependence of ${\ensuremath{\chi}}_{\mathrm{ac}}$ at $T=0.03\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ shows a peak at $B\ensuremath{\parallel}a=3.5\phantom{\rule{0.16em}{0ex}}\mathrm{T}$, confirming the spin-flop crossover in the field applied along the hard axis. The temperature dependence of ${\ensuremath{\chi}}_{\mathrm{ac}}$ shows a broad maximum at 0.1 K whereas $C/T$ continues to increase down to 0.08 K. For $x\ensuremath{\geqq}0.1,\ensuremath{\rho}(T)$ is dominated by incoherent Kondo scattering and both $C/T$ and ${\ensuremath{\chi}}_{\mathrm{ac}}(T)$ exhibit peaks, indicating the development of an antiferromagnetic order. The ordering temperature rises to 2.5 K as $x$ is increased to 0.75. Our results indicate that the ground state in the quasikagome Kondo lattice $\mathrm{CeR}{\mathrm{h}}_{1\ensuremath{-}x}\mathrm{P}{\mathrm{d}}_{x}\mathrm{Sn}$ leaves the quantum critical point at $x=0$ with increasing $x$ as a consequence of suppression of both the magnetic frustration and Kondo effect.

Twenty-two new lanthanide tellurite sulfates with five distinct structures, Ln2(Te2O5)(SO4)2 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb; LnTeSO-1), Ho3(TeO3)2(SO4)2(OH)(H2O) (LnTeSO-2), Ln2TeO3(SO4)2(H2O)2 (Ln = Dy, Ho, Er; LnTeSO-3), Ln2(Te2O5)(SO4)2 (Ln = Er, Tm, Yb, Lu; LnTeSO-4), and Ln2(Te4O10)(SO4) (Ln = Gd, Dy, Ho, Er, Tm, Yb; LnTeSO-5), have been prepared and characterized. The topologies of LnTeSO-1, LnTeSO-2, LnTeSO-3, LnTeSO-4, and LnTeSO-5 are substantially different with respect to the connectivity between Ln polyhedra and the coordination environments of the lanthanide ions. For the first four topologies, the dimensionality changes from layered (LnTeSO-1) to chains (LnTeSO-2) to tetramers (LnTeSO-3) and finally to a monomer (LnTeSO-4). The coordination numbers of lanthanides decrease from nine (LnTeSO-1) to eight (LnTeSO-2 and LnTeSO-3) to seven and six (LnTeSO-4). We attribute the transitions to a decrease in the ionic radii of the 4f ions. Magnetic susceptibility measurements reveal no evidence for long-range magnetic ordering in these materials. However, diverse short-range magnetic correlations were observed within LnTeSO-1.

Magnetic torque measurements using a microcantilever have been performed to investigate the superconducting phase of ${\mathrm{Sr}}_{2}{\mathrm{RuO}}_{4}$ down to 40 mK. For high-quality single crystals with the transition temperature $({T}_{\mathrm{c}})$ of 1.48--1.49 K, an abrupt jump of the torque signal is found near 1.5 T in field parallel to the conducting ${\mathrm{RuO}}_{2}$ planes below $\ensuremath{\sim}0.8\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. The jump corresponds to the first order transition recently revealed by magnetocaloric and magnetization measurements [Yonezawa et al., Phys. Rev. Lett. 110, 077003 (2013); Kittaka et al., Phys. Rev. B 90, 220502(R) (2014)]. Furthermore, weak diamagnetic and irreversible signals are found to persist above the first order transition up to 1.85 T. The result indicates the presence of a subphase boundary separating low- and high-field phases in the superconducting phase. The high-field subphase disappears when the field is tilted from the conducting planes only by a few degrees. Quantum oscillation measurements are also reported to clarify the strong sample-quality dependence of the high-field subphase.

The gap structure of Sr$_2$RuO$_4$, which is a longstanding candidate for a chiral p-wave superconductor, has been investigated from the perspective of the dependence of its specific heat on magnetic field angles at temperatures as low as 0.06 K ($\sim 0.04T_{\rm c}$). Except near $H_{\rm c2}$, its fourfold specific-heat oscillation under an in-plane rotating magnetic field is unlikely to change its sign down to the lowest temperature of 0.06 K. This feature is qualitatively different from nodal quasiparticle excitations of a quasi-two-dimensional superconductor possessing vertical lines of gap minima. The overall specific-heat behavior of Sr$_2$RuO$_4$ can be explained by Doppler-shifted quasiparticles around horizontal line nodes on the Fermi surface, whose in-plane Fermi velocity is highly anisotropic, along with the occurrence of the Pauli-paramagnetic effect. These findings, in particular, the presence of horizontal line nodes in the gap, call for a reconsideration of the order parameter of Sr$_2$RuO$_4$., Comment: 5 pages, 3 figures (main text) + 3 pages, 3 figures (supplemental material), accepted for publication in J. Phys. Soc. Jpn

We examine the low temperature states of two transition metal compounds: (i) NbFe 2 is poised on the threshold of ferromagnetism and can be pushed into a spin-aligned state at low temperature by modifying the composition slightly. Stoichiometric NbFe 2 has been reported as a rare example of low-temperature spin density wave order in a d-metal system. We have used pressure, field and composition tuning to examine the phase diagram of NbFe 2 . Near the quantum critical point, we find distinct non-Fermi liquid forms of the resistivity and heat capacity, whereas we observe strong, hysteretic magnetoresistance effects deep in the ordered phase. (ii) Ca 3 Ru 2 O 7 undergoes first a magnetic transition (T N = 56 K) and then a structural transition (T s = 48 K) on cooling. Most of the Fermi surface is gapped out at low temperature, leading to a very low carrier density and small Fermi surface pockets. Pressure suppresses both T N and T S and, for p > 3.5 GPa, induces a third low temperature state, which is robust up to at least 7.5 GPa.

We report dye-degradation effects of a semiconductor LiBiO3 revealed under illumination of a conventionally used white fluorescent light. Optical absorbance spectra of LiBiO3 were broadened so smoothly, with the absorption edge penetrated to around 730 nm, that the material was able to absorb a wide range of visible light. Results showed that solution of a standard dye, methylene blue, was degraded completely after 4 h illumination. Furthermore, the value of total organic carbon decreased 70% in the decolorized solution, suggesting that the molecular form of the original methylene blue was mineralized effectively to nonorganic fragments by the photoinduced oxidization effect. Moreover, the wavelength dependence of apparent photonic efficiency was evaluated using a standard Xe lamp coupled with monochromatic filters. These results were interpreted from the viewpoint of this material’s electronic structure.

A silver germanium oxide, Ag 2 GeO 3 , was developed as a novel photocatalyst for degradation of organic dyes. The chemical composition of the sample was investigated via the SEM/EDX, ICP-AES, and TG-DTA techniques. The general activity of the material was characterized by testing the photodegradations of typical organic dyes, such as Methylene Blue (one of the heteropolyaromatic dyes), Rhodamine B (one of the xanthene dyes), Fuchsin Acid (one of the sulfonic dyes), and Orange II (one of the azoic dyes). All of these dyes were degraded more than 90% within 25 min under the visible-light irradiation of Xe lamp. Besides, with a commercial white fluorescent lamp as testing light source (light intensity, 61 μW/cm 2 ), the efficient decolorizations and mineralizations of the organic dyes were achieved over this material: 79% (90%) of the organic carbon in the Methylene Blue (Rhodamine B) solution was photooxidatized to inorganic carbon forms, when these dyes were totally decolorized. The high performance of this material is due to the photophysical properties of the wide-visible-range absorption and response, and the sufficient oxidative potential of the top of the valence band.

A solid-state reaction method with urea as a nitrogen precursor was used to prepare nitrogen-doped lamellar niobic and titanic solid acids (i.e., HNb(3)O(8) and H(2)Ti(4)O(9)) with different acidities for visible-light photocatalysis. The photocatalytic activities of the nitrogen-doped solid acids were evaluated for rhodamine B (RhB) degradation and the results were compared with those obtained over the corresponding nitrogen-doped potassium salts. Techniques such as XRD, BET, SEM, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy were adopted to explore the nature of the materials as well as the characteristics of the doped nitrogen species. It was found that the intercalation of the urea precursor helped to stabilize the layered structures of both lamellar solid acids and enabled easier nitrogen doping. The effects of urea intercalation were more significant for the more acidic HNb(3)O(8) sample than for the less acidic H(2)Ti(4)O(9). Compared with the nitrogen-doped KNb(3)O(8) and K(2)Ti(4)O(9) samples, the nitrogen-doped HNb(3)O(8) and H(2)Ti(4)O(9) solid acids absorb more visible light and exhibit a superior activity for RhB photodegradation under visible-light irradiation. The nitrogen-doped HNb(3)O(8) sample performed the best among all the samples. The results of the current study suggest that the protonic acidity of the lamellar solid-acid sample is a key factor that influences nitrogen doping and the resultant visible-light photocatalysis.

Four Ag-based semiconductor oxides with visible-light absorption, α-AgGaO2, α-AgInO2, β-AgAlO2, and β-AgGaO2, were prepared to investigate the influences of chemical composition and the crystal structure on the electronic structures and photocatalytic properties of AgMO2 (M = Al, Ga, In). The catalytic efficiencies of these oxides were characterized by testing the photooxidation of gaseous 2-propanol to acetone under visible-light irradiation. The ranking of the activity was α-AgGaO2 > β-AgAlO2 > β-AgGaO2 > α-AgInO2. The electronic structures of these compounds were investigated in terms of density functional theory. These experimental and computational studies of these materials reveal the following: (1) regarding chemical compositions, the conduction bands constructed through hybridization of the Ag 5s5p states with Ga 4s4p states and Al 3s3p states are necessary for promotion of photocatalytic activities under visible light for α-phase and β-phase, respectively, and (2) regarding crystal structures, th...

A novel visible light sensitive photocatalyst, AgSbO3 was prepared by a conventional solid-state reaction method. This oxide belonging to a cubic-pyrochlore structure can absorb visible light with wavelength up to about 480 nm. From the band structure calculation, we found that the top of the valence band consists of the hybridized Ag 4d and O 2p orbitals and the bottom of the conduction band mainly consists of the Ag 5s and the Sb 5s orbitals. Photocatalytic activities were evaluated using O2 evolution from an aqueous silver nitrate solution and decomposition of gaseous 2-propanol under visible light irradiation. We found that AgSbO3 shows a higher O2 evolution activity than WO3 and 2-propanol can be mineralized by the AgSbO3 photocatalysis under visible light irradiation.

We report a multiple-metal oxide Ag2ZnGeO4 with cristobalite-related structure as a visible light-sensitive photocatalyst (Eg 2.29 eV) for dye degradation. The physical characteristics of the samples were examined by techniques such as XRD, UV–vis diffuse reflectance spectroscopy and SEM. The photocatalytic activity of Ag2ZnGeO4 was confirmed by Rhodamine B (RhB) and Orange II photodegradation in aqueous phase. After 360 min of visible light (λ > 420 nm) irradiation, the conversions of RhB and Orange II reached 100% and 69.2%, respectively. The electronic structure of Ag2ZnGeO4 was investigated by band structure calculation based on the density function theory (DFT). Results revealed that the hybridized Ag 4d10 and O 2p6 orbitals form the valence band top of Ag2ZnGeO4, which leads to a much narrowed band gap as compared with that of the Na2ZnGeO4 parent sample. We propose that the specific cristobalite structure of Ag2ZnGeO4 favors the mobility of photo-generated carriers, and that this contributes positively to the observed photocatalytic activity for dye degradation.

The magnetic field-induced changes in the conductivity of metals are the subject of intense interest, both for revealing new phenomena and as a valuable tool for determining their Fermi surface. Here, we report a hitherto unobserved magnetoresistive effect in ultra-clean layered metals, namely a negative longitudinal magnetoresistance that is capable of overcoming their very pronounced orbital one. This effect is correlated with the inter-layer coupling disappearing for fields applied along the so-called Yamaji angles where the inter-layer coupling vanishes. Therefore, it is intrinsically associated with the Fermi points in the field-induced quasi-one-dimensional electronic dispersion, implying that it results from the axial anomaly among these Fermi points. In its original formulation, the anomaly is predicted to violate separate number conservation laws for left- and right-handed chiral- (e.g. Weyl) fermions. Its observation in PdCoO$_2$, PtCoO$_2$ and Sr$_2$RuO$_4$ suggests that the anomaly affects the transport of clean conductors, particularly near the quantum limit., Comment: Nature Communications (in press)